WO2019026751A1 - Stratifié destiné à un dispositif d'affichage d'image flexible, et dispositif d'affichage d'image flexible - Google Patents

Stratifié destiné à un dispositif d'affichage d'image flexible, et dispositif d'affichage d'image flexible Download PDF

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Publication number
WO2019026751A1
WO2019026751A1 PCT/JP2018/028067 JP2018028067W WO2019026751A1 WO 2019026751 A1 WO2019026751 A1 WO 2019026751A1 JP 2018028067 W JP2018028067 W JP 2018028067W WO 2019026751 A1 WO2019026751 A1 WO 2019026751A1
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WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
meth
adhesive layer
image display
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Application number
PCT/JP2018/028067
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English (en)
Japanese (ja)
Inventor
昌邦 藤田
雄祐 外山
大器 下栗
Original Assignee
日東電工株式会社
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Priority to JP2019534446A priority Critical patent/JPWO2019026751A1/ja
Publication of WO2019026751A1 publication Critical patent/WO2019026751A1/fr

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80Constructional details
    • H10K59/8791Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • FIG. 1 is a cross-sectional view of a flexible image display according to an embodiment of the present invention.
  • FIG. 7 is a cross-sectional view of a flexible image display according to another embodiment of the present invention.
  • FIG. 7 is a cross-sectional view of a flexible image display according to another embodiment of the present invention. It is a figure which shows a bending test ((A) bending angle 0 degree, (B) bending angle 180 degree). It is sectional drawing which shows the sample for evaluation used in an Example. It is a figure which shows the manufacturing method of the phase difference used in an Example.
  • the polarizing film (also referred to as a polarizer) contained in the optical film of the present invention is an iodine-oriented polyvinyl alcohol (PVA) drawn by a drawing process such as air drawing (dry drawing) or a drawing process in boric acid water. Based resins can be used.
  • PVA polyvinyl alcohol
  • the optical film used in the present invention can include a protective film formed of a transparent resin material, and the protective film (also referred to as a transparent protective film) is a cycloolefin resin such as a norbornene resin, polyethylene, An olefin resin such as polypropylene, a polyester resin, a (meth) acrylic resin or the like can be used.
  • a transparent protective film is a cycloolefin resin such as a norbornene resin, polyethylene, An olefin resin such as polypropylene, a polyester resin, a (meth) acrylic resin or the like can be used.
  • the copolymerizable monomer is not particularly limited, but it is preferable to contain a (meth) acrylic polymer containing a hydroxyl group-containing monomer having a reactive functional group.
  • a pressure-sensitive adhesive layer having excellent adhesion and flexibility can be obtained.
  • the hydroxyl group-containing monomer is a compound containing a hydroxyl group in the structure and containing a polymerizable unsaturated double bond such as (meth) acryloyl group or vinyl group.
  • hydroxyl group-containing monomers 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of durability and adhesion.
  • hydroxyl group containing monomer 1 type (s) or 2 or more types can be used.
  • a (meth) acrylic polymer containing a carboxyl group-containing monomer having a reactive functional group can be contained as a monomer unit.
  • the carboxyl group-containing monomer is a compound containing a carboxyl group in the structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • polyfunctional monomers polyfunctional monomers
  • a crosslinking effect can be obtained by polymerization, and adjustment of gel fraction and improvement of cohesive strength can be easily performed. For this reason, cutting becomes easy, and processability is likely to be improved. Furthermore, it is possible to prevent peeling of the pressure-sensitive adhesive layer due to cohesive failure during bending (particularly under a high temperature environment).
  • the polyfunctional monomer is not particularly limited.
  • a pressure-sensitive adhesive composition containing the (meth) acrylic polymer as an essential component is preferably mentioned.
  • a pressure-sensitive adhesive composition containing a mixture of monomer components (monomer mixture) constituting the (meth) acrylic polymer or a partial polymer thereof as an essential component is preferable. It can be mentioned.
  • the term "partially polymerized product” means a composition in which one or two or more components of the monomer components contained in the monomer mixture are partially polymerized.
  • the “monomer mixture” includes the case where there is only one monomer component.
  • the weight average molecular weight is less than 600,000, when crosslinking polymer chains to ensure durability, the crosslinking point is increased compared to the one having a weight average molecular weight of 600,000 or more, and the pressure-sensitive adhesive (layer Since the flexibility of the above is lost, the distortions on the outside (convex side) and the inside (concave side) of bending occurring between layers (each film) can not be relieved, and breakage of each layer tends to occur.
  • the weight average molecular weight is larger than 2.5 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable because the cost is increased, and (meth) acrylic resin is obtained.
  • those having a cyclic structure in terms of bulkiness are highly effective, and those containing a plurality of rings are even more effective.
  • those having a saturated bond are preferable in that they are unlikely to cause polymerization inhibition, and alkyl groups are preferred.
  • An alkyl (meth) acrylate having a branched structure or an ester with an alicyclic alcohol can be suitably used as a monomer constituting a (meth) acrylic oligomer.
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer used in the solvent type pressure-sensitive adhesive composition is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, and particularly preferably 4000 or more.
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer is preferably 30000 or less, more preferably 15000 or less, still more preferably 10000 or less, and particularly preferably 7000 or less.
  • the weight-average molecular weight (Mw) of the (meth) acrylic oligomer within the above range, for example, when using in combination with the (meth) acrylic polymer, it is possible to ) An acrylic oligomer intervenes, the entanglement of the (meth) acrylic polymer is reduced, the pressure-sensitive adhesive layer is easily deformed to a minute strain, the strain applied to other layers can be reduced, and cracking or adhesion of each layer Peeling or the like between the agent layer and the other layers can be suppressed, which is a preferred embodiment.
  • polyvalent metal atoms examples include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. It can be mentioned.
  • An oxygen atom etc. are mentioned as an atom in the organic compound which carries out covalent bond or coordinate bond,
  • An alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound etc. are mentioned as an organic compound.
  • peroxide-based crosslinking agents and isocyanate crosslinking agents are preferable, and among these, peroxide-based crosslinking agents are preferably used.
  • a crosslinking agent is mixed with a mixture of monomer components (monomer mixture) constituting the (meth) acrylic polymer or a partial polymer thereof, and the adhesive composition is thermally dried and crosslinked before and after active energy ray curing.
  • the reaction of the agent can be completed.
  • the amount of the crosslinking agent used is, for example, preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Parts by weight are more preferred. If it is in the said range, it is excellent in bending resistance and it becomes a preferable aspect.
  • the active energy ray-curable acrylic pressure-sensitive adhesive composition may be a monomer mixture or a partial polymer thereof, a component to be added if necessary (for example, the photopolymerization initiator, polyfunctional monomer, (Meth) acrylic oligomers, crosslinking agents, silane coupling agents, solvents, additives, etc. are mixed to prepare.
  • a component to be added if necessary for example, the photopolymerization initiator, polyfunctional monomer, (Meth) acrylic oligomers, crosslinking agents, silane coupling agents, solvents, additives, etc. are mixed to prepare.
  • the sol component easily segregates on the adherend surface, and the low molecular weight sol component having a weight average molecular weight of less than 1,000,000 lowers the material strength at the interface between the pressure-sensitive adhesive layer and the adherend (pressure-sensitive adhesive layer It is speculated that this may lead to a reduction in adhesion, which may cause cohesive failure or the like in the pressure-sensitive adhesive layer, not the interface of the adherend.
  • the stress of 100% modulus of the pressure-sensitive adhesive layer used in the laminate for a flexible image display device of the present invention is 0.01 to 0.08 N / mm 2
  • the stress of 500% modulus is 0.085 to 0.
  • solution polymerization is carried out using a (meth) acrylic monomer having an alkyl group having 4 to 12 carbon atoms, and further, an isocyanate crosslinking agent is used here.
  • a weight ratio of peroxide crosslinking agent to isocyanate crosslinking agent is 1.5 to 200 in combination with peroxide crosslinking agent.
  • the stress (X) of 100% modulus of the pressure-sensitive adhesive layer and the modulus ratio (Y / X) of stress (Y) of 500% modulus of the pressure-sensitive adhesive layer used in the laminate for a flexible image display device of the present invention are And 1.2 to 20 is preferable, 2 to 10 is more preferable, 2.4 to 8 is more preferable, and 2.7 to 6 is particularly preferable.
  • the modulus ratio (Y / X) is in the above range, the cohesion can be enhanced while maintaining the ease of deformation due to a minute strain, which is a preferable embodiment.
  • the transparent base material is previously subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical formation, oxidation or undercoating on the surface, and the transparent conductive layer provided thereon
  • an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical formation, oxidation or undercoating on the surface, and the transparent conductive layer provided thereon
  • the adhesion to the transparent substrate may be improved.
  • the constituent material of the transparent conductive layer is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten and molybdenum Or at least one metal or metal oxide, or an organic conductive polymer such as polythiophene.
  • the said metal oxide may contain the metal atom further shown by the said group as needed.
  • indium oxide (ITO) containing tin oxide, tin oxide containing antimony, etc. are preferably used, and ITO is particularly preferably used.
  • the ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
  • Crystalline ITO can be obtained by applying a high temperature at the time of sputtering or by further heating amorphous ITO.
  • the total light transmittance of the transparent conductive layer of the present invention is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
  • the surface resistance value of the transparent conductive layer of the present invention is preferably 0.1 to 1000 ⁇ / ⁇ , more preferably 0.5 to 500 ⁇ / ⁇ , and still more preferably 1 to 250 ⁇ / ⁇ .
  • an undercoat layer, an oligomer prevention layer, etc. can be provided as needed between a transparent conductive layer and a transparent base material.
  • the transparent conductive layer constituting the touch sensor can be disposed between the protective film and the window film (OCA) (see FIG. 3).
  • FIG. 2 is a cross-sectional view of one embodiment of a flexible image display according to the present invention.
  • the flexible image display device 100 includes a laminate 11 for flexible image display device and an organic EL display panel 10 configured to be foldable. Then, the laminate 11 for flexible image display device is disposed on the viewing side with respect to the organic EL display panel 10, and the flexible image display device 100 is configured to be bendable.
  • a transparent window 40 can be disposed on the viewing side with respect to the flexible image display device laminate 11 via the first pressure-sensitive adhesive layer 12-1.
  • the possibility that the stress generated by the shrinkage of the polarizing film causes the deformation such as warping in the adjacent organic EL display panel 10 is greatly reduced, and the display quality deterioration due to the deformation and the breakage of the panel sealing material are significantly reduced. It is possible to In addition, the use of a thin polarizing film does not inhibit bending, which is a preferred embodiment.
  • the third pressure-sensitive adhesive layer 12-3 can be disposed when the window 40 is disposed on the viewing side with respect to the laminate 11 for flexible image display device.
  • the numerical values in the table are the blending amount (addition amount), and indicate the solid content or the solid content ratio (based on weight).
  • the contents of the formulation and the evaluation results are shown in Tables 1 to 6.
  • acetoacetyl-modified PVA manufactured by Japan Synthetic Chemical Industry Co., Ltd., trade name: GOCEFIMER Z 200 (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%)
  • GOCEFIMER Z 200 average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%
  • a 1 wt% added PVA degree of polymerization 4200, degree of saponification 99.2%
  • prepare a coating solution of a PVA aqueous solution of 5.5 wt% PVA resin and dry the film thickness And dried for 10 minutes by hot-air drying in an atmosphere of 60 ° C. to produce a laminate having a layer of PVA resin on the substrate.
  • this laminate was first subjected to free end stretching at a temperature of 130 ° C. in air at 1.8 times (air-assisted stretching) to form a stretched laminate.
  • a step of insolubilizing the PVA layer in which the PVA molecules contained in the stretched laminate were oriented was performed by immersing the stretched laminate in a boric acid insolubilizing aqueous solution at a liquid temperature of 30 ° C. for 30 seconds.
  • the boric acid insolubilizing aqueous solution of this step had a boric acid content of 3 parts by weight with respect to 100 parts by weight of water.
  • a colored laminate was produced by dyeing this stretched laminate.
  • the polarizing film and the protective film were bonded to each other using an adhesive shown below to obtain a polarizing film.
  • the adhesive after laminating the protective film and the polarizing film through the adhesive, the adhesive is cured by irradiating ultraviolet rays, and the adhesive layer Formed.
  • a gallium-filled metal halide lamp Fusion UV Systems, Inc., trade name “Light HAMMER 10”, bulb: V bulb, peak illuminance: 1600 mW / cm 2 , integrated dose 1000 / mJ / cm 2 (wavelength 380-440 nm) was used.
  • the liquid crystal material was cured by irradiation of ultraviolet rays by the ultraviolet irradiation device 27, and thereby, a configuration relating to the retardation layer for a 1 ⁇ 4 wavelength plate was created.
  • the substrate 14 is conveyed to the die 32 by the conveyance roller 31, and the coating liquid of the ultraviolet curable resin 12 is applied onto the retardation layer for quarter wave plate of the substrate 14 by the die 32.
  • the roll plate 40 was a cylindrical shaping mold in which the concavo-convex shape of the alignment film for a half wave plate of the quarter wave retardation plate was formed on the peripheral side.
  • the first pressure-sensitive adhesive layer is formed into a first pressure-sensitive adhesive layer having a thickness of 50 ⁇ m based on the contents of the formulations in Tables 2 and 3, and a polyimide film having a thickness of 75 ⁇ m
  • a separator with a first pressure-sensitive adhesive layer was transferred to the surface (corona-treated) of (PI film, Toray DuPont Co., Ltd., Kapton 300V, base material) to form a pressure-sensitive adhesive layer-attached PI film .
  • the third pressure-sensitive adhesive layer is formed into a 50 ⁇ m-thick third pressure-sensitive adhesive layer based on the formulation contents in Tables 2 and 3, and a 125 ⁇ m-thick PET film A separator with a third pressure-sensitive adhesive layer was transferred to the surface (corona-treated) of a transparent substrate (Mitsubishi Resins Co., Ltd., trade name: diamond foil) to form a PET film with a pressure-sensitive adhesive layer. .

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention a pour objet de fournir un stratifié destiné à un dispositif d'affichage d'image flexible dans lequel, suite à l'utilisation d'un film optique, qui comprend au moins un film polarisant, et une couche adhésive sensible à la pression comprenant un module spécifique, une excellente résistance à la flexion et une excellente adhérence sont mises en évidence sans l'apparition de décollement ou de fissuration lors d'une flexion répétée à température ordinaire et même dans un environnement à haute température, et également de fournir un dispositif d'affichage d'image flexible sur lequel le stratifié destiné à un dispositif d'affichage d'image flexible est disposé. Le stratifié destiné à un dispositif d'affichage d'image flexible comprenant une couche adhésive sensible à la pression et un film optique comprenant au moins un film polarisant est caractérisé en ce qu'une contrainte à un module de 100 % de la couche adhésive sensible à la pression est comprise entre 0,01 et 0,1 N/mm2, et qu'une contrainte à un module de 500 % de la couche adhésive sensible à la pression est comprise entre 0,05 et 0,2 N/mm2.
PCT/JP2018/028067 2017-07-31 2018-07-26 Stratifié destiné à un dispositif d'affichage d'image flexible, et dispositif d'affichage d'image flexible WO2019026751A1 (fr)

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JP2019534446A JPWO2019026751A1 (fr) 2017-07-31 2018-07-26

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JP2017148688 2017-07-31
JP2017-148688 2017-07-31

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112213810A (zh) * 2019-07-12 2021-01-12 住友化学株式会社 光学层叠体和显示装置
WO2022255210A1 (fr) * 2021-05-31 2022-12-08 日東電工株式会社 Composition d'agent adhésif, agent adhésif et film de protection de surface
WO2024106096A1 (fr) * 2022-11-15 2024-05-23 三菱ケミカル株式会社 Feuille adhésive, feuille adhésive avec film antiadhésif l'utilisant, stratifié pour dispositif d'écran, dispositif d'écran flexible, feuille adhésive pour élément constitutif de dispositif d'écran flexible, et composition adhésive

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1044294A (ja) * 1996-08-01 1998-02-17 Nitto Denko Corp 光学フィルム及び液晶表示装置
JP2004083837A (ja) * 2002-06-24 2004-03-18 Dainippon Ink & Chem Inc オーバーラミネート用粘着シート
JP2004085522A (ja) * 2002-06-24 2004-03-18 Dainippon Ink & Chem Inc 粘着シートの評価方法及び該方法により得られる粘着シート
JP2004323543A (ja) * 2003-04-21 2004-11-18 Nitto Denko Corp 光学部材用粘着剤組成物、光学部材用粘着剤層、粘着型光学部材および画像表示装置
US20160231486A1 (en) * 2015-02-11 2016-08-11 Dongwoo Fine-Chem Co., Ltd. Highly Durable Polarizing Plate And Display Device Comprising The Same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1044294A (ja) * 1996-08-01 1998-02-17 Nitto Denko Corp 光学フィルム及び液晶表示装置
JP2004083837A (ja) * 2002-06-24 2004-03-18 Dainippon Ink & Chem Inc オーバーラミネート用粘着シート
JP2004085522A (ja) * 2002-06-24 2004-03-18 Dainippon Ink & Chem Inc 粘着シートの評価方法及び該方法により得られる粘着シート
JP2004323543A (ja) * 2003-04-21 2004-11-18 Nitto Denko Corp 光学部材用粘着剤組成物、光学部材用粘着剤層、粘着型光学部材および画像表示装置
US20160231486A1 (en) * 2015-02-11 2016-08-11 Dongwoo Fine-Chem Co., Ltd. Highly Durable Polarizing Plate And Display Device Comprising The Same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112213810A (zh) * 2019-07-12 2021-01-12 住友化学株式会社 光学层叠体和显示装置
WO2022255210A1 (fr) * 2021-05-31 2022-12-08 日東電工株式会社 Composition d'agent adhésif, agent adhésif et film de protection de surface
WO2024106096A1 (fr) * 2022-11-15 2024-05-23 三菱ケミカル株式会社 Feuille adhésive, feuille adhésive avec film antiadhésif l'utilisant, stratifié pour dispositif d'écran, dispositif d'écran flexible, feuille adhésive pour élément constitutif de dispositif d'écran flexible, et composition adhésive

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TW201910460A (zh) 2019-03-16
JPWO2019026751A1 (fr) 2019-02-07

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