WO2023276654A1 - Film optique avec film de recouvrement - Google Patents

Film optique avec film de recouvrement Download PDF

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Publication number
WO2023276654A1
WO2023276654A1 PCT/JP2022/023779 JP2022023779W WO2023276654A1 WO 2023276654 A1 WO2023276654 A1 WO 2023276654A1 JP 2022023779 W JP2022023779 W JP 2022023779W WO 2023276654 A1 WO2023276654 A1 WO 2023276654A1
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Prior art keywords
film
adhesive layer
cover film
less
pressure
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PCT/JP2022/023779
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English (en)
Japanese (ja)
Inventor
大生 三浦
美菜子 野田
翔 寳田
Original Assignee
日東電工株式会社
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Priority to CN202280046835.3A priority Critical patent/CN117580709A/zh
Priority to KR1020237044074A priority patent/KR20240027606A/ko
Publication of WO2023276654A1 publication Critical patent/WO2023276654A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering

Definitions

  • the present invention relates to an optical film with a cover film.
  • a display panel has a laminated structure including, for example, a pixel panel, a touch panel, and a transparent cover film.
  • An optical film having a predetermined optical function is provided in the laminated structure of the display panel.
  • optical films include film-like polarizing films and retardation films.
  • the optical film is produced, for example, as an optical film with an adhesive layer in which an adhesive layer is provided on each of both surfaces of the optical film.
  • the optical film with a pressure-sensitive adhesive layer is manufactured as an optical film with a cover film in which the pressure-sensitive adhesive layer is covered with a cover film, for example.
  • Such an optical film with a cover film is described, for example, in Patent Document 1 below.
  • Foldable display panels require that each element in the laminate structure be thin and flexible.
  • Optical films for foldable display panels are also required to be thin and flexible.
  • the thinner the optical film with an adhesive layer the more the load for starting peeling when one cover film is peeled from the adhesive layer at the end of the optical film. It tends to cause significant deformation of the optical film. Therefore, when one cover film is peeled off, the other cover film is likely to be peeled off. In addition, cracks are likely to occur at the edges of the optical film when one of the cover films is peeled off.
  • optical films with pressure-sensitive adhesive layers for foldable display panels are required to exhibit sufficient adhesion reliability of the pressure-sensitive adhesive layer to the optical film even when folded.
  • the pressure-sensitive adhesive layer tends to peel off from the optical film at the bending portion of the device. This is because when the device is folded, stress such as shear stress locally acts on the pressure-sensitive adhesive layer at the folded portion. Occurrence of the peeling causes malfunction of the device and is not preferable.
  • the present invention is suitable for peeling one cover film from a thin optical film with an adhesive layer while suppressing peeling of the other cover film and cracking at the edge of the optical film, and is suitable for peeling the optical film during bending.
  • the present invention [1] provides a cover film-attached optical film comprising a first cover film, a first pressure-sensitive adhesive layer, an optical film, a second pressure-sensitive adhesive layer, and a second cover film in this order in the thickness direction.
  • the second pressure-sensitive adhesive layer has a third thickness of 5 ⁇ m or more and 100 ⁇ m or less, and the second pressure-sensitive adhesive layer has a thickness of 20 kPa or more and 100 kPa at 25 ° C. having the following second shear storage modulus, the first cover film having a fourth thickness of 40 ⁇ m or more and 80 ⁇ m or less, the second cover film having a fifth thickness of 40 ⁇ m or more and 80 ⁇ m or less, The ratio of the fourth thickness to the fifth thickness is 1 or less, and the second cover film has a first peel force for peeling the first cover film from the first pressure-sensitive adhesive layer. It includes an optical film with a cover film, wherein the ratio to the second peeling force for peeling from the two pressure-sensitive adhesive layers is 0.9 or less, and the first peeling force is 10 gf/25 mm or less.
  • the present invention [2] includes the optical film with a cover film according to [1] above, wherein the ratio of the third thickness to the third thickness is 0.1 or more and 2 or less.
  • the present invention [3] includes the optical film with a cover film according to [1] or [2] above, wherein the ratio of the first shear storage modulus to the second shear storage modulus is 0.5 or more. .
  • the present invention [4] is an optical film with a cover film, comprising a first cover film, a first pressure-sensitive adhesive layer, an optical film, a second pressure-sensitive adhesive layer, and a second cover film in this order in the thickness direction.
  • the second pressure-sensitive adhesive layer has a first shear storage modulus of 20 kPa or more and 100 kPa or less at , the second pressure-sensitive adhesive layer has a third thickness of 5 ⁇ m or more and 30 ⁇ m or less, and the second pressure-sensitive adhesive layer has a viscosity of 150 kPa or more at 25 ° C.
  • the first cover film has a fourth thickness of 40 ⁇ m or more and 80 ⁇ m or less
  • the second cover film has a fifth thickness of 40 ⁇ m or more and 80 ⁇ m or less
  • the 5 The ratio of the fourth thickness to the thickness is 1 or more
  • the second pressure-sensitive adhesive layer and the second cover film form a second pressure-sensitive adhesive layer-attached second cover film
  • the first cover film The ratio of the first peel force for peeling from the first pressure-sensitive adhesive layer to the second peel force for peeling the second cover film with the second pressure-sensitive adhesive layer from the optical film is 0.9 or less. and wherein the first peel force is 10 gf/25 mm or less.
  • the present invention [5] includes the optical film with a cover film according to [4] above, wherein the ratio of the second thickness to the third thickness is 1 or more and 100 or less.
  • the present invention [6] includes the optical film with a cover film according to [4] or [5] above, wherein the ratio of the first shear storage modulus to the second shear storage modulus is 0.5 or less. .
  • the present invention [7] includes the optical film with a cover film according to any one of [1] to [6] above, wherein the optical film is a polarizing film.
  • the present invention [8] is the optical film with a cover film according to any one of [1] to [7] above, wherein the polarizing film has a third shear storage elastic modulus of 1.0 ⁇ 10 6 kPa or more. including.
  • the optical film with a cover film of the present invention is suitable for peeling one cover film from a thin optical film with an adhesive layer while suppressing peeling of the other cover film and cracking at the edge of the optical film. .
  • the optical film with a cover film of the present invention is suitable for suppressing peeling of the adhesive layer from the optical film during folding.
  • FIG. 1 represents the first peeling step of peeling the first cover film
  • FIG. 2B represents the first bonding step of bonding the optical film and the first adherend via the first pressure-sensitive adhesive layer
  • 2C represents a second peeling step of peeling the second cover film
  • FIG. 2D represents a second bonding step of bonding the optical film and the second adherend via the second adhesive layer.
  • 2nd Embodiment of the optical film with a cover film of this invention It is a cross-sectional schematic diagram of 2nd Embodiment of the optical film with a cover film of this invention.
  • FIG. 4A shows a peeling step of peeling the first cover film
  • FIG. 4B shows a bonding step of bonding the optical film and the first adherend via the first pressure-sensitive adhesive layer.
  • Optical film X1 as a first embodiment of the optical film with a cover film of the present invention comprises, as shown in FIG. (second adhesive layer), cover film 40 (first cover film), and cover film 50 (second cover film).
  • the optical film X1 has a sheet shape with a predetermined thickness and spreads in a direction orthogonal to the thickness direction T (surface direction).
  • the optical film X1 includes a cover film 50, an adhesive layer 30, an optical film 10, an adhesive layer 20, and a cover film 40 in the thickness direction T in this order.
  • the optical film 10 is a functional optical film in this embodiment.
  • Functional optical films include, for example, film-like polarizing plates (polarizing films) and retardation films.
  • the optical film 10 has a first surface 11 as one surface in the thickness direction and a second surface 12 opposite to the first surface 11 .
  • the adhesive layer 20 adheres to the first surface 11 and has an adhesive surface 21 (first adhesive surface) on the side opposite to the optical film 10 .
  • the adhesive layer 30 adheres to the second surface 12 and has an adhesive surface 31 (second adhesive surface) on the side opposite to the optical film 10 .
  • the optical film 10 and the pressure-sensitive adhesive layers 20 and 30 form the pressure-sensitive adhesive layer-attached optical film Y1.
  • the pressure-sensitive adhesive layer-attached optical film Y1 is an optical film to be incorporated into the laminated structure of the foldable display panel.
  • the optical film X1 includes such an optical film Y1 with an adhesive layer and cover films 40 and 50.
  • the cover film 40 is releasably arranged on the adhesive surface 21 of the optical film Y1 with an adhesive layer.
  • the cover film 50 is releasably arranged on the adhesive surface 31 .
  • the cover films 40, 50 have flexibility.
  • Such an optical film X1 is used as a supply material for the pressure-sensitive adhesive layer-attached optical film Y1 incorporated in the laminated structure of the foldable display panel in the manufacturing process of the same panel.
  • the cover films 40 and 50 are each peeled off from the pressure-sensitive adhesive layer-attached optical film Y1 at a predetermined timing during the manufacturing process of the foldable display panel.
  • the cover film 40 is peeled off before the cover film 50 is removed. That is, in the optical film X1, the cover film 40 is the pre-release film and the cover film 50 is the post-release film.
  • the optical film 10 has a thickness H1 (first thickness) of 100 ⁇ m or less.
  • the thickness H1 is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 40 ⁇ m or less.
  • the thickness H1 is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
  • the adhesive layer 20 has a thickness H2 (second thickness) of 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness H2 is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
  • the thickness H2 is preferably 90 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 70 ⁇ m or less.
  • the adhesive layer 20 has a shear storage modulus M1 (first shear storage modulus) of 20 kPa or more and 100 kPa or less at 25°C.
  • the shear storage elastic modulus M1 is preferably 30 kPa or more, more preferably 40 kPa or more, It is more preferably 45 kPa or more, preferably 90 kPa or less, more preferably 80 kPa or less, and still more preferably 75 kPa or less.
  • the shear storage modulus M1 can be measured with a dynamic viscoelasticity measuring device.
  • the measurement mode is the torsion mode
  • the measurement temperature range is -50 ° C. to 150 ° C.
  • the temperature increase rate is 5 ° C./min
  • the frequency is 1 Hz (also in the measurement of the shear storage elastic modulus M2 described later) similar).
  • Methods for adjusting the shear storage modulus M1 include, for example, selection of the type of base polymer for the pressure-sensitive adhesive layer 20, adjustment of the molecular weight, adjustment of the compounding amount, and selection of the type of cross-linking agent that cross-links the base polymer. Selection and adjustment of compounding amount are included.
  • the adhesive layer 30 has a thickness H3 (third thickness) of 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness H3 is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
  • the thickness H3 is preferably 90 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 70 ⁇ m or less.
  • the adhesive layer 30 has a shear storage modulus M2 (second shear storage modulus) of 20 kPa or more and 100 kPa or less at 25°C.
  • the shear storage elastic modulus M2 is preferably 30 kPa or more, more preferably 40 kPa or more, It is more preferably 45 kPa or more, preferably 90 kPa or less, more preferably 80 kPa or less, and still more preferably 75 kPa or less.
  • Methods for adjusting the shear storage modulus M2 include, for example, selection of the type of base polymer for the adhesive layer 30, adjustment of the molecular weight, adjustment of the compounding amount, and selection of the type of cross-linking agent that cross-links the base polymer. Selection and adjustment of compounding amount are included.
  • the cover film 40 has a thickness H4 (fourth thickness) of 40 ⁇ m or more and 80 ⁇ m or less. From the viewpoint of ensuring the flexibility of the cover film 40, the thickness H4 is preferably 75 ⁇ m or less, more preferably 70 ⁇ m or less. From the viewpoint of strength of the cover film 40, the thickness H4 is preferably 45 ⁇ m or more, more preferably 48 ⁇ m or more, and even more preferably 50 ⁇ m or more.
  • the cover film 50 has a thickness H5 (fifth thickness) of 40 ⁇ m or more and 80 ⁇ m or less.
  • the thickness H5 is preferably 75 ⁇ m or less, more preferably 70 ⁇ m or less, from the viewpoint of ensuring the flexibility of the cover film 50 and from the viewpoint of suppressing cracks at the ends of the optical film 10 when the cover film is peeled off.
  • the thickness H5 is preferably 45 ⁇ m or more, more preferably 48 ⁇ m or more, and even more preferably 50 ⁇ m or more.
  • the ratio (H4/H5) of the thickness H4 to the thickness H5 is 1 or less in this embodiment. From the viewpoint of suppressing peeling of the cover film 50 when the cover film 40 is peeled off, the ratio (H4/H5) is preferably 0.9 or less, more preferably 0.8 or less. The ratio (H4/H5) is, for example, 0.1 or more.
  • the ratio (F1 /F2) is 0.9 or less. From the viewpoint of suppressing peeling of the cover film 50 when the cover film 40 is peeled off, the ratio (F1/F2) is preferably 0.8 or less, more preferably 0.7 or less, and even more preferably 0.6 or less. The ratio (F1/F2) is, for example, 0.1 or more.
  • the peel force F1 and the peel force F2 are each measured in a peel test under conditions of a measurement temperature of 25° C., a peel angle of 180°, and a tensile speed of 300 mm/min.
  • the peeling force F1 is 10 gf/25 mm or less. From the viewpoint of ensuring a good peeling operation when peeling the cover film 40 from the adhesive layer 20, the peeling force F1 is preferably 7 gf/25 mm or less, more preferably 5 gf/25 mm or less, and even more preferably 3 gf/25 mm or less. Particularly preferably, it is 2.5 gf/25 mm or less. From the viewpoint of suppressing unintended peeling of the cover film 40 from the adhesive layer 20, the peel force F1 is preferably 0.1 gf/25 mm or more, more preferably 0.3 gf/25 mm or more, and still more preferably 0.5 gf/25 mm or more. 25 mm or more.
  • Methods for adjusting the peel force F1 include, for example, selection of the type of base polymer for the adhesive layer 20, adjustment of the molecular weight, and adjustment of the blending amount.
  • Selection of the type of base polymer includes selection of the type (structure) of the main chain in the base polymer, and selection of the type and adjustment of the amount of functional groups (the selection of the type of base polymer described later also includes similar).
  • Methods for adjusting the peeling force F1 include selection of types of components other than the base polymer in the pressure-sensitive adhesive layer 20 and adjustment of the compounding amounts of the components. Such components include crosslinkers, silane coupling agents, and oligomers.
  • the thickness H1 of the optical film 10 is 100 ⁇ m or less
  • the thickness H2 of the adhesive layer 20 is 5 ⁇ m or more and 100 ⁇ m or less
  • the thickness H3 of the adhesive layer 30 is the adhesive layer 20 has a shear storage modulus M1 of 20 kPa or more and 100 kPa or less
  • the adhesive layer 30 has a shear storage modulus M2 of 20 kPa or more and 100 kPa or less
  • the cover film 40 has a thickness H4.
  • Such an optical film X1 is obtained by removing the cover film 50 from the optical film Y1 (the thin optical film 10 with the pressure-sensitive adhesive layers 20 and 30) and the edge of the optical film 10, as shown in Examples and Comparative Examples below. It is suitable for peeling off the cover film 40 while suppressing cracks in the film.
  • the ratio of the thickness H2 of the adhesive layer 20 to the thickness H3 of the adhesive layer 30 depends on the ease of folding (bendability) of the optical film X1 and the adherence of the adhesive layer. From the viewpoint of followability (step absorbability) when there is a step on the body surface, it is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. From the viewpoint of bendability and step absorbability, the ratio (H2/H3) is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.2 or less.
  • the ratio (M1/M2) of the shear storage modulus M1 of the adhesive layer 20 to the shear storage modulus M2 of the adhesive layer 30 is preferably 0.5 or more, more preferably It is 1 or more, more preferably 1.3 or more, and particularly preferably 1.5 or more.
  • the ratio (M1/M2) is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less, from the viewpoint of bendability and step absorbability.
  • the peel force F2 of the cover film 50 is preferably 0.11 gf/25 mm or more, more preferably 0.33 gf/25 mm or more, and still more preferably 0.55gf/25mm or more.
  • the peeling force F2 is preferably 10 gf/25 mm or less, more preferably 8 gf/25 mm or less, and even more preferably 6 gf/25 mm or less. Particularly preferably, it is 5 gf/25 mm or less.
  • Methods for adjusting the peel force F2 include, for example, selection of the type of base polymer for the pressure-sensitive adhesive layer 30, adjustment of the molecular weight, and adjustment of the blending amount.
  • Methods for adjusting the peel force F2 include selection of types of components other than the base polymer in the pressure-sensitive adhesive layer 30 and adjustment of the compounding amounts of the components. Such components include crosslinkers, silane coupling agents, and oligomers.
  • the polarizing film includes, for example, a polarizing film including a polarizer and a transparent protective film attached to one or both sides of the polarizer.
  • Polarizers include, for example, uniaxially stretched hydrophilic polymer films to which a dichroic substance is adsorbed, and oriented polyene films.
  • Hydrophilic polymer films include, for example, polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and partially saponified ethylene-vinyl acetate copolymer films.
  • Dichroic substances include, for example, iodine and dichroic dyes.
  • Examples of oriented polyene films include dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride.
  • a thin polarizer with a thickness of 10 ⁇ m or less may be used as the polarizer.
  • Examples of thin polarizers include polarizers described in JP-A-51-069644, JP-A-2000-338329, WO2010/100917, Japanese Patent No. 4691205, and Japanese Patent No. 4751481. .
  • the transparent protective film a film that is excellent in transparency, mechanical strength, thermal stability, water barrier properties, and optical isotropy is preferred.
  • Materials for such transparent protective films include, for example, cellulose resins, cyclic polyolefin resins, acrylic resins, phenylmaleimide resins, and polycarbonate resins.
  • the adhesive layer 20 is a pressure-sensitive adhesive layer formed from the first adhesive composition.
  • the adhesive layer 20 has transparency (visible light transmittance).
  • the first PSA composition contains at least a base polymer.
  • the base polymer is an adhesive component that makes the adhesive layer 20 exhibit adhesiveness.
  • Base polymers include, for example, acrylic polymers, silicone polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyvinyl ether polymers, vinyl acetate/vinyl chloride copolymers, modified polyolefin polymers, epoxy polymers, fluoropolymers, and rubber polymers.
  • the base polymer may be used alone or in combination of two or more. From the viewpoint of ensuring good transparency and adhesiveness in the pressure-sensitive adhesive layer 20, an acrylic polymer is preferably used as the base polymer.
  • the acrylic polymer is a copolymer of monomer components containing 50% by mass or more of (meth)acrylic acid alkyl ester.
  • (Meth)acrylic acid means acrylic acid and/or methacrylic acid.
  • the (meth)acrylic acid alkyl ester a (meth)acrylic acid alkyl ester in which the alkyl group has 1 to 20 carbon atoms is preferably used.
  • the (meth)acrylic acid alkyl ester may have a linear or branched alkyl group, or may have a cyclic alkyl group such as an alicyclic alkyl group.
  • Examples of (meth)acrylic acid alkyl esters having a linear or branched alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate.
  • Examples of (meth)acrylic acid alkyl esters having an alicyclic alkyl group include (meth)acrylic acid cycloalkyl esters, (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring, and tricyclic (Meth)acrylic acid esters having the above aliphatic hydrocarbon ring can be mentioned.
  • Cycloalkyl (meth)acrylates include, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate.
  • Examples of (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring include isobornyl (meth)acrylate.
  • (Meth)acrylic esters having a tricyclic or higher aliphatic hydrocarbon ring include, for example, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate , 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.
  • an acrylate alkyl ester having an alkyl group having 3 to 15 carbon atoms is preferably used, and more preferably n-butyl acrylate, 2-ethylhexyl acrylate, and acrylic acid. At least one selected from the group consisting of dodecyl is used.
  • the ratio of the (meth)acrylic acid alkyl ester in the monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably from the viewpoint of appropriately expressing basic properties such as adhesiveness in the adhesive layer 20. is 70% by mass or more. The same ratio is, for example, 99% by mass or less.
  • the monomer component may contain a copolymerizable monomer that can be copolymerized with the (meth)acrylic acid alkyl ester.
  • copolymerizable monomers include monomers having a polar group.
  • Polar group-containing monomers include, for example, nitrogen atom-containing ring-containing monomers, hydroxy group-containing monomers, and carboxy group-containing monomers.
  • the polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing cross-linking points into the acrylic polymer and securing the cohesive strength of the acrylic polymer.
  • Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -vinylthiazole,
  • the ratio of the monomer having a nitrogen atom-containing ring in the monomer component is preferably 0.1 mass from the viewpoint of ensuring the cohesive force in the adhesive layer 20 and ensuring the adhesive strength of the adhesive layer 20 to the adherend. % or more, more preferably 0.3 mass % or more, and still more preferably 0.55 mass % or more.
  • the same ratio is preferably 30% by mass from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to compatibility between various additive components and the acrylic polymer in the adhesive layer 20). Below, more preferably 20% by mass or less.
  • hydroxy group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 4-hydroxybutyl meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • 4-hydroxybutyl (meth)acrylate is preferably used, and 4-hydroxybutyl acrylate is more preferably used.
  • the ratio of the hydroxy group-containing monomer in the monomer component is preferably 0.1% by mass or more, more preferably 0.5, from the viewpoint of introducing a crosslinked structure into the acrylic polymer and ensuring cohesive force in the pressure-sensitive adhesive layer 20. It is at least 0.8% by mass, more preferably at least 0.8% by mass. The same ratio is preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of adjusting the polarity of the acrylic polymer (related to compatibility between various additive components and the acrylic polymer in the pressure-sensitive adhesive layer 20). .
  • Carboxy group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • the ratio of the carboxyl group-containing monomer in the monomer component is preferable from the viewpoint of introducing a crosslinked structure into the acrylic polymer, ensuring cohesive force in the adhesive layer 20, and ensuring adhesion to the adherend in the adhesive layer 20. is 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more.
  • the same ratio is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoints of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of acid corrosion of the adherend.
  • the adhesive layer 20 preferably has a small acid content.
  • the acid content of the adhesive layer 20 is preferably small in order to suppress polyene formation of the polyvinyl alcohol polarizer due to the acid component.
  • the content of organic acid monomers (for example, (meth)acrylic acid and carboxyl group-containing monomers) in such an acid-free pressure-sensitive adhesive layer 20 is preferably 100 ppm or less, more preferably 70 ppm or less, and still more preferably 50 ppm or less. be.
  • the organic acid monomer content of the adhesive layer 20 is obtained by quantifying the acid monomer extracted into water by immersing the adhesive layer 20 in pure water and heating at 100° C. for 45 minutes by ion chromatography. is required by
  • the base polymer in the pressure-sensitive adhesive layer 20 does not substantially contain an organic acid monomer as a monomer component.
  • the ratio of the organic acid monomer in the monomer component is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.05% by mass. is 0% by mass.
  • the monomer component may contain other copolymerizable monomers.
  • Other copolymerizable monomers include, for example, acid anhydride monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, alkoxy group-containing monomers, and aromatic vinyl compounds. be done. These other copolymerizable monomers may be used alone, or two or more of them may be used in combination.
  • the base polymer has a crosslinked structure in this embodiment.
  • the base polymer having a functional group capable of reacting with the crosslinker and the crosslinker are blended in the first adhesive composition, and the base polymer and the crosslinker are added to the adhesive layer 20.
  • a base in which a polyfunctional monomer is included in the monomer components forming the base polymer and a branched structure (crosslinked structure) is introduced into the polymer chain by polymerization of the monomer components.
  • a method of forming a polymer (second method) is included. These methods may be used in combination.
  • cross-linking agent used in the first method examples include compounds that react with functional groups (hydroxy groups, carboxy groups, etc.) contained in the base polymer.
  • Such crosslinkers include, for example, isocyanate crosslinkers, peroxide crosslinkers, epoxy crosslinkers, oxazoline crosslinkers, aziridine crosslinkers, carbodiimide crosslinkers, and metal chelate crosslinkers.
  • the cross-linking agents may be used alone, or two or more of them may be used in combination.
  • an isocyanate cross-linking agent As the cross-linking agent, an isocyanate cross-linking agent, a peroxide cross-linking agent, and an epoxy cross-linking agent are preferably used because they are highly reactive with the hydroxy groups and carboxy groups in the base polymer and facilitate the introduction of a cross-linked structure. be done.
  • isocyanate cross-linking agents examples include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, isocyanates, and polymethylene polyphenyl isocyanates.
  • the isocyanate cross-linking agent also includes derivatives of these isocyanates.
  • isocyanate derivative examples include isocyanurate-modified products and polyol-modified products.
  • Commercially available isocyanate cross-linking agents include, for example, Coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh), Coronate HL (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Tosoh), Coronate HX (hexa isocyanurate of methylene diisocyanate, manufactured by Tosoh), and Takenate D110N (trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals).
  • Peroxide crosslinking agents include dibenzoyl peroxide, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t- butyl peroxyneodecanoate, t-hexyl peroxypivalate, and t-butyl peroxypivalate.
  • epoxy cross-linking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether. , diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.
  • An isocyanate cross-linking agent (especially a bifunctional isocyanate cross-linking agent) and a peroxide cross-linking agent are preferable from the viewpoint of ensuring appropriate flexibility (thus flexibility) of the pressure-sensitive adhesive layer 20 .
  • An isocyanate cross-linking agent (especially a trifunctional isocyanate cross-linking agent) is preferable from the viewpoint of ensuring the durability of the pressure-sensitive adhesive layer 20 .
  • difunctional isocyanate and peroxide crosslinkers form softer two-dimensional crosslinks, while trifunctional isocyanate crosslinkers form stronger three-dimensional crosslinks.
  • a trifunctional isocyanate cross-linking agent together with a peroxide cross-linking agent and/or a bifunctional isocyanate cross-linking agent.
  • the amount of the cross-linking agent is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and more preferably 100 parts by mass of the base polymer. is 0.07 parts by mass or more.
  • the amount of the cross-linking agent blended with respect to 100 parts by mass of the base polymer is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. is.
  • the monomer components may be polymerized at once or in multiple stages.
  • a monofunctional monomer for forming the base polymer is polymerized (prepolymerization), thereby containing a partially polymerized product (a mixture of a polymerized product with a low degree of polymerization and an unreacted monomer).
  • a prepolymer composition is prepared.
  • the partial polymer and the polyfunctional monomer are polymerized (main polymerization).
  • polyfunctional monomers examples include polyfunctional (meth)acrylates containing two or more ethylenically unsaturated double bonds in one molecule.
  • a polyfunctional acrylate is preferable from the viewpoint that a crosslinked structure can be introduced by active energy ray polymerization (photopolymerization).
  • Polyfunctional (meth)acrylates include bifunctional (meth)acrylates, trifunctional (meth)acrylates, and tetrafunctional or higher polyfunctional (meth)acrylates.
  • bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol di (meth)acrylate, 1,9-nonanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, dicyclopentenyl diacrylate, Examples include di(meth)acryloyl isocyanurate and alkylene oxide-modified bisphenol di(meth)acrylate.
  • trifunctional (meth)acrylates examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(acryloyloxyethyl) isocyanurate.
  • Tetrafunctional or higher polyfunctional (meth)acrylates include, for example, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, and alkyl-modified dipentaerythritol pentaacrylate. , and dipentaerythritol hexa(meth)acrylate.
  • the molecular weight of the polyfunctional monomer is preferably 1500 or less, more preferably 1000 or less.
  • the functional group equivalent (g/eq) of the polyfunctional monomer is preferably 50 or more, more preferably 70 or more, and even more preferably 80 or more.
  • the functional group equivalent weight is preferably 500 or less, more preferably 300 or less, still more preferably 200 or less.
  • the acrylic polymer can be formed by polymerizing the above monomer components.
  • Polymerization methods include, for example, solution polymerization, active energy ray polymerization (eg, UV polymerization), bulk polymerization, and emulsion polymerization.
  • Solution polymerization and UV polymerization are preferred from the viewpoints of transparency, water resistance, and cost of the pressure-sensitive adhesive layer 20 .
  • Ethyl acetate and toluene for example, are used as solvents for solution polymerization.
  • a polymerization initiator for example, a thermal polymerization initiator and a photopolymerization initiator are used as a polymerization initiator.
  • the amount of the polymerization initiator to be used is, for example, 0.05 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the monomer component.
  • Thermal polymerization initiators include, for example, azo polymerization initiators and peroxide polymerization initiators.
  • azo polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionate)dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2- imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, and 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride mentioned.
  • Peroxide polymerization initiators include, for example, dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxid
  • photopolymerization initiators examples include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, photoactive oxime photopolymerization initiators, and benzoin photopolymerization initiators.
  • Initiators include benzyl photoinitiators, benzophenone photoinitiators, ketal photoinitiators, thioxanthone photoinitiators, and acylphosphine oxide photoinitiators.
  • a chain transfer agent and/or a polymerization inhibitor may be used for the purpose of molecular weight adjustment.
  • Chain transfer agents include ⁇ -thioglycerol, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol, and ⁇ -methylstyrene. Dimers are included.
  • the molecular weight of the base polymer can be adjusted by adjusting the type and/or amount of the polymerization initiator.
  • the type and/or amount of the polymerization initiator For example, in radical polymerization, the larger the amount of the polymerization initiator, the higher the radical concentration in the reaction system, the higher the density of reaction initiation points, and the smaller the molecular weight of the base polymer formed.
  • the smaller the amount of the polymerization initiator the lower the density of the reaction initiation points, the easier it is for the polymer chain to extend, and the greater the molecular weight of the base polymer formed.
  • the weight-average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 500,000 or more, from the viewpoint of securing the cohesive force in the pressure-sensitive adhesive layer 20 .
  • the weight-average molecular weight is preferably 5 million or less, more preferably 3 million or less, still more preferably 2 million or less.
  • the weight average molecular weight of the acrylic polymer is calculated by measuring by gel permeation chromatography (GPC) and converting to polystyrene.
  • the glass transition temperature (Tg) of the base polymer is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower.
  • the glass transition temperature is, for example, ⁇ 80° C. or higher.
  • the glass transition temperature (Tg) of the base polymer the glass transition temperature (theoretical value) obtained based on the following Fox formula can be used.
  • the Fox equation is a relational expression between the glass transition temperature Tg of a polymer and the glass transition temperature Tgi of a homopolymer of monomers constituting the polymer.
  • Tg represents the glass transition temperature (° C.) of the polymer
  • Wi represents the weight fraction of the monomer i constituting the polymer
  • Tgi represents the glass transition of the homopolymer formed from the monomer i.
  • Literature values can be used for the glass transition temperature of homopolymers.
  • glass transition temperature of a homopolymer of a monomer can also be determined by the method specifically described in JP-A-2007-51271.
  • the first adhesive composition may contain one or more oligomers in addition to the base polymer.
  • an acrylic polymer is used as the base polymer, preferably an acrylic oligomer is used as the oligomer.
  • the acrylic oligomer is a copolymer of monomer components containing 50% by mass or more of (meth)acrylic acid alkyl ester, and has a weight average molecular weight of, for example, 1,000 or more and 30,000 or less.
  • the glass transition temperature of the acrylic oligomer is preferably 60°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 110°C or higher.
  • the glass transition temperature of the acrylic oligomer is, for example, 200° C. or lower, preferably 180° C. or lower, more preferably 160° C. or lower.
  • the combined use of a low-Tg acrylic polymer (base polymer) introduced with a cross-linked structure and a high-Tg acrylic oligomer can increase the adhesive strength of the pressure-sensitive adhesive layer 20, especially at high temperatures.
  • the glass transition temperature of the acrylic oligomer is calculated by the above Fox formula.
  • the acrylic oligomer having a glass transition temperature of 60° C. or higher is preferably a (meth)acrylic acid alkyl ester having a chain alkyl group (chain alkyl (meth)acrylate) and a (meth)acrylic acid having an alicyclic alkyl group. It is a polymer of a monomer component containing an acid alkyl ester (alicyclic alkyl (meth)acrylate). Specific examples of these (meth)acrylic acid alkyl esters include, for example, the (meth)acrylic acid alkyl esters described above as the monomer component of the acrylic polymer.
  • methyl methacrylate is preferable because it has a high glass transition temperature and excellent compatibility with the base polymer.
  • Preferred alicyclic alkyl (meth)acrylates are dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate. That is, the acrylic oligomer is a monomer component containing methyl methacrylate and at least one selected from the group consisting of dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. A coalescence is preferred.
  • the proportion of the alicyclic alkyl (meth)acrylate in the monomer component of the acrylic oligomer is preferably 10% by weight or more, more preferably 20% by weight or more, and even more preferably 30% by weight or more.
  • the same ratio is preferably 90% by weight or less, more preferably 80% by weight or less, and even more preferably 70% by weight or less.
  • the proportion of chain alkyl (meth)acrylate in the monomer component of the acrylic oligomer is preferably 90% by weight or less, more preferably 80% by weight or less, and even more preferably 70% by weight or less.
  • the ratio is preferably 10% by weight or more, more preferably 20% by weight or more, and still more preferably 30% by weight or more.
  • the weight average molecular weight of the acrylic oligomer is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more.
  • the molecular weight is preferably 30,000 or less, more preferably 10,000 or less, still more preferably 8,000 or less.
  • Such a molecular weight range of the acrylic oligomer is preferable for ensuring the adhesive strength and adhesive holding power of the pressure-sensitive adhesive layer 20 .
  • the acrylic oligomer is obtained by polymerizing the monomer component of the acrylic oligomer.
  • Polymerization methods include, for example, solution polymerization, active energy ray polymerization (eg, UV polymerization), bulk polymerization, and emulsion polymerization.
  • a polymerization initiator may be used, and a chain transfer agent may be used for the purpose of adjusting the molecular weight.
  • the content of the acrylic oligomer in the pressure-sensitive adhesive layer 20 is preferably 0.5 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the base polymer, in order to sufficiently increase the adhesive strength of the pressure-sensitive adhesive layer 20 . It is 8 parts by mass or more, more preferably 1 part by mass or more.
  • the content of the acrylic oligomer in the adhesive layer 20 is preferably 5 parts by mass or less, more preferably 4 parts by mass with respect to 100 parts by mass of the base polymer. 3 parts by mass or less, more preferably 3 parts by mass or less.
  • the pressure-sensitive adhesive layer 20 when the content of the acrylic oligomer is too large, the haze tends to increase and the transparency tends to decrease due to the decrease in compatibility of the acrylic oligomer.
  • the first adhesive composition may contain a silane coupling agent.
  • the content of the silane coupling agent in the first pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the base polymer.
  • the content is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.
  • the first adhesive composition may contain other components as necessary.
  • Other ingredients include, for example, tackifiers, plasticizers, softeners, antidegradants, fillers, colorants, UV absorbers, antioxidants, surfactants, and antistatic agents.
  • the haze of the adhesive layer 20 is preferably 3% or less, more preferably 2% or less, and more preferably 1% or less.
  • the haze of the pressure-sensitive adhesive layer 20 can be measured using a haze meter according to JIS K7136 (2000). Examples of the haze meter include "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd. and "HM-150 type” manufactured by Murakami Color Research Laboratory.
  • the total light transmittance of the adhesive layer 20 is preferably 60% or higher, more preferably 80% or higher, and even more preferably 85% or higher.
  • the total light transmittance of the adhesive layer 20 is, for example, 100% or less.
  • the total light transmittance of the adhesive layer 20 can be measured according to JIS K 7375 (2008).
  • the adhesive layer 30 is a pressure-sensitive adhesive layer formed from the second adhesive composition.
  • the adhesive layer 30 has transparency.
  • the second PSA composition contains at least a base polymer. Examples of the base polymer contained in the second pressure-sensitive adhesive composition include the base polymers described above with respect to the first pressure-sensitive adhesive composition.
  • the base polymer in the first PSA composition and the base polymer in the second PSA composition may be the same or different.
  • the second PSA composition may contain components other than the base polymer. Examples of the components contained in the second pressure-sensitive adhesive composition include the components other than the base polymer described above for the first pressure-sensitive adhesive composition.
  • the composition of the first pressure-sensitive adhesive composition and the composition of the second pressure-sensitive adhesive composition may be the same or different. From the viewpoint of adjusting the peeling forces F1 and F2 described above, it is preferable that the composition of the first pressure-sensitive adhesive composition and the composition of the second pressure-sensitive adhesive composition are different.
  • the haze of the adhesive layer 30 is preferably 3% or less, more preferably 2% or less, and more preferably 1% or less.
  • the haze of the adhesive layer 30 can be measured using a haze meter according to JIS K7136 (2000).
  • the total light transmittance of the adhesive layer 30 is preferably 60% or higher, more preferably 80% or higher, and even more preferably 85% or higher.
  • the total light transmittance of the adhesive layer 30 is, for example, 100% or less.
  • the total light transmittance of the adhesive layer 30 can be measured according to JIS K 7375 (2008).
  • cover film 40 examples include a flexible plastic film.
  • plastic film examples include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film.
  • the surface of the cover film 40 on the pressure-sensitive adhesive layer 20 side is preferably subjected to release treatment.
  • release treatment examples include silicone release treatment and fluorine release treatment (the same applies to the release treatment described below).
  • the peeling force F1 for peeling the cover film 40 from the pressure-sensitive adhesive layer 20 can be adjusted by adjusting the presence or absence of the peeling treatment, the selection of the type, and the conditions.
  • cover film 50 examples include the plastic films described above with respect to the cover film 40 .
  • the surface of the cover film 50 on the pressure-sensitive adhesive layer 30 side is preferably subjected to release treatment.
  • the peeling force F2 for peeling the cover film 50 from the pressure-sensitive adhesive layer 30 can be adjusted by the presence or absence of the peeling treatment, selection of the type, and adjustment of the conditions.
  • the optical film X1 can be produced, for example, as follows.
  • the optical film 10, the adhesive layer 20 with the cover film 40, and the adhesive layer 30 with the cover film 50 are prepared (preparation step).
  • the adhesive layer 20 with the cover film 40 can be formed by applying the first adhesive composition (varnish) on the cover film 40 to form a coating film, and then drying the coating film.
  • first adhesive composition varnish
  • Examples of the method of applying the first pressure-sensitive adhesive composition include roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, Lip coating and die coating can be mentioned (the same applies to other methods of applying other pressure-sensitive adhesive compositions described below).
  • Another release film may be laminated on the adhesive layer 20 on the cover film 40 . This peeling film is peeled off before bonding the optical film 10 and the pressure-sensitive adhesive layer 20 together.
  • the adhesive layer 30 with the cover film 50 can be formed by applying the second adhesive composition (varnish) on the cover film 50 to form a coating film, and then drying the coating film.
  • Another release film may be laminated on the adhesive layer 30 on the cover film 50 . This peeling film is peeled off before bonding the optical film 10 and the adhesive layer 30 together.
  • the first surface 11 of the optical film 10 and the pressure-sensitive adhesive layer 20 side of the pressure-sensitive adhesive layer 20 with the cover film 40 are pasted together (first pasting step).
  • the second surface 12 of the optical film 10 and the pressure-sensitive adhesive layer 30 side of the pressure-sensitive adhesive layer 30 with the cover film 50 are pasted together (second pasting step).
  • the first surface 11 and the second surface 12 of the optical film 10, the exposed surface of the pressure-sensitive adhesive layer 20 with the cover film 40, and the exposed surface of the pressure-sensitive adhesive layer 30 with the cover film 50 are preferably attached before the bonding. is plasma treated.
  • the optical film X1 (optical film with cover film) can be manufactured.
  • the optical film X1 may be formed by punching. In punching, for example, a punching machine and a Thomson blade are used.
  • 2A to 2D show an example of how to use the optical film X1.
  • the cover film 40 is peeled off from the adhesive layer 20 of the optical film X1.
  • the cover film 50 side of the optical film X1 is fixed on a work table, force is applied to the edge of the cover film 40 to separate the cover film 40 from the adhesive layer 20 .
  • the adhesive surface 21 of the adhesive layer 20 is exposed.
  • the optical film X1 is formed from the thin optical film 10 with the pressure-sensitive adhesive layers 20 and 30 as described above, while suppressing peeling of the cover film 50 and cracks at the edges of the optical film 10. suitable for stripping.
  • the first member M1 is, for example, one element in the laminated structure of the flexible panel. Examples of such elements include a pixel panel, a touch panel, and a transparent cover film (the same applies to the second member M2 described later).
  • the cover film 50 is peeled off from the adhesive layer 30 as shown in FIG. 2C. Thereby, the adhesive surface 31 of the adhesive layer 30 is exposed.
  • the optical film 10 and the second member M2 are bonded with the adhesive layer 30 interposed therebetween.
  • the optical film X1 is used as described above.
  • Optical film X2 as a second embodiment of the optical film with a cover film of the present invention comprises, as shown in FIG. (second adhesive layer), cover film 40 (first cover film), and cover film 60 (second cover film).
  • the optical film X2 has a sheet shape with a predetermined thickness and spreads in a direction orthogonal to the thickness direction T (surface direction).
  • the optical film X2 includes a cover film 60, an adhesive layer 30, an optical film 10, an adhesive layer 20, and a cover film 40 in the thickness direction T in this order.
  • the optical film X2 differs from the optical film X1 in that it includes an optical film Y2 with an adhesive layer and a cover film 60 with an adhesive layer 30 instead of the optical film Y1 with an adhesive layer and the cover films 40 and 50.
  • the pressure-sensitive adhesive layer-attached optical film Y2 is the same as the pressure-sensitive adhesive layer-attached optical film Y1 except that the pressure-sensitive adhesive layer 30 is not provided.
  • the cover film 60 with the adhesive layer 30 includes the cover film 60 and the adhesive layer 30 on one side of the cover film 60 in the thickness direction T.
  • the cover film 60 is a flexible, transparent surface protection film.
  • the adhesive layer 30 contacts the second surface 12 of the optical film 10 of the optical film Y2 with an adhesive layer.
  • the cover film 60 with the adhesive layer 30 is a surface protective film with an adhesive layer that is detachably arranged on the second surface 12 of the optical film Y2 with the adhesive layer.
  • Other configurations of the optical film X2 are the same as those of the optical film X1.
  • Such an optical film X2 is used as a supply material for the pressure-sensitive adhesive layer-attached optical film Y2 incorporated in the laminated structure of the foldable display panel in the manufacturing process of the same panel.
  • the cover film 40 is peeled off from the pressure-sensitive adhesive layer-attached optical film Y2 at a predetermined timing during the manufacturing process of the foldable display panel.
  • the cover film 60 with the adhesive layer 30 may not be peeled off from the optical film Y2 with the adhesive layer.
  • the optical film 10 has a thickness H1 (first thickness) of 100 ⁇ m or less.
  • the thickness H1 is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 40 ⁇ m or less.
  • the thickness H1 is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
  • the adhesive layer 20 has a thickness H2 (second thickness) of 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness H2 is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
  • the thickness H2 is preferably 90 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 70 ⁇ m or less.
  • the adhesive layer 20 has a shear storage modulus M1 (first shear storage modulus) of 20 kPa or more and 100 kPa or less at 25°C.
  • the shear storage elastic modulus M1 is preferably 30 kPa or more, more preferably 40 kPa or more, It is more preferably 45 kPa or more, preferably 90 kPa or less, more preferably 80 kPa or less, and still more preferably 75 kPa or less.
  • the shear storage modulus M1 can be measured with a dynamic viscoelasticity measuring device.
  • the measurement mode is the torsion mode
  • the measurement temperature range is -50 ° C. to 150 ° C.
  • the temperature increase rate is 5 ° C./min
  • the frequency is 1 Hz (also in the measurement of the shear storage elastic modulus M2 described later) similar).
  • Methods for adjusting the shear storage modulus M1 include, for example, selection of the type of base polymer for the pressure-sensitive adhesive layer 20, adjustment of the molecular weight, adjustment of the compounding amount, and selection of the type of cross-linking agent that cross-links the base polymer. Selection and adjustment of compounding amount are included.
  • the adhesive layer 30 has a thickness H3 (third thickness) of 5 ⁇ m or more and 30 ⁇ m or less. From the viewpoint of ensuring sufficient adhesive strength in the adhesive layer 30, the thickness H3 is preferably 7 ⁇ m or more, more preferably 10 ⁇ m or more. The thickness H3 is preferably 25 ⁇ m or less, more preferably 20 ⁇ m or less, from the viewpoint of suppressing the peeling force for peeling the cover film 60 with the pressure-sensitive adhesive layer 30 from the optical film 10 .
  • the adhesive layer 30 has a shear storage modulus M2 (second shear storage modulus) of 150 kPa or more at 25°C.
  • the shear storage elastic modulus M2 is preferably 500 kPa or more, more preferably It is 1500 kPa or more, more preferably 2000 kPa or more, and preferably 5000 kPa or less, more preferably 4500 kPa or less, and still more preferably 4000 kPa or less.
  • Methods for adjusting the shear storage modulus M2 include, for example, selection of the type of base polymer for the adhesive layer 30, adjustment of the molecular weight, adjustment of the compounding amount, and selection of the type of cross-linking agent that cross-links the base polymer. Selection and adjustment of compounding amount are included.
  • the cover film 40 has a thickness H4 (fourth thickness) of 40 ⁇ m or more and 80 ⁇ m or less. From the viewpoint of ensuring the flexibility of the cover film 40, the thickness H4 is preferably 75 ⁇ m or less, more preferably 70 ⁇ m or less. From the viewpoint of strength of the cover film 40, the thickness H4 is preferably 45 ⁇ m or more, more preferably 48 ⁇ m or more, and even more preferably 50 ⁇ m or more.
  • the cover film 60 has a thickness H5 (fifth thickness) of 40 ⁇ m or more and 80 ⁇ m or less.
  • the thickness H5 is preferably 75 ⁇ m or less, more preferably 70 ⁇ m or less, from the viewpoint of ensuring the flexibility of the cover film 60 and from the viewpoint of suppressing cracks at the edges of the optical film 10 when the cover film is peeled off.
  • the thickness H5 is preferably 45 ⁇ m or more, more preferably 48 ⁇ m or more, and even more preferably 50 ⁇ m or more.
  • the ratio (H4/H5) of the thickness H4 to the thickness H5 is 1 or more in this embodiment. From the viewpoint of suppressing peeling of the cover film 60 with the adhesive layer 30 when the cover film 40 is peeled off, the ratio (H4/H5) is preferably 1.1 or more, more preferably 1.2 or more. The ratio (H4/H5) is, for example, 5 or less.
  • the peeling force F1 (first peeling force) for peeling the cover film 40 from the adhesive layer 20, and the peeling force F2 (second peeling force) for peeling the cover film 60 with the adhesive layer 30 from the optical film 10 ratio (F1/F2) to is 0.9 or less.
  • the ratio (F1/F2) is preferably 0.8 or less, more preferably 0.7 or less, and even more preferably 0.7. 6 or less.
  • the ratio (F1/F2) is, for example, 0.1 or more.
  • the peel force F1 and the peel force F2 are each measured in a peel test under conditions of a measurement temperature of 25° C., a peel angle of 180°, and a tensile speed of 300 mm/min.
  • the peeling force F1 is 10 gf/25 mm or less. From the viewpoint of ensuring a good peeling operation when peeling the cover film 40 from the adhesive layer 20, the peeling force F1 is preferably 7 gf/25 mm or less, more preferably 5 gf/25 mm or less, and even more preferably 3 gf/25 mm or less. Particularly preferably, it is 2.5 gf/25 mm or less. From the viewpoint of suppressing unintended peeling of the cover film 40 from the adhesive layer 20, the peel force F1 is preferably 0.1 gf/25 mm or more, more preferably 0.3 gf/25 mm or more, and still more preferably 0.5 gf/25 mm or more. 25 mm or more.
  • Methods for adjusting the peel force F1 include, for example, selection of the type of base polymer for the adhesive layer 20, adjustment of the molecular weight, and adjustment of the blending amount.
  • Selection of the type of base polymer includes selection of the type (structure) of the main chain in the base polymer, and selection of the type and adjustment of the amount of functional groups (the selection of the type of base polymer described later also includes similar).
  • Methods for adjusting the peeling force F1 include selection of types of components other than the base polymer in the pressure-sensitive adhesive layer 20 and adjustment of the compounding amounts of the components. Such components include crosslinkers, silane coupling agents, and oligomers.
  • the thickness H1 of the optical film 10 is 100 ⁇ m or less
  • the thickness H2 of the adhesive layer 20 is 5 ⁇ m or more and 100 ⁇ m or less
  • the thickness H3 of the adhesive layer 30 is the adhesive layer 20 has a shear storage modulus M1 of 20 kPa or more and 100 kPa or less
  • the adhesive layer 30 has a shear storage modulus M2 of 150 kPa or more
  • the thickness H4 of the cover film 40 is 40 ⁇ m.
  • the thickness H5 of the cover film 60 is 40 ⁇ m or more and 80 ⁇ m or less, the ratio (H4/H5) is 1 or more, and the ratio of the peel force F1 of the cover film 40 to the peel force F2 of the cover film 60 (F1/F2) is 0.9 or less, and the peel force F1 is 10 gf/25 mm or less.
  • Such an optical film X2 is obtained by peeling the cover film 60 with the pressure-sensitive adhesive layer 30 from the optical film Y2 (thin optical film 10 with the pressure-sensitive adhesive layer 20) and the optical film 10 Suitable for peeling off the cover film 40 while suppressing cracks at the ends.
  • the ratio (H2/H3) of the thickness H2 of the pressure-sensitive adhesive layer 20 to the thickness H3 of the pressure-sensitive adhesive layer 30 is preferably 1 or more, more preferably 2, from the viewpoint of bendability and step absorption. Above, more preferably 3 or more, particularly preferably 5 or more. From the viewpoint of bendability and step absorbability, the ratio (H2/H3) is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and particularly preferably 20 or less.
  • the ratio (M1/M2) of the shear storage modulus M1 of the adhesive layer 20 to the shear storage modulus M2 of the adhesive layer 30 is preferably 0.5 or less, more preferably It is 0.2 or less, more preferably 0.1 or less, particularly preferably 0.05 or less, particularly preferably 0.02 or less.
  • the ratio (M1/M2) is preferably 0.005 or more, more preferably 0.01 or more, and still more preferably 0.015 or more, from the viewpoint of bendability and step absorbability.
  • the peeling force F2 of the cover film 60 with the adhesive layer 30 is preferably 0.11 gf/25 mm or more, more preferably 0. It is 33 gf/25 mm or more, more preferably 0.55 gf/25 mm or more. From the viewpoint of ensuring a good peeling operation when peeling the cover film 60 from the adhesive layer 30, the peeling force F2 is preferably 20 gf/25 mm or less, more preferably 19 gf/25 mm or less, and even more preferably 18 gf/25 mm or less. be.
  • Methods for adjusting the peel force F2 include, for example, selection of the type of base polymer for the pressure-sensitive adhesive layer 30, adjustment of the molecular weight, and adjustment of the blending amount.
  • Methods for adjusting the peel force F2 include selection of types of components other than the base polymer in the pressure-sensitive adhesive layer 30 and adjustment of the compounding amounts of the components. Such components include crosslinkers, silane coupling agents, and oligomers.
  • cover film 60 surface protection film
  • plastic film having both flexibility and transparency.
  • plastic film include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film.
  • the optical film X2 can be produced, for example, as follows.
  • the optical film 10, the adhesive layer 20 with the cover film 40, and the cover film 60 with the adhesive layer 30 are prepared (preparation step).
  • the method for forming the pressure-sensitive adhesive layer 20 with the cover film 40 is as described above for the first embodiment.
  • the cover film 60 with the adhesive layer 30 In forming the cover film 60 with the adhesive layer 30, first, the surface of the cover film 60 is plasma-treated. Next, a predetermined adhesive composition (varnish) is applied to the plasma-treated surface of the cover film 60 to form a coating film, and then the coating film is dried. Thereby, the cover film 60 with the adhesive layer 30 is obtained. Another release film may be laminated on the adhesive layer 30 on the cover film 60 . This peeling film is peeled off before bonding the optical film 10 and the adhesive layer 30 together.
  • a predetermined adhesive composition varnish
  • the first surface 11 of the optical film 10 and the pressure-sensitive adhesive layer 20 side of the pressure-sensitive adhesive layer 20 with the cover film 40 are pasted together (first pasting step).
  • the first surface 11 of the optical film 10 and the exposed surface of the pressure-sensitive adhesive layer 20 with the cover film 40 are plasma-treated prior to this lamination.
  • the optical film X2 (optical film with cover film) can be produced.
  • the optical film X2 may be formed by punching. In punching, for example, a punching machine and a Thomson blade are used.
  • 4A and 4B show an example of how to use the optical film X2.
  • the cover film 40 is peeled off from the adhesive layer 20 of the optical film X2.
  • the cover film 60 side of the optical film X2 is fixed on a work table, force is applied to the edge of the cover film 40 to separate the cover film 40 from the adhesive layer 20 .
  • the adhesive surface 21 of the adhesive layer 20 is exposed.
  • the optical film X2 suppresses peeling of the cover film 60 with the adhesive layer 30 from the thin optical film 10 with the adhesive layer 20 and cracks at the edges of the optical film 10. Suitable for peeling off the cover film 40 .
  • the first member M1 is, for example, one element in the laminated structure of the flexible panel.
  • Such elements include, for example, pixel panels and touch panels.
  • the optical film X2 is used as described above.
  • ⁇ Preparation of first acrylic base polymer > 63 parts by mass of 2-ethylhexyl acrylate (2EHA), 27 parts by mass of n-butyl acrylate (BA), acrylic acid 7.5 parts by mass of 4-hydroxybutyl (4HBA), 1 part by mass of acrylic acid (AA), and 0.3 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator , and ethyl acetate as solvent was stirred at 56° C. for 6 hours under a nitrogen atmosphere (polymerization reaction). This gave a first polymer solution containing the first acrylic base polymer. The weight average molecular weight of the first acrylic base polymer in this polymer solution was about 2 million.
  • 2EHA 2-ethylhexyl acrylate
  • BA n-butyl acrylate
  • lauryl acrylate lauryl acrylate
  • LA 8 parts by mass
  • 4-hydroxybutyl acrylate (4HBA) 1 part by mass
  • N-vinyl-2-pyrrolidone (NVP) 0.6 parts by mass
  • 2,2′- as a thermal polymerization initiator
  • a mixture containing 0.3 parts by mass of azobisisobutyronitrile (AIBN) and ethyl acetate as a solvent was stirred at 56° C. for 6 hours under a nitrogen atmosphere (polymerization reaction).
  • AIBN azobisisobutyronitrile
  • ethyl acetate 0.6 parts by mass
  • 2,2′- 2,2′- as a thermal polymerization initiator
  • ⁇ Preparation of the third acrylic base polymer 60 parts by mass of 2-ethylhexyl acrylate (2EHA), 36.5 parts by mass of lauryl acrylate (LA), and 4 parts by mass of acrylic acid were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. - 8 parts by weight of hydroxybutyl (4HBA), 2.5 parts by weight of N-vinyl-2-pyrrolidone (NVP), and 0.5 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator. A mixture containing 3 parts by mass and ethyl acetate as a solvent was stirred at 56° C. for 6 hours under a nitrogen atmosphere (polymerization reaction). This gave a third polymer solution containing a third acrylic base polymer. The weight average molecular weight of the third acrylic base polymer in this polymer solution was about 2 million.
  • ⁇ Preparation of the fourth acrylic base polymer 99 parts by mass of butyl acrylate (BA), 1 part by mass of 4-hydroxybutyl acrylate (4HBA), and thermal polymerization start in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube.
  • a mixture containing 0.3 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as an agent and ethyl acetate as a solvent was stirred at 60° C. for 4 hours under a nitrogen atmosphere (polymerization reaction ).
  • the weight average molecular weight of the fourth acrylic base polymer in this polymer solution was about 1.7 million.
  • ⁇ Preparation of the fifth acrylic base polymer > 66 parts by mass of 2-ethylhexyl acrylate (2EHA), 18 parts by mass of 2-hydroxyethyl acrylate (HEA), N - A mixture containing 15 parts by mass of vinyl-2-pyrrolidone (NVP), 0.3 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator, and ethyl acetate as a solvent was stirred at 56° C. for 6 hours under a nitrogen atmosphere (polymerization reaction). This gave a fifth polymer solution containing the fifth acrylic base polymer. The weight average molecular weight of the fifth acrylic base polymer in this polymer solution was about 2 million.
  • ⁇ Preparation of the sixth acrylic base polymer 96.2 parts by mass of 2-ethylhexyl acrylate (2EHA) and 3.8 parts by mass of 2-hydroxyethyl acrylate (HEA) were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. parts, 0.3 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator, and 150 parts by mass of ethyl acetate as a solvent, at 65 ° C. for 6 hours, Stirred under a nitrogen atmosphere (polymerization reaction). This gave a sixth polymer solution containing a sixth acrylic base polymer. The weight average molecular weight of the sixth acrylic base polymer in this polymer solution was 540,000.
  • AIBN 2,2'-azobisisobutyronitrile
  • Example 1 ⁇ Production of first adhesive sheet> A first pressure-sensitive adhesive sheet in Example 1 was produced as follows.
  • first adhesive composition 1.5 parts by mass of an acrylic oligomer per 100 parts by mass of the first acrylic base polymer in the polymer solution, and a first cross-linking agent (product name "Niper BMT-40SV", dibenzoyl peroxide, NOF ), 0.3 parts by mass of the second cross-linking agent (product name "Coronate L", trimethylolpropane / tolylene diisocyanate trimer adduct, manufactured by Tosoh) 0.02 parts by mass, and a silane coupling agent (product name "KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.) (0.3 parts by mass) was added and mixed to prepare a first adhesive composition.
  • a first cross-linking agent product name "Niper BMT-40SV", dibenzoyl peroxide, NOF
  • second cross-linking agent product name "Coronate L", trimethylolpropane / tolylene diisocyanate trimer adduct, manufactured by Tosoh
  • a coating film was formed by applying the first pressure-sensitive adhesive composition onto the release-treated surface of release film L1, one surface of which had been subjected to silicone release treatment.
  • the release film L1 is a polyethylene terephthalate (PET) film (product name “DIAFOIL MHE50”, thickness 50 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) with one side subjected to silicone release treatment.
  • PET polyethylene terephthalate
  • the release-treated surface of the release film L2 one side of which was subjected to silicone release treatment, was attached to the coating film on the release film L1.
  • the release film L2 is a PET film (product name “DIAFOIL MRV75”, thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) one side of which is subjected to silicone release treatment.
  • the coating film sandwiched between the release film L1 and the release film L2 is dried by heating at 100° C. for 1 minute and then heating at 150° C. for 3 minutes to form a transparent first adhesive having a thickness of 50 ⁇ m.
  • a first pressure-sensitive adhesive sheet consisting of an agent layer was formed. As described above, the first pressure-sensitive adhesive sheets with release films L1 and L2 were produced.
  • a second pressure-sensitive adhesive sheet in Example 1 was produced as follows.
  • ⁇ Preparation of second adhesive composition> 1.5 parts by mass of an acrylic oligomer per 100 parts by mass of the solid content of the polymer solution, 0.26 parts by mass of a first cross-linking agent (product name "Nyper BMT-40SV", manufactured by NOF), 0.02 parts by mass of a second cross-linking agent (product name “Coronate L”, manufactured by Tosoh) and 0.3 parts by mass of a silane coupling agent (product name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed, and the second An adhesive composition was prepared.
  • a first cross-linking agent product name "Nyper BMT-40SV”, manufactured by NOF
  • a second cross-linking agent product name “Coronate L”, manufactured by Tosoh
  • silane coupling agent product name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.
  • a coating film was formed by applying the second pressure-sensitive adhesive composition onto the release-treated surface of release film L3, one surface of which had been subjected to silicone release treatment.
  • the release film L3 is a polyethylene terephthalate (PET) film (product name “DIAFOIL MHE50”, thickness 50 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) having one side subjected to silicone release treatment.
  • PET polyethylene terephthalate
  • the release-treated surface of the release film L4 one side of which was subjected to silicone release treatment, was attached to the coating film on the release film L3.
  • the release film L4 is a PET film (product name “DIAFOIL MRV75”, thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) one side of which is subjected to silicone release treatment.
  • the coating film sandwiched between the release film L3 and the release film L4 is dried by heating at 100° C. for 1 minute and then heating at 150° C. for 3 minutes to obtain a transparent second adhesive having a thickness of 50 ⁇ m.
  • a second pressure-sensitive adhesive sheet consisting of an agent layer was formed. As described above, the second adhesive sheets with release films L3 and L4 were produced.
  • the release film L2 was peeled off from the first pressure-sensitive adhesive sheet with a double-sided release film, and the exposed surface thereby exposed was plasma-treated.
  • both surfaces (first surface and second surface) of the polarizing film having a thickness of 31 ⁇ m were also plasma-treated.
  • a plasma irradiation device product name “AP-TO5”, manufactured by Sekisui Kogyo Co., Ltd.
  • the voltage was 160 V
  • the frequency was 10 kHz
  • the treatment speed was 5000 mm / min (also in the plasma treatment described later similar).
  • the exposed surface of the first adhesive sheet and the first surface of the polarizing film were bonded together.
  • the first pressure-sensitive adhesive sheet with the release film L1 and the polarizing film were pressure-bonded by reciprocating a 2-kg roller one time in an environment of 25°C.
  • the release film L3 was peeled off from the second adhesive sheet with the release films L3 and L4, and the exposed surface was plasma-treated. Then, the exposed surface of the second adhesive sheet and the second surface of the polarizing film were bonded together. In this bonding, the second pressure-sensitive adhesive sheet with the release film L4 and the polarizing film were pressure-bonded by reciprocating a 2-kg roller one time in an environment of 25°C. As a result, the release film L1 (thickness 50 ⁇ m), the first adhesive sheet (thickness 50 ⁇ m), the polarizing film (thickness 31 ⁇ m), the second adhesive sheet (thickness 50 ⁇ m), the release film L4 (thickness 75 ⁇ m) was obtained.
  • the laminated film was punched into a size of 150 mm x 120 mm (punching).
  • This optical film with a cover film of Example 1 was produced as described above.
  • This optical film with a cover film includes a release film L1 as a first cover film, a first adhesive layer (first adhesive sheet), a polarizing film as an optical film, and a second adhesive layer (second adhesive sheet ) and a release film L4 as a second cover film are provided in order in the thickness direction.
  • Example 2 a polarizing film with a thickness of 51 ⁇ m was used in place of the polarizing film with a thickness of 31 ⁇ m.
  • Example 3 a polarizing film with a thickness of 25 ⁇ m was used in place of the polarizing film with a thickness of 31 ⁇ m.
  • Example 4 the thickness of the first adhesive sheet was changed from 50 ⁇ m to 25 ⁇ m.
  • Example 5 the thickness of the first adhesive sheet was changed from 50 ⁇ m to 25 ⁇ m, and the thickness of the second adhesive sheet was changed from 50 ⁇ m to 75 ⁇ m.
  • Example 6 An optical film with a cover film of Example 6 was produced in the same manner as the optical film with a cover film of Example 1 except for the following.
  • a second polymer solution was used in place of the first polymer solution, and a first pressure-sensitive adhesive sheet was produced using the first pressure-sensitive adhesive composition.
  • a third polymer solution was used instead of the second polymer solution, and a second pressure-sensitive adhesive sheet having a thickness of 75 ⁇ m was produced using the second pressure-sensitive adhesive composition.
  • the second polymer solution was added with 1.5 parts by weight of an acrylic oligomer per 100 parts by weight of the second acrylic base polymer in the polymer solution, 1 cross-linking agent (product name “Nyper BMT-40SV”, manufactured by NOF) 0.26 parts by mass, second cross-linking agent (product name “Coronate L”, manufactured by Tosoh) 0.02 parts by mass, silane coupling agent (product name 0.3 parts by mass of "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed.
  • 1 cross-linking agent product name “Nyper BMT-40SV”, manufactured by NOF
  • second cross-linking agent product name “Coronate L”, manufactured by Tosoh
  • silane coupling agent product name 0.3 parts by mass of "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed.
  • the third polymer solution was added with 1.5 parts by weight of an acrylic oligomer per 100 parts by weight of the third acrylic base polymer in the polymer solution, 1 cross-linking agent (product name "Nyper BMT-40SV", manufactured by NOF) 0.08 parts by mass, second cross-linking agent (product name "Coronate L", manufactured by Tosoh) 0.02 parts by mass, silane coupling agent (product name 0.3 parts by mass of "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed.
  • 1 cross-linking agent product name "Nyper BMT-40SV", manufactured by NOF
  • second cross-linking agent product name "Coronate L", manufactured by Tosoh
  • silane coupling agent product name 0.3 parts by mass of "KBM403” (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed.
  • Example 7 An optical film with a cover film of Example 7 was produced in the same manner as the optical film with a cover film of Example 1 except for the following.
  • a fourth polymer solution was used in place of the first polymer solution, and a first pressure-sensitive adhesive sheet was produced using the first pressure-sensitive adhesive composition.
  • the thickness of the second adhesive sheet was changed from 50 ⁇ m to 75 ⁇ m.
  • the fourth polymer solution was added with a first cross-linking agent (product name: Nyper BMT- 40SV", manufactured by NOF) 0.3 parts by mass, a third cross-linking agent (product name "Takenate D110N", trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals) 0.1 parts by mass, and a silane coupling agent (product name " KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 parts by mass were added and mixed.
  • a first cross-linking agent product name: Nyper BMT- 40SV", manufactured by NOF
  • a third cross-linking agent product name "Takenate D110N", trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals
  • a silane coupling agent product name " KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.
  • Comparative Examples 1 to 5 Optical films with cover films of Comparative Examples 1 to 5 were produced in the same manner as the optical film with cover film of Example 1 except for the following.
  • a release film L5 was used instead of the release film L4 (thickness 75 ⁇ m).
  • the release film L5 is a PET film (thickness: 125 ⁇ m) with one side subjected to silicone release treatment.
  • a release film L6 was used instead of the release film L1 (thickness 50 ⁇ m), and a release film L6 was used instead of the release film L4 (thickness 75 ⁇ m).
  • the release film L6 is a PET film (product name “Diafoil MRF38”, thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) one side of which is subjected to silicone release treatment.
  • a fifth polymer solution was used in place of the first polymer solution in the preparation of the first pressure-sensitive adhesive composition, and the first pressure-sensitive adhesive composition was used to prepare the first pressure-sensitive adhesive sheet.
  • the fifth polymer solution was added with a first cross-linking agent (product name: Nyper BMT- 40SV", manufactured by NOF) 0.3 parts by mass, a third cross-linking agent (product name "Takenate D110N", manufactured by Mitsui Chemicals) 0.1 parts by mass, and a silane coupling agent (product name "KBM403", manufactured by Shin-Etsu Chemical Co., Ltd. ) and 0.3 parts by mass were added and mixed.
  • a first cross-linking agent product name: Nyper BMT- 40SV", manufactured by NOF
  • a third cross-linking agent product name "Takenate D110N", manufactured by Mitsui Chemicals
  • a silane coupling agent product name "KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.
  • the release film L2 was used instead of the release film L1 (thickness 50 ⁇ m)
  • the release film L7 was used instead of the release film L4 (thickness 50 ⁇ m)
  • the thickness of the second adhesive sheet was was changed from 50 ⁇ m to 75 ⁇ m.
  • the release film L7 is a PET film (product name “Diafoil MRF50”, thickness 50 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) one side of which is subjected to silicone release treatment.
  • the release film L2 was used instead of the release film L1 (thickness of 50 ⁇ m)
  • the release film L2 was used instead of the release film L4 (thickness of 50 ⁇ m)
  • the second adhesive sheet was The thickness was changed from 50 ⁇ m to 75 ⁇ m.
  • Example 8 ⁇ Production of first adhesive sheet> A first pressure-sensitive adhesive sheet in Example 8 was produced in the same manner as the above-described first pressure-sensitive adhesive sheet in Example 1.
  • the first pressure-sensitive adhesive sheet in Example 8 is the same as the first pressure-sensitive adhesive sheet in Example 1, specifically the first pressure-sensitive adhesive sheet with release films L1 and L2.
  • This first pressure-sensitive adhesive sheet consists of a transparent first pressure-sensitive adhesive layer with a thickness of 50 ⁇ m.
  • This first pressure-sensitive adhesive layer is composed of 100 parts by mass of the first acrylic base polymer, 1.5 parts by mass of the above acrylic oligomer, and 0.3 parts by mass of the first cross-linking agent (product name "Niper BMT-40SV", manufactured by NOF).
  • a cover film with an adhesive layer in Example 8 was produced as follows.
  • a fourth cross-linking agent product name “Coronate HX”, isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh
  • 0.03 parts by mass of dibutyltin dilaurate as a cross-linking catalyst was added and mixed to prepare a second pressure-sensitive adhesive composition in Example 8.
  • the second pressure-sensitive adhesive composition described above in Example 8 was applied on the corona-treated surface of a surface protective film (product name “T100C-38”, polyester film, thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Corporation) one side of which was corona-treated.
  • a material was applied to form a coating film.
  • the release-treated surface of the release film L8 was attached to the coating film on the surface protection film.
  • the release film L8 is a polyester film (thickness: 25 ⁇ m) with one side subjected to silicone release treatment.
  • the coating film sandwiched between both films was dried by heating at 130° C. for 2 minutes to form a transparent second pressure-sensitive adhesive layer with a thickness of 10 ⁇ m. After that, the release film L8 was peeled off from the second pressure-sensitive adhesive layer.
  • a surface protective film with an adhesive layer cover film with an adhesive layer
  • the release film L2 was peeled off from the first pressure-sensitive adhesive sheet with the double-sided release films L1 and L2, and the exposed surface was plasma-treated.
  • both surfaces (first surface and second surface) of the polarizing film having a thickness of 31 ⁇ m were also plasma-treated.
  • the exposed surface of the first adhesive sheet and the first surface of the polarizing film were bonded together.
  • the first pressure-sensitive adhesive sheet with the release film L1 and the polarizing film were pressure-bonded by reciprocating a 2-kg roller one time in an environment of 25°C.
  • the pressure-sensitive adhesive layer side of the surface protective film with the pressure-sensitive adhesive layer and the second surface of the polarizing film were adhered together.
  • the pressure-sensitive adhesive layer-attached surface protective film and the polarizing film were pressure-bonded by reciprocating a 2-kg roller once in an environment of 25°C.
  • the release film L1 (thickness 50 ⁇ m), the first adhesive sheet (thickness 50 ⁇ m), the polarizing film (thickness 31 ⁇ m), and the surface protective film (thickness 38 ⁇ m) with the adhesive layer (thickness 10 ⁇ m)
  • the laminated film was punched into a size of 150 mm x 120 mm (punching).
  • This optical film with a cover film of Example 8 was produced as described above.
  • This optical film with a cover film includes a release film L1 as a first cover film, a first pressure-sensitive adhesive layer (first pressure-sensitive adhesive sheet), a polarizing film as an optical film, and a second cover film with a second pressure-sensitive adhesive layer.
  • Example 9 a polarizing film with a thickness of 51 ⁇ m was used in place of the polarizing film with a thickness of 31 ⁇ m.
  • Example 10 a polarizing film with a thickness of 25 ⁇ m was used in place of the polarizing film with a thickness of 31 ⁇ m.
  • Example 11 the thickness of the first adhesive sheet was changed from 50 ⁇ m to 25 ⁇ m.
  • Example 12 An optical film with a cover film of Example 12 was produced in the same manner as the optical film with a cover film of Example 8 except for the following.
  • a second polymer solution was used in place of the first polymer solution, and a first pressure-sensitive adhesive sheet was produced using the first pressure-sensitive adhesive composition.
  • the second polymer solution was added with 1.5 parts by weight of an acrylic oligomer per 100 parts by weight of the second acrylic base polymer in the polymer solution, 1 cross-linking agent (product name “Nyper BMT-40SV”, manufactured by NOF) 0.26 parts by mass, second cross-linking agent (product name “Coronate L”, manufactured by Tosoh) 0.02 parts by mass, silane coupling agent (product name 0.3 parts by mass of "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed.
  • 1 cross-linking agent product name “Nyper BMT-40SV”, manufactured by NOF
  • second cross-linking agent product name “Coronate L”, manufactured by Tosoh
  • silane coupling agent product name 0.3 parts by mass of "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed.
  • Example 13 An optical film with a cover film of Example 13 was produced in the same manner as the optical film with a cover film of Example 8 except for the following.
  • a fourth polymer solution was used in place of the first polymer solution, and a first pressure-sensitive adhesive sheet was produced using the first pressure-sensitive adhesive composition.
  • the fourth polymer solution was added with a first cross-linking agent (product name: Nyper BMT- 40SV", manufactured by NOF) 0.3 parts by mass, a third cross-linking agent (product name "Takenate D110N", trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals) 0.1 parts by mass, and a silane coupling agent (product name " KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 parts by mass were added and mixed.
  • a first cross-linking agent product name: Nyper BMT- 40SV", manufactured by NOF
  • a third cross-linking agent product name "Takenate D110N", trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals
  • a silane coupling agent product name " KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.
  • Comparative Examples 6 to 9 Optical films with cover films of Comparative Examples 6 to 9 were produced in the same manner as the optical film with cover film of Example 8 except for the following.
  • Comparative Example 6 a surface protection film with a thickness of 125 ⁇ m was used as the second cover film instead of the surface protection film with a thickness of 38 ⁇ m.
  • the surface protective film in Comparative Example 6 is a PET film (product name: "Lumirror S10", manufactured by Toray Industries, Inc.) on one side of which is subjected to release treatment with a silicone-based release agent.
  • a fifth polymer solution was used in place of the first polymer solution in the preparation of the first pressure-sensitive adhesive composition, and the first pressure-sensitive adhesive composition was used to prepare the first pressure-sensitive adhesive sheet.
  • the fifth polymer solution was added with a first cross-linking agent (product name: Nyper BMT- 40SV", manufactured by NOF) 0.3 parts by mass, a third cross-linking agent (product name "Takenate D110N", manufactured by Mitsui Chemicals) 0.1 parts by mass, and a silane coupling agent (product name "KBM403", manufactured by Shin-Etsu Chemical Co., Ltd. ) and 0.3 parts by mass were added and mixed.
  • a first cross-linking agent product name: Nyper BMT- 40SV", manufactured by NOF
  • a third cross-linking agent product name "Takenate D110N", manufactured by Mitsui Chemicals
  • a silane coupling agent product name "KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.
  • the thickness of the second pressure-sensitive adhesive layer on the surface protection film with the pressure-sensitive adhesive layer was changed from 10 ⁇ m to 1 ⁇ m.
  • a release film L9 was used instead of the release film L1 (thickness: 50 ⁇ m).
  • the release film L9 is a PET film (product name “Diafoil MRF75”, thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) one side of which is subjected to silicone release treatment.
  • Shear storage modulus The shear storage elastic modulus at 25° C. was measured as follows for each pressure-sensitive adhesive layer in each optical film with a cover film of Examples 1 to 13 and Comparative Examples 1 to 9.
  • a sample for measurement we prepared a sample for measurement. Specifically, after laminating a plurality of adhesive layer pieces to prepare an adhesive sheet with a thickness of about 1.5 mm, the sheet is punched to obtain a cylindrical pellet (diameter 7 .9 mm). Then, the measurement sample was fixed to a parallel plate jig with a diameter of 7.9 mm using a dynamic viscoelasticity measuring device (trade name "Advanced Rheometric Expansion System (ARES)", manufactured by Rheometric Scientific). Dynamic viscoelasticity measurements were performed. In this measurement, the measurement mode was the torsion mode, the measurement temperature range was -50° C. to 150° C., the temperature increase rate was 5° C./min, and the frequency was 1 Hz.
  • AWS Advanced Rheometric Expansion System
  • the shear storage modulus G' at 25°C was read.
  • Tables 1 to 4 show the shear storage modulus G' of the first pressure-sensitive adhesive layer at 25°C as the storage modulus M1 (kPa) at 25°C, and the shear storage modulus of the second pressure-sensitive adhesive layer at 25°C.
  • the elastic modulus G′ is given as the storage modulus M2 (kPa) at 25° C. and the ratio of M1 to M2 is also given.
  • a test piece for measurement (about 25 mm short side x 150 mm long side) was cut out from the optical film with the cover film.
  • the test piece was fixed to a fixing table of a tensile tester (product name: "Autograph", manufactured by Shimadzu Corporation). Specifically, after peeling and removing one cover film (second cover film or first cover film) from the test piece, the test piece is fixed to the table through the adhesive layer exposed by the peeling. pasted on.
  • a gripping tape was attached to the other cover film (first cover film or second cover film) located on the exposed surface side of the test piece. This gripping tape had a strong adhesive surface, and the gripping tape was attached to the cover film of the test piece via the strong adhesive surface.
  • a peel test was conducted in which the cover film of the pressure-sensitive adhesive layer in the test piece was peeled off from the pressure-sensitive adhesive layer, and the peel strength was measured as the peel force.
  • the measurement temperature was 25° C.
  • the cover film was peeled off by pulling the gripping tape
  • the peeling angle was 180°
  • the pulling speed was 300 mm/min
  • the peeling length was 100 mm.
  • Tables 1 and 2 show the measured peel forces F1 and F2 (gf/25 mm).
  • Tables 1 and 2 also show the ratio of the peeling force F1 to the peeling force F2.
  • the peel strengths F1 and F2 are average values of the peel strength at a peel length of 20 to 100 mm (the peel strength is stable after passing through the peel initiation force at the start of peeling).
  • a test piece for measurement (about 25 mm short side x 150 mm long side) was cut out from the optical film with the cover film.
  • the test piece was fixed to a fixing table of a tensile tester (product name: "Autograph", manufactured by Shimadzu Corporation).
  • the second cover film side of the test piece for measuring the first peel strength was attached to a fixing table with a strong adhesive double-faced tape.
  • the test piece for measuring the second peel force after peeling and removing the first cover film from the test piece, the test piece is placed on the fixing table through the first adhesive layer exposed by the peeling. pasted.
  • a gripping tape was attached to the cover film (first cover film or second cover film) positioned on the exposed surface side of the test piece.
  • This gripping tape had a strong adhesive surface, and the gripping tape was attached to the cover film of the test piece via the strong adhesive surface.
  • a peel test was carried out by peeling the cover film (the first cover film or the second cover film with the pressure-sensitive adhesive layer), and the peel strength was measured as the peel force.
  • the measurement temperature was 25° C.
  • the cover film was peeled off by pulling the gripping tape
  • the peeling angle was 180°
  • the pulling speed was 300 mm/min
  • the peeling length was 100 mm.
  • Tables 1 and 2 show the measured peel forces F1 and F2 (gf/25 mm).
  • Tables 1 and 2 also show the ratio of the peeling force F1 to the peeling force F2.
  • the peel strengths F1 and F2 are average values of the peel strength at a peel length of 20 to 100 mm (the peel strength is stable after passing through the peel initiation force at the start of peeling).
  • samples for evaluation were cut out from the optical films (polarizing films) with double-sided cover films thus prepared. Specifically, a rectangular sample of 35 mm ⁇ 100 mm was cut out from the optical film with the cover film so that the absorption axis direction of the polarizing film was parallel to the long side direction in the sample cut out. The samples were then autoclaved at 35° C. and 0.35 MPa for 15 minutes. Next, the sample was subjected to a flexing test using a planar object no-load U-shaped stretching tester (manufactured by Yuasa System Co., Ltd.).
  • a bending jig was attached to a range of 20 mm from the edge of the sample to each of both ends of the sample in the long side direction, and the sample was fixed to the tester (region of 60 mm in the center of the long side of the sample is in an unfixed state).
  • the sample was bent with a bending radius of 1.3 mm and a bending angle of 180° (the axial direction of the bending moment acting on the sample and the absorption of the polarizing film).
  • the same sample was held in a form perpendicular to the axial direction), and the same sample in this state was held for 240 hours in a thermo-hygrostat at a temperature of 25° C. and a relative humidity of 95% (bending test).
  • the samples were visually observed to confirm the presence or absence of peeling between the optical film (polarizing film) and each cover film at the bent portion.
  • peeling occurred from the ends in the short side direction of the sample.
  • the length (mm) of the gap in the short side direction of the sample was measured.
  • the case where the length of the gap is less than 1 mm is defined as " A case where the length of the void was 1 mm or more and less than 2 mm was evaluated as “Good”, and a case where the length of the void was 2 mm or more was evaluated as "Poor”. Table 1 shows the evaluation results.
  • the optical film with cover film of the present invention is used, for example, as a supply material for the optical film included in the laminated structure of the foldable display panel in the manufacturing process of the same panel.
  • Optical film 11 First surface 12
  • Second surface 20 Adhesive layer (first adhesive layer) 21, 31 Adhesive surface 30

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)

Abstract

Selon la présente invention, un film optique (X1) doté d'un film de recouvrement est pourvu d'un film optique (10), de couches adhésives (20, 30) et de films de recouvrement (40, 50). Le film optique (10) présente une épaisseur inférieure ou égale à 100 µm, les couches adhésives (20, 30) présentent une épaisseur de 5 à 100 µm, le film de recouvrement (40) présente une épaisseur H4 de 40 à 80 µm, le film de recouvrement (50) présente une épaisseur H5 de 40 à 80 µm, et le rapport (H4/H5) est inférieur ou égal à 1. Les couches adhésives (20, 30) ont un module de conservation de 20 à 100 kPa. Le film de recouvrement (40) présente une première force de libération inférieure ou égale à 10 gf/25 mm, et le rapport de la première force de libération sur une seconde force de libération du film de recouvrement (50) est inférieur ou égal à 0,9.
PCT/JP2022/023779 2021-06-30 2022-06-14 Film optique avec film de recouvrement WO2023276654A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014115468A (ja) * 2012-12-10 2014-06-26 Nitto Denko Corp 両面粘着剤付き光学フィルム、およびそれを用いた画像表示装置の製造方法
JP2016080830A (ja) * 2014-10-15 2016-05-16 日東電工株式会社 両面粘着剤付き光学フィルム、およびそれを用いた画像表示装置の製造方法、ならびに両面粘着剤付き光学フィルムのカール抑制方法
JP2020157577A (ja) * 2019-03-26 2020-10-01 住友化学株式会社 積層体及び表示装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020190754A (ja) 2020-08-18 2020-11-26 日東電工株式会社 光学フィルム、剥離方法及び光学表示パネルの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014115468A (ja) * 2012-12-10 2014-06-26 Nitto Denko Corp 両面粘着剤付き光学フィルム、およびそれを用いた画像表示装置の製造方法
JP2016080830A (ja) * 2014-10-15 2016-05-16 日東電工株式会社 両面粘着剤付き光学フィルム、およびそれを用いた画像表示装置の製造方法、ならびに両面粘着剤付き光学フィルムのカール抑制方法
JP2020157577A (ja) * 2019-03-26 2020-10-01 住友化学株式会社 積層体及び表示装置

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