JP4926002B2 - Optical laminate - Google Patents
Optical laminate Download PDFInfo
- Publication number
- JP4926002B2 JP4926002B2 JP2007291345A JP2007291345A JP4926002B2 JP 4926002 B2 JP4926002 B2 JP 4926002B2 JP 2007291345 A JP2007291345 A JP 2007291345A JP 2007291345 A JP2007291345 A JP 2007291345A JP 4926002 B2 JP4926002 B2 JP 4926002B2
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- JP
- Japan
- Prior art keywords
- functional layer
- layer
- optical functional
- optical
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000003287 optical effect Effects 0.000 title claims abstract description 98
- 239000010410 layer Substances 0.000 claims abstract description 75
- 239000002346 layers by function Substances 0.000 claims abstract description 66
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- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 44
- 238000000576 coating method Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 18
- -1 polyethylene terephthalate Polymers 0.000 description 18
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
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- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
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- 239000003822 epoxy resin Substances 0.000 description 2
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- 235000019382 gum benzoic Nutrition 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
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- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
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- 229920003002 synthetic resin Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- INPHIYULSHLAHR-UHFFFAOYSA-N 1-pentylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCCC INPHIYULSHLAHR-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- SNFRKUNAXTXJEN-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene ethyl carbamate [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound NC(=O)OCC.CC=1C(=CC(=CC1)N=C=O)N=C=O.C(C=C)(=O)OCC(COC(C=C)=O)(COC(C=C)=O)CO SNFRKUNAXTXJEN-UHFFFAOYSA-N 0.000 description 1
- KVLHRMQNRDJRKW-UHFFFAOYSA-N 2-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoroundecyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 KVLHRMQNRDJRKW-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- VUXJDZVQYBZCFC-UHFFFAOYSA-N 2-[2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,11,11,11-icosafluoro-10-(trifluoromethyl)undecyl]oxirane Chemical compound FC(F)(F)C(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 VUXJDZVQYBZCFC-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- FQHLOOOXLDQLPF-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FQHLOOOXLDQLPF-UHFFFAOYSA-N 0.000 description 1
- FIAHOPQKBBASOY-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C FIAHOPQKBBASOY-UHFFFAOYSA-N 0.000 description 1
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Liquid Crystal (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
Description
本発明は、液晶ディスプレイ（ＬＣＤ）やプラズマディスプレイ（ＰＤＰ）等のディスプレイ表面に設ける光学積層体に関し、特に耐擦傷性、耐薬品性、画面の視認性を改善するための光学積層体に関する。 The present invention relates to an optical laminate provided on a display surface such as a liquid crystal display (LCD) or a plasma display (PDP), and more particularly to an optical laminate for improving scratch resistance, chemical resistance, and screen visibility.
各種画像表示装置の一つにＬＣＤがあるが、ＬＣＤの高視野角化、高精細化、高速応答性、色再現性などに関する技術革新に伴い、ＬＣＤを利用するアプリケーションもノートパソコンやモニターからテレビへと変化しつつある。ＬＣＤの基本的な構成は、二枚の透明電極を有する平板状ガラスの間に一定間隔のギャップがスペーサーにより設けられており、そこに、液晶材料が注入、封止されて、平板状ガラスの表裏面には偏光板が貼付されている。偏光板は傷付き易いため、従来は、ＬＣＤ表面にガラスやプラスチックからなるカバープレートを装着し、ＬＣＤ表面に貼付している偏光板への傷付き防止を図っていた。しかし、カバープレートを装着するとコスト、重量の面で不利であり、次第に表面に光学機能層処理が施された偏光板が用いられるようになってきた。ハードコート処理は、通常、透明プラスチックフィルム基体にハードコート層を設けたハードコートフィルムを偏光板表面に設けることにより行われる。 One of the various image display devices is the LCD. With technological innovations related to LCDs with higher viewing angles, higher definition, faster response, and color reproducibility, applications that use LCDs can change from notebook computers and monitors to televisions. It is changing to. The basic structure of an LCD is that a gap with a constant interval is provided between a flat glass plate having two transparent electrodes by a spacer, and a liquid crystal material is injected and sealed there to seal the flat glass plate. Polarizing plates are attached to the front and back surfaces. Since the polarizing plate is easily damaged, conventionally, a cover plate made of glass or plastic is attached to the LCD surface to prevent the polarizing plate attached to the LCD surface from being damaged. However, mounting a cover plate is disadvantageous in terms of cost and weight, and a polarizing plate having an optical functional layer treatment on the surface has been gradually used. The hard coat treatment is usually performed by providing a hard coat film in which a hard coat layer is provided on a transparent plastic film substrate on the polarizing plate surface.
光学機能層は、通常、熱硬化型樹脂または紫外線硬化型樹脂等の電離放射線硬化型樹脂を用いて透明プラスチックフィルム上に数μｍ程度の薄い塗膜として形成される。しかし、光学機能層の厚さが十分でないと、下地である透明プラスチックフィルム基体の影響を受け、光学機能層表面に傷が入ってしまう。ＬＣＤ用途では、主にトリアセチルセルロース（ＴＡＣ）フィルムが透明プラスチックフィルム基体として使用されているが、上記の場合、ハードコート表面の耐擦傷性を評価する代表的測定法の鉛筆硬度（ＪＩＳ Ｋ５６００）で、２〜３Ｈ程度が一般的であった。 The optical functional layer is usually formed as a thin coating of about several μm on a transparent plastic film using an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. However, if the thickness of the optical functional layer is not sufficient, the surface of the optical functional layer is damaged due to the influence of the transparent plastic film substrate as a base. In LCD applications, a triacetyl cellulose (TAC) film is mainly used as a transparent plastic film substrate. In the above case, pencil hardness (JIS K5600) is a typical measurement method for evaluating scratch resistance of a hard coat surface. And about 2-3H was common.
ＬＣＤやＰＤＰのテレビ市場への普及は目覚ましいが、家庭用テレビの一般消費者は、これらのディスプレイに対しても、従来ＣＲＴテレビと同様、厳しい取り扱い（物理的・機械的・化学的刺激などによる負荷）が予想される。例えば、ディスプレイ表面に付着した埃や指紋などの汚れを、ガラスクリーナー（界面活性剤系、有機溶剤系など様々）を染み込ませた雑巾で拭いたり、子供がおもちゃなどで表面を擦ったり、叩いたりなどである。ＣＲＴのブラウン管は耐薬品性に優れたガラス製で、しかも、表面硬度が鉛筆硬度で９Ｈ程度あるため、これらの負荷に対する耐久性は充分であった。しかし、上記ディスプレイに搭載されているハードコートフィルム表面は鉛筆硬度が低いために耐擦傷性に欠け、耐薬品性もハードコート層が薄いために充分とは言えず、改善が求められている。 The spread of LCD and PDP in the TV market is remarkable, but general consumers of home TVs also handle these displays, as with conventional CRT TVs, due to strict handling (physical, mechanical, chemical stimulation, etc.) Load) is expected. For example, dust or fingerprints adhering to the display surface may be wiped with a rag soaked with glass cleaner (surfactant or organic solvent), or the child may rub or hit the surface with a toy. Etc. The cathode ray tube of CRT is made of glass with excellent chemical resistance, and the surface hardness is about 9H in pencil hardness, so the durability against these loads was sufficient. However, since the surface of the hard coat film mounted on the display has a low pencil hardness, it lacks scratch resistance, and the chemical resistance is not sufficient because the hard coat layer is thin, and improvement is required.
また、ハードコートフィルムを各種画像表示装置に貼着した場合、ディスプレイ表面、すなわち、ハードコートフィルム表面の光の反射によるコントラストの低下、並びにハードコート層の微小な膜厚のバラツキなどによって生じる光の干渉縞（詳細後述）などにより、視認性が低下するという問題も有していた。そのため、ハードコートフィルムには、上記表面硬度の他に視認性の向上も要求されている。 In addition, when the hard coat film is attached to various image display devices, the light generated by the decrease in contrast due to the reflection of light on the display surface, that is, the hard coat film surface, and the variation in the minute thickness of the hard coat layer, etc. There was also a problem that visibility was lowered due to interference fringes (described later in detail). Therefore, the hard coat film is required to improve visibility in addition to the surface hardness.
ハードコート層の表面硬度を向上させる方法として、単純にハードコート層の厚みを増加させることが考えられる。しかし、前記方法では硬度はより硬くなるものの、ハードコート層の割れや剥がれが生じやすくなると同時に、ハードコート層の硬化収縮によるシワやカールが大きくなり、実用上使用できるものではなかった。そこで、近年、ハードコートフィルムの高硬度化を実現するとともに、ハードコート層の割れや硬化収縮によるカールの課題を解決する方法が幾つか提案されている（特許文献１乃至特許文献４）。 As a method for improving the surface hardness of the hard coat layer, it is conceivable to simply increase the thickness of the hard coat layer. However, although the hardness is increased by the above method, cracks and peeling of the hard coat layer are likely to occur, and at the same time, wrinkles and curls due to curing shrinkage of the hard coat layer are increased, and thus the method cannot be used practically. Thus, in recent years, several methods have been proposed for achieving high hardness of the hard coat film and solving the problem of curling due to cracking of the hard coat layer and curing shrinkage (Patent Documents 1 to 4).
特許文献１には、透明プラスチックフィルム基体の少なくとも片面に紫外線硬化型ポリオールアクリレート系樹脂を含む組成物から成る硬化塗膜層（光学機能層）を形成した偏光板用保護フィルムが提案されている。紫外線硬化型ポリオールアクリレート系樹脂としては、ジペンタエリスリトールヘキサアクリレートが主に例示されている。当該樹脂をプラスチックフィルム基材上に塗工を行った場合、硬化塗膜層の厚みを１０μｍ以上にすることで鉛筆硬度が４Ｈ以上の硬度を確保することは可能であるが、硬化収縮によるカールを同時に抑制することは困難である。 Patent Document 1 proposes a protective film for a polarizing plate in which a cured coating film layer (optical functional layer) made of a composition containing an ultraviolet curable polyol acrylate resin is formed on at least one surface of a transparent plastic film substrate. Dipentaerythritol hexaacrylate is mainly exemplified as the ultraviolet curable polyol acrylate resin. When the resin is coated on a plastic film substrate, it is possible to secure a hardness of 4H or more by setting the thickness of the cured coating layer to 10 μm or more. It is difficult to suppress these simultaneously.
特許文献２には、透明プラスチックフィルム基体の少なくとも一方の面に、厚み３〜５０μｍの１層または多層からなる緩衝層を設け、更に緩衝層上に厚み３〜１５μｍのハードコート層を形成してなるハードコートフィルムが提案されている。前記透明プラスチックフィルム基体、緩衝層および光学機能層の各々の鉛筆硬度は、この順序で増大した値を有し、これによりハードコートフィルム全体としての鉛筆硬度４Ｈ〜８Ｈを有するように設計されている。しかし、特許文献２では、光学機能層の他に緩衝層が必要であり、少なくとも二層構成にすることが要求されるため生産工程に負荷を与えるという欠点がある。 In Patent Document 2, a buffer layer composed of one layer or multiple layers having a thickness of 3 to 50 μm is provided on at least one surface of a transparent plastic film substrate, and a hard coat layer having a thickness of 3 to 15 μm is further formed on the buffer layer. A hard coat film is proposed. The pencil hardness of each of the transparent plastic film substrate, the buffer layer, and the optical functional layer has an increased value in this order, and is thus designed to have a pencil hardness of 4H to 8H as the entire hard coat film. . However, in Patent Document 2, a buffer layer is required in addition to the optical functional layer, and since it is required to have at least a two-layer structure, there is a drawback in that a load is imposed on the production process.
特許文献３には、透明プラスチックフィルムもしくはシート基材の少なくとも一方の面に、第１ハードコート層として無機質或いは有機質の内部架橋超微粒子を含有する硬化光学機能層を設けた後、更に第２ハードコート層として無機質或いは有機費に内部架橋粒子を含有しないクリア硬化樹脂の薄膜を設けたものが提案される。しかし、特許文献３も特許文献２と同様に二層構成にすることで生産工程に負荷を与えるという欠点がある。 In Patent Document 3, a hardened optical functional layer containing inorganic or organic internally crosslinked ultrafine particles is provided as a first hard coat layer on at least one surface of a transparent plastic film or sheet substrate, and then a second hard A coating layer provided with a thin film of a clear curable resin that does not contain internal cross-linked particles in the inorganic or organic cost is proposed. However, Patent Document 3 also has a drawback in that a load is applied to the production process by adopting a two-layer structure as in Patent Document 2.
特許文献４には、透明プラスチックフィルム基体の少なくとも一方の面に、少なくとも１層のハードコート層が形成されているハードコートフィルムであって、ハードコート層形成材料が樹脂１００重量部当たり無機微粒子を２０〜８０重量部含有し、且つハードコート層全体の厚みが１０μｍ〜５０μｍであり、且つ表面の鉛筆硬度が４Ｈ以上であるものが提案されている。しかし、特許文献４で用いている、ポリエステルアクリレートまたはポリウレタンアクリレート等の樹脂に対して無機微粒子を前記割合で含有したハードコート層形成材料により、透明プラスチックフィルム基体上に１０μｍ以上の厚みでハードコート層を形成した場合には、十分な硬度の確保と硬化収縮によるカールの抑制のバランスをとることが困難である。 Patent Document 4 discloses a hard coat film in which at least one hard coat layer is formed on at least one surface of a transparent plastic film substrate, and the hard coat layer forming material contains inorganic fine particles per 100 parts by weight of resin. It has been proposed that it contains 20 to 80 parts by weight, the entire hard coat layer has a thickness of 10 μm to 50 μm, and the surface has a pencil hardness of 4H or more. However, with the hard coat layer forming material containing inorganic fine particles in the above ratio with respect to the resin such as polyester acrylate or polyurethane acrylate used in Patent Document 4, the hard coat layer has a thickness of 10 μm or more on the transparent plastic film substrate. Is formed, it is difficult to balance the securing of sufficient hardness and curling suppression due to curing shrinkage.
ハードコートフィルムの視認性を向上させる方法として、透明プラスチックフィルム基体上に、ウレタンアクリレート、イソシアヌル酸アクリレート、及び無機の超微粒子を含むハードコート層を有するハードコートフィルムが提案されている（特許文献５）。これは、無機の超微粒子により、透明プラスチック基体とハードコート層の屈折率の差を合わせ込むことで、ハードコートフィルムの反射と光の干渉縞を防止するといった内容のものである。確かに、無機の超微粒子によるハードコート層の屈折率調整により、ハードコートフィルムの反射は軽減されるものの、ハードコート層構成材料の相溶性や分散性が不十分なために成膜性が悪く、ハードコート層厚が微妙にばらつくために、干渉縞克服が困難であった。また、成膜性の悪さから加工性も充分といえるものではなかった。 As a method for improving the visibility of the hard coat film, a hard coat film having a hard coat layer containing urethane acrylate, isocyanuric acid acrylate, and inorganic ultrafine particles on a transparent plastic film substrate has been proposed (Patent Document 5). ). This is to prevent reflection of the hard coat film and interference fringes of light by combining the difference in refractive index between the transparent plastic substrate and the hard coat layer with inorganic ultrafine particles. Although the reflection of the hard coat film is reduced by adjusting the refractive index of the hard coat layer with inorganic ultrafine particles, the film formability is poor due to insufficient compatibility and dispersibility of the hard coat layer constituent materials. Since the hard coat layer thickness varies slightly, it is difficult to overcome the interference fringes. In addition, the processability was not sufficient due to the poor film formability.
本発明は、優れた表面硬度を備えながら、割れや硬化収縮によるカールが抑制されていて、かつ、画面の視認性が良好で、ＬＣＤやＰＤＰのＴＶ用途にも好適に使用できる光学積層体を提供することを目的とする。 The present invention provides an optical layered body that has excellent surface hardness, curling due to cracking and curing shrinkage, good screen visibility, and suitable for use in TV applications such as LCDs and PDPs. The purpose is to provide.
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、下記光学積層体により上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the following optical laminate, and have completed the present invention.
すなわち本発明（１）は、厚さ１〜７００μｍの範囲にある透光性基体上に、化１よりなるε-カプロラクトン変性のイソシアヌレート、多官能アクリレートおよび多官能ウレタンアクリレートを含む樹脂からなる光学機能層を有し、上記ε−カプロラクトン変性のイソシアヌレートの配合量は光学機能層を形成する構成材料の全固形分比率で５〜５０％の範囲にあり、上記多官能アクリレートに対する上記多官能ウレタンアクリレートの混合比率が０．２〜０．７の範囲にあることを特徴とする光学積層体である。 That is, the present invention (1) is an optical system comprising a resin containing a ε-caprolactone-modified isocyanurate, a polyfunctional acrylate and a polyfunctional urethane acrylate of Chemical Formula 1 on a translucent substrate having a thickness of 1 to 700 μm. The polyfunctional urethane with respect to the polyfunctional acrylate has a functional layer, and the amount of the isocyanurate modified with ε-caprolactone is in the range of 5 to 50% in terms of the total solid content of the constituent material forming the optical functional layer. The optical laminate is characterized in that the mixing ratio of acrylate is in the range of 0.2 to 0.7 .
本発明（２）前記光学機能層上に低反射層を設けることを特徴とする本発明（１）の光学積層体である。 Invention (2) The optical layered body of the invention (1), wherein a low reflection layer is provided on the optical functional layer.
本発明の光学積層体は、耐擦傷性、耐薬品性、視認性に優れているため、ディスプレイに使用した場合は、ディスプレイ表面を物理的刺激、機械的刺激・化学的刺激などから保護し、更に、視認性の良い高画質の表示を可能とするものである。更に、本発明の光学積層体は、割れや、カールが抑制されているため、取り扱いが簡単で、搭載するディスプレイの生産コスト低減も可能とするものである。 The optical layered body of the present invention is excellent in scratch resistance, chemical resistance, and visibility, so when used in a display, the display surface is protected from physical stimulation, mechanical stimulation, chemical stimulation, etc. Furthermore, high-quality display with good visibility is possible. Furthermore, since the optical laminate of the present invention is suppressed from cracking and curling, it is easy to handle and can reduce the production cost of the display to be mounted.
本最良形態に係る光学積層体は、透光性基体上に、光学機能層が積層されたものを基本構成とする。ここで、前記光学機能層は透光性基体の片面に積層されていても両面に積層されていてもよい。更には、当該光学積層体は他の層を有していてもよい。ここで他の層としては、例えば、偏光基体、低反射層、他の機能付与層（例えば、帯電防止層、近赤外線（ＮＩＲ）吸収層、ネオンカット層、電磁波シールド層、光学機能層）、を挙げることができる。また、当該他の層の位置は、例えば、偏光基体の場合には前記光学機能層とは反対面の前記透光性基体上とし、低反射層の場合には前記光学機能層上とし、他の機能性付与層の場合には前記光学機能層の下層とする。以下、本最良形態に係る光学積層体の各構成要素（透光性基体、光学機能層等）を詳述する。 The optical laminate according to the best mode has a basic configuration in which an optical functional layer is laminated on a translucent substrate. Here, the optical functional layer may be laminated on one side of the translucent substrate or on both sides. Furthermore, the optical layered body may have other layers. Here, as other layers, for example, a polarizing substrate, a low reflection layer, other function-imparting layers (for example, an antistatic layer, a near infrared (NIR) absorption layer, a neon cut layer, an electromagnetic wave shielding layer, an optical functional layer), Can be mentioned. In addition, the position of the other layer is, for example, on the light-transmitting substrate opposite to the optical function layer in the case of a polarizing substrate, and on the optical function layer in the case of a low reflection layer. In the case of the functional provision layer, it is the lower layer of the optical functional layer. Hereafter, each component (a translucent base | substrate, an optical function layer, etc.) of the optical laminated body which concerns on this best form is explained in full detail.
はじめに、本最良形態に係る透光性基体としては、透光性である限り特に限定されず、石英ガラスやソーダガラス等のガラスも使用可能であるが、ポリエチレンテレフタレート（ＰＥＴ）、トリアセチルセルロース（ＴＡＣ）、ポリエチレンナフタレート（ＰＥＮ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリカーボネート（ＰＣ）、ポリイミド（ＰＩ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリビニルアルコール（ＰＶＡ）、ポリ塩化ビニル（ＰＶＣ）、シクロオレフィンコポリマー（ＣＯＣ）、含ノルボルネン樹脂、ポリエーテルスルホン、セロファン、芳香族ポリアミド等の各種樹脂フィルムを好適に使用することができる。これらのフィルムは無延伸のものも、延伸加工を施したものも使用可能である。特に二軸延伸加工されたポリエチレンテレフタレートフィルムが、機械的強度や寸法安定性に優れる点で好ましく、無延伸のトリアセチルセルロース（ＴＡＣ）はフィルム面内の位相差が非常に少ないという点で好ましい。なお、ＰＤＰ、ＬＣＤに用いる場合は、これらのＰＥＴ、ＴＡＣフィルムがより好ましい。 First, the translucent substrate according to the best mode is not particularly limited as long as it is translucent, and glass such as quartz glass and soda glass can also be used, but polyethylene terephthalate (PET), triacetyl cellulose ( TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), Various resin films such as cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide can be suitably used. These films can be unstretched or stretched. In particular, a biaxially stretched polyethylene terephthalate film is preferable from the viewpoint of excellent mechanical strength and dimensional stability, and unstretched triacetyl cellulose (TAC) is preferable from the viewpoint of very little in-plane retardation. In addition, when using for PDP and LCD, these PET and TAC films are more preferable.
これら透光性基体の透明性は高いものほど良好であるが、全光線透過率（ＪＩＳ Ｋ７１０５）としては８０％以上、より好ましくは９０％以上が良い。また、透光性基体の厚さとしては、軽量化の観点からは薄い方が好ましいが、その生産性やハンドリング性を考慮すると、１〜７００μｍの範囲のものが必要であり、好ましくは２５〜２５０μｍを使用することが好適である。 The higher the transparency of these translucent substrates, the better. However, the total light transmittance (JIS K7105) is 80% or more, more preferably 90% or more. The thickness of the light-transparent substrate, but thinner is preferable from the viewpoint of weight reduction, when considering its productivity and handling properties, it is necessary also to the range of 1～700Myuemu, preferably 25 It is preferred to use ˜250 μm.
また、透光性基体に、アルカリ処理、コロナ処理、プラズマ処理、スパッタ処理、ケン化処理等の表面処理や、界面活性剤、シランカップリング剤等の塗布、またはＳｉ蒸着などの表面改質処理を行うことにより、透光性基体と光学機能層との密着性を向上させることができる。 In addition, surface treatment such as alkali treatment, corona treatment, plasma treatment, sputtering treatment, saponification treatment, application of surfactant, silane coupling agent, etc., or surface modification treatment such as Si deposition on the translucent substrate. By performing this, the adhesion between the translucent substrate and the optical functional layer can be improved.
次に、本最良形態に係る光学機能層について詳述する。
本最良形態に係る光学機能層は、下記化１式より成るε-カプロラクトン変性のイソシアヌレートを、少なくとも１種類含む層である限り特に限定されない。該ε−カプロラクトンのセグメント部分は混合する樹脂、無機顔料、その添加剤との親和性が良いため、例えば、光学機能層の塗料製造工程においては生産の効率化、成膜工程においては成膜安定性（膜厚バラツキの軽減）などに寄与する。また、光学機能層全体に柔軟性を生み、内部応力の緩和などに効果的である（カールの抑制）。
Next, the optical functional layer according to the best mode will be described in detail.
The optical functional layer according to the best mode is not particularly limited as long as it is a layer containing at least one ε-caprolactone-modified isocyanurate having the following chemical formula 1. The ε-caprolactone segment has good affinity with the resin, inorganic pigment, and additives to be mixed. For example, production efficiency is improved in the coating process of the optical functional layer, and film formation is stable in the film formation process. Contributes to reduction of film thickness variation. In addition, the entire optical functional layer is made flexible, and is effective in reducing internal stress (suppression of curling).
光学機能層にε-カプロラクトン変性のイソシアヌレートと共に、熱硬化型樹脂、放射線硬化型樹脂を混合し、使用することができるが、放射線で光学機能層を硬化させることができる放射線硬化型樹脂を用いた系のほうが、生産効率、エネルギーコストなどの点において、有利で好ましい。放射線硬化型樹脂の例としては、アクリロイル基、メタクリロイル基、アクリロイルオキシ基、メタクリロイルオキシ基等のラジカル重合性官能基や、エポキシ基、ビニルエーテル基、オキセタン基等のカチオン重合性官能基を有するモノマー、オリゴマー、プレポリマーを単独で、または適宜混合した組成物が用いられる。モノマーの例としては、アクリル酸メチル、メチルメタクリレート、メトキシポリエチレンメタクリレート、シクロヘキシルメタクリレート、フェノキシエチルメタクリレート、エチレングリコールジメタクリレート、ジペンタエリスリトールヘキサアクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート等を挙げることができる。オリゴマー、プレポリマーとしては、ポリエステルアクリレート、ポリウレタンアクリレート、フェニレングリシジルエーテルヘキサメチレンジイソシアネートウレタンプレポリマー、フェニルグリシジルエーテルトリエンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートトルエンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートイソホロンジイソシアネートウレタンプレポリマーなどの多官能ウレタンアクリレート、エポキシアクリレート、ポリエーテルアクリレート、アルキットアクリレート、メラミンアクリレート、シリコーンアクリレート等のアクリレート化合物、不飽和ポリエステル、テトラメチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ビスフェノールＡジグリシジルエーテルや各種脂環式エポキシ等のエポキシ系化合物、３−エチル−３−ヒドロキシメチルオキセタン、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン、ジ［１−エチル（３−オキセタニル）］メチルエーテル等のオキセタン化合物を挙げることができる。 A thermosetting resin and a radiation curable resin can be mixed and used with ε-caprolactone-modified isocyanurate in the optical functional layer, but a radiation curable resin that can cure the optical functional layer with radiation is used. The conventional system is advantageous and preferable in terms of production efficiency and energy cost. Examples of radiation curable resins include monomers having radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, and cationic polymerizable functional groups such as epoxy group, vinyl ether group, oxetane group, A composition in which an oligomer and a prepolymer are used alone or appropriately mixed is used. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. it can. As oligomers and prepolymers, polyester acrylate, polyurethane acrylate, phenylene glycidyl ether hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether triene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane Prepolymer, polyfunctional urethane acrylate such as pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, epoxy acrylate, polyether acrylate, alkit acrylate, melamine acrylate, silicone acrylate Japanese polyester, tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, epoxy compounds such as bisphenol A diglycidyl ether and various alicyclic epoxies, 3-ethyl-3-hydroxymethyloxetane, Examples include oxetane compounds such as 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene and di [1-ethyl (3-oxetanyl)] methyl ether.
これらは単独、もしくは複数混合して使用することができるが、光学機能層の硬化スピード、耐擦傷性に優れたジペンタエリスリトールヘキサアクリレートなどの多官能アクリレートと、透光性基体と光学機能層との密着性、光学機能層の柔軟性、可撓性に優れた多官能ウレタンアクリレートとの混合系が、より好ましい。多官能アクリレートに対する多官能ウレタンアクリレートの混合比率は０．２〜０．７の範囲が必要である。多官能アクリレートに対する多官能ウレタンアクリレートの比率が低すぎると、光学機能層にシワや割れが生じる。逆に多すぎると光学機能層の耐擦傷性が低下する。
These can be used singly or in combination, but the functional speed of the optical functional layer, polyfunctional acrylate such as dipentaerythritol hexaacrylate excellent in scratch resistance, translucent substrate and optical functional layer A mixed system with a polyfunctional urethane acrylate having excellent adhesion, flexibility of the optical functional layer, and flexibility is more preferable. The mixing ratio of the polyfunctional urethane acrylate to the polyfunctional acrylate needs to be in the range of 0.2 to 0.7 . If the ratio of the polyfunctional urethane acrylate to the polyfunctional acrylate is too low, wrinkles and cracks occur in the optical functional layer. On the other hand, if the amount is too large, the scratch resistance of the optical functional layer is lowered.
ε-カプロラクトン変性のイソシアヌレートの配合量は特に限定されないが、光学機能層を形成する構成材料の全固形分比率で、５〜５０％の範囲が必要であり、１０〜３０％の範囲がより好ましい。ε-カプロラクトン変性のイソシアヌレートの配合量が少ないと、透光性基体と光学機能層の密着性が低下したり、カールが強くなる。また、成膜性の悪化で、干渉縞（光学機能層の微妙な厚さムラによる干渉縞）が発生し、視認性が悪くなる。更に、光学機能層の厚膜化で、光学機能層にシワや割れが生じる場合がある。一方、配合量が多すぎると光学機能層の耐擦傷性が低下する。 The blending amount of ε-caprolactone-modified isocyanurate is not particularly limited, but the total solid content ratio of the constituent material forming the optical functional layer needs to be in the range of 5 to 50%, more preferably in the range of 10 to 30%. preferable. When the amount of ε-caprolactone-modified isocyanurate is small, the adhesion between the translucent substrate and the optical functional layer is lowered or the curl is increased. Moreover, due to the deterioration of film formability, interference fringes (interference fringes due to subtle thickness unevenness of the optical function layer) are generated, and visibility is deteriorated. Furthermore, wrinkles and cracks may occur in the optical functional layer due to the thickening of the optical functional layer. On the other hand, when there are too many compounding quantities, the abrasion resistance of an optical function layer will fall.
上記の放射線硬化型樹脂を用いた系を硬化せしめる放射線としては、紫外線、可視光線、赤外線、電子線のいずれであってもよい。また、これらの放射線は、偏光であっても無偏光であってもよい。特に、設備コスト、安全性、ランニングコスト等の観点から紫外線が好適である。紫外線のエネルギー線源としては、例えば、高圧水銀ランプ、ハロゲンランプ、キセノンランプ、メタルハライドランプ、窒素レーザー、電子線加速装置、放射性元素などが好ましい。エネルギー線源の照射量は、紫外線波長３６５ｎｍでの積算露光量として、１００〜５，０００ｍＪ／ｃｍ2の範囲が好ましく、３００〜３,０００ｍＪ／ｃｍ2照射量が、１００ｍＪ／ｃｍ2未満の場合は、硬化が不十分となるため、光学機能層の硬度が低下する場合がある。また５，０００ｍＪ／ｃｍ2を超えると、光学機能層が着色して透明性が低下する。紫外線照射による硬化を行う場合は、光重合開始剤の添加が必要である。光重合開始剤としては、従来公知のものを用いることができる。例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、Ｎ，Ｎ，Ｎ，Ｎ−テトラメチル−４，４´−ジアミノベンゾフェノン、ベンジルメチルケタールなどのベンゾインとそのアルキルエーテル類；アセトフェノン、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４´−ジメトキレベンゾフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトンなどのアセトフェノン類；メチルアントラキノン、２−エチルアントラキノン、２−アミルアントラキノンなどのアントラキノン類；キサントン；チオキサントン、２，４−ジエチルチオキサントン、２，４−ジイソプロピルチオキサントンなどのチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタールなどのケタール類；ベンゾフェノン、４，４−ビスメチルアミノベンゾフェノンなどのベンゾフェノン類；その他、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン等を例示できる。これらは単独でまたは２種以上の混合物として使用できる。光重合開始剤の使用量は、放射線硬化型樹脂組成物に対して、全固形分比で５％以下程度、さらには１〜４％が好ましい。 The radiation that cures the system using the radiation curable resin may be any of ultraviolet rays, visible rays, infrared rays, and electron beams. Further, these radiations may be polarized or non-polarized. In particular, ultraviolet rays are suitable from the viewpoints of equipment cost, safety, running cost, and the like. As the ultraviolet energy beam source, for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, a radioactive element, and the like are preferable. The amount of irradiation with the energy radiation source of accumulative exposure at an ultraviolet wavelength of 365 nm, preferably in the range of 100~5,000mJ / cm 2, 300~3,000mJ / cm 2 irradiation amount, of less than 100 mJ / cm 2 Since the curing becomes insufficient, the hardness of the optical functional layer may be lowered. On the other hand, if it exceeds 5,000 mJ / cm 2 , the optical functional layer is colored and the transparency is lowered. When curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. A conventionally well-known thing can be used as a photoinitiator. For example, benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, N, N, N, N-tetramethyl-4,4′-diaminobenzophenone, benzylmethyl ketal; acetophenone, 3 Acetophenones such as methyl acetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone; methyl anthraquinone, 2-ethylanthraquinone, 2- Anthraquinones such as amylanthraquinone; xanthone; thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; Ketals such as cetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and others, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON etc. can be illustrated. These can be used alone or as a mixture of two or more. The amount of the photopolymerization initiator used is preferably about 5% or less, more preferably 1 to 4% in terms of the total solid content, relative to the radiation curable resin composition.
ε-カプロラクトン変性のイソシアヌレートを含む上記放射線硬化型樹脂組成物の系に、その重合硬化を妨げない範囲で高分子樹脂を添加使用することができる。この高分子樹脂は、後述する光学機能層塗料に使用される有機溶剤に可溶な熱可塑性樹脂であり、具体的にはアクリル樹脂、アルキッド樹脂、ポリエステル樹脂等が挙げられ、これらの樹脂中には、カルボキシル基やリン酸基、スルホン酸基等の酸性官能基を有することが好ましい。 A polymer resin can be added to the radiation-curable resin composition system containing ε-caprolactone-modified isocyanurate as long as the polymerization and curing are not hindered. This polymer resin is a thermoplastic resin that is soluble in an organic solvent used in the optical functional layer coating described later, and specifically includes acrylic resins, alkyd resins, polyester resins, and the like. Preferably has an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group.
また、レベリング剤、増粘剤、帯電防止剤、充填剤、体質顔料等の添加剤を使用することができる。レベリング剤は、塗膜表面の張力均一化を図り塗膜形成前に欠陥を直す働きがあり、上記放射線硬化型樹脂組成物より界面張力、表面張力共に低い物質が用いられる。 In addition, additives such as a leveling agent, a thickener, an antistatic agent, a filler, and an extender can be used. The leveling agent has a function of uniforming the tension on the surface of the coating film and correcting defects before forming the coating film, and a substance having lower interfacial tension and surface tension than the radiation curable resin composition is used.
光学機能層は、主に上述の樹脂組成物などの硬化物により構成されるが、その形成方法は、樹脂組成物と有機溶剤からなる塗料を塗工し、有機溶剤を揮発させた後に放射線（例えば電子線または紫外線照射）や熱により硬化せしめるものである。ここで使用される有機溶剤としては、樹脂組成物を溶解するのに適したものを選ぶ必要がある。具体的には、透光性基体への濡れ性、粘度、乾燥速度といった塗工適性を考慮して、アルコール系、エステル系、ケトン系、エーテル系、芳香族炭化水素から選ばれた単独または混合溶剤を使用することができる。 The optical functional layer is mainly composed of a cured product such as the above-described resin composition, but the formation method is to apply a paint composed of the resin composition and an organic solvent, volatilize the organic solvent, and then apply radiation ( For example, it is cured by electron beam or ultraviolet irradiation) or heat. As the organic solvent used here, it is necessary to select an organic solvent suitable for dissolving the resin composition. Specifically, in consideration of coating suitability such as wettability to a light-transmitting substrate, viscosity, and drying speed, an alcohol type, an ester type, a ketone type, an ether type, or an aromatic hydrocarbon is used alone or in combination. Solvents can be used.
光学機能層の厚さは３．０〜２０．０μｍの範囲であり、より好ましくは５．０〜１５．０μｍの範囲であり、さらに好ましくは７．０〜１３．０μｍの範囲がよい。光学機能層が３．０μｍより薄い場合は、耐擦傷性が劣化し、２０．０μｍより厚い場合は、光学機能層の硬化収縮によりカールが発生したり、光学機能層表面にマイクロクラックが発生したり、透光性基体との密着性が低下したり、さらには光透過性が低下したりする。そして、膜厚の増加に伴う必要塗料量の増加によるコストアップの原因ともなる。 The thickness of the optical functional layer is in the range of 3.0 to 20.0 μm, more preferably in the range of 5.0 to 15.0 μm, and still more preferably in the range of 7.0 to 13.0 μm. When the optical functional layer is thinner than 3.0 μm, the scratch resistance is deteriorated, and when it is thicker than 20.0 μm, curling occurs due to curing shrinkage of the optical functional layer or micro cracks occur on the surface of the optical functional layer. Or the adhesiveness with the translucent substrate is lowered, or the light transmittance is further lowered. And it becomes a cause of the cost increase by the increase in the amount of required coating materials accompanying the increase in film thickness.
本発明の光学積層体において、透光性基体の屈折率と光学機能層の屈折率の差が０．１０以下、好ましく０．０５以下であることが好ましい。前記屈折率差を前記範囲となるように制御することにより、表面での光の反射を低く抑えることができる。 In the optical layered body of the present invention, the difference between the refractive index of the translucent substrate and the refractive index of the optical functional layer is preferably 0.10 or less, and preferably 0.05 or less. By controlling the refractive index difference to be in the above range, reflection of light on the surface can be suppressed to a low level.
前記屈折率の制御は、無機の超微粒子を光学機能層中に適宜含有させしめることでできる。無機の超微粒子は、その配合量に応じて光学機能層の見かけの屈折率を調整する機能を有する。透光性基体の屈折率と光学機能層の屈折率は上述の通り、近似していることが好ましい。そのため、光学機能層形成材料の調製にあたっては、前記透光性基体の屈折率と光学機能層の屈折率の差が小さくなるように、無機の超微粒子の配合量を適宜に調整するのが好ましい。前記屈折率差が大きいと、光学積層体に入射した外光の反射光が虹色の色相を呈する干渉縞と呼ばれる現象が発生し、表示品位を落としてしまう。特に、光学積層体を備えた画像表示装置が使用される頻度の高いオフィスでは、蛍光灯として、三波長蛍光灯が非常に増加してきている。三波長蛍光灯は、特定の波長の発光強度が強く、物がはっきり見える特徴を有するが、この三波長蛍光灯下では更に干渉縞が顕著に現れることが判っている。 The refractive index can be controlled by appropriately containing inorganic ultrafine particles in the optical functional layer. The inorganic ultrafine particles have a function of adjusting the apparent refractive index of the optical functional layer according to the blending amount. As described above, it is preferable that the refractive index of the translucent substrate and the refractive index of the optical functional layer are approximate. Therefore, in the preparation of the optical functional layer forming material, it is preferable to appropriately adjust the blending amount of the inorganic ultrafine particles so that the difference between the refractive index of the translucent substrate and the refractive index of the optical functional layer is reduced. . When the difference in refractive index is large, a phenomenon called interference fringes in which reflected light of external light incident on the optical laminate exhibits a rainbow hue occurs, and the display quality is deteriorated. In particular, three-wavelength fluorescent lamps have been greatly increased as fluorescent lamps in offices where an image display device including an optical laminate is frequently used. The three-wavelength fluorescent lamp has a characteristic that the emission intensity of a specific wavelength is strong and the object can be clearly seen, but it has been found that interference fringes appear more significantly under this three-wavelength fluorescent lamp.
無機の超微粒子としては、例えば、酸化チタン、酸化ケイ素、酸化アルミニウム、酸化亜鉛、酸化錫、酸化ジルコニウム、酸化カルシウム、酸化インジウム、酸化アンチモン等があげられる。またこれらの複合物も使用することができる。これらのなかでも酸化チタン、酸化ケイ素（シリカ）、酸化アルミニウム、酸化亜鉛、酸化錫、酸化ジルコニウムが好ましい。これら超微粒子は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of inorganic ultrafine particles include titanium oxide, silicon oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, calcium oxide, indium oxide, and antimony oxide. These composites can also be used. Among these, titanium oxide, silicon oxide (silica), aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. These ultrafine particles may be used alone or in combination of two or more.
無機の超微粒子の平均粒径は１００ｎｍ以下であるのが好ましい。平均粒径１００ｎｍを超える場合には、光の散乱が発生し、光学機能層の透過率が低下したり、着色したりして、透明性の点では好ましくない。無機の超微粒子の平均粒径は、５０ｎｍ以下であるのが好ましく、さらには３０ｎｍ以下であるのが好ましい。 The average particle size of the inorganic ultrafine particles is preferably 100 nm or less. When the average particle diameter exceeds 100 nm, light scattering occurs, and the transmittance of the optical functional layer is lowered or colored, which is not preferable in terms of transparency. The average particle size of the inorganic ultrafine particles is preferably 50 nm or less, and more preferably 30 nm or less.
無機の超微粒子の配合量は、光学機能層形成材料の全樹脂成分に対し、１０〜６０重量％程度とすることが好ましい。より好ましくは２０〜５０重量％である。無機の超微粒子の配合量を、光学機能層形成材料の全樹脂成分に対し６０重量％を超える割合にすると、前記超微粒子の凝集物が発生しやすく、前記同様の欠点が生じる。また塗工性が悪くなるため好ましくない。一方、２０重量％未満の割合では、カールの発生が増大する傾向があり好ましくない。 The blending amount of the inorganic ultrafine particles is preferably about 10 to 60% by weight with respect to all the resin components of the optical functional layer forming material. More preferably, it is 20 to 50% by weight. When the blending amount of the inorganic ultrafine particles is more than 60% by weight with respect to the total resin components of the optical functional layer forming material, the ultrafine particles are likely to be aggregated, resulting in the same disadvantages as described above. Moreover, since coating property worsens, it is not preferable. On the other hand, a ratio of less than 20% by weight is not preferable because curling tends to increase.
本発明においては、光学機能層とは反対面の透光性基体上に、偏光基体を積層してもよい。ここで、当該偏光基体は、特定の偏光のみを透過し他の光を吸収する光吸収型の偏光フィルムや、特定の偏光のみを透過し他の光を反射する光反射型の偏光フィルムを使用することが出来る。光吸収型の偏光フィルムとしては、ポリビニルアルコール、ポリビニレン等を延伸させて得られるフィルムが使用可能であり、例えば、２色性素子として沃素または染料を吸着させたポリビニルアルコールを一軸延伸して得られたポリビニルアルコール（ＰＶＡ）フィルムが挙げられる。光反射型の偏光フィルムとしては、例えば、延伸した際に延伸方向の屈折率が異なる２種類のポリエステル樹脂（ＰＥＮ及びＰＥＮ共重合体）を、押出成形技術により数百層交互に積層し延伸した構成の３Ｍ社製「ＤＢＥＦ」や、コレステリック液晶ポリマー層と１／４波長板とを積層してなり、コレステリック液晶ポリマー層側から入射した光を互いに逆向きの２つの円偏光に分離し、一方を透過、他方を反射させ、コレステリック液晶ポリマー層を透過した円偏光を１／４波長板により直線偏光に変換させる構成の日東電工社製「ニポックス」やメルク社製「トランスマックス」等が挙げられる。 In the present invention, a polarizing substrate may be laminated on a light transmitting substrate opposite to the optical functional layer. Here, the polarizing substrate uses a light-absorbing polarizing film that transmits only specific polarized light and absorbs other light, or a light reflective polarizing film that transmits only specific polarized light and reflects other light. I can do it. As the light-absorbing polarizing film, a film obtained by stretching polyvinyl alcohol, polyvinylene or the like can be used. For example, it can be obtained by uniaxially stretching polyvinyl alcohol adsorbed with iodine or a dye as a dichroic element. Polyvinyl alcohol (PVA) film. As the light reflection type polarizing film, for example, two kinds of polyester resins (PEN and PEN copolymer) having different refractive indexes in the stretching direction when stretched are alternately laminated and stretched by several hundreds of extrusion techniques. "DBEF" manufactured by 3M, or a cholesteric liquid crystal polymer layer and a quarter-wave plate are laminated, and light incident from the cholesteric liquid crystal polymer layer side is separated into two circularly polarized light beams that are opposite to each other. Nitto Denko's “Nipox” and Merck's “Transmax”, which are configured to convert circularly polarized light that is transmitted through the cholesteric liquid crystal polymer layer and converted into linearly polarized light by a quarter-wave plate, and the like. .
更に、コントラストを向上させるために、光学機能層上に低反射層を設けることが好ましい。この場合、低反射層の屈折率が光学機能層の屈折率より低いことが必要であり、１．４５以下であることが好ましい。これらの特徴を有する材料としては、例えばＬｉＦ（屈折率ｎ＝１．４）、ＭｇＦ２（ｎ＝１．４）、３ＮａＦ・ＡｌＦ３（ｎ＝１．４）、ＡｌＦ３（ｎ＝１．４）、Ｎａ３ＡｌＦ６（ｎ＝１．３３）、等の無機材料を微粒子化し、アクリル系樹脂やエポキシ系樹脂等に含有させた無機系低反射材料、フッ素系、シリコーン系の有機化合物、熱可塑性樹脂、熱硬化型樹脂、放射線硬化型樹脂等の有機低反射材料を挙げることができる。その中で、特に、フッ素系の含フッ素材料が汚れの防止の点において好ましい。また、低反射層は、臨界表面張力が２０ｄｙｎｅ／ｃｍ以下であることが好ましい。臨界表面張力が２０ｄｙｎｅ／ｃｍより大きい場合は、低反射層に付着した汚れが取れにくくなる。 Furthermore, in order to improve contrast, it is preferable to provide a low reflection layer on the optical functional layer. In this case, the refractive index of the low reflective layer needs to be lower than the refractive index of the optical functional layer, and is preferably 1.45 or less. Examples of the material having these characteristics include LiF (refractive index n = 1.4), MgF 2 (n = 1.4), 3NaF · AlF 3 (n = 1.4), AlF 3 (n = 1. 4), inorganic low reflection material in which inorganic material such as Na 3 AlF 6 (n = 1.33) is finely divided and contained in acrylic resin or epoxy resin, fluorine-based, silicone-based organic compound, Examples thereof include organic low reflection materials such as thermoplastic resins, thermosetting resins, and radiation curable resins. Among them, a fluorine-based fluorine-containing material is particularly preferable in terms of preventing contamination. The low reflective layer preferably has a critical surface tension of 20 dyne / cm or less. When the critical surface tension is larger than 20 dyne / cm, it becomes difficult to remove the dirt adhered to the low reflection layer.
上記含フッ素材料としては、有機溶剤に溶解し、その取り扱いが容易であるフッ化ビニリデン系共重合体や、フルオロオレフィン／炭化水素共重合体、含フッ素エポキシ樹脂、含フッ素エポキシアクリレート、含フッ素シリコーン、含フッ素アルコキシシラン、等を挙げることができる。これらは単独でも複数組み合わせて使用することも可能である。 Examples of the fluorine-containing material include vinylidene fluoride copolymers, fluoroolefin / hydrocarbon copolymers, fluorine-containing epoxy resins, fluorine-containing epoxy acrylates, fluorine-containing silicones, which are easily dissolved in organic solvents. , Fluorine-containing alkoxysilanes, and the like. These can be used alone or in combination.
また、２−（パーフルオロデシル）エチルメタクリレート、２−（パーフルオロ−７−メチルオクチル）エチルメタクリレート、３−（パーフルオロ−７−メチルオクチル）−２−ヒドロキシプロピルメタクリレート、２−（パーフルオロ−９−メチルデシル）エチルメタクリレート、３−（パーフルオロ−８−メチルデシル）−２−ヒドロキシプロピルメタクリレート等の含フッ素メタクリレート、３−パーフルオロオクチル−２−ヒドロキシルプロピルアクリレート、２−（パーフルオロデシル）エチルアクリレート、２−（パーフルオロ−９−メチルデシル）エチルアクリレート等の含フッ素アクリレート、３−パーフルオロデシル−１，２−エポキシプロパン、３−（パーフルオロ−９−メチルデシル）−１，２−エポキシプロパン等のエポキサイド、エポキシアクリレート等の放射線硬化型の含フッ素モノマー、オリゴマー、プレポリマー等を挙げることができる。これらは単独若しくは複数種類混合して使用することも可能である。 Further, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 2- (perfluoro- 9-methyldecyl) ethyl methacrylate, fluorine-containing methacrylate such as 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl methacrylate, 3-perfluorooctyl-2-hydroxylpropyl acrylate, 2- (perfluorodecyl) ethyl acrylate , Fluorine-containing acrylates such as 2- (perfluoro-9-methyldecyl) ethyl acrylate, 3-perfluorodecyl-1,2-epoxypropane, 3- (perfluoro-9-methyldecyl) -1,2-epoxypropane It epoxide, radiation-curable fluorine-containing monomers such as epoxy acrylate, oligomers, and the like prepolymer. These can be used alone or in combination.
さらに、５〜３０ｎｍのシリカ超微粒子を水若しくは有機溶剤に分散したゾルとフッ素系の皮膜形成剤を混合した低反射材料を使用することもできる。５〜３０ｎｍのシリカ超微粒子を水若しくは有機溶剤に分散したゾルは、ケイ酸アルカリ塩中のアルカリ金属イオンをイオン交換等で脱アルカリする方法や、ケイ酸アルカリ塩を鉱酸で中和する方法等で知られた活性ケイ酸を縮合して得られる公知のシリカゾル、アルコキシシランを有機溶媒中で塩基性触媒の存在下に加水分解と縮合することにより得られる公知のシリカゾル、さらには上記の水性シリカゾル中の水を蒸留法等により有機溶剤に置換することにより得られる有機溶剤系のシリカゾル（オルガノシリカゾル）が用いられる。これらのシリカゾルは水系及び有機溶剤系のどちらでも使用することができる。有機溶剤系シリカゾルの製造に際し、完全に水を有機溶剤に置換する必要はない。上記シリカゾルは、ＳｉＯ２として０．５〜５０重量％濃度の固形分を含有する。シリカゾル中のシリカ超微粒子の構造は、球状、針状、板状等様々なものが使用可能である。 Furthermore, a low-reflective material in which a sol obtained by dispersing ultrafine silica particles of 5 to 30 nm in water or an organic solvent and a fluorine-based film forming agent can be used. A sol in which 5 to 30 nm ultrafine silica particles are dispersed in water or an organic solvent is a method in which alkali metal ions in an alkali silicate salt are dealkalized by ion exchange or the like, or a method in which an alkali silicate salt is neutralized with a mineral acid A known silica sol obtained by condensing active silicic acid known in the art, a known silica sol obtained by condensing alkoxysilane with hydrolysis in an organic solvent in the presence of a basic catalyst, and the above-mentioned aqueous sol An organic solvent-based silica sol (organosilica sol) obtained by substituting water in the silica sol with an organic solvent by a distillation method or the like is used. These silica sols can be used in both aqueous and organic solvent systems. In producing the organic solvent-based silica sol, it is not necessary to completely replace water with the organic solvent. The silica sol, a solid content of 0.5 to 50% strength by weight as SiO 2. Various structures such as a spherical shape, a needle shape, and a plate shape can be used as the structure of the silica ultrafine particles in the silica sol.
また、皮膜形成剤としては、アルコキシシラン、金属アルコキシドや金属塩の加水分解物や、ポリシロキサンをフッ素変性したものなどを用いることができる。上記のような皮膜形成剤の中でも、特にフッ素化合物を用いることにより、低反射層の臨界表面張力が低下して油分の付着を抑制することができるので好ましい。本発明の低反射層は、上記で述べた材料を例えば溶剤で希釈し、スピンコーター、ロールコーター、印刷等の方法で光学機能層上に設けて乾燥後、熱や放射線（紫外線の場合は上記の光重合開始剤を使用する）等により硬化させることによって得ることができる。放射線硬化型の含フッ素モノマー、オリゴマー、プレポリマーは耐汚染性には優れているが、濡れ性が悪いため、組成によっては光学機能層上で低反射層をはじくという問題や、低反射層が光学機能層から剥がれるという問題が生じるおそれがあるため、光学機能層に使用する前述の放射線硬化型樹脂として説明した、アクリロイル系、メタクリロイル系、アクリロイルオキシ基、メタクリロイルオキシ基等重合性不飽和結合を有するモノマー、オリゴマー、プレポリマーを適宜混合し、使用することが望ましい。 As the film forming agent, alkoxysilane, metal alkoxide, hydrolyzate of metal salt, or fluorine-modified polysiloxane can be used. Among the film forming agents as described above, it is particularly preferable to use a fluorine compound because the critical surface tension of the low reflection layer is lowered and adhesion of oil can be suppressed. The low reflection layer of the present invention is prepared by diluting the above-mentioned materials with, for example, a solvent, and providing it on the optical functional layer by a method such as a spin coater, roll coater, printing, etc. The photopolymerization initiator can be used for curing. Radiation curable fluorine-containing monomers, oligomers, and prepolymers are excellent in stain resistance, but have poor wettability, so depending on the composition, the problem of repelling the low reflection layer on the optical functional layer, Since the problem of peeling off from the optical functional layer may occur, the polymerizable unsaturated bond such as acryloyl-based, methacryloyl-based, acryloyloxy group, methacryloyloxy group, etc. described as the radiation curable resin used in the optical functional layer is provided. It is desirable to mix and use monomers, oligomers and prepolymers as appropriate.
なお、熱によるダメージを受けやすいＰＥＴ、ＴＡＣ等のプラスチック系フィルムを透光性基体に使用する場合は、これら低反射層の材料としては、放射線硬化型樹脂を選択することが好ましい。 When a plastic film such as PET or TAC, which is easily damaged by heat, is used for the translucent substrate, it is preferable to select a radiation curable resin as the material for these low reflection layers.
低反射層が良好な反射防止機能を発揮するための厚さについては、公知の計算式で算出することができる。入射光が低反射層に垂直に入射する場合に、低反射層が光を反射せず、かつ１００％透過するための条件は次の関係式を満たせばよいとされている。なお、式中Ｎ０は低反射層の屈折率、Ｎｓは光学機能層の屈折率、ｈは低反射層の厚さ、λ０は光の波長を示す。 The thickness for the low reflection layer to exhibit a good antireflection function can be calculated by a known calculation formula. In the case where incident light is perpendicularly incident on the low reflection layer, the condition for the low reflection layer not to reflect light and to transmit 100% should satisfy the following relational expression. In the formula, N 0 represents the refractive index of the low reflective layer, N s represents the refractive index of the optical functional layer, h represents the thickness of the low reflective layer, and λ 0 represents the wavelength of light.
上記（１）式によれば、光の反射を１００％防止するためには、低反射層の屈折率が下層（光学機能層）の屈折率の平方根になるような材料を選択すればよいことが分かる。ただし、実際は、この数式を完全に満たす材料は見出し難く、限りなく近い材料を選択することになる。上記（２）式では（１）式で選択した低反射層の屈折率と、光の波長から低反射層の反射防止膜としての最適な厚さが計算される。例えば、光学機能層、低反射層の屈折率をそれぞれ１．５０、１．３８、光の波長を５５０ｎｍ（視感度の基準）とし、これらの値を上記（２）式に代入すると、低反射層の厚さは０．１μｍ前後の光学膜厚、好ましくは０．１±０．０１μｍの範囲が最適であると計算される。
According to the above formula (1), in order to prevent light reflection by 100%, it is only necessary to select a material in which the refractive index of the low reflective layer is the square root of the refractive index of the lower layer (optical functional layer). I understand. However, in reality, it is difficult to find a material that completely satisfies this mathematical formula, and a material that is as close as possible is selected. In the above equation (2), the optimum thickness as the antireflection film of the low reflection layer is calculated from the refractive index of the low reflection layer selected in the equation (1) and the wavelength of light. For example, if the refractive indexes of the optical functional layer and the low reflection layer are 1.50 and 1.38, the wavelength of light is 550 nm (visibility standard), and these values are substituted into the above equation (2), the low reflection The layer thickness is calculated to be optimal with an optical film thickness of around 0.1 μm, preferably in the range of 0.1 ± 0.01 μm.
本発明の光学積層体の製造方法は、従来のハードコートフィルムの製造法同様の手法が適用され得る。例えば、透光性基体上に、ε-カプロラクトン変性のイソシアヌレートを含む放射線硬化型樹脂塗料を塗工し、乾燥後、放射線硬化させ作成することにより行う。透光性基体上に塗料を塗工する手法としては、通常の塗工方式や印刷方式が適用される。具体的には、エアドクターコーティング、バーコーティング、ブレードコーティング、ナイフコーティング、リバースコーティング、トランスファロールコーティング、グラビアロールコーティング、キスコーティング、キャストコーティング、スプレーコーティング、スロットオリフィスコーティング、カレンダーコーティング、ダムコーティング、ディップコーティング、ダイコーティング等のコーティングや、グラビア印刷等の凹版印刷、スクリーン印刷等の孔版印刷等の印刷等が使用できる。 The method similar to the manufacturing method of the conventional hard coat film can be applied to the manufacturing method of the optical laminated body of this invention. For example, a radiation curable resin coating containing ε-caprolactone-modified isocyanurate is coated on a light-transmitting substrate, dried, and then cured by radiation. As a method for applying the paint on the translucent substrate, a normal coating method or printing method is applied. Specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating Coating such as die coating, intaglio printing such as gravure printing, printing such as stencil printing such as screen printing, and the like can be used.
本発明の実施例および比較例を以下に説明する。なお、「部」は「重量部」を意味するものとする。 Examples of the present invention and comparative examples will be described below. “Parts” means “parts by weight”.
樹脂層用塗料として表１の塗料成分からなる混合物をサンドミルにて１時間分散することによって得られた塗料を、膜厚８０μｍ、全光線透過率９２％からなる透光性基体のＴＡＣの片面上に、ダイヘッドコーティング方式にて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射（照射距離１０ｃｍ、照射時間３０秒）を行い、塗工膜を硬化させた。このようにして、実施例１〜３、並びに比較例１及び２の光学積層体を得た。また、透光性基体をＴＡＣから膜厚７５μｍ、透過率８９％のＰＥＴ（易接着処理層有）に変更した以外は、比較例１と同様にして、本発明の比較例３を得た。尚、以下の表に示されている樹脂層用塗料における屈折率は原料の数値であり、硬化後の屈折率は僅かながら変動した数値である（一般に０．０１〜０．０３）。 As a coating for the resin layer, a coating obtained by dispersing a mixture of coating components in Table 1 with a sand mill for 1 hour was applied to one side of TAC of a translucent substrate having a film thickness of 80 μm and a total light transmittance of 92%. Next, after applying by die head coating method, drying at 100 ° C. for 1 minute, and then applying UV irradiation (irradiation distance 10 cm, irradiation time 30 seconds) with one 120 W / cm condensing type high pressure mercury lamp in nitrogen atmosphere, coating The film was cured. Thus, the optical laminated body of Examples 1-3 and Comparative Examples 1 and 2 was obtained. In addition, Comparative Example 3 of the present invention was obtained in the same manner as Comparative Example 1, except that the translucent substrate was changed from TAC to PET (with an easy adhesion treatment layer) having a film thickness of 75 μm and a transmittance of 89%. In addition, the refractive index in the coating material for resin layers shown in the following table | surface is a numerical value of a raw material, and the refractive index after hardening is a numerical value which fluctuated slightly (generally 0.01-0.03).
実施例１乃至３並びに比較例１乃至３の光学積層体を用い、透過率、密着性、鉛筆硬度、ＳＷ（スチールウールラビング試験）、耐薬品性、Ｃ／Ｒ（コントラスト）、干渉縞、カール、割れ、を下記方法により測定、評価した。 Using the optical laminates of Examples 1 to 3 and Comparative Examples 1 to 3, transmittance, adhesion, pencil hardness, SW (steel wool rubbing test), chemical resistance, C / R (contrast), interference fringes, curl , Cracks were measured and evaluated by the following methods.
全光線透過率は、ＪＩＳ Ｋ７１０５に従い、上記ヘイズメーターを用いて測定した。 The total light transmittance was measured using the haze meter according to JIS K7105.
密着性は、ＪＩＳ Ｋ５６００のクロスカット法に従い、行った。
尚、カットの間隔は１ｍｍとし、カット数は１１個とする。評価はクロスカットした格子の剥がれていない個数の割合を、％で表示する。例えば、５個剥がれていれば、９５／１００と表示する。
Adhesion was performed according to the cross-cut method of JIS K5600.
The cut interval is 1 mm and the number of cuts is 11. In the evaluation, the ratio of the number of cross-cut lattices that have not been peeled is displayed in%. For example, if 5 pieces are peeled, 95/100 is displayed.
鉛筆硬度は、ＪＩＳ Ｋ５６００−５−４に従い、５回試験し、傷がついてない本数をカウントした。例えば、３Ｈの鉛筆で、３本傷がなければ、３／５（３Ｈ）というようにした。 The pencil hardness was tested five times according to JIS K5600-5-4, and the number of scratches was counted. For example, with 3H pencil, if there are no 3 scratches, 3/5 (3H).
ＳＷ試験は、スチールウール＃００００を使用し、２．４５［Ｎ］で１０往復した時のヘイズ変化量（試験前後の差の絶対値）を測定し、変化量が０．０〜０．２を○、０．２〜０．５を△、０．５以上を×とした。
ヘイズ値は、ＪＩＳ Ｋ７１０５に従い、ヘイズメーター（商品名：ＮＤＨ２０００、日本電色社製）を用いて測定した。
In the SW test, steel wool # 0000 was used, and the amount of change in haze (absolute value of the difference between before and after the test) was measured after 10 reciprocations at 2.45 [N]. ◯, 0.2 to 0.5 is Δ, and 0.5 or more is ×.
The haze value was measured according to JIS K7105 using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku).
耐薬品性は、リグロイン、トルエン、硫酸（１０％）、ＮａＯＨ（６％）、エタノール、中性洗剤（ファミリーピュア）、ハンドクリーム（ニベア）、ヘアリキッド（サクセス：モーニングヘアウォータ）の各試薬を光学機能層表面に滴下後、１０時間放置してから拭き取り、外観の変化の有無を目視評価した。全ての薬品に対し、変化無き場合を○、白化等どれかひとつの薬品においても変化が認められる場合を×とした。 Chemical resistance includes reagents for ligroin, toluene, sulfuric acid (10%), NaOH (6%), ethanol, neutral detergent (family pure), hand cream (Nivea), and hair liquid (success: morning hair water). After dropping on the surface of the optical functional layer, it was left for 10 hours and then wiped off, and the presence or absence of a change in appearance was visually evaluated. For all chemicals, the case where there was no change was marked as ◯, and the case where any one of the chemicals such as whitening was changed was marked as x.
密着性は、ＪＩＳ Ｋ５６００のクロスカット法に従い、行った。
尚、カットの間隔は１ｍｍとし、カット数は１１個とする。評価はクロスカットした格子の剥がれていない個数の割合を、％で表示する。例えば、５個剥がれていれば、９５／１００と表示する。
Adhesion was performed according to the cross-cut method of JIS K5600.
The cut interval is 1 mm and the number of cuts is 11. In the evaluation, the ratio of the number of cross-cut lattices that have not been peeled is displayed in%. For example, if 5 pieces are peeled, 95/100 is displayed.
コントラストは、各実施例および各比較例の光学積層体の樹脂層形成面と反対面に、無色透明な粘着層を介して液晶ディスプレイ（商品名：ＬＣ−３７ＧＸ１Ｗ、シャープ社製）の画面表面に貼り合せ、液晶ディスプレイ画面の正面上方６０°の方向から蛍光灯（商品名：ＨＨ４１２５ＧＬ、ナショナル社製）にて液晶ディスプレイ表面の照度が２００ルクスとなるようにした後、液晶ディスプレイを白表示及び黒表示としたときの輝度を色彩輝度計（商品名：ＢＭ−５Ａ、トプコン社製）にて測定し、得られた黒表示時の輝度（ｃｄ／ｍ２）と白表示時の輝度（ｃｄ／ｍ２）を以下の式にて算出した時の値が、６００〜８００のとき×、８０１〜１０００のとき○、１００１〜１２００のとき◎とした。
コントラスト＝白表示の輝度／黒表示の輝度
The contrast is on the screen surface of the liquid crystal display (trade name: LC-37GX1W, manufactured by Sharp Corporation) through the colorless and transparent adhesive layer on the surface opposite to the resin layer forming surface of the optical layered body of each example and each comparative example. After bonding, the illuminance on the surface of the liquid crystal display is set to 200 lux with a fluorescent lamp (product name: HH4125GL, manufactured by National Corporation) from the direction 60 ° above the front of the liquid crystal display screen, and then the liquid crystal display is displayed in white and black The luminance at the time of display is measured with a color luminance meter (trade name: BM-5A, manufactured by Topcon Corporation), and the obtained luminance at the time of black display (cd / m 2 ) and luminance at the time of white display (cd / When the value when m 2 ) was calculated by the following equation was 600 to 800, x was 801 to 1000, and ◎ was 1001 to 1200.
Contrast = Brightness of white display / Brightness of black display
干渉縞と割れは、クロスニコルの偏光板表面に光学機能層が表側になるように、屈折率１．５の粘着層（膜厚２０μｍ）を介して貼合し、三波長の蛍光灯下（松下電器産業社製：ＦＬＲ４０Ｓ・ＥＸ−Ｎ／Ｍ−Ｘ、照度約５００ルクス）の反射にて、目視評価した。干渉縞や割れが確認できない場合を○、僅かに薄く確認できる場合を△、ハッキリ確認できる場合を×とした。 The interference fringes and cracks are bonded to the surface of the crossed Nicol polarizing plate via an adhesive layer having a refractive index of 1.5 (film thickness 20 μm) so that the optical functional layer is on the front side, and under a three-wavelength fluorescent lamp ( (Matsushita Electric Industrial Co., Ltd .: FLR40S · EX-N / MX, illuminance of about 500 lux) was used for visual evaluation. The case where interference fringes and cracks could not be confirmed was indicated as ◯, the case where slight interference could be confirmed as Δ, and the case where clear confirmation could be confirmed as X.
カールは、サンプルを１０００ｍｍ（ＴＤ：塗工の幅方向）×５００ｍｍ（ＭＤ：塗工方向のサイズにカット。ＴＤ方向のカールの曲率（直径）を測定し、５０ｍｍ以上を○、３０以上〜５０ｍｍ未満を△、３０ｍｍ未満を×とした。 For curling, the sample is 1000 mm (TD: coating width direction) x 500 mm (MD: cut to size in coating direction. Curvature (diameter) of TD direction is measured. Less than was made into (triangle | delta) and less than 30 mm was made into x.
上記評価方法による評価結果を表２に示す。 Table 2 shows the evaluation results obtained by the above evaluation method.
ε-カプロラクトン変性のイソシアヌレートを含む実施例１乃至３の光学積層体は、耐擦傷性、耐薬品性、視認性などの要求特性を充足するものであったが、ε-カプロラクトン変性のイソシアヌレートを含まない比較例１乃至３の光学積層体は耐擦傷性、耐薬品性、視認性をバランス良く満足することができなかった。 The optical laminates of Examples 1 to 3 containing ε-caprolactone-modified isocyanurate satisfy the required properties such as scratch resistance, chemical resistance, and visibility, but ε-caprolactone-modified isocyanurate The optical laminates of Comparative Examples 1 to 3 that did not contain No could not satisfy the scratch resistance, chemical resistance, and visibility in a well-balanced manner.
以上のように、透光性基体上に、ε-カプロラクトン変性のイソシアヌレートを含む光学機能層を設けたことで、耐擦傷性、耐薬品性、視認性をバランスよく満足する光学積層体を提供することができる。 As described above, by providing an optical functional layer containing ε-caprolactone-modified isocyanurate on a translucent substrate, an optical layered body satisfying a good balance of scratch resistance, chemical resistance and visibility is provided. can do.
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