JP2008094062A - Metal oxide laminated substrate - Google Patents
Metal oxide laminated substrate Download PDFInfo
- Publication number
- JP2008094062A JP2008094062A JP2006281871A JP2006281871A JP2008094062A JP 2008094062 A JP2008094062 A JP 2008094062A JP 2006281871 A JP2006281871 A JP 2006281871A JP 2006281871 A JP2006281871 A JP 2006281871A JP 2008094062 A JP2008094062 A JP 2008094062A
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- oxide film
- film
- laminated substrate
- transparent
- 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.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 89
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 69
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 29
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 29
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 25
- 239000004626 polylactic acid Substances 0.000 claims abstract description 25
- 239000011342 resin composition Substances 0.000 claims abstract description 14
- 239000010408 film Substances 0.000 claims description 133
- 230000004888 barrier function Effects 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- 239000011135 tin Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003437 indium oxide Inorganic materials 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 31
- 238000000576 coating method Methods 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 6
- -1 tile Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 7
- 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 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000007733 ion plating Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940022769 d- lactic acid Drugs 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 208000023514 Barrett esophagus Diseases 0.000 description 2
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910020286 SiOxNy Inorganic materials 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Chemical class 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RWCHFQMCWQLPAS-UHFFFAOYSA-N (1-tert-butylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C(C)(C)C)CCCCC1 RWCHFQMCWQLPAS-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- XKNLMAXAQYNOQZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(CO)(CO)CO XKNLMAXAQYNOQZ-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- CKSAKVMRQYOFBC-UHFFFAOYSA-N 2-cyanopropan-2-yliminourea Chemical compound N#CC(C)(C)N=NC(N)=O CKSAKVMRQYOFBC-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910017107 AlOx Inorganic materials 0.000 description 1
- 229910017105 AlOxNy Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
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- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
本発明は、金属酸化物膜を形成してなる金属酸化物積層基板に関するものであり、詳しくは金属酸化物がガスバリア膜であり、もしくは透明導電膜が液晶ディスプレイ・プラズマディスプレイ・無機ＥＬディスプレイ・有機ＥＬディスプレイ・電子ペーパー等の透明電極、太陽電池の光電変換素子の窓電極、透明タッチパネル等の入力装置の電極、電磁シールドの電磁遮蔽膜、透明電波吸収体、紫外線吸収体等に好適に用いられ、光学特性、導電性、透明導電膜との密着性およびシート抵抗値の安定性に優れた金属酸化物積層基板に関する。 The present invention relates to a metal oxide laminated substrate formed with a metal oxide film. Specifically, the metal oxide is a gas barrier film, or the transparent conductive film is a liquid crystal display, plasma display, inorganic EL display, or organic. It is suitably used for transparent electrodes such as EL displays and electronic paper, window electrodes for photoelectric conversion elements of solar cells, electrodes for input devices such as transparent touch panels, electromagnetic shielding films for electromagnetic shields, transparent radio wave absorbers, ultraviolet absorbers, etc. The present invention relates to a metal oxide multilayer substrate excellent in optical properties, electrical conductivity, adhesion to a transparent conductive film, and stability of sheet resistance.
透明樹脂基材上にアルミニウム、ケイ素、チタン、インジウム、亜鉛などの金属酸化物を真空蒸着法やスパッタリング法により積層することが広く検討されている。
酸化ケイ素膜や酸化窒化ケイ素膜は水蒸気や酸素の透過を阻止する高いガスバリア性を有するとともに、さらに高い透明性を有するためディスプレイ用途として期待されている。
酸化チタン膜は光触媒作用があり、基板、ガラス、タイルおよびレンガなどにコーティングして脱臭、消臭、防汚、除菌など身近な環境汚染物質の浄化に利用され注目されている。
It has been widely studied to laminate a metal oxide such as aluminum, silicon, titanium, indium, and zinc on a transparent resin substrate by a vacuum deposition method or a sputtering method.
A silicon oxide film or a silicon oxynitride film is expected to be used for a display because it has a high gas barrier property that prevents permeation of water vapor and oxygen and also has a higher transparency.
The titanium oxide film has a photocatalytic action, and is used for purification of familiar environmental pollutants such as deodorizing, deodorizing, antifouling, and sterilization by coating on a substrate, glass, tile, brick, and the like.
透明導電膜は可視光透過性と電気伝導性を兼ね備えた膜として広く知られており、その代表的なものとして、スズ添加酸化インジウム膜（以下「ITO膜」という）が挙げられる。ITO膜を透明基材上に積層した積層体は、電極、通電による発熱体、電磁波の遮蔽材や透光体として広く用いられている。透光体の用途としては、自動車、航空機や、建物の窓、スクリーン、モニター等の電磁波シールド板、液晶表示基板等がある。透光体の形状としては、使用する用途に応じた平面形状や曲面形状等がある。透明基材上にITO膜を形成する手段としては、スパッタリング法、真空蒸着法、イオンプレーティング法等が知られている。 The transparent conductive film is widely known as a film having both visible light transmittance and electrical conductivity, and a typical example thereof is a tin-added indium oxide film (hereinafter referred to as “ITO film”). A laminate in which an ITO film is laminated on a transparent substrate is widely used as an electrode, a heating element by energization, an electromagnetic wave shielding material, and a translucent body. Applications of the light transmitting body include automobiles, aircraft, building windows, screens, electromagnetic wave shielding plates such as monitors, liquid crystal display substrates, and the like. Examples of the shape of the translucent body include a planar shape and a curved surface shape according to the intended use. As means for forming an ITO film on a transparent substrate, a sputtering method, a vacuum deposition method, an ion plating method, and the like are known.
このような透光体の基材としては、これまでガラスが主に用いられてきたが、需要や用途が増えるにつれ、加工性や生産性の向上が求められるようになってきた。そのため近年、ガラスに比べ軽量で加工性・生産性に優れたプラスチックが注目されポリエチレンテレフタレートやポリカーボネート、環状オレフィン樹脂などが用いられるようになってきた。液晶ディスプレイに用いられる電極基板では、全光線透過率が同じであっても複屈折がより小さい高分子材料成形体が必要とされ、さらに近年、液晶ディスプレイが大型化し、それに必要な高分子光学材料成形品が大型化するにつれて、外力の偏りによって生じる複屈折の分布を小さくするために、外力による複屈折の変化、即ち光弾性係数の小さい材料が求められている。 As a base material for such a light transmitting body, glass has been mainly used so far. However, as demand and applications increase, improvement in workability and productivity has been demanded. Therefore, in recent years, plastics that are lighter than glass and superior in workability and productivity have attracted attention, and polyethylene terephthalate, polycarbonate, cyclic olefin resins, and the like have been used. For electrode substrates used in liquid crystal displays, a polymer material molded body having a smaller birefringence is required even if the total light transmittance is the same, and in recent years, the liquid crystal display has become larger in size and the polymer optical material necessary for it. In order to reduce the birefringence distribution caused by the bias of the external force as the size of the molded product increases, a material having a small change in birefringence due to the external force, that is, a material having a small photoelastic coefficient is required.
中でもアクリル系樹脂は、その透明性の高さから幅広く用いられており、基材に使用する場合、基材とITO膜との密着力不足を補うために、アクリル系樹脂基材とITO膜との間に３次元架橋したアクリル系樹脂系の中間層を介することが知られている（例えば、特許文献１、特許文献２参照）。また、ＩＴＯ膜とアクリル基材を直接密着させる試みとして、アクリル基材においてメチルメタクリレートを主成分としてエチレングリコールジアクリレートなどを共重合している（例えば、特許文献３参照）。 Among these, acrylic resins are widely used due to their high transparency. When used as a base material, acrylic resin base materials and ITO films are used to compensate for the lack of adhesion between the base material and the ITO film. It is known that a three-dimensionally cross-linked acrylic resin-based intermediate layer is interposed between them (for example, see Patent Document 1 and Patent Document 2). Further, as an attempt to directly adhere the ITO film and the acrylic base material, ethylene glycol diacrylate or the like is copolymerized with methyl methacrylate as a main component in the acrylic base material (see, for example, Patent Document 3).
しかし、アクリル系樹脂基材にＩＴＯ膜を形成してなる透明導電膜基板は実用化には至っておらず、基材とＩＴＯ膜との密着性不良、基材の変形によるＩＴＯ膜の破壊のため、抵抗値の安定性が保たれないものと考えられる。
本発明は、透明樹脂基板、その中でも特に外力による複屈折の変化、即ち光弾性係数の小さいアクリル系樹脂およびポリ乳酸系樹脂からなる透明基板上にハードコート層を設け、その上に金属酸化物膜を形成することにより、光学特性、金属酸化物膜と透明基板の密着性に優れた金属酸化物積層基板を提供することにある。 The present invention provides a hard coat layer on a transparent resin substrate, in particular, a change in birefringence due to an external force, that is, a transparent substrate made of an acrylic resin and a polylactic acid resin having a small photoelastic coefficient, and a metal oxide on the hard coat layer. An object of the present invention is to provide a metal oxide laminated substrate having excellent optical properties and adhesion between the metal oxide film and the transparent substrate by forming the film.
これらの問題を解決するために鋭意研究を重ねた結果、基材に極性基を有しているアクリル系樹脂およびポリ乳酸系樹脂の樹脂組成物を用い、その透明樹脂基板にハードコート処理を施したこの透明基板上に金属酸化物膜を形成することにより、光学特性、金属酸化物膜と透明基板の密着性に優れた金属酸化物積層基板が出来ることを見出した。 As a result of intensive research to solve these problems, a hard coat treatment was applied to the transparent resin substrate using a resin composition of an acrylic resin and a polylactic acid resin having a polar group as a base material. It has been found that by forming a metal oxide film on the transparent substrate, a metal oxide laminated substrate having excellent optical properties and adhesion between the metal oxide film and the transparent substrate can be obtained.
すなわち、本発明は以下の通りである。
（１）アクリル系樹脂（ａ）５０〜９９．９質量％、およびポリ乳酸系樹脂（ｂ）５０〜０．１質量％からなる樹脂組成物の透明基板に片面又は両面に、１種以上のハードコート層が被覆され、該ハードコート層上に、金属酸化物膜が形成されてなる金属酸化物膜積層基板、
（２）金属酸化物膜が、ガリウム、アルミニウム、ホウ素、ケイ素、スズ、亜鉛、インジウム、ゲルマニウム、チタン、アンチモン、イリジウム、レニウム、セリウム、ジルコニウム、スカンジウム、及びイットリウムから選ばれる元素を少なくとも１種以上を含む事を特徴とする（１）に記載の金属酸化物膜積層基板、
（３）金属酸化物膜が、酸化ケイ素、窒化ケイ素、酸化窒化ケイ素又はこれらの２種以上からなる無機バリア層の薄膜であることを特徴とする（１）または（２）に記載の金属酸化物膜積層基板、
（４）金属酸化物膜が、スズ添加酸化インジウム膜、亜鉛添加酸化インジウム膜からなる透明導電膜であることを特徴とする（１）または（２）に記載の金属酸化物膜積層基板、
（５）透明基板が、フィルム、もしくはシートであることを特徴とする（１）〜（４）に記載の金属酸化物膜積層基板であることを特徴とする（１）〜（４）に記載の金属酸化物膜積層基板、
（６）全光線透過率が７０％以上、シート抵抗値が１００Ω／□以下であることを特徴とする請求項４または５に記載の金属酸化物膜積層基板のディスプレイ用透明電極への使用、
である。
That is, the present invention is as follows.
(1) A transparent substrate of a resin composition comprising acrylic resin (a) 50 to 99.9% by mass and polylactic acid resin (b) 50 to 0.1% by mass on one side or both sides with one or more types A metal oxide film laminated substrate in which a hard coat layer is coated and a metal oxide film is formed on the hard coat layer;
(2) The metal oxide film has at least one element selected from gallium, aluminum, boron, silicon, tin, zinc, indium, germanium, titanium, antimony, iridium, rhenium, cerium, zirconium, scandium, and yttrium. The metal oxide film laminated substrate according to (1), characterized by comprising:
(3) The metal oxide according to (1) or (2), wherein the metal oxide film is a thin film of an inorganic barrier layer composed of silicon oxide, silicon nitride, silicon oxynitride, or two or more of these. Multilayer substrate,
(4) The metal oxide film laminated substrate according to (1) or (2), wherein the metal oxide film is a transparent conductive film comprising a tin-added indium oxide film and a zinc-added indium oxide film,
(5) The transparent substrate is a metal oxide film laminated substrate according to (1) to (4), wherein the transparent substrate is a film or a sheet. (1) to (4) Metal oxide film laminated substrate,
(6) Use of the metal oxide film laminated substrate for a transparent electrode for display according to claim 4 or 5, wherein the total light transmittance is 70% or more and the sheet resistance value is 100Ω / □ or less.
It is.
アクリル系樹脂およびポリ乳酸系樹脂からなる樹脂組成物を用いる事でハードコート層の形成を容易にし、さらにハードコート層を被覆する事で表面硬度が高まり金属酸化物膜の形成を容易にし、光学特性、金属酸化物膜と透明基板の密着性に優れた金属酸化物膜積層基板を得る事ができる。さらに、得られた金属酸化物積層基板はディスプレイ用透明電極に好適である。 By using a resin composition comprising an acrylic resin and a polylactic acid resin, the formation of a hard coat layer is facilitated, and further the coating of the hard coat layer increases the surface hardness and facilitates the formation of a metal oxide film. A metal oxide film laminated substrate having excellent properties and adhesion between the metal oxide film and the transparent substrate can be obtained. Furthermore, the obtained metal oxide laminated substrate is suitable for a transparent electrode for display.
以下本発明をさらに詳細に説明する。
本発明は、アクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）からなる樹脂組成物の透明基板上にハードコート処理を施し、この透明基板上に金属酸化物膜が形成されている金属酸化物膜積層基板である。
本発明におけるアクリル系樹脂（ａ）としては、メタクリル酸シクロヘキシル、メタクリル酸ｔ−ブチルシクロヘキシル、メタクリル酸メチル等のメタクリル酸エステル、及びアクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸イソプロピル、アクリル酸２−エチルヘキシル等のアクリル酸エステルから選ばれる１種以上の単量体を重合したものが挙げられる。なかでも、メタクリル酸メチルの単独重合体又は他の単量体との共重合体が好ましい。
The present invention is described in further detail below.
The present invention provides a metal oxide in which a hard coating treatment is performed on a transparent substrate of a resin composition comprising an acrylic resin (a) and a polylactic acid resin (b), and a metal oxide film is formed on the transparent substrate. It is a material film laminated substrate.
Examples of the acrylic resin (a) in the present invention include methacrylic acid esters such as cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, and methyl methacrylate, and methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, and acrylic. What polymerized 1 or more types of monomers chosen from acrylic acid esters, such as acid 2-ethylhexyl, is mentioned. Of these, a homopolymer of methyl methacrylate or a copolymer with other monomers is preferable.
メタクリル酸メチルと共重合可能な単量体としては、他のメタクリル酸アルキルエステル類、アクリル酸アルキルエステル類、スチレン及びｏ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン、ｏ−エチルスチレン，ｐ−エチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン等の核アルキル置換スチレン、α−メチルスチレン、α−メチル−ｐ−メチルスチレン等のα−アルキル置換スチレン等の芳香族ビニル化合物類、アクリロニトリル、メタクリルニトリル等のシアン化ビニル類、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等のマレイミド類、無水マレイン酸等の不飽和カルボン酸無水物類、アクリル酸、メタクリル酸、マレイン酸等の不飽和酸類等が挙げられる。 Examples of monomers copolymerizable with methyl methacrylate include other alkyl methacrylates, alkyl acrylates, styrene and o-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethyl. Aromatic vinyl compounds such as styrene, p-ethylstyrene, nuclear alkyl-substituted styrene such as p-tert-butylstyrene, α-alkylstyrene such as α-methylstyrene and α-methyl-p-methylstyrene, acrylonitrile, Vinyl cyanides such as methacrylonitrile, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, unsaturated carboxylic acid anhydrides such as maleic anhydride, unsaturated acids such as acrylic acid, methacrylic acid and maleic acid, etc. Is mentioned.
メタクリル酸メチルと共重合可能な単量体の中でも、特にアクリル酸アルキルエステル類は耐熱分解性に優れ、またアクリル酸アルキルエステル類を共重合させて得られるメタクリル系樹脂は成形加工時の流動性が高く好ましい。メタクリル酸メチルにアクリル酸アルキルエステル類を共重合させる場合のアクリル酸アルキルエステル類の使用量は、耐熱分解性の観点から０．１質量％以上であることが好ましく、耐熱性の観点から１５質量％以下であることが好ましい。０．２〜１４質量％であることがさらに好ましく、１〜１２質量％であることがとりわけ好ましい。このアクリル酸アルキルエステル類の中でも、特にアクリル酸メチル及びアクリル酸エチルは、それを少量メタクリル酸メチルと共重合させても上記改良効果は著しく最も好ましい。上記メタクリル酸メチルと共重合可能な単量体は一種又は二種以上組み合わせて使用することもできる。 Among monomers copolymerizable with methyl methacrylate, alkyl acrylates are particularly excellent in thermal decomposition resistance, and methacrylic resins obtained by copolymerizing alkyl acrylates are fluid during molding. Is preferable. The amount of alkyl acrylates used when methyl acrylate is copolymerized with methyl methacrylate is preferably 0.1% by mass or more from the viewpoint of heat decomposability, and 15% from the viewpoint of heat resistance. % Or less is preferable. More preferably, it is 0.2-14 mass%, and it is especially preferable that it is 1-12 mass%. Among these alkyl acrylates, especially methyl acrylate and ethyl acrylate are remarkably most preferable even when they are copolymerized with a small amount of methyl methacrylate. The said monomer which can be copolymerized with methyl methacrylate can also be used 1 type or in combination of 2 or more types.
アクリル系樹脂の重量平均分子量は５万〜２０万のものが望ましい。重量平均分子量は成形品の強度の観点から５万以上が望ましく、成形加工性、流動性の観点から２０万以下が望ましい。さらに望ましい範囲は７万〜１５万である。また、アイソタクチックポリメタクリル酸エステルとシンジオタクチックポリメタクリル酸エステルを同時に用いることもできる。 The acrylic resin preferably has a weight average molecular weight of 50,000 to 200,000. The weight average molecular weight is desirably 50,000 or more from the viewpoint of the strength of the molded product, and desirably 200,000 or less from the viewpoint of molding processability and fluidity. A more desirable range is 70,000 to 150,000. Further, isotactic polymethacrylic acid ester and syndiotactic polymethacrylic acid ester can be used simultaneously.
アクリル系樹脂を製造する方法として、例えばキャスト重合、塊状重合、懸濁重合、溶液重合、乳化重合、アニオン重合等の一般に行われている重合方法を用いることができるが、光学用途としては微小な異物の混入はできるだけ避けるのが好ましく、この観点からは懸濁剤や乳化剤を用いない塊状重合や溶液重合が望ましい。溶液重合を行う場合には、単量体の混合物をトルエン、エチルベンゼン等の芳香族炭化水素の溶媒に溶解して調製した溶液を用いることができる。塊状重合により重合させる場合には、通常行われるように加熱により生じる遊離ラジカルや電離性放射線照射により重合を開始させることができる。 As a method for producing an acrylic resin, for example, generally used polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and anionic polymerization can be used. It is preferable to avoid mixing of foreign substances as much as possible. From this viewpoint, bulk polymerization or solution polymerization without using a suspending agent or an emulsifier is desirable. When solution polymerization is performed, a solution prepared by dissolving a mixture of monomers in an aromatic hydrocarbon solvent such as toluene or ethylbenzene can be used. In the case of polymerization by bulk polymerization, the polymerization can be started by irradiation with free radicals generated by heating or ionizing radiation as is usually done.
重合反応に用いられる開始剤としては、一般にラジカル重合において用いられる任意の開始剤を使用することができ、例えばアゾビスイソブチルニトリル等のアゾ化合物、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエート等の有機過酸化物が用いられ、また特に９０℃以上の高温下で重合を行わせる場合には、溶液重合が一般的であるので、１０時間半減期温度が８０℃以上であり、かつ用いる有機溶媒に可溶である過酸化物、アゾビス開始剤等が好ましく、具体的には１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン、シクロヘキサンパーオキシド、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、１，１−アゾビス（１−シクロヘキサンカルボニトリル）、２−（カルバモイルアゾ）イソブチロニトリル等を挙げることができる。これらの開始剤は０．００５〜５質量％の範囲で用いられる。重合反応に必要に応じて用いられる分子量調節剤は、一般的なラジカル重合において用いる任意のものが使用され、例えばブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、チオグリコール酸２−エチルヘキシル等のメルカプタン化合物が特に好ましいものとして挙げられる。これらの分子量調節剤は、重合度が上記の範囲内に制御されるような濃度範囲で添加される。アクリル系樹脂は、分子量、組成等が異なる２種以上のものを同時に用いることができる。 As the initiator used in the polymerization reaction, any initiator generally used in radical polymerization can be used. For example, azo compounds such as azobisisobutylnitrile, benzoyl peroxide, lauroyl peroxide, t-butylperoxy When an organic peroxide such as 2-ethylhexanoate is used and the polymerization is carried out at a high temperature of 90 ° C. or higher, solution polymerization is common, so that the 10-hour half-life temperature is 80 Preferred are peroxides, azobis initiators, and the like that are not lower than ° C. and soluble in the organic solvent to be used. Specifically, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, Cyclohexane peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1,1-azobis (1-cycl Hexane-carbonitrile), and 2- (carbamoylazo) isobutyronitrile. These initiators are used in the range of 0.005 to 5% by mass. As the molecular weight regulator used as necessary for the polymerization reaction, any one used in general radical polymerization is used, for example, mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate, It is mentioned as preferable. These molecular weight regulators are added in a concentration range such that the degree of polymerization is controlled within the above range. Two or more kinds of acrylic resins having different molecular weights and compositions can be used at the same time.
ポリ乳酸系樹脂（ｂ）の製造方法としては、既知の重合方法を用いることができ、乳酸からの直接重合法、ラクチドを介する開環重合法等を採用することができる。本発明におけるポリ乳酸系樹脂（ｂ）は乳酸、すなわちＬ−乳酸、Ｄ−乳酸を主とする重合体である。ポリ乳酸系樹脂（ｂ）において、Ｌ−乳酸単位と、Ｄ−乳酸単位の構成モル比は、Ｌ体とＤ体あわせて１００％に対し、Ｌ体ないしＤ体いずれかが８５％以上が好ましく、更に好ましくは一方が９０％以上であり、更に好ましくは一方が９４％以上の重合体である。本発明においてはＬ−乳酸を主体とするポリＬ−乳酸とＤ−乳酸を主体とするポリＤ−乳酸を同時に用いることもできる。 As a method for producing the polylactic acid resin (b), a known polymerization method can be used, and a direct polymerization method from lactic acid, a ring-opening polymerization method via lactide, or the like can be employed. The polylactic acid resin (b) in the present invention is a polymer mainly composed of lactic acid, that is, L-lactic acid and D-lactic acid. In the polylactic acid-based resin (b), the constituent molar ratio of the L-lactic acid unit and the D-lactic acid unit is preferably 85% or more for either the L-form or the D-form relative to 100% for the L-form and D-form. More preferably, one is 90% or more, and more preferably one is a polymer of 94% or more. In the present invention, poly-L-lactic acid mainly composed of L-lactic acid and poly-D-lactic acid mainly composed of D-lactic acid can be used simultaneously.
ポリ乳酸系樹脂（ｂ）は、Ｌ体ないしＤ体以外の乳酸誘導体モノマーまたは、ラクチドと共重合可能な他成分を共重合していてもよく、このような成分としてはジカルボン酸、多価アルコール、ヒドロキシカルボン酸、ラクトン等が例示される。ポリ乳酸系樹脂（ｂ）は、直接脱水縮合、ラクチドの開環重合等公知の重合法で重合することが出来る。また必要に応じてポリイソシアネートや他の結合剤を用いて、高分子量化することも出来る。
ポリ乳酸系樹脂（ｂ）に含まれる低分子微量成分である乳酸やその他の酸等は、残存することにより黄変着色の原因となるため、含量は５０００ｐｐｍ以下が好ましく、より好ましくは１０００ｐｐｍ以下、最も好ましくは５００ｐｐｍ以下である。
ポリ乳酸系樹脂（ｂ）の好ましい質量平均分子量範囲は、機械的性質の観点から質量平均分子量が３０，０００以上であることが好ましく、加工性の観点から１０００，０００以下であることが好ましい。更に好ましくは５０，０００〜５００，０００、最も好ましくは１００，０００〜２８０，０００である。
The polylactic acid-based resin (b) may be copolymerized with a lactic acid derivative monomer other than the L-form or D-form or other components copolymerizable with lactide, such as dicarboxylic acid, polyhydric alcohol , Hydroxycarboxylic acid, lactone and the like. The polylactic acid resin (b) can be polymerized by a known polymerization method such as direct dehydration condensation or ring-opening polymerization of lactide. If necessary, the molecular weight can be increased by using polyisocyanate or other binders.
Lactic acid, which is a low molecular weight trace component contained in the polylactic acid resin (b), and other acids cause yellowing coloring by remaining, so the content is preferably 5000 ppm or less, more preferably 1000 ppm or less, Most preferably, it is 500 ppm or less.
The mass average molecular weight range of the polylactic acid-based resin (b) is preferably 30,000 or more from the viewpoint of mechanical properties, and preferably 1,000,000 or less from the viewpoint of workability. More preferably, it is 50,000-500,000, Most preferably, it is 100,000-280,000.
本発明のアクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）を含有する樹脂組成物におけるアクリル系樹脂（ａ）の含有割合（質量部）は、光弾性係数、強度、耐熱性等の点から５０質量部以上９９．９質量部以下であることが好ましく、７０質量部以上９８質量部以下であることがさらに好ましく、９０質量部以上９５質量部以下であることがとりわけ好ましい。この樹脂組成物中の組成において、透明性を損なわない限り、ポリ乳酸系樹脂（ｂ）の量が多いほどハードコート層とアクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）を含有する樹脂組成物透明基板との密着性が向上すると考えられる。 The content ratio (parts by mass) of the acrylic resin (a) in the resin composition containing the acrylic resin (a) and the polylactic acid resin (b) of the present invention is a point of photoelastic coefficient, strength, heat resistance, etc. To 50 parts by mass or more and 99.9 parts by mass or less, more preferably 70 parts by mass or more and 98 parts by mass or less, and particularly preferably 90 parts by mass or more and 95 parts by mass or less. In the composition in the resin composition, as long as the transparency is not impaired, the greater the amount of the polylactic acid resin (b), the more the hard coat layer, the acrylic resin (a), and the resin containing the polylactic acid resin (b). It is considered that the adhesion to the composition transparent substrate is improved.
本発明におけるアクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）を含有する樹脂組成物の透明基板を製造する際、必要に応じて染料、顔料、ヒンダードフェノール系やリン酸塩等の熱安定剤、ベンゾトリアゾール系、２-ヒドロキシベンゾフェノン系、サリチル酸フェニルエステル系などの紫外線吸収剤、フタル酸エステル系、脂肪酸エステル系、トリメリット酸エステル系、リン酸エステル系、ポリエステル系などの可塑剤、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸のモノ、ジ、またはトリグリセリド系などの離型剤、高級脂肪酸エステル、ポリオレフィン系などの滑剤、ポリエーテル系、ポリエーテルエステル系、ポリエーテルエステルアミド系、アルキルスフォン酸塩、アルキルベンゼンスルフォン酸塩などの帯電防止剤、リン系、リン／塩素系、リン／臭素系などの難燃剤、反射光のぎらつきを防止するためにメタクリル酸メチル／スチレン共重合体ビーズなどの有機系光拡散剤、硫酸バリウム、酸化チタン、炭酸カルシウム、タルクなどの無機系光拡散剤、補強剤として多段重合で得られるアクリル系ゴム等を使用してもよい。これらの添加剤を配合するときには、公知の方法で実施しうる。例えば、単量体混合物にあらかじめ添加剤を溶解しておき重合する方法や、溶融状態、ビーズ状あるいはペレット状の樹脂に添加剤をミキサー等でドライブレンドし、押出し機を用いて混練、造粒する方法などが挙げられる。 When producing a transparent substrate of the resin composition containing the acrylic resin (a) and the polylactic acid resin (b) in the present invention, heat such as dyes, pigments, hindered phenols, and phosphates as necessary. Stabilizers, UV absorbers such as benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester, plasticizers such as phthalate, fatty acid ester, trimellitic acid ester, phosphate ester, and polyester, Release agents such as higher fatty acids, higher fatty acid esters, mono-, di- or triglycerides of higher fatty acids, lubricants such as higher fatty acid esters and polyolefins, polyethers, polyether esters, polyether ester amides, alkyls Antistatic agents such as phosphonates and alkylbenzene sulfonates, phosphorus , Flame retardants such as phosphorus / chlorine and phosphorus / bromine, organic light diffusers such as methyl methacrylate / styrene copolymer beads to prevent glare from reflected light, barium sulfate, titanium oxide, carbonic acid Inorganic light diffusing agents such as calcium and talc, and acrylic rubbers obtained by multistage polymerization may be used as reinforcing agents. When these additives are blended, it can be carried out by a known method. For example, a method in which an additive is dissolved in a monomer mixture in advance and polymerized, or an additive is dry-blended with a mixer or the like in a molten state, bead-like or pellet-like resin, and kneaded and granulated using an extruder The method of doing is mentioned.
本発明のアクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）を含有する樹脂組成物の透明基板は、フィルム、もしくはシートであることが好ましい。フィルム・シートは、厚さの違いのみであり、フィルムは３００μｍ以下の厚さのものを言い、シートは３００μｍを超えるものである。透明樹脂基板の厚さは、０．０１〜１０．０ｍｍの範囲のフィルムまたはシートであることが好ましい。０．０１〜１０．０ｍｍの範囲のフィルムまたはシートは、パネル加工時に変形しにくく取り扱いやすい。また、基板の荷重による変形も生じにくくなるので、液晶表示素子を組み立てた際に、二重像が顕著になり表示品位が損なわれにくくなる。さらに好ましい厚さは０．１〜５．０ｍｍの範囲である。 The transparent substrate of the resin composition containing the acrylic resin (a) and the polylactic acid resin (b) of the present invention is preferably a film or a sheet. A film / sheet is only a difference in thickness, and a film has a thickness of 300 μm or less, and a sheet has a thickness exceeding 300 μm. The thickness of the transparent resin substrate is preferably a film or sheet in the range of 0.01 to 10.0 mm. A film or sheet in the range of 0.01 to 10.0 mm is hard to be deformed during panel processing and easy to handle. Further, since deformation due to the load on the substrate is less likely to occur, a double image becomes prominent when the liquid crystal display element is assembled, and the display quality is unlikely to be impaired. A more preferred thickness is in the range of 0.1 to 5.0 mm.
本発明におけるアクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）を含有する樹脂組成物の透明基板のフィルムまたはシートは透明性が必須であり、その透明性の指標として全光線透過率が８０％以上、ヘイズ値が５％以下であることが好ましい。さらに好ましくは全光線透過率が８５％以上、ヘイズ値が２％以下である。ただし、ディスプレイ用透明電極に適しているのは７０％以上であれば適用できる。 In the present invention, the transparent substrate film or sheet of the resin composition containing the acrylic resin (a) and the polylactic acid resin (b) must be transparent, and the total light transmittance is 80 as an index of the transparency. % Or more and a haze value of 5% or less is preferable. More preferably, the total light transmittance is 85% or more and the haze value is 2% or less. However, 70% or more is suitable for the transparent electrode for display.
本発明におけるアクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）を含有する樹脂組成物の透明基板のフィルムまたはシートは光学等方性が優れるものが好ましく、リタデーション値が３０ｎｍ以下、遅相軸のバラツキが４０度以内、より好ましくはリタデーション値が２０ｎｍ以下、遅相軸のバラツキが２０度以内のものが好適である。ここで、リタデーション値は、公知の測定装置を用いて測定した波長５９０ｎｍにおける複屈折の屈折率の差△ｎと膜厚ｄとの積△ｎ・ｄで表されるものである。 The transparent substrate film or sheet of the resin composition containing the acrylic resin (a) and the polylactic acid resin (b) in the present invention preferably has excellent optical isotropy, a retardation value of 30 nm or less, and a slow axis. The retardation value is within 40 degrees, more preferably the retardation value is 20 nm or less, and the slow axis dispersion is within 20 degrees. Here, the retardation value is represented by a product Δn · d of a refractive index difference Δn of birefringence at a wavelength of 590 nm and a film thickness d measured using a known measuring apparatus.
本発明におけるアクリル系樹脂（ａ）およびポリ乳酸系樹脂（ｂ）を含有する樹脂組成物の透明基板のフィルム又はシートは光弾性係数の絶対値が３．０×１０−１２／Ｐａ未満であることが好ましい。光弾性係数がこの範囲内であれば、応力による複屈折の変化が少ないため、液晶表示装置等に使用した場合にコントラストや画面の均一性に優れる。 The transparent substrate film or sheet of the resin composition containing the acrylic resin (a) and the polylactic acid resin (b) in the present invention has an absolute value of the photoelastic coefficient of less than 3.0 × 10 −12 / Pa. It is preferable. If the photoelastic coefficient is within this range, the change in birefringence due to stress is small, so that the contrast and the uniformity of the screen are excellent when used in a liquid crystal display device or the like.
光弾性係数は種々の文献に記載があり（例えばＭａｃｒｏｍｏｌｅｃｕｌｅｓ ２００４，３７，１０６２−１０６６参照）、下式により定義される。
｜ＣＲ｜＝｜Δｎ｜／σＲ ｜Δｎ｜＝｜ｎ１−ｎ２｜
（式中、｜ＣＲ｜：光弾性係数の絶対値、σＲ：伸張応力、｜Δｎ｜：複屈折の絶対値、ｎ１：伸張方向の屈折率、ｎ２：伸張方向と垂直な屈折率）
光弾性係数の値がゼロに近いほど外力による複屈折の変化が小さいことを示しており、各用途において設計された複屈折の変化が小さいことを意味する。
The photoelastic coefficient is described in various documents (see, for example, Macromolecules 2004, 37, 1062-1066), and is defined by the following equation.
| CR | = | Δn | / σR | Δn | = | n1-n2 |
(Where: | CR |: absolute value of photoelastic coefficient, σR: stretching stress, | Δn |: absolute value of birefringence, n1: refractive index in stretching direction, n2: refractive index perpendicular to stretching direction)
The closer the value of the photoelastic coefficient is to zero, the smaller the change in birefringence due to external force, which means that the change in birefringence designed for each application is small.
本発明における金属酸化物膜に用いる材料としては、ガリウム、アルミニウム、ホウ素、ケイ素、スズ、亜鉛、インジウム、ゲルマニウム、チタン、アンチモン、イリジウム、レニウム、セリウム、ジルコニウム、スカンジウム、及びイットリウムから選ばれる元素を少なくとも１種以上を含む金属酸化物膜を利用することができる。
金属酸化物膜は、無機バリア層として用いることが好ましい。
無機バリア層に用いる材料としては、ケイ素やアルミニウムの金属酸化物、金属酸化窒化物、又はこれらの混合物で構成された薄膜であることが好ましい。具体的な無機バリア層の構成成分としては、一般的に真空成膜される材料であれば原則的に使用可能であり、中でもセラミック材料を用いると、透明性の高い薄膜を形成することができる。セラミック材料としては、ＳｉＯｘ、ＡｌＯｘ、ＳｉＯｘＮｙ、ＳｉＯｘＮｙＣｚ、ＳｉＮｘＣｙ、ＡｌＯｘＮｙ、ＡｌＯｘＮｙＣｚ、及びＡｌＮｘＣｙ等を例示することができる。ここで、ｘ、ｙ、ｚは、それぞれ数を表す。
As a material used for the metal oxide film in the present invention, an element selected from gallium, aluminum, boron, silicon, tin, zinc, indium, germanium, titanium, antimony, iridium, rhenium, cerium, zirconium, scandium, and yttrium is used. A metal oxide film containing at least one kind can be used.
The metal oxide film is preferably used as an inorganic barrier layer.
The material used for the inorganic barrier layer is preferably a thin film composed of a metal oxide of silicon or aluminum, a metal oxynitride, or a mixture thereof. As a specific component of the inorganic barrier layer, in general, any material that can be vacuum-deposited can be used in principle. In particular, when a ceramic material is used, a highly transparent thin film can be formed. . Examples of the ceramic material include SiOx, AlOx, SiOxNy, SiOxNyCz, SiNxCy, AlOxNy, AlOxNyCz, and AlNxCy. Here, x, y, and z each represent a number.
これらの金属化合物材料の中でも、酸化ケイ素、窒化ケイ素、酸化窒化ケイ素、及び、これらの混合材料が無機バリア層として好ましい。さらに好ましくは、ＳｉＯｘ（ただし、１＜ｘ≦２）膜であり、表面硬度が硬く、非導電性である。この中で、ガスバリア性、透明性、表面平滑性、屈曲性、膜応力、コスト等の点からケイ素原子数に対する酸素原子数の割合ｘが１．５〜２．０のケイ素酸化物を主成分とする金属酸化物が良好である。ケイ素酸化物のケイ素原子数に対する酸素原子数の割合は、Ｘ線光電子分光法、Ｘ線マイクロ分光法、オージェ電子分光法、ラザホード後方散乱法等により分析、決定される。この割合の範囲であると、透明性が良好である。更に上記ケイ素酸化物中に、酸化マグネシウム及び／又はフッ化マグネシウムを全体の重量に対して５〜３０質量％含有すると、透明性をより高くすることができる。
無機バリア層の厚さは１〜１０００ｎｍが好ましく、より好ましくは２〜１００ｎｍ、さらに好ましくは３〜５０ｎｍである。
Among these metal compound materials, silicon oxide, silicon nitride, silicon oxynitride, and mixed materials thereof are preferable as the inorganic barrier layer. More preferably, it is a SiOx (where 1 <x ≦ 2) film, has a high surface hardness, and is non-conductive. Among these, the main component is a silicon oxide having a ratio x of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0 in terms of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, etc. The metal oxide is good. The ratio of the number of oxygen atoms to the number of silicon atoms in the silicon oxide is analyzed and determined by X-ray photoelectron spectroscopy, X-ray microspectroscopy, Auger electron spectroscopy, Rutherford backscattering, and the like. When it is within this range, the transparency is good. Further, when the silicon oxide contains 5 to 30% by mass of magnesium oxide and / or magnesium fluoride based on the total weight, the transparency can be further increased.
As for the thickness of an inorganic barrier layer, 1-1000 nm is preferable, More preferably, it is 2-100 nm, More preferably, it is 3-50 nm.
さらに、金属酸化物膜は、透明導電膜として使用することも好ましい。
透明導電膜に用いる材料としては、スズ、ゲルマニウム、亜鉛、ガリウム、マグネシウムのうち少なくとも１種類を含む酸化インジウム膜、アンチモン、フッ素、亜鉛のうち少なくとも１種類を含む酸化スズ膜を利用することができる。
酸化インジウム膜に添加されるスズ、ゲルマニウム、亜鉛、ガリウム、マグネシウムの含有量は、これらのうち１種類を添加する場合は、インジウムに対するこれらの材料の原子比（Ｓｎ／Ｉｎ，Ｇｅ／Ｉｎ，Ｚｎ／Ｉｎ，Ｇａ／Ｉｎ，Ｍｇ／Ｉｎ）をいずれも０．５〜２０．０％が好ましい。より好ましくは５〜１０％が好ましい。中でも導電性と透明性のバランスがよいスズが最も好ましい。
このような比率で添加すると、膜の導電性及び透明性を良好に維持できる。また、これらの材料の複数種類を添加する場合は、添加する材料の全体の添加量をインジウムに対して２０．０％以下が好ましい。
Further, the metal oxide film is also preferably used as a transparent conductive film.
As a material used for the transparent conductive film, an indium oxide film containing at least one of tin, germanium, zinc, gallium, and magnesium, and a tin oxide film containing at least one of antimony, fluorine, and zinc can be used. .
The content of tin, germanium, zinc, gallium, and magnesium added to the indium oxide film is the atomic ratio of these materials to indium (Sn / In, Ge / In, Zn) when one of these is added. / In, Ga / In, Mg / In) are all preferably 0.5 to 20.0%. More preferably, it is 5 to 10%. Of these, tin having the best balance between conductivity and transparency is most preferable.
When added at such a ratio, the conductivity and transparency of the film can be maintained well. Moreover, when adding multiple types of these materials, 20.0% or less of the total addition amount of the material to add is preferable with respect to indium.
酸化スズ膜に添加されるアンチモン、フッ素、亜鉛の含有量は、これらのうち１種類を添加する場合は、インジウムに対するこれらの材料の原子比（Ｓｂ／Ｓｎ，Ｆ／Ｓｎ，Ｚｎ／Ｓｎ）をいずれも０．５〜２０．０％が好ましい。このような比率で添加すると、膜の導電性及び透明性を良好に維持できる。また、これらの材料の複数種類を添加する場合は、添加する材料の全体の添加量をスズに対して２０．０％以下が好ましい。
これらの透明導電性金属酸化物膜の膜厚は、１０ｎｍ〜１０００ｎｍの範囲が好ましい。この膜厚の範囲では、用途によって異なるが、可撓性が保たれた連続的な膜を得る事が出来る。さらに、本発明の透明導電膜の膜厚は用途に応じて２０〜５００ｎｍとすることが望ましい。
The content of antimony, fluorine and zinc added to the tin oxide film is the atomic ratio of these materials to indium (Sb / Sn, F / Sn, Zn / Sn) when one of these is added. In any case, 0.5 to 20.0% is preferable. When added at such a ratio, the conductivity and transparency of the film can be maintained well. Moreover, when adding two or more types of these materials, 20.0% or less of the total addition amount of the material to add is preferable with respect to tin.
The thickness of these transparent conductive metal oxide films is preferably in the range of 10 nm to 1000 nm. In this film thickness range, although it varies depending on the application, it is possible to obtain a continuous film in which flexibility is maintained. Furthermore, the film thickness of the transparent conductive film of the present invention is desirably 20 to 500 nm depending on the application.
金属酸化物膜積層基板のシート抵抗値は、用途によって異なるが、５〜１００００Ω／□の範囲のものが導電性材料として好ましい。さらに好ましくは１０〜３００Ω／□の範囲のものが好ましい。ただし、ディスプレイ用透明電極に適しているのは１０〜１００Ω／□の範囲のものが好ましい。 Although the sheet resistance value of a metal oxide film laminated substrate changes with uses, the thing of the range of 5-10000 ohms / square is preferable as an electroconductive material. More preferably, the range of 10 to 300Ω / □ is preferable. However, those suitable for the transparent electrode for display are preferably in the range of 10 to 100Ω / □.
本発明のハードコート層としては、例えば、分子中に少なくとも２個の官能基を有する化合物からなる被膜を硬化したもの等が挙げられる。ハードコート層を形成するための官能基としては、例えば、（メタ）アクリロイルオキシ基のような不飽和二重結合を有する基、エポキシ基やシラノール基のような反応性の置換基等が挙げられる。なかでも、不飽和二重結合を有する基は、紫外線や電子線のような活性化エネルギー線の照射により容易に硬化しうるので、好ましく用いられる。不飽和二重結合を有する基を分子中に少なくとも２個有する化合物としては、例えば、多官能アクリレート化合物等が挙げられる。ここで、多官能アクリレート化合物とは、分子中に少なくとも２個のアクリロイルオキシ基及び／又はメタクロイルオキシ基を有する化合物をいう。以下、アクリロイルオキシ基とメタクロイルオキシ基とをまとめて（メタ）アクリロイルオキシ基と呼ぶ。 Examples of the hard coat layer of the present invention include those obtained by curing a film made of a compound having at least two functional groups in the molecule. Examples of the functional group for forming the hard coat layer include a group having an unsaturated double bond such as a (meth) acryloyloxy group, a reactive substituent such as an epoxy group or a silanol group, and the like. . Among these, a group having an unsaturated double bond is preferably used because it can be easily cured by irradiation with an activation energy ray such as an ultraviolet ray or an electron beam. Examples of the compound having at least two groups having an unsaturated double bond in the molecule include polyfunctional acrylate compounds. Here, the polyfunctional acrylate compound refers to a compound having at least two acryloyloxy groups and / or methacryloyloxy groups in the molecule. Hereinafter, the acryloyloxy group and the methacryloyloxy group are collectively referred to as a (meth) acryloyloxy group.
多官能アクリレート化合物としては、例えば、次のようなものを挙げることができる。エチレングリコールジアクリレート、ジエチレングリコールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、テトラメチロールメタントリアクリレート、テトラメチロールメタンテトラアクリレート、ペンタグリセロールトリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、グリセリントリアクリレート、ジペンタエリスリトールトリアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、トリス（アクリロイルオキシエチル）イソシアヌレート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、テトラメチロールメタントリメタクリレート、テトラメチロールメタンテトラメタクリレート、ペンタグリセロールトリメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、グリセリントリメタクリレート、ジペンタエリスリトールトリメタクリレート、ジペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールペンタメタクリレート、ジペンタエリスリトールヘキサメタクリレート、トリス（アクリロイルオキシエチル）イソシアヌレート、ホスファゼン化合物のホスファゼン環に（メタ）アクリロイルオキシ基が導入されたホスファゼン系（メタ）アクリレート化合物、分子中に少なくとも２個のイソシアネート基を有するポリイソシアネート化合物と少なくとも１個の（メタ）アクリロイルオキシ基及び少なくとも１個の水酸基を有するポリオール化合物とを反応させて得られるウレタン（メタ）アクリレート化合物、分子中に少なくとも２個のカルボニル基を有するカルボン酸ハロゲン化物と少なくとも１個の（メタ）アクリロイルオキシ基を有するポリオール化合物とを反応させて得られるポリエステル（メタ）アクリレート化合物等である。 Examples of the polyfunctional acrylate compound include the following. Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, pentaglycerol Triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane tetramethacrylate, pentaglycerol Trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, tris (acrylo (Luoxyethyl) isocyanurate, a phosphazene (meth) acrylate compound in which a (meth) acryloyloxy group is introduced into the phosphazene ring of the phosphazene compound, a polyisocyanate compound having at least two isocyanate groups in the molecule, and at least one (meta ) A urethane (meth) acrylate compound obtained by reacting an acryloyloxy group and a polyol compound having at least one hydroxyl group, a carboxylic acid halide having at least two carbonyl groups in the molecule and at least one (meta ) A polyester (meth) acrylate compound obtained by reacting with a polyol compound having an acryloyloxy group.
これらの化合物は、それぞれ単独で又は２種以上混合して用いることができる。またこれら各化合物の２量体、３量体等のオリゴマーであってもよい。
ハードコート層は、通常の方法、例えば、ハードコート剤を樹脂基材の表面に塗布することにより被膜とし、これに活性化エネルギー線を照射すること等により設けることができる。塗布方法としては、例えば、マイクログラビアコート法、ロールコート法、ディッピングコート法、スピンコート法、ダイコート法、フローコート法、スプレーコート法等が挙げられる。ハードコート層の厚みは、０．５〜５０μｍが好ましく、さらに好ましくは１〜２０μｍで、より好ましくは２〜１０μｍである。その厚みが０．５〜５０μｍであると、耐擦傷性が良く、亀裂の発生が起こりにくくなる。
These compounds can be used alone or in admixture of two or more. Moreover, oligomers, such as a dimer of this each compound and a trimer, may be sufficient.
The hard coat layer can be provided by a normal method, for example, by applying a hard coat agent to the surface of the resin base material to form a film and irradiating it with an activation energy ray. Examples of the coating method include a micro gravure coating method, a roll coating method, a dipping coating method, a spin coating method, a die coating method, a flow coating method, and a spray coating method. As for the thickness of a hard-coat layer, 0.5-50 micrometers is preferable, More preferably, it is 1-20 micrometers, More preferably, it is 2-10 micrometers. When the thickness is 0.5 to 50 μm, the scratch resistance is good and cracks are less likely to occur.
本発明のハードコート層は、帯電防止性のハードコート層であってもよい。帯電防止性のハードコート層としては、例えば、導電性粒子が分散されたハードコート層、界面活性剤を含有するハードコート層等が挙げられる。導電性粒子が分散されたハードコート層としては、不飽和二重結合を少なくとも２個有する化合物が硬化されてなる硬化被膜に、導電性粒子が分散されてなる層等が挙げられる。導電性粒子としては、例えば、スズ、アンチモン、チタン、インジウムの如き金属の酸化物や、これらの金属の複合酸化物、例えば、インジウムスズ複合酸化物（ＩＴＯ）やアンチモンドープ酸化スズ等の粒子が挙げられる。導電性粒子の粒子径は、一次粒子径で通常、０．００１〜０．１μｍ程度が好ましい。この範囲内では、透明性が維持される傾向にある。 The hard coat layer of the present invention may be an antistatic hard coat layer. Examples of the antistatic hard coat layer include a hard coat layer in which conductive particles are dispersed and a hard coat layer containing a surfactant. Examples of the hard coat layer in which conductive particles are dispersed include a layer in which conductive particles are dispersed in a cured coating obtained by curing a compound having at least two unsaturated double bonds. Examples of the conductive particles include oxides of metals such as tin, antimony, titanium, and indium, and composite oxides of these metals, such as particles of indium tin composite oxide (ITO) and antimony-doped tin oxide. Can be mentioned. The particle diameter of the conductive particles is usually about 0.001 to 0.1 μm in terms of primary particle diameter. Within this range, transparency tends to be maintained.
塗膜の耐摩耗性の向上と硬化時における体積収縮率の減少のために、無機微粒子を含有させても構わない。無機微粒子としては、シリカ、酸化チタン等の金属酸化物からなる微粒子が好ましい。かかる無機微粒子の含有量は２０〜６０質量％が好ましく、無機微粒子の平均粒径は１００μｍ以下のものが好ましい。この含有量の範囲内では、製品フィルムのカール発生を抑えられ、ハードコート樹脂の伸縮性不良と屈曲によるクラックの発生も低減できる。また、この平均粒径は１００ｎｍ以上であることが好ましい。
反射防止層のハードコート性（傷防止性）向上のために、無機微粒子表面に光重合反応性を有する感光性基を導入したものが好ましい。この感光性基としては単官能性又は多官能性アクリレートが好ましい。
In order to improve the abrasion resistance of the coating film and to reduce the volume shrinkage during curing, inorganic fine particles may be contained. As the inorganic fine particles, fine particles made of a metal oxide such as silica and titanium oxide are preferable. The content of the inorganic fine particles is preferably 20 to 60% by mass, and the average particle size of the inorganic fine particles is preferably 100 μm or less. Within this content range, the curling of the product film can be suppressed, and the occurrence of cracks due to poor stretchability and bending of the hard coat resin can also be reduced. The average particle size is preferably 100 nm or more.
In order to improve the hard coat property (scratch prevention property) of the antireflection layer, it is preferable to introduce a photosensitive group having photopolymerization reactivity on the surface of the inorganic fine particles. The photosensitive group is preferably a monofunctional or polyfunctional acrylate.
本発明におけるハードコート層は、その表面が鉛筆硬度で４Ｈ以上の硬さを有することが好ましい。
本発明の透明導電性金属酸化物積層基板は、ハードコート層を施した透明樹脂基板に透明導電膜を形成できるが、透明樹脂基板に無機バリア層を介して透明導電膜を形成しても構わない。透明樹脂基板の片面又は両面に層構成を有しても構わない。
無機バリア層は、透明樹脂基板に耐スクラッチ性、表面硬度、耐透湿性、耐透気性、耐熱性、耐溶剤性等の性質を付与するのに貢献する。透明樹脂基板に無機バリア層を介して透明導電膜を形成する際、耐スクラッチ性及び表面硬度を一段と向上させる役割を果たすと共に、透明導電性金属酸化物膜の形成時、熱によるダメージをさらに軽減化させていると考えられる。
The surface of the hard coat layer in the present invention preferably has a pencil hardness of 4H or higher.
In the transparent conductive metal oxide laminated substrate of the present invention, a transparent conductive film can be formed on a transparent resin substrate provided with a hard coat layer, but a transparent conductive film may be formed on the transparent resin substrate via an inorganic barrier layer. Absent. You may have a layer structure in the single side | surface or both surfaces of a transparent resin substrate.
The inorganic barrier layer contributes to imparting properties such as scratch resistance, surface hardness, moisture permeability resistance, gas resistance, heat resistance, and solvent resistance to the transparent resin substrate. When forming a transparent conductive film on a transparent resin substrate via an inorganic barrier layer, it plays a role in further improving scratch resistance and surface hardness, and further reduces heat damage when forming a transparent conductive metal oxide film. It is thought that
さらに透明導電性金属酸化物積層基板に最外層として、任意の樹脂又は無機化合物の層を１層又は２層以上積層してもよい。このような最外層には、保護膜、反射防止膜、フィルター等の役割、又は、液晶の視野角の調整、曇り止め等の機能を持たせることができる。
上記金属酸化物膜積層基板は、全光線透過率が７０％以上、ヘイズ値が１０％以下であることが好ましく、この範囲では、透明感が良好である。さらに好ましくは全光線透過率が８０％以上、ヘイズ値が５％以下である。ただし、ディスプレイ用透明電極に適しているのは７０％以上であれば適用できる。
金属酸化物膜を形成してなる金属酸化物膜積層基板の製造方法において、成膜法は、特に限定するものではなく、スパッタリング法や、真空蒸着法、CVD法を用いることもできるが、好適な方法は、スパッタリング法やイオンプレーティング法によるものである。
Furthermore, you may laminate | stack the layer of arbitrary resin or an inorganic compound as an outermost layer on a transparent conductive metal oxide laminated substrate. Such an outermost layer can have a role of a protective film, an antireflection film, a filter, or the like, or functions such as adjustment of the viewing angle of liquid crystal and anti-fogging.
The metal oxide film laminated substrate preferably has a total light transmittance of 70% or more and a haze value of 10% or less. In this range, the transparency is good. More preferably, the total light transmittance is 80% or more and the haze value is 5% or less. However, 70% or more is suitable for the transparent electrode for display.
In the method for manufacturing a metal oxide film laminated substrate formed by forming a metal oxide film, the film forming method is not particularly limited, and a sputtering method, a vacuum evaporation method, or a CVD method can also be used. Such a method is based on a sputtering method or an ion plating method.
以下に実施例、比較例を用いて本発明をさらに具体的に説明する。
＜評価法＞
（Ａ）無機バリア膜を有したアクリル系樹脂積層基板の評価
（Ａ−１）全光線透過率、ヘイズ
ＪＩＳ Ｋ ６７１１に準拠して評価した。
（Ａ−２）面内レタデーション（Ｒｅ）の測定
大塚電子（株）社製複屈折測定装置ＲＥＴＳ−１００を用いて、回転検光子法により２３℃における面内レタデーション（Ｒｅ）を測定した。
（Ａ−３）無機バリア膜の状態
無機バリア膜を有したアクリル系樹脂積層基板表面を顕微鏡で８００倍に拡大し、無機バリア膜の亀裂が認められない場合は「○」（良好）と評価し、亀裂が認められる場合は「×」（不良）と評価した。
（Ａ−４）密着性評価
密着性の評価方法として粘着テープ（ニチバン製１．８cm幅のセロテープ）の粘着面を透明導電性積層基板の無機バリア膜に密着させ、引き剥がす剥離テストにより評価する。無機バリア膜が全く剥離しない場合を「○」（良好）とし、全面剥離した場合を「×」（不良）と表示した。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
<Evaluation method>
(A) Evaluation of Acrylic Resin Multilayer Substrate Having Inorganic Barrier Film (A-1) Total Light Transmittance, Haze Evaluation was made according to JIS K 6711.
(A-2) Measurement of in-plane retardation (Re) In-plane retardation (Re) at 23 ° C. was measured by a rotating analyzer method using a birefringence measuring apparatus RETS-100 manufactured by Otsuka Electronics Co., Ltd.
(A-3) State of the inorganic barrier film The surface of the acrylic resin laminated substrate having the inorganic barrier film is magnified 800 times with a microscope, and when the crack of the inorganic barrier film is not observed, it is evaluated as “◯” (good). When a crack was observed, it was evaluated as “x” (defective).
(A-4) Adhesion evaluation As an evaluation method for adhesion, the adhesive surface of an adhesive tape (1.8 cm wide cello tape made by Nichiban) is adhered to the inorganic barrier film of the transparent conductive laminated substrate, and evaluated by a peeling test. . The case where the inorganic barrier film was not peeled at all was indicated as “◯” (good), and the case where the entire surface was peeled off was indicated as “x” (defective).
（Ａ−５）光弾性係数の測定
Macromolecules 2004,37,1062-1066に詳細の記載のある複屈折測定装置を用いた。レーザー光の経路にシート片の引張装置を配置し、２３℃で伸張応力をかけながら複屈折を測定した。伸張時の歪速度は２０％／分（チャック間：３０ｍｍ、チャック移動速度：６ｍｍ／分）、試験片幅は７ｍｍで測定を行った。複屈折（Δｎ）と伸張応力（σＲ）の関係から、最小二乗近似により線形領域の直線の傾きをもとめ光弾性係数（ＣＲ）を計算し、光惰性係数の絶対値（｜ＣＲ｜）を求めた。傾きの絶対値が小さいほど光弾性係数が０に近いことを示し、好ましい光学特性であることを示す。
｜ＣＲ｜＝｜Δｎ｜／σＲ
（ＣＲ：光弾性係数、σＲ：伸張応力、Δｎ：複屈折、ｎ１：伸張方向の屈折率、ｎ２：伸張方向と垂直な屈折率）
(A-5) Measurement of photoelastic coefficient
A birefringence measuring apparatus described in detail in Macromolecules 2004, 37, 1062-1066 was used. A sheet piece tensioning device was placed in the laser beam path, and birefringence was measured while applying an extensional stress at 23 ° C. The strain rate during stretching was 20% / min (chuck interval: 30 mm, chuck moving speed: 6 mm / min), and the test piece width was 7 mm. From the relationship between birefringence (Δn) and tensile stress (σR), the photoelastic coefficient (CR) is calculated by finding the slope of the straight line in the linear region by least square approximation, and the absolute value (| CR |) of the optical inertia coefficient is obtained. It was. The smaller the absolute value of the slope is, the closer the photoelastic coefficient is to 0, indicating a preferable optical characteristic.
| CR | = | Δn | / σR
(CR: photoelastic coefficient, σR: stretching stress, Δn: birefringence, n1: refractive index in the stretching direction, n2: refractive index perpendicular to the stretching direction)
（Ｂ）透明導電膜を形成してなる透明導電性積層基板の評価
（Ｂ−１）全光線透過率、ヘイズ
上記（Ａ−１）と同様に測定した。
（Ｂ−２）面内レタデーション（Ｒｅ）の測定
上記（Ａ−２）と同様に測定した。
（Ｂ−３）ＩＴＯ膜の外観評価：
透明導電性積層基板表面を顕微鏡で８００倍に拡大し、ＩＴＯ膜の亀裂が認められない場合は「○」（良好）と評価し、亀裂が認められる場合は「×」（不良）と評価した。
（Ｂ−４）密着性評価
密着性の評価方法として粘着テープ（ニチバン製１．８cm幅のセロテープ）の粘着面を透明導電性積層基板のＩＴＯ膜に密着させ、引き剥がす剥離テストにより評価する。ＩＴＯＯ膜が全く剥離しない場合を「○」（良好）とし、全面剥離した場合を「×」（不良）と表示した。
（Ｂ−５）基板の変形評価：熱オーブンテスト
温度８０℃の雰囲気下、約３０分間静置して目視でそり・変形を評価した。透明導電性積層基板が全く変形・そりがない場合を「○」（良好）、変形・そりがわずかに認められる場合を「△」（可）とし、変形・そりが認められる場合を「×」（不良）と表示する。
(B) Evaluation of transparent conductive laminated substrate formed with transparent conductive film (B-1) Total light transmittance, haze Measured in the same manner as (A-1) above.
(B-2) Measurement of in-plane retardation (Re) Measurement was performed in the same manner as in (A-2) above.
(B-3) Appearance evaluation of ITO film:
The surface of the transparent conductive laminated substrate was magnified 800 times with a microscope, and when a crack of the ITO film was not observed, it was evaluated as “◯” (good), and when a crack was observed, it was evaluated as “×” (bad). .
(B-4) Adhesive evaluation As an evaluation method for adhesiveness, the adhesive surface of an adhesive tape (1.8 cm wide cello tape made by Nichiban) is closely attached to the ITO film of the transparent conductive laminated substrate and evaluated by a peeling test. The case where the ITOO film did not peel at all was indicated as “◯” (good), and the case where the ITO film was peeled off was indicated as “x” (defective).
(B-5) Evaluation of Deformation of Substrate: Thermal Oven Test The substrate was left to stand for about 30 minutes in an atmosphere at a temperature of 80 ° C., and the warpage and deformation were evaluated visually. “○” (good) when the transparent conductive laminated substrate is not deformed or warped at all, “△” (good) when it is slightly deformed or warped, and “×” when deformed or warped is recognized. (Bad) is displayed.
＜用いた原材料＞
（ａ）アクリル系樹脂
メタクリル酸メチル９６．７質量％、アクリル酸メチル２．１質量％、及びキシレン１質量％からなる単量体混合物に、１，１-ジ-ｔ-ブチルパーオキシ-３，３，３-トリメチルシクロヘキサン０．０２９４質量％、及びｎ-オクチルメルカプタン０．２８質量％を添加し、均一に混合する。この溶液を内容積１０リットルの密閉耐圧反応器に連続的に供給し、攪拌下に平均温度１３０℃、平均滞留時間２時間で重合した後、反応器に接続された貯層に連続的に送り出し、一定条件下で揮発分を除去し、さらに押出機に連続的に溶融状態で移送し、以下の実施例に使用したアクリル系樹脂である（メタクリル酸メチル／アクリル酸メチル）共重合体ペレットを得た。得られた共重合体のアクリル酸メチル含量は２．０％、重量平均分子量は１０２，０００、ＡＳＴＭ-Ｄ１２３８に準拠して測定した２３０℃３．８ｋｇ荷重のメルトフロー値は２．０ｇ／分であった。
（ｂ）ポリ乳酸系樹脂
カーギル・ダウ（株）社製ＮａｔｕｒｅＷｏｒｋｓ ４０４０Ｄ（質量平均分子量 約１８万）を用い、ホッパードライヤーで６０℃で１時間乾燥した後、真空乾燥機で６０℃で２４時間乾燥し、微量不純物を除去した。
<Raw materials used>
(A) Acrylic resin 1,1-di-t-butylperoxy-3 was added to a monomer mixture consisting of 96.7% by weight of methyl methacrylate, 2.1% by weight of methyl acrylate, and 1% by weight of xylene. , 3,3-trimethylcyclohexane 0.0294 mass% and n-octyl mercaptan 0.28 mass% are added and mixed uniformly. This solution is continuously supplied to a closed pressure-resistant reactor having an internal volume of 10 liters, polymerized with stirring at an average temperature of 130 ° C. and an average residence time of 2 hours, and then continuously sent to a reservoir connected to the reactor. The volatile matter is removed under a certain condition, and further transferred to the extruder in a molten state. The acrylic resin (methyl methacrylate / methyl acrylate) copolymer pellets used in the following examples Obtained. The resulting copolymer had a methyl acrylate content of 2.0%, a weight average molecular weight of 102,000, and a melt flow value at 230 ° C. and a load of 3.8 kg measured in accordance with ASTM-D1238 was 2.0 g / min. Met.
(B) Polylactic acid-based resin Using NatureWorks 4040D (mass average molecular weight of about 180,000) manufactured by Cargill Dow Co., Ltd., dried at 60 ° C. for 1 hour with a hopper dryer, and then dried at 60 ° C. for 24 hours with a vacuum dryer. Trace impurities were removed.
［実施例１および比較例１］
クロックナー社製 Ｆ４０の射出成形機を利用し、（ａ）アクリル系樹脂と（ｂ）ポリ乳酸系樹脂を表１に記載の組成で押出し、各樹脂について平板シート（８０×８０×２ｍｍｔ）を成形温度２６０℃で作成した。その透明樹脂基板のシート（８０×８０×２ｍｍｔ）について、市販のＪＰＣ製ハードコート液ＴＫＨ-３６Ａに、シートを浸漬し、引き上げて、紫外線を照射し、ハードコート層をシート表面に形成した。ハードコート層の膜厚は約５μｍに調整した。そして成膜前にあらかじめ真空乾燥機で６０℃、約１時間乾燥し、水分などの微量不純物を除去した。そのシート上に無機バリア層としてＳｉＯｘ（ただし、１＜ｘ≦２）膜をイオンプレーティング法により成膜した。ＳｉＯｘ膜の膜厚は約１０ｎｍに調整した。この金属酸化物積層基板の評価結果を表１に併記する。
[Example 1 and Comparative Example 1]
Using an F40 injection molding machine manufactured by Crockner Co., Ltd., (a) acrylic resin and (b) polylactic acid resin were extruded with the composition shown in Table 1, and a flat sheet (80 × 80 × 2 mmt) for each resin. It was created at a molding temperature of 260 ° C. About the sheet | seat (80 * 80 * 2mmt) of the transparent resin substrate, the sheet | seat was immersed in the commercially available hard coat liquid TKH-36A made from JPC, it pulled up, and the ultraviolet-ray was irradiated and the hard-coat layer was formed in the sheet | seat surface. The film thickness of the hard coat layer was adjusted to about 5 μm. Prior to film formation, the substrate was dried in a vacuum dryer at 60 ° C. for about 1 hour in advance to remove trace impurities such as moisture. A SiOx (where 1 <x ≦ 2) film was formed as an inorganic barrier layer on the sheet by an ion plating method. The film thickness of the SiOx film was adjusted to about 10 nm. The evaluation results of this metal oxide multilayer substrate are also shown in Table 1.
［実施例２］
無機バリア層として酸化窒化ケイ素膜（ＳｉＯｘＮｙ）をイオンプレーティング法により成膜した以外は、実施例１と同様にして金属酸化物積層基板を得た。酸化窒化ケイ素膜の厚みは１００ｎｍであった。この金属酸化物積層基板の評価結果を表１に併記する。
[Example 2]
A metal oxide multilayer substrate was obtained in the same manner as in Example 1 except that a silicon oxynitride film (SiOxNy) was formed by ion plating as an inorganic barrier layer. The thickness of the silicon oxynitride film was 100 nm. The evaluation results of this metal oxide multilayer substrate are also shown in Table 1.
［実施例３、４、５、６および比較例２］
クロックナー社製 Ｆ４０の射出成形機を利用し、（ａ）アクリル系樹脂と（ｂ）ポリ乳酸系樹脂を各々任意の組成で押出し、各樹脂について平板（８０＊８０＊２ｍｍｔ）を作成した。成形温度は２６０℃で行った。その透明樹脂基板のシート（８０×８０×２ｍｍｔ）について、市販のＪＰＣ製ハードコート液ＴＫＨ-３６Ａに、シートを浸漬し、引き上げて、紫外線を照射し、ハードコート層をシート表面に形成した。ハードコート層の膜厚は約５μｍに調整した。そして成膜前にあらかじめ真空乾燥機で６０℃、約１時間乾燥し、水分などの微量不純物を除去した。各樹脂組成のシート上に、DCマグネトロンスパッタリング法により透明導電膜としてＩＴＯを製膜し、透明導電性金属酸化物積層基板を得た。透明導電膜の膜厚は約１２００ｎｍに調整した。また、このスパッタリングにおいては、質量比９０／１０のＩｎ2Ｏ3／ＳｎＯ2をターゲットとし、１０-3Ｐａまで排気し、体積比９２.５／７.５のアルゴン／酸素を導入ガスとし、室温下でDCマグネトロンスパッタリングを行った。成膜時間は約３０分とした。透明導電性金属酸化物積層基板の評価結果を表２に併記する。
[Examples 3, 4, 5, 6 and Comparative Example 2]
Using an F40 injection molding machine manufactured by Crockner Co., Ltd., (a) acrylic resin and (b) polylactic acid resin were extruded with arbitrary compositions, and flat plates (80 * 80 * 2 mmt) were prepared for each resin. The molding temperature was 260 ° C. About the sheet | seat (80x80x2mmt) of the transparent resin substrate, the sheet | seat was immersed in the commercially available hard coat liquid TKH-36A made from JPC, it pulled up, and the ultraviolet-ray was irradiated and the hard-coat layer was formed in the sheet | seat surface. The film thickness of the hard coat layer was adjusted to about 5 μm. Prior to film formation, the substrate was dried in a vacuum dryer at 60 ° C. for about 1 hour in advance to remove trace impurities such as moisture. On the sheet | seat of each resin composition, ITO was formed into a film as a transparent conductive film by DC magnetron sputtering method, and the transparent conductive metal oxide laminated substrate was obtained. The film thickness of the transparent conductive film was adjusted to about 1200 nm. In this sputtering, In2O3 / SnO2 with a mass ratio of 90/10 is used as a target, exhausted to 10-3 Pa, argon / oxygen with a volume ratio of 92.5 / 7.5 as an introduced gas, and DC magnetron at room temperature. Sputtering was performed. The film formation time was about 30 minutes. The evaluation results of the transparent conductive metal oxide multilayer substrate are also shown in Table 2.
［実施例７］
実施例１で得られたＳｉＯｘ膜の金属酸化物積層基板上に実施例３、４、５、６と同様にしてＩＴＯ膜の透明導電性金属酸化物積層基板を得た。この透明導電性金属酸化物積層基板の評価結果を表２に併記する。
[Example 7]
An ITO film transparent conductive metal oxide laminated substrate was obtained in the same manner as in Examples 3, 4, 5, and 6 on the SiOx film metal oxide laminated substrate obtained in Example 1. The evaluation results of this transparent conductive metal oxide multilayer substrate are also shown in Table 2.
本発明は金属酸化物膜を形成してなる金属酸化物積層基板に関するものであり、詳しくは透明導電膜を形成した透明導電性積層基板、すなわち光学特性、透明導電膜密着性、抵抗値の安定性、耐熱性に優れた透明導電性積層基板は、太陽電池の光電変換素子の窓電極、電磁シールドの電磁遮蔽膜、透明電波吸収体、透明タッチパネル等の入力装置の電極、液晶表示体，ＥＬ（エレクトロルミネセンス）発光体，ＥＣ（エレクトロクロミック）表示体等の透明電極などの基板を提供することが可能となる。 The present invention relates to a metal oxide laminated substrate formed with a metal oxide film, and more specifically, a transparent conductive laminated substrate on which a transparent conductive film is formed, that is, optical properties, transparent conductive film adhesion, and stability of resistance value. Transparent conductive laminated substrate with excellent heat resistance and heat resistance, such as window electrodes of photoelectric conversion elements of solar cells, electromagnetic shielding films of electromagnetic shields, transparent radio wave absorbers, electrodes of input devices such as transparent touch panels, liquid crystal displays, EL It is possible to provide a substrate such as a transparent electrode such as an (electroluminescence) light emitter or an EC (electrochromic) display.
Claims (6)
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| JP2006281871A JP2008094062A (en) | 2006-10-16 | 2006-10-16 | Metal oxide laminated substrate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110224A1 (en) * | 2009-03-27 | 2010-09-30 | リンテック株式会社 | Conductive zinc oxide multilayer body and method for producing same |
| JP2012000808A (en) * | 2010-06-15 | 2012-01-05 | Teijin Ltd | Transparent conductive laminate |
| JP2012192636A (en) * | 2011-03-17 | 2012-10-11 | Toray Ind Inc | Polylactic acid biaxially stretched film |
| JPWO2014129171A1 (en) * | 2013-02-20 | 2017-02-02 | 凸版印刷株式会社 | Transparent conductive film, touch panel and display device including the same |
| CN115449750A (en) * | 2022-08-10 | 2022-12-09 | 江西沃格光电股份有限公司 | Composite membrane, coated product, preparation method and application thereof |
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2006
- 2006-10-16 JP JP2006281871A patent/JP2008094062A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110224A1 (en) * | 2009-03-27 | 2010-09-30 | リンテック株式会社 | Conductive zinc oxide multilayer body and method for producing same |
| JP5373887B2 (en) * | 2009-03-27 | 2013-12-18 | リンテック株式会社 | Zinc oxide conductive laminate and method for producing the same |
| TWI462121B (en) * | 2009-03-27 | 2014-11-21 | Lintec Corp | Zinc oxide conductive laminate and manufacturing method thereof |
| JP2012000808A (en) * | 2010-06-15 | 2012-01-05 | Teijin Ltd | Transparent conductive laminate |
| JP2012192636A (en) * | 2011-03-17 | 2012-10-11 | Toray Ind Inc | Polylactic acid biaxially stretched film |
| JPWO2014129171A1 (en) * | 2013-02-20 | 2017-02-02 | 凸版印刷株式会社 | Transparent conductive film, touch panel and display device including the same |
| CN115449750A (en) * | 2022-08-10 | 2022-12-09 | 江西沃格光电股份有限公司 | Composite membrane, coated product, preparation method and application thereof |
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