WO2021200733A1 - Produit optique multicouche - Google Patents

Produit optique multicouche Download PDF

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Publication number
WO2021200733A1
WO2021200733A1 PCT/JP2021/013066 JP2021013066W WO2021200733A1 WO 2021200733 A1 WO2021200733 A1 WO 2021200733A1 JP 2021013066 W JP2021013066 W JP 2021013066W WO 2021200733 A1 WO2021200733 A1 WO 2021200733A1
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Prior art keywords
sensitive adhesive
pressure
weight
optical laminate
meth
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PCT/JP2021/013066
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English (en)
Japanese (ja)
Inventor
かさね 眞田
恵太 家原
量子 浅井
武史 仲野
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202180025907.1A priority Critical patent/CN115362234A/zh
Priority to KR1020227037330A priority patent/KR20220160631A/ko
Publication of WO2021200733A1 publication Critical patent/WO2021200733A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/04—Thixotropic paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to an optical laminate suitable for sealing a light emitting element of a self-luminous display device such as a mini / micro LED.
  • a self-luminous display device represented by a mini / micro LED display device (Mini / Micro Light Emitting Diode Display) has been devised.
  • a substrate in which a large number of minute LED light emitting elements (LED chips) are arranged at high density is used as a display panel, and the LED chips are sealed with a sealing material.
  • a cover member such as a resin film or a glass plate is laminated on the outermost layer.
  • mini / micro LED display devices such as a white backlight system, a white emission color filter system, and an RGB system.
  • the display panel is used.
  • a black encapsulant may be used to prevent reflection of metal wiring or metal oxides such as ITO arranged on the substrate (see, for example, Patent Documents 1 to 3).
  • the black encapsulant can contribute to the prevention of RGB color mixing and the improvement of contrast.
  • a liquid curable resin or an adhesive containing a black colorant is used as the black encapsulant.
  • a liquid curable resin containing a black colorant is used, there is a problem that the blackness becomes uneven due to the uneven thickness.
  • pigments are often selected because they are superior in heat resistance and weather resistance to dyes.
  • liquid curability Problems such as uneven filling during resin filling and uneven dispersion of pigments during flow occur.
  • the surface of the liquid curable resin cured after sealing has no adhesive force, it is necessary to laminate the cover members using an adhesive or the like, which also causes a problem that additional man-hours and members are required. there were.
  • the present invention has been conceived under the above circumstances, and an object of the present invention is to provide an antireflection function and / or an antiglare function, a mini / micro LED display device having improved contrast, and the like. This is to reduce the number of processes and necessary members in the manufacturing process of the light emitting display device.
  • the present inventors self-luminous an optical laminate in which a base material having an antireflection treatment and / or an antiglare treatment on one side and an adhesive layer containing a colorant is laminated.
  • a base material having an antireflection treatment and / or an antiglare treatment on one side and an adhesive layer containing a colorant is laminated.
  • the first aspect of the present invention is an optical laminate containing a base material and an adhesive layer containing a colorant, and one side of the base material is antireflection-treated and / or antiglare-treated.
  • an optical laminate in which the pressure-sensitive adhesive layer is laminated on a surface of the base material that has not been subjected to the antireflection treatment and / or the antiglare treatment.
  • the pressure-sensitive adhesive layer serves as a sealing material for sealing the light-emitting elements arranged on the display panel, and the base material becomes a base material. Since it is the cover member of the outermost layer, it is not necessary to separately stack the cover member after sealing, the number of steps and the required member can be reduced, and the manufacturing efficiency is improved.
  • the pressure-sensitive adhesive layer is formed of a photocurable pressure-sensitive adhesive composition containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant. It is preferably a pressure-sensitive adhesive layer. It is preferable that the maximum value of the transmittance at a wavelength of 330 to 400 nm is larger than the maximum value of the transmittance at a wavelength of 400 to 700 nm.
  • the photopolymerization initiator preferably has at least one absorption maximum in the wavelength range of 330 to 400 nm.
  • the optical laminate preferably has a maximum transmittance at 350 nm to 450 nm.
  • the total light transmittance of the pressure-sensitive adhesive layer is preferably 80% or less.
  • the thickness of the pressure-sensitive adhesive layer is preferably 10 to 500 ⁇ m. These configurations are preferable in that the pressure-sensitive adhesive layer can impart photocurability by ultraviolet irradiation while having sufficient light-shielding property in the visible light region.
  • the polymer is preferably an acrylic polymer.
  • the glass transition temperature of the polymer is preferably 0 ° C. or lower.
  • the shear storage elastic modulus of the pressure-sensitive adhesive layer at a temperature of 85 ° C. is preferably 3 to 300 kPa.
  • the photocurable pressure-sensitive adhesive composition preferably further contains a cross-linking agent capable of cross-linking with the polymer.
  • the shear storage elastic modulus of the pressure-sensitive adhesive layer at a temperature of 25 ° C. is preferably 10 to 1000 kPa.
  • the antireflection treatment and / or the antiglare treatment is preferably an antiglare layer provided on one side of the base material.
  • the anti-glare layer is formed by using an anti-glare layer forming material containing a resin, particles and a thixotropy-imparting agent, and the anti-glare layer is formed on the surface of the anti-glare layer by aggregating the particles and the thixotropy-imparting agent. It is preferable to have an agglomerated portion that forms a convex portion.
  • the average inclination angle ⁇ a (°) is preferably in the range of 0.1 to 5.0.
  • These configurations impart an antireflection function and / or an antiglare treatment to the surface of the optical laminate on the first side surface of the present invention, and prevent deterioration of visibility due to reflection of external light, reflection of an image, or the like.
  • a surface protective film may be further laminated on the antireflection treatment and / or antiglare treatment surface of the base material.
  • Such a configuration is suitable for preventing the adhesion of scratches and stains during the manufacture, transportation, and shipment of the optical laminate and the optical products containing the same.
  • the second side surface of the present invention is a self-luminous display device including a display panel in which a plurality of light emitting elements are arranged on one side of a substrate and an optical laminate of the first side surface of the present invention.
  • a self-luminous display device in which a surface on which light emitting elements of a display panel are arranged and an adhesive layer of the optical laminate are laminated.
  • the display panel may be an LED panel in which a plurality of LED chips are arranged on one side of a substrate.
  • the self-luminous display device on the second side of the present invention is visually recognized by preventing reflection of metal wiring on the substrate, preventing RGB color mixing, improving contrast, reflecting external light, reflecting an image, and the like. It is preferable in that it can prevent deterioration of the property or adjust the appearance such as glossiness.
  • the optical laminate of the present invention in the manufacture of a self-luminous display device, it is possible to reduce the number of steps and necessary members, and the self-luminous type with improved antireflection function and / or antiglare function and contrast.
  • the display device can be manufactured efficiently.
  • FIG. 1 is a schematic view (cross-sectional view) showing an embodiment of the optical laminate of the present invention.
  • FIG. 2 is a schematic view (cross-sectional view) showing another embodiment of the optical laminate of the present invention.
  • FIG. 3 is a schematic view (cross-sectional view) showing an embodiment of the self-luminous display device (mini / micro LED display device) of the present invention.
  • FIG. 4 is a schematic view (cross-sectional view) showing another embodiment of the self-luminous display device (mini / micro LED display device) of the present invention.
  • the optical laminate on the first side surface of the present invention is an optical laminate containing a base material and an adhesive layer containing a colorant, and one side of the base material is subjected to antireflection treatment and / or antiglare treatment.
  • the pressure-sensitive adhesive layer is laminated on the surface of the base material that has not been subjected to the antireflection treatment and / or the antiglare treatment.
  • optical in the optical laminate on the first side surface of the present invention means that it is used for optical purposes, and more specifically, it is used for manufacturing a product (optical product) using an optical member or the like. Means to be.
  • optical products include an image display device, an input device such as a touch panel, and a self-luminous display device such as a mini / micro LED display device and an organic EL (electroluminescence) display device is preferable, and a mini is particularly preferable.
  • FIG. 1 is a schematic view (cross-sectional view) showing an embodiment of an optical laminate on the first side surface of the present invention.
  • the optical laminate 10 includes a base material 1 and a pressure-sensitive adhesive layer 2 containing a colorant.
  • the base material 1 is subjected to antireflection treatment and / or antiglare treatment 3 on one side 1a thereof.
  • the adhesive layer 2 is laminated on the surface 1b on the side of the base material 1 that has not been subjected to the antireflection treatment and / or the antiglare treatment.
  • the base material 1 is not particularly limited, and examples thereof include glass and a transparent plastic film base material.
  • the transparent plastic film base material is not particularly limited, but is preferably one having excellent visible light transmittance (preferably 90% or more) and excellent transparency (preferably one having a haze value of 5% or less).
  • the transparent plastic film base material described in JP-A-2008-90263 can be mentioned.
  • the transparent plastic film base material one having less birefringence optically is preferably used.
  • the base material 1 can be used, for example, as a cover member of a self-luminous display device.
  • the transparent plastic film base material includes triacetyl cellulose (TAC), polycarbonate, or acrylic.
  • the base material 1 may be the cover member itself.
  • the cover member can be made thinner.
  • the antireflection-treated and / or anti-glare-treated surface 1a becomes the outermost surface of the self-luminous display device, and is visually recognized by reflection of external light or reflection of an image. It plays a role of preventing deterioration of the property and adjusting the appearance such as glossiness.
  • the thickness of the base material 1 is not particularly limited, but is preferably in the range of 10 to 500 ⁇ m, more preferably 20 in consideration of workability such as strength and handleability and thin layerability. It is in the range of ⁇ 300 ⁇ m, and optimally in the range of 30 to 200 ⁇ m.
  • the refractive index of the base material 1 is not particularly limited, but is, for example, in the range of 1.30 to 1.80, preferably in the range of 1.40 to 1.70.
  • the visible light transmittance of the base material 1 is not particularly limited, but may be, for example, 85 to 100%, 88% or more, 90% or more, or 92% or more.
  • a known antireflection treatment can be used without particular limitation, and examples thereof include an antireflection (AR) treatment.
  • AR antireflection
  • the AR layer exhibits an antireflection function by canceling each other's reversed phases of incident light and reflected light by utilizing the interference effect of light.
  • the wavelength region of visible light that exhibits the antireflection function is, for example, 380 to 780 nm, and the wavelength region having particularly high luminosity factor is in the range of 450 to 650 nm, which minimizes the reflectance of 550 nm, which is the central wavelength thereof. It is preferable to design the AR layer as described above.
  • the AR layer examples include a multi-layer antireflection layer having a structure in which two or five optical thin layers (thin films whose thickness and refractive index are strictly controlled) are laminated, and components having different refractive indexes are specified.
  • a multi-layer antireflection layer having a structure in which two or five optical thin layers (thin films whose thickness and refractive index are strictly controlled) are laminated, and components having different refractive indexes are specified.
  • the degree of freedom in the optical design of the AR layer is increased, the antireflection effect can be further improved, and the spectral reflection characteristics can be made uniform (flat) in the visible light region. become. Since high thickness accuracy is required for the optical thin film, the formation of each layer is generally carried out by a dry method such as vacuum vapor deposition, sputtering, or CVD.
  • FIG. 2 is a schematic view (cross-sectional view) showing another embodiment of the optical laminate of the first side surface of the present invention.
  • the anti-glare layer 3a is formed on one side 1a of the base material 1.
  • known ones can be adopted without limitation, and generally, it is formed as a layer in which inorganic or organic particles are dispersed as an anti-glare agent in a resin.
  • the anti-glare layer 3a is formed by using an anti-glare layer forming material containing a resin, particles and a thixotropy-imparting agent, and the surface of the anti-glare layer 3a is formed by agglomeration of the particles and the thixotropy-imparting agent. A convex portion is formed on the surface. Due to this configuration, the anti-glare layer 3a has excellent display characteristics that achieve both anti-glare properties and prevention of white blur, and despite the fact that the anti-glare layer is formed by utilizing the aggregation of particles, the appearance is defective. It is possible to prevent the generation of protrusions on the surface of the anti-glare layer and improve the yield of the product.
  • the resin examples include thermosetting resins and ionizing radiation curable resins that are cured by ultraviolet rays or light.
  • thermosetting resins examples include thermosetting resins and ionizing radiation curable resins that are cured by ultraviolet rays or light.
  • a commercially available thermosetting resin, an ultraviolet curable resin, or the like can also be used.
  • the heat-curable resin or the ultraviolet-curable resin for example, a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (ultraviolet rays, etc.), an electron beam, or the like can be used.
  • Silicone resin, polyester resin, polyether resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin, oligomers such as methacrylate and prepolymers of polyfunctional compounds such as polyhydric alcohol can give.
  • One of these may be used alone, or two or more thereof may be used in combination.
  • a reactive diluent having at least one group of an acrylate group and a methacrylate group can be used.
  • the reactive diluent for example, the reactive diluent described in JP-A-2008-88309 can be used, and includes, for example, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, polyfunctional methacrylate and the like.
  • the reactive diluent trifunctional or higher functional acrylates and trifunctional or higher functional methacrylates are preferable. This is because the hardness of the anti-glare layer 3a can be made excellent.
  • Examples of the reactive diluent include butanediol glycerin ether diacrylate, isocyanuric acid acrylate, and isocyanuric acid methacrylate. One of these may be used alone, or two or more thereof may be used in combination.
  • the main function of the particles for forming the anti-glare layer 3a is to shape the surface of the formed anti-glare layer 3a into an uneven shape to impart anti-glare properties, and to control the haze value of the anti-glare layer 3a.
  • the haze value of the anti-glare layer 3a can be designed by controlling the difference in refractive index between the particles and the resin.
  • the particles include inorganic particles and organic particles.
  • the inorganic particles are not particularly limited, and for example, silicon oxide particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc particles, kaolin particles, calcium sulfate particles and the like. Can be given.
  • the organic particles are not particularly limited, and for example, polymethylmethacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, and polyolefin.
  • PMMA fine particles polymethylmethacrylate resin powder
  • silicone resin powder silicone resin powder
  • polystyrene resin powder polycarbonate resin powder
  • acrylic styrene resin powder acrylic styrene resin powder
  • benzoguanamine resin powder benzoguanamine resin powder
  • melamine resin powder melamine resin powder
  • polyolefin examples thereof include resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluorinated ethylene resin powder.
  • One type of these inorganic particles and organic particles may be used alone, or two or more types may be used in combination.
  • the weight average particle size (D) of the particles is preferably in the range of 2.5 to 10 ⁇ m. By setting the weight average particle size of the particles in the above range, for example, more excellent anti-glare properties and white blurring can be prevented.
  • the weight average particle size of the particles is more preferably in the range of 3 to 7 ⁇ m.
  • the weight average particle size of the particles can be measured by, for example, the Coulter counting method. For example, using a particle size distribution measuring device (trade name: Coulter Multisizer, manufactured by Beckman Coulter) using the pore electric resistance method, an electrolytic solution corresponding to the volume of the particles when the particles pass through the pores. By measuring the electric resistance, the number and volume of the particles are measured, and the weight average particle size is calculated.
  • the shape of the particles is not particularly limited, and may be, for example, a bead-shaped substantially spherical shape or an irregular shape such as powder, but a substantially spherical shape is preferable, and an aspect ratio is more preferable. It is a substantially spherical particle having a ratio of 1.5 or less, and most preferably a spherical particle.
  • the proportion of the particles in the anti-glare layer 3a is preferably in the range of 0.2 to 12 parts by weight, more preferably in the range of 0.5 to 12 parts by weight, still more preferably 1 with respect to 100 parts by weight of the resin. It is in the range of ⁇ 7 parts by weight. Within the above range, for example, more excellent anti-glare property and white blurring can be prevented.
  • thixotropy-imparting agent for forming the anti-glare layer 3a examples include organic clay, polyolefin oxide, modified urea and the like.
  • the organic clay is preferably an organically treated clay in order to improve the affinity with the resin.
  • the organic clay include layered organic clay.
  • the organic clay may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN, Somasif ME-100, Somasif MAE, Somasif MTE, Somasif MEE, and Somasif MPE (trade names, all of which are CO-OP CHEMICAL CO., LTD.
  • the above-mentioned polyolefin oxide may be prepared in-house or a commercially available product may be used.
  • the commercially available product include Disparon 4200-20 (trade name, manufactured by Kusumoto Kasei Co., Ltd.), Fronon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
  • the modified urea is a reaction product of an isocyanate monomer or an adduct thereof and an organic amine.
  • the modified urea may be prepared in-house or a commercially available product may be used. Examples of the commercially available product include BYK410 (manufactured by Big Chemie).
  • the thixotropy-imparting agent may be used alone or in combination of two or more.
  • the height of the convex portion from the roughness average line of the anti-glare layer 3a is preferably less than 0.4 times the thickness of the anti-glare layer 3a. More preferably, it is in the range of 0.01 times or more and less than 0.4 times, and further preferably, it is in the range of 0.01 times or more and less than 0.3 times. Within this range, it is possible to suitably prevent the formation of protrusions, which are defects in appearance, on the convex portion.
  • the anti-glare layer 3a of the present embodiment has a convex portion having such a height, so that appearance defects can be less likely to occur.
  • the height from the average line can be measured by, for example, the method described in JP-A-2017-138620.
  • the ratio of the thixotropy-imparting agent in the anti-glare layer 3a is preferably in the range of 0.1 to 5 parts by weight, more preferably in the range of 0.2 to 4 parts by weight, based on 100 parts by weight of the resin.
  • the thickness (d) of the anti-glare layer 3a is not particularly limited, but is preferably in the range of 3 to 12 ⁇ m. By setting the thickness (d) of the anti-glare layer 3a within the above range, for example, the occurrence of curl of the optical laminate 11 can be prevented, and the problem of reduced productivity such as poor transportability can be avoided.
  • the weight average particle size (D) of the particles is preferably in the range of 2.5 to 10 ⁇ m as described above.
  • the thickness (d) of the anti-glare layer 3a is more preferably in the range of 3 to 8 ⁇ m.
  • the relationship between the thickness (d) of the anti-glare layer 3a and the weight average particle size (D) of the particles is preferably in the range of 0.3 ⁇ D / d ⁇ 0.9.
  • the anti-glare layer 3a forms a convex portion on the surface of the anti-glare layer 3a due to the aggregation of the particles and the thixotropy-imparting agent.
  • the agglomerated portion forming the convex portion a plurality of the particles are present in a state of being gathered in the plane direction of the anti-glare layer 3a.
  • the convex portion has a gentle shape.
  • the surface shape of the anti-glare layer 3a can be arbitrarily designed by controlling the aggregated state of the particles contained in the anti-glare layer forming material.
  • the agglomerated state of the particles can be controlled by, for example, the material of the particles (for example, the chemically modified state of the particle surface, the affinity for a solvent or a resin, etc.), the type of the resin (binder) or the solvent, the combination, and the like.
  • the aggregated state of the particles can be controlled by the thixotropy-imparting agent contained in the antiglare layer forming material.
  • the agglomerated state of the particles can be made as described above, and the convex portion can be made into a gentle shape.
  • the base material 1 when the base material 1 is formed of a resin or the like, it is preferable to have a permeation layer at the interface between the base material 1 and the anti-glare layer 3a.
  • the permeation layer is formed by permeating the resin component contained in the material for forming the anti-glare layer 3a into the base material 1.
  • the permeation layer preferably has a thickness in the range of 0.2 to 3 ⁇ m, more preferably in the range of 0.5 to 2 ⁇ m.
  • the permeation layer can be formed.
  • the permeation layer can be confirmed, for example, by observing the cross section of the optical laminate 11 with a transmission electron microscope (TEM), and the thickness can be measured.
  • TEM transmission electron microscope
  • the permeation layer is formed thicker as the base material 1 has poor adhesion to the anti-glare layer 3a in order to improve the adhesion.
  • the maximum diameter is 200 ⁇ m or more and the number of appearance defects is one or less per 1 m 2 of the anti-glare layer 3a. More preferably, there is no such appearance defect.
  • the base material 1 on which the anti-glare layer 3a is formed preferably has a haze value in the range of 0 to 10%.
  • the haze value is a haze value (cloudiness) according to JIS K 7136 (2000 version).
  • the haze value is more preferably in the range of 0 to 5%, and even more preferably in the range of 0 to 3%.
  • the haze value is in the above range, a clear image can be obtained and the contrast in a dark place can be improved.
  • the average inclination angle ⁇ a (°) is preferably in the range of 0.1 to 5.0, and preferably in the range of 0.3 to 4.5 in the uneven shape of the surface of the anti-glare layer 3a. It is more preferably in the range of 1.0 to 4.0, particularly preferably 1.6 to 4.0.
  • the average inclination angle ⁇ a is a value defined by the following mathematical formula (1).
  • the average inclination angle ⁇ a is, for example, a value measured by the method described in JP-A-2017-138620.
  • Average inclination angle ⁇ a tan-1 ⁇ a (1)
  • ⁇ a is the peak and valley of the adjacent peaks in the reference length L of the roughness curve defined in JIS B 0601 (1994 version), as shown in the following formula (2). It is a value obtained by dividing the total (h1 + h2 + h3 ... + Hn) of the difference (height h) from the lowest point by the reference length L.
  • ⁇ a is within the above range, it is more excellent in anti-glare property and white blur can be prevented.
  • the prepared anti-glare layer forming material exhibits thixotropic properties, and the Ti value defined below is in the range of 1.3 to 3.5. It is preferably in the range of 1.3 to 2.8.
  • Ti value ⁇ 1 / ⁇ 2
  • ⁇ 1 is a viscosity measured under the condition of a shear rate of 20 (1 / s) using a HAAKE Leostress 6000
  • ⁇ 2 is a viscosity of 200 (1 / s) using a HAAKE Leostress 6000. Viscosity measured under conditions.
  • the Ti value is less than 1.3, appearance defects are likely to occur, and the characteristics regarding anti-glare property and white blur are deteriorated. Further, when the Ti value exceeds 3.5, the particles are less likely to aggregate and are likely to be in a dispersed state.
  • the method for producing the anti-glare layer 3a of the present embodiment is not particularly limited and may be produced by any method.
  • the anti-glare layer forming material (coating) containing the resin, the particles, the thixotropy-imparting agent and the solvent. Liquid) is prepared, the anti-glare layer forming material (coating liquid) is applied to one side 1a of the base material 1 to form a coating film, and the coating film is cured to form an anti-glare layer 3a.
  • a transfer method using a mold, a method of imparting an uneven shape by an appropriate method such as sandblasting or embossing roll, or the like can also be used.
  • the solvent is not particularly limited, and various solvents can be used, and one type may be used alone or two or more types may be used in combination. There are optimum solvent types and solvent ratios depending on the composition of the resin, the types of the particles and the thixotropy-imparting agent, the content, and the like.
  • the solvent is not particularly limited, but for example, alcohols such as methanol, ethanol, isopropyl alcohol, butanol and 2-methoxyethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; methyl acetate and ethyl acetate.
  • Esters such as butyl acetate; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane and octane.
  • Kind Aromatic hydrocarbons such as benzene, toluene, xylene and the like.
  • TAC triacetyl cellulose
  • a good solvent for TAC can be preferably used.
  • the solvent include ethyl acetate, methyl ethyl ketone, cyclopentanone and the like.
  • the thixotropic property of the thixotropy-imparting agent on the antiglare layer forming material (coating liquid) can be satisfactorily exhibited.
  • organic clay toluene and xylene can be preferably used alone or in combination.
  • polyolefin oxide when polyolefin oxide is used, methyl ethyl ketone, ethyl acetate, and propylene glycol monomethyl ether are preferably used alone. It can be used or used in combination.
  • modified urea is used, butyl acetate and methyl isobutyl ketone can be preferably used alone or in combination.
  • leveling agents can be added to the anti-glare layer forming material.
  • a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing uneven coating (uniformizing the coated surface).
  • the leveling agent can be appropriately selected depending on the case where the surface of the anti-glare layer 3a is required to have antifouling property, or the case where an antireflection layer (low refractive index layer) or a layer containing an interlayer filler is formed on the anti-glare layer 3a. Therefore, the leveling agent can be appropriately selected.
  • the present embodiment for example, by incorporating the thixotropy-imparting agent, the thixotropy can be exhibited in the coating liquid, so that uneven coating is less likely to occur. Therefore, the present embodiment has an advantage that, for example, the options of the leveling agent can be expanded.
  • the blending amount of the leveling agent is, for example, 5 parts by weight or less, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin.
  • Pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, antioxidants and the like are added to the anti-glare layer forming material, if necessary, as long as the performance is not impaired. You may.
  • One type of these additives may be used alone, or two or more types may be used in combination.
  • anti-glare layer forming material for example, a conventionally known photopolymerization initiator as described in JP-A-2008-88309 can be used.
  • Examples of the method of applying the anti-glare layer forming material on one side 1a of the base material 1 include a fanten coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, a roll coating method, and a bar coating method. Etc. can be used.
  • the anti-glare layer forming material is applied to form a coating film on the base material 1, and the coating film is cured. It is preferable to dry the coating film prior to the curing.
  • the drying may be, for example, natural drying, air drying by blowing wind, heat drying, or a method in which these are combined.
  • the means for curing the coating film of the anti-glare layer forming material is not particularly limited, but ultraviolet curing is preferable.
  • the irradiation amount of the energy radiation source is preferably 50 to 500 mJ / cm 2 as the integrated exposure amount at the ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ / cm 2 or more, the curing becomes more sufficient, and the hardness of the formed anti-glare layer becomes more sufficient. Further, if it is 500 mJ / cm 2 or less, coloring of the formed anti-glare layer can be prevented.
  • the anti-glare layer 3a can be formed on one side 1a of the base material 1.
  • the anti-glare layer 3a may be formed by a manufacturing method other than the above-mentioned method.
  • the hardness of the anti-glare layer 3a of the present embodiment is affected by the thickness of the layer in terms of pencil hardness, but it is preferably 2H or more.
  • the anti-glare layer 3a may have a multi-layer structure in which two or more layers are laminated.
  • the above-mentioned AR layer (low refractive index layer) may be arranged on the anti-glare layer 3a.
  • the optical laminate 11 according to the present embodiment is attached to the self-luminous display device, one of the factors that reduce the visibility of the image is the reflection of light at the interface between the air and the anti-glare layer.
  • the AR layer reduces its surface reflection.
  • the anti-glare layer 3a and the AR layer may each have a multi-layer structure in which two or more layers are laminated.
  • a contamination prevention layer formed of a fluorine group-containing silane compound, a fluorine group-containing organic compound, or the like is provided on the antiglare layer 3a. It is preferable to stack them.
  • the adhesion to the anti-glare layer 3a is further improved. Further, if the surface of the anti-glare layer 3a is surface-treated, the adhesion to the AR layer is further improved.
  • the other surface of the anti-glare layer 3a may be treated with a solvent. Further, in order to prevent the occurrence of curl, a transparent resin layer may be formed on the other surface of the anti-glare layer 3a.
  • the pressure-sensitive adhesive layer 2 is preferably a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition selected from a photocurable pressure-sensitive adhesive composition containing a colorant and a solvent-type pressure-sensitive adhesive composition.
  • the photocurable pressure-sensitive adhesive composition contains a polymer, a photopolymerizable compound, and a photopolymerization initiator in addition to a colorant. That is, the photocurable pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer 2 of the present embodiment contains a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant.
  • the pressure-sensitive adhesive layer 2 of the present embodiment is a pressure-sensitive adhesive layer having light absorption in visible light.
  • the pressure-sensitive adhesive layer formed by using the photocurable pressure-sensitive adhesive composition is a type that performs photo-curing (first form) and a type that does not perform photo-curing and is photo-cured after being bonded to a display panel described later. It is roughly divided into types (second form).
  • a photocurable pressure-sensitive adhesive composition containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant is applied onto a release film and photocured. Thereby, it can be formed.
  • Photocurable adhesive composition (polymer)
  • the polymer contained in the photocurable pressure-sensitive adhesive composition include acrylic polymers, silicone-based polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy-based polymers, fluorine-based polymers, and natural rubbers. , Rubber-based polymers such as synthetic rubber, and the like.
  • an acrylic polymer is preferably used because it exhibits adhesive properties such as appropriate wettability, cohesiveness and adhesiveness, and is also excellent in weather resistance and heat resistance.
  • the acrylic polymer contains (meth) acrylic acid alkyl ester as a main constituent monomer component.
  • (meth) acrylic means acrylic and / or methacryl.
  • the amount of the (meth) acrylic acid alkyl ester with respect to the total amount of the monomer components constituting the acrylic polymer is preferably 50% by weight or more, more preferably 55% by weight or more, still more preferably 60% by weight or more.
  • the (meth) acrylic acid alkyl ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is preferably used.
  • the (meth) acrylic acid alkyl ester may have a branched alkyl group or a cyclic alkyl group.
  • (meth) acrylic acid alkyl ester having a chain alkyl group examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth).
  • Examples of the (meth) acrylic acid alkyl ester having a preferable chain alkyl group used in the first form include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octadecyl (meth) acrylate, and (meth) acrylic. Dodecyl acid.
  • the amount of the (meth) acrylic acid alkyl ester having a chain alkyl group with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 40 to 90% by weight, and 45 to 80% by weight or 50 to 70% by weight. There may be.
  • (meth) acrylate alkyl ester having an alicyclic alkyl group examples include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate and the like.
  • Examples of the (meth) acrylic acid alkyl ester having a preferable alicyclic alkyl group used in the first form are cyclohexyl (meth) acrylic acid and isobornyl (meth) acrylic acid.
  • the amount of the (meth) acrylic acid alkyl ester having an alicyclic alkyl group with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, and 5 to 40% by weight or 10 to 30% by weight. It may be.
  • the acrylic polymer may contain a polar group-containing monomer such as a hydroxyl group-containing monomer, a carboxy group-containing monomer, and a nitrogen-containing monomer as a constituent monomer component.
  • a polar group-containing monomer such as a hydroxyl group-containing monomer, a carboxy group-containing monomer, and a nitrogen-containing monomer as a constituent monomer component.
  • Preferred polar group-containing monomers used in the first form are hydroxyl group-containing monomers and nitrogen-containing monomers.
  • the amount of the polar group-containing monomer (total of the hydroxy group-containing monomer, the carboxy group-containing monomer, and the nitrogen-containing monomer) with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, and 5 to 40%. It may be% by weight or 10 to 30% by weight.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and (meth) acrylic.
  • acrylic acid esters such as 8-hydroxyoctyl acid, 10-hydroxydecyl (meth) acrylic acid, 12-hydroxylauryl (meth) acrylic acid and (4-hydroxymethylcyclohexyl) -methyl (meth) acrylate. ..
  • the hydroxyl group can be a reaction point (cross-linking point) with the isocyanate group.
  • Preferred hydroxyl group-containing monomers used in the first form are 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the amount of the hydroxyl group-containing monomer with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, and may be 5 to 40% by weight or 10 to 30% by weight.
  • carboxy group-containing monomer examples include acrylic monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate, and itaconic acid, maleic acid, fumaric acid, and crotonic acid. ..
  • acrylic monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate
  • itaconic acid maleic acid, fumaric acid, and crotonic acid. ..
  • a preferred carboxy group-containing monomer used in the first form is (meth) acrylic acid.
  • the amount of the carboxy group-containing monomer with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, and may be 5 to 40% by weight or 10 to 30% by weight.
  • nitrogen-containing monomers examples include N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholin, (meth) acryloylmorpholin, and N-vinyl.
  • vinyl-based monomers such as carboxylic acid amides, N-vinylcaprolactam and acrylamide, and cyano group-containing monomers such as acrylonitrile and methacrylonitrile.
  • the preferred nitrogen-containing monomer used in the first form is N-vinylpyrrolidone.
  • the amount of the nitrogen-containing monomer with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, and may be 5 to 40% by weight or 10 to 30% by weight.
  • Acrylic polymers contain acid anhydride group-containing monomers, (meth) acrylic acid caprolactone adducts, sulfonic acid group-containing monomers, and phosphoric acid groups as monomer components other than the above (sometimes referred to as "other monomers").
  • Vinyl-based monomers such as monomers, vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, etc .; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Polyethylene glycol (meth) acrylate, Polypropylene glycol (meth) acrylate Glycol-based acrylic ester monomers such as methoxyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and (meth) It may contain an acrylic acid ester-based monomer such as 2-methoxyethyl acrylate.
  • the glass transition temperature (Tg) of the polymer contained in the photocurable pressure-sensitive adhesive composition is preferably 0 ° C. or lower.
  • the glass transition temperature of the polymer may be ⁇ 5 ° C. or lower, ⁇ 10 ° C. or lower, or ⁇ 15 ° C. or lower.
  • the glass transition temperature of the polymer is the peak top temperature of loss tangent (tan ⁇ ) by dynamic viscoelasticity measurement.
  • the glass transition temperature may be calculated from the composition of the polymer based on the theoretical Tg.
  • the theoretical Tg is calculated by the Fox formula described later.
  • a polymer can be obtained by polymerizing the above-mentioned monomer components by various known methods.
  • the polymerization method is not particularly limited, but it is preferable to prepare the polymer by photopolymerization. Since the polymer can be prepared without using a solvent in photopolymerization, it is not necessary to dry and remove the solvent when forming the pressure-sensitive adhesive layer, and a thick pressure-sensitive adhesive layer can be uniformly formed.
  • the composition used for preparing the prepolymer preferably contains a photopolymerization initiator in addition to the monomer.
  • the photopolymerization initiator may be appropriately selected depending on the type of monomer. For example, a photoradical polymerization initiator is used for the polymerization of an acrylic polymer.
  • the photopolymerization initiator examples include a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an ⁇ -ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, and a photoactive oxime-based photopolymerization initiator.
  • Examples thereof include benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.
  • a chain transfer agent such as ⁇ -thioglycerol, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
  • thiols such as ⁇ -thioglycerol, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
  • thiols such as ⁇ -thioglycerol, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-
  • the polymerization rate of the prepolymer is not particularly limited, but is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, from the viewpoint of obtaining a viscosity suitable for coating on a substrate.
  • the polymerization rate of the prepolymer can be adjusted to a desired range by adjusting the type and amount of the photopolymerization initiator, the irradiation intensity and irradiation time of active light such as UV light, and the like.
  • the polymerization rate of the prepolymer is a non-volatile component when heated at 130 ° C. for 3 hours, and is calculated by the following formula.
  • the photocurable pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer contains a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant.
  • a photocurable pressure-sensitive adhesive composition can be obtained by adding a photopolymerizable compound, a photopolymerization initiator and a colorant to the prepolymer.
  • a prepolymer a low molecular weight polymer (oligomer) is used, and the low molecular weight polymer is mixed with a photopolymerizable compound, a photopolymerization initiator and a colorant to prepare a photocurable pressure-sensitive adhesive composition. You may.
  • the photopolymerizable compound contained in the photocurable pressure-sensitive adhesive composition has one or more photopolymerizable functional groups in one molecule.
  • the photopolymerizable functional group may be radically polymerizable, cationically polymerizable or anionically polymerizable, but since it is excellent in reactivity, it is a radically polymerizable functional group having an unsaturated double bond (ethylenically unsaturated group). Is preferable.
  • the prepolymer contains a monomer that has not reacted with the polymer, and the unreacted monomer retains photopolymerizability. Therefore, it is not always necessary to add a photopolymerizable compound in the preparation of the photocurable pressure-sensitive adhesive composition.
  • the photopolymerizable compound to be added may be the same as or different from the monomer used for preparing the prepolymer.
  • the compound added as the photopolymerizable compound is preferably a monomer or oligomer having a (meth) acryloyl group as the photopolymerizable functional group because it has high compatibility with the polymer.
  • the photopolymerizable compound may be a polyfunctional compound having two or more photopolymerizable functional groups in one molecule. Examples of the photopolymerizable polyfunctional compound include polyfunctional (meth) acrylate.
  • polyfunctional (meth) acrylate examples include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, and bisphenol A propylene oxide.
  • tetrafunctional (meth) acrylic acid ester such as ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaeristol tetra (meth) acrylate, pentaeristol tetra (meth) acrylate; dipentaeryristol penta Examples thereof include (meth) acrylates and the like, and pentafunctional or higher functional (meth) acrylic acid esters such as dipentaeryristolhexa (meth) acrylate.
  • the amount of the polyfunctional compound used is preferably 10 parts by weight or less, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the polymer (including the prepolymer). Parts, more preferably 0.005 to 0.5 parts by weight.
  • the amount of the polyfunctional compound used may be 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.
  • the amount of the polyfunctional monomer used may be 0, and may be 0.001 part by weight or more, 0.01 part by weight or more, or 0.1 part by weight or more.
  • a hydroxyl group-containing monomer is preferable, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are more preferable.
  • the amount of the hydroxyl group-containing monomer used is preferably 40 parts by weight or less, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polymer (including the prepolymer). Yes, more preferably 5 to 20 parts by weight.
  • the amount of the hydroxyl group-containing monomer used may be 40 parts by weight or less, 30 parts by weight or less, and 20 parts by weight or less.
  • the amount of the hydroxyl group-containing monomer used may be 0, or may be 1 part by weight or more, 5 parts by weight or more, or 10 parts by weight or more.
  • the photocurable pressure-sensitive adhesive composition contains a photopolymerization initiator.
  • the photopolymerization initiator generates radicals, acids, bases and the like by irradiation with active light such as ultraviolet rays, and can be appropriately selected depending on the type of the photopolymerizable compound and the like.
  • the photopolymerizable compound is a compound having a (meth) acryloyl group (for example, a monofunctional or polyfunctional (meth) acrylate)
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • the addition of the photopolymerization initiator may be omitted.
  • the photopolymerization initiator added may be the same as or different from the photopolymerization initiator used in the preparation of the polymer.
  • the photopolymerization initiator contained in the photocurable pressure-sensitive adhesive composition preferably has an absorption maximum in a wavelength region where light absorption by a colorant described later is small. Specifically, the photopolymerization initiator preferably has an absorption maximum in the wavelength region of 330 to 400 nm. Since the photopolymerization initiator has an absorption maximum in a region where the light absorption by the colorant is small, the curing inhibition by the colorant is suppressed, so that the polymerization rate can be sufficiently increased by the photocuring.
  • Examples of the photoradical polymerization initiator having an absorption maximum in the region of a wavelength of 330 to 400 nm include hydroxyketones, benzyldimethylketals, aminoketones, acylphosphine oxides, benzophenones, trichloromethyl group-containing triazine derivatives and the like. ..
  • the content of the photopolymerization initiator in the photocurable pressure-sensitive adhesive composition is 0.01 to 10% by weight with respect to 100 parts by weight of the total amount of the monomers (monomer used for polymer preparation and photopolymerizable compound added to the polymer).
  • the amount is about 0.05 to 5 parts by weight, preferably about 0.05 to 5 parts by weight.
  • the photocurable pressure-sensitive adhesive composition used to form the pressure-sensitive adhesive layer contains a colorant.
  • the colorant may be a dye or a pigment as long as it can be dissolved or dispersed in the photocurable pressure-sensitive adhesive composition. Dyes are preferable because low haze can be achieved even with a small amount of addition, and unlike pigments, they do not have sedimentation properties and can be easily distributed uniformly. In addition, pigments are also preferable because they have high color development even when added in a small amount. When a pigment is used as a colorant, it preferably has low or no conductivity. In addition, when a dye is used, it is preferable to use it in combination with an antioxidant described later.
  • the colorant preferably absorbs visible light and has ultraviolet transparency is used.
  • the colorant preferably has a maximum transmittance at a wavelength of 330 to 400 nm larger than a maximum value of a transmittance at a wavelength of 400 to 700 nm. Further, the colorant preferably has an average transmittance at a wavelength of 330 to 400 nm higher than the average transmittance at a wavelength of 400 to 700 nm.
  • the transmittance of the colorant is adjusted by using an appropriate solvent such as tetrahydrofuran (THF) or a dispersion medium (an organic solvent having a small absorption in the wavelength range of 330 to 700 nm) so that the transmittance at a wavelength of 400 nm is about 50 to 60%. Measure with a diluted solution or dispersion.
  • Examples of the ultraviolet-transparent black pigment that absorbs ultraviolet rays less than the absorption of visible light include “9050BLACK” and “UVBK-0001” manufactured by Tokushiki.
  • Examples of the ultraviolet-transparent black dye include “SOC-L-0123” manufactured by Orient Chemical Industries.
  • Carbon black and titanium black which are generally used as black colorants, absorb ultraviolet rays more than they absorb visible light (ultraviolet transmittance is smaller than visible light transmittance). Therefore, when a colorant such as carbon black is added to the photocurable pressure-sensitive adhesive composition having sensitivity to ultraviolet rays, most of the ultraviolet rays irradiated for photocuring are absorbed by the colorant, and the amount of light absorbed by the photopolymerization initiator. Is small, and it takes time to photo-cure (the amount of integrated irradiation light increases).
  • the thickness of the pressure-sensitive adhesive layer is large, the amount of ultraviolet rays reaching the surface opposite to the light irradiation surface is small, so that the photocuring tends to be insufficient even if the light irradiation is performed for a long time.
  • a colorant having a higher transmittance of ultraviolet rays than visible light it is possible to suppress curing inhibition caused by the colorant.
  • the content of the colorant in the photocurable pressure-sensitive adhesive composition is, for example, about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the monomers, and the type of the colorant, the color tone of the pressure-sensitive adhesive layer, and the light. It may be set appropriately according to the transmittance and the like.
  • the colorant may be added to the composition as a solution or dispersion dissolved or dispersed in an appropriate solvent.
  • the photocurable pressure-sensitive adhesive composition may contain a silane coupling agent as long as the effects of the present invention are not impaired.
  • the photocurable pressure-sensitive adhesive composition contains a silane coupling agent, the adhesion reliability to the glass (particularly, the adhesion reliability to the glass in a high temperature and high humidity environment) is improved, which is preferable.
  • the silane coupling agent is not particularly limited, but is limited to ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and N-phenyl-aminopropyltrimethoxysilane. , 3-Acryloxypropyltrimethoxysilane and the like are preferable. Of these, ⁇ -glycidoxypropyltrimethoxysilane is preferable. Further, as a commercially available product, for example, the product name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.
  • the silane coupling agent may be used alone or in combination of two or more.
  • the content of the silane coupling agent in the photocurable pressure-sensitive adhesive composition is not particularly limited, but is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 parts by weight with respect to 100 parts by weight of the polymer. It is a part by weight.
  • the photocurable pressure-sensitive adhesive composition may contain components other than the polymer, the photopolymerizable compound, the photopolymerization initiator and the colorant.
  • a chain transfer agent may be contained for the purpose of adjusting the photocuring rate or the like.
  • an oligomer or a tackifier may be contained for the purpose of adjusting the viscosity of the photocurable pressure-sensitive adhesive composition, adjusting the adhesive force of the pressure-sensitive adhesive layer, and the like.
  • the oligomer for example, one having a weight average molecular weight of about 1000 to 30,000 is used.
  • an acrylic oligomer is preferable because it has excellent compatibility with an acrylic polymer.
  • the photocurable pressure-sensitive adhesive composition may contain additives such as a plasticizer, a softener, an antioxidant, a filler, an antioxidant, a surfactant, and an antistatic agent.
  • the pressure-sensitive adhesive layer of the second form is a type of pressure-sensitive adhesive layer that is not photo-cured, and the photo-curable pressure-sensitive adhesive composition is formed in the form of a sheet. Since the pressure-sensitive adhesive layer of the second form contains the photopolymerizable compound in an unreacted state, the pressure-sensitive adhesive layer has photocurability.
  • the photocurable pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer of the second form contains a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant.
  • polymer As the polymer contained in the photocurable pressure-sensitive adhesive composition, various polymers can be applied as in the first form, and an acrylic polymer is preferably used.
  • the monomer components constituting the acrylic polymer are the same as those in the first form.
  • the monomer component constituting the polymer contains a hydroxy group-containing monomer and / or a carboxy group-containing monomer.
  • the monomer component constituting the polymer contains a hydroxy group-containing monomer and / or a carboxy group-containing monomer.
  • an isocyanate-based cross-linking agent it is preferable to contain a hydroxy group-containing monomer as a monomer component.
  • an epoxy-based cross-linking agent it is preferable to contain a carboxy group-containing monomer as the monomer.
  • a polymer having a relatively large molecular weight is used as a polymer contained in the photocurable pressure-sensitive adhesive composition in order to form a solid (standard) pressure-sensitive adhesive layer. Used.
  • the weight average molecular weight of the polymer is, for example, about 100,000 to 2 million.
  • the photocurable pressure-sensitive adhesive composition is preferably a solution in which the polymer is dissolved in an organic solvent.
  • a polymer solution can be obtained by solution-polymerizing the monomer components.
  • a polymer solution may be prepared by dissolving a solid polymer in an organic solvent.
  • the polymerization initiator includes an azo-based initiator, a peroxide-based initiator, a redox-based initiator that combines a peroxide and a reducing agent (for example, a combination of a persulfate and sodium hydrogen sulfite, a peroxide and an ascorbin).
  • a thermal polymerization initiator such as (combination of sodium acid acid) is preferably used.
  • the amount of the polymerization initiator used is not particularly limited, but for example, it is preferably about 0.005 to 5 parts by weight, more preferably about 0.02 to 3 parts by weight, based on 100 parts by weight of the total amount of the monomer components forming the polymer. preferable.
  • photopolymerizable compound contained in the photocurable pressure-sensitive adhesive composition in the second form is the same as that described above for the first form, and a compound having one or more photopolymerizable functional groups is used.
  • the photopolymerization initiator contained in the photocurable pressure-sensitive adhesive composition in the second form is the same as that described above for the first form, and preferably has an absorption maximum in the wavelength region of 330 to 400 nm.
  • the amount of the photopolymerization initiator is about 0.01 to 10 parts by weight, preferably about 0.05 to 5 parts by weight, based on 100 parts by weight of the polymer.
  • the colorant contained in the photocurable pressure-sensitive adhesive composition in the second form is the same as that described above for the first form, and the maximum value of the transmittance at a wavelength of 330 to 400 nm is the transmittance at a wavelength of 400 to 700 nm. It is preferably larger than the maximum value. Further, the colorant preferably has an average transmittance at a wavelength of 330 to 400 nm higher than the average transmittance at a wavelength of 400 to 700 nm.
  • the photocurable pressure-sensitive adhesive composition of the second form preferably contains a crosslinkable crosslinkable agent with the above polymer.
  • a crosslinkable crosslinkable agent with the above polymer.
  • the cross-linking agent for introducing a cross-linked structure into the polymer include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, a carbodiimide-based cross-linking agent, a metal chelate-based cross-linking agent, and the like. Be done.
  • isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferable because they have high reactivity with the hydroxyl groups and carboxy groups of the polymer and the cross-linked structure can be easily introduced.
  • These cross-linking agents react with functional groups such as hydroxyl groups and carboxy groups introduced into the polymer to form a cross-linked structure.
  • polyisocyanate-based cross-linking agent polyisocyanate having two or more isocyanate groups in one molecule is used.
  • examples of the isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate.
  • Aromatic isocyanates such as isocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / trimylene diisocyanate trimer adduct (eg, "Coronate L” manufactured by Toso), trimethylolpropane / hexamethylene Diisocyanate trimeric adduct (eg, Tosoh's "Coronate HL”), xylylene diisocyanate trimethylolpropane adduct (eg, Mitsui Chemicals' "Takenate D110N", hexamethylene diisocyanate isocyanurate (eg, Tosoh's "Coronate HL”) Examples thereof include isocyanate additives such as "Coronate HX").
  • the epoxy-based cross-linking agent a polyfunctional epoxy compound having two or more epoxy groups in one molecule is used.
  • the epoxy group of the epoxy-based cross-linking agent may be a glycidyl group.
  • Examples of the epoxy-based cross-linking agent include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 1, 6-Hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, penta Ellisritol polyglycid
  • the amount of the cross-linking agent is about 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer, and may be 0.05 parts by weight or more, 0.1 parts by weight or more, or 0.2 parts by weight or more. It may be 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less.
  • the photocurable pressure-sensitive adhesive composition of the second form includes oligomers, tackifiers, silane coupling agents, chain transfer agents, plasticizers, softeners, deterioration inhibitors, fillers, and antioxidants. , Surfactant, antistatic agent and the like may be contained.
  • the pressure-sensitive adhesive layer 2 may be a pressure-sensitive adhesive layer (third form) formed from a solvent-type pressure-sensitive adhesive composition containing a colorant.
  • the solvent-type pressure-sensitive adhesive composition may contain at least a polymer and a solvent in addition to a colorant, and may contain a cross-linking agent . That is, the solvent-type pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer 2 of this embodiment contains a polymer, a solvent, and a colorant, and may contain a cross-linking agent if necessary.
  • the pressure-sensitive adhesive layer 2 of the present embodiment is a pressure-sensitive adhesive layer having light absorption in visible light.
  • the pressure-sensitive adhesive layer of the third form contains a polymer, a solvent, and a colorant, and if necessary, a solvent-type pressure-sensitive adhesive composition containing a cross-linking agent is applied onto a release film, and the solvent is dried and removed. As a result, it can be formed.
  • the solvent-type pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer of the third form contains a polymer, a solvent, a colorant, and if necessary, a cross-linking agent.
  • polymer As the polymer contained in the solvent-type pressure-sensitive adhesive composition, various polymers can be applied as in the first form, and an acrylic polymer is preferably used.
  • the monomer components constituting the acrylic polymer are the same as those in the first form.
  • a polymer having a relatively large molecular weight is used as the polymer contained in the solvent-type pressure-sensitive adhesive composition.
  • the weight average molecular weight of the polymer is, for example, about 100,000 to 2 million.
  • the acrylic polymer contained in the solvent-based pressure-sensitive adhesive composition of the third form may be a (meth) acrylic block copolymer.
  • the pressure-sensitive adhesive layer 2 is formed from a solvent-type pressure-sensitive adhesive composition containing a (meth) acrylic block copolymer, it is excellent in step absorption and processability, and is therefore arranged on the substrate 5 of the display panel. Since it is possible to seal the plurality of LED chips without leaving any gaps on the steps and the workability is excellent, the problem that the adhesive layer protrudes from the end portion during storage is unlikely to occur.
  • the (meth) acrylic block copolymer comprises a high Tg segment having a glass transition temperature of 0 ° C. or higher and 100 ° C. or lower and a low Tg segment having a glass transition temperature of ⁇ 100 ° C. or higher and lower than 0 ° C. It is preferable to have a peak of tan ⁇ in a region of 0 ° C. or higher and a region of lower than 0 ° C., respectively.
  • high Tg segment having a glass transition temperature of 0 ° C. or higher and 100 ° C. or lower is simply referred to as “high Tg segment”
  • low Tg segment having a glass transition temperature of -100 ° C. or higher and lower than 0 ° C.” is simply referred to as “high Tg segment”.
  • the “segment” in the high Tg segment and the low Tg segment means a partial structure constituting each block unit of the (meth) acrylic block copolymer A.
  • the structure of the (meth) acrylic block copolymer A may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof.
  • the structure of such a block copolymer may be appropriately selected according to the required physical properties of the block copolymer, but from the viewpoint of cost and ease of manufacture, it is preferably a linear block copolymer.
  • the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the solvent-type pressure-sensitive adhesive composition A, (AB) n- type, ( AB) It is preferable that the block copolymer has at least one structure selected from the group consisting of n- A type (n is an integer of 1 or more, for example, an integer of 1 to 3).
  • a and B mean segments composed of different monomer compositions.
  • the segment represented by A constituting the linear block copolymer may be referred to as "A segment”
  • the segment represented by B may be referred to as "B segment”.
  • AB type diblock copolymers represented by AB and ABA type triblock copolymers represented by ABA are selected from the viewpoints of ease of production, physical properties of the solvent-based pressure-sensitive adhesive composition A, and the like.
  • it is an ABA type triblock copolymer.
  • ABA-type triblock copolymers the cross-linking structure between block copolymers becomes higher due to pseudo-crosslinking between A segments at both ends, the cohesive force of block copolymers is improved, and higher adhesion (adhesive force) is exhibited. It is thought that it can be done.
  • the two A segments located at both ends may be the same or different from each other.
  • the (meth) acrylic block copolymer A is an ABA type triblock copolymer
  • at least one is a high Tg segment and at least one is a low Tg segment in two A segments and one B segment (three in total). It can be a segment.
  • an ABA-type triblock copolymer in which the A segment is the high Tg segment and the B segment is the low Tg segment is preferable.
  • an ABA-type triblock copolymer in which at least one of the two A segments is a high Tg segment and the B segment is a low Tg segment is preferred, and both of the two A segments are high Tg segments and the B segment.
  • ABA-type triblock copolymers having a low Tg segment are more preferable.
  • the glass transition temperature (Tg) of the high Tg segment constituting the (meth) acrylic block copolymer A is 0 ° C. or higher and 100 ° C. or lower.
  • the storage elastic modulus of the solvent-type pressure-sensitive adhesive composition A at room temperature (25 ° C.) can be easily controlled to be high, and the solvent-type pressure-sensitive adhesive composition A is hard and has excellent workability, and in a region exceeding 50 ° C.
  • the storage elastic modulus tends to be significantly reduced, resulting in a highly fluid pressure-sensitive adhesive composition.
  • the Tg of the high Tg segment is preferably 4 ° C. or higher, more preferably 6 ° C. or higher, further preferably 8 ° C. or higher. 10 ° C. or higher is even more preferable, and 12 ° C. or higher is particularly preferable.
  • the Tg of the high Tg segment is 90 ° C. or lower from the viewpoint that the storage elastic modulus (G') of the solvent-type pressure-sensitive adhesive composition A is remarkably lowered in the region exceeding 50 ° C. and tends to have high fluidity.
  • G' storage elastic modulus
  • 85 ° C. or lower is more preferable, 60 ° C. or lower is further preferable, 50 ° C. or lower is even more preferable, and 35 ° C. or lower is particularly preferable.
  • the Tg of the low Tg segment constituting the (meth) acrylic block copolymer A is ⁇ 100 ° C. or higher and lower than 0 ° C.
  • the Tg of the low Tg segment is preferably ⁇ 95 ° C. or higher, more preferably ⁇ 90 ° C. or higher, from the viewpoint that the storage elastic modulus of the solvent-type pressure-sensitive adhesive composition A does not easily decrease at room temperature (25 ° C.) and the processability can be improved.
  • the Tg of the low Tg segment is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 10 ° C. or lower, from the viewpoint of improving the appropriate adhesive strength and processability of the solvent-type pressure-sensitive adhesive composition A at room temperature (25 ° C.).
  • it is more preferably ⁇ 20 ° C. or lower, even more preferably ⁇ 30 ° C. or lower, and particularly preferably ⁇ 40 ° C. or lower.
  • the difference between the Tg of the high Tg segment and the Tg of the low Tg segment (Tg of the high Tg segment-Tg of the low Tg segment) constituting the (meth) acrylic block copolymer A is not particularly limited, but is the solvent-type pressure-sensitive adhesive composition A.
  • the glass transition temperature (Tg) of the high Tg segment and the low Tg segment constituting the (meth) acrylic block copolymer A is a calculated glass transition temperature calculated from the following Fox formula. This calculated glass transition temperature is calculated based on the type and amount of each monomer component constituting the high Tg segment or the low Tg segment of the (meth) acrylic block copolymer A, and therefore the monomer component of each segment. It can be adjusted by selecting the type and amount of the above.
  • W1, W2, ... Wn are the respective weight fractions (% by weight) of the monomer component (1), the monomer component (2), ... the monomer component (n) constituting the copolymer with respect to all the monomer components. )
  • Tg (1), Tg (2), ... Tg (n) is a glass transition of the homopolymer of the monomer component (1), the monomer component (2), ... Represents temperature (unit is absolute temperature: K).
  • the glass transition temperature of homopolymers is known from various documents and catalogs, and is described in, for example, J. Brandup, E. H. Immergut, E. A. Grulke: Polymer Handbook: JOHNWILEY & SONS, INC.
  • values measured by general thermal analysis for example, differential thermal analysis, dynamic viscoelasticity measurement method, or the like can be adopted.
  • the temperature region in which the high temperature region tan ⁇ peak of the (meth) acrylic block copolymer A appears is 0 ° C. or higher (for example, 0 ° C. or higher and 100 ° C. or lower) as described above.
  • the storage elastic modulus of the solvent-type pressure-sensitive adhesive composition A at room temperature (25 ° C.) can be easily controlled to be high, and it is hard and excellent in workability, and in the region exceeding 50 ° C.
  • the storage elastic modulus tends to be significantly reduced, resulting in a highly fluid pressure-sensitive adhesive composition.
  • the temperature at which the tan ⁇ peak in the high temperature region appears is preferably 3 ° C. or higher, more preferably 6 ° C. or higher, and further 9 ° C. or higher.
  • 12 ° C. or higher is even more preferable, and 15 ° C. or higher is particularly preferable.
  • the temperature at which the tan ⁇ peak in the high temperature region appears is 90 ° C. from the viewpoint that the storage elastic modulus (G') of the solvent-type pressure-sensitive adhesive composition A is remarkably lowered in the region exceeding 50 ° C. and tends to have high fluidity.
  • the following is preferable, 80 ° C. or lower is more preferable, 70 ° C. or lower is further preferable, 65 ° C. or lower is further preferable, and 60 ° C. or lower is particularly preferable.
  • the temperature region in which the low temperature region tan ⁇ peak of the (meth) acrylic block copolymer A appears is less than 0 ° C. (for example, ⁇ 100 ° C. or higher and lower than 0 ° C.) as described above. Since the tan ⁇ peak in the low temperature region is in this temperature range, only the low Tg segment is fluidized at room temperature (25 ° C.), and an appropriate adhesive force is imparted to the solvent-type pressure-sensitive adhesive composition A while ensuring processability. There is a tendency to be able to do it.
  • the temperature at which the tan ⁇ peak in the low temperature region appears is preferably ⁇ 95 ° C. or higher, preferably ⁇ 90 ° C.
  • the above is more preferable, ⁇ 80 ° C. or higher is further preferable, and ⁇ 70 ° C. or higher is further preferable.
  • the temperature at which the tan ⁇ peak in the low temperature region appears is preferably ⁇ 5 ° C. or lower, preferably ⁇ 10 ° C. or lower. Is more preferable, ⁇ 20 ° C. or lower is further preferable, ⁇ 30 ° C. or lower is even more preferable, and ⁇ 40 ° C. or lower is particularly preferable.
  • the maximum value of the tan ⁇ peak in the high temperature region is not particularly limited, but is preferably 0.5 to 3.0. When the maximum value of the tan ⁇ peak in the high temperature region is in this range, it is preferable in that excellent processability and shape stability of the (meth) acrylic block copolymer A can be realized.
  • the maximum value of the tan ⁇ peak in the high temperature region is preferably 0.6 or more, more preferably 0.7 or more, in that excellent workability can be realized. Further, the maximum value of the tan ⁇ peak in the high temperature region is preferably 2.5 or less, more preferably 2.2 or less, from the viewpoint that dents are unlikely to occur.
  • the maximum value of the tan ⁇ peak in the low temperature region is not particularly limited, but is preferably 0.1 to 2.0. When the maximum value of the tan ⁇ peak in the low temperature region is in this range, it is preferable in that excellent processability and shape stability of the (meth) acrylic block copolymer A can be realized.
  • the maximum value of the tan ⁇ peak in the high temperature region is preferably 0.2 or more, more preferably 0.3 or more, in that excellent workability can be realized. Further, the maximum value of the tan ⁇ peak in the low temperature region is preferably 1.5 or less, more preferably 1 or less, from the viewpoint that dents are unlikely to occur.
  • the high temperature region tan ⁇ peak and the low temperature region tan ⁇ peak, and the temperature and maximum value at which they appear are measured by dynamic viscoelasticity measurement.
  • the (meth) acrylic block copolymer A is composed of a plurality of segments (including a high Tg segment and a low Tg segment) obtained by polymerizing a monomer component, and the monomer component has a (meth) acryloyl group in the molecule. It contains a monomer (acrylic monomer) having.
  • the (meth) acrylic block copolymer A or each segment thereof preferably contains an acrylic monomer in an amount of 70% by weight or more, more preferably 80% by weight or more, and 90% by weight, based on the total amount (100% by weight) of the monomer components. It is particularly preferable to contain% or more.
  • Examples of the acrylic monomer constituting the (meth) acrylic block copolymer A or each segment thereof (including a high Tg segment and a low Tg segment) include an acrylic acid alkyl ester having a linear or branched alkyl group, and an acrylic acid alkyl ester having a linear or branched alkyl group. / Or, a monomer component derived from a methacrylic acid alkyl ester having a linear or branched alkyl group is contained as the main monomer unit having the largest weight ratio.
  • the (meth) acrylic acid alkyl ester having a linear or branched alkyl group for forming a segment of the (meth) acrylic block copolymer A is a (meth) acrylic acid having the above-mentioned chain alkyl group. Specific examples of alkyl esters can be given.
  • the (meth) acrylic acid alkyl ester for the segment one kind of (meth) acrylic acid alkyl ester may be used, or two or more kinds of (meth) acrylic acid alkyl esters may be used.
  • the (meth) acrylic acid alkyl ester for the segment is preferably methyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, t-butyl acrylate, hexyl acrylate, heptyl acrylate, acrylic. At least one selected from the group consisting of octyl acid acid and isononyl acrylate is used.
  • the segment of the (meth) acrylic block copolymer A may contain a monomer unit derived from an alicyclic monomer.
  • the alicyclic monomer for forming the monomer unit of the segment include specific examples of the (meth) acrylic acid alkyl ester having the alicyclic alkyl group described above.
  • the alicyclic alkyl group may have a substituent. Examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom) and a linear or branched alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, n-propyl).
  • the number of the substituents is not particularly limited and can be appropriately selected from 1 to 6. When there are two or more substituents, the two or more substituents may be the same or different.
  • the alicyclic monomer for the segment one kind of alicyclic monomer may be used, or two or more kinds of alicyclic monomers may be used.
  • the alicyclic monomer for the segment is preferably a cyclo having 4 to 10 carbon atoms which may have a substituent (eg, a linear or branched alkyl group having 1 to 6 carbon atoms).
  • the segment of the (meth) acrylic block copolymer A may contain a monomer unit derived from a hydroxyl group-containing monomer.
  • the hydroxyl group-containing monomer is a monomer having at least one hydroxyl group in the monomer unit.
  • hydroxyl group-containing monomer for forming the monomer unit of the segment.
  • the hydroxyl group-containing monomer for the segment one type of hydroxyl group-containing monomer may be used, or two or more types of hydroxyl group-containing monomers may be used.
  • the hydroxyl group-containing monomer for the segment is preferably a hydroxyl group-containing (meth) acrylic acid ester, more preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and methacrylic acid. At least one selected from the group consisting of 2-hydroxypropyl, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate is used.
  • the segment of the (meth) acrylic block copolymer A may contain a monomer unit derived from a nitrogen atom-containing monomer.
  • a nitrogen atom-containing monomer is a monomer that will have at least one nitrogen atom in the monomer unit.
  • nitrogen atom-containing monomer for forming the segment.
  • the nitrogen atom-containing monomer for the acrylic polymer one kind of nitrogen atom-containing monomer may be used, or two or more kinds of nitrogen atom-containing monomers may be used.
  • the nitrogen atom-containing monomer for the segment N-vinyl-2-pyrrolidone is preferably used.
  • the segment of the (meth) acrylic block copolymer A may contain a monomer unit derived from a carboxy group-containing monomer.
  • the carboxy group-containing monomer is a monomer having at least one carboxy group in the monomer unit.
  • good adhesive reliability may be obtained in the solvent-based pressure-sensitive adhesive composition A.
  • carboxy group-containing monomer for forming the monomer unit of the segment.
  • carboxy group-containing monomer for the segment one kind of carboxy group-containing monomer may be used, or two or more kinds of carboxy group-containing monomers may be used.
  • Acrylic acid is preferably used as the carboxy group-containing monomer for the segment.
  • examples of the monomer unit for forming the segment include the above-mentioned other monomers.
  • the content of other monomers in the monomer unit constituting the segment of the (meth) acrylic block copolymer A is not particularly limited as long as it is 30% by weight or less with respect to the total amount of the monomer components (100% by weight), and the present invention. It is appropriately selected within the range that does not impair the effect of.
  • the monomer component constituting the high Tg segment of the (meth) acrylic block copolymer A it is easy to control the Tg of the high Tg segment within a predetermined range, and it is possible to impart desired physical properties to the (meth) acrylic block copolymer A.
  • a (meth) acrylic acid alkyl ester having a linear alkyl group having 1 to 3 carbon atoms hereinafter, may be referred to as "(meth) acrylic acid C 1-3 linear alkyl ester".
  • (Meta) acrylic acid alkyl ester having a branched alkyl group having 3 or 4 carbon atoms (hereinafter, may be referred to as "(meth) acrylic acid C 3-4 branched chain alkyl ester"). And at least one selected from the group consisting of an alicyclic monomer is preferably contained. Since homopolymers of these monomers have a relatively high Tg, it is easy to control the Tg of the high Tg segment within a predetermined range of the present invention by containing a monomer selected from these as a monomer component constituting the high Tg segment.
  • the alicyclic monomer has a cycloalkyl group having 4 to 10 carbon atoms which may have a substituent (eg, a linear or branched alkyl group having 1 to 6 carbon atoms) (meth).
  • a substituent eg, a linear or branched alkyl group having 1 to 6 carbon atoms
  • Acrylic acid cycloalkyl ester is preferable, and an acrylic having a cycloalkyl group having 4 to 10 carbon atoms, which may have a substituent (eg, a linear or branched alkyl group having 1 to 6 carbon atoms).
  • Acid cycloalkyl esters are more preferred, and cyclohexyl acrylate (homopolymer Tg: 15 ° C.) and (meth) acrylic acid 3,3,5-trimethylcyclohexyl (homopolymer Tg: 52 ° C.) are particularly preferred.
  • the content of the alicyclic monomer with respect to the total amount (100% by weight) of the monomer component makes it easy to control the Tg of the high Tg segment within a predetermined range.
  • it is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20% by weight or more, and more preferably 30% by weight or more. , More preferably 30% by weight or more, more preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, more preferably 70% by weight or more, more preferably 80% by weight or more, more. It is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • acrylic acid C 1-3 linear alkyl ester acrylic acid C 1-3 linear alkyl ester is preferable, and methyl acrylate (tg of homopolymer: 8 ° C.) is particularly preferable.
  • acrylic acid C 3-4 branched chain alkyl ester acrylic acid C 3-4 branched chain alkyl ester is preferable, and t-butyl acrylate (tg of homopolymer: 35 ° C.) is particularly preferable.
  • (meth) acrylic acid C 1-3 linear alkyl ester and / or (meth) acrylic acid C 3-4 branched chain alkyl ester is contained as a monomer component constituting the high Tg segment
  • (meth) acrylic acid The content of C 1-3 linear alkyl ester and / or (meth) acrylic acid C 3-4 branched chain alkyl ester with respect to the total amount (100% by weight) of the monomer components is such that Tg of the high Tg segment is within a predetermined range.
  • it is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20% by weight or more, and more preferably.
  • the monomer component constituting the low Tg segment of the (meth) acrylic block copolymer A it is easy to control the Tg of the low Tg segment within a predetermined range, and it is possible to impart desired physical properties to the (meth) acrylic block copolymer A.
  • a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 4 to 18 carbon atoms hereinafter, may be referred to as "(meth) acrylic acid C 4-18 alkyl ester".
  • at least one selected from the group consisting of hydroxyl group-containing monomers at least one selected from the group consisting of hydroxyl group-containing monomers.
  • the Tg of the low Tg segment is defined in the present invention. Easy to control within the range of.
  • the hydroxyl group-containing monomer also has a relatively low Tg, and the (meth) acrylic block copolymer A can easily obtain adhesiveness and appropriate cohesive force. Therefore, it is more preferable to contain both the (meth) acrylic acid C 4-18 alkyl ester and the hydroxyl group-containing monomer as the monomer component constituting the low Tg segment of the (meth) acrylic block copolymer A.
  • acrylic acid C 4-18 alkyl ester acrylic acid C 4-18 alkyl ester is preferable, and butyl acrylate (Tg of homopolymer: -55 ° C.) and 2-ethylhexyl acrylate (Tg of homopolymer). : -70 ° C), n-hexyl acrylate (Tg of homopolymer: -57 ° C), n-octyl acrylate (Tg of homopolymer: -65 ° C), isononyl acrylate (Tg of homopolymer: -58 ° C) ) Is particularly preferable.
  • the content of the (meth) acrylic acid C 4-18 alkyl ester with respect to the total amount (100% by weight) of the monomer component is from the viewpoint that the Tg of the low Tg segment can be easily controlled within a predetermined range and the desired physical properties can be imparted to the (meth) acrylic block copolymer A, it is preferably 10% by weight or more (for example, 10 to 100% by weight). It is preferably 20% by weight or more, more preferably 30% by weight or more, more preferably 30% by weight or more, more preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, more preferably. It is 70% by weight or more, more preferably 80% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • hydroxyl group-containing monomer a hydroxyl group-containing (meth) acrylic acid alkyl ester is preferable, and 4-hydroxybutyl acrylate (Tg of homopolymer: ⁇ 65 ° C.) and 2-hydroxyethyl acrylate (Tg of homopolymer: ⁇ 15 ° C.) are preferable. °C) is particularly preferable.
  • the content of the hydroxyl group-containing monomer with respect to the total amount (100% by weight) of the monomer component makes it easy to control the Tg of the low Tg segment within a predetermined range (meth).
  • it is preferably 1% by weight or more, more preferably 1.5% by weight or more, more preferably 2% by weight or more, still more preferably 2.5% by weight. As mentioned above, it is particularly preferably 3% by weight or more.
  • the content of the hydroxyl group-containing monomer with respect to the total amount (100% by weight) of the monomer components is preferably 50% by weight or less, more preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less. It is more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
  • the hydroxyl group-containing monomer and the (meth) acrylic acid are contained as the monomer components constituting the low Tg segment of the (meth) acrylic block copolymer A, the hydroxyl group-containing monomer and the (meth) acrylic acid
  • the ratio of the C 4-18 alkyl ester (hydroxyl-containing monomer / (meth) acrylic acid C 4-18 alkyl ester) is not particularly limited, but the lower limit is preferably 1/99, more preferably 1.5 / 98. 5, more preferably 2/98, still more preferably 2.5 / 97.5, particularly preferably 3/97, while the upper limit is 50/50, more preferably 40/60, more preferably 30/97. 70, more preferably 20/80.
  • the (meth) acrylic block copolymer A can be produced by the living radical polymerization method of the above-mentioned monomer components.
  • the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, but is less likely to cause a termination reaction or chain transfer, and grows without deactivating the growth end. Therefore, the molecular weight distribution is precisely controlled and uniform. It is preferable in that it is easy to produce a polymer having a suitable composition.
  • the high Tg segment may be produced first and the monomer of the low Tg segment may be polymerized on the high Tg segment; the low Tg segment may be produced first and the monomer of the high Tg segment may be produced on the low Tg segment. May be polymerized.
  • the (meth) acrylic block copolymer A is an ABA type triblock copolymer
  • RAFT agent cleavage chain transfer agent
  • TRIP method organic tellurium compound
  • RAFT method a known method can be used without particular limitation.
  • a step 1 first RAFT polymerization in which a monomer component is polymerized using a RAFT agent to prepare a first segment (first RAFT polymerization).
  • first segment first RAFT polymerization
  • second segment is added to the first segment in step 2 (first segment).
  • 2 RAFT polymerization After the second RAFT polymerization, the RAFT polymerizations of the third, fourth ... May be carried out in the same manner as the second RAFT polymerization, and the segments of the third, fourth ... May be further added.
  • the steps 1 and 2 can be carried out by a known and commonly used method, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by irradiation with heat or active energy rays (thermal polymerization method, active energy ray polymerization). Method) and so on.
  • the solution polymerization method is preferable in terms of transparency, water resistance, cost and the like.
  • the polymerization is preferably carried out while avoiding contact with oxygen from the viewpoint of suppressing polymerization inhibition by oxygen. For example, it is preferable to carry out the polymerization in a nitrogen atmosphere.
  • the (meth) acrylic block copolymer A is an ABA-type triblock copolymer
  • the A segment is preferably a high Tg segment
  • the B segment is preferably a low Tg segment.
  • RAFT agent known ones can be used without particular limitation, and for example, compounds represented by the following formulas (1), (2), or formulas (3) (trithiocarbonate, dithioester, etc.) can be used. Dithiocarbonate) is preferred.
  • R 1a and R 1b have the same or different hydrogen atoms, hydrocarbon groups, or cyano groups. show.
  • R 1c represents a hydrocarbon group which may have a cyano group.
  • the hydrocarbon groups as R 1a , R 1b , and R 1c include hydrocarbon groups having 1 to 20 carbon atoms (straight, branched, or cyclic saturated or unsaturated hydrocarbon groups, etc.). Among them, a hydrocarbon group having 1 to 12 carbon atoms is preferable.
  • hydrocarbon group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclohexyl group, a dodecyl group, an octadecyl group and the like.
  • examples of the hydrocarbon group having a cyano group as R 1c include a group in which 1 to 3 hydrogen atoms of the above-mentioned hydrocarbon group are substituted with a cyano group.
  • R 2 represents a hydrocarbon group or a group in which a part of the hydrogen atom of the hydrocarbon group is substituted with a carboxyl group (for example, a carboxylalkyl group).
  • a hydrocarbon group include hydrocarbon groups having 1 to 20 carbon atoms (straight chain, branched chain, cyclic saturated or unsaturated hydrocarbon groups, etc.), and among them, hydrocarbon groups having 1 to 12 carbon atoms. Hydrocarbon groups are preferred.
  • hydrocarbon group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, dodecyl group, octadecyl group and the like.
  • Linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms; arylalkyl groups having a total carbon number of 7 to 10 such as benzyl group and phenethyl group can be mentioned.
  • the polymerization proceeds by reacting so that the raw material monomer is inserted between the sulfur atom in the RAFT agent represented by the formulas (1) to (3) and the methylene group adjacent to the sulfur atom.
  • RAFT agents are commercially available. Those that are not commercially available can be easily synthesized by known or conventional methods. In the present invention, one type of RAFT agent may be used alone, or two or more types may be used in combination.
  • RAFT agents include trithiocarbonates such as dibenzyltrithiocarbonate and S-cyanomethyl-S-dodecyltrithiocarbonate; cyanoethyl dithiopropionate, benzyl dithiopropionate, benzyl dithiobenzoate, acetoxyethyl dithiobenzoate and the like.
  • Dithioesters O-ethyl-S- (1-phenylethyl) dithiocarbonate, O-ethyl-S- (2-propoxyethyl) dithiocarbonate, O-ethyl-S- (1-cyano-1-methylethyl)
  • dithiocarbonates such as dithiocarbonate, of which trithiocarbonates are preferable, trithiocarbonates having a symmetrical structure in the formula (1) are more preferable, and dibenzyltrithiocarbonate and bis ⁇ 4 are particularly preferable.
  • -[Ethyl- (2-acetyloxyethyl) carbamoyl] benzyl ⁇ trithiocarbonate is preferred.
  • the step 1 can be performed by polymerizing the monomer components in the presence of a RAFT agent.
  • the amount of the RAFT agent used in step 1 is usually 0.05 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the total amount of the monomer components. With such an amount, the reaction can be easily controlled, and the weight average molecular weight of the obtained segment can be easily controlled.
  • the step 2 can be performed by adding a monomer component to the polymerization reaction mixture obtained in the step 1 and further polymerizing the mixture.
  • the RAFT method is preferably carried out in the presence of a polymerization initiator.
  • a polymerization initiator examples include ordinary organic polymerization initiators, and specific examples thereof include peroxides and azo compounds. Among these, azo compounds are preferable.
  • the polymerization initiator may be used alone or in combination of two or more.
  • peroxide-based polymerization initiator examples include benzoyl peroxide and tert-butyl permalate.
  • azo compound examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis (2-cyclopropyl).
  • the amount of the polymerization initiator used is usually 0.001 to 2 parts by weight, preferably 0.002 to 1 part by weight, based on 100 parts by weight of the total amount of the monomer components. With such an amount, it is easy to control the weight average molecular weight of the obtained segment.
  • the RAFT method may be bulk polymerization that does not use a polymerization solvent, but it is preferable to use a polymerization solvent.
  • the polymerization solvent include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane and cyclo.
  • Alicyclic hydrocarbons such as octane; halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole , Ethers such as phenylethyl ether and diphenyl ether; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; N, N-dimethylformamide, N , N-dimethylacetamide, amides such as N-methylpyrrolidone; nitriles such as acetonit
  • the amount of the polymerization solvent used is not particularly limited, and is, for example, 0.01 mL or more, more preferably 0.05 mL or more, still more preferably 0.1 mL or more, and 50 mL or less with respect to 1 g of the monomer component. It is preferably 10 mL or less, still more preferably 1 mL or less.
  • the reaction temperature in the RAFT method is usually 60 to 120 ° C., preferably 70 to 110 ° C., and is usually carried out in an atmosphere of an inert gas such as nitrogen gas. This reaction can be carried out under normal pressure, pressurization and reduced pressure, and is usually carried out at normal pressure.
  • the reaction time is usually 1 to 20 hours, preferably 2 to 14 hours.
  • the above-mentioned polymerization reaction conditions of the RAFT method can be applied to step 1 and step 2, respectively.
  • the target (meth) acrylic block copolymer A can be separated from the obtained reaction mixture by removing the solvent used and residual monomers by ordinary separation and purification means.
  • the weight average molecular weight (Mw) of the high Tg segment or the low Tg segment is not particularly limited, but is preferably 10. It is 000 to 1,000,000, more preferably 50,000 to 500,000, and even more preferably 100,000 to 300,000. The fact that the Mw of the high Tg segment or the low Tg segment is within this range is suitable for the above-mentioned effect of the present invention.
  • the Mw is the sum of Mw when two or more high Tg segments or low Tg segments are present in the (meth) acrylic block copolymer A.
  • the weight average molecular weight (Mw) of the (meth) acrylic block copolymer A is not particularly limited, but is preferably 200,000 (200,000) or more, more preferably 300,000 to 5,000,000, and even more preferably. Is between 400,000 and 2,500,000. It is suitable for the above-mentioned effect of the present invention that the Mw of the (meth) acrylic block copolymer A is within this range.
  • the molecular weight distribution (Mw / Mn) of the (meth) acrylic block copolymer A is not particularly limited, but is preferably larger than 1, more preferably 1.5 or more, still more preferably 2 or more, and particularly preferably 2. It is 5 or more, preferably 5 or less, more preferably 4.5 or less, still more preferably 4 or less, and particularly preferably 3.5 or less.
  • the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) are measured by the GPC method.
  • the content of the high Tg segment in the (meth) acrylic block copolymer A is preferably 10% by weight or more, more preferably 20% by weight or more, still more preferably 20% by weight or more in 100% by weight of the entire (meth) acrylic block copolymer A. It is 25% by weight or more, particularly preferably 30% by weight or more, preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less.
  • the content of the low Tg segment in the (meth) acrylic block copolymer A is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 10% by weight or more in 100% by weight of the entire (meth) acrylic block copolymer A. It is 15% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight or less.
  • the content of each of the segments and their ratio can be calculated from the weight average molecular weight (Mw) of each segment or the (meth) acrylic block copolymer A obtained in each step of the RAFT method, and when each segment is formed. It can be controlled by the charging ratio of the monomers, the polymerization rate of each monomer, and the like.
  • the content of the (meth) acrylic block copolymer A in the solvent-based pressure-sensitive adhesive composition A is not particularly limited, but is excellent in processability at room temperature (25 ° C.) and excellent step absorption in a region exceeding 50 ° C.
  • the amount is preferably 50% by weight or more (for example, 50 to 100% by weight), more preferably 60% by weight, based on the total amount (total weight, 100% by weight) of the solvent-type pressure-sensitive adhesive composition A. As mentioned above, it is more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the solvent-based pressure-sensitive adhesive composition is a solution in which the polymer is dissolved in an organic solvent.
  • a polymer solution can be obtained by solution-polymerizing the monomer components.
  • a polymer solution may be prepared by dissolving a solid polymer in an organic solvent.
  • Ethyl acetate, toluene, etc. are generally used as the solvent.
  • the solution concentration is usually about 20 to 80% by weight.
  • Examples of the polymerization initiator when the monomer component is solution-polymerized include an azo-based initiator, a peroxide-based initiator, and a redox-based initiator that combines a peroxide and a reducing agent (for example, persulfate and sodium hydrogen sulfite). , A combination of peroxide and sodium ascorbate) and other thermal polymerization initiators are preferably used.
  • the amount of the polymerization initiator used is not particularly limited, but for example, it is preferably about 0.005 to 5 parts by weight, more preferably about 0.02 to 3 parts by weight, based on 100 parts by weight of the total amount of the monomer components forming the polymer. preferable.
  • the solvent-based pressure-sensitive adhesive composition used to form the pressure-sensitive adhesive layer of the third form contains a colorant.
  • the colorant may be a dye or a pigment as long as it can be dissolved or dispersed in the solvent-type pressure-sensitive adhesive composition. Dyes are preferable because low haze can be achieved even with a small amount of addition, and unlike pigments, they do not have sedimentation properties and can be easily distributed uniformly. In addition, pigments are also preferable because they have high color development even when added in a small amount. When a pigment is used as a colorant, it preferably has low or no conductivity. When a dye is used, it is preferably used in combination with an antioxidant or the like.
  • the colorant contained in the solvent-type pressure-sensitive adhesive composition in the third form includes an ultraviolet-absorbing colorant in addition to the ultraviolet-transmissive colorant described above for the first form.
  • Examples of the ultraviolet-transparent black pigment include “9050BLACK” and “UVBK-0001” manufactured by Tokushiki.
  • Examples of the ultraviolet-absorbing black dye include “VALIFAST BLACK 3810” and “NUBIAN Black PA-2802” manufactured by Orient Chemical Industries.
  • Examples of the ultraviolet-absorbing black pigment include carbon black and titanium black.
  • the content of the colorant in the solvent-type pressure-sensitive adhesive composition is, for example, about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the monomers, and the type of colorant, the color tone of the pressure-sensitive adhesive layer, and light transmittance. It may be set appropriately according to the rate and the like.
  • the colorant may be added to the composition as a solution or dispersion dissolved or dispersed in an appropriate solvent.
  • the solvent-based pressure-sensitive adhesive composition of the third form may contain a cross-linking agent capable of cross-linking with the above polymer.
  • the solvent-based pressure-sensitive adhesive composition contains a (meth) acrylic block copolymer
  • the pressure-sensitive adhesive layer of the third form has sufficient shape stability and may not contain a cross-linking agent.
  • the cross-linking agent is the same as that described above for the second form, and an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent are preferable.
  • the content thereof is about 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer, and 0.05 parts by weight or more, 0. It may be 1 part by weight or more or 0.2 parts by weight or more, and may be 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less.
  • the solvent-based pressure-sensitive adhesive composition of the third form includes oligomers, tackifiers, silane coupling agents, chain transfer agents, plasticizers, softeners, deterioration inhibitors, fillers, antioxidants, and the like. It may contain a surfactant, an antistatic agent and the like.
  • the optical laminate 10 or 11 can be prepared by laminating the pressure-sensitive adhesive layer 2 on the surface 1b of the base material 1 which has not been subjected to the antireflection treatment and / or the antiglare treatment.
  • the method of laminating the pressure-sensitive adhesive layer of the first form on the surface 1b is not particularly limited.
  • the photocurable pressure-sensitive adhesive composition of the first form is applied on a release film, molded on a sheet, and light. This can be done by curing to prepare a sheet-like pressure-sensitive adhesive layer and then laminating it on the surface 1b of the base material 1.
  • the photocurable pressure-sensitive adhesive composition of the first form is applied in a sheet form (layered form) on a release film, and the coating film of the photocurable pressure-sensitive adhesive composition on the release film is irradiated with ultraviolet rays to perform photo-curing. Thereby, the pressure-sensitive adhesive layer of the first form is obtained.
  • a release film is further attached to the surface of the coating film, and the photocurable pressure-sensitive adhesive composition is sandwiched between the two release films and irradiated with ultraviolet rays to inhibit polymerization by oxygen. It is preferable to prevent it.
  • the sheet-like coating film may be heated for the purpose of removing the solvent or dispersion medium of the colorant. When removing the solvent or the like by heating, it is preferable to carry out before attaching the release film.
  • Resin materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth) acrylic resins.
  • polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth) acrylic resins.
  • polyester resins such as polyethylene terephthalate are particularly preferable.
  • the thickness of the film substrate is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
  • the material of the release layer include a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, a fatty acid amide-based release agent, and the like.
  • the thickness of the release layer is generally about 10 to 2000 nm.
  • the thickness of the pressure-sensitive adhesive layer containing the colorant is not particularly limited, and is appropriately set to be equal to or higher than the height of the light-emitting element so that the light-emitting elements arranged on the display panel described later can be sufficiently sealed. Just do it.
  • the thickness of the pressure-sensitive adhesive layer containing the colorant is 1.0 to 4.0 times, preferably 1.1 to 3.0 times, more preferably 1.2 to 2. times the height of the light emitting element. It is adjusted to be 5 times, more preferably 1.3 to 2.0 times.
  • the thickness of the pressure-sensitive adhesive layer containing the colorant is, for example, about 10 to 500 ⁇ m, and may be 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, or 50 ⁇ m or more.
  • the photocurable pressure-sensitive adhesive composition can be uniformly photo-cured in the thickness direction even when the thickness of the pressure-sensitive adhesive layer is large. ..
  • the thickness of the pressure-sensitive adhesive layer containing the colorant may be 400 ⁇ m or less, 300 ⁇ m or less, 250 ⁇ m or less, or 200 ⁇ m or less.
  • the photocurable pressure-sensitive adhesive composition coated in layers on the release film By irradiating the photocurable pressure-sensitive adhesive composition coated in layers on the release film with ultraviolet rays, active species are generated from the photopolymerization initiator, the photopolymerizable compound is polymerized, and the polymerization rate is increased (unreacted). As the monomer is reduced), the liquid photocurable pressure-sensitive adhesive composition becomes a solid (standard) pressure-sensitive adhesive layer.
  • the light source for ultraviolet irradiation is not particularly limited as long as the photopolymerization initiator contained in the pressure-sensitive adhesive composition can irradiate light in a sensitive wavelength range, and is an LED light source, a high-pressure mercury lamp, and ultra-high pressure mercury. Lamps, metal halide lamps, xenon lamps, etc. are used.
  • the integrated light amount of the irradiation light is, for example, about 100 to 5000 mJ / cm 2.
  • the polymerization rate (nonvolatile content) of the pressure-sensitive adhesive layer made of the photo-curable product of the photocurable pressure-sensitive adhesive composition is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more.
  • the polymerization rate may be 93% or more or 95% or more.
  • the pressure-sensitive adhesive layer may be heated to remove volatile components such as residual monomers, unreacted polymerization initiators, and solvents.
  • the thickness of one release film and the thickness of the other release film may be the same or different.
  • the peeling force when peeling the release film temporarily attached to one surface from the pressure-sensitive adhesive layer and the peeling force when peeling the release film temporarily attached to the other surface from the pressure-sensitive adhesive layer are the same but different. You may.
  • the peeling film (light peeling film) having a relatively small peeling force is peeled off from the adhesive layer first and bonded to the surface 1b of the base material 1, thereby performing the first embodiment.
  • An optical laminate having the pressure-sensitive adhesive layer of the above can be produced.
  • the photocurable pressure-sensitive adhesive composition is applied to the surface 1b of the base material 1, molded on a sheet, and then a release film is attached to the surface of the coating film and irradiated with ultraviolet rays. It is also possible to prepare an optical laminate having the pressure-sensitive adhesive layer of the first form.
  • the pressure-sensitive adhesive layer containing the colorant has light absorption in visible light.
  • the total light transmittance of the optical laminate of the first form is, for example, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5 It may be less than or equal to%.
  • the average transmittance T UV at a wavelength of 330 to 400 nm is larger than the average transmittance T VIS at a wavelength of 400 to 700 nm.
  • the average transmittance T VIS of the pressure-sensitive adhesive layer at a wavelength of 400 to 700 nm is, for example, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less or 10% or less. It may be.
  • Average transmittance T UV of wavelength 330 ⁇ 400 nm of the pressure-sensitive adhesive layer is preferably at least 5%, 10% or more, 15% or more, may be 20% or more or 25% or more.
  • the difference T UV -T VIS between T UV and T VIS is more than 3%, 5% or more, or may be more than 8% or 10% or more.
  • the shear storage elastic modulus G'25 ° C. at a temperature of 25 ° C. of the pressure-sensitive adhesive layer is, for example, about 10 to 1000 kPa, and may be 30 kPa or more, 50 kPa or more, 70 kPa or more, or 100 kPa or more, and 700 kPa or less. , 500 kPa or less, 300 kPa or less, or 200 kPa or less.
  • the shear storage elastic modulus G'85 ° C. at a temperature of the pressure-sensitive adhesive layer at 85 ° C.
  • shear storage elastic modulus of the pressure-sensitive adhesive layer is, for example, about 3 to 300 kPa, may be 5 kPa or more, 7 kPa or more, or 10 kPa or more, and is 200 kPa or less, 150 kPa or less, or 100 kPa. It may be as follows.
  • the shear storage elastic modulus is a value measured by dynamic viscoelasticity measurement at a frequency of 1 Hz.
  • the curable pressure-sensitive adhesive composition of the second form is applied onto a release film, the solvent is dried and removed as necessary, and the surface 1b of the base material 1 is removed. It can be prepared by laminating with. Further, in the optical laminate having the pressure-sensitive adhesive layer of the second form, the curable pressure-sensitive adhesive composition of the second form is applied on the surface 1b of the base material 1, and the solvent is dried and removed as necessary. Can also be prepared.
  • the photocurable pressure-sensitive adhesive composition contains a solvent
  • the heating and drying temperature is preferably 40 ° C. to 200 ° C., more preferably 50 ° C. to 180 ° C., and particularly preferably 70 ° C. to 170 ° C.
  • the drying time an appropriate time can be adopted as appropriate.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 10 seconds to 10 minutes.
  • a crosslinked structure is introduced into the polymer by heating as necessary.
  • the heating temperature and heating time may be appropriately set depending on the type of the cross-linking agent used, and are usually in the range of 20 ° C. to 160 ° C. for about 1 minute to 7 days.
  • the heating for drying the solvent may also serve as the heating for crosslinking.
  • the introduction of the crosslinked structure does not necessarily have to be accompanied by heating.
  • the pressure-sensitive adhesive layer of the second form preferably has the same thickness, light transmittance, and shear storage elastic modulus as the pressure-sensitive adhesive layer of the first form. Since the pressure-sensitive adhesive layer of the second form is not photocured, it contains a photopolymerizable compound in an unreacted state. That is, the pressure-sensitive adhesive layer of the second form is a photocurable pressure-sensitive adhesive layer containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant.
  • the optical laminate having the photocurable pressure-sensitive adhesive layer of the second form can be photocured by irradiating with ultraviolet rays after being bonded to a display panel described later.
  • the adhesive force between the optical laminate and the display panel can be changed by photocuring. For example, since the adhesive layer before photo-curing has high flexibility, it is possible to fill the uneven shape and steps formed by the light emitting elements arranged on the display panel, and after photo-curing, the adhesive force to the display panel. And adhesion reliability can be improved.
  • Ultraviolet rays are used as the active rays for photocuring the pressure-sensitive adhesive layer of the second form. Similar to the pressure-sensitive adhesive layer of the first form, since the colorant has a higher transmittance of ultraviolet rays than visible light, it is possible to suppress curing inhibition during photo-curing even when the pressure-sensitive adhesive layer is thick.
  • the optical laminate having the pressure-sensitive adhesive layer of the third form is prepared by applying the solvent-type pressure-sensitive adhesive composition on a release film, removing the solvent by drying, and laminating it on the surface 1b of the base material 1. Can be done.
  • the optical laminate having the pressure-sensitive adhesive layer of the third form can also be prepared by applying the solvent-type pressure-sensitive adhesive composition on the surface 1b of the base material 1 and drying and removing the solvent.
  • the solvent is dried.
  • the heating and drying temperature is preferably 40 ° C. to 200 ° C., more preferably 50 ° C. to 180 ° C., and particularly preferably 70 ° C. to 170 ° C.
  • the drying time an appropriate time can be adopted as appropriate.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 10 seconds to 10 minutes.
  • heating may be performed if necessary.
  • the heating temperature and heating time may be appropriately set depending on the type of the cross-linking agent used, and are usually in the range of 20 ° C. to 160 ° C. for about 1 minute to 7 days.
  • the pressure-sensitive adhesive layer of the third form preferably has the same thickness, light transmittance, and shear storage elastic modulus as the pressure-sensitive adhesive layer of the first form.
  • the storage elastic modulus (G'25) of the pressure-sensitive adhesive layer at 25 ° C. is not particularly limited, but improves workability at room temperature. From the viewpoint, it is preferably 1 MPa or more, more preferably 1.5 MPa or more, more preferably 2 MPa or more, more preferably 2.5 MPa or more, more preferably 3 MPa or more, and from the viewpoint of improving the adhesive reliability at room temperature, 50 MPa. The following is preferable, more preferably 45 MPa or less, more preferably 40 MPa or less, still more preferably 35 MPa or less, and even more preferably 30 MPa or less.
  • the storage elasticity (G'50) of the pressure-sensitive adhesive layer at 50 ° C. is not particularly limited, but the step absorption in the region exceeding 50 ° C. 0.5 MPa or less, more preferably 0.45 MPa or less, more preferably 0.4 MPa or less, more preferably 0.35 MPa or less, more preferably 0.3 MPa or less, and 50 ° C. From the viewpoint of improving the handleability of the region exceeding the range, 0.0001 MPa or more is preferable, 0.0005 MPa or more is more preferable, 0.001 MPa or more is more preferable, 0.005 MPa or more is more preferable, and 0.01 MPa or more is more preferable. be.
  • the ratio of the storage elastic modulus at 25 ° C. to the storage elastic modulus at 50 ° C. (G'25 / G'50) of the pressure-sensitive adhesive layer is particularly high.
  • 3 or more is preferable, 5 or more is more preferable, 10 or more is more preferable, and 15 or more is further preferable.
  • the storage elastic modulus at 25 ° C. (G'25), the storage elastic modulus at 50 ° C. (G'25), and their ratio (G'25 / G'50) are measured by dynamic viscoelasticity measurement. Is to be done.
  • An optical laminate having an adhesive layer containing a colorant has light absorption in visible light.
  • the optical laminate of the present embodiment preferably has a maximum transmittance at 350 nm to 450 nm.
  • the total light transmittance of the optical laminate of the present embodiment is, for example, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5 It may be less than or equal to%.
  • the optical laminate of the present embodiment may be provided with a release film on the adhesive layer until use. Further, in the optical laminate of the present embodiment, a surface protective film may be laminated on the antireflection treatment and / or antiglare treatment surface 1a of the base material 1. The surface protective film formation is suitable for preventing the adhesion of scratches and stains during the manufacture, transportation, and shipment of the optical laminate and the optical products containing the same.
  • the optical laminate of the present embodiment includes other layers, for example, groups other than the base material 1, as long as the effects of the present invention are not impaired.
  • a material, a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer 2, an intermediate layer, an undercoat layer, and the like may be provided on the surface or between arbitrary layers.
  • ⁇ Self-luminous display device In the self-luminous display device according to the second aspect of the present invention, a small number of light emitting elements are arranged on a wiring substrate, and each light emitting element is selectively emitted by a light emitting control means connected thereto.
  • a display device capable of directly displaying visual information such as characters, images, and moving images on a display screen by blinking each light emitting element.
  • Examples of the self-luminous display device include a mini / micro LED display device and an organic EL (electroluminescence) display device.
  • the optical laminate according to the first aspect of the present invention is particularly preferably used for manufacturing a mini / micro LED display device.
  • FIG. 3 is a schematic view (cross-sectional view) showing an embodiment of a self-luminous display device (mini / micro LED display device) according to the second aspect of the present invention.
  • the mini / micro LED display device 20 according to the present embodiment includes a display panel in which a plurality of LED chips 6 are arranged on one side of a substrate 4, and an optical laminate 10 according to the first side surface of the present invention.
  • the surface on the display panel on which the LED chips 6 are arranged is laminated with the adhesive layer 2 of the optical laminate 10.
  • a metal wiring layer 5 for sending a light emission control signal to each LED chip 6 is laminated on the substrate 4 of the display panel.
  • the LED chips 6 that emit light of each color of red (R), green (G), and blue (B) are alternately arranged on the substrate 4 of the display panel via the metal wiring layer 5.
  • the metal wiring layer 5 is formed of a metal such as copper, and reflects the light emitted from each LED chip 6 to reduce the visibility of the image. Further, the light emitted from each LED chip 6 of each color of RGB is mixed, and the contrast is lowered.
  • each LED chip 6 arranged on the display panel is tightly sealed by the adhesive layer 2. Since the pressure-sensitive adhesive layer 2 contains a colorant, it has sufficient light-shielding properties in the visible light region. Since each LED chip 6 is sealed by the adhesive layer 2 having a high light-shielding property, reflection by the metal wiring layer 5 can be prevented. Further, since the adhesive layer 2 also seals between the LED chips 6 without gaps, it is possible to prevent color mixing between the LED chips 6 and improve the contrast.
  • the reflectance of the base material surface 1a in the visible light region of 5 ° specular reflection is preferably 50% or less, and is preferably 30%. It is more preferably% or less, further preferably 15% or less, and particularly preferably 10% or less.
  • the glossiness (based on JIS Z 8741-1997) of the base material surface 1a when the metal adherend is laminated on the pressure-sensitive adhesive layer of the optical laminate of the present embodiment is preferably 100% or less, preferably 80%. It is more preferably less than or equal to, more preferably 60% or less, and particularly preferably 50% or less.
  • the metal adherend copper, aluminum, stainless steel, or the like can be used.
  • FIG. 4 is a schematic view (cross-sectional view) showing another embodiment of the self-luminous display device (mini / micro LED display device) according to the second aspect of the present invention.
  • the mini / micro LED display device 21 according to the present embodiment is the same as FIG. 3 except that the anti-glare layer 3a is formed on the surface 1a of the base material 1.
  • the average inclination angle ⁇ a (°) of the anti-glare layer 3a of the mini / micro LED display device 21 according to the present embodiment is the same as described above.
  • the self-luminous display device of the present embodiment may include an optical member other than the display panel and the optical laminate.
  • the optical member is not particularly limited, and examples thereof include a polarizing plate, a retardation plate, an antireflection film, a viewing angle adjusting film, and an optical compensation film.
  • the optical member shall also include a member (design film, decorative film, surface protective plate, etc.) that plays a role of decoration and protection while maintaining the visibility of the display device and the input device.
  • the mini / micro LED display device of the present embodiment is manufactured by laminating a display panel in which a plurality of LED chips are arranged on one side of a substrate and an adhesive layer of an optical laminate according to the first side surface of the present invention. be able to.
  • the optical laminate having the display panel and the adhesive layer of the first form can be attached by laminating under heating and / or pressure.
  • the optical laminate having the display panel and the adhesive layer of the second form can be carried out by laminating under heating and / or pressurization and then performing photocuring.
  • the photo-curing can be performed in the same manner as the photo-curing that forms the pressure-sensitive adhesive layer of the first form.
  • the pressure-sensitive adhesive layer is formed from a solvent-type pressure-sensitive adhesive composition containing (meth) acrylic block copolymer A
  • the pressure-sensitive adhesive layer becomes highly fluid, sufficiently follows the steps of the LED chips arranged on the substrate, and can adhere to each other without gaps.
  • the heating is carried out at 50 ° C. or higher, preferably 60 ° C. or higher, and more preferably 70 ° C. or higher.
  • the pressurization is not particularly limited, but is performed at, for example, 1.5 atm or more, preferably 2 atm or more, and more preferably 3 atm or more.
  • the heating and pressurizing can be performed using, for example, an autoclave or the like. After the mini / micro LED display device manufactured by this method is returned to room temperature (25 ° C.), the storage elastic modulus of the pressure-sensitive adhesive layer is increased, and the processability and adhesive reliability are improved.
  • the surface shape of the anti-glare layer was measured under the condition of a cutoff value of 0.8 mm, and an average inclination angle ⁇ a was obtained.
  • the high-precision fine shape measuring instrument automatically calculates the average inclination angle ⁇ a.
  • the average inclination angle ⁇ a is based on JIS B 0601 (1994 edition).
  • a haze meter manufactured by Murakami Color Science Laboratory Co., Ltd., trade name "HN-150" was installed so that light was incident from the anti-glare layer surface of the anti-glare film, and the haze value was measured.
  • a light diffusing element forming material (coating liquid) was prepared by diluting this mixture with a mixed solvent of toluene / ethyl acetate (weight ratio 90/10) so that the solid content concentration was 30% by weight.
  • An anti-glare layer forming material (coating liquid) is applied to one side of a triacetyl cellulose (TAC) film (manufactured by FUJIFILM Corporation, product name "TG60UL", thickness: 60 ⁇ m) that can function as a protective layer using a bar coater.
  • TAC triacetyl cellulose
  • the transparent TAC film base material on which this coating film was formed was transported to a drying step. In the drying step, the coating film was dried by heating at 110 ° C. for 1 minute.
  • an ultraviolet ray having an integrated light amount of 300 mJ / cm 2 is irradiated with a high-pressure mercury lamp, and the coating film is cured to form a light diffusing element having a thickness of 5.0 ⁇ m on one side of the TAC film to obtain an antiglare film 1. rice field.
  • the haze value of the anti-glare film 1 was 42%.
  • the ⁇ a (°) of the anti-glare layer of the anti-glare film 1 was 1.22.
  • a coating film of the anti-glare layer forming material was formed on one side of the transparent plastic film base material using a bar coater. Then, the transparent plastic film base material on which this coating film was formed was transported to a drying step. In the drying step, the coating film was dried by heating at 110 ° C. for 1 minute. Then, an ultraviolet ray having an integrated light intensity of 300 mJ / cm 2 was irradiated with a high-pressure mercury lamp, and the coating film was cured to form an anti-glare layer having a thickness of 5.0 ⁇ m to obtain an anti-glare film 3. The ⁇ a (°) of the anti-glare layer of the anti-glare film 3 was 3.5.
  • Production example 6 (Preparation of black adhesive composition) 9 parts by weight of 2-hydroxyethyl acrylate (HEA) and 8 parts by weight of 4-hydroxybutyl acrylate (4-HBA) in the acrylic prepolymer solution obtained in Production Example 5 (the total amount of the prepolymer is 100 parts by weight).
  • HOA 2-hydroxyethyl acrylate
  • 4-HBA 4-hydroxybutyl acrylate
  • photopolymerizable pressure-sensitive adhesive composition solution obtained above, 0.2 part by weight of a photopolymerization initiator (manufactured by BASF, trade name “Irgacure 651”) and a black pigment dispersion (manufactured by Tokushiki Co., Ltd., A photopolymerizable black pressure-sensitive adhesive composition solution was prepared by adding 4 parts by weight (trade name “Tokushiki 9050 Black”).
  • Production example 7 (Preparation of adhesive composition) 9 parts by weight of 2-hydroxyethyl acrylate (HEA) and 8 parts by weight of 4-hydroxybutyl acrylate (4-HBA) in the acrylic prepolymer solution obtained in Production Example 5 (the total amount of the prepolymer is 100 parts by weight). , 0.12 parts by weight of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Kogyo Kagaku, trade name "KAYARAD DPHA”) as a polyfunctional monomer, and 0.35 parts by weight of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent. was added to prepare a photopolymerizable pressure-sensitive adhesive composition solution.
  • HOA 2-hydroxyethyl acrylate
  • 4-HBA 4-hydroxybutyl acrylate
  • Production Example 8 (Preparation of adhesive sheet)
  • the black pressure-sensitive adhesive composition solution prepared in Production Example 6 is cured on the peeling surface of a release film R1 (manufactured by Mitsubishi Resin Co., Ltd., trade name "MRF # 38") having a thickness of 38 ⁇ m in which one side of the polyester film is a peeling surface. After that, the film was applied so as to have a thickness of 100 ⁇ m, and the polyester film was covered with a release film R2 (MRE # 38 manufactured by Mitsubishi Resin Co., Ltd.) having a release surface on one side to block air.
  • MRF # 38 manufactured by Mitsubishi Resin Co., Ltd.
  • Ultraviolet rays were irradiated from one side of this laminate using a black light (manufactured by Toshiba Corporation, trade name "FL15BL") under the conditions of an illuminance of 5 mW / cm 2 and an integrated light intensity of 1300 mJ / cm 2.
  • a pressure-sensitive adhesive sheet 1 having a thickness of 100 ⁇ m in which the photocrosslinkable pressure-sensitive adhesive, which is a cured product of the black pressure-sensitive adhesive composition, was sandwiched between the release films R1 and R2 was obtained in the form of a base material-less pressure-sensitive adhesive sheet.
  • the illuminance value of the black light is a value measured by an industrial UV checker (manufactured by Topcon Corporation, trade name: UVR-T1, light receiving unit model UD-T36) having a peak sensitivity wavelength of about 350 nm.
  • an industrial UV checker manufactured by Topcon Corporation, trade name: UVR-T1, light receiving unit model UD-T36 having a peak sensitivity wavelength of about 350 nm.
  • Production Example 10 (Preparation of adhesive sheet)
  • the photocrosslinkable pressure-sensitive adhesive which is a cured product of the pressure-sensitive adhesive composition, was sandwiched between the release films R1 and R2 in the same manner as in Production Example 8 except that the pressure-sensitive adhesive composition solution prepared in Production Example 7 was used.
  • a pressure-sensitive adhesive sheet 3 having a thickness of 50 ⁇ m was obtained in the form of a base material-less pressure-sensitive adhesive sheet.
  • Examples 5-8 Preparation of optical laminate
  • An optical laminate composed of antiglare films 1 to 4 / adhesive sheet 2 / release film was obtained in the same manner as in Examples 1 to 4 except that the adhesive sheet 2 obtained in Production Example 9 was used.
  • Comparative Examples 1 to 4 (Preparation of optical laminate) An optical laminate composed of antiglare films 1 to 4 / adhesive sheet 3 / release film was obtained in the same manner as in Examples 1 to 4 except that the adhesive sheet 3 obtained in Production Example 10 was used.
  • Comparative Example 5 (Preparation of optical laminate) From the TAC film / adhesive sheet 1 / release film in the same manner as in Examples 1 to 4 except that the TAC film (manufactured by Konica Minolta Co., Ltd., trade name "KC4UY”) was used instead of the anti-glare film. An optical laminate was obtained.
  • Comparative Example 6 (Preparation of optical laminate) From the TAC film / adhesive sheet 2 / release film in the same manner as in Examples 5 to 8 except that the TAC film (manufactured by Konica Minolta Co., Ltd., trade name "KC4UY”) was used instead of the anti-glare film. An optical laminate was obtained.
  • Comparative Example 7 (Preparation of optical laminate) From the TAC film / adhesive sheet 3 / release film in the same manner as in Comparative Examples 1 to 4 except that the TAC film (manufactured by Konica Minolta Co., Ltd., trade name "KC4UY”) was used instead of the anti-glare film. An optical laminate was obtained.
  • a plate was prepared by pasting an aluminum foil on a black acrylic plate and laminating it.
  • the adhesive surface exposed by peeling off the release film of the optical laminate obtained in the above Examples and Comparative Examples was laminated on the aluminum foil side of the above plate to prepare a sample.
  • the obtained sample was placed on a spectrophotometer U4100 (manufactured by Hitachi High-Technology Co., Ltd.) with an antiglare film / TAC film on the light source side, and the reflectance (%) in the visible light region of 5 ° specular reflection was measured.
  • the obtained sample was transferred to a gloss meter (manufactured by Murakami Color Chemistry Laboratory, trade name "GM-26 PRO") by the method specified in JIS Z8741-1997, and an antiglare film / TAC film was placed on the light source side. It was installed and the glossiness (%) was measured.
  • GM-26 PRO Murakami Color Chemistry Laboratory
  • the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed of a photocurable pressure-sensitive adhesive composition containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant.
  • the optical laminate according to the description.
  • the anti-glare layer is formed by using an anti-glare layer forming material containing a resin, particles and a thixotropy-imparting agent.
  • the optical laminate according to Appendix 13 wherein the anti-glare layer has an agglomerated portion that forms a convex portion on the surface of the anti-glare layer by aggregating the particles and the thixotropy-imparting agent.
  • [Appendix 15] The optical laminate according to Appendix 14, wherein the average inclination angle ⁇ a (°) is in the range of 0.1 to 5.0 in the convex portion on the surface of the antiglare layer.
  • [Supplementary Note 16] The optical laminate according to any one of Supplementary note 1 to 15, wherein a surface protective film is laminated on the antireflection-treated and / or anti-glare-treated surface of the base material.
  • Appendix 17 A display panel in which a plurality of light emitting elements are arranged on one side of a substrate, and A self-luminous display device including the optical laminate according to any one of Supplementary Notes 1 to 16.
  • Appendix 18 The self-luminous display device according to Appendix 17, wherein the display panel is an LED panel in which a plurality of LED chips are arranged on one side of a substrate.
  • optical pressure-sensitive adhesive composition and the optical laminate of the present invention are suitable for sealing the light emitting element of a self-luminous display device such as a mini / micro LED.

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Abstract

Le but de la présente invention est de parvenir à réduire le nombre d'étapes et les éléments nécessaires lors des étapes de production de dispositifs d'affichage auto-luminescents, tels que des dispositifs d'affichage à mini/micro-diodes électroluminescentes (LED) présentant une fonction antireflet et/ou anti-éblouissement améliorée, ainsi qu'un contraste amélioré. Ce produit optique multicouche 10 comprend un support 1 et une couche adhésive autocollante 2 contenant un colorant. Une surface 1a du support 1 a subi un traitement antireflet et/ou anti-éblouissement 3. Le traitement antireflet et/ou anti-éblouissement 3 consiste, de préférence, en une couche anti-éblouissement. Dans ce produit optique multicouche 10, la couche adhésive autocollante 2 a été superposée sur la surface 1b du support 1 qui n'a pas reçu le traitement antireflet et/ou anti-éblouissement.
PCT/JP2021/013066 2020-03-31 2021-03-26 Produit optique multicouche WO2021200733A1 (fr)

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JP7369761B2 (ja) * 2021-12-24 2023-10-26 日東電工株式会社 光半導体素子封止用シート
CN116031351B (zh) * 2022-03-25 2024-03-08 日东电工株式会社 光半导体元件密封用片和显示体

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