JP7480512B2 - Hard Coat Film - Google Patents
Hard Coat Film Download PDFInfo
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- JP7480512B2 JP7480512B2 JP2020011950A JP2020011950A JP7480512B2 JP 7480512 B2 JP7480512 B2 JP 7480512B2 JP 2020011950 A JP2020011950 A JP 2020011950A JP 2020011950 A JP2020011950 A JP 2020011950A JP 7480512 B2 JP7480512 B2 JP 7480512B2
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- hard coat
- film
- coat layer
- coat film
- adhesion
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- 239000000758 substrate Substances 0.000 claims description 24
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 10
- 238000010998 test method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 description 95
- 239000010410 layer Substances 0.000 description 35
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 150000003457 sulfones Chemical class 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004695 Polyether sulfone Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229920006393 polyether sulfone Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 230000005865 ionizing radiation Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 2
- 229960004419 dimethyl fumarate Drugs 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 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
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 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
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
本発明は、スルホン系樹脂を主成分とする基材フィルム上に、ハードコート層を設けたハードコートフィルムに関する。更に詳しくは、エレクトロルミネッセンス（ＥＬ）表示装置、液晶表示装置（ＬＣＤ）、プラズマ表示装置等のパネルディスプレイ、フレキシブルディスプレイ、タッチパネル等の表示装置部品等に用いるフィルムとして使用することができるハードコートフィルムに関する。 The present invention relates to a hard coat film in which a hard coat layer is provided on a substrate film mainly composed of a sulfone-based resin. More specifically, the present invention relates to a hard coat film that can be used as a film for use in panel displays such as electroluminescence (EL) displays, liquid crystal displays (LCDs), and plasma displays, flexible displays, and display device components such as touch panels.
たとえば、エレクトロルミネッセンス（ＥＬ）表示装置の表示面には、取り扱い時に傷が付いて視認性が低下しないように耐擦傷性を付与することが要求されている。そのため、基材フィルムにハードコート層を設けたハードコートフィルムを利用して、ディスプレイの表示面の耐擦傷性を付与することが一般的に行われている。近年、表示画面上で表示を見ながら指やペン等でタッチすることでデータや指示を入力できるタッチパネルの普及により、この様な光学部材に用いるハードコートフィルムに対する機能的要求はさらに高まっている。 For example, the display surface of an electroluminescence (EL) display device must be scratch-resistant to prevent scratches during handling and loss of visibility. For this reason, it is common to use a hard coat film, which is a base film with a hard coat layer, to impart scratch resistance to the display surface of the display. In recent years, with the widespread use of touch panels that allow users to input data and instructions by touching the display screen with a finger or pen while viewing the display, the functional requirements for hard coat films used in such optical components have increased.
このようなハードコートフィルムとしては、トリアセチルセルロース（ＴＡＣ）フィルム等の基材フィルム上に、ハードコート層を形成したものが一般的に用いられているが、ＴＡＣフィルムは耐湿熱性に劣るという欠点があり、耐久性を改善するためにポリエチレンテレフタレート（ＰＥＴ）フィルムやポリエチレンナフタレート（ＰＥN）フィルムを用いることが開示されている（特許文献１、２）。 Such hard coat films are generally made by forming a hard coat layer on a base film such as triacetyl cellulose (TAC) film, but TAC film has the disadvantage of being poor in resistance to moist heat, and it has been disclosed that polyethylene terephthalate (PET) film or polyethylene naphthalate (PEN) film can be used to improve durability (Patent Documents 1 and 2).
しかしながら、特許文献１，２では、耐薬品性や熱収縮率等の面でハードコートフィルムとして用いるには不十分であった。 However, the chemical resistance and heat shrinkage rate of the films disclosed in Patent Documents 1 and 2 were insufficient for use as hard coat films.
そこで、本発明は高い耐熱性、寸法安定性、を有しているとともに、耐擦傷性、鉛筆硬度、インク密着性、耐薬品性、透過率、表面平滑性、水蒸気バリア性、滑り性、巻取適正が向上したハードコートフィルムを得ることを目的とする。 The present invention aims to provide a hard-coated film that has high heat resistance and dimensional stability, as well as improved scratch resistance, pencil hardness, ink adhesion, chemical resistance, transmittance, surface smoothness, water vapor barrier properties, slipperiness, and winding suitability.
上記課題を解決するために、本発明は下記の（１）～（４）を提供する。
（１） スルホン系樹脂を主成分とする基材フィルム上にハードコート層を設けたハードコートフィルム。
（２） 前記スルホン系樹脂が、ポリエーテルスルホンであることを特徴とする（１）に記載のハードコートフィルム。
（３） 前記スルホン系樹脂が、ポリフェニルスルホンであることを特徴とする（１）に記載のハードコートフィルム。
（４） スルホン系樹脂を主成分とする基材フィルム上にハードコート層を設けたハードコートフィルムの製造方法。
In order to solve the above problems, the present invention provides the following (1) to (4).
(1) A hard coat film in which a hard coat layer is provided on a substrate film mainly composed of a sulfone-based resin.
(2) The hard coat film according to (1), wherein the sulfone-based resin is polyethersulfone.
(3) The hard coat film according to (1), wherein the sulfone-based resin is polyphenylsulfone.
(4) A method for producing a hard coat film, comprising providing a hard coat layer on a substrate film mainly composed of a sulfone-based resin.
本発明によれば、高い耐熱性、寸法安定性、を有しているとともに、耐擦傷性、鉛筆硬度、インク密着性、ハードコート層密着性、耐薬品性、熱安定性、透過率、表面平滑性、水蒸気バリア性、滑り性、巻取適正が向上したハードコートフィルムを得ることができる。 According to the present invention, it is possible to obtain a hard coat film that has high heat resistance and dimensional stability, as well as improved scratch resistance, pencil hardness, ink adhesion, hard coat layer adhesion, chemical resistance, thermal stability, transmittance, surface smoothness, water vapor barrier properties, slipperiness, and winding suitability.
本発明はスルホン系樹脂を主成分とする基材フィルム上に、ハードコート層を設けたハードコートフィルムである。 The present invention is a hard coat film in which a hard coat layer is provided on a substrate film whose main component is a sulfone-based resin.
本発明において、スルホン系樹脂を主成分とする基材フィルムとは、その主鎖に少なくとも炭素およびスルホニル基を含む結合を形成する反応によって得られる高分子化合物の組成物からなるスルホン系樹脂を主成分とする透明な基材フィルムのことである。 In the present invention, a substrate film mainly composed of a sulfone-based resin refers to a transparent substrate film mainly composed of a sulfone-based resin made of a composition of polymeric compounds obtained by a reaction that forms a bond containing at least carbon and a sulfonyl group in the main chain.
本発明において、スルホン系樹脂とは、その主鎖に少なくとも炭素およびスルホニル基を含む結合を形成する反応によって得られる高分子化合物の組成物からなるスルホン系樹脂であり、具体的にはポリエーテルスルホン（ＰＥＳ）、ポリフェニルスルホン（ＰＰＳＵ）などが挙げられる。これらのPES、PPSUを主成分とする基材フィルムの膜厚は、PESは25～100μｍ程度、PPSUは30～100μｍ程度であることが好ましいが、その限りではない。 In the present invention, the sulfone resin is a sulfone resin consisting of a composition of polymer compounds obtained by a reaction that forms a bond containing at least carbon and a sulfonyl group in the main chain, and specific examples include polyethersulfone (PES) and polyphenylsulfone (PPSU). The thickness of the substrate film mainly composed of PES or PPSU is preferably about 25 to 100 μm for PES and about 30 to 100 μm for PPSU, but is not limited to this.
上記基材フィルム成形の方法としては、例えば、溶液キャスト法（溶液流延法）、溶融押出法、カレンダー法、圧縮成形法等、任意の適切なフィルム成形法が挙げられる。溶融押出法が好ましい。溶融押出法は溶剤を使用しないので、製造コストや溶剤による地球環境や作業環境への負荷を低減することができる。 Methods for forming the above-mentioned substrate film include any suitable film forming method, such as solution casting, melt extrusion, calendaring, and compression molding. The melt extrusion method is preferred. Since the melt extrusion method does not use solvents, it can reduce manufacturing costs and the burden on the global environment and working environment caused by solvents.
上記溶融押出法としては、例えば、Ｔダイ法、インフレーション法等が挙げられる。成形温度は、好ましくは１５０～３５０℃、より好ましくは２００～３００℃である。 Examples of the melt extrusion method include the T-die method and the inflation method. The molding temperature is preferably 150 to 350°C, more preferably 200 to 300°C.
上記Ｔダイ法でフィルム成形する場合は、公知の単軸押出機や二軸押出機の先端部にＴダイを取り付け、フィルム状に押出されたフィルムを巻取って、ロール状のフィルムを得ることができる。この際、巻取りロールの温度を適宜調整して、押出方向に延伸を加えることで、１軸延伸することも可能である。また、押出方向と垂直な方向にフィルムを延伸することにより、同時２軸延伸、逐次２軸延伸等を行うこともできる。 When forming a film using the T-die method, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, and the film extruded into a film shape is wound up to obtain a rolled film. At this time, it is possible to perform uniaxial stretching by appropriately adjusting the temperature of the winding roll and applying stretching in the extrusion direction. It is also possible to perform simultaneous biaxial stretching, sequential biaxial stretching, etc. by stretching the film in a direction perpendicular to the extrusion direction.
本発明において、ハードコート層は、電離線硬化型樹脂及びレベリング剤の他に、必要に応じて重合開始剤、消泡剤、滑剤、紫外線吸収剤、光安定剤、重合禁止剤、湿潤分散剤、レオロジーコントロール剤、酸化防止剤、防汚剤、帯電防止剤、導電剤、その他の添加剤等を、本発明の効果を阻害しない範囲で配合することができ、これらを適当な溶媒に溶解、分散したハードコート塗料を基材フィルム上に塗工、乾燥、硬化して形成される。 In the present invention, in addition to the ionizing radiation curable resin and leveling agent, the hard coat layer can contain, as necessary, a polymerization initiator, an antifoaming agent, a lubricant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, a wetting and dispersing agent, a rheology control agent, an antioxidant, an antifouling agent, an antistatic agent, a conductive agent, and other additives within a range that does not impair the effects of the present invention. These are dissolved and dispersed in a suitable solvent, and the hard coat paint is applied onto the substrate film, dried, and cured to form the hard coat layer.
本発明において、ハードコート層の電離線（電離放射線）硬化型樹脂は、電子線または紫外線等を照射することによって硬化する透明な樹脂であれば、特に限定されるものではなく、例えば、ウレタンアクリレート系樹脂、ポリエステルアクリレート系樹脂、及びエポキシアクリレート系樹脂等の中から適宜選択することができる。これらの中で電離線硬化型樹脂として好ましいものは、透明フィルム基材との良好な密着性を得るために分子内
に２個以上の（メタ）アクリロイル基を有する紫外線硬化可能な多官能アクリレートからなるものが挙げられる。分子内に２個以上の（メタ）アクリロイル基を有する紫外線硬化可能な多官能アクリレートの具体例としては、ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等のポリオールポリアクリレート、ビスフェノールＡジグリシジルエーテルのジアクリレート、ネオペンチルグリ
コールジグリシジルエーテルのジアクリレート、１，６－ヘキサンジオールジグリシジルエーテルのジ（メタ）アクリレートなどのエポキシ（メタ）アクリレート、多価アルコールと多価カルボン酸及び／またはその無水物とアクリル酸とをエステル化することによって得ることができるポリエステル（メタ）アクリレート、多価アルコール、多価イソシアネート及び水酸基主成分と（メタ）アクリレートを反応させることによって得られるウレタン（メタ）アクリレート、ポリシロキサンポリ（メタ）アクリレート等を挙げることができる。これらの中で、ハードコート層を形成した際のハード性と柔軟性の両方に優れる、ウレタンアクリレートを用いることが望ましい。
In the present invention, the ionizing ray (ionizing radiation) curable resin of the hard coat layer is not particularly limited as long as it is a transparent resin that is cured by irradiation with electron beams, ultraviolet rays, etc., and can be appropriately selected from, for example, urethane acrylate resins, polyester acrylate resins, epoxy acrylate resins, etc. Among these, preferred ionizing ray curable resins include those made of ultraviolet-curable polyfunctional acrylates having two or more (meth)acryloyl groups in the molecule in order to obtain good adhesion to the transparent film substrate. Specific examples of ultraviolet-curable polyfunctional acrylates having two or more (meth)acryloyl groups in the molecule include polyol polyacrylates such as neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; diacryloyl ether of bisphenol A; Examples of suitable epoxy (meth)acrylates include epoxy (meth)acrylates such as diacrylate of neopentyl glycol diglycidyl ether and di(meth)acrylate of 1,6-hexanediol diglycidyl ether, polyester (meth)acrylates obtained by esterifying a polyhydric alcohol with a polycarboxylic acid and/or its anhydride and acrylic acid, urethane (meth)acrylates obtained by reacting a polyhydric alcohol, a polyisocyanate and a hydroxyl group-based component with a (meth)acrylate, polysiloxane poly(meth)acrylate, etc. Among these, it is preferable to use urethane acrylates, which are excellent in both hardness and flexibility when a hard coat layer is formed.
これらハードコート層の電離線硬化型樹脂は、単独でも２種以上を混合し使用しても良い。 These ionizing radiation curable resins for the hard coat layer may be used alone or in combination of two or more types.
本発明において、ハードコート層の厚さは、特に制約されるわけではないが、例えば１．０μｍから１２．０μｍの範囲であることが好適である。塗膜厚さが１．０μｍ未満では必要な表面硬度が得られ難くなる。また、塗膜厚さが１２．０μｍ超の場合はカールが強く筒カール製造工程などで取扱い性が低下するため好ましくない。なお、ハードコート層の厚さは、マイクロメーターで実測することにより測定可能である。 In the present invention, the thickness of the hard coat layer is not particularly limited, but is preferably in the range of, for example, 1.0 μm to 12.0 μm. If the coating thickness is less than 1.0 μm, it is difficult to obtain the required surface hardness. Furthermore, if the coating thickness exceeds 12.0 μm, curling is strong and handling is reduced during the cylinder curl manufacturing process, etc., which is not preferable. The thickness of the hard coat layer can be measured by actual measurement with a micrometer.
本発明のハードコート層にはシリカ等の無機粒子かつ／または有機粒子を含有していても良い。フィルム同士が圧着しにくくなり、巻取適性が向上するため、シリカを含有することが特に好ましい。シリカ等の無機粒子かつ／または有機粒子の含有率は、１０～９０％が好ましく、３０～７０％がより好ましく、４０～６０％がさらに好ましい。 The hard coat layer of the present invention may contain inorganic particles such as silica and/or organic particles. It is particularly preferable to contain silica, as this makes it difficult for films to be pressed together and improves winding suitability. The content of inorganic particles such as silica and/or organic particles is preferably 10 to 90%, more preferably 30 to 70%, and even more preferably 40 to 60%.
本発明のハードコート層は、電離放射線（ＵＶ）照射にて硬化することが好ましく、さらに窒素雰囲気下で硬化することがより好ましい。 The hard coat layer of the present invention is preferably cured by exposure to ionizing radiation (UV), and more preferably cured under a nitrogen atmosphere.
本発明に用いることができる溶媒としては、配合される前記樹脂の溶解性に応じて適宜選択でき、少なくとも固形分（樹脂、重合開始剤、その他添加剤）を均一に溶解あるいは分散できる溶媒であればよい。そのような溶媒としては、例えば、トルエン、キシレン、ｎ－ヘプタンなどの芳香族系溶剤、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂肪族系溶剤、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピ
ル、酢酸ブチル、乳酸メチル等のエステル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、メタノール、エタノール、イソプロピルアルコール、ｎ－プロピルアルコール系等のアルコール系溶剤等の公知の有機溶剤を単独或いは適宜数種類組み合わせて使用することもできる。
The solvent that can be used in the present invention can be appropriately selected depending on the solubility of the resin to be blended, and may be any solvent that can uniformly dissolve or disperse at least the solid contents (resin, polymerization initiator, and other additives). Examples of such solvents include known organic solvents such as aromatic solvents such as toluene, xylene, and n-heptane, aliphatic solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and methyl lactate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and alcohol solvents such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol. These solvents may be used alone or in combination.
本発明のハードコート層の塗工方法については、特に限定はないが、グラビア塗工、マイクログラビア塗工、ファウンテンバー塗工、スライドダイ塗工、スロットダイ塗工、スクリーン印刷法、スプレーコート法等の公知の塗工方式で塗設した後、通常５０～１２０℃程度の温度で乾燥し、溶媒が除去される。該乾燥温度は、特に１００℃以上１４０℃以下が望ましい。１００℃未満では溶剤が揮発した後の紫外線硬化性樹脂の流動性が得られず、フィルム基材との密着性が十分に得られない。また、１４０℃よりも高いと、フィルム基材のガラス転移温度より高くなり、基材自身の平坦性が損なわれる恐れがあるため好ましくない。ハードコート層はフィルム基材の片面もしくは両面に、単層もしくは多層の塗工を行うことで得られる。 The coating method for the hard coat layer of the present invention is not particularly limited, but after coating by a known coating method such as gravure coating, microgravure coating, fountain bar coating, slide die coating, slot die coating, screen printing, or spray coating, the coating is usually dried at a temperature of about 50 to 120°C to remove the solvent. The drying temperature is preferably 100°C or higher and 140°C or lower. If the drying temperature is lower than 100°C, the flowability of the ultraviolet curable resin after the solvent has evaporated is not obtained, and sufficient adhesion to the film substrate is not obtained. If the drying temperature is higher than 140°C, the glass transition temperature of the film substrate is higher, and the flatness of the substrate itself may be impaired, which is not preferable. The hard coat layer is obtained by coating one or both sides of the film substrate in a single layer or multiple layers.
基材フィルム上に塗工し、溶媒を除去されたハードコート塗料を硬化させる方法としては、電子線又は紫外線を照射させる方法を用いることができる。その照射条件などは、使用する電子線硬化型樹脂、その他添加する各種薬品にあわせて適宜調整すればよいが、例えば、紫外線を用いた場合には波長２００～４００ｎｍの範囲が好ましく、照度８０～１２０ｍＷ／ｃｍ2、照射量７０～５００ｍＪ／ｃｍ2であることが望ましい。紫外線の照射
装置としては、例えば、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、エキシマランプなどのランプ光源、アルゴンイオンレーザーやヘリウムネオンレーザーなどのパルス、連続のレーザー光源などを備える照射装置を用いることが可能である。なお、硬化反応時に窒素ガス雰囲気下など、酸素濃度を低下させ実施することができる。
As a method for curing the hard coat coating material applied on the substrate film and from which the solvent has been removed, a method of irradiating with electron beams or ultraviolet rays can be used. The irradiation conditions can be appropriately adjusted according to the electron beam curable resin used and various other chemicals added. For example, when ultraviolet rays are used, the wavelength is preferably in the range of 200 to 400 nm, the illuminance is preferably 80 to 120 mW/cm2, and the dose is preferably 70 to 500 mJ/cm2. As an ultraviolet ray irradiation device, for example, an irradiation device equipped with a lamp light source such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp, or a pulsed or continuous laser light source such as an argon ion laser or a helium neon laser can be used. The curing reaction can be carried out in a nitrogen gas atmosphere or the like to reduce the oxygen concentration.
ハードコートフィルムに形成されたハードコート層の塗工厚みは、マイクロメーターを用いて測定するなどの既知の方法によって測定することができる。 The coating thickness of the hard coat layer formed on the hard coat film can be measured by known methods, such as measuring with a micrometer.
本発明において、ハードコード層に主成分とされるレベリング剤は、フッ素系、アクリル系、シロキサン系のレベリング剤を挙げることができる。 In the present invention, the leveling agent that is the main component of the hard coat layer can be a fluorine-based, acrylic-based, or siloxane-based leveling agent.
本発明に用いるレベリング剤としては、フッ素系が好ましく、反応性を有しているものがより好ましい。さらに、塗工後の水接触角が６０～９０度になるのが好ましく、７０～８０度になることがより好ましい。 The leveling agent used in the present invention is preferably a fluorine-based agent, and more preferably one that has reactivity. Furthermore, the water contact angle after coating is preferably 60 to 90 degrees, and more preferably 70 to 80 degrees.
以下、具体的実施例により本発明を説明するが、本発明は以下の実施例の態様に限定されるものではない。 The present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples.
＜実施例１＞
ポリエーテルスルホン（ＰＥＳ）からなる基材フィルム（フィルム厚25μｍ）の両面に、下記組成からなるハードコート層形成用樹脂組成物を、バーコーターを用いて塗工し、８０℃の乾燥炉で６０秒間乾燥させ膜厚が３μｍのハードコート層を形成した。これを、塗布面より６０ｍｍの高さにセットされたＵＶ照射装置を用いＵＶ照射量２００ｍＪ／ｃｍ２にて硬化させハードコートフィルムを作製した。
Example 1
A resin composition for forming a hard coat layer having the following composition was applied to both sides of a substrate film (film thickness 25 μm) made of polyethersulfone (PES) using a bar coater, and dried for 60 seconds in a drying oven at 80° C. to form a hard coat layer having a film thickness of 3 μm. This was cured with a UV irradiation device set at a height of 60 mm from the coating surface at a UV irradiation dose of 200 mJ/ cm2 to produce a hard coat film.
（ハードコート層形成用樹脂組成物）
電離線硬化型樹脂（ウレタンアクリレートおよびアクリルエステルを合計で１９％、非晶質シリカを２８％、光重合開始剤を２％、添加剤を４％含有し、溶剤としてプロピレングリコールモノメチルエーテルを４７％含有する樹脂）を２９．５％と、レベリング剤(フタージェント６８１を０．５％で配合し、メチルエチルケトン（ＭＥＫ）にて最終濃度を３０％に調製した。
(Resin composition for forming hard coat layer)
A mixture of 29.5% ionizing radiation curable resin (a resin containing 19% urethane acrylate and acrylic ester in total, 28% amorphous silica, 2% photopolymerization initiator, 4% additives, and 47% propylene glycol monomethyl ether as a solvent) and 0.5% leveling agent (Ftergent 681) was mixed, and the final concentration was adjusted to 30% with methyl ethyl ketone (MEK).
＜実施例２＞
実施例１のポリエーテルスルホンからなる基材フィルムを、ポリフェニルスルホンからなる基材フィルム（フィルム厚５０μｍ）としたこと以外は実施例１と同様にしてハードコートフィルムを作成した。
Example 2
A hard coat film was prepared in the same manner as in Example 1, except that the substrate film made of polyethersulfone in Example 1 was changed to a substrate film made of polyphenylsulfone (film thickness: 50 μm).
＜比較例１＞
実施例１のポリエーテルスルホンからなる基材フィルムを、ポリエチレンテレフタレート（ＰＥＴ）からなる基材フィルム（フィルム厚５０μｍ）としたこと以外は実施例１と同様にしてハードコートフィルムを作成した。
<Comparative Example 1>
A hard coat film was prepared in the same manner as in Example 1, except that the substrate film made of polyethersulfone in Example 1 was replaced with a substrate film made of polyethylene terephthalate (PET) (film thickness: 50 μm).
＜比較例２＞
実施例１のポリエーテルスルホンからなる基材フィルム（フィルム厚２５μｍ）を評価した。
<Comparative Example 2>
The substrate film (film thickness: 25 μm) made of polyethersulfone in Example 1 was evaluated.
＜比較例３＞
実施例２のポリフェニルスルホンからなる基材フィルム(５０μｍ)を評価した。
<Comparative Example 3>
The substrate film (50 μm) made of polyphenylsulfone in Example 2 was evaluated.
＜評価＞
以上のようにして作製された実施例及び比較例のハードコートフィルムおよび基材フィルムを次の項目について評価し、その結果を纏めて表１に示した。
<Evaluation>
The hard coat films and base films of the Examples and Comparative Examples prepared as described above were evaluated for the following items. The results are summarized in Table 1.
＜塗膜の厚み＞
易接着層及びハードコート層の塗膜の形成厚みは、Ｔｈｉｎ－Ｆｉｌｍ Ａｎａｌｙｚｅｒ Ｆ２０（商品名）（ＦＩＬＭＥＴＲＩＣＳ社製）を用いて測定した。
<Coating film thickness>
The thicknesses of the coating films of the easy-adhesion layer and the hard coat layer were measured using a Thin-Film Analyzer F20 (trade name) (manufactured by FILMETRICS).
＜密着性＞
（初期密着性、湿熱密着性及び耐光密着性及びインク密着性） 初期密着性は、ＪＩＳ－Ｋ５６００－５－６に準じて、通常条件下、すなわち恒温恒湿条件下（２３℃、５０％ＲＨ）で、碁盤目剥離試験治具を用い１ｍｍ2のクロスカットを１００個作製し、積水化学工業株式会社製の粘着テープNo.２５２をその上に貼り付け、ヘラを用いて均一に押し付け後、１８０度方向に剥離し、ハードコート層の残存個数を４段階評価した。評価基準は下記の通りであり、◎と○評価品（つまりハードコート層の残存率９０％以上）を密着性は合格と判定した（◎：１００個、○：９９～９０個、△：８９～５０個、×：４９～０個）。
<Adhesion>
(Initial Adhesion, Humidity and Heat Adhesion, Light Resistance Adhesion, and Ink Adhesion) Initial adhesion was evaluated in accordance with JIS-K5600-5-6 under normal conditions, i.e., constant temperature and humidity conditions (23°C, 50% RH), by preparing 100 cross-cuts of 1 mm2 using a checkerboard peel test tool, attaching adhesive tape No. 252 manufactured by Sekisui Chemical Co., Ltd. onto the cuts, pressing them evenly with a spatula, and peeling them off in a 180° direction, and evaluating the number of remaining hard coat layers in four stages. The evaluation criteria are as follows, and products rated as ◎ or ○ (i.e., the remaining rate of the hard coat layer is 90% or more) were judged to have passed adhesion (◎: 100 pieces, ○: 99-90 pieces, △: 89-50 pieces, ×: 49-0 pieces).
また、湿熱密着性（湿熱条件下での経時密着性）は、各ハードコートフィルムを湿熱条件下（８０℃、９０％ＲＨ）に３０日間保存した後、上記と同様にして碁盤目剥離試験を行い、ハードコート層の密着性を４段階評価した。評価基準は上記の初期密着性の場合と同様である。 In addition, for the moist heat adhesion (adhesion over time under moist heat conditions), each hard coat film was stored under moist heat conditions (80°C, 90% RH) for 30 days, and then a cross-cut peel test was carried out in the same manner as above, and the adhesion of the hard coat layer was evaluated on a four-point scale. The evaluation criteria were the same as for the initial adhesion described above.
また、耐光密着性については、各ハードコートフィルムについて、スガ試験（株）紫外線オートフェードメーター「Ｕ４８ＡＵ」（紫外線カーボンアークランプ）を用いて、試験条件を照射照度５００Ｗ／ｍ2、温度４３度、湿度５０％ＲＨとし、照射時間が１００時間の時点で、ＪＩＳ－Ｋ５６００－５－６に準じて、ハードコート層の密着性を上記と同様の碁盤目試験法で実施した。評価基準は上記の初期密着性の場合と同様である。 In addition, for light resistance adhesion, the adhesion of the hard coat layer was measured for each hard coat film using the same cross-cut test method as above, in accordance with JIS-K5600-5-6, under test conditions of irradiation illuminance 500 W/m2, temperature 43 degrees, humidity 50% RH, and irradiation time 100 hours. The evaluation criteria were the same as for initial adhesion above.
また、インク密着性については、各ハードコートフィルムのハードコート層Ａ上に、銅ナノ粒子ペースト（商品名：ＣＰ－１００、ハリマ化成株式会社製）を用いて、小型手動印刷機（商品名：ＭＴ－Ｍｉｎｉ、マイクロ・テック株式会社製）で１辺５ｃｍの正方形の印刷部を形成した。１５０度雰囲気下で３０分間放置し乾燥させた後、評価を行った。インクの密着性を前述と同様の碁盤目試験法で実施した。評価基準は上記の初期密着性の場合と同様である。 Regarding ink adhesion, a square print with sides of 5 cm was formed on the hard coat layer A of each hard coat film using copper nanoparticle paste (product name: CP-100, manufactured by Harima Chemicals Co., Ltd.) with a small manual printer (product name: MT-Mini, manufactured by Micro-Tec Co., Ltd.). The print was left in an atmosphere of 150 degrees for 30 minutes and dried, after which it was evaluated. The ink adhesion was evaluated using the same cross-cut test method as described above. The evaluation criteria were the same as those for the initial adhesion described above.
＜ヘイズ＞
実施例、比較例で作製した各ハードコートフィルムのヘイズは、ＪＩＳ－Ｋ７１３６に基づき、村上色彩技術研究所製ヘイズメーター「ＨＭ１５０」を用いて測定した。
<HAZE>
The haze of each of the hard coat films produced in the Examples and Comparative Examples was measured using a haze meter "HM150" manufactured by Murakami Color Research Laboratory in accordance with JIS-K7136.
＜耐熱クラック＞
実施例、比較例で作製した各ハードコートフィルムを、１００℃の乾燥機中でサンプル掛けを用い５分間吊るし保存した後、ハードコートフィルムを取り出し、クラックの発生有無を目視評価した。クラックの発生程度を次の基準で評価した。
○：クラックの発生なし。
△：試験片端部にクラックが若干みられる。
×：試験片全面にクラックがみられる。
<Heat-resistant crack>
Each hard coat film produced in the Examples and Comparative Examples was hung in a dryer at 100° C. for 5 minutes using a sample hanger, and then the hard coat film was taken out and visually evaluated for the presence or absence of cracks. The degree of cracks was evaluated according to the following criteria.
◯: No cracks were observed.
△: Some cracks were observed at the ends of the test piece.
×: Cracks were observed over the entire surface of the test piece.
＜鉛筆硬度＞
実施例、比較例で作製した各ハードコートフィルムについて、ＪＩＳ－Ｋ－５６００－５－４に準じた試験法により鉛筆硬度を測定した。表面に傷の発生なき硬度を標記した。判定基準については、硬度２B以上は合格とした。
<Pencil hardness>
The pencil hardness of each hard coat film produced in the Examples and Comparative Examples was measured by a test method conforming to JIS-K-5600-5-4. The hardness at which no scratches were generated on the surface was recorded. As for the evaluation criteria, a hardness of 2B or more was considered to be acceptable.
＜耐擦傷性＞
実施例、比較例で作製した各ハードコートフィルムについて、ＪＩＳ－Ｋ－５６００－５－１０に準じた試験法にて、ハードコート層面を、スチールウール＃００００を用い、荷重１ｋｇを掛け１０往復摩擦し、傷のつき具合を次の基準で評価した。○評価品を耐擦傷性は良好とした。△評価品も製品として使用可能である。
○：傷の発生なし
△：傷が少し発生する
×：傷が無数に発生する
<Scratch resistance>
For each of the hard coat films produced in the Examples and Comparative Examples, the hard coat layer surface was rubbed 10 times with steel wool #0000 under a load of 1 kg in a test method conforming to JIS-K-5600-5-10, and the degree of scratching was evaluated according to the following criteria: ◯: The scratch resistance of the evaluated product was good. △: The evaluated product was also usable as a product.
○: No scratches
△: A few scratches
×: Numerous scratches
＜全光線透過率＞
各ハードコートフィルムについて、村上色彩技術研究所（株）製ヘーズメータHM-150Nを用いて測定した。測定は、JIS-K7361の規格に基づき実施した。評価基準については、光線透過率９０％以上を合格とした。
<Total light transmittance>
Each hard coat film was measured using a haze meter HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd. The measurement was carried out based on the standard JIS-K7361. The evaluation criteria were a light transmittance of 90% or more was considered to be acceptable.
＜カール特性＞
実施例、比較例で作製した各ハードコートフィルムについて、図２のように塗布方向（図示のＭＤ方向）を基軸とした１辺１０ｃｍの正方形菱形状の試験片を切り出し、水平面にハードコート層面を上にして設置し、２３℃、５０％ＲＨ環境下に３０分間保存した後、反り立っている４頂点（Ａ，Ｂ，Ｃ，Ｄ）の水平面からの高さを測定し、その平均値をカール高さとした。評価基準については、カール高さ４０ｍｍ以下であれば実用上用いることができ、数値が低いほど好ましい。
<Curling characteristics>
For each hard-coated film produced in the examples and comparative examples, a square diamond-shaped test piece with a side length of 10 cm was cut out with the coating direction (MD direction in the figure) as shown in Figure 2, placed on a horizontal surface with the hard-coated layer surface facing up, and stored for 30 minutes under a 23°C, 50% RH environment, and then the heights of the four warped vertices (A, B, C, D) from the horizontal surface were measured, and the average value was taken as the curl height. Regarding the evaluation criteria, if the curl height is 40 mm or less, it can be used practically, and the lower the value, the better.
＜ｂ*値＞
実施例、比較例で作製した各ハードコートフィルムについて、村上色彩技術研究所製ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＴＲ ＤＯＴ－３Ｃにて測定した。評価基準については、ｂ*値が１．５以下を合格と判定した。
<b* value>
Each hard coat film produced in the Examples and Comparative Examples was measured using a SPECTROPHOTOMETER DOT-3C manufactured by Murakami Color Research Laboratory Co., Ltd. As for the evaluation criteria, a b* value of 1.5 or less was judged to be acceptable.
＜耐薬品性＞
各ハードコートフィルムのハードコート層A上に、フマル酸ジメチル（DMF）、ジメチルカーボネート（DMC）、ジメチルスルホキシド（DMSO）を８０度に加温した状態で滴下し、３分間放置後のフィルム表面を観察した。評価基準は以下の通りである。
○：フィルム損傷なし
×：フィルム損傷あり
<Chemical resistance>
Dimethyl fumarate (DMF), dimethyl carbonate (DMC), and dimethyl sulfoxide (DMSO) were dropped onto the hard coat layer A of each hard coat film while heated to 80°C, and the film surface was observed after leaving it for 3 minutes. The evaluation criteria are as follows.
○: No film damage
×: Film damaged
＜熱収縮率＞
各ハードコートフィルムを１５０度雰囲気下で３０分間放置後のフィルムの収縮率を算出した。（熱処理後のサンプル長）/（熱処理前のサンプル長）の算出結果を％で表記した。また、熱収救率は、フィルム流れ方向（Ｍａｃｈｉｎｅ Ｄｉｒｅｃｔｉｏｎ；ＭＤ）及びフィルム幅方向（Ｔｒａｎｓｖｅｒｓｅ Ｄｉｒｅｃｔｉｏｎ；ＴＤ）の二方向について評価した。
<Heat shrinkage rate>
The shrinkage rate of each hard coat film was calculated after leaving it in an atmosphere of 150 degrees for 30 minutes. The calculation result of (sample length after heat treatment)/(sample length before heat treatment) was expressed in %. The heat shrinkage rate was evaluated in two directions, the machine direction (MD) and the transverse direction (TD).
＜インク密着性＞
各ハードコートフィルムのハードコート層Ａ上に、銅ナノ粒子ペースト（商品名：ＣＰ－１００、ハリマ化成株式会社製）を用いて、小型手動印刷機（商品名：ＭＴ－Ｍｉｎｉ、マイクロ・テック株式会社製）で１辺５ｃｍの正方形の印刷部を形成した。１５０度雰囲気下で３０分間放置し乾燥させた後、評価を行った。インクの密着性を前述と同様の碁盤目試験法で実施した。評価基準は上記の初期密着性の場合と同様である。
<Ink adhesion>
On the hard coat layer A of each hard coat film, a copper nanoparticle paste (product name: CP-100, manufactured by Harima Chemical Co., Ltd.) was used to form a square print portion with a side length of 5 cm using a small manual printer (product name: MT-Mini, manufactured by Micro-Tec Co., Ltd.). After leaving it for 30 minutes in a 150°C atmosphere and drying, evaluation was performed. The adhesion of the ink was performed using the same cross-cut test method as described above. The evaluation criteria are the same as those for the initial adhesion described above.
＜表面粗さ＞
（株）日立ハイテクサイエンス製のＶｅｒｔＳｃａｎのR3300G Ｌｉｔｅにて測定し、ＪＩＳ－Ｂ０６０１の規格に基づき実施した。
<Surface roughness>
The measurement was carried out using a VertScan R3300G Lite manufactured by Hitachi High-Tech Science Corporation, in accordance with the JIS-B0601 standard.
＜巻取適性＞
各ハードコートフィルムを１辺１０ｃｍの正方形に裁断したものを重ね合わせ、４０度の雰囲気下にて１０ｋｇの重りを載せて２４時間放置後のフィルムの圧着状態を観察した。評価基準は以下の通りである。
○：フィルム圧着なし
×：フィルム圧着あり
<Winding suitability>
Each hard coat film was cut into a square with a side length of 10 cm, which was then stacked, placed under a 10 kg weight in an atmosphere of 40° C., and allowed to stand for 24 hours, after which the state of compression of the film was observed. The evaluation criteria were as follows:
○: No film bonding
×: Film is crimped
＜透湿度（水蒸気バリア性）＞
ＪＩＳ－０２０８の規格に準じた方法にて測定した。
<Moisture permeability (water vapor barrier properties)>
The measurement was performed according to the method of JIS-0208.
＜滑り性＞
協和界面科学（株）製の自動摩擦摩耗解析装置 ＴＳｆ－５０２を用いた。各ハードコートフィルムを５ｃｍ×１０ｃｍに裁断したものの上に１ｃｍ×１ｃｍ片を設置し、２００ｇの荷重をかけて１００ｍｍ／ｍｉｎの速度で5ｃｍ移動させたときの静摩擦係数および動摩擦係数を測定した。
<Slipperiness>
An automatic friction and wear analyzer TSf-502 manufactured by Kyowa Interface Science Co., Ltd. was used. Each hard coat film was cut to 5 cm x 10 cm, on which a 1 cm x 1 cm piece was placed, and a load of 200 g was applied and moved 5 cm at a speed of 100 mm/min to measure the static and dynamic friction coefficients.
＜接触角＞
ＪＩＳ－３２５７の規格に準じた方法にて測定した。
<Contact angle>
The measurement was performed according to the method of JIS-3257.
本発明によれば、表１に示される実施例１，２で明らかにされるように、高い耐熱性、寸法安定性、耐薬品性、を有しているとともに、耐擦傷性、鉛筆硬度、インク密着性、ハードコート層密着性、熱安定性、透過率、表面平滑性、水蒸気バリア性、巻取適正が向上したハードコートフィルムを得ることができる。特に基材フィルムにＰＥＴを用いた比較例１に比べ、本発明の実施例は表面粗さ、熱収縮率について優れている。 According to the present invention, as shown in Examples 1 and 2 in Table 1, it is possible to obtain a hard coat film that has high heat resistance, dimensional stability, and chemical resistance, as well as improved scratch resistance, pencil hardness, ink adhesion, hard coat layer adhesion, thermal stability, transmittance, surface smoothness, water vapor barrier properties, and winding suitability. In particular, compared to Comparative Example 1, which uses PET as the base film, the Examples of the present invention are superior in terms of surface roughness and thermal shrinkage rate.
本発明のハードコートフィルムは、各種製品やその部材又は部品の構成材として使用することができる。上記製品としては、例えば、液晶ディスプレイ、有機ＥＬディスプレイなどの表示装置；タッチパネルなどの入力装置：太陽電池；各種家電製品；各種電気・電子製品；携帯電子端末（例えば、ゲーム機器、パソコン、タブレット、スマートフォン、携帯電話等）の各種電気・電子製品；各種光学機器等が挙げられる。 The hard coat film of the present invention can be used as a component material for various products or their parts or components. Examples of such products include display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; various home appliances; various electric and electronic products; various electric and electronic products such as portable electronic terminals (e.g., game devices, personal computers, tablets, smartphones, mobile phones, etc.); and various optical devices.
本発明のハードコートフィルムは、例えば、各種製品における表面保護フィルム、各種製品の部材又は部品における表面保護フィルム等として使用することもできる。また、本発明のハードコートフィルムが各種製品やその部材又は部品の構成材として使用される態様としては、例えば、タッチパネルにおけるハードコートフィルムと透明導電フィルムの積層体等に使用される態様等が挙げられる。本発明のハードコートフィルムは金属インキ密着性が優れるためフレキシブル配線板用ベースフィルム等に用いることが特に好ましい。 The hard coat film of the present invention can be used, for example, as a surface protection film for various products, or as a surface protection film for members or parts of various products. Examples of the hard coat film of the present invention used as a component of various products or their members or parts include a laminate of a hard coat film and a transparent conductive film in a touch panel. The hard coat film of the present invention has excellent adhesion to metal ink, so it is particularly preferable to use it as a base film for flexible wiring boards, etc.
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