WO2020121965A1 - Laminate and image display device using same - Google Patents

Laminate and image display device using same Download PDF

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Publication number
WO2020121965A1
WO2020121965A1 PCT/JP2019/047800 JP2019047800W WO2020121965A1 WO 2020121965 A1 WO2020121965 A1 WO 2020121965A1 JP 2019047800 W JP2019047800 W JP 2019047800W WO 2020121965 A1 WO2020121965 A1 WO 2020121965A1
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WO
WIPO (PCT)
Prior art keywords
support
laminate
transparent resin
hard coat
film
Prior art date
Application number
PCT/JP2019/047800
Other languages
French (fr)
Japanese (ja)
Inventor
寿和 松本
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
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201980080961.9A priority Critical patent/CN113167931A/en
Priority to KR1020217017356A priority patent/KR20210102245A/en
Publication of WO2020121965A1 publication Critical patent/WO2020121965A1/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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a laminate and an image display device using the same.
  • a transparent resin film having such a hard coat layer is vulnerable to impact, and even when incorporated in an image display device, for example, an external impact such as a touch pen dropping from the pen tip is applied to the display surface of the image display device. It has become clear that in such cases, cracks may occur in the hard coat layer, which may cause a problem.
  • the present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to provide a laminate including a hard coat layer and a transparent resin film having a very thin and excellent impact resistance, and the laminate.
  • An object of the present invention is to provide an image display device provided with the method and a method for manufacturing the laminate.
  • the present invention provides the following laminate, image display device, and method for producing the laminate.
  • a laminate having a transparent resin film, a support formed on at least one surface of the transparent resin film, and a hard coat layer formed on the support in this order, and the support having a patterned structure.
  • the support has at least one structure selected from the group consisting of a honeycomb structure, a truss structure, a rigid frame structure, a stripe structure, and a circular structure.
  • An image display device including the laminate according to any one of [1] to [8].
  • a method for manufacturing a laminate which includes a step of forming.
  • a laminate including a hard coat layer having a very thin and excellent impact resistance and a transparent resin film, an image display device including the laminate, and a method for producing the laminate. it can.
  • FIG. 3 is a plan view showing a support formed on a transparent resin film in the laminate according to one embodiment of the present invention. It is sectional drawing of the laminated body which concerns on one Embodiment of this invention.
  • FIG. 6 is a plan view showing a support formed on a transparent resin film in a laminate according to another embodiment of the present invention.
  • FIG. 9 is a plan view showing a support formed on a transparent resin film in a laminate according to still another embodiment of the present invention.
  • FIG. 9 is a plan view showing a support formed on a transparent resin film in a laminate according to still another embodiment of the present invention.
  • FIG. 9 is a plan view showing a support formed on a transparent resin film in a laminate according to still another embodiment of the present invention. It is sectional drawing of the laminated body which concerns on another embodiment of this invention. It is sectional drawing of the laminated body which concerns on another embodiment of this invention.
  • Refractive index (nx, ny, nz) “Nx” is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), “ny” is the in-plane direction orthogonal to the slow axis, and “nz” is the thickness direction. Is the refractive index.
  • Refractive index (nx, ny, nz) “Nx” is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), “ny” is the in-plane direction orthogonal to the slow axis, and “nz” is the thickness direction. Is the refractive index.
  • Re( ⁇ ) refers to the in-plane retardation value at 23° C. and wavelength ⁇ (nm).
  • FIG. 1 is a plan view showing a support formed on a transparent resin film in a laminate according to one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a laminate according to one embodiment of the present invention.
  • the laminated body 10 includes a transparent resin film 1, a support 2 formed on one surface of the transparent resin film 1, and a hard coat layer 5 formed on the support 2.
  • the hard coat layer 5 formed on the support 2 means that a part or all of the hard coat layer 5 exists above the support 2, and a form formed in contact with the support 2 Both the form formed so as to embed the body 2 and the form formed via the other layer are included.
  • the hard coat layer may be formed on the support 2 so as to embed the support 2 as shown in FIG. 2, or the embedding for embedding the support 2 as shown in FIG. It may be formed on the support 2 via the resin layer 4.
  • the laminated body 10 may have a sheet-like shape or a long shape.
  • the thickness of the transparent resin film is typically 100 ⁇ m or less.
  • the thickness of the support 2 is typically 1 ⁇ m to 15 ⁇ m, and the width of the support 2 in plan view is typically 500 ⁇ m to 3000 ⁇ m.
  • the support 2 is preferably transparent, more preferably transparent and substantially optically isotropic.
  • the support 2 has a pattern structure, and typically has a honeycomb structure as shown in FIG. 1 as the pattern structure.
  • the thickness of the hard coat layer is typically 1 ⁇ m to 15 ⁇ m.
  • the thickness of the hard coat layer means the thickness of the thickest part of the hard coat layer.
  • FIGS. 3 to 6 are plan views showing a support formed on a transparent resin film in a laminate according to another embodiment of the present invention.
  • the support may have a rigid frame structure as shown in FIG. 3 or a truss structure as shown in FIG. 4, and may have a circular structure as shown in FIG. (Arranged structure), or may have a stripe structure as shown in FIG.
  • Arrowd structure a structure as shown in FIG.
  • FIG. 7 is a sectional view of a laminate according to still another embodiment of the present invention.
  • the laminated body 11 has a support 2 (hereinafter sometimes referred to as a first support 2) on one surface of the transparent resin film 1, and the other of the transparent resin film 1 has the support 2.
  • the surface has a support 3 (hereinafter sometimes referred to as a second support 3).
  • the second support 3 has a patterned structure.
  • the pattern structure of the second support 3 may be the same as or different from the pattern structure of the first support 2.
  • the first support 2 and the second support 3 are formed. And are arranged such that the areas of the portions overlapping each other in plan view are small.
  • the hard coat layer 5 is formed on the support 2 and the support 3.
  • FIG. 8 is a sectional view of a laminate according to still another embodiment of the present invention.
  • the laminate 12 includes the embedded resin layer 4 that embeds the support 2 on one surface of the transparent resin film 1.
  • the step formed by the support 2 can be smoothed.
  • the surface of the transparent resin film 1 can be protected.
  • a hard coat layer 5 is formed on the embedded resin layer 4. Note that two or more of the above embodiments may be combined.
  • the transparent resin film used in the present invention has a visible light transmittance of 70% or more, preferably 80% or more.
  • any transparent polymer film can be used. Specifically, polyolefins such as polyethylene, polypropylene, polymethylpentene, norbornene or cycloolefin derivatives having a unit of a monomer containing cycloolefin, diacetyl cellulose, triacetyl cellulose, (modified) cellulose such as propionyl cellulose.
  • Acrylics such as methylmethacrylate (co)polymers, polystyrenes such as styrene (co)polymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers
  • the transparent resin film has a thickness of 5 to 200 ⁇ m, preferably 20 to 100 ⁇ m.
  • the laminate of the present invention has a support on at least one surface of the transparent resin film.
  • the support has a pattern structure as described above.
  • the support preferably has at least one structure selected from the group consisting of a honeycomb structure, a truss structure, a rigid frame structure, a stripe structure, and a circular structure.
  • the support more preferably has a honeycomb structure, a truss structure, or a circular structure, and particularly preferably has a honeycomb structure or a circular structure.
  • the support has a honeycomb structure, a truss structure, or a circular structure
  • the stress can be dispersed in a direction different from that direction, and as a result, the hard This is because the external impact on the coat layer can be mitigated and cracking can be suppressed.
  • the support is preferably transparent and substantially optically isotropic.
  • “having substantially optical isotropy” means that the in-plane retardation Re (550) and the thickness direction retardation Rth (550) of the support are preferably 20 nm or less, respectively. Yes, and more preferably 10 nm or less.
  • the second support is It is preferably arranged such that the area of the portion overlapping the first support is small in plan view.
  • the thickness of the support is preferably 1 ⁇ m to 15 ⁇ m, more preferably 3 ⁇ m to 8 ⁇ m.
  • the compressive elastic modulus of the support at 23° C. is preferably 0.01 GPa to 8.0 GPa, more preferably 0.02 GPa to 6.0 GPa. As a result, it is possible to improve the workability and flexibility of the laminate of the present invention while suppressing cracking of the hard coat layer due to external impact.
  • the compression elastic modulus can be measured by the nanoindentation method.
  • the support can be formed of any appropriate material and method as long as it satisfies the above configuration and has sufficient adhesion to the transparent resin film.
  • the adhesion of the support to the transparent resin film can be evaluated according to the cross-cut peeling test of JIS K5400.
  • the adhesion of the support to the transparent resin film is preferably 0 in the cross-cut peeling test (the number of substrates: 100).
  • the support having a pattern structure is formed by forming a pattern of a resin material or a coating liquid containing a resin material on the surface of a transparent resin film and curing (or solidifying) the resin material. be able to.
  • the support can be formed by depositing an inorganic oxide such as SiO 2 on the surface of the transparent resin film.
  • the resin material any appropriate material can be used as long as the effects of the present invention can be obtained.
  • the resin material include polyester resin, polyether resin, polycarbonate resin, polyurethane resin, silicone resin, polyamide resin, polyimide resin, PVA resin, acrylic resin, epoxy resin, and fluorine.
  • An example is a resin. These may be used alone or in combination (eg, blending, copolymerization).
  • the method of forming the pattern of the resin material or the coating liquid on the surface of the transparent resin film is not particularly limited. Examples of the above method include printing, photolithography, inkjet, nozzle, die coating and the like.
  • the pattern of the resin material or the coating liquid is preferably formed by printing. Examples of the method of printing the coating liquid in a pattern include a relief printing method, a direct gravure printing method, an intaglio printing method, a lithographic printing method, a stencil printing method and the like.
  • the coating liquid may contain any appropriate other component as long as the effect of the present invention is not impaired.
  • Such other components include, for example, resin components other than the above-mentioned resin materials as main components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and antioxidants. , A conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.
  • the conditions for curing (or solidifying) the above resin material (coating liquid) can be appropriately set according to the type of resin material and the composition of the composition.
  • the resin material can be cured (or solidified) by drying, curing with active energy rays, heat curing, or the like.
  • the embedding resin layer embeds the support formed on one surface of the transparent resin film as described above.
  • the thickness of the embedding resin layer is larger than the thickness of the support, preferably 3 ⁇ m to 150 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m.
  • the embedding resin layer may be any appropriate functional layer formed according to the characteristics required for the transparent resin film. Examples of the functional layer include a hard coat layer, a pressure-sensitive adhesive layer, a transparent optical pressure-sensitive adhesive layer, and the like.
  • the embedding resin layer is a hard coat layer
  • its thickness is, for example, 5 ⁇ m to 15 ⁇ m
  • the embedding resin layer is an adhesive layer
  • its thickness is, for example, 5 ⁇ m to 30 ⁇ m
  • the embedding resin layer is transparent.
  • an optical adhesive layer its thickness is, for example, 25 ⁇ m to 125 ⁇ m.
  • the embedding resin layer is preferably transparent and has substantially optical isotropy.
  • the embedding resin layer may be formed of the same material as the hard coat layer described later, or may be formed of a different material.
  • the embedding resin layer can be formed by any appropriate material and method as long as it has sufficient adhesion to the transparent resin film and the support.
  • the embedded resin layer can be formed of a resin material different from that of the support.
  • the embedding resin layer can be formed by forming a resin layer on the surface of the transparent resin film so as to embed the support and curing the resin layer.
  • the method of forming the resin layer on the surface of the transparent resin film is not particularly limited.
  • the resin layer can be formed by applying a coating liquid containing a resin material onto the surface of the transparent resin film.
  • Any appropriate coating method can be used as the coating method. Specific examples include curtain coating method, dip coating method, spin coating method, printing coating method, spray coating method, slot coating method, roll coating method, slide coating method, blade coating method, gravure coating method, and wire bar method. Be done.
  • the curing conditions can be appropriately set according to the type of resin material used, the composition of the composition, and the like.
  • the coating liquid may contain any appropriate other component as long as the effect of the present invention is not impaired.
  • Such other components include, for example, resin components other than the above-mentioned resin materials as main components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and antioxidants. , A conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.
  • the laminate has a hard coat layer on the support.
  • the hard coat layer may be substituted with the embedding resin layer. If the material forming the hard coat layer and the material forming the embedding resin layer are the same, it can be said that the hard coat layer also serves as the embedding resin layer.
  • the thickness of the hard coat layer is not particularly limited and may be, for example, 2 to 100 ⁇ m. If the thickness of the hard coat layer is less than 2 ⁇ m, it is difficult to secure sufficient scratch resistance, and if it exceeds 100 ⁇ m, the flex resistance may be deteriorated and curling due to curing shrinkage may occur. ..
  • the hard coat layer can be formed by curing a hard coat composition containing a reactive material that forms a crosslinked structure by irradiating with active energy rays or heat energy, but is preferably cured by active energy rays.
  • An active energy ray is defined as an energy ray capable of decomposing a compound generating an active species to generate an active species. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X rays, ⁇ rays, ⁇ rays, ⁇ rays and electron rays. Ultraviolet light is particularly preferred.
  • the hard coat composition contains at least one polymer of a radically polymerizable compound and a cationically polymerizable compound.
  • the above-mentioned radical polymerizable compound is a compound having a radical polymerizable group.
  • the radical polymerizable group contained in the radical polymerizable compound may be a functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond. Specific examples thereof include a vinyl group and a (meth)acryloyl group.
  • the radical-polymerizable compound has two or more radical-polymerizable groups, these radical-polymerizable groups may be the same or different.
  • the number of radically polymerizable groups contained in one molecule of the radically polymerizable compound is preferably 2 or more from the viewpoint of improving the hardness of the hard coat layer.
  • a compound having a (meth)acryloyl group is preferable from the viewpoint of high reactivity, and a polyfunctional acrylate monomer having 2 to 6 (meth)acryloyl groups in one molecule is preferable.
  • Preferred compounds and oligomers having several (meth)acryloyl groups in the molecule which are called compounds and epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, and whose molecular weight is several hundred to several thousand Can be used. It is preferable to include at least one selected from epoxy (meth)acrylate, urethane (meth)acrylate and polyester (meth)acrylate.
  • the above-mentioned cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, a vinyl ether group.
  • the number of cationically polymerizable groups contained in one molecule of the cationically polymerizable compound is preferably 2 or more, and more preferably 3 or more, from the viewpoint of improving the hardness of the hard coat layer.
  • a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable.
  • a cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint that the shrinkage accompanying the polymerization reaction is small.
  • compounds having an epoxy group are readily available as compounds having various structures, do not adversely affect the durability of the obtained hard coat layer, and easily control the compatibility with the radically polymerizable compound.
  • the oxetanyl group is more likely to have a higher degree of polymerization than the epoxy group and has low toxicity, and accelerates the network formation rate obtained from the cationically polymerizable compound of the obtained hard coat layer, and radicals. Even in a region mixed with the polymerizable compound, there is an advantage that an unreacted monomer is not left in the film and an independent network is formed.
  • the cationically polymerizable compound having an epoxy group for example, polyglycidyl ether of a polyhydric alcohol having an alicyclic ring, or cyclohexene ring, a cyclopentene ring-containing compound, hydrogen peroxide, with a suitable oxidizing agent such as peracid Alicyclic epoxy resin obtained by epoxidation; polyglycidyl ether of aliphatic polyhydric alcohol or alkylene oxide adduct thereof, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer of glycidyl (meth)acrylate, Aliphatic epoxy resins such as copolymers; glycidyl ethers produced by the reaction of bisphenol A, bisphenol F, bisphenols such as hydrogenated bisphenol A, or derivatives thereof such as alkylene oxide adducts and caprolactone adducts with epichlorohydrin, And glycidyl ether type epoxy
  • the hard coat composition may further include a polymerization initiator.
  • the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., which can be appropriately selected and used. These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations to promote radical polymerization and cation polymerization.
  • the radical polymerization initiator may be any substance that can release a substance that initiates radical polymerization by at least one of irradiation with active energy rays and heating.
  • thermal radical polymerization initiators include hydrogen peroxide, organic peroxides such as perbenzoic acid, and azo compounds such as azobisbutyronitrile.
  • Type 1 type radical polymerization initiators that generate radicals by decomposition of molecules and Type 2 type radical polymerization initiators that generate radicals by hydrogen abstraction type reaction in coexistence with tertiary amines are used. Yes, they can be used alone or in combination.
  • the cationic polymerization initiator may be any substance that can release a substance that initiates cationic polymerization by at least one of irradiation with active energy rays and heating.
  • an aromatic iodonium salt, an aromatic sulfonium salt, a cyclopentadienyl iron(II) complex or the like can be used as the cationic polymerization initiator. These can initiate cationic polymerization either by irradiation with active energy rays or by heating, or both, depending on the difference in structure.
  • the polymerization initiator may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the total hard coat composition.
  • the content of the polymerization initiator is less than 0.1% by weight, curing cannot be sufficiently progressed, and it is difficult to realize mechanical properties and adhesion of the finally obtained coating film. If the content is more than wt%, poor adhesion, cracking and curling may occur due to curing shrinkage.
  • the hard coat composition may further include one or more selected from the group consisting of a solvent and an additive.
  • the solvent can dissolve or disperse the polymerizable compound and the polymerization initiator, and any solvent known as a solvent for a hard coat composition in the technical field can be used without limitation.
  • the additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.
  • the ratio (t2/t1) of the thickness (t2) of the support to the thickness (t1) of the hard coat layer is preferably 0.13 to 5.00, more preferably 0.38 to 4.00. , And more preferably 0.63 to 3.33.
  • the laminated body of the present invention may have a form in which any other functional layer is laminated.
  • a circularly polarizing plate or a touch sensor may be laminated on the laminate of the present invention to further impart a function.
  • An image display device of the present invention is characterized by having the laminate of the present invention.
  • the laminate of the present invention can function as a window film in an image display device.
  • the laminate of the present invention can be preferably used for an organic EL display device.
  • it can be suitably used as an antireflection polarizing plate of a flexible organic EL display device.
  • These layers can be laminated on each other via an adhesive or a pressure-sensitive adhesive described below.
  • the flexible image display device includes a flexible image display device laminate and an organic EL display panel.
  • the flexible image display device laminate is arranged on the viewer side of the organic EL display panel and is configured to be bendable.
  • the laminate for a flexible image display device may contain the laminate of the present invention, a circularly polarizing plate, and a touch sensor, and the stacking order thereof is arbitrary, but the laminate of the present invention from the viewing side, It is preferable that the circularly polarizing plate, the touch sensor or the laminate of the present invention, the touch sensor and the circularly polarizing plate are laminated in this order.
  • the presence of the circularly polarizing plate on the viewing side of the touch sensor is preferable because the pattern of the touch sensor is less visible and the visibility of the display image is improved.
  • Each member can be laminated using an adhesive, a pressure sensitive adhesive or the like.
  • a light-shielding pattern formed on at least one surface of any one of the layered product, the circularly polarizing plate, and the touch sensor of the present invention can be provided.
  • Each layer (laminate of the present invention, circularly polarizing plate, touch sensor) forming the laminate for flexible image display device can be laminated with an adhesive.
  • an adhesive a water-based adhesive, an organic solvent-based adhesive, a solvent-free adhesive, a solid adhesive, a solvent volatilizing adhesive, a moisture-curable adhesive, a heat-curable adhesive, an anaerobic-curable adhesive, an active energy ray-curable adhesive
  • Adhesives, hardener-mixed adhesives, hot-melt adhesives, pressure-sensitive adhesives (adhesives), rewet adhesives, and other commonly used adhesives can be used.
  • the thickness of the adhesive layer can be appropriately adjusted according to the required adhesive strength and the like, and is 0.01 ⁇ m to 500 ⁇ m, preferably 0.1 ⁇ m to 300 ⁇ m, and the laminate for flexible image display device has a plurality of layers. Although present, the respective thickness types may be the same or different.
  • polyvinyl alcohol-based polymer As the water-based solvent volatilizing adhesive, polyvinyl alcohol-based polymer, water-soluble polymer such as starch, water-dispersed polymer such as ethylene-vinyl acetate emulsion and styrene-butadiene-based emulsion can be used as a main polymer.
  • a cross-linking agent a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent and the like may be added.
  • the water-based solvent volatilization type adhesive may be injected between the adhered layers to bond the adhered layers and then dried to impart adhesiveness.
  • the thickness of the adhesive layer when the water-based solvent volatilizing adhesive is used may be 0.01 to 10 ⁇ m, preferably 0.1 to 1 ⁇ m. When a plurality of layers of the water-based solvent volatilizing adhesive are used, the thickness of each layer may be the same or different.
  • the active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that irradiates an active energy ray to form an adhesive layer.
  • the active energy ray-curable composition may contain at least one polymer of a radically polymerizable compound and a cationically polymerizable compound, which are similar to those of the hard coat composition.
  • the radically polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used.
  • As the radically polymerizable compound used in the adhesive layer a compound having an acryloyl group is preferable. It is also preferable to include a monofunctional compound in order to reduce the viscosity of the adhesive composition.
  • the cationically polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used.
  • An epoxy compound is particularly preferred as the cationically polymerizable compound used in the active energy ray-curable composition. It is also preferable to include a monofunctional compound as a reactive diluent in order to reduce the viscosity of the adhesive composition.
  • the active energy ray composition may further contain a polymerization initiator.
  • the polymerization initiator includes radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., which can be appropriately selected and used.
  • These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations to promote radical polymerization and cation polymerization.
  • an initiator capable of initiating radical polymerization and/or cationic polymerization by irradiation with active energy rays can be used.
  • the active energy ray-curable composition is further an ion scavenger, an antioxidant, a chain transfer agent, an adhesion promoter, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, a defoaming agent solvent, an additive, a solvent. Can be included.
  • the active energy ray-curable composition is applied to either or both of the adherend layers and then laminated, and activated through either adherent layer or both adherent layers. Adhesion can be achieved by irradiating an energy ray and curing it.
  • the thickness of the adhesive layer may be 0.01 to 20 ⁇ m, preferably 0.1 to 10 ⁇ m.
  • the thickness of each layer may be the same or different.
  • the pressure-sensitive adhesive may be classified into an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, etc., depending on the base polymer, and any of these may be used.
  • the adhesive may contain a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like.
  • the components constituting the pressure-sensitive adhesive are dissolved and dispersed in a solvent to obtain a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is applied onto a substrate and then dried to form a pressure-sensitive adhesive layer adhesive layer.
  • the adhesive layer may be directly formed, or may be formed separately on the substrate and transferred. It is also preferable to use a release film to cover the adhesive surface before adhesion.
  • the thickness of the adhesive layer may be 0.1 to 500 ⁇ m, preferably 1 to 300 ⁇ m.
  • the pressure-sensitive adhesive is used in multiple layers, the thickness of each layer may be the same or different.
  • the touch sensor is used as an input means.
  • various types such as a resistance film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and a capacitance type have been proposed, and any type may be used. Of these, the capacitance method is preferable.
  • the capacitive touch sensor is divided into an active region and a non-active region located outside the active region.
  • the active region is a region corresponding to a region where the screen is displayed on the display panel (display unit), and is a region where the user's touch is sensed
  • the inactive region is a region where the screen is not displayed on the display device (non-display region). This is an area corresponding to the display section).
  • the touch sensor has a substrate having flexible characteristics; a sensing pattern formed in an active region of the substrate; formed in an inactive region of the substrate and connected to an external driving circuit through the sensing pattern and a pad unit. Each sensing line can be included.
  • the substrate having flexible characteristics the same material as the transparent substrate for the window can be used.
  • the substrate of the touch sensor preferably has a toughness of 2,000 MPa% or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness may be 2,000 MPa% to 30,000 MPa%.
  • the sensing pattern may include a first pattern formed in the first direction and a second pattern formed in the second direction.
  • the first pattern and the second pattern are arranged in different directions.
  • the first pattern and the second pattern are formed on the same layer, and the respective patterns must be electrically connected in order to detect a touched point.
  • the first pattern has a form in which the unit patterns are connected to each other through a joint, but the second pattern has a structure in which the unit patterns are separated from each other in an island form.
  • a separate bridge electrode is required to make the connection.
  • a known transparent electrode material can be applied to the sensing pattern.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • ZnO zinc oxide
  • IZTO indium zinc tin oxide
  • CTO cadmium tin oxide
  • PEDOT poly(3,4- Ethylenedioxythiophene)
  • carbon nanotube carbon nanotube
  • the bridge electrode can be formed on the insulating layer on the sensing pattern via an insulating layer, and the bridge electrode is formed on the substrate, and the insulating layer and the sensing pattern can be formed on the bridge electrode.
  • the bridge electrode may be formed of the same material as the sensing pattern, and may be formed of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. You can also do it. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the joint of the first pattern and the bridge electrode, or may be formed in the structure of the layer covering the sensing pattern.
  • the bridge electrode can connect the second pattern through a contact hole formed in the insulating layer.
  • the touch sensor has a transmittance difference between a patterned area where a pattern is formed and a non-patterned area where a pattern is not formed, specifically, a light transmittance induced by a difference in refractive index in these areas.
  • An optical adjustment layer may be further included between the substrate and the electrode as a means for appropriately compensating for the difference, and the optical adjustment layer may include an inorganic insulating material or an organic insulating material.
  • the optical adjustment layer may be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate.
  • the photocurable composition may further include inorganic particles. The inorganic particles may increase the refractive index of the optical adjustment layer.
  • the photocurable organic binder may include, for example, a copolymer of each monomer such as an acrylate monomer, a styrene monomer, and a carboxylic acid monomer.
  • the photocurable organic binder may be, for example, a copolymer containing different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit.
  • the inorganic particles can include, for example, zirconia particles, titania particles, alumina particles, and the like.
  • the photocurable composition may further include additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.
  • the light shielding pattern may be applied as at least a part of a bezel or a housing of the flexible image display device. The visibility is improved by hiding the wiring arranged at the peripheral portion of the flexible image display device by the light-shielding pattern and making it difficult to see.
  • the light-shielding pattern may have a single-layer structure or a multi-layer structure.
  • the color of the light-shielding pattern is not particularly limited, and has various colors such as black, white, and metallic color.
  • the light-shielding pattern can be formed of a pigment for realizing a color and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane or silicone. These can be used alone or as a mixture of two or more kinds.
  • the light shielding pattern can be formed by various methods such as printing, lithography and inkjet.
  • the thickness of the light shielding pattern may be 1 ⁇ m to 100 ⁇ m, preferably 2 ⁇ m to 50 ⁇ m. It is also preferable to give a shape such as an inclination in the thickness direction of the light pattern.
  • the circularly polarizing plate is a functional layer having a function of transmitting only the right or left circularly polarized light component by laminating a ⁇ /4 retardation plate on a linearly polarizing plate. For example, by converting the external light into right circularly polarized light and blocking the external light reflected by the organic EL panel to become left circularly polarized light, and transmitting only the luminescence component of the organic EL, the influence of reflected light is suppressed and the image is displayed. It is used to make it easier to see.
  • the absorption axis of the linear polarizing plate and the slow axis of the ⁇ /4 retardation plate need to be 45° theoretically, but they are practically 45 ⁇ 10°.
  • the linearly polarizing plate and the ⁇ /4 retardation plate do not necessarily have to be laminated adjacent to each other, as long as the relationship between the absorption axis and the slow axis satisfies the above range. It is preferable to achieve perfect circularly polarized light at all wavelengths, but this is not always necessary in practice, so the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable to further laminate a ⁇ /4 phase difference plate on the visible side of the linear polarizing plate to make the emitted light circularly polarized light to improve the visibility in the state where the polarized sunglasses are worn.
  • ⁇ A linear polarizing plate is a functional layer that has the function of transmitting the light vibrating in the transmission axis direction, but blocking the polarization of the vibration component perpendicular to it.
  • the linear polarizing plate may be configured to include a linear polarizer alone or a linear polarizer and a protective film attached to at least one surface thereof.
  • the thickness of the linear polarizing plate may be 200 ⁇ m or less, preferably 0.5 ⁇ m to 100 ⁇ m. If the thickness exceeds 200 ⁇ m, the flexibility may decrease.
  • the linear polarizer may be a stretched film type polarizer produced by dyeing and stretching a polyvinyl alcohol (PVA) film.
  • a dichroic dye such as iodine is adsorbed on a PVA-based film oriented by stretching, or stretched in a state of being adsorbed on PVA, whereby the dichroic dye is oriented and exhibits polarization performance.
  • the production of the film-type polarizer may include other steps such as swelling, crosslinking with boric acid, washing with an aqueous solution, and drying.
  • the stretching and dyeing steps may be performed on the PVA-based film alone or may be performed in a state of being laminated with another film such as polyethylene terephthalate.
  • the PVA film used is preferably 10 to 100 ⁇ m, and the stretching ratio is preferably 2 to 10 times.
  • the linear polarizer may be a liquid crystal coating type polarizer formed by coating a composition containing a liquid crystal compound.
  • the composition may include a liquid crystal compound and a dichroic dye.
  • the liquid crystal compound is only required to have a property of exhibiting a liquid crystal state, and particularly preferably has a higher order alignment state such as a smectic phase because high polarization performance can be exhibited. It is also preferable to have a polymerizable group.
  • the dichroic dye is a dye that is aligned with the liquid crystal compound and exhibits dichroism, and the dichroic dye itself may have liquid crystallinity or has a polymerizable group. You can also Any compound in the composition has a polymerizable group.
  • the composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like.
  • the liquid crystal coating type polarizer can be manufactured by coating a composition containing a liquid crystal compound on an alignment film and curing the composition in a state where the liquid crystal compound is aligned.
  • the liquid crystal coating type polarizer can be formed thinner than the stretched film type polarizer.
  • the thickness of the liquid crystal coating type polarizer may be 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
  • the alignment film can be produced, for example, by applying the composition for forming an alignment film on a substrate and imparting the alignment property by rubbing, irradiation with polarized light, or the like.
  • the composition for forming an alignment film may contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent and the like in addition to the alignment agent.
  • the aligning agent for example, polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides can be used. When photo-alignment is applied, it is preferable to use an aligning agent containing a cinnamate group.
  • the polymer used as the aligning agent may have a weight average molecular weight of about 10,000 to 1,000,000.
  • the alignment film preferably has a thickness of 5 nm to 10,000 nm, and particularly preferably has a thickness of 10 to 500 nm because the alignment regulating force is sufficiently exhibited.
  • the liquid crystal coated polarizer can be peeled from the substrate and transferred to another member, or the substrate can be laminated as it is. It is also preferable that the base material plays a role as a transparent base material of a protective film, a retardation plate, and a window.
  • a transparent polymer film may be used, and materials and additives used for the transparent resin film can be used.
  • Cellulose type films, olefin type films, acrylic films and polyester type films are preferable.
  • It may be a coating type protective film obtained by applying a cationically curable composition such as an epoxy resin or a radical curable composition such as an acrylate and curing it.
  • plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc. May be included.
  • the thickness of the protective film may be 200 ⁇ m or less, preferably 1 ⁇ m to 100 ⁇ m. If the thickness exceeds 200 ⁇ m, the flexibility may decrease. It can also serve as a transparent resin film.
  • the ⁇ /4 retardation plate is a film that gives a ⁇ /4 retardation in a direction (in-plane direction of the film) orthogonal to the traveling direction of incident light.
  • the ⁇ /4 retardation plate may be a stretched film type retardation plate produced by stretching a polymer film such as a cellulose film, an olefin film or a polycarbonate film. If necessary, phase difference adjuster, plasticizer, ultraviolet absorber, infrared absorber, colorant such as pigment or dye, fluorescent whitening agent, dispersant, heat stabilizer, light stabilizer, antistatic agent, antioxidant. , A lubricant, a solvent, etc. may be contained.
  • the thickness of the stretchable retardation plate may be 200 ⁇ m or less, preferably 1 ⁇ m to 100 ⁇ m. If the thickness exceeds 200 ⁇ m, the flexibility may decrease.
  • a liquid crystal coating type retardation plate formed by applying a composition containing a liquid crystal compound may be used.
  • the composition includes a liquid crystal compound having a property of exhibiting a liquid crystal state such as nematic, cholesteric, and smectic. Any compound in the composition, including the liquid crystal compound, has a polymerizable group.
  • the liquid crystal coated retardation plate may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like.
  • the liquid crystal coating type retardation plate may be produced by coating a composition containing a liquid crystal compound on an alignment film as in the case of the liquid crystal coating type polarizer, and curing the liquid crystal compound in an aligned state. it can.
  • the liquid crystal coating type retardation plate can be formed thinner than the stretched film type retardation plate.
  • the thickness of the liquid crystal coating type polarizing layer may be 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
  • the liquid crystal coating type retardation plate can be peeled from the base material and transferred to another member, or the base material can be laminated as it is. It is also preferable that the substrate plays a role as a protective film, a retardation plate, or a transparent resin film.
  • a material having a birefringence wavelength dispersion characteristic opposite to the usual one because the visibility can be improved.
  • those described in JP 2007-232873 A in the case of a stretched film type retardation plate and those disclosed in JP 2010-30979 A in the case of a liquid crystal coating type retardation plate may be used. preferable.
  • a technique for obtaining a broadband ⁇ /4 retardation plate by combining it with a ⁇ /2 retardation plate Japanese Patent Laid-Open No. 10-90521.
  • the ⁇ /2 retardation plate is also manufactured by the same material method as that of the ⁇ /4 retardation plate.
  • the combination of the stretched film type retardation plate and the liquid crystal coating type retardation plate is arbitrary, but it is preferable to use the liquid crystal coating type retardation plate for both of them because the film thickness can be reduced.
  • a method is also known in which a positive C plate is laminated on the circularly polarizing plate in order to enhance visibility in an oblique direction (Japanese Patent Laid-Open No. 2014-224837).
  • the positive C plate may be a liquid crystal coating type retardation plate or a stretched film type retardation plate.
  • the retardation in the thickness direction of the positive C plate is ⁇ 200 to ⁇ 20 nm, preferably ⁇ 140 to ⁇ 40 nm at a wavelength of 560 nm.
  • a laminate including a hard coat layer and a transparent resin film which are very thin and have excellent impact resistance an image display device including the laminate, and a method for producing the laminate. It is useful because it can.

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Abstract

It has become clear that a transparent resin film having a hard coat layer is susceptible to impact and, for example, when incorporated in an image display device, has the following problem: when external impact is applied by, for example, a touch pen dropped on the tip on a display surface of the image display device, the hard coat layer cracks. The purpose of the present invention is to provide: a laminate comprising a very thin hard coat layer having excellent impact resistance and a transparent resin film; an image display device provided with the laminate; and a method for producing the laminate. The laminate is provided with a transparent resin film, a support body formed on at least one surface of the transparent resin film, and a hard coat layer formed on the support body. The support body has a patterned structure.

Description

積層体およびそれを用いた画像表示装置Laminated body and image display device using the same
　本発明は、積層体およびそれを用いた画像表示装置に関するものである。 The present invention relates to a laminate and an image display device using the same.
　近年、携帯電話やタブレット端末などの普及が進み、画像表示装置として液晶表示装置や有機ＥＬ表示装置（ＯＬＥＤ）が広く用いられるようになってきた。そうした中で、特に、フレキシブル性を有する画像表示装置が種々提案されてきている。このようなフレキシブル性を持つ画像表示装置では、用いるフィルムに薄型で曲げ特性が良好なものが求められ画像表示装置を保護するためのハードコート層を有する透明樹脂フィルムについても例外ではない（特許文献１）。 In recent years, mobile phones and tablet terminals have become widespread, and liquid crystal display devices and organic EL display devices (OLEDs) have been widely used as image display devices. Under such circumstances, various image display devices having flexibility have been proposed. In such an image display device having flexibility, a thin film having good bending characteristics is required for a film to be used, and a transparent resin film having a hard coat layer for protecting the image display device is no exception (Patent Document 1).
特開２０１８－５９０６９号公報Japanese Patent Laid-Open No. 2018-59069
　しかし、このようなハードコート層を有する透明樹脂フィルムは衝撃に弱く、例えば、画像表示装置に組み込んだ場合においても、画像表示装置の表示面にタッチペンがペン先から落下したような外部衝撃が加わった場合にハードコート層にクラックが発生し問題となる場合があることが明らかになった。 However, a transparent resin film having such a hard coat layer is vulnerable to impact, and even when incorporated in an image display device, for example, an external impact such as a touch pen dropping from the pen tip is applied to the display surface of the image display device. It has become clear that in such cases, cracks may occur in the hard coat layer, which may cause a problem.
　本発明は上記従来の課題を解決するためになされたものであり、その主たる目的は、非常に薄く、優れた耐衝撃性を有するハードコート層と透明樹脂フィルムを含む積層体、前記積層体を備えた画像表示装置、および前記積層体の製造方法を提供することにある。 The present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to provide a laminate including a hard coat layer and a transparent resin film having a very thin and excellent impact resistance, and the laminate. An object of the present invention is to provide an image display device provided with the method and a method for manufacturing the laminate.
　すなわち、本発明は、以下の積層体、画像表示装置および前記積層体の製造方法を提供する。
［１］　透明樹脂フィルムと透明樹脂フィルムの少なくとも一方の面に形成された支持体と支持体上に形成されたハードコート層をこの順に備え、前記支持体がパターン構造を有する積層体。
［２］　前記支持体が、ハニカム構造、トラス構造、ラーメン構造、ストライプ構造、および円構造からなる群より選択される少なくともいずれか一つの構造を有する、［１］に記載の積層体。
［３］　前記支持体の厚みが１μｍ～１５μｍである、［１］または［２］に記載の積層体。
［４］　平面視における前記支持体の幅が５００μｍ～３０００μｍである、［１］～［３］のいずれかに記載の積層体。
［５］　前記支持体が光学的に等方性を有する、［１］～［４］のいずれかに記載の積層体。
［６］　前記透明樹脂フィルムの前記一方の面に、前記支持体を包埋する包埋樹脂層を備える、［１］～［５］のいずれかに記載の積層体。
［７］　前記支持体の２３℃における圧縮弾性率が０．０１ＧＰａ～８．０ＧＰａである、［１］～［６］のいずれかに記載の積層体。
［８］　［１］～［７］のいずれかに記載の積層体と円偏光板とを有する積層体。
［９］　［１］～［８］のいずれかに記載の積層体を備える画像表示装置。
［１０］　透明樹脂フィルムの少なくとも一方の面に樹脂材料のパターンを形成する工程と、前記樹脂材料を硬化させることによりパターン構造を有する支持体とする工程と、前記支持体上にハードコート層を形成する工程を含む、積層体の製造方法。 That is, the present invention provides the following laminate, image display device, and method for producing the laminate.
[1] A laminate having a transparent resin film, a support formed on at least one surface of the transparent resin film, and a hard coat layer formed on the support in this order, and the support having a patterned structure.
[2] The laminate according to [1], wherein the support has at least one structure selected from the group consisting of a honeycomb structure, a truss structure, a rigid frame structure, a stripe structure, and a circular structure.
[3] The laminate according to [1] or [2], wherein the support has a thickness of 1 μm to 15 μm.
[4] The laminate according to any one of [1] to [3], wherein the width of the support in plan view is 500 μm to 3000 μm.
[5] The laminate according to any one of [1] to [4], wherein the support has optical isotropy.
[6] The laminated body according to any one of [1] to [5], which includes an embedded resin layer that embeds the support on the one surface of the transparent resin film.
[7] The laminate according to any one of [1] to [6], wherein the support has a compressive elastic modulus at 23° C. of 0.01 GPa to 8.0 GPa.
[8] A laminate having the laminate according to any one of [1] to [7] and a circularly polarizing plate.
[9] An image display device including the laminate according to any one of [1] to [8].
[10] A step of forming a pattern of a resin material on at least one surface of the transparent resin film, a step of curing the resin material to form a support having a pattern structure, and a hard coat layer on the support. A method for manufacturing a laminate, which includes a step of forming.
　本発明によれば、非常に薄く、優れた耐衝撃性を有するハードコート層と透明樹脂フィルムを含む積層体、前記積層体を備えた画像表示装置、および前記積層体の製造方法を得ることができる。 According to the present invention, it is possible to obtain a laminate including a hard coat layer having a very thin and excellent impact resistance and a transparent resin film, an image display device including the laminate, and a method for producing the laminate. it can.
本発明の１つの実施形態に係る積層体において、透明樹脂フィルム上に形成された支持体を示す平面図である。FIG. 3 is a plan view showing a support formed on a transparent resin film in the laminate according to one embodiment of the present invention. 本発明の１つの実施形態に係る積層体の断面図である。It is sectional drawing of the laminated body which concerns on one Embodiment of this invention. 本発明の別の実施形態に係る積層体において、透明樹脂フィルム上に形成された支持体を示す平面図である。FIG. 6 is a plan view showing a support formed on a transparent resin film in a laminate according to another embodiment of the present invention. 本発明のさらに別の実施形態に係る積層体において、透明樹脂フィルム上に形成された支持体を示す平面図である。FIG. 9 is a plan view showing a support formed on a transparent resin film in a laminate according to still another embodiment of the present invention. 本発明のさらに別の実施形態に係る積層体において、透明樹脂フィルム上に形成された支持体を示す平面図である。FIG. 9 is a plan view showing a support formed on a transparent resin film in a laminate according to still another embodiment of the present invention. 本発明のさらに別の実施形態に係る積層体において、透明樹脂フィルム上に形成された支持体を示す平面図である。FIG. 9 is a plan view showing a support formed on a transparent resin film in a laminate according to still another embodiment of the present invention. 本発明のさらに別の実施形態に係る積層体の断面図である。It is sectional drawing of the laminated body which concerns on another embodiment of this invention. 本発明のさらに別の実施形態に係る積層体の断面図である。It is sectional drawing of the laminated body which concerns on another embodiment of this invention.
以下、本発明の好ましい実施形態について説明するが、本発明はこれらの実施形態には限定されない。 Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
　（用語および記号の定義）
　本明細書における用語および記号の定義は下記の通りである。
（１）屈折率（ｎｘ、ｎｙ、ｎｚ）
　「ｎｘ」は面内の屈折率が最大となる方向（すなわち、遅相軸方向）の屈折率であり、「ｎｙ」は面内で遅相軸と直交する方向、「ｎｚ」は厚み方向の屈折率である。
（２）面内の位相差値
　面内の位相差値（Ｒｅ（λ））は、２３℃、波長λ（ｎｍ）におけるフィルムの面内の位相差値をいう。Ｒｅ（λ）は、フィルムの厚みをｄ（ｎｍ）としたとき、Ｒｅ（λ）＝（ｎｘ－ｎｙ）×ｄによって求められる。
（３）厚み方向の位相差値
　面内の位相差値（Ｒｔｈ（λ））は、２３℃、波長λ（ｎｍ）におけるフィルムの厚み方向の位相差値をいう。Ｒｔｈ（λ）は、フィルムの厚みをｄ（ｎｍ）としたとき、Ｒｔｈ（λ）＝（（ｎｘ＋ｎｙ）／２－ｎｚ）×ｄによって求められる。 (Definition of terms and symbols)
The definitions of terms and symbols in the present specification are as follows.
(1) Refractive index (nx, ny, nz)
“Nx” is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), “ny” is the in-plane direction orthogonal to the slow axis, and “nz” is the thickness direction. Is the refractive index.
(2) In-plane retardation value The in-plane retardation value (Re(λ)) refers to the in-plane retardation value at 23° C. and wavelength λ (nm). Re(λ) is calculated by Re(λ)=(nx−ny)×d, where d(nm) is the thickness of the film.
(3) Retardation Value in Thickness Direction The in-plane retardation value (Rth(λ)) refers to the retardation value in the thickness direction of the film at 23° C. and the wavelength λ(nm). Rth(λ) is calculated by Rth(λ)=((nx+ny)/2−nz)×d when the film thickness is d(nm).
（層全体の構成）
　図１は、本発明の１つの実施形態による積層体において、透明樹脂フィルム上に形成された支持体を示す平面図である。図２は、本発明の１つの実施形態による積層体の断面図である。図２に示すように、積層体１０は、透明樹脂フィルム１と、透明樹脂フィルム１の一方の面に形成された支持体２と、支持体２上に形成されたハードコート層５とを有する。支持体２上に形成されたハードコート層５とは、ハードコート層５の一部または全部が、支持体２よりも上方に存在すればよく、支持体２に接して形成される形態、支持体２を包埋するように形成される形態、および他の層を介して形成される形態のいずれの形態も含む。すなわち、ハードコート層は、図２に示すように、支持体２を包埋するように支持体２上に形成されてもよく、図８に示すように、支持体２を包埋する包埋樹脂層４を介して支持体２上に形成されてもよい。積層体１０は、枚葉状であってもよく、長尺状であってもよい。透明樹脂フィルムの厚みは、代表的には１００μｍ以下である。支持体２の厚みは、代表的には１μｍ～１５μｍであり、平面視における支持体２の幅は、代表的には５００μｍ～３０００μｍである。支持体２は、好ましくは透明であり、より好ましくは透明であるとともに実質的に光学的に等方性を有する。支持体２は、パターン構造を有し、パターン構造として、代表的には図１に示すようなハニカム構造を有する。ハードコート層の厚みは、代表的には１μｍ～１５μｍである。ハードコート層の厚みとは、ハードコート層の最も厚い部分の厚みを意味する。 (Structure of the whole layer)
FIG. 1 is a plan view showing a support formed on a transparent resin film in a laminate according to one embodiment of the present invention. FIG. 2 is a cross-sectional view of a laminate according to one embodiment of the present invention. As shown in FIG. 2, the laminated body 10 includes a transparent resin film 1, a support 2 formed on one surface of the transparent resin film 1, and a hard coat layer 5 formed on the support 2. . The hard coat layer 5 formed on the support 2 means that a part or all of the hard coat layer 5 exists above the support 2, and a form formed in contact with the support 2 Both the form formed so as to embed the body 2 and the form formed via the other layer are included. That is, the hard coat layer may be formed on the support 2 so as to embed the support 2 as shown in FIG. 2, or the embedding for embedding the support 2 as shown in FIG. It may be formed on the support 2 via the resin layer 4. The laminated body 10 may have a sheet-like shape or a long shape. The thickness of the transparent resin film is typically 100 μm or less. The thickness of the support 2 is typically 1 μm to 15 μm, and the width of the support 2 in plan view is typically 500 μm to 3000 μm. The support 2 is preferably transparent, more preferably transparent and substantially optically isotropic. The support 2 has a pattern structure, and typically has a honeycomb structure as shown in FIG. 1 as the pattern structure. The thickness of the hard coat layer is typically 1 μm to 15 μm. The thickness of the hard coat layer means the thickness of the thickest part of the hard coat layer.
　図３～図６は、本発明の別の実施形態による積層体において、透明樹脂フィルム上に形成された支持体を示す平面図である。支持体は、図３に示すようなラーメン構造を有していてもよく、図４に示すようなトラス構造を有していてもよく、図５に示すような円構造（円がマトリクス状に配置された構造）を有していてもよく、図６に示すようなストライプ構造を有していてもよい。このように、透明樹脂フィルム１の表面にパターン状の支持体２を形成する場合、透明樹脂フィルム１の表面の全面に支持体を形成する場合に比べて、支持体を構成する材料の使用量を低減することできる。 FIGS. 3 to 6 are plan views showing a support formed on a transparent resin film in a laminate according to another embodiment of the present invention. The support may have a rigid frame structure as shown in FIG. 3 or a truss structure as shown in FIG. 4, and may have a circular structure as shown in FIG. (Arranged structure), or may have a stripe structure as shown in FIG. In this way, when the patterned support 2 is formed on the surface of the transparent resin film 1, the amount of the material constituting the support is used as compared with the case where the support is formed on the entire surface of the transparent resin film 1. Can be reduced.
　図７は、本発明のさらに別の実施形態による積層体の断面図である。図７に示すように、積層体１１は、透明樹脂フィルム１の一方の面に支持体２（以下、第１の支持体２と称する場合がある）を有し、透明樹脂フィルム１の他方の面に支持体３（以下、第２の支持体３と称する場合がある）を有する。第２の支持体３はパターン構造を有する。第２の支持体３のパターン構造は、第１の支持体２のパターン構造を同じであってもよいし、異なっていてもよい。第１の支持体２のパターン構造と第２の支持体３のパターン構造とが同じものである場合、好ましくは、図７に示すように、第１の支持体２と第２の支持体３とは、平面視において互いに重なる部分の面積が小さくなるように配置される。さらに支持体２上および支持体３上にはハードコート層５が形成される。 FIG. 7 is a sectional view of a laminate according to still another embodiment of the present invention. As shown in FIG. 7, the laminated body 11 has a support 2 (hereinafter sometimes referred to as a first support 2) on one surface of the transparent resin film 1, and the other of the transparent resin film 1 has the support 2. The surface has a support 3 (hereinafter sometimes referred to as a second support 3). The second support 3 has a patterned structure. The pattern structure of the second support 3 may be the same as or different from the pattern structure of the first support 2. When the pattern structure of the first support 2 and the pattern structure of the second support 3 are the same, preferably, as shown in FIG. 7, the first support 2 and the second support 3 are formed. And are arranged such that the areas of the portions overlapping each other in plan view are small. Further, the hard coat layer 5 is formed on the support 2 and the support 3.
　図８は、本発明のさらに別の実施形態による積層体の断面図である。図８に示すように、積層体１２は、透明樹脂フィルム１の一方の面に、支持体２を包埋する包埋樹脂層４を備える。これにより、支持体２によって形成された段差を平滑化することができる。透明樹脂フィルム１の露出部分を包埋樹脂層４が覆うことで、透明樹脂フィルム１の表面を保護することができる。さらに、包埋樹脂層４上にハードコート層５が形成されている。なお、２つ以上の上記実施形態を組み合わせてもよい。 FIG. 8 is a sectional view of a laminate according to still another embodiment of the present invention. As shown in FIG. 8, the laminate 12 includes the embedded resin layer 4 that embeds the support 2 on one surface of the transparent resin film 1. Thereby, the step formed by the support 2 can be smoothed. By covering the exposed portion of the transparent resin film 1 with the embedding resin layer 4, the surface of the transparent resin film 1 can be protected. Further, a hard coat layer 5 is formed on the embedded resin layer 4. Note that two or more of the above embodiments may be combined.
＜透明樹脂フィルム＞
　本発明で用いる透明樹脂フィルムは、可視光線の透過率が７０％以上、好ましくは８０％以上である。前記透明樹脂フィルムは、透明性のある高分子フィルムなら、どのようなものでも使用可能である。具体的には、ポリエチレン、ポリプロピレン、ポリメチルペンテン、ノルボルネンまたはシクロオレフィンを含む単量体の単位を有するシクロオレフィン系誘導体等のポリオレフィン類、ジアセチルセルロース、トリアセチルセルロース、プロピオニルセルロース等の（変性）セルロース類、メチルメタクリレート（共）重合体等のアクリル類、スチレン（共）重合体等のポリスチレン類、アクリロニトリル・ブタジエン・スチレン共重合体類、アクリロニトリル・スチレン共重合体類、エチレン‐酢酸ビニル共重合体類、ポリ塩化ビニル類、ポリ塩化ビニリデン類、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、ポリアリレート等のポリエステル類、ナイロン等のポリアミド類、ポリイミド類、ポリアミドイミド類、ポリエーテルイミド類、ポリエーテルスルホン類、ポリスルホン類、ポリビニルアルコール類、ポリビニルアセタール類、ポリウレタン類、エポキシ樹脂類などの高分子で形成されたフィルムであってもよく、未延伸、1軸または２軸延伸フィルムを使用することができる。これらの高分子はそれぞれ単独または２種以上混合して使用することができる。好ましくは、前記記載の透明樹脂フィルムの中でも透明性及び耐熱性に優れたポリアミドフィルム、ポリアミドイミドフィルムまたはポリイミドフィルム、ポリエステル系フィルム、オレフィン系フィルム、アクリルフィルム、セルロース系フィルムが好ましい。高分子フィルムの中には、シリカ等の無機粒子、有機微粒子、ゴム粒子等を分散させることも好ましい。さらに、顔料や染料のような着色剤、蛍光増白剤、分散剤、可塑剤、熱安定剤、光安定剤、赤外線吸収剤、紫外線吸収剤、帯電防止剤、酸化防止剤、滑剤、溶剤などの配合剤を含有させてもよい。前記透明樹脂フィルムの厚さは５～２００μｍ、好ましくは、２０～１００μｍである。 <Transparent resin film>
The transparent resin film used in the present invention has a visible light transmittance of 70% or more, preferably 80% or more. As the transparent resin film, any transparent polymer film can be used. Specifically, polyolefins such as polyethylene, polypropylene, polymethylpentene, norbornene or cycloolefin derivatives having a unit of a monomer containing cycloolefin, diacetyl cellulose, triacetyl cellulose, (modified) cellulose such as propionyl cellulose. , Acrylics such as methylmethacrylate (co)polymers, polystyrenes such as styrene (co)polymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers Polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyesters such as polyarylate, polyamides such as nylon, polyimides, polyamideimides, polyetherimides, It may be a film formed of a polymer such as polyether sulfones, polysulfones, polyvinyl alcohols, polyvinyl acetals, polyurethanes, and epoxy resins, and an unstretched, uniaxially or biaxially stretched film is used. be able to. These polymers can be used alone or in admixture of two or more. Among the above-mentioned transparent resin films, a polyamide film, a polyamideimide film or a polyimide film having excellent transparency and heat resistance, a polyester film, an olefin film, an acrylic film, and a cellulose film are preferable. It is also preferable to disperse inorganic particles such as silica, organic fine particles, and rubber particles in the polymer film. Furthermore, colorants such as pigments and dyes, optical brighteners, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants, solvents, etc. You may contain the compounding agent of. The transparent resin film has a thickness of 5 to 200 μm, preferably 20 to 100 μm.
（支持体）
　本発明の積層体は、透明樹脂フィルムの少なくとも一方の面に支持体を有する。支持体は、上記のとおりパターン構造を有する。支持体は、好ましくは、ハニカム構造、トラス構造、ラーメン構造、ストライプ構造、および円構造からなる群より選択される少なくとも一つの構造を有する。支持体は、より好ましくはハニカム構造、トラス構造、または円構造を有し、特に好ましくはハニカム構造または円構造を有する。支持体がハニカム構造、トラス構造、または円構造を有する場合、後述のハードコート層が一方向に応力を受けたとき、当該方向とは異なる方向に応力を分散することができ、その結果、ハードコート層における外部からの衝撃を緩和し、割れを抑制することができるからである。 (Support)
The laminate of the present invention has a support on at least one surface of the transparent resin film. The support has a pattern structure as described above. The support preferably has at least one structure selected from the group consisting of a honeycomb structure, a truss structure, a rigid frame structure, a stripe structure, and a circular structure. The support more preferably has a honeycomb structure, a truss structure, or a circular structure, and particularly preferably has a honeycomb structure or a circular structure. When the support has a honeycomb structure, a truss structure, or a circular structure, when the hard coat layer described below is stressed in one direction, the stress can be dispersed in a direction different from that direction, and as a result, the hard This is because the external impact on the coat layer can be mitigated and cracking can be suppressed.
　支持体は、好ましくは透明であり実質的に光学的に等方性を有する。本明細書において「実質的に光学的に等方性を有する」とは、例えば、支持体の面内位相差Ｒｅ（５５０）および厚み方向位相差Ｒｔｈ（５５０）はそれぞれ、好ましくは２０ｎｍ以下であり、より好ましくは１０ｎｍ以下であることを言う。 The support is preferably transparent and substantially optically isotropic. In the present specification, “having substantially optical isotropy” means that the in-plane retardation Re (550) and the thickness direction retardation Rth (550) of the support are preferably 20 nm or less, respectively. Yes, and more preferably 10 nm or less.
　透明樹脂フィルムの一方の面に形成される第１の支持体のパターン構造ともう一方の面に形成される第２の支持体のパターン構造とが同じものである場合、第２の支持体は、好ましくは平面視において第１の支持体に重なる部分の面積が小さくなるように配置される。 When the pattern structure of the first support formed on one surface of the transparent resin film and the pattern structure of the second support formed on the other surface are the same, the second support is It is preferably arranged such that the area of the portion overlapping the first support is small in plan view.
　支持体の厚みは、上記のとおり、好ましくは１μｍ～１５μｍであり、より好ましくは３μｍ～８μｍである。 As described above, the thickness of the support is preferably 1 μm to 15 μm, more preferably 3 μm to 8 μm.
　支持体の２３℃における圧縮弾性率は、好ましくは０．０１ＧＰａ～８．０ＧＰａであり、より好ましくは０．０２ＧＰａ～６．０ＧＰａである。これにより、ハードコート層の外部衝撃による割れを抑制しつつ、本発明の積層体の加工性およびフレキシブル性を高めることができる。圧縮弾性率は、ナノインデンテーション法により測定をすることができる。 The compressive elastic modulus of the support at 23° C. is preferably 0.01 GPa to 8.0 GPa, more preferably 0.02 GPa to 6.0 GPa. As a result, it is possible to improve the workability and flexibility of the laminate of the present invention while suppressing cracking of the hard coat layer due to external impact. The compression elastic modulus can be measured by the nanoindentation method.
　支持体は、上記の構成を満足し、かつ、透明樹脂フィルムとの十分な密着性を有する限り任意の適切な材料および方法で形成することができる。透明樹脂フィルムに対する支持体の密着性は、ＪＩＳ　Ｋ５４００の碁盤目剥離試験に準じて評価することができる。透明樹脂フィルムに対する支持体の密着性は、好ましくは、上記碁盤目剥離試験（基板目数：１００個）において剥離数が０である。 The support can be formed of any appropriate material and method as long as it satisfies the above configuration and has sufficient adhesion to the transparent resin film. The adhesion of the support to the transparent resin film can be evaluated according to the cross-cut peeling test of JIS K5400. The adhesion of the support to the transparent resin film is preferably 0 in the cross-cut peeling test (the number of substrates: 100).
　１つの実施形態においては、パターン構造を有する支持体は、透明樹脂フィルムの表面に樹脂材料または樹脂材料を含む塗工液のパターンを形成し、樹脂材料を硬化（または固化）することにより形成することができる。別の実施形態においては、支持体は、透明樹脂フィルムの表面にＳｉＯ２等の無機酸化物を蒸着することで形成することができる。 In one embodiment, the support having a pattern structure is formed by forming a pattern of a resin material or a coating liquid containing a resin material on the surface of a transparent resin film and curing (or solidifying) the resin material. be able to. In another embodiment, the support can be formed by depositing an inorganic oxide such as SiO 2 on the surface of the transparent resin film.
　上記樹脂材料としては、本発明の効果が得られる限りにおいて、任意の適切な材料を用いることができる。上記樹脂材料としては、例えば、ポリエステル系樹脂、ポリエーテル系樹脂、ポリカーボネート系樹脂、ポリウレタン系樹脂、シリコーン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ＰＶＡ系樹脂、アクリル系樹脂、エポキシ系樹脂、フッ素系樹脂を挙げることができる。これらは、単独で用いてもよく、組み合わせて（例えば、ブレンド、共重合）用いてもよい。 As the resin material, any appropriate material can be used as long as the effects of the present invention can be obtained. Examples of the resin material include polyester resin, polyether resin, polycarbonate resin, polyurethane resin, silicone resin, polyamide resin, polyimide resin, PVA resin, acrylic resin, epoxy resin, and fluorine. An example is a resin. These may be used alone or in combination (eg, blending, copolymerization).
　透明樹脂フィルムの表面に上記樹脂材料または上記塗工液のパターンを形成する方法は特に限定されない。上記方法として、例えば、印刷、フォトリソグラフィ、インクジェット、ノズル、ダイ塗布等が挙げられる。上記樹脂材料または上記塗工液のパターンは、好ましくは、印刷により形成される。塗工液をパターン状に印刷する方法としては、凸版印刷法、ダイレクトグラビア印刷法、凹版印刷法、平版印刷法、孔版印刷法等が挙げられる。塗工液は、上記樹脂材料以外に、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、主成分としての上記樹脂材料以外の樹脂成分、粘着付与剤、無機充填剤、有機充填剤、金属粉、顔料、箔状物、軟化剤、老化防止剤、導電剤、紫外線吸収剤、酸化防止剤、光安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 The method of forming the pattern of the resin material or the coating liquid on the surface of the transparent resin film is not particularly limited. Examples of the above method include printing, photolithography, inkjet, nozzle, die coating and the like. The pattern of the resin material or the coating liquid is preferably formed by printing. Examples of the method of printing the coating liquid in a pattern include a relief printing method, a direct gravure printing method, an intaglio printing method, a lithographic printing method, a stencil printing method and the like. In addition to the above resin material, the coating liquid may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include, for example, resin components other than the above-mentioned resin materials as main components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and antioxidants. , A conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.
　上記樹脂材料（塗工液）を硬化（または固化）する条件としては、樹脂材料の種類および組成物の組成等に応じて適切に設定され得る。例えば、乾燥、活性エネルギー線硬化、熱硬化等により上記樹脂材料を硬化（または固化）することができる。 The conditions for curing (or solidifying) the above resin material (coating liquid) can be appropriately set according to the type of resin material and the composition of the composition. For example, the resin material can be cured (or solidified) by drying, curing with active energy rays, heat curing, or the like.
（包埋樹脂層）
　包埋樹脂層は、上記のとおり、透明樹脂フィルムの一方の面に形成された支持体を包埋する。包埋樹脂層の厚みは、支持体の厚みよりも厚く、好ましくは３μｍ～１５０μｍであり、より好ましくは５μｍ～１００μｍである。包埋樹脂層は、透明樹脂フィルムに求められる特性に応じて形成された任意の適切な機能層であってもよい。上記機能層としては、例えば、ハードコート層、粘着剤層、透明光学粘着層等が挙げられる。包埋樹脂層がハードコート層である場合、その厚みは例えば５μｍ～１５μｍであり、包埋樹脂層が粘着剤層である場合、その厚みは例えば５μｍ～３０μｍであり、包埋樹脂層が透明光学粘着層である場合、その厚みは例えば２５μｍ～１２５μｍである。包埋樹脂層は、好ましくは透明であり実質的に光学的に等方性を有する。包埋樹脂層は、後述のハードコート層と同じ材料から形成されてもよいし、異なる材料から形成されてもよい。 (Embedded resin layer)
The embedding resin layer embeds the support formed on one surface of the transparent resin film as described above. The thickness of the embedding resin layer is larger than the thickness of the support, preferably 3 μm to 150 μm, more preferably 5 μm to 100 μm. The embedding resin layer may be any appropriate functional layer formed according to the characteristics required for the transparent resin film. Examples of the functional layer include a hard coat layer, a pressure-sensitive adhesive layer, a transparent optical pressure-sensitive adhesive layer, and the like. When the embedding resin layer is a hard coat layer, its thickness is, for example, 5 μm to 15 μm, and when the embedding resin layer is an adhesive layer, its thickness is, for example, 5 μm to 30 μm, and the embedding resin layer is transparent. In the case of an optical adhesive layer, its thickness is, for example, 25 μm to 125 μm. The embedding resin layer is preferably transparent and has substantially optical isotropy. The embedding resin layer may be formed of the same material as the hard coat layer described later, or may be formed of a different material.
　包埋樹脂層は、透明樹脂フィルムおよび支持体との十分な密着性を有する限り任意の適切な材料および方法で形成することができる。１つの実施形態においては、包埋樹脂層は、支持体とは異なる種類の樹脂材料で形成することができる。包埋樹脂層は、支持体を包埋するように透明樹脂フィルムの表面に樹脂層を形成し、樹脂層を硬化することにより形成することができる。 The embedding resin layer can be formed by any appropriate material and method as long as it has sufficient adhesion to the transparent resin film and the support. In one embodiment, the embedded resin layer can be formed of a resin material different from that of the support. The embedding resin layer can be formed by forming a resin layer on the surface of the transparent resin film so as to embed the support and curing the resin layer.
　透明樹脂フィルムの表面に上記樹脂層を形成する方法は特に限定されない。１つの実施形態においては、樹脂材料を含む塗工液を透明樹脂フィルムの表面に塗布することにより、樹脂層を形成することができる。塗布方法としては、任意の適切な塗布方法を用いることができる。具体例としては、カーテンコーティング法、ディップコーティング法、スピンコーティング法、印刷コーティング法、スプレーコーティング法、スロットコーティング法、ロールコーティング法、スライドコーティング法、ブレードコーティング法、グラビアコーティング法、ワイヤーバー法が挙げられる。硬化条件は、使用する樹脂材料の種類および組成物の組成等に応じて適切に設定され得る。塗工液は、上記樹脂材料以外に、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、主成分としての上記樹脂材料以外の樹脂成分、粘着付与剤、無機充填剤、有機充填剤、金属粉、顔料、箔状物、軟化剤、老化防止剤、導電剤、紫外線吸収剤、酸化防止剤、光安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 The method of forming the resin layer on the surface of the transparent resin film is not particularly limited. In one embodiment, the resin layer can be formed by applying a coating liquid containing a resin material onto the surface of the transparent resin film. Any appropriate coating method can be used as the coating method. Specific examples include curtain coating method, dip coating method, spin coating method, printing coating method, spray coating method, slot coating method, roll coating method, slide coating method, blade coating method, gravure coating method, and wire bar method. Be done. The curing conditions can be appropriately set according to the type of resin material used, the composition of the composition, and the like. In addition to the above resin material, the coating liquid may contain any appropriate other component as long as the effect of the present invention is not impaired. Examples of such other components include, for example, resin components other than the above-mentioned resin materials as main components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and antioxidants. , A conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.
＜ハードコート層＞
　積層体は、支持体上にハードコート層を有する。ハードコート層は、前記包埋樹脂層で代用することもできる。ハードコート層を形成する材料と包埋樹脂層を形成する材料とが同じであれば、ハードコート層は、包埋樹脂層を兼ねているということができる。ハードコート層の厚さは特に限定されず、例えば、２～１００μｍであってもよい。前記ハードコート層の厚さが２μｍ未満の場合、十分な耐擦傷性を確保することが難しく、１００μｍを超えると、耐屈曲性が低下し、硬化収縮によるカール発生の問題が発生することがある。 <Hard coat layer>
The laminate has a hard coat layer on the support. The hard coat layer may be substituted with the embedding resin layer. If the material forming the hard coat layer and the material forming the embedding resin layer are the same, it can be said that the hard coat layer also serves as the embedding resin layer. The thickness of the hard coat layer is not particularly limited and may be, for example, 2 to 100 μm. If the thickness of the hard coat layer is less than 2 μm, it is difficult to secure sufficient scratch resistance, and if it exceeds 100 μm, the flex resistance may be deteriorated and curling due to curing shrinkage may occur. ..
　前記ハードコート層は、活性エネルギー線或いは熱エネルギーを照射して架橋構造を形成する反応性材料を含むハードコート組成物の硬化により形成することができるが活性エネルギー線硬化によるものが好ましい。活性エネルギー線とは、活性種を発生する化合物を分解して活性種を発生させることができるエネルギー線と定義される。活性エネルギー線としては、可視光、紫外線、赤外線、Ｘ線、α線、β線、γ線及び電子線などを挙げることができる。紫外線が特に好ましい。前記ハードコート組成物は、ラジカル重合性化合物及びカチオン重合性化合物の少なくとも１種の重合物を含有する。 The hard coat layer can be formed by curing a hard coat composition containing a reactive material that forms a crosslinked structure by irradiating with active energy rays or heat energy, but is preferably cured by active energy rays. An active energy ray is defined as an energy ray capable of decomposing a compound generating an active species to generate an active species. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays and electron rays. Ultraviolet light is particularly preferred. The hard coat composition contains at least one polymer of a radically polymerizable compound and a cationically polymerizable compound.
　前記ラジカル重合性化合物とは、ラジカル重合性基を有する化合物である。前記ラジカル重合性化合物が有するラジカル重合性基としては、ラジカル重合反応を生じ得る官能基であればよく、炭素－炭素不飽和二重結合を含む基などが挙げられる。具体的には、ビニル基、（メタ）アクリロイル基などが挙げられる。なお、前記ラジカル重合性化合物が２個以上のラジカル重合性基を有する場合、これらのラジカル重合性基はそれぞれ同一であってもよいし、異なっていてもよい。前記ラジカル重合性化合物が１分子中に有するラジカル重合性基の数は、ハードコート層の硬度を向上する点から、２つ以上であることが好ましい。前記ラジカル重合性化合物としては、反応性の高さの点から、中でも（メタ）アクリロイル基を有する化合物が好ましく、１分子中に２～６個の（メタ）アクリロイル基を有する多官能アクリレートモノマーと称される化合物やエポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレートと称される分子内に数個の（メタ）アクリロイル基を有する分子量が数百から数千のオリゴマーを好ましく使用できる。エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート及びポリエステル（メタ）アクリレートから選択された１種以上を含むことが好ましい。 The above-mentioned radical polymerizable compound is a compound having a radical polymerizable group. The radical polymerizable group contained in the radical polymerizable compound may be a functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond. Specific examples thereof include a vinyl group and a (meth)acryloyl group. When the radical-polymerizable compound has two or more radical-polymerizable groups, these radical-polymerizable groups may be the same or different. The number of radically polymerizable groups contained in one molecule of the radically polymerizable compound is preferably 2 or more from the viewpoint of improving the hardness of the hard coat layer. As the radically polymerizable compound, a compound having a (meth)acryloyl group is preferable from the viewpoint of high reactivity, and a polyfunctional acrylate monomer having 2 to 6 (meth)acryloyl groups in one molecule is preferable. Preferred compounds and oligomers having several (meth)acryloyl groups in the molecule, which are called compounds and epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, and whose molecular weight is several hundred to several thousand Can be used. It is preferable to include at least one selected from epoxy (meth)acrylate, urethane (meth)acrylate and polyester (meth)acrylate.
　前記カチオン重合性化合物とは、エポキシ基、オキセタニル基、ビニルエーテル基等のカチオン重合性基を有する化合物である。前記カチオン重合性化合物が１分子中に有するカチオン重合性基の数は、ハードコート層の硬度を向上する点から、２つ以上であることが好ましく、更に３つ以上であることが好ましい。また、前記カチオン重合性化合物としては、中でも、カチオン重合性基としてエポキシ基及びオキセタニル基の少なくとも１種を有する化合物が好ましい。エポキシ基、オキセタニル基等の環状エーテル基は、重合反応に伴う収縮が小さいという点から好ましい。また、環状エーテル基のうちエポキシ基を有する化合物は多様な構造の化合物が入手し易く、得られたハードコート層の耐久性に悪影響を与えず、ラジカル重合性化合物との相溶性もコントロールし易いという利点がある。また、環状エーテル基のうちオキセタニル基は、エポキシ基と比較して重合度が高くなりやすく、低毒性であり、得られたハードコート層のカチオン重合性化合物から得られるネットワーク形成速度を早め、ラジカル重合性化合物と混在する領域でも未反応のモノマーを膜中に残さずに独立したネットワークを形成する等の利点がある。 The above-mentioned cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, a vinyl ether group. The number of cationically polymerizable groups contained in one molecule of the cationically polymerizable compound is preferably 2 or more, and more preferably 3 or more, from the viewpoint of improving the hardness of the hard coat layer. In addition, as the cationically polymerizable compound, among others, a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable. A cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint that the shrinkage accompanying the polymerization reaction is small. Further, among the cyclic ether groups, compounds having an epoxy group are readily available as compounds having various structures, do not adversely affect the durability of the obtained hard coat layer, and easily control the compatibility with the radically polymerizable compound. There is an advantage that. Further, among the cyclic ether groups, the oxetanyl group is more likely to have a higher degree of polymerization than the epoxy group and has low toxicity, and accelerates the network formation rate obtained from the cationically polymerizable compound of the obtained hard coat layer, and radicals. Even in a region mixed with the polymerizable compound, there is an advantage that an unreacted monomer is not left in the film and an independent network is formed.
　エポキシ基を有するカチオン重合性化合物としては、例えば、脂環族環を有する多価アルコールのポリグリシジルエーテル又は、シクロヘキセン環、シクロペンテン環含有化合物を、過酸化水素、過酸等の適当な酸化剤でエポキシ化する事によって得られる脂環族エポキシ樹脂；脂肪族多価アルコール、又はそのアルキレンオキサイド付加物のポリグリシジルエーテル、脂肪族長鎖多塩基酸のポリグリシジルエステル、グリシジル（メタ）アクリレートのホモポリマー、コポリマーなどの脂肪族エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦや水添ビスフェノールＡ等のビスフェノール類、又はそれらのアルキレンオキサイド付加体、カプロラクトン付加体等の誘導体と、エピクロルヒドリンとの反応によって製造されるグリシジルエーテル、及びノボラックエポキシ樹脂等でありビスフェノール類から誘導されるグリシジルエーテル型エポキシ樹脂等が挙げられる。 As the cationically polymerizable compound having an epoxy group, for example, polyglycidyl ether of a polyhydric alcohol having an alicyclic ring, or cyclohexene ring, a cyclopentene ring-containing compound, hydrogen peroxide, with a suitable oxidizing agent such as peracid Alicyclic epoxy resin obtained by epoxidation; polyglycidyl ether of aliphatic polyhydric alcohol or alkylene oxide adduct thereof, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer of glycidyl (meth)acrylate, Aliphatic epoxy resins such as copolymers; glycidyl ethers produced by the reaction of bisphenol A, bisphenol F, bisphenols such as hydrogenated bisphenol A, or derivatives thereof such as alkylene oxide adducts and caprolactone adducts with epichlorohydrin, And glycidyl ether type epoxy resins derived from bisphenols such as novolac epoxy resins.
　前記ハードコート組成物は重合開始剤をさらに含むことができる。重合開始剤としては、ラジカル重合開始剤、カチオン重合開始剤、ラジカル及びカチオン重合開始剤等であり、適宜選択して用いることができる。これらの重合開始剤は、活性エネルギー線照射及び加熱の少なくとも一種により分解されて、ラジカルもしくはカチオンを発生してラジカル重合とカチオン重合を進行させるものである。 The hard coat composition may further include a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., which can be appropriately selected and used. These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations to promote radical polymerization and cation polymerization.
　ラジカル重合開始剤は、活性エネルギー線照射及び加熱の少なくともいずれかによりラジカル重合を開始させる物質を放出することが可能であればよい。例えば、熱ラジカル重合開始剤としては、過酸化水素、過安息香酸等の有機過酸化物、アゾビスブチロニトリル等のアゾ化合物等があげられる。 The radical polymerization initiator may be any substance that can release a substance that initiates radical polymerization by at least one of irradiation with active energy rays and heating. Examples of thermal radical polymerization initiators include hydrogen peroxide, organic peroxides such as perbenzoic acid, and azo compounds such as azobisbutyronitrile.
　活性エネルギー線ラジカル重合開始剤としては、分子の分解でラジカルが生成されるＴｙｐｅ１型ラジカル重合開始剤と、３級アミンと共存して水素引き抜き型反応でラジカルを生成するＴｙｐｅ２型ラジカル重合開始剤があり、それぞれ単独でまたは併用して使用することもできる。 As the active energy ray radical polymerization initiator, Type 1 type radical polymerization initiators that generate radicals by decomposition of molecules and Type 2 type radical polymerization initiators that generate radicals by hydrogen abstraction type reaction in coexistence with tertiary amines are used. Yes, they can be used alone or in combination.
　カチオン重合開始剤は、活性エネルギー線照射及び加熱の少なくともいずれかによりカチオン重合を開始させる物質を放出することが可能であればよい。カチオン重合開始剤としては、芳香族ヨードニウム塩、芳香族スルホニウム塩、シクロペンタジエニル鉄（ＩＩ）錯体等が使用できる。これらは、構造の違いによって活性エネルギー線照射または加熱のいずれかまたはいずれでもカチオン重合を開始することができる。前記重合開始剤は、前記ハードコート組成物全体１００重量％に対して０．１～１０重量％を含むことができる。前記重合開始剤の含量が０．１重量％未満の場合、硬化を十分に進行させることができず、最終的に得られた塗膜の機械的物性や密着力を具現することが難しく、１０重量％を超える場合、硬化収縮による接着力不良や割れ現象及びカール現象が発生することがある。 The cationic polymerization initiator may be any substance that can release a substance that initiates cationic polymerization by at least one of irradiation with active energy rays and heating. As the cationic polymerization initiator, an aromatic iodonium salt, an aromatic sulfonium salt, a cyclopentadienyl iron(II) complex or the like can be used. These can initiate cationic polymerization either by irradiation with active energy rays or by heating, or both, depending on the difference in structure. The polymerization initiator may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the total hard coat composition. When the content of the polymerization initiator is less than 0.1% by weight, curing cannot be sufficiently progressed, and it is difficult to realize mechanical properties and adhesion of the finally obtained coating film. If the content is more than wt%, poor adhesion, cracking and curling may occur due to curing shrinkage.
　前記ハードコート組成物はさらに溶剤、添加剤からなる群から選択される一つ以上をさらに含むことができる。前記溶剤は、前記重合性化合物および重合開始剤を溶解または分散させることができるもので、本技術分野のハードコート組成物の溶剤として知られているものなら制限なく使用することができる。前記添加剤は、無機粒子、レベリング剤、安定剤、界面活性剤、帯電防止剤、潤滑剤、防汚剤などをさらに含むことができる。 The hard coat composition may further include one or more selected from the group consisting of a solvent and an additive. The solvent can dissolve or disperse the polymerizable compound and the polymerization initiator, and any solvent known as a solvent for a hard coat composition in the technical field can be used without limitation. The additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.
　ハードコート層の厚み（ｔ１）に対する、支持体の厚み（ｔ２）の比（ｔ２／ｔ１）は、好ましくは０．１３～５．００であり、より好ましくは０．３８～４．００であり、さらに好ましくは０．６３～３．３３である。 The ratio (t2/t1) of the thickness (t2) of the support to the thickness (t1) of the hard coat layer is preferably 0.13 to 5.00, more preferably 0.38 to 4.00. , And more preferably 0.63 to 3.33.
　本発明の積層体は、そのほかの任意の機能層を積層させた形態としてもよい。例えば、本発明の積層体に円偏光板やタッチセンサを積層しさらに機能付与したりすることができる。 The laminated body of the present invention may have a form in which any other functional layer is laminated. For example, a circularly polarizing plate or a touch sensor may be laminated on the laminate of the present invention to further impart a function.
＜画像表示装置＞
　本発明の画像表示装置は、本発明の積層体を有することを特徴とする。本発明の積層体は、画像表示装置において、ウインドウフィルムとして機能することができる。 <Image display device>
An image display device of the present invention is characterized by having the laminate of the present invention. The laminate of the present invention can function as a window film in an image display device.
　画像表示装置としての種類は問わず公知のものが使用できる。例えば、有機ＥＬ表示装置に本発明の積層体が好適に用いることができる。例えば、フレキシブル有機ＥＬ表示装置の反射防止偏光板として好適に用いることができる。これらの層は、互いに後述の接着剤または粘着剤を介して積層されることができる。 Any known image display device can be used. For example, the laminate of the present invention can be preferably used for an organic EL display device. For example, it can be suitably used as an antireflection polarizing plate of a flexible organic EL display device. These layers can be laminated on each other via an adhesive or a pressure-sensitive adhesive described below.
＜フレキシブル画像表示装置＞
　フレキシブル画像表示装置は、フレキシブル画像表示装置用積層体と、有機ＥＬ表示パネルとからなり、有機ＥＬ表示パネルに対して視認側にフレキシブル画像表示装置用積層体が配置され、折り曲げ可能に構成されている。フレキシブル画像表示装置用積層体としては、本発明の積層体、円偏光板、およびタッチセンサを含有していてもよく、それらの積層順は任意であるが、視認側から本発明の積層体、円偏光板、タッチセンサまたは本発明の積層体、タッチセンサ、円偏光板の順に積層されていることが好ましい。タッチセンサの視認側に円偏光板が存在すると、タッチセンサのパターンが視認されにくくなり表示画像の視認性が良くなるので好ましい。それぞれの部材は接着剤、粘着剤等を用いて積層することができる。また、本発明の積層体、円偏光板、タッチセンサのいずれかの層の少なくとも一面に形成された遮光パターンを具備することができる。 <Flexible image display device>
The flexible image display device includes a flexible image display device laminate and an organic EL display panel. The flexible image display device laminate is arranged on the viewer side of the organic EL display panel and is configured to be bendable. There is. The laminate for a flexible image display device may contain the laminate of the present invention, a circularly polarizing plate, and a touch sensor, and the stacking order thereof is arbitrary, but the laminate of the present invention from the viewing side, It is preferable that the circularly polarizing plate, the touch sensor or the laminate of the present invention, the touch sensor and the circularly polarizing plate are laminated in this order. The presence of the circularly polarizing plate on the viewing side of the touch sensor is preferable because the pattern of the touch sensor is less visible and the visibility of the display image is improved. Each member can be laminated using an adhesive, a pressure sensitive adhesive or the like. In addition, a light-shielding pattern formed on at least one surface of any one of the layered product, the circularly polarizing plate, and the touch sensor of the present invention can be provided.
　前記フレキシブル画像表示装置用積層体を形成する各層（本発明の積層体、円偏光板、タッチセンサ）は接着剤によって積層することができる。接着剤としては、水系接着剤、有機溶剤系、無溶剤系接着剤、固体接着剤、溶剤揮散型接着剤、湿気硬化型接着剤、加熱硬化型接着剤、嫌気硬化型、活性エネルギー線硬化型接着剤、硬化剤混合型接着剤、熱溶融型接着剤、感圧型接着剤（粘着剤）、再湿型接着剤等汎用に使用されているものが使用できる。中でも水系溶剤揮散型接着剤、活性エネルギー線硬化型接着剤、粘着剤がよくもちいられる。接着剤層の厚さは、求められる接着力等に応じて適宜調節することができ、０．０１μｍ～５００μｍ、好ましくは０．１μｍ～３００μｍであり、前記フレキシブル画像表示装置用積層体には複数存在するがそれぞれの厚み種類は同じであってもよいし、異なっていてもよい。 Each layer (laminate of the present invention, circularly polarizing plate, touch sensor) forming the laminate for flexible image display device can be laminated with an adhesive. As the adhesive, a water-based adhesive, an organic solvent-based adhesive, a solvent-free adhesive, a solid adhesive, a solvent volatilizing adhesive, a moisture-curable adhesive, a heat-curable adhesive, an anaerobic-curable adhesive, an active energy ray-curable adhesive Adhesives, hardener-mixed adhesives, hot-melt adhesives, pressure-sensitive adhesives (adhesives), rewet adhesives, and other commonly used adhesives can be used. Among them, water-based solvent volatilizing adhesives, active energy ray-curing adhesives, and pressure-sensitive adhesives are often used. The thickness of the adhesive layer can be appropriately adjusted according to the required adhesive strength and the like, and is 0.01 μm to 500 μm, preferably 0.1 μm to 300 μm, and the laminate for flexible image display device has a plurality of layers. Although present, the respective thickness types may be the same or different.
　前記水系溶剤揮散型接着剤としてはポリビニルアルコール系ポリマー、でんぷん等の水溶性ポリマー、エチレン－酢酸ビニル系エマルジョン、スチレン－ブタジエン系エマルジョン等水分散状態のポリマーを主剤ポリマーとして使用することができる。水、前記主剤ポリマーに加えて、架橋剤、シラン系化合物、イオン性化合物、架橋触媒、酸化防止剤、染料、顔料、無機フィラー、有機溶剤等を配合してもよい。前記水系溶剤揮散型接着剤によって接着する場合、前記水系溶剤揮散型接着剤を被接着層間に注入して被着層を貼合した後、乾燥させることで接着性を付与することができる。前記水系溶剤揮散型接着剤を用いる場合の接着層の厚さは０．０１～１０μｍ、好ましくは０．１～１μｍであってもよい。前記水系溶剤揮散型接着剤を複数層用いる場合には、それぞれの層の厚み種類は同じであってもよいし、異なっていてもよい。 As the water-based solvent volatilizing adhesive, polyvinyl alcohol-based polymer, water-soluble polymer such as starch, water-dispersed polymer such as ethylene-vinyl acetate emulsion and styrene-butadiene-based emulsion can be used as a main polymer. In addition to water and the base polymer, a cross-linking agent, a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent and the like may be added. In the case of bonding with the water-based solvent volatilization type adhesive, the water-based solvent volatilization type adhesive may be injected between the adhered layers to bond the adhered layers and then dried to impart adhesiveness. The thickness of the adhesive layer when the water-based solvent volatilizing adhesive is used may be 0.01 to 10 μm, preferably 0.1 to 1 μm. When a plurality of layers of the water-based solvent volatilizing adhesive are used, the thickness of each layer may be the same or different.
　前記活性エネルギー線硬化型接着剤は、活性エネルギー線を照射して接着剤層を形成する反応性材料を含む活性エネルギー線硬化組成物の硬化により形成することができる。前記活性エネルギー線硬化組成物は、ハードコート組成物と同様のラジカル重合性化合物及びカチオン重合性化合物の少なくとも１種の重合物を含有することができる。前記ラジカル重合性化合物とは、ハードコート組成物と同様であり、ハードコート組成物と同様の種類のものが使用できる。接着層に用いられるラジカル重合性化合物としてはアクリロイル基を有する化合物が好ましい。接着剤組成物としての粘度を下げるために単官能の化合物を含むことも好ましい。 The active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that irradiates an active energy ray to form an adhesive layer. The active energy ray-curable composition may contain at least one polymer of a radically polymerizable compound and a cationically polymerizable compound, which are similar to those of the hard coat composition. The radically polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used. As the radically polymerizable compound used in the adhesive layer, a compound having an acryloyl group is preferable. It is also preferable to include a monofunctional compound in order to reduce the viscosity of the adhesive composition.
　前記カチオン重合性化合物は、ハードコート組成物と同様であり、ハードコート組成物と同様の種類のものが使用できる。活性エネルギー線硬化組成物に用いられるカチオン重合性化合物としては、エポキシ化合物が特に好ましい。接着剤組成物としての粘度を下げるために単官能の化合物を反応性希釈剤として含むことも好ましい。
活性エネルギー線組成物には重合開始剤をさらに含むことができる。重合開始剤としては、ラジカル重合開始剤、カチオン重合開始剤、ラジカル及びカチオン重合開始剤等であり、適宜選択して用いることができる。これらの重合開始剤は、活性エネルギー線照射及び加熱の少なくとも一種により分解されて、ラジカルもしくはカチオンを発生してラジカル重合とカチオン重合を進行させるものである。ハードコート組成物の記載の中で活性エネルギー線照射によりラジカル重合またはカチオン重合の内の少なくともいずれか開始することができる開始剤を使用することができる。 The cationically polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used. An epoxy compound is particularly preferred as the cationically polymerizable compound used in the active energy ray-curable composition. It is also preferable to include a monofunctional compound as a reactive diluent in order to reduce the viscosity of the adhesive composition.
The active energy ray composition may further contain a polymerization initiator. The polymerization initiator includes radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., which can be appropriately selected and used. These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations to promote radical polymerization and cation polymerization. In the description of the hard coat composition, an initiator capable of initiating radical polymerization and/or cationic polymerization by irradiation with active energy rays can be used.
　前記活性エネルギー線硬化組成物はさらに、イオン捕捉剤、酸化防止剤、連鎖移動剤、密着付与剤、熱可塑性樹脂、充填剤、流動粘度調整剤、可塑剤、消泡剤溶剤、添加剤、溶剤を含むことができる。前記活性エネルギー線硬化型接着剤によって接着する場合、前記活性エネルギー線硬化組成物を被接着層のいずれかまたは両方に塗布後貼合し、いずれかの被着層または両方の被着層を通して活性エネルギー線を照射して硬化させることで接着することができる。前記活性エネルギー線硬化型接着剤を用いる場合の接着層の厚さは０．０１～２０μｍ、好ましくは０．１～１０μｍであってもよい。前記活性エネルギー線硬化型接着剤を複数層用いる場合には、それぞれの層の厚み種類は同じであってもよいし、異なっていてもよい。 The active energy ray-curable composition is further an ion scavenger, an antioxidant, a chain transfer agent, an adhesion promoter, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, a defoaming agent solvent, an additive, a solvent. Can be included. In the case of adhering with the active energy ray-curable adhesive, the active energy ray-curable composition is applied to either or both of the adherend layers and then laminated, and activated through either adherent layer or both adherent layers. Adhesion can be achieved by irradiating an energy ray and curing it. When the active energy ray-curable adhesive is used, the thickness of the adhesive layer may be 0.01 to 20 μm, preferably 0.1 to 10 μm. When a plurality of layers of the active energy ray-curable adhesive are used, the thickness of each layer may be the same or different.
　前記粘着剤としては、主剤ポリマーに応じて、アクリル系粘着剤、ウレタン系粘着剤、ゴム系粘着剤、シリコーン系粘着剤等に分類され何れを使用することもできる。粘着剤には主剤ポリマーに加えて、架橋剤、シラン系化合物、イオン性化合物、架橋触媒、酸化防止剤、粘着付与剤、可塑剤、染料、顔料、無機フィラー等を配合してもよい。前記粘着剤を構成する各成分を溶剤に溶解・分散させて粘着剤組成物を得て、該粘着剤組成物を基材上に塗布した後に乾燥させることで、粘着剤層接着層が形成される。粘着層は直接形成されてもよいし、別途基材に形成したものを転写することもできる。接着前の粘着面をカバーするためには離型フィルムを使用することも好ましい。前記活性エネルギー線硬化型接着剤を用いる場合の接着層の厚さは０．１～５００μｍ、好ましくは１～３００μｍであってもよい。前記粘着剤を複数層用いる場合には、それぞれの層の厚み種類は同じであってもよいし、異なっていてもよい。 The pressure-sensitive adhesive may be classified into an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, etc., depending on the base polymer, and any of these may be used. In addition to the base polymer, the adhesive may contain a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like. The components constituting the pressure-sensitive adhesive are dissolved and dispersed in a solvent to obtain a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is applied onto a substrate and then dried to form a pressure-sensitive adhesive layer adhesive layer. It The adhesive layer may be directly formed, or may be formed separately on the substrate and transferred. It is also preferable to use a release film to cover the adhesive surface before adhesion. When the active energy ray-curable adhesive is used, the thickness of the adhesive layer may be 0.1 to 500 μm, preferably 1 to 300 μm. When the pressure-sensitive adhesive is used in multiple layers, the thickness of each layer may be the same or different.
＜タッチセンサ＞
　タッチセンサは入力手段として用いられる。タッチセンサとしては、抵抗膜方式、表面弾性波方式、赤外線方式、電磁誘導方式、静電容量方式等様々な様式が提案されており、いずれの方式でも構わない。中でも静電容量方式が好ましい。静電容量方式タッチセンサは活性領域及び前記活性領域の外郭部に位置する非活性領域に区分される。活性領域は表示パネルで画面が表示される領域（表示部）に対応する領域であって、使用者のタッチが感知される領域であり、非活性領域は表示装置で画面が表示されない領域（非表示部）に対応する領域である。タッチセンサはフレキシブルな特性を有する基板と；前記基板の活性領域に形成された感知パターンと；前記基板の非活性領域に形成され、前記感知パターンとパッド部を介して外部の駆動回路と接続するための各センシングラインを含むことができる。フレキシブルな特性を有する基板としては、前記ウインドウの透明基板と同様の材料が使用できる。タッチセンサの基板は、靱性が２，０００ＭＰａ％以上のものがタッチセンサのクラック抑制の面から好ましい。より好ましくは靱性が２，０００ＭＰａ％～３０，０００ＭＰａ％であってもよい。 <Touch sensor>
The touch sensor is used as an input means. As the touch sensor, various types such as a resistance film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and a capacitance type have been proposed, and any type may be used. Of these, the capacitance method is preferable. The capacitive touch sensor is divided into an active region and a non-active region located outside the active region. The active region is a region corresponding to a region where the screen is displayed on the display panel (display unit), and is a region where the user's touch is sensed, and the inactive region is a region where the screen is not displayed on the display device (non-display region). This is an area corresponding to the display section). The touch sensor has a substrate having flexible characteristics; a sensing pattern formed in an active region of the substrate; formed in an inactive region of the substrate and connected to an external driving circuit through the sensing pattern and a pad unit. Each sensing line can be included. As the substrate having flexible characteristics, the same material as the transparent substrate for the window can be used. The substrate of the touch sensor preferably has a toughness of 2,000 MPa% or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness may be 2,000 MPa% to 30,000 MPa%.
　前記感知パターンは、第１方向に形成された第１パターン及び第２方向に形成された第２パターンを備えることができる。第１パターンと第２パターンは互いに異なる方向に配置される。第１パターン及び第２パターンは、同一層に形成され、タッチされる地点を感知するためには、それぞれのパターンが電気的に接続されなければならない。第１パターンは各単位パターンが継ぎ手を介して互いに接続された形態であるが、第２パターンは各単位パターンがアイランド形態に互いに分離された構造になっているので、第２パターンを電気的に接続するためには別途のブリッジ電極が必要である。感知パターンは周知の透明電極素材を適用することができる。例えば、インジウムスズ酸化物（ＩＴＯ）、インジウム亜鉛酸化物（ＩＺＯ）、亜鉛酸化物（ＺｎＯ）、インジウム亜鉛スズ酸化物（ＩＺＴＯ）、カドミウムスズ酸化物（ＣＴＯ）、ＰＥＤＯＴ（ｐｏｌｙ（３，４―ｅｔｈｙｌｅｎｅｄｉｏｘｙｔｈｉｏｐｈｅｎｅ））、炭素ナノチューブ（ＣＮＴ）、グラフェン、金属ワイヤなどを挙げることができ、これらは単独または２種以上混合して使用することができる。好ましくはＩＴＯを使用することができる。金属ワイヤに使用される金属は特に限定されず、例えば、銀、金、アルミニウム、銅、鉄、ニッケル、チタン、テルル、クロムなどを挙げることができる。これらは単独または２種以上混合して使用することができる。 The sensing pattern may include a first pattern formed in the first direction and a second pattern formed in the second direction. The first pattern and the second pattern are arranged in different directions. The first pattern and the second pattern are formed on the same layer, and the respective patterns must be electrically connected in order to detect a touched point. The first pattern has a form in which the unit patterns are connected to each other through a joint, but the second pattern has a structure in which the unit patterns are separated from each other in an island form. A separate bridge electrode is required to make the connection. A known transparent electrode material can be applied to the sensing pattern. For example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), cadmium tin oxide (CTO), PEDOT(poly(3,4- Ethylenedioxythiophene)), carbon nanotube (CNT), graphene, metal wire and the like, and these may be used alone or in combination of two or more. Preferably ITO can be used. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, tellurium, and chromium. These may be used alone or in combination of two or more.
　ブリッジ電極は感知パターン上部に絶縁層を介して前記絶縁層上部に形成することができ、基板上にブリッジ電極が形成されており、その上に絶縁層及び感知パターンを形成することができる。前記ブリッジ電極は感知パターンと同じ素材で形成することもでき、モリブデン、銀、アルミニウム、銅、パラジウム、金、白金、亜鉛、スズ、チタンまたはこれらのうちの２種以上の合金などの金属で形成することもできる。第１パターンと第２パターンは電気的に絶縁されなければならないので、感知パターンとブリッジ電極の間には絶縁層が形成される。絶縁層は第１パターンの継ぎ手とブリッジ電極の間にのみ形成することもでき、感知パターンを覆う層の構造に形成することもできる。後者の場合は、ブリッジ電極は絶縁層に形成されたコンタクトホールを介して第２パターンを接続することができる。前記タッチセンサはパターンが形成されたパターン領域と 、パターンが形成されていない非パターン領域間の透過率の差、具体的には、これらの領域における屈折率の差によって誘発される光透過率の差を適切に補償するための手段として基板と電極の間に光学調節層をさらに含むことができ、前記光学調節層は無機絶縁物質または有機絶縁物質を含むことができる。光学調節層は光硬化性有機バインダー及び溶剤を含む光硬化組成物を基板上にコーティングして形成することができる。前記光硬化組成物は無機粒子をさらに含むことができる。前記無機粒子によって光学調節層の屈折率が上昇することができる。 The bridge electrode can be formed on the insulating layer on the sensing pattern via an insulating layer, and the bridge electrode is formed on the substrate, and the insulating layer and the sensing pattern can be formed on the bridge electrode. The bridge electrode may be formed of the same material as the sensing pattern, and may be formed of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. You can also do it. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the joint of the first pattern and the bridge electrode, or may be formed in the structure of the layer covering the sensing pattern. In the latter case, the bridge electrode can connect the second pattern through a contact hole formed in the insulating layer. The touch sensor has a transmittance difference between a patterned area where a pattern is formed and a non-patterned area where a pattern is not formed, specifically, a light transmittance induced by a difference in refractive index in these areas. An optical adjustment layer may be further included between the substrate and the electrode as a means for appropriately compensating for the difference, and the optical adjustment layer may include an inorganic insulating material or an organic insulating material. The optical adjustment layer may be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate. The photocurable composition may further include inorganic particles. The inorganic particles may increase the refractive index of the optical adjustment layer.
　前記光硬化性有機バインダーは、例えば、アクリレート系単量体、スチレン系単量体、カルボン酸系単量体などの各単量体の共重合体を含むことができる。前記光硬化性有機バインダーは、例えば、エポキシ基含有繰り返し単位、アクリレート繰り返し単位、カルボン酸繰り返し単位などの互いに異なる各繰り返し単位を含む共重合体であってもよい。
前記無機粒子は、例えば、ジルコニア粒子、チタニア粒子、アルミナ粒子などを含むことができる。 前記光硬化組成物は、光重合開始剤、重合性モノマー、硬化補助剤などの各添加剤をさらに含むこともできる。 The photocurable organic binder may include, for example, a copolymer of each monomer such as an acrylate monomer, a styrene monomer, and a carboxylic acid monomer. The photocurable organic binder may be, for example, a copolymer containing different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit.
The inorganic particles can include, for example, zirconia particles, titania particles, alumina particles, and the like. The photocurable composition may further include additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.
（遮光パターン）
　前記遮光パターンは前記フレキシブル画像表示装置のベゼルまたはハウジングの少なくとも一部として適用することができる。遮光パターンによって前記フレキシブル画像表示装置の辺縁部に配置される配線が隠されて視認されにくくすることで、画像の視認性が向上する。前記遮光パターンは単層または複層の形態であってもよい。遮光パターンのカラーは特に制限されることはなく、黒色、白色、金属色などの多様なカラーを有する。遮光パターンはカラーを具現するための顔料と、アクリル系樹脂、エステル系樹脂、エポキシ系樹脂、ポリウレタン、シリコーンなどの高分子で形成することができる。これらの単独または２種類以上の混合物で使用することもできる。前記遮光パターンは、印刷、リソグラフィ、インクジェットなど各種の方法にて形成することができる。遮光パターンの厚さは１μｍ～１００μｍであってもよく、好ましくは２μｍ～５０μｍである。また、光パターンの厚み方向に傾斜等の形状を付与することも好ましい。
(Shading pattern)
The light shielding pattern may be applied as at least a part of a bezel or a housing of the flexible image display device. The visibility is improved by hiding the wiring arranged at the peripheral portion of the flexible image display device by the light-shielding pattern and making it difficult to see. The light-shielding pattern may have a single-layer structure or a multi-layer structure. The color of the light-shielding pattern is not particularly limited, and has various colors such as black, white, and metallic color. The light-shielding pattern can be formed of a pigment for realizing a color and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane or silicone. These can be used alone or as a mixture of two or more kinds. The light shielding pattern can be formed by various methods such as printing, lithography and inkjet. The thickness of the light shielding pattern may be 1 μm to 100 μm, preferably 2 μm to 50 μm. It is also preferable to give a shape such as an inclination in the thickness direction of the light pattern.
（円偏光板）
　前記円偏光板は、直線偏光板にλ／４位相差板を積層することにより右若しくは左円偏光成分のみを透過させる機能を有する機能層である。たとえば外光を右円偏光に変換して有機ＥＬパネルで反射されて左円偏光となった外光を遮断し、有機ＥＬの発光成分のみを透過させることで反射光の影響を抑制して画像を見やすくするために用いられる。 (Circular polarizing plate)
The circularly polarizing plate is a functional layer having a function of transmitting only the right or left circularly polarized light component by laminating a λ/4 retardation plate on a linearly polarizing plate. For example, by converting the external light into right circularly polarized light and blocking the external light reflected by the organic EL panel to become left circularly polarized light, and transmitting only the luminescence component of the organic EL, the influence of reflected light is suppressed and the image is displayed. It is used to make it easier to see.
　円偏光機能を達成するためには、直線偏光板の吸収軸とλ／４位相差板の遅相軸は理論上４５°である必要があるが、実用的には４５±１０°である。直線偏光板とλ／４位相差板とは必ずしも隣接して積層される必要はなく、吸収軸と遅相軸との関係が前述の範囲を満足していればよい。全波長において完全な円偏光を達成することが好ましいが実用上は必ずしもその必要はないので本発明における円偏光板は楕円偏光板をも包含する。直線偏光板の視認側にさらにλ／４位相差板を積層して、出射光を円偏光とすることで偏光サングラスをかけた状態での視認性を向上させることも好ましい。 In order to achieve the circular polarization function, the absorption axis of the linear polarizing plate and the slow axis of the λ/4 retardation plate need to be 45° theoretically, but they are practically 45±10°. The linearly polarizing plate and the λ/4 retardation plate do not necessarily have to be laminated adjacent to each other, as long as the relationship between the absorption axis and the slow axis satisfies the above range. It is preferable to achieve perfect circularly polarized light at all wavelengths, but this is not always necessary in practice, so the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable to further laminate a λ/4 phase difference plate on the visible side of the linear polarizing plate to make the emitted light circularly polarized light to improve the visibility in the state where the polarized sunglasses are worn.
　直線偏光板は、透過軸方向に振動している光は通すが、それとは垂直な振動成分の偏光を遮断する機能を有する機能層である。前記直線偏光板は、直線偏光子単独または直線偏光子及びその少なくとも一面に貼り付けられた保護フィルムを備えた構成であってもよい。前記直線偏光板の厚さは、２００μｍ以下であってもよく、好ましくは、０．５μｍ～１００μｍである。厚さが２００μｍを超えると柔軟性が低下することがある。 ▽A linear polarizing plate is a functional layer that has the function of transmitting the light vibrating in the transmission axis direction, but blocking the polarization of the vibration component perpendicular to it. The linear polarizing plate may be configured to include a linear polarizer alone or a linear polarizer and a protective film attached to at least one surface thereof. The thickness of the linear polarizing plate may be 200 μm or less, preferably 0.5 μm to 100 μm. If the thickness exceeds 200 μm, the flexibility may decrease.
　前記直線偏光子は、ポリビニルアルコール（ＰＶＡ）系フィルムを染色、延伸することで製造される延伸フィルム型偏光子であってもよい。延伸によって配向したＰＶＡ系フィルムに、ヨウ素等の二色性色素が吸着、またはＰＶＡに吸着した状態で延伸されることで二色性色素が配向し、偏光性能を発揮する。前記フィルム型偏光子の製造においては、他に膨潤、ホウ酸による架橋、水溶液による洗浄、乾燥等の工程を有していてもよい。延伸や染色工程はＰＶＡ系フィルム単独で行ってもよいし、ポリエチレンテレフタレートのような他のフィルムと積層された状態で行うこともできる。用いられるＰＶＡ系フィルムとしては１０～１００μｍ、延伸倍率は２～１０倍が好ましい。 The linear polarizer may be a stretched film type polarizer produced by dyeing and stretching a polyvinyl alcohol (PVA) film. A dichroic dye such as iodine is adsorbed on a PVA-based film oriented by stretching, or stretched in a state of being adsorbed on PVA, whereby the dichroic dye is oriented and exhibits polarization performance. The production of the film-type polarizer may include other steps such as swelling, crosslinking with boric acid, washing with an aqueous solution, and drying. The stretching and dyeing steps may be performed on the PVA-based film alone or may be performed in a state of being laminated with another film such as polyethylene terephthalate. The PVA film used is preferably 10 to 100 μm, and the stretching ratio is preferably 2 to 10 times.
　さらに前記直線偏光子の他の一例としては、液晶化合物を含む組成物を塗布して形成する液晶塗布型偏光子であってもよい。前記組成物は、液晶化合物及び二色性色素を含むことができる。前記液晶化合物としては液晶状態を示す性質を有していればよく、特にスメクチック相等の高次の配向状態を有していることが高い偏光性能を発揮することができるため好ましい。また、重合性基を有していることも好ましい。前記二色性色素は、前記液晶化合物とともに配向して二色性を示す色素であって、二色性色素自身が液晶性を有していてもよいし、重合性基を有していることもできる。組成物の中のいずれかの化合物は重合性基を有している。前記組成物はさらに開始剤、溶剤、分散剤、レベリング剤、安定剤、界面活性剤、架橋剤、シランカップリング剤などを含むことができる。前記液晶塗布型偏光子は、配向膜上に液晶化合物を含む組成物を塗布し、液晶化合物が配向した状態で硬化させることで製造することができる。液晶塗布型偏光子は、延伸フィルム型偏光子に比べて厚さを薄く形成することができる。前記液晶塗布型偏光子の厚さは０．５～１０μｍ、好ましくは１～５μｍであってもよい。 Further, another example of the linear polarizer may be a liquid crystal coating type polarizer formed by coating a composition containing a liquid crystal compound. The composition may include a liquid crystal compound and a dichroic dye. The liquid crystal compound is only required to have a property of exhibiting a liquid crystal state, and particularly preferably has a higher order alignment state such as a smectic phase because high polarization performance can be exhibited. It is also preferable to have a polymerizable group. The dichroic dye is a dye that is aligned with the liquid crystal compound and exhibits dichroism, and the dichroic dye itself may have liquid crystallinity or has a polymerizable group. You can also Any compound in the composition has a polymerizable group. The composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like. The liquid crystal coating type polarizer can be manufactured by coating a composition containing a liquid crystal compound on an alignment film and curing the composition in a state where the liquid crystal compound is aligned. The liquid crystal coating type polarizer can be formed thinner than the stretched film type polarizer. The thickness of the liquid crystal coating type polarizer may be 0.5 to 10 μm, preferably 1 to 5 μm.
　前記配向膜は、例えば基材上に配向膜形成組成物を塗布し、ラビング、偏光照射等により配向性を付与することで製造することができる。前記配向膜形成組成物は、配向剤の他に溶剤、架橋剤、開始剤、分散剤、レベリング剤、シランカップリング剤等を含んでいてもよい。前記配向剤としては、例えば、ポリビニルアルコール類、ポリアクリレート類、ポリアミック酸類、ポリイミド類を使用することができる。光配向を適用する場合にはシンナメート基を含む配向剤を使用することが好ましい。前記配向剤として使用される高分子は重量平均分子量が１０，０００～１０００，０００程度であってもよい。前記配向膜は５ｎｍ～１００００ｎｍが好ましく、特に１０～５００ｎｍであれば、配向規制力が十分に発現されるため好ましい。前記液晶塗布型偏光子は基材から剥離して、さらにほかの部材に転写することもできるし、前記基材をそのまま積層することもできる。前記基材が、保護フィルムや位相差板、ウインドウの透明基材としての役割を担うことも好ましい The alignment film can be produced, for example, by applying the composition for forming an alignment film on a substrate and imparting the alignment property by rubbing, irradiation with polarized light, or the like. The composition for forming an alignment film may contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent and the like in addition to the alignment agent. As the aligning agent, for example, polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides can be used. When photo-alignment is applied, it is preferable to use an aligning agent containing a cinnamate group. The polymer used as the aligning agent may have a weight average molecular weight of about 10,000 to 1,000,000. The alignment film preferably has a thickness of 5 nm to 10,000 nm, and particularly preferably has a thickness of 10 to 500 nm because the alignment regulating force is sufficiently exhibited. The liquid crystal coated polarizer can be peeled from the substrate and transferred to another member, or the substrate can be laminated as it is. It is also preferable that the base material plays a role as a transparent base material of a protective film, a retardation plate, and a window.
　前記保護フィルムとしては、透明な高分子フィルムであればよく前記透明樹脂フィルムに使用される材料、添加剤が使用できる。セルロース系フィルム、オレフィン系フィルム、アクリルフィルム、ポリエステル系フィルムが好ましい。エポキシ樹脂等のカチオン硬化組成物やアクリレート等のラジカル硬化組成物を塗布して硬化して得られる塗布型の保護フィルムであってもよい。必要により可塑剤、紫外線吸収剤、赤外線吸収剤、顔料や染料のような着色剤、蛍光増白剤、分散剤、熱安定剤、光安定剤、帯電防止剤、酸化防止剤、滑剤、溶剤等を含んでいてもよい。前記保護フィルムの厚さは、２００μｍ以下であってもよく、好ましくは、１μｍ～１００μｍである。厚さが２００μｍを超えると柔軟性が低下することがある。透明樹脂フィルムの役割を兼ねることもできる。 As the protective film, a transparent polymer film may be used, and materials and additives used for the transparent resin film can be used. Cellulose type films, olefin type films, acrylic films and polyester type films are preferable. It may be a coating type protective film obtained by applying a cationically curable composition such as an epoxy resin or a radical curable composition such as an acrylate and curing it. If necessary, plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc. May be included. The thickness of the protective film may be 200 μm or less, preferably 1 μm to 100 μm. If the thickness exceeds 200 μm, the flexibility may decrease. It can also serve as a transparent resin film.
　前記λ／４位相差板は、入射光の進行方向に直交する方向（フィルムの面内方向）にλ／４の位相差を与えるフィルムである。前記λ／４位相差板は、セルロース系フィルム、オレフィン系フィルム、ポリカーボネート系フィルム等の高分子フィルムを延伸することで製造される延伸フィルム型位相差板であってもよい。必要により位相差調整剤、可塑剤、紫外線吸収剤、赤外線吸収剤、顔料や染料のような着色剤、蛍光増白剤、分散剤、熱安定剤、光安定剤、帯電防止剤、酸化防止剤、滑剤、溶剤等を含んでいてもよい。前記延伸型位相差板の厚さは、２００μｍ以下であってもよく、好ましくは、１μｍ～１００μｍである。厚さが２００μｍを超えると柔軟性が低下することがある。 The λ/4 retardation plate is a film that gives a λ/4 retardation in a direction (in-plane direction of the film) orthogonal to the traveling direction of incident light. The λ/4 retardation plate may be a stretched film type retardation plate produced by stretching a polymer film such as a cellulose film, an olefin film or a polycarbonate film. If necessary, phase difference adjuster, plasticizer, ultraviolet absorber, infrared absorber, colorant such as pigment or dye, fluorescent whitening agent, dispersant, heat stabilizer, light stabilizer, antistatic agent, antioxidant. , A lubricant, a solvent, etc. may be contained. The thickness of the stretchable retardation plate may be 200 μm or less, preferably 1 μm to 100 μm. If the thickness exceeds 200 μm, the flexibility may decrease.
　さらに前記λ／４位相差板の他の一例としては、液晶化合物を含む組成物を塗布して形成する液晶塗布型位相差板であってもよい。前記組成物は、ネマチック、コレステリック、スメクチック等の液晶状態を示す性質を有する液晶化合物を含む。組成物の中の液晶化合物を含むいずれかの化合物は重合性基を有している。前記液晶塗布型位相差板はさらに開始剤、溶剤、分散剤、レベリング剤、安定剤、界面活性剤、架橋剤、シランカップリング剤などを含むことができる。前記液晶塗布型位相差板は、前記液晶塗布型偏光子での記載と同様に配向膜上に液晶化合物を含む組成物を塗布し、液晶化合物が配向した状態で硬化させることで製造することができる。液晶塗布型位相差板は、延伸フィルム型位相差板に比べて厚さを薄く形成することができる。前記液晶塗布型偏光層の厚さは０．５～１０μｍ、好ましくは１～５μｍであってもよい。前記液晶塗布型位相差板は基材から剥離して、さらにほかの部材に転写することもできるし、前記基材をそのまま積層することもできる。前記基材が、保護フィルムや位相差板、透明樹脂フィルムとしての役割を担うことも好ましい。 Further, as another example of the λ/4 retardation plate, a liquid crystal coating type retardation plate formed by applying a composition containing a liquid crystal compound may be used. The composition includes a liquid crystal compound having a property of exhibiting a liquid crystal state such as nematic, cholesteric, and smectic. Any compound in the composition, including the liquid crystal compound, has a polymerizable group. The liquid crystal coated retardation plate may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like. The liquid crystal coating type retardation plate may be produced by coating a composition containing a liquid crystal compound on an alignment film as in the case of the liquid crystal coating type polarizer, and curing the liquid crystal compound in an aligned state. it can. The liquid crystal coating type retardation plate can be formed thinner than the stretched film type retardation plate. The thickness of the liquid crystal coating type polarizing layer may be 0.5 to 10 μm, preferably 1 to 5 μm. The liquid crystal coating type retardation plate can be peeled from the base material and transferred to another member, or the base material can be laminated as it is. It is also preferable that the substrate plays a role as a protective film, a retardation plate, or a transparent resin film.
　一般的には、短波長ほど複屈折が大きく長波長になるほど小さな複屈折を示す材料が多い。この場合には全可視光領域でλ／４の位相差を達成することはできないので、視感度の高い５６０ｎｍ付近に対してλ／４となるような面内位相差１００～１８０ｎｍ、好ましくは１３０～１５０ｎｍとなるように設計されることが多い。通常とは逆の複屈折率波長分散特性を有する材料を用いた逆分散λ／４位相差板を用いることは視認性をよくすることができるので好ましい。このような材料としては延伸フィルム型位相差板の場合は特開２００７‐２３２８７３号公報等、液晶塗布型位相差板の場合には特開２０１０－３０９７９号公報記載されているものを用いることも好ましい。 Generally, many materials exhibit large birefringence at shorter wavelengths and smaller birefringence at longer wavelengths. In this case, since a phase difference of λ/4 cannot be achieved in the entire visible light region, an in-plane phase difference of 100 to 180 nm, preferably 130, which is λ/4 near 560 nm where the visibility is high. Often designed to be ~150 nm. It is preferable to use an inverse dispersion λ/4 retardation plate made of a material having a birefringence wavelength dispersion characteristic opposite to the usual one because the visibility can be improved. As such a material, those described in JP 2007-232873 A in the case of a stretched film type retardation plate and those disclosed in JP 2010-30979 A in the case of a liquid crystal coating type retardation plate may be used. preferable.
　また、他の方法としてはλ／２位相差板と組み合わせることで広帯域λ／４位相差板を得る技術も知られている（特開平１０－９０５２１号公報）。λ／２位相差板もλ／４位相差板と同様の材料方法で製造される。延伸フィルム型位相差板と液晶塗布型位相差板の組み合わせは任意であるが、どちらも液晶塗布型位相差板を用いることは膜厚を薄くすることができるので好ましい。 Also, as another method, there is known a technique for obtaining a broadband λ/4 retardation plate by combining it with a λ/2 retardation plate (Japanese Patent Laid-Open No. 10-90521). The λ/2 retardation plate is also manufactured by the same material method as that of the λ/4 retardation plate. The combination of the stretched film type retardation plate and the liquid crystal coating type retardation plate is arbitrary, but it is preferable to use the liquid crystal coating type retardation plate for both of them because the film thickness can be reduced.
　前記円偏光板には斜め方向の視認性を高めるために、正のＣプレートを積層する方法も知られている（特開２０１４－２２４８３７号公報）。正のＣプレートも液晶塗布型位相差板であっても延伸フィルム型位相差板であってもよい。正のＣプレートの厚み方向の位相差は、波長５６０ｎｍにおいて－２００～－２０ｎｍ好ましくは－１４０～－４０ｎｍである。 A method is also known in which a positive C plate is laminated on the circularly polarizing plate in order to enhance visibility in an oblique direction (Japanese Patent Laid-Open No. 2014-224837). The positive C plate may be a liquid crystal coating type retardation plate or a stretched film type retardation plate. The retardation in the thickness direction of the positive C plate is −200 to −20 nm, preferably −140 to −40 nm at a wavelength of 560 nm.
　本発明によれば、非常に薄く、優れた耐衝撃性を有するハードコート層と透明樹脂フィルムを含む積層体、前記積層体を備えた画像表示装置、および前記積層体の製造方法を得ることができるので有用である。 According to the present invention, it is possible to obtain a laminate including a hard coat layer and a transparent resin film which are very thin and have excellent impact resistance, an image display device including the laminate, and a method for producing the laminate. It is useful because it can.
　１　　　透明樹脂フィルム
　２　　　支持体（第１の支持体）
　３　　　支持体（第２の支持体）
　４　　　包埋樹脂層
　５　　　ハードコート層
　１０　　積層体
　１１　　積層体
　１２　　積層体 1 transparent resin film 2 support (first support)
3 Supports (second support)
4 Embedded resin layer 5 Hard coat layer 10 Laminated body 11 Laminated body 12 Laminated body

Claims (10)

  1. 透明樹脂フィルムと当該透明樹脂フィルムの少なくとも一方の面に形成された支持体と当該支持体上に形成されたハードコート層とを備え、前記支持体がパターン構造を有する積層体。 A laminate comprising a transparent resin film, a support formed on at least one surface of the transparent resin film, and a hard coat layer formed on the support, wherein the support has a patterned structure.
  2. 前記支持体が、ハニカム構造、トラス構造、ラーメン構造、ストライプ構造、および円構造からなる群より選択される少なくとも一つの構造を有する、請求項１に記載の積層体。 The laminate according to claim 1, wherein the support has at least one structure selected from the group consisting of a honeycomb structure, a truss structure, a rigid frame structure, a stripe structure, and a circular structure.
  3. 前記支持体の厚みが１μｍ～１５μｍである、請求項１または２に記載の積層体。 The laminate according to claim 1, wherein the support has a thickness of 1 μm to 15 μm.
  4. 平面視における前記支持体の幅が５００μｍ～３０００μｍである、請求項１～３のいずれかに記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the width of the support in a plan view is 500 µm to 3000 µm.
  5. 前記支持体が光学的に等方性を有する、請求項１～４のいずれかに記載の積層体。 The laminate according to any one of claims 1 to 4, wherein the support has optical isotropy.
  6. 前記透明樹脂フィルムの前記一方の面に、前記支持体を包埋する包埋樹脂層を備える、請求項１～５のいずれかに記載の積層体。 The laminate according to any one of claims 1 to 5, wherein an embedded resin layer that embeds the support is provided on the one surface of the transparent resin film.
  7. 前記支持体の２３℃における圧縮弾性率が０．０１ＧＰａ～８．０ＧＰａである、請求項１～６のいずれかに記載の積層体。 7. The laminate according to claim 1, wherein the support has a compressive elastic modulus at 23° C. of 0.01 GPa to 8.0 GPa.
  8. 請求項１～７のいずれかに記載の積層体と円偏光板とを有する積層体。 A laminate comprising the laminate according to any one of claims 1 to 7 and a circularly polarizing plate.
  9. 請求項１～８のいずれか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 8.
  10. 透明樹脂フィルムの少なくとも一方の面に樹脂材料のパターンを形成する工程と、
    前記樹脂材料を硬化させることによりパターン構造を有する支持体とする工程と、
    前記支持体上にハードコート層を形成する工程を含む、積層体の製造方法。     A step of forming a pattern of a resin material on at least one surface of the transparent resin film,
    A step of forming a support having a pattern structure by curing the resin material,
    A method for producing a laminate, which comprises the step of forming a hard coat layer on the support.
PCT/JP2019/047800 2018-12-10 2019-12-06 Laminate and image display device using same WO2020121965A1 (en)

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