WO2017111038A1 - 有機el表示装置 - Google Patents
有機el表示装置 Download PDFInfo
- Publication number
- WO2017111038A1 WO2017111038A1 PCT/JP2016/088410 JP2016088410W WO2017111038A1 WO 2017111038 A1 WO2017111038 A1 WO 2017111038A1 JP 2016088410 W JP2016088410 W JP 2016088410W WO 2017111038 A1 WO2017111038 A1 WO 2017111038A1
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- Prior art keywords
- pressure
- sensitive adhesive
- adhesive layer
- layer
- film
- Prior art date
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- 229920001194 natural rubber Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- TWCBCCIODCKPGX-UHFFFAOYSA-N octyl 2-[4-[4,6-bis(4-phenylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoate Chemical compound OC1=CC(OC(C)C(=O)OCCCCCCCC)=CC=C1C1=NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=N1 TWCBCCIODCKPGX-UHFFFAOYSA-N 0.000 description 1
- REJKHFKLPFJGAQ-UHFFFAOYSA-N oxiran-2-ylmethanethiol Chemical compound SCC1CO1 REJKHFKLPFJGAQ-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- YKEAZOGAZWPICS-UHFFFAOYSA-N phenyl 2-hydroxy-3-methoxybenzoate Chemical compound COC1=CC=CC(C(=O)OC=2C=CC=CC=2)=C1O YKEAZOGAZWPICS-UHFFFAOYSA-N 0.000 description 1
- YEBPMWUBZDANBU-UHFFFAOYSA-N phenyl 2-hydroxy-3-methylbenzoate Chemical compound CC1=CC=CC(C(=O)OC=2C=CC=CC=2)=C1O YEBPMWUBZDANBU-UHFFFAOYSA-N 0.000 description 1
- HFZCMVHAJOXWIY-UHFFFAOYSA-N phenyl 2-hydroxy-4-methylbenzoate Chemical compound OC1=CC(C)=CC=C1C(=O)OC1=CC=CC=C1 HFZCMVHAJOXWIY-UHFFFAOYSA-N 0.000 description 1
- AMLDDICCKSCSQI-UHFFFAOYSA-N phenyl 2-hydroxy-5-methylbenzoate Chemical compound CC1=CC=C(O)C(C(=O)OC=2C=CC=CC=2)=C1 AMLDDICCKSCSQI-UHFFFAOYSA-N 0.000 description 1
- KTOUIDNVCQYAQQ-UHFFFAOYSA-N phenyl 2-prop-2-enoyloxybenzoate Chemical compound C=CC(=O)OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 KTOUIDNVCQYAQQ-UHFFFAOYSA-N 0.000 description 1
- VBJPJCCADDYOSB-UHFFFAOYSA-N phenyl 3-methoxy-2-prop-2-enoyloxybenzoate Chemical compound COC1=CC=CC(C(=O)OC=2C=CC=CC=2)=C1OC(=O)C=C VBJPJCCADDYOSB-UHFFFAOYSA-N 0.000 description 1
- ABLABINHTJNBGN-UHFFFAOYSA-N phenyl 3-methyl-2-prop-2-enoyloxybenzoate Chemical compound CC1=CC=CC(C(=O)OC=2C=CC=CC=2)=C1OC(=O)C=C ABLABINHTJNBGN-UHFFFAOYSA-N 0.000 description 1
- VHDQRJJAZGSSIV-UHFFFAOYSA-N phenyl 5-methyl-2-prop-2-enoyloxybenzoate Chemical compound CC1=CC=C(OC(=O)C=C)C(C(=O)OC=2C=CC=CC=2)=C1 VHDQRJJAZGSSIV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
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- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007965 rubber solvent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- RKYSDIOEHLMYRS-UHFFFAOYSA-N triethoxy(hex-5-enyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCC=C RKYSDIOEHLMYRS-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
Definitions
- the present invention relates to an organic EL (electroluminescence) display device (OLED).
- OLED organic EL
- an organic EL display device has a circularly polarizing plate (polarizing plate 1 and a polarizing plate 1) on a surface on the viewing side of an organic EL panel in order to prevent external light from being reflected by a metal electrode (cathode) and viewed like a mirror surface. / 4 wavelength plate laminate or the like) is disposed.
- a decorative panel etc. may be further laminated
- the constituent members of the organic EL display device such as the circularly polarizing plate and the decorative panel are usually laminated via a bonding material such as an adhesive layer and an adhesive layer.
- a component or the like in the image display device may be deteriorated by incident ultraviolet light, and a layer containing an ultraviolet absorber in order to suppress deterioration due to the ultraviolet light. It is known to provide Specifically, for example, it has at least one ultraviolet absorbing layer, the light transmittance at a wavelength of 380 nm is 30% or less, and the visible light transmittance at a wavelength longer than the wavelength of 430 nm is 80% or more.
- Transparent double-sided pressure-sensitive adhesive sheets for image display devices for example, see Patent Document 1
- pressure-sensitive adhesive sheets having a pressure-sensitive adhesive layer containing an acrylic polymer and a triazine-based ultraviolet absorber are known (for example, see Patent Document 2).
- the pressure-sensitive adhesive sheets described in Patent Documents 1 and 2 can control the transmittance of light having a wavelength of 380 nm.
- the organic EL element can be used over a long period of time. May deteriorate and was not sufficient.
- the pressure-sensitive adhesive sheets described in Patent Documents 1 and 2 can absorb light having a wavelength of 380 nm, but the wavelength region on the shorter wavelength side (380 nm) than the light emitting region of the organic EL element (longer wavelength side than 430 nm). ( ⁇ 430 nm) light is not sufficiently absorbed, and it is considered that deterioration is caused by the transmitted light.
- an object of the present invention is to provide an organic EL display device having a mechanism capable of suppressing deterioration of an organic EL element.
- the present invention is an organic EL display device including a polarizer, a retardation film, an optical laminate including at least one other layer, and an organic EL panel,
- the ultraviolet absorber and the dye compound present in the wavelength region of the absorption spectrum having a maximum absorption wavelength of 380 to 430 nm are blended in separate layers constituting the optical laminate,
- the present invention relates to an organic EL display device characterized in that a layer having an ultraviolet absorber is present on the viewer side of a layer having a dye compound.
- the optical laminate includes at least an adhesive layer, a transparent protective film, a polarizer, a retardation film, and an adhesive layer in this order,
- the ultraviolet absorber is blended in the layer on the viewing side from the polarizer,
- the dye compound is preferably blended in a layer closer to the organic EL panel than the polarizer.
- the ultraviolet absorber is blended in at least one layer selected from the group consisting of the adhesive layer, the transparent protective film, and the retardation film, and the dye compound is blended in the pressure-sensitive adhesive layer. It is preferable.
- the dye compound is preferably an organic dye compound.
- the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength region of 300 to 400 nm.
- the organic EL display device of the present invention has a light emitting region of an organic EL element because a layer containing an ultraviolet absorber and a dye compound existing in a wavelength region having a maximum absorption wavelength of 380 to 430 nm in a specific order exists. Light with a wavelength shorter than 430 nm (380 nm to 430 nm) is sufficiently absorbed, and deterioration of the organic EL element can be suppressed.
- the layer containing the ultraviolet absorber is present on the viewer side from the layer containing the dye compound, it is possible to prevent the dye compound from being deteriorated by being exposed to ultraviolet rays. The deterioration of the organic EL element can be suppressed.
- the organic EL display device of the present invention includes a polarizer, a retardation film, an optical laminate including at least one other layer, and an organic EL panel,
- the ultraviolet absorber and the dye compound present in the wavelength region of the absorption spectrum having a maximum absorption wavelength of 380 to 430 nm are blended in separate layers constituting the optical laminate,
- the layer having an ultraviolet absorber exists on the viewer side from the layer having a dye compound.
- the optical layered body only needs to include a polarizer, a retardation film, and at least one other layer, and the other layers are not particularly limited.
- a preferred embodiment of the optical layered body is shown in FIG. 1, but the present invention is not limited to this.
- the optical laminate 1 has at least an adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 6 laminated in this order from the viewing side.
- the film 5 / (organic EL panel side second) pressure-sensitive adhesive layer 6 may be laminated in this order.
- the transparent protective film 4 / polarizer 5 may be referred to as a polarizing film.
- the ultraviolet absorber and the dye compound may be blended in separate layers constituting the optical layered body, and the layer containing the ultraviolet absorber may be disposed on the viewer side from the layer containing the dye compound.
- the layer containing the dye compound is closer to the organic EL panel than the layer containing the ultraviolet absorber
- the layer to be blended is not particularly limited.
- the layer containing the ultraviolet absorber is disposed on the viewing side from the polarizer, and the layer containing the dye compound is on the organic EL panel side than the polarizer.
- the layer in which the ultraviolet absorber is blended is preferably at least one layer selected from the group consisting of the adhesive layer 2, the transparent protective film 3, and the retardation film 5.
- the adhesive layer 2 or the transparent protective film 3 is more preferable, and the adhesive layer 2 is particularly preferable.
- the ultraviolet absorber may be mix
- the layer in which the dye compound is blended is preferably the retardation film 5 or the pressure-sensitive adhesive layer 6, and more preferably the pressure-sensitive adhesive layer 6.
- dye compound may be mix
- dye compound may be added to the transparent protective film by the side of an organic EL panel.
- the ultraviolet absorber is not particularly limited.
- a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, an oxybenzophenone ultraviolet absorber, or a salicylic acid ester ultraviolet ray An absorber, a cyanoacrylate type ultraviolet absorber, etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
- triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable, triazine-based UV absorbers having 2 or less hydroxyl groups in one molecule, and benzones having one benzotriazole skeleton in one molecule.
- triazine ultraviolet absorbers having 2 or less hydroxyl groups in one molecule include 2,4-bis-[ ⁇ 4- (4-ethylhexyloxy) -4-hydroxy ⁇ -phenyl] -6. -(4-Methoxyphenyl) -1,3,5-triazine (Tinosorb S, manufactured by BASF), 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine (TINUVIN 460, manufactured by BASF), 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl And [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane reaction product (TINUVIN400, manufactured by BASF), 2- [4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazin-2-yl]
- benzophenone ultraviolet absorber (benzophenone compound) and oxybenzophenone ultraviolet absorber (oxybenzophenone compound)
- examples of the benzophenone ultraviolet absorber (benzophenone compound) and oxybenzophenone ultraviolet absorber (oxybenzophenone compound) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy. -4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone (SeeSorb 106, manufactured by Cypro Kasei Co., Ltd.) , , 2'-dihydroxy-4-
- salicylic acid ester ultraviolet absorber examples include, for example, phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, and phenyl-2-acryloyloxy.
- cyanoacrylate ultraviolet absorber examples include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl- Examples include 2-cyanoacrylate.
- the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength region of 300 to 400 nm, and more preferably in the wavelength region of 300 to 380 nm.
- the maximum absorption wavelength means the absorption maximum wavelength exhibiting the maximum absorbance among the plurality of absorption maximums in the spectral absorption spectrum in the wavelength region of 300 to 460 nm. .
- the ultraviolet absorber may be used alone or in combination of two or more, but the total content is the total weight of the layer to which the ultraviolet absorber is added (100% by weight). ) Is preferably about 0.1 to 10% by weight, more preferably about 0.1 to 8% by weight. It is preferable to set the addition amount of the ultraviolet absorber within the above range since the ultraviolet absorber addition layer can sufficiently exhibit the ultraviolet absorption function. Moreover, when adding an ultraviolet absorber to 2 or more layers, it is preferable that the amount of ultraviolet absorbers in all the layers becomes the said range.
- the said ultraviolet absorber when adding the said ultraviolet absorber to the said adhesive layer 2, the said ultraviolet absorber may be used independently and may be used in mixture of 2 or more types, The content of is preferably about 0.1 to 8 parts by weight with respect to 100 parts by weight of the monofunctional monomer component forming the base polymer for forming the adhesive layer 2; More preferably, it is about parts by weight.
- the addition amount of the ultraviolet absorber within the above range, it is preferable that the ultraviolet ray absorbing function of the pressure-sensitive adhesive layer can be sufficiently exhibited, and when the ultraviolet polymerization is performed, the polymerization is not hindered.
- the amount of ultraviolet absorbers in all the layers becomes the said range.
- the dye compound used in the present invention is not particularly limited as long as it is a compound having a maximum absorption wavelength of an absorption spectrum in a wavelength region of 380 to 430 nm.
- the maximum absorption wavelength of the absorption spectrum of the dye compound is more preferably in the wavelength region of 380 to 420 nm.
- the maximum absorption wavelength means the absorption maximum wavelength exhibiting the maximum absorbance among the plurality of absorption maximums in the spectral absorption spectrum in the wavelength region of 300 to 460 nm.
- the dye compound is not particularly limited as long as it has the above-mentioned wavelength characteristics, but a material that does not have fluorescence and phosphorescence performance (photoluminescence) so as not to hinder the display properties of the organic EL element is preferable.
- the full width at half maximum of the dye compound is not particularly limited, but is preferably 80 nm or less, more preferably 5 to 70 nm, and still more preferably 10 to 60 nm.
- the half-value width of the dye compound is in the above range, it is possible to control to sufficiently transmit light having a wavelength longer than 430 nm while sufficiently absorbing light in a region that does not affect light emission of the organic EL element. Therefore, it is preferable.
- the measuring method of a half value width is based on the method as described below.
- ⁇ Measurement method of half width> The full width at half maximum of the dye compound was measured from a transmission absorption spectrum of the solution of the dye compound under the following conditions using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science Co., Ltd.). From the spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength is 1.0, the wavelength interval (full width at half maximum) between two points at 50% of the peak value is defined as the half width of the dye compound. . (Measurement condition) Solvent: Toluene or chloroform Cell: Quartz cell Optical path length: 10 mm
- the dye compound may be any compound that has a maximum absorption wavelength in the absorption spectrum in the wavelength region of 380 to 430 nm, and the structure thereof is not particularly limited.
- the dye compound include an organic dye compound and an inorganic dye compound.
- an organic dye is used from the viewpoint of maintaining dispersibility in a resin component such as a base polymer and transparency. Compounds are preferred.
- the organic dye compound is preferably a material having no fluorescence and phosphorescence performance (photoluminescence).
- organic dye compound examples include azomethine compounds, indole compounds, cinnamic acid compounds, pyrimidine compounds, porphyrin compounds, and the like.
- the organic dye compound a commercially available product can be suitably used.
- the indole compound BONASORB UA3911 (trade name, maximum absorption wavelength of absorption spectrum: 398 nm, half width: 48 nm, manufactured by Orient Chemical Industry Co., Ltd.), BONASORB UA3912 (trade name, maximum absorption wavelength of absorption spectrum: 386 nm, half width: 53 nm, manufactured by Orient Chemical Industry Co., Ltd.), and cinnamate compounds as SOM -5-0106 (trade name, absorption spectrum maximum absorption wavelength: 416 nm, full width at half maximum: 50 nm, manufactured by Orient Chemical Co., Ltd.), porphyrin compounds include FDB-001 (trade name, absorption spectrum maximum absorption wavelength : 420 nm, half width: 14 nm, manufactured by Yamada Chemical Co., Ltd.) It can gel.
- the dye compound may be used alone or in combination of two or more, but the total content is the total weight (100% by weight) of the layer to which the dye compound is added. On the other hand, it is preferably about 0.01 to 10% by weight, more preferably about 0.02 to 7% by weight.
- the addition amount of the dye compound in the above range, it is preferable because light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed and deterioration of the organic EL element can be suppressed.
- dye compound when adding the said pigment
- the addition amount of the dye compound in the above range it is preferable because light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed and deterioration of the organic EL element can be suppressed.
- the optical laminate used in the present invention is at least the adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer from the viewing side. 6 are preferably laminated in this order (FIG. 1), adhesive layer 2 / (viewing side) transparent protective film 3 / polarizer 4 / organic EL panel side transparent protective film / organic EL panel side
- the first pressure-sensitive adhesive layer (or adhesive layer) / retardation film 5 / (organic EL panel side second) pressure-sensitive adhesive layer 6 may be laminated in this order.
- functional layers such as a hard coat layer, an antiglare treatment layer, and an antireflection layer, a sensor layer, and a pressure-sensitive adhesive layer and an adhesive layer for laminating them can be included.
- Adhesive layer 2 refers to a pressure-sensitive adhesive layer or an adhesive layer.
- Adhesive Layer As the adhesive layer, a layer made of any appropriate adhesive can be adopted. Examples of such adhesives include natural rubber adhesives, ⁇ -olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin hot melt adhesives, and epoxy resins.
- Adhesives vinyl chloride resin solvent adhesives, chloroprene rubber adhesives, cyanoacrylate adhesives, silicone adhesives, styrene-butadiene rubber solvent adhesives, nitrile rubber adhesives, nitrocellulose adhesives, Reactive hot melt adhesives, phenol resin adhesives, modified silicone adhesives, polyester hot melt adhesives, polyamide resin hot melt adhesives, polyimide adhesives, polyurethane resin hot melt adhesives, polyolefin resin hot melt adhesives
- Adhesive polyvinyl acetate resin solvent-based adhesive, Styrene resin solvent adhesive, polyvinyl alcohol adhesive, polyvinyl pyrrolidone resin adhesive, polyvinyl butyral adhesive, polybenzimidazole adhesive, polymethacrylate resin solvent adhesive, melamine resin adhesive, urea resin adhesive Agents, resorcinol adhesives, and the like.
- Such an adhesive agent can be used individually by 1 type or in mixture of 2 or more types.
- adhesives include, for example, thermosetting adhesives and hot-melt adhesives when classified according to the adhesive form. Only one kind of such an adhesive may be used, or two or more kinds thereof may be used.
- thermosetting adhesive exhibits an adhesive force when cured by heating and solidified.
- thermosetting adhesive include an epoxy thermosetting adhesive, a urethane thermosetting adhesive, and an acrylic thermosetting adhesive.
- the curing temperature of the thermosetting adhesive is, for example, 100 to 200 ° C.
- the hot melt adhesive is melted or softened by heating, thermally fused to the adherend, and then solidified by cooling to adhere to the adherend.
- hot melt adhesives include rubber hot melt adhesives, polyester hot melt adhesives, polyolefin hot melt adhesives, ethylene-vinyl acetate resin hot melt adhesives, polyamide resin hot melt adhesives, and polyurethane resins. Examples thereof include hot melt adhesives.
- the softening temperature (ring ball method) of the hot melt adhesive is, for example, 100 to 200 ° C.
- the melt viscosity of the hot melt adhesive is 180 ° C., for example, 100 to 30000 mPa ⁇ s.
- the thickness of the adhesive layer is not particularly limited, but is preferably about 0.01 to 10 ⁇ m, and more preferably about 0.05 to 8 ⁇ m.
- the type of pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, Examples thereof include urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, and cellulose adhesives.
- acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate adhesiveness, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like.
- an acrylic pressure-sensitive adhesive composition containing a (meth) acrylic polymer as a base polymer is preferable.
- the acrylic pressure-sensitive adhesive composition preferably includes, for example, a partial polymer of a monomer component containing an alkyl (meth) acrylate and / or a (meth) acrylic polymer obtained from the monomer component.
- An ultraviolet absorber or a dye compound can be added to the agent composition.
- the acrylic pressure-sensitive adhesive composition includes a partially polymerized monomer component containing an alkyl (meth) acrylate and / or a (meth) acrylic polymer obtained from the monomer component.
- alkyl (meth) acrylate examples include those having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester end.
- Alkyl (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.
- Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
- alkyl (meth) acrylate examples include the aforementioned linear or branched alkyl (meth) acrylates having 1 to 24 carbon atoms, and among these, alkyl (meth) having 1 to 9 carbon atoms. Acrylates are preferred, and alkyl (meth) acrylates having 4 to 9 carbon atoms are preferred.
- the alkyl (meth) acrylate is preferable in terms of easily balancing the adhesive properties.
- Specific examples of the alkyl (meth) acrylate having 4 to 9 carbon atoms include n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (meth).
- n-pentyl (meth) acrylate isopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, etc.
- These can be used alone or in combination of two or more.
- the alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms at the ester terminal is 40% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. It is preferably 50% by weight or more, more preferably 60% by weight or more.
- the monomer component may contain a copolymerization monomer other than the alkyl (meth) acrylate as a monofunctional monomer component.
- a copolymerization monomer can be used as the remainder of the said alkyl (meth) acrylate in a monomer component.
- a cyclic nitrogen-containing monomer can be included.
- a polymerizable functional group which has unsaturated double bonds such as a (meth) acryloyl group or a vinyl group
- has a cyclic nitrogen structure can be especially used without a restriction
- the cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure.
- cyclic nitrogen-containing monomers examples include lactam vinyl monomers such as N-vinyl pyrrolidone, N-vinyl- ⁇ -caprolactam, and methyl vinyl pyrrolidone; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as imidazole, vinyl oxazole and vinyl morpholine. Moreover, the (meth) acryl monomer containing heterocyclic rings, such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, is mentioned.
- N-acryloylmorpholine N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like.
- lactam vinyl monomers are preferable.
- the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by weight, and preferably 0.5 to 40% by weight, based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable, and 0.5 to 30% by weight is even more preferable.
- the monomer component used in the present invention can contain a hydroxyl group-containing monomer as a monofunctional monomer component.
- a hydroxyl group-containing monomer a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; -Hydroxyalkylcycloalkane (meth) acrylates such as -hydroxymethylcyclohexyl) methyl (meth) acrylate.
- hydroxyethyl (meth) acrylamide examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. These can be used alone or in combination. Of these, hydroxyalkyl (meth) acrylate is preferred.
- the hydroxyl group-containing monomer is preferably 1% by weight or more from the viewpoint of enhancing adhesive force and cohesive force with respect to the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, It is more preferably 2% by weight or more, and further preferably 3% by weight or more.
- the amount of the hydroxyl group-containing monomer is too large, the pressure-sensitive adhesive layer becomes hard and the adhesive strength may decrease, and the viscosity of the pressure-sensitive adhesive may become too high or gel.
- the hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 27% by weight or less, and more preferably 25% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable.
- the monomer component that forms the (meth) acrylic polymer can contain other functional group-containing monomers as monofunctional monomers, such as carboxyl group-containing monomers and monomers having a cyclic ether group. It is done.
- carboxyl group-containing monomer a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation.
- the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Can be used alone or in combination. These anhydrides can be used for itaconic acid and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.
- a carboxyl group-containing monomer can be arbitrarily used for the monomer component used for manufacture of the (meth) acrylic-type polymer of this invention, On the other hand, it is not necessary to use a carboxyl group-containing monomer.
- a monomer having a cyclic ether group a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group.
- the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like.
- Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl-oxetanylmethyl (meth) acrylate and the like. These can be used alone or in combination.
- the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, and 27% by weight. % Or less is more preferable, and 25% by weight or less is more preferable.
- the monomer component forming the (meth) acrylic polymer of the present invention includes, for example, CH 2 ⁇ C (R 1 ) COOR 2 (wherein R 1 is hydrogen or a methyl group, and R 2 is the number of carbon atoms). And an alkyl (meth) acrylate represented by 1 to 3 substituted alkyl groups and cyclic cycloalkyl groups.
- the substituent of the substituted alkyl group having 1 to 3 carbon atoms as R 2 is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms.
- the aryl group is not limited, but is preferably a phenyl group.
- Examples of such a monomer represented by CH 2 ⁇ C (R 1 ) COOR 2 include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl. (Meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned. These can be used alone or in combination.
- the (meth) acrylate represented by CH 2 ⁇ C (R 1 ) COOR 2 is 50% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. 45% by weight or less is preferable, 40% by weight or less is more preferable, and 35% by weight or less is more preferable.
- copolymerization monomers include vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; Monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers and the like can also be used. Moreover, as a copolymerization monomer, the monomer which has cyclic structures, such as terpene (meth) acrylate and dicyclopentanyl (meth) acrylate, can be used.
- silane monomers containing silicon atoms examples include silane monomers containing silicon atoms.
- examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
- the monomer component that forms the (meth) acrylic polymer of the present invention contains a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive, in addition to the monofunctional monomer exemplified above. be able to.
- the polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as (poly) ethylene glycol di (meth) acrylate, (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) acrylate Ester compounds of poly
- trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used.
- a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
- the amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but it is preferably used at 3 parts by weight or less, more preferably 2 parts by weight or less, with respect to a total of 100 parts by weight of the monofunctional monomer. 1 part by weight or less is more preferable. Moreover, it does not specifically limit as a lower limit, However It is preferable that it is 0 weight part or more, and it is more preferable that it is 0.001 weight part or more. Adhesive force can be improved when the usage-amount of a polyfunctional monomer exists in the said range.
- the production of the (meth) acrylic polymer can be appropriately selected from known production methods such as radiation polymerization such as solution polymerization and ultraviolet (UV) polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
- a partial polymer of the monomer component can also be suitably used.
- polymerization can be carried out by appropriately adding a polymerization initiator, a chain transfer agent, an emulsifier and the like used for radical polymerization to the monomer component.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for the radical polymerization are not particularly limited and can be appropriately selected and used.
- the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, and the usage-amount is suitably adjusted according to these kinds.
- solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
- the reaction is carried out in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
- thermal polymerization initiators used for solution polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (2 -Methylpropionic acid) 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, 2,2′-azobis (N, N′-dimethyleneisobutyl) Amidine), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, Wako Pure Chemical Industries, Ltd.) Azo initiators such as potassium persulfate, ammonium persulfate,
- Examples include oxide initiators, redox initiators that combine a peroxide and a reducing agent, such as a combination of persulfate and sodium bisulfite, and a combination of peroxide and sodium ascorbate. It is not limited to.
- the polymerization initiator may be used alone or in combination of two or more, but is preferably about 1 part by weight or less with respect to 100 parts by weight of the total amount of monomer components.
- the amount is more preferably about 0.005 to 1 part by weight, and further preferably about 0.02 to 0.5 part by weight.
- the amount of the polymerization initiator used is about 0.2 parts by weight or less with respect to 100 parts by weight of the total amount of monomer components.
- the amount is preferably about 0.06 to 0.2 parts by weight.
- chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
- the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.3 parts by weight relative to 100 parts by weight of the total amount of monomer components. Less than or equal to
- emulsifier used in emulsion polymerization examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer and the like can be mentioned. These emulsifiers may be used alone or in combination of two or more.
- reactive emulsifiers as emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SE10N (manufactured by ADEKA), and the like.
- the amount of the emulsifier used is preferably 5 parts by weight or less with respect to 100 parts by weight of the total amount of the monomer components.
- the (meth) acrylic polymer when produced by radiation polymerization, it can be produced by polymerizing the monomer component by irradiating the monomer component with radiation such as an electron beam or ultraviolet (UV). Among these, ultraviolet polymerization is preferable.
- ultraviolet polymerization which is a preferable embodiment in radiation polymerization will be described.
- the photopolymerization initiator examples include a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm. Moreover, it is preferable that a photoinitiator (B) does not have an absorption band in wavelength 400nm or more.
- the photopolymerization initiator (B) is not particularly limited as long as it generates radicals by ultraviolet rays and starts photopolymerization and has an absorption band at a wavelength of less than 400 nm. Any initiator can be suitably used.
- benzoin ether photopolymerization initiator acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone A photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or the like can be used.
- examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- Examples thereof include 1-one and anisole methyl ether.
- acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4-t-butyldichloroacetophenone. Etc.
- Examples of ⁇ -ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy-2-methylpropan-1-one, and the like. Is mentioned.
- Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.
- benzoin photopolymerization initiator examples include benzoin.
- benzyl photopolymerization initiator examples include benzyl and the like.
- benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
- Ketal photopolymerization initiators include benzyl dimethyl ketal and the like.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthioxanthone, dodecylthioxanthone and the like are included.
- acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
- the photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be used alone or in combination of two or more.
- the photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be added within a range that does not impair the effects of the present invention, and the addition amount is a monofunctional that forms a (meth) acrylic polymer.
- the amount is preferably about 0.005 to 0.5 part by weight, more preferably about 0.02 to 0.1 part by weight based on 100 parts by weight of the monomeric monomer component.
- the pressure-sensitive adhesive layer contains an ultraviolet absorber (or a dye compound) and ultraviolet polymerization is performed, for example, the monomer component containing the alkyl (meth) acrylate and / or the monomer component It is preferably formed by ultraviolet polymerization of an ultraviolet curable acrylic pressure-sensitive adhesive composition containing a partial polymer, an ultraviolet absorber (or a dye compound), and a photopolymerization initiator. Since the pressure-sensitive adhesive layer formed by ultraviolet polymerization of the ultraviolet curable acrylic pressure-sensitive adhesive composition can be formed to have a thickness of 150 ⁇ m or more, and a pressure-sensitive adhesive layer having a wide thickness can be formed. preferable.
- the photopolymerization initiator preferably contains a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or longer.
- a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or longer When an ultraviolet absorber (or a dye compound) is included in the pressure-sensitive adhesive composition, when ultraviolet polymerization is performed, ultraviolet rays are absorbed by the ultraviolet absorber (or the dye compound), and there is a case where the polymerization cannot be sufficiently performed.
- the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is preferable because it can be sufficiently polymerized even if it contains an ultraviolet absorber (or a dye compound).
- photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF), 2,4,6-trimethylbenzoyl- And diphenyl-phosphine oxide (LUCIRIN TPO, manufactured by BASF).
- the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more may be used alone or in combination of two or more.
- the addition amount of the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is not particularly limited, but is preferably smaller than the addition amount of the ultraviolet absorber (or dye compound).
- the amount of the monofunctional monomer component forming the (meth) acrylic polymer is preferably about 0.005 to 1 part by weight and preferably about 0.02 to 0.8 part by weight. More preferred. It is preferable that the amount of the photopolymerization initiator (A) added is in the above range because ultraviolet polymerization can sufficiently proceed.
- a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm is included in the monomer component.
- the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is added to the partial polymerization product (prepolymer composition) of the monomer component partially polymerized by ultraviolet irradiation, the photopolymerization is started. It is preferable to add the agent after dissolving it in the monomer.
- the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent.
- the compounding amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. More preferred is 0.02 to 0.6 parts by weight.
- silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxy cyclohexyl).
- Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, (3-dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane ( (Meth) acrylic group-containing sila Coupling agents, such as isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like.
- the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent.
- crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Crosslinkers such as oxides are included.
- a crosslinking agent can be used alone or in combination of two or more. Among these, an isocyanate type crosslinking agent is preferably used.
- the crosslinking agent may be used alone or in combination of two or more, but the total content is a monofunctional monomer that forms a (meth) acrylic polymer.
- the amount is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 4 parts by weight, and 0.02 to 3 parts by weight with respect to 100 parts by weight of the component. Particularly preferred.
- the isocyanate-based cross-linking agent refers to a compound having two or more isocyanate groups (including an isocyanate-regenerating functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification) in one molecule.
- the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
- lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
- alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
- 2,4-tolylene diisocyanate Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethyle Isocyan
- the pressure-sensitive adhesive composition of the present invention may contain appropriate additives in addition to the above components depending on the application.
- tackifiers for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc., solid, semi-solid, or liquid at room temperature
- fillers such as hollow glass balloons; plasticizers; aging Inhibitors; antioxidants and the like.
- the pressure-sensitive adhesive composition is adjusted to a viscosity suitable for work such as coating on a substrate. Adjustment of the viscosity of the pressure-sensitive adhesive composition is performed, for example, by adding various polymers such as thickening additives, polyfunctional monomers, or the like, or by partially polymerizing the monomer components in the pressure-sensitive adhesive composition. The partial polymerization may be performed before or after adding various polymers such as thickening additives, polyfunctional monomers, and the like.
- the viscosity of the pressure-sensitive adhesive composition varies depending on the amount of the additive and the like, the polymerization rate when the monomer component in the pressure-sensitive adhesive composition is partially polymerized cannot be uniquely determined, but as a guideline, it is about 20% or less. It is preferably about 3 to 20%, more preferably about 5 to 15%. If it exceeds 20%, the viscosity becomes too high, so that it is difficult to apply to the substrate.
- the method for forming the pressure-sensitive adhesive layer is not particularly limited, and can be formed by a method usually used in this field. Specifically, the pressure-sensitive adhesive composition is applied to at least one surface of the substrate, and a coating film formed from the pressure-sensitive adhesive composition is formed by drying, or irradiated with active energy rays such as ultraviolet rays. Can be formed. The pressure-sensitive adhesive layer formed on the substrate can be transferred to a polarizing film or the like.
- the substrate is not particularly limited, and for example, various substrates such as a release film and a transparent resin film substrate, and a polarizing film described later can also be suitably used as the substrate.
- constituent material of the release film examples include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Suitable thin leaf bodies and the like can be mentioned, but a resin film is suitably used from the viewpoint of excellent surface smoothness.
- the resin film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
- -Vinyl acetate copolymer film and the like examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
- -Vinyl acetate copolymer film and the like examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthal
- the thickness of the release film is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- release agent and antifouling treatment with silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed.
- the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.
- the transparent resin film substrate is not particularly limited, and various resin films having transparency are used.
- the resin film is formed of a single layer film.
- the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins.
- polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
- the thickness of the film substrate is preferably 15 to 200 ⁇ m, and more preferably 25 to 188 ⁇ m.
- the pressure-sensitive adhesive composition is applied onto the substrate by roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain.
- a known and appropriate method such as a coat, a lip coat, or a die coater can be used and is not particularly limited.
- the drying conditions are not particularly limited, and the composition of the pressure-sensitive adhesive composition,
- the concentration can be appropriately set depending on the concentration or the like, and is, for example, about 60 to 170 ° C., preferably 60 to 150 ° C., for 1 to 60 minutes, preferably 2 to 30 minutes.
- the pressure-sensitive adhesive composition is an ultraviolet curable pressure-sensitive adhesive composition and is formed by irradiating a coating film formed from the ultraviolet-curable pressure-sensitive adhesive composition with ultraviolet rays
- the illuminance of the irradiated ultraviolet rays is 5 mW / cm 2 or more is preferable.
- the illuminance of the ultraviolet light is less than 5 mW / cm 2 , the polymerization reaction time becomes long and the productivity may be inferior.
- the illuminance of the ultraviolet light is preferably 200 mW / cm 2 or less.
- the photopolymerization initiator is consumed rapidly, so that the polymer has a low molecular weight, and the holding power particularly at high temperatures may be reduced.
- the integrated quantity of ultraviolet light is preferably 100mJ / cm 2 ⁇ 5000mJ / cm 2.
- the ultraviolet lamp used in the present invention is not particularly limited, but an LED lamp is preferable. Since the LED lamp has a lower emission heat than other ultraviolet lamps, the temperature during polymerization of the pressure-sensitive adhesive layer can be suppressed. Therefore, the molecular weight reduction of the polymer can be prevented, the cohesive strength of the pressure-sensitive adhesive layer can be prevented from being lowered, and the holding power at a high temperature when the pressure-sensitive adhesive sheet is used can be increased. It is also possible to combine a plurality of ultraviolet lamps. Further, it is possible to intermittently irradiate ultraviolet rays, and to provide a light period in which ultraviolet rays are irradiated and a dark period in which ultraviolet rays are not irradiated.
- the final polymerization rate of the monomer component in the ultraviolet curable pressure-sensitive adhesive composition is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.
- the peak wavelength of ultraviolet rays irradiated to the ultraviolet curable pressure-sensitive adhesive composition is preferably in the range of 200 to 500 nm, and more preferably in the range of 300 to 450 nm.
- the peak wavelength of ultraviolet rays exceeds 500 nm, the photopolymerization initiator may not be decomposed and the polymerization reaction may not start.
- the peak wavelength of the ultraviolet light is less than 200 nm, the polymer chain may be cut and the adhesive properties may be deteriorated.
- a release film or the like is formed on the coating film formed from the ultraviolet curable acrylic pressure-sensitive adhesive composition to block oxygen, or the photopolymerization reaction is performed by nitrogen. It is preferable to carry out in an atmosphere.
- the above-mentioned thing can be mentioned as a release film.
- the said release film can be used as a separator of a polarizing film with an adhesive layer as it is.
- the ultraviolet curable adhesive composition used by this invention contains a ultraviolet absorber (or pigment
- the composition containing the “addition polymerization initiator” may be irradiated with ultraviolet rays to form a partial polymer of the monomer component, and an ultraviolet absorber (or dye compound) is formed on the partial polymer of the monomer component.
- a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more (sometimes referred to as “post-addition polymerization initiator”) to prepare an ultraviolet curable pressure-sensitive adhesive composition.
- the polymerization rate of the partially polymerized product is preferably about 20% or less, more preferably about 3 to 20%, and further preferably about 5 to 15%.
- the ultraviolet irradiation conditions are as described above.
- the pressure-sensitive adhesive layer is formed from the ultraviolet curable pressure-sensitive adhesive composition containing the ultraviolet absorber (or dye compound), the polymerization rate of the monomer component is increased by polymerizing in the two steps as described above.
- the ultraviolet absorbing function of the finally produced pressure-sensitive adhesive layer can be improved.
- the thickness of the pressure-sensitive adhesive layer is preferably 12 ⁇ m or more, more preferably 50 ⁇ m or more, further preferably 100 ⁇ m or more, and particularly preferably 150 ⁇ m or more.
- the upper limit of the thickness of an adhesive layer is not specifically limited, It is preferable that it is 1 mm or less. When the thickness of the pressure-sensitive adhesive layer exceeds 1 mm, it becomes difficult to transmit ultraviolet rays, and it takes time to polymerize the monomer component, and causes problems in workability, winding in the process, and transportability, resulting in poor productivity. This is not preferable.
- the gel fraction of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 35% or more, more preferably 50% or more, and further preferably 75% or more, It is particularly preferably 85% or more. When the gel fraction of the pressure-sensitive adhesive layer is small, there may be a problem in workability and handling properties.
- the pressure-sensitive adhesive layer has a haze value measured at a thickness of 25 ⁇ m of preferably 2% or less, more preferably 0 to 1.5%, and further preferably 0 to 1%. It is preferable that the haze is in the above range because the pressure-sensitive adhesive layer has high transparency.
- the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until practical use.
- Polarizing film examples include those having a transparent protective film on at least one surface of a polarizer.
- Polarizer 4 The polarizer is not particularly limited, and various types can be used.
- polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
- the polyvinyl alcohol film In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
- a thin polarizer having a thickness of 10 ⁇ m or less can also be used.
- the thickness is preferably 1 to 7 ⁇ m.
- Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
- the thin polarizer typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or a patent.
- the thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned.
- These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
- PVA-based resin polyvinyl alcohol-based resin
- International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing.
- those obtained by a production method including a step of stretching in an aqueous boric acid solution as described in International Publication No. 2010/100917 pamphlet or Japanese Patent No. 47514881 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
- Those obtained by a production method including a step of stretching in the air before stretching in a boric acid aqueous solution described in the specification of 4751481 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
- a transparent protective film formed from a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable.
- a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate
- Cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- acrylic polymers such as polymethyl methacrylate
- styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
- AS resin acrylonitrile / styrene copolymer
- polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends.
- the transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
- the thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin film properties.
- the polarizer and the transparent protective film are in close contact with each other through an aqueous adhesive or the like.
- the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
- the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
- the electron beam curable polarizing film adhesive exhibits suitable adhesiveness with respect to the various viewing-side transparent protective films.
- the adhesive used in the present invention can contain a metal compound filler.
- a functional layer such as a hard coat layer, an antireflection layer, or an antisticking layer can be formed on the surface of the transparent protective film to which the polarizer is not adhered, and a treatment for diffusion or antiglare is performed. It may be.
- the hard coat layer for example, a cured film made of a curable resin such as a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, or a silicone resin is preferably used.
- the thickness of the hard coat layer is preferably 0.1 to 30 ⁇ m.
- An ultraviolet absorber a light stabilizer (HALS), an antioxidant, or a dye compound can be added to the functional layer.
- HALS light stabilizer
- an antioxidant an antioxidant
- a dye compound can be added to the functional layer.
- nx ny includes not only the case where nx and ny are completely the same, but also the case where nx and ny are substantially the same.
- ny nz includes not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.
- the retardation film is preferably a 1 ⁇ 4 wavelength plate with a front retardation of 1 ⁇ 4 wavelength (about 100 to 170 nm).
- Lamination of the polarizing film and the quarter wave plate is preferable because it functions as a circularly polarizing film for preventing reflection of an organic EL display device.
- This linearly polarized light is generally elliptically polarized light by the retardation film, but becomes circularly polarized light particularly when the retardation film is a quarter wavelength plate and the angle formed by the polarization direction with the retardation film is ⁇ / 4.
- This circularly polarized light is transmitted through the transparent substrate, transparent electrode and organic thin film in the organic EL panel, reflected by the metal electrode, again transmitted through the organic thin film, transparent electrode and transparent substrate, and again linearly polarized by the retardation film. It becomes. And since this linearly polarized light is orthogonal to the polarization direction of a polarizing film, it cannot permeate
- Adhesive layer 6 examples of the pressure-sensitive adhesive layer 6 (pressure-sensitive adhesive layer on the organic EL panel side) used in the present invention include the same as the pressure-sensitive adhesive layer of the above-mentioned pressure-sensitive adhesive layer.
- An acrylic pressure-sensitive adhesive layer formed from a (meth) acrylic pressure-sensitive adhesive composition having a polymer as a base polymer is preferred.
- the manufacturing method of a pressure-sensitive adhesive layer, a preferable aspect, and the like can be exemplified.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably about 10 to 75 ⁇ m, and more preferably about 12 to 50 ⁇ m.
- the (organic EL panel side) transparent protective film can be exemplified by those similar to the transparent protective film 3, and the organic EL panel side first pressure-sensitive adhesive layer (or adhesive) As the layer), any pressure-sensitive adhesive layer and adhesive layer in the present specification can be suitably used.
- the transmittance at a wavelength of 380 nm of the layer containing the ultraviolet absorber is preferably 9% or less, more preferably 7% or less, and 5% or less. It is more preferable that it is 3% or less. Since the transmittance at a wavelength of 380 nm is in the above range, incident ultraviolet rays can be blocked to a higher degree, and thus the deterioration of the organic EL element can be remarkably suppressed.
- the transmittance of the layer containing the ultraviolet absorber at a wavelength of 450 nm is preferably 60% or more, preferably 70% or more, and more preferably 75% or more. It is preferable that the transmittance at a wavelength of 450 nm is in the above range because the light emitted from the organic EL element can be sufficiently transmitted, and sufficient display performance can be secured in the organic EL display device.
- the transmittance at 400 nm is preferably 50% or less, and preferably 35% or less. % Or less is more preferable. Since the transmittance at a wavelength of 400 nm is in the above range, incident ultraviolet rays can be blocked to a higher degree, and thus the deterioration of the organic EL element can be remarkably suppressed.
- the transmittance of the layer containing the dye compound at a wavelength of 450 nm is preferably 60% or more, preferably 70% or more, and more preferably 75% or more. It is preferable that the transmittance at a wavelength of 450 nm is in the above range because the light emitted from the organic EL element can be sufficiently transmitted and sufficient display performance can be secured in the organic EL display device.
- the transmittance of the optical laminate at a wavelength of 380 nm is preferably 9% or less, more preferably 7% or less, and further preferably 5% or less, It is particularly preferable that it is 3% or less. Since the transmittance at a wavelength of 380 nm is within the above range, it is preferable because incident ultraviolet rays can be blocked to a higher degree and deterioration of the organic EL element can be remarkably suppressed.
- the transmittance of the optical layered body at a wavelength of 400 nm is preferably 20% or less, preferably 15% or less, and more preferably 10% or less.
- the transmittance at a wavelength of 400 nm is in the above range, it is preferable because incident ultraviolet rays can be blocked to a higher degree and deterioration of the organic EL element can be remarkably suppressed.
- the transmittance of the optical laminate at a wavelength of 450 nm is preferably 25% or more, preferably 30% or more, and more preferably 33% or more. It is preferable that the transmittance at a wavelength of 450 nm is in the above range because the light emitted from the organic EL element can be sufficiently transmitted and sufficient display performance can be secured in the organic EL display device.
- Organic EL Display Device includes the optical laminate 1 and an organic EL panel, and can also include other layers. Specifically, as shown in FIG. 2, from the viewing side, cover member 7 / adhesive layer 2 / protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 6 / organic EL panel 8 The organic EL display device 10 laminated in this order is preferable, and cover member 7 / adhesive layer 2 / (viewing side) protective film 3 / polarizer 4 / organic EL panel side protective film / organic EL panel side first adhesive.
- An organic EL display device in which an agent layer (or adhesive layer) / retardation film 5 / (organic EL panel side second) pressure-sensitive adhesive layer 6 / organic EL panel 8 are laminated in this order can also be exemplified.
- functional layers such as a hard coat layer, an antiglare treatment layer, an antireflection layer, a sensor layer, a pressure-sensitive adhesive layer or an adhesive layer for laminating them, and the like can be mentioned. it can.
- the cover member is not particularly limited, and those normally used in this field can be suitably used, and examples thereof include cover glass and cover plastic.
- the organic EL panel is not particularly limited, and those normally used in this field can be suitably used. For example, a plurality of base materials and a plurality of side by side provided on the base material can be used. The panel which has the organic EL element of this, the protective layer provided on the said organic EL element, and the sealing film provided on the said protective layer can be mentioned.
- Production Example 1 (Production of acrylic pressure-sensitive adhesive composition (a)) Photopolymerization started on a monomer mixture composed of 78 parts by weight of 2-ethylhexyl acrylate (2EHA), 18 parts by weight of N-vinyl-2-pyrrolidone (NVP), and 15 parts by weight of 2-hydroxyethyl acrylate (HEA).
- EHA 2-ethylhexyl acrylate
- NDP N-vinyl-2-pyrrolidone
- HSA 2-hydroxyethyl acrylate
- 0.035 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, having an absorption band at a wavelength of 200 to 370 nm, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane-1 -ON (trade name: Irgacure 651, having an absorption band at a wavelength of 200 to 380 nm, manufactured by BASF) 0.035 parts by weight, and then viscosity (measurement conditions: BH viscometer No.
- Production Example 2 (Production of pressure-sensitive adhesive layer (B1))
- a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube 95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 part by weight of azobisisobutyronitrile as a polymerization initiator, and After 233 parts by weight of ethyl acetate was added, nitrogen gas was passed, and nitrogen substitution was performed for about 1 hour while stirring. Thereafter, the flask was heated to 60 ° C. and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million.
- Mw weight average molecular weight
- a pressure-sensitive adhesive composition (solution) was prepared by adding 0.1 part by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
- the obtained pressure-sensitive adhesive composition solution was applied onto a 38 ⁇ m thick separator (polyethylene terephthalate film whose surface was peeled) so that the thickness after drying was 12 ⁇ m, and dried at 100 ° C. for 3 minutes.
- the solvent was removed by layering to obtain an adhesive layer.
- the crosslinking process was performed by heating at 50 degreeC for 48 hours.
- this pressure-sensitive adhesive layer is referred to as “pressure-sensitive adhesive layer (B1)”.
- Production Example 3 (Production of dye compound-containing pressure-sensitive adhesive layer (B1-1)) In Production Example 2, dissolved in toluene as a coloring compound together with an isocyanate crosslinking agent and a silane coupling agent in the acrylic polymer solution (with a solid content of 100 parts by weight) in toluene.
- BONASORB UA3911 (trade name, indole compound, “pigment compound (c1)” in Table 1, maximum absorption wavelength of absorption spectrum: 398 nm, half-value width: 48 nm, manufactured by Orient Chemical Co., Ltd.) 1.5 weight Part (solid content weight) was added to prepare an adhesive composition (solution).
- the obtained pressure-sensitive adhesive composition solution was applied on a 38 ⁇ m thick separator (polyethylene terephthalate film whose surface was peeled) so that the thickness after drying was 15 ⁇ m, and dried at 100 ° C. for 3 minutes. The solvent was removed by layering to obtain an adhesive layer. Then, the crosslinking process was performed by heating at 50 degreeC for 48 hours.
- this pressure-sensitive adhesive layer is referred to as “pressure-sensitive adhesive layer (B1-1)”.
- the amount of the dye compound added was 1.5% by weight relative to the total weight (100% by weight) of the pressure-sensitive adhesive layer (B1-1).
- Production Example 4 (Production of dye compound-containing pressure-sensitive adhesive layer (B1-2)) A pressure-sensitive adhesive layer was formed in the same manner as in Production Example 3 except that the amount of the dye compound (c) added was changed to 2.5 parts by weight (solid content weight). Hereinafter, this pressure-sensitive adhesive layer is referred to as “pressure-sensitive adhesive layer (B1-2)”. The amount of the dye compound added was 2.5% by weight relative to the total weight (100% by weight) of the pressure-sensitive adhesive layer (B1-2).
- the dye compound (c) is a cinnamic acid compound (trade name: SOM-5-0106, “UV absorber (c3)” in Table 1, maximum absorption wavelength of absorption spectrum: 416 nm, half-value width: 50 nm, Orient A pressure-sensitive adhesive layer was formed in the same manner as in Production Example 3 except that 1.0 part by weight was made by Chemical Industries Co., Ltd. Hereinafter, this pressure-sensitive adhesive layer is referred to as “pressure-sensitive adhesive layer (B1-3)”. The amount of the dye compound added was 1.0% by weight relative to the total weight (100% by weight) of the pressure-sensitive adhesive layer (B1-3).
- Production Example 6 (Production of pressure-sensitive adhesive layer (B2))
- the pressure-sensitive adhesive composition solution obtained in Production Example 2 was applied on a 38 ⁇ m-thick separator (polyethylene terephthalate film whose surface was release-treated) so that the thickness after drying was 23 ⁇ m.
- the solvent was removed by drying at 3 ° C. for 3 minutes to obtain a pressure-sensitive adhesive layer.
- the crosslinking process was performed by heating at 50 degreeC for 48 hours.
- this pressure-sensitive adhesive layer is referred to as “pressure-sensitive adhesive layer (B2)”.
- Production Example 7 (Production of dye compound-containing pressure-sensitive adhesive layer (B2-1))
- BONASORB UA3912 (trade name, indole compound, dissolved in toluene at a solid content of 5% as a pigment compound in the acrylic polymer solution obtained in Production Example 2 (solid content is 100 parts by weight) “Dye compound (c2)” in Table 1, maximum absorption wavelength of absorption spectrum: 386 nm, half width: 53 nm, manufactured by Orient Chemical Co., Ltd.) 1.0 part by weight (solid content weight), as an isocyanate-based crosslinking agent 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
- An adhesive composition (solution) was prepared by adding 1 part by weight.
- the pressure-sensitive adhesive composition solution was applied on a 38 ⁇ m-thick separator (polyethylene terephthalate film whose surface was subjected to a release treatment) so that the thickness after drying was 23 ⁇ m, and a dry layer at 100 ° C. for 3 minutes. The solvent was removed to obtain an adhesive layer. Then, the crosslinking process was performed by heating at 50 degreeC for 48 hours.
- this pressure-sensitive adhesive layer is referred to as “pressure-sensitive adhesive layer (B2-1)”.
- the amount of the dye compound added was 1.0% by weight relative to the total weight (100% by weight) of the pressure-sensitive adhesive layer (B2-1).
- Production Example 8 (Production of protective film (C1)) 100 parts by weight of imidized MS resin described in Production Example 1 of JP 2010-284840 A and 6,6 ′, 6 ′′-(1,3,5-triazine-2,4,6-triyl) tris (3-Hexyloxy-2-methylphenol) (trade name: LA-F70, “UV absorber (b1)” in Table 1, maximum absorption wavelength of absorption spectrum: 357 nm, manufactured by ADEKA Corporation) 0.65 Weight parts were mixed at 220 ° C. with a twin-screw kneader to produce resin pellets. The obtained resin pellets were dried at 100.5 kPa and 100 ° C.
- the substrate film A thus obtained had a light transmittance of 7% and a light transmittance of 68% at a wavelength of 380 nm of 68%.
- this protective film layer with a surface treatment layer is referred to as “protective film layer (C1)”.
- the addition amount of the ultraviolet absorber was 0.77% by weight relative to the total weight (100% by weight) of the protective film (C1).
- Production Example 9 (Preparation of protective film (C2-1)) 100 parts by weight of imidized MS resin described in Production Example 1 of JP 2010-284840 A was dissolved in methylene chloride to prepare a 12 wt% dope solution. Cinnamic acid compounds (trade name: SOM-5-0106, “UV absorber (c3)” in Table 1, maximum absorption wavelength of absorption spectrum: 416 nm, half-value width: 50 nm, manufactured by Orient Chemical Co., Ltd.) After adding 0.3 part by weight, the pressure-sensitive adhesive composition solution is applied on a glass plate that has been subjected to a release treatment so that the thickness after drying is 40 ⁇ m, and a dry layer is formed at 100 ° C. for 3 minutes.
- Cinnamic acid compounds trade name: SOM-5-0106, “UV absorber (c3)” in Table 1, maximum absorption wavelength of absorption spectrum: 416 nm, half-value width: 50 nm, manufactured by Orient Chemical Co., Ltd.
- the solvent was removed to obtain a protective film (C2-1) having a thickness of 40 ⁇ m.
- the obtained protective film (C2-1) had a light transmittance of 14% and a light transmittance of 2.6% at a wavelength of 380 nm of 2.6%.
- the addition amount of the coloring compound was 0.3% by weight relative to the total weight (100% by weight) of the protective film (C2-1).
- Example 1 (Production of pressure-sensitive adhesive composition (A1)) With respect to the acrylic pressure-sensitive adhesive composition (a) obtained in Production Example 1 (the monomer component forming the acrylic polymer is 100 parts by weight), it was dissolved in butyl acrylate so as to have a solid content of 15%.
- the pressure-sensitive adhesive composition (A1) is applied on the release-treated film so that the thickness after forming the pressure-sensitive adhesive layer is 150 ⁇ m, and then applied to the surface of the pressure-sensitive adhesive composition layer.
- the release film was bonded together. Thereafter, the pressure-sensitive adhesive composition layer was photocured by irradiating with ultraviolet rays under the conditions of illuminance: 6.5 mW / cm 2 , light quantity: 1500 mJ / cm 2 , and peak wavelength: 350 nm to form a pressure-sensitive adhesive layer (A1). .
- the addition amount of the ultraviolet absorber was 1.4% by weight relative to the total weight (100% by weight) of the pressure-sensitive adhesive layer (A1).
- polarizing film (P1) Manufacture of polarizing film (P1)
- a 25 ⁇ m thick cycloolefin polymer film is bonded to the viewing side of a polarizer made of a stretched polyvinyl alcohol film 5 ⁇ m thick impregnated with iodine, using a polyvinyl alcohol adhesive, and the surface of the polarizer on the side of the organic EL panel
- a polarizing film (P1) was obtained by laminating an acrylic film having a thickness of 20 ⁇ m using a polyvinyl alcohol-based adhesive.
- the single transmittance Y value of the polarizing film was 42.4%, and the degree of polarization was 99.995.
- the pressure-sensitive adhesive layer (A1) was laminated on the viewing side of the polarizing film (P1) (that is, the surface of a cycloolefin polymer film having a thickness of 25 ⁇ m).
- the pressure-sensitive adhesive layer (B1-1) obtained in Production Example 3 was laminated on the surface of the polarizing film (P) on the organic EL panel side (that is, the surface of the acrylic film having a thickness of 20 ⁇ m).
- the retardation film (thickness: 56 ⁇ m, material: polycarbonate) and the pressure-sensitive adhesive layer (B2-1) obtained in Production Example 7 were laminated to form a polarizing film with a pressure-sensitive adhesive layer.
- the obtained polarizing film with the pressure-sensitive adhesive layer was a pressure-sensitive adhesive layer (A1) / cycloolefin polymer film / polarizer / acrylic film / pressure-sensitive adhesive layer (B1-1) / retardation film / pressure-sensitive adhesive layer (B2-1). ).
- Example 2 (Production of pressure-sensitive adhesive composition (A2)) To the acrylic pressure-sensitive adhesive composition (a) obtained in Production Example 1, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1 , 3,3-tetramethylbutyl) phenol (trade name: TINUVIN 928, “UV absorber b3” in Table 1, maximum absorption wavelength of absorption spectrum: 349 nm, manufactured by BASF Japan Ltd.) 1.5 parts by weight (solid content Weight) and 0.2 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, having an absorption band at a wavelength of 200 to 450 nm, manufactured by BASF Japan Ltd.) The pressure-sensitive adhesive composition (A2) was obtained by stirring.
- the obtained pressure-sensitive adhesive composition (A2) was applied on the release film of the release film so that the thickness after forming the pressure-sensitive adhesive layer was 150 ⁇ m, and then the pressure-sensitive adhesive composition layer A release film was bonded to the surface of the film. Thereafter, the pressure-sensitive adhesive composition layer was photocured by irradiating with ultraviolet rays under the conditions of illuminance: 6.5 mW / cm 2 , light quantity: 1500 mJ / cm 2 , and peak wavelength: 350 nm to form a pressure-sensitive adhesive layer (A2). .
- the addition amount of the ultraviolet absorber was 1.5% by weight relative to the total weight (100% by weight) of the pressure-sensitive adhesive layer (A2).
- polarizing film (P2) A 25 ⁇ m thick cycloolefin polymer film is bonded to the viewing side of a polarizer made of a stretched polyvinyl alcohol film 5 ⁇ m thick impregnated with iodine, using a polyvinyl alcohol adhesive, and the surface of the polarizer on the side of the organic EL panel Further, the protective film (C2-1) obtained in Production Example 9 was laminated using a polyvinyl alcohol-based adhesive to obtain a polarizing film (P2). The single transmittance Y value of the polarizing film was 42.5%, and the degree of polarization was 99.995.
- the produced pressure-sensitive adhesive layer (A2) was laminated on the viewing side of the polarizing film (P2) (that is, the surface of a cycloolefin polymer film having a thickness of 25 ⁇ m).
- the pressure-sensitive adhesive layer (B1) obtained in Production Example 2 is laminated on the surface of the polarizing film (P) on the organic EL panel side (that is, the surface of the protective film (C2-1)), and further, a retardation film. (Thickness: 56 ⁇ m, material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film with a pressure-sensitive adhesive layer.
- the obtained polarizing film with the pressure-sensitive adhesive layer was a pressure-sensitive adhesive layer (A2) / cycloolefin polymer film / polarizer / protective film (C2-1) / pressure-sensitive adhesive layer (B1) / retardation film / pressure-sensitive adhesive layer (B2 ).
- Example 3 (Production of pressure-sensitive adhesive composition (A3)) 2,4-bis-[ ⁇ 4- (4-ethylhexyloxy) -4 dissolved in butyl acrylate to a solid content of 15% in the acrylic pressure-sensitive adhesive composition (a) obtained in Production Example 1.
- the pressure-sensitive adhesive composition (A3) is applied on the release-treated film so that the thickness after forming the pressure-sensitive adhesive layer is 150 ⁇ m, and then applied to the surface of the pressure-sensitive adhesive composition layer.
- the release film was bonded together. Thereafter, ultraviolet irradiation was performed under the conditions of illuminance: 6.5 mW / cm 2 , light amount: 1500 mJ / cm 2 , peak wavelength: 350 nm, and the pressure-sensitive adhesive composition layer was photocured to form a pressure-sensitive adhesive layer (A3).
- the addition amount of the ultraviolet absorber was 0.7% by weight relative to the total weight (100% by weight) of the pressure-sensitive adhesive layer (A3).
- the protective film (C1) obtained in Production Example 8 using a polyvinyl alcohol-based adhesive is used on the viewing side of a polarizer made of a stretched polyvinyl alcohol film having a thickness of 5 ⁇ m impregnated with iodine.
- the organic EL side protective film (C2-2) obtained in Production Example 10 was laminated using a polyvinyl alcohol-based adhesive on the surface of the polarizer on the organic EL panel side, and the polarizing film ( P3).
- the single transmittance Y value of the polarizing film was 42.4%, and the degree of polarization was 99.995.
- the produced pressure-sensitive adhesive layer (A3) was laminated on the viewing side of the polarizing film (P3) (that is, the surface of the protective film (C1)).
- the pressure-sensitive adhesive layer (B1-2) obtained in Production Example 4 is laminated on the surface of the polarizing film (P) on the organic EL panel side (that is, the surface of the protective film (C2-2)).
- the retardation film (thickness: 56 ⁇ m, material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film with a pressure-sensitive adhesive layer.
- the obtained polarizing film with the pressure-sensitive adhesive layer is pressure-sensitive adhesive layer (A3) / protective film (C1) / polarizer / protective film (C2-2) / pressure-sensitive adhesive layer (B1-2) / retardation film / organic EL. It had the structure of the display panel side adhesive layer (B2).
- the pressure-sensitive adhesive layer (A3) obtained in Example 3 was laminated on the viewing side of the polarizing film (P1) obtained in Example 1 (that is, the surface of a cycloolefin polymer film having a thickness of 25 ⁇ m).
- the pressure-sensitive adhesive layer (B1) obtained in Production Example 2 is laminated on the surface of the polarizing film (P) on the side of the organic EL panel (that is, the surface of the acrylic film having a thickness of 20 ⁇ m). Thickness: 56 ⁇ m, material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film with a pressure-sensitive adhesive layer.
- the obtained polarizing film with a pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer (A3) / cycloolefin polymer film / polarizer / acrylic film / pressure-sensitive adhesive layer (B1) / retardation film / organic EL display panel-side pressure-sensitive adhesive layer ( B2).
- Example 1 Production of pressure-sensitive adhesive composition (A1)
- a pressure-sensitive adhesive composition (A4) was obtained in the same manner as in Example 1 except that the ultraviolet absorber (b2) was not included.
- Example 1 manufactured of an adhesive layer (A1)
- the adhesive layer (A4) whose thickness is 150 micrometers. Formed.
- the pressure-sensitive adhesive layer (A4) was laminated on the viewing side of the polarizing film (P1) obtained in Example 1 (that is, the surface of a cycloolefin polymer film having a thickness of 25 ⁇ m).
- the pressure-sensitive adhesive layer (B1-3) obtained in Production Example 5 was laminated on the surface of the polarizing film (P) on the side of the organic EL panel (that is, the surface of the acrylic film having a thickness of 20 ⁇ m).
- the retardation film (thickness: 56 ⁇ m, material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film with a pressure-sensitive adhesive layer.
- the obtained polarizing film with the pressure-sensitive adhesive layer is: pressure-sensitive adhesive layer (A4) / cycloolefin polymer film / polarizer / acrylic film / pressure-sensitive adhesive layer (B1-3) / retardation film / pressure-sensitive adhesive layer (B2). Had a configuration.
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Abstract
Description
紫外線吸収剤と吸収スペクトルの最大吸収波長が380~430nmの波長領域に存在する色素化合物が、前記光学積層体を構成する別々の層に配合されており、
紫外線吸収剤を有する層が、色素化合物を有する層より視認側に存在することを特徴とする有機EL表示装置に関する。
前記紫外線吸収剤が、前記偏光子よりも視認側の層に配合されており、
前記色素化合物が、前記偏光子よりも有機ELパネル側の層に配合されていることが好ましい。
紫外線吸収剤と吸収スペクトルの最大吸収波長が380~430nmの波長領域に存在する色素化合物が、前記光学積層体を構成する別々の層に配合されており、
紫外線吸収剤を有する層が、色素化合物を有する層より視認側に存在することを特徴とする。
前記紫外線吸収剤としては、特に限定されないが、例えば、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、オキシベンゾフェノン系紫外線吸収剤、サリチル酸エステル系紫外線吸収剤、シアノアクリレート系紫外線吸収剤等を挙げることができ、これらを1種単独で又は2種以上を組み合わせて用いることができる。これらの中でも、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤が好ましく、1分子中にヒドロキシル基を2個以下有するトリアジン系紫外線吸収剤、及び、1分子中にベンゾトリアゾール骨格を1個有するベンゾトリアゾール系紫外線吸収剤からなる群から選択される少なくとも1種の紫外線吸収剤であることが、アクリル系粘着剤組成物の形成に用いられるモノマーへの溶解性が良好であり、かつ、波長380nm付近での紫外線吸収能力が高いため好ましい。
本発明で使用する色素化合物としては、吸収スペクトルの最大吸収波長が380~430nmの波長領域に存在する化合物であればよく、特に限定されるものではない。色素化合物の吸収スペクトルの最大吸収波長は、380~420nmの波長領域に存在することがより好ましい。ここで、最大吸収波長とは、300~460nmの波長領域での分光吸収スペクトルにおいて、複数の吸収極大が存在する場合には、その中で最大の吸光度を示す吸収極大波長を意味するものである。また、色素化合物は前記波長特性を有するものであれば特に限定されないが、有機EL素子の表示性を阻害しないような、蛍光及び燐光性能(フォトルミネセンス)を有しない材料が好ましい。
<半値幅の測定方法>
色素化合物の半値幅は、紫外可視分光光度計(U-4100、(株)日立ハイテクサイエンス製)を使用し、以下の条件で色素化合物の溶液の透過吸光スペクトルから測定した。最大吸収波長の吸光度が1.0となるよう濃度を調整して測定した分光スペクトルから、ピーク値の50%になる2点間の波長の間隔(半値全幅)をその色素化合物の半値幅とした。
(測定条件)
溶媒:トルエン又はクロロホルム
セル:石英セル
光路長:10mm
本発明で使用する光学積層体は、前述の通り、視認側から、少なくとも、粘接着剤層2/透明保護フィルム3/偏光子4/位相差フィルム5/粘着剤層6がこの順に積層されたものであることが好ましく(図1)、粘接着剤層2/(視認側)透明保護フィルム3/偏光子4/有機ELパネル側透明保護フィルム/有機ELパネル側第1粘着剤層(又は接着剤層)/位相差フィルム5/(有機ELパネル側第2)粘着剤層6がこの順に積層されたものであってもよい。これら以外にも、例えば、ハードコート層、防眩処理層、反射防止層等の機能層や、センサー層、またこれらを積層するための粘着剤層や接着剤層等を含むことができる。
本発明において「接着剤層」とは、粘着剤層又は接着剤層のことをいう。
接着剤層としては、任意の適切な接着剤からなる層を採用し得る。このような接着剤としては、例えば、天然ゴム接着剤、α-オレフィン系接着剤、ウレタン樹脂系接着剤、エチレン-酢酸ビニル樹脂エマルション接着剤、エチレン-酢酸ビニル樹脂系ホットメルト接着剤、エポキシ樹脂系接着剤、塩化ビニル樹脂溶剤系接着剤、クロロプレンゴム系接着剤、シアノアクリレート系接着剤、シリコーン系接着剤、スチレン-ブタジエンゴム溶剤系接着剤、ニトリルゴム系接着剤、ニトロセルロース系接着剤、反応性ホットメルト接着剤、フェノール樹脂系接着剤、変性シリコーン系接着剤、ポリエステル系ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリイミド系接着剤、ポリウレタン樹脂ホットメルト接着剤、ポリオレフィン樹脂ホットメルト接着剤、ポリ酢酸ビニル樹脂溶剤系接着剤、ポリスチレン樹脂溶剤系接着剤、ポリビニルアルコール系接着剤、ポリビニルピロリドン樹脂系接着剤、ポリビニルブチラール系接着剤、ポリベンズイミダゾール接着剤、ポリメタクリレート樹脂溶剤系接着剤、メラミン樹脂系接着剤、ユリア樹脂系接着剤、レゾルシノール系接着剤等が挙げられる。このような接着剤は、1種単独又は2種以上を混合して使用することができる。
粘着剤層を形成する粘着剤組成物の種類としては、特に限定されるものではなく、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤等を挙げることができる。これら粘着剤の中でも、光学的透明性に優れ、適宜な密着性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性等に優れる点から、アクリル系粘着剤が好ましく使用される。本発明においては、(メタ)アクリル系ポリマーをベースポリマーとして含有するアクリル系粘着剤組成物であることが好ましい。
前記アクリル系粘着剤組成物は、アルキル(メタ)アクリレートを含有するモノマー成分の部分重合物及び/又は前記モノマー成分から得られる(メタ)アクリル系ポリマーを含む。
さらに、本発明の粘着剤組成物にはシランカップリング剤を含有することができる。シランカップリング剤の配合量は、(メタ)アクリル系ポリマーを形成する単官能性モノマー成分100重量部に対して1重量部以下であるのが好ましく、0.01~1重量部がより好ましく、0.02~0.6重量部がさらに好ましい。
本発明の粘着剤組成物は、架橋剤を含有することができる。架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤、過酸化物等の架橋剤が含まれる。架橋剤は1種を単独で又は2種以上を組み合わせることができる。これらの中でも、イソシアネート系架橋剤が好ましく用いられる。
本発明の粘着剤組成物には、前記成分の他に、用途に応じて、適宜な添加剤が含まれていてもよい。例えば、粘着付与剤(例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂等からなる常温で固体、半固体、あるいは液状のもの);中空ガラスバルーン等の充填剤;可塑剤;老化防止剤;酸化防止剤等が挙げられる。
粘着剤層の形成方法としては、特に限定されるものではなく、通常本分野において用いられる方法により形成することができる。具体的には、前記粘着剤組成物を基材の少なくとも片面に塗工し、当該粘着剤組成物から形成される塗布膜を乾燥して形成するか、又は、紫外線等の活性エネルギー線を照射して形成することができる。また、前記基材に形成した粘着剤層を、偏光フィルム等に転写することもできる。
前記偏光フィルムは、偏光子の少なくとも一方の面に透明保護フィルムを有するものを挙げることができる。
偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素等の二色性物質からなる偏光子が好適である。これらの偏光子の厚さは特に制限されないが、一般的に5~80μm程度である。
本発明で用いる透明保護フィルム3は、偏光子4の視認側に配置されるものであるが、偏光子4の有機ELパネル側にも透明保護フィルムを配置することができる。
前記位相差フィルムは、遅相軸方向の屈折率をnx、面内の進相軸方向の屈折率をny、厚み方向の屈折率をnzとした場合に、nx=ny>nz、nx>ny>nz、nx>ny=nz、nx>nz>ny、nz=nx>ny、nz>nx>ny、nz>nx=ny、の関係を満足するものが、各種用途に応じて選択して用いられる。なお、nx=nyとは、nxとnyが完全に同一である場合だけでなく、実質的にnxとnyが同じ場合も含む。また、ny=nzとは、nyとnzが完全に同一である場合だけでなく、実質的にnyとnzが同じ場合も含む。
本発明で用いる粘着剤層6(有機ELパネル側の粘着剤層)としては、前記粘接着剤層の粘着剤層と同様のものを挙げることができるが、その中でも、(メタ)アクリル系ポリマーをベースポリマーとする(メタ)アクリル系粘着剤組成物から形成されるアクリル系粘着剤層が好ましい。また、粘着剤層の製造方法や好ましい態様等も同様のものを挙げることができる。
前記(有機ELパネル側)透明保護フィルムとしては、透明保護フィルム3と同様のものを例示することができ、前記有機ELパネル側第1粘着剤層(又は接着剤層)としては、本明細書中のいかなる粘着剤層、接着剤層も好適に使用することができる。
前記紫外線吸収剤を含む層の、波長380nmにおける透過率は、9%以下であることが好ましく、7%以下であることがより好ましく、5%以下であることがさらに好ましく、3%以下であることが特に好ましい。波長380nmにおける透過率が前記範囲であることにより、入射する紫外線をより高度に遮断することができるため、有機EL素子の劣化を著しく抑制することができる。
前記粘着剤層が色素化合物を含む場合の透過率は、400nmの透過率は50%以下であることが好ましく、35%以下であることが好ましく、20%以下であることがより好ましい。波長400nmにおける透過率が前記範囲であることにより、入射する紫外線をより高度に遮断することができるため、有機EL素子の劣化を著しく抑制することができる。
前記光学積層体の波長380nmにおける透過率が、9%以下であることが好ましく、7%以下であることがより好ましく、5%以下であることがさらに好ましく、3%以下であることが特に好ましい。波長380nmにおける透過率が前記範囲であることにより、入射する紫外線をより高度に遮断することができるため、有機EL素子の劣化を著しく抑制することができるため、好ましい。
本発明の有機EL表示装置は、前記光学積層体1と、有機ELパネルを含むものであって、その他の層を含むこともできる。具体的には、図2に示すように、視認側から、カバー部材7/粘接着剤層2/保護フィルム3/偏光子4/位相差フィルム5/粘着剤層6/有機ELパネル8がこの順に積層された有機EL表示装置10が好ましく、カバー部材7/粘接着剤層2/(視認側)保護フィルム3/偏光子4/有機ELパネル側保護フィルム/有機ELパネル側第1粘着剤層(又は接着剤層)/位相差フィルム5/(有機ELパネル側第2)粘着剤層6/有機ELパネル8がこの順に積層された有機EL表示装置等も挙げることができる。また、これら以外にも、ハードコート層、防眩処理層、反射防止層等の機能層や、センサー層、またこれらを積層するための粘着剤層や接着剤層等を含む構成を挙げることができる。
アクリル酸2-エチルヘキシル(2EHA)78重量部、N-ビニル-2-ピロリドン(NVP)18重量部、及びアクリル酸2-ヒドロキシエチル(HEA)15重量部から構成されるモノマー混合物に、光重合開始剤として、1-ヒドロキシシクロヘキシルフェニルケトン(商品名:イルガキュア184、波長200~370nmに吸収帯を有する、BASF社製)0.035重量部、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(商品名:イルガキュア651、波長200~380nmに吸収帯を有する、BASF社製)0.035重量部を配合した後、粘度(計測条件:BH粘度計No.5ローター、10rpm、測定温度30℃)が約20Pa・sになるまで紫外線を照射して、上記モノマー成分の一部が重合したプレポリマー組成物(重合率:8%)を得た。次に、該プレポリマー組成物に、ヘキサンジオールジアクリレート(HDDA)0.15重量部、シランカップリング剤(商品名:KBM-403、信越化学工業(株)製)0.3重量部を添加して混合し、アクリル系粘着剤組成物(a)を得た。
温度計、攪拌機、還流冷却管及び窒素ガス導入管を備えたセパラブルフラスコに、ブチルアクリレート95重量部、アクリル酸5重量部、重合開始剤としてアゾビスイソブチロニトリル0.2重量部、及び酢酸エチル233重量部を投入した後、窒素ガスを流し、攪拌しながら約1時間窒素置換を行った。その後、60℃にフラスコを加熱し、7時間反応させて、重量平均分子量(Mw)110万のアクリル系ポリマーを得た。
上記アクリル系ポリマー溶液(固形分を100重量部とする)に、イソシアネート系架橋剤として、トリメチロールプロパントリレンジイソシアネート(商品名:コロネートL、日本ポリウレタン工業(株)製)0.8重量部、シランカップリング剤(商品名:KBM-403、信越化学工業(株)製)0.1重量部を加えて粘着剤組成物(溶液)を調製した。
厚さ38μmのセパレータ(表面が剥離処理されたポリエチレンテレフタレート系フィルム)上に、得られた粘着剤組成物溶液を、乾燥後の厚さが12μmとなるように塗布し、100℃で3分間乾燥層させて溶媒を除去し、粘着剤層を得た。その後、50℃で48時間加熱して架橋処理を行った。以下、この粘着剤層を「粘着剤層(B1)」と言う。
製造例2において、上記アクリル系ポリマー溶液(固形分を100重量部とする)に、イソシアネート系架橋剤、シランカップリング剤と伴に、色素化合物として、トルエンに固形分1%となるように溶解させたBONASORB UA3911(商品名、インドール系化合物、表1中の「色素化合物(c1)」、吸収スペクトルの最大吸収波長:398nm、半値幅:48nm、オリエント化学工業(株)製)1.5重量部(固形分重量)を加えて粘着剤組成物(溶液)を調製した。
厚さ38μmのセパレータ(表面が剥離処理されたポリエチレンテレフタレート系フィルム)上に、得られた粘着剤組成物溶液を、乾燥後の厚さが15μmとなるように塗布し、100℃で3分間乾燥層させて溶媒を除去し、粘着剤層を得た。その後、50℃で48時間加熱して架橋処理を行った。以下、この粘着剤層を「粘着剤層(B1-1)」と言う。粘着剤層(B1-1)全重量(100重量%)に対して、色素化合物の添加量は、1.5重量%であった。
色素化合物(c)の添加量を2.5重量部(固形分重量)に変更した以外は、製造例3と同様にして粘着剤層を形成した。以下、この粘着剤層を「粘着剤層(B1-2)」と言う。粘着剤層(B1-2)全重量(100重量%)に対して、色素化合物の添加量は、2.5重量%であった。
色素化合物(c)を、けい皮酸系化合物(商品名:SOM-5-0106、表1中の「紫外線吸収剤(c3)」、吸収スペクトルの最大吸収波長:416nm、半値幅:50nm、オリエント化学工業(株)製)1.0重量部とした以外は、製造例3と同様にして粘着剤層を形成した。以下、この粘着剤層を「粘着剤層(B1-3)」と言う。粘着剤層(B1-3)全重量(100重量%)に対して、色素化合物の添加量は、1.0重量%であった。
厚さ38μmのセパレータ(表面が離型処理されたポリエチレンテレフタレート系フィルム)上に、製造例2で得られた粘着剤組成物溶液を、乾燥後の厚さが23μmとなるように塗布し、100℃で3分間乾燥層させて溶媒を除去し、粘着剤層を得た。その後、50℃で48時間加熱して架橋処理を行った。以下、この粘着剤層を「粘着剤層(B2)」と言う。
製造例2で得られたアクリル系ポリマー溶液(固形分を100重量部とする)に、色素化合物として、トルエンに固形分5%となるように溶解させたBONASORB UA3912(商品名、インドール系化合物、表1中の「色素化合物(c2)」、吸収スペクトルの最大吸収波長:386nm、半値幅:53nm、オリエント化学工業(株)製)1.0重量部(固形分重量)、イソシアネート系架橋剤として、トリメチロールプロパントリレンジイソシアネート(商品名:コロネートL、日本ポリウレタン工業(株)製)0.8重量部、シランカップリング剤(商品名:KBM-403、信越化学工業(株)製)0.1重量部を加えて粘着剤組成物(溶液)を調製した。
厚さ38μmのセパレータ(表面が離型処理されたポリエチレンテレフタレート系フィルム)上に、前記粘着剤組成物溶液を、乾燥後の厚さが23μmとなるように塗布し、100℃で3分間乾燥層させて溶媒を除去し、粘着剤層を得た。その後、50℃で48時間加熱して架橋処理を行った。以下、この粘着剤層を「粘着剤層(B2-1)」と言う。粘着剤層(B2-1)全重量(100重量%)に対して、色素化合物の添加量は、1.0重量%であった。
特開2010-284840号公報の製造例1に記載のイミド化MS樹脂100重量部、及び6,6’,6’’-(1,3,5-トリアジン-2,4,6-トリイル)トリス(3-ヘキシルオキシ-2-メチルフェノール)(商品名:LA-F70、表1中の「紫外線吸収剤(b1)」、吸収スペクトルの最大吸収波長:357nm、(株)ADEKA製)0.65重量部を、2軸混練機にて220℃にて混合し、樹脂ペレットを作製した。得られた樹脂ペレットを、100.5kPa、100℃で12時間乾燥させ、単軸の押出機にてダイス温度270℃でTダイから押出してフィルム状に成形した(厚み160μm)。さらに当該フィルムを、その搬送方向に150℃の雰囲気下に延伸し(厚み80μm)、次いでフィルム搬送方向と直交する方向に150℃の雰囲気下に延伸して、厚み40μmの基材フィルムA((メタ)アクリル系樹脂フィルム)を得た。得られた基材フィルムAの波長380nmの光の透過率は、7%、波長400nmの光の透過率は68%であった。
特開2010-284840号公報の製造例1に記載のイミド化MS樹脂100重量部を塩化メチレンに溶解させて12重量%のドープ溶液を作製した。けい皮酸系化合物(商品名:SOM-5-0106、表1中の「紫外線吸収剤(c3)」、吸収スペクトルの最大吸収波長:416nm、半値幅:50nm、オリエント化学工業(株)製)0.3重量部を添加した後、離型処理を施したガラス板上に、前記粘着剤組成物溶液を、乾燥後の厚さが40μmとなるように塗布し、100℃で3分間乾燥層させて溶媒を除去し、厚み40μmの保護フィルム(C2-1)を得た。得られた保護フィルム(C2-1)の波長380nmの光の透過率は14%、波長400nmの光の透過率は2.6%であった。保護フィルム(C2-1)全重量(100重量%)に対して、色素化合物の添加量は、0.3重量%であった。
色素化合物(c)として、BONASORB UA3912(商品名、インドール系化合物、表1中の「色素化合物(c2)」、吸収スペクトルの最大吸収波長:386nm、半値幅:53nm、オリエント化学工業(株)製)を1.3重量部用いた以外は、製造例9と同様にして保護フィルム(C2-2)を得た。得られた保護フィルム(C2-2)の波長380nmの光の透過率は0.3%、波長400nmの光の透過率は0.8%であった。保護フィルム(C2-2)全重量(100重量%)に対して、色素化合物の添加量は、1.3重量%であった。
(粘着剤組成物(A1)の製造)
製造例1で得られたアクリル系粘着剤組成物(a)に対して(アクリル系ポリマーを形成するモノマー成分を100重量部とする)、ブチルアクリレートに固形分15%となるように溶解させた2,4-ビス-[{4-(4-エチルヘキシルオキシ)-4-ヒドロキシ}-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン(商品名:Tinosorb S、表1中の「紫外線吸収剤b2」、吸収スペクトルの最大吸収波長:346nm、BASFジャパン社製)1.4重量部(固形分重量)と、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(商品名:イルガキュア819、波長200~450nmに吸収帯域を有する、BASFジャパン社製)0.2重量部を添加し撹拌することにより粘着剤組成物(A1)を得た。
前記粘着剤組成物(A1)を、離型フィルムの剥離処理されたフィルム上に、粘着剤層形成後の厚さが150μmとなるように塗布し、次いで、該粘着剤組成物層の表面に、離型フィルムを貼り合わせた。その後、照度:6.5mW/cm2、光量:1500mJ/cm2、ピーク波長:350nmの条件で紫外線照射を行い、粘着剤組成物層を光硬化させて、粘着剤層(A1)を形成した。粘着剤層(A1)全重量(100重量%)に対して、紫外線吸収剤の添加量は、1.4重量%であった。
ヨウ素が含浸された厚さ5μmの延伸ポリビニルアルコールフィルムからなる偏光子の視認側に、ポリビニルアルコール系接着剤を用いて厚さ25μmのシクロオレフィンポリマーフィルムを貼り合せ、偏光子の有機ELパネル側表面に、ポリビニルアルコール系接着剤を用いて厚さ20μmのアクリル系フィルムを積層し、偏光フィルム(P1)とした。偏光フィルムの単体透過率Y値は、42.4%、偏光度は99.995であった。
前記偏光フィルム(P1)の視認側(すなわち、厚さ25μmのシクロオレフィンポリマーフィルムの表面)に、粘着剤層(A1)を積層した。前記偏光フィルム(P)の有機ELパネル側表面(すなわち、厚さ20μmのアクリル系フィルムの表面)に、製造例3で得られた粘着剤層(B1-1)を積層して、さらに、位相差フィルム(厚み:56μm、材料:ポリカーボネート)と製造例7で得られた粘着剤層(B2-1)を積層し、粘着剤層付き偏光フィルムを形成した。得られた粘着剤層付き偏光フィルムは、粘着剤層(A1)/シクロオレフィンポリマーフィルム/偏光子/アクリル系フィルム/粘着剤層(B1-1)/位相差フィルム/粘着剤層(B2-1)の構成を有していた。
(粘着剤組成物(A2)の製造)
製造例1で得られたアクリル系粘着剤組成物(a)に、2-(2H-ベンゾトリアゾール-2-イル)-6-(1-メチル-1-フェニルエチル)-4-(1,1,3,3-テトラメチルブチル)フェノール(商品名:TINUVIN 928、表1中の「紫外線吸収剤b3」、吸収スペクトルの最大吸収波長:349nm、BASFジャパン社製)1.5重量部(固形分重量)と、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(商品名:イルガキュア819、波長200~450nmに吸収帯域を有する、BASFジャパン社製)0.2重量部を添加し撹拌することにより粘着剤組成物(A2)を得た。
前記得られた粘着剤組成物(A2)を、離型フィルムの剥離処理されたフィルム上に、粘着剤層形成後の厚さが150μmとなるように塗布し、次いで、該粘着剤組成物層の表面に、離型フィルムを貼り合わせた。その後、照度:6.5mW/cm2、光量:1500mJ/cm2、ピーク波長:350nmの条件で紫外線照射を行い、粘着剤組成物層を光硬化させて、粘着剤層(A2)を形成した。粘着剤層(A2)全重量(100重量%)に対して、紫外線吸収剤の添加量は、1.5重量%であった。
ヨウ素が含浸された厚さ5μmの延伸ポリビニルアルコールフィルムからなる偏光子の視認側に、ポリビニルアルコール系接着剤を用いて厚さ25μmのシクロオレフィンポリマーフィルムを貼り合せ、偏光子の有機ELパネル側表面に、ポリビニルアルコール系接着剤を用いて、製造例9で得られた保護フィルム(C2-1)を積層し、偏光フィルム(P2)とした。偏光フィルムの単体透過率Y値は、42.5%、偏光度は99.995であった。
前記偏光フィルム(P2)の視認側(すなわち、厚さ25μmのシクロオレフィンポリマーフィルムの表面)に、作製した粘着剤層(A2)を積層した。前記偏光フィルム(P)の有機ELパネル側表面(すなわち、保護フィルム(C2-1)の表面)に、製造例2で得られた粘着剤層(B1)を積層して、さらに、位相差フィルム(厚み:56μm、材料:ポリカーボネート)と製造例6で得られた粘着剤層(B2)を積層し、粘着剤層付き偏光フィルムを形成した。得られた粘着剤層付き偏光フィルムは、粘着剤層(A2)/シクロオレフィンポリマーフィルム/偏光子/保護フィルム(C2-1)/粘着剤層(B1)/位相差フィルム/粘着剤層(B2)の構成を有していた。
(粘着剤組成物(A3)の製造)
製造例1で得られたアクリル系粘着剤組成物(a)に、ブチルアクリレートに固形分15%となるように溶解させた2,4-ビス-[{4-(4-エチルヘキシルオキシ)-4-ヒドロキシ}-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン(商品名:Tinosorb S、表1中の「紫外線吸収剤b2」、吸収スペクトルの最大吸収波長:346nm、BASFジャパン社製)0.7重量部(固形分重量)と、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(商品名:イルガキュア819、波長200~450nmに吸収帯域を有する、BASFジャパン社製)0.2重量部を添加し撹拌することにより粘着剤組成物(A3)を得た。
前記粘着剤組成物(A3)を、離型フィルムの剥離処理されたフィルム上に、粘着剤層形成後の厚さが150μmとなるように塗布し、次いで、該粘着剤組成物層の表面に、離型フィルムを貼り合わせた。その後、照度:6.5mW/cm2、光量:1500mJ/cm2、ピーク波長:350nmの条件で紫外線照射を行い、粘着剤組成物層を光硬化させて、粘着剤層(A3)を形成した。粘着剤層(A3)全重量(100重量%)に対して、紫外線吸収剤の添加量は、0.7重量%であった。
ヨウ素が含浸された厚さ5μmの延伸ポリビニルアルコールフィルムからなる偏光子の視認側に、ポリビニルアルコール系接着剤を用いて製造例8で得られた保護フィルム(C1)を基材フィルムA側が偏光子と接するように貼り合せ、偏光子の有機ELパネル側表面に、ポリビニルアルコール系接着剤を用いて、製造例10で得られた有機EL側保護フィルム(C2-2)を積層し、偏光フィルム(P3)とした。偏光フィルムの単体透過率Y値は、42.4%、偏光度は99.995であった。
前記偏光フィルム(P3)の視認側(すなわち、保護フィルム(C1)の表面)に、作製した粘着剤層(A3)を積層した。前記偏光フィルム(P)の有機ELパネル側表面(すなわち、保護フィルム(C2-2)の表面)に、製造例4で得られた粘着剤層(B1-2)を積層して、さらに、位相差フィルム(厚み:56μm、材料:ポリカーボネート)と製造例6で得られた粘着剤層(B2)を積層し、粘着剤層付き偏光フィルムを形成した。得られた粘着剤層付き偏光フィルムは、粘着剤層(A3)/保護フィルム(C1)/偏光子/保護フィルム(C2-2)/粘着剤層(B1-2)/位相差フィルム/有機EL表示パネル側粘着剤層(B2)の構成を有していた。
実施例1で得られた偏光フィルム(P1)の視認側(すなわち、厚さ25μmのシクロオレフィンポリマーフィルムの表面)に、実施例3で得られた粘着剤層(A3)を積層した。前記偏光フィルム(P)の有機ELパネル側表面(すなわち、厚さ20μmのアクリルフィルムの表面)に、製造例2で得られた粘着剤層(B1)を積層して、さらに、位相差フィルム(厚み:56μm、材料:ポリカーボネート)と製造例6で得られた粘着剤層(B2)を積層し、粘着剤層付き偏光フィルムを形成した。得られた粘着剤層付き偏光フィルムは、粘着剤層(A3)/シクロオレフィンポリマーフィルム/偏光子/アクリル系フィルム/粘着剤層(B1)/位相差フィルム/有機EL表示パネル側粘着剤層(B2)の構成を有していた。
(粘着剤層の製造)
実施例1の(粘着剤組成物(A1)の製造)において、紫外線吸収剤(b2)を含まない以外は、実施例1と同様にして粘着剤組成物(A4)を得た。また、実施例1の(粘着剤層(A1)の製造)において、前記粘着剤組成物(A4)を用いる以外は、実施例1と同様にして、厚さが150μmの粘着剤層(A4)を形成した。
実施例1で得られた偏光フィルム(P1)の視認側(すなわち、厚さ25μmのシクロオレフィンポリマーフィルムの表面)に、前記粘着剤層(A4)を積層した。前記偏光フィルム(P)の有機ELパネル側表面(すなわち、厚さ20μmのアクリル系フィルムの表面)に、製造例5で得られた粘着剤層(B1-3)を積層して、さらに、位相差フィルム(厚み:56μm、材料:ポリカーボネート)と製造例6で得られた粘着剤層(B2)を積層し、粘着剤層付き偏光フィルムを形成した。得られた粘着剤層付き偏光フィルムは、粘着剤層(A4)/シクロオレフィンポリマーフィルム/偏光子/アクリル系フィルム/粘着剤層(B1-3)/位相差フィルム/粘着剤層(B2)の構成を有していた。
実施例及び比較例で得られた紫外線吸収剤を含有する層(粘着剤層)の離型フィルムを剥離して、測定用治具に取り付け、分光光度計(製品名:U4100、(株)日立ハイテクノロジーズ製)で測定した。透過率は、波長350nm~780nmの範囲における透過率を測定した。なお、実施例3の紫外線吸収剤を含有する保護フィルムの場合、フィルムホルダを介して測定用治具に取り付ける以外は、粘着剤層の場合と同様に透過率を測定した。
実施例及び比較例で得られた色素吸収剤を含有する層(粘着剤層)の離型フィルムを剥離して、測定用治具に取り付け、分光光度計(製品名:U4100、(株)日立ハイテクノロジーズ製)で測定した。透過率は、波長350nm~780nmの範囲における透過率を測定した。なお、実施例2及び3の色素化合物を含有する保護フィルムの場合は、フィルムホルダを介して測定用治具に取り付ける以外は、粘着剤層の場合と同様に透過率を測定した。
実施例及び比較例で得られた粘着剤層付偏光フィルムの離型フィルムを剥離して、測定用治具に取り付け、分光光度計(製品名:U4100、(株)日立ハイテクノロジーズ製)で測定した。透過率は、波長350nm~780nmの範囲における透過率を測定した。
2 粘接着剤層
3 透明保護フィルム
4 偏光子
5 位相差フィルム
6 粘着剤層
7 カバー部材
8 有機ELパネル
10 有機EL表示装置
Claims (5)
- 偏光子、位相差フィルム、及びそれ以外の少なくとも1層の層を含む光学積層体、並びに有機ELパネルを含む有機EL表示装置であって、
紫外線吸収剤と吸収スペクトルの最大吸収波長が380~430nmの波長領域に存在する色素化合物が、前記光学積層体を構成する別々の層に配合されており、
紫外線吸収剤を有する層が、色素化合物を有する層より視認側に存在することを特徴とする有機EL表示装置。 - 前記光学積層体が、視認側から、少なくとも、粘接着剤層、透明保護フィルム、偏光子、位相差フィルム、及び粘着剤層をこの順に含み、
前記紫外線吸収剤が、前記偏光子よりも視認側の層に配合されており、
前記色素化合物が、前記偏光子よりも有機ELパネル側の層に配合されていることを特徴とする請求項1に記載の有機EL表示装置。 - 前記紫外線吸収剤が、前記粘接着剤層、前記透明保護フィルム、及び前記位相差フィルムからなる群から選ばれる少なくとも1つの層に配合されており、
前記色素化合物が、前記粘着剤層に配合されていることを特徴とする請求項2に記載の有機EL表示装置。 - 前記色素化合物が、有機系色素化合物であることを特徴とする請求項1~3のいずれかに記載の有機EL表示装置。
- 前記紫外線吸収剤の吸収スペクトルの最大吸収波長が、300~400nmの波長領域に存在することを特徴とする請求項1~4のいずれかに記載の有機EL表示装置。
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