JP5191097B2 - Polyester film for molding - Google Patents
Polyester film for molding Download PDFInfo
- Publication number
- JP5191097B2 JP5191097B2 JP2005513581A JP2005513581A JP5191097B2 JP 5191097 B2 JP5191097 B2 JP 5191097B2 JP 2005513581 A JP2005513581 A JP 2005513581A JP 2005513581 A JP2005513581 A JP 2005513581A JP 5191097 B2 JP5191097 B2 JP 5191097B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- molding
- polyester
- polyester film
- stretching
- 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.)
- Expired - Fee Related
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 57
- 238000000465 moulding Methods 0.000 title claims description 97
- 238000003860 storage Methods 0.000 claims abstract description 19
- 229920001634 Copolyester Polymers 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 103
- 238000001816 cooling Methods 0.000 claims description 36
- 229920000728 polyester Polymers 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- -1 polyethylene terephthalate Polymers 0.000 claims description 22
- 238000009998 heat setting Methods 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 230000001965 increasing effect Effects 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 230000007246 mechanism Effects 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 16
- 239000002245 particle Substances 0.000 description 42
- 238000010438 heat treatment Methods 0.000 description 36
- SFDGJDBLYNJMFI-UHFFFAOYSA-N 3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC=NC2=C1 SFDGJDBLYNJMFI-UHFFFAOYSA-N 0.000 description 27
- 238000007639 printing Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 4
- 239000011146 organic particle Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 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
- 230000008901 benefit Effects 0.000 description 2
- HTTLBYITFHMYFK-UHFFFAOYSA-N bentranil Chemical compound N=1C2=CC=CC=C2C(=O)OC=1C1=CC=CC=C1 HTTLBYITFHMYFK-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WKYQIWUAPDQQRV-UHFFFAOYSA-N 2-(3-nitrophenyl)-3,1-benzoxazin-4-one Chemical compound [O-][N+](=O)C1=CC=CC(C=2OC(=O)C3=CC=CC=C3N=2)=C1 WKYQIWUAPDQQRV-UHFFFAOYSA-N 0.000 description 1
- KIKBFYZALDDEEA-UHFFFAOYSA-N 2-(4-benzoylphenyl)-3,1-benzoxazin-4-one Chemical compound C=1C=C(C=2OC(=O)C3=CC=CC=C3N=2)C=CC=1C(=O)C1=CC=CC=C1 KIKBFYZALDDEEA-UHFFFAOYSA-N 0.000 description 1
- DOBFHWQIDTXPFM-UHFFFAOYSA-N 2-(4-methoxyphenyl)-3,1-benzoxazin-4-one Chemical compound C1=CC(OC)=CC=C1C1=NC2=CC=CC=C2C(=O)O1 DOBFHWQIDTXPFM-UHFFFAOYSA-N 0.000 description 1
- WDCDVVORESXHQH-UHFFFAOYSA-N 2-(4-nitrophenyl)-3,1-benzoxazin-4-one Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=NC2=CC=CC=C2C(=O)O1 WDCDVVORESXHQH-UHFFFAOYSA-N 0.000 description 1
- VLHWFGPIHRTPLY-UHFFFAOYSA-N 2-[2-(4-oxo-3,1-benzoxazin-2-yl)ethyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(CCC=3OC(=O)C4=CC=CC=C4N=3)=NC2=C1 VLHWFGPIHRTPLY-UHFFFAOYSA-N 0.000 description 1
- YXSKBXJKNVWUBF-UHFFFAOYSA-N 2-[3,5-bis(4-oxo-3,1-benzoxazin-2-yl)phenyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(C=3C=C(C=C(C=3)C=3OC(=O)C4=CC=CC=C4N=3)C=3OC(C4=CC=CC=C4N=3)=O)=NC2=C1 YXSKBXJKNVWUBF-UHFFFAOYSA-N 0.000 description 1
- SORNEPWIFZWRMH-UHFFFAOYSA-N 2-[3-(4-oxo-3,1-benzoxazin-2-yl)phenyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(C=3C=CC=C(C=3)C=3OC(C4=CC=CC=C4N=3)=O)=NC2=C1 SORNEPWIFZWRMH-UHFFFAOYSA-N 0.000 description 1
- OFLPBAZQIRUWFV-UHFFFAOYSA-N 2-[3-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 OFLPBAZQIRUWFV-UHFFFAOYSA-N 0.000 description 1
- UIBLWXYRKDJRSG-UHFFFAOYSA-N 2-[3-(5-cyanobenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(C=CC3=N2)C#N)=C1 UIBLWXYRKDJRSG-UHFFFAOYSA-N 0.000 description 1
- GSNJIHDWUJXETP-UHFFFAOYSA-N 2-[3-(5-tert-butylbenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(C=CC3=N2)C(C)(C)C)=C1 GSNJIHDWUJXETP-UHFFFAOYSA-N 0.000 description 1
- FVBOXNUYGKJKAI-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(C)(C)C1=CC(CCOC(=O)C(=C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O FVBOXNUYGKJKAI-UHFFFAOYSA-N 0.000 description 1
- JPHVHSYZNRQYKP-UHFFFAOYSA-N 2-[3-chloro-4-(4-oxo-3,1-benzoxazin-2-yl)phenyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(C=3C=C(C(=CC=3)C=3OC(=O)C4=CC=CC=C4N=3)Cl)=NC2=C1 JPHVHSYZNRQYKP-UHFFFAOYSA-N 0.000 description 1
- MPLFLOQPUPLZHI-UHFFFAOYSA-N 2-[3-methyl-4-(4-oxo-3,1-benzoxazin-2-yl)phenyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(C=3C=C(C(=CC=3)C=3OC(=O)C4=CC=CC=C4N=3)C)=NC2=C1 MPLFLOQPUPLZHI-UHFFFAOYSA-N 0.000 description 1
- XXKGLWFBWIYJEH-UHFFFAOYSA-N 2-[3-nitro-4-(4-oxo-3,1-benzoxazin-2-yl)phenyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(C=3C=C(C(=CC=3)C=3OC(=O)C4=CC=CC=C4N=3)[N+](=O)[O-])=NC2=C1 XXKGLWFBWIYJEH-UHFFFAOYSA-N 0.000 description 1
- IQDGOCFFOPHWLN-UHFFFAOYSA-N 2-[4-(4-oxo-3,1-benzoxazin-2-yl)butyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(CCCCC=3OC(=O)C4=CC=CC=C4N=3)=NC2=C1 IQDGOCFFOPHWLN-UHFFFAOYSA-N 0.000 description 1
- BBITXNWQALLODC-UHFFFAOYSA-N 2-[4-(4-oxo-3,1-benzoxazin-2-yl)phenyl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(C3=CC=C(C=C3)C=3OC(C4=CC=CC=C4N=3)=O)=NC2=C1 BBITXNWQALLODC-UHFFFAOYSA-N 0.000 description 1
- SAOSFCLPXMYGNW-UHFFFAOYSA-N 2-[4-hydroxy-3-(5-methoxybenzotriazol-2-yl)phenyl]ethyl 2-methylprop-2-enoate Chemical compound N1=C2C=C(OC)C=CC2=NN1C1=CC(CCOC(=O)C(C)=C)=CC=C1O SAOSFCLPXMYGNW-UHFFFAOYSA-N 0.000 description 1
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- WFMPKGCBPCILFP-UHFFFAOYSA-N 2-[5,7-bis(4-oxo-3,1-benzoxazin-2-yl)naphthalen-1-yl]-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(C3=CC=CC4=C(C=5OC(=O)C6=CC=CC=C6N=5)C=C(C=C43)C=3OC(C4=CC=CC=C4N=3)=O)=NC2=C1 WFMPKGCBPCILFP-UHFFFAOYSA-N 0.000 description 1
- PHBUSJPKDGHRSF-UHFFFAOYSA-N 2-butyl-3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC(CCCC)=NC2=C1 PHBUSJPKDGHRSF-UHFFFAOYSA-N 0.000 description 1
- MAKPFHFTCPNVEO-UHFFFAOYSA-N 2-cyclohexyl-3,1-benzoxazin-4-one Chemical compound N=1C2=CC=CC=C2C(=O)OC=1C1CCCCC1 MAKPFHFTCPNVEO-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- KARGMXZXPAWXQJ-UHFFFAOYSA-N 3-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 KARGMXZXPAWXQJ-UHFFFAOYSA-N 0.000 description 1
- FRTQVKXQJAQXQY-UHFFFAOYSA-N 6-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 FRTQVKXQJAQXQY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- BRTMLDAYGUXKNK-UHFFFAOYSA-N [3-(benzotriazol-2-yl)-4-hydroxyphenyl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 BRTMLDAYGUXKNK-UHFFFAOYSA-N 0.000 description 1
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- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
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- IVKNUIVDQMARCO-UHFFFAOYSA-N oxazin-4-one Chemical compound O=C1C=CON=C1 IVKNUIVDQMARCO-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【技術分野】
【０００１】
本発明は、成型性、特に低い温度および低い圧力での成型性に優れ、かつ耐溶剤性や耐熱性に優れ、さらに環境負荷の小さい、家電、自動車の銘板用または建材用部材として好適に用いることのできる成型用ポリエステルフィルムに関する。
【背景技術】
【０００２】
従来、成型用シートとしては、ポリ塩化ビニルフィルムが代表的であり、加工性などの点で好ましく使用されてきた。一方、該フィルムは火災などによりフィルムが燃焼した際の有毒ガス発生の問題、可塑剤のブリードアウトなどの問題があり、近年の耐環境性のニーズにより、環境負荷の小さい新しい素材が求められてきている。
【０００３】
上記要求を満足させるために、非塩素系素材としてポリエステル、ポリカーボネートおよびアクリル系樹脂よるなる未延伸シートが広い分野において使用されてきている。特に、ポリエステル樹脂よりなる未延伸シートは、機械的特性、透明性が良く、かつ経済性に優れており注目されている。例えば、ポリエチレンテレフタレートにおけるエチレングリコール成分の約３０モル％を１，４−シクロヘキサンジメタノールで置換した、実質的に非結晶のポリエステル系樹脂を構成成分とする未延伸ポリエステル系シートが開示されている（例えば、特許文献１〜５を参照）。
【０００４】
【特許文献１】
特開平９−１５６２６７号公報
【特許文献２】
特開２００１−７１６６９号公報
【特許文献３】
特開２００１−８０２５１号公報
【特許文献４】
特開２００１−１２９９５１号公報
【特許文献５】
特開２００２−２４９６５２号公報
【０００５】
上記の未延伸ポリエステルシートは、成型性やラミネート適性に関しては市場要求を満足するものではあるが、未延伸シートであるため、耐熱性や耐溶剤性が充分ではなく市場の高度な要求を満足させるまでには至っていない。
【０００６】
上記の課題を解決する方法として、二軸延伸ポリエチレンテレフタレートフィルムを用いる方法が開示されている（例えば、特許文献６〜９を参照）。
【０００７】
【特許文献６】
特開平９−１８７９０３号公報
【特許文献７】
特開平１０−２９６９３７号公報
【特許文献８】
特開平１１−１０８１６号公報
【特許文献９】
特開平１１−２６８２１５号公報
【０００８】
しかしながら、上記方法は、耐熱性や耐溶剤性は改善されるものの、成型性が不十分となり、総合的な品質のバランスの点で、市場要求を満足させるものではなかった。
【０００９】
上記課題を解決する方法として、フィルムの１００％伸張時応力を特定化する方法が開示されている（例えば、特許文献１０を参照）
【００１０】
【特許文献１０】
特開２００１−３４７５６５号公報
【００１１】
該方法は前記の方法に比べ、成型性は改善されているものの、成型性に関する市場の高度な要求に十分に答えられるレベルには達していない。特に、成型温度の低温化に適合できる成型性や得られた成型品の仕上がり性に課題が残されていた。
【００１２】
本発明者等は、上記の課題解決について検討をし、すでに、特定した組成の共重合ポリエステル樹脂を原料とし、かつフィルムの１００％伸張時応力を特定化することにより上記課題を改善する方法を提案している（例えば、特許文献１１、１２を参照）。
【００１３】
【特許文献１１】
特願２００２−２３３６９４
【特許文献１２】
特願２００３−３０９８９４
【００１４】
これらの方法により成型時の成型圧力の高い金型成型法においては、市場要求を満たす成型温度の低温化に適合できる成型性や得られた成型品の仕上がり性は大幅に改善することができる。しかしながら、市場要求が近年強くなっている圧空成型法や真空成型法等の成型時の成型圧力が低い成型方法の場合、成型品の仕上がり性をさらに改善することが要望されている。
【発明の開示】
【発明が解決しようとする課題】
【００１５】
本発明の目的は、前記の従来技術における課題を解決するものであり、成型性、特に低い温度および低い圧力での成型性に優れ、かつ耐溶剤性や耐熱性に優れ、さらに環境負荷の小さい、成型用ポリエステルフィルムを提供することにある。
【課題を解決するための手段】
【００１６】
上記の課題を解決することができる本発明の成型用ポリエステルフィルムは、以下の構成からなる。
【００１７】
すなわち、本発明の第１の発明は、二軸配向ポリエステルフィルムよりなる成型用ポリエステルフィルムであって、前記フィルムは共重合ポリエステルを構成成分とし、
（１）構成成分となる共重合ポリエステルは、テレフタル酸と、エチレングリコールと、共重合成分としてネオペンチルグリコール及び／または１、４−シクロヘキサンジメタノールからなり、
（２）前記共重合ポリエステル中、共重合成分は１〜４０モル％であり、
（３）前記フィルムの融点が２００〜２４５℃であり、
（４）フィルムの長手方向及び幅方向における１００％伸張時応力が、いずれも２５℃において１０〜１０００ＭＰａ及び１００℃において１〜１００ＭＰａであり、
（５）フィルムの長手方向及び幅方向における貯蔵粘弾性率（Ｅ′）が、いずれも１００℃において１０〜１０００ＭＰａで、かつ１８０℃において５〜４０ＭＰａであり、
（６）フィルムの長手方向における熱変形率（初期荷重４９ｍＮ）が、１７５℃において−３％〜＋３％である、
ことを特徴とする成型用ポリエステルフィルムである。
第２の発明は、前記フィルムが前記共重合ポリエステルとホモポリエステルをブレンドしてなり、
前記ホモポリエステルが、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、もしくはポリブチレンテレフタレートであることを特徴とする第１の発明に記載の成型用ポリエステルフィルムである。
第３の発明は、前記成型用ポリエステルフィルムは、フィルムの長手方向及び横方向の１５０℃での熱収縮率が６．０％以下であることを特徴とする第１または２の発明に記載の成型用ポリエステルフィルムである。
第４の発明は、前記フィルムが逐次二軸延伸法により得られるものであり、縦延伸後に行う横延伸において、横延伸の後半部では延伸温度を横延伸の前半部の延伸温度に対して−５〜−４０℃の範囲で行なうことを特徴とする第１〜３のいずれかの発明に記載の成型用ポリエステルフィルムである。
第５の発明は、前記フィルムが１２０〜２４５℃で熱処理を行うものであり、
（ａ）クリップ部分に熱遮蔽壁を設ける方法、
（ｂ）クリップ冷却機構をテンターに付加する方法、
（ｃ）熱固定後の冷却区間を長く設定し、フィルム全体の冷却を十分行う方法、
（ｄ）冷却区間の長さ、区画数を増やして、冷却効率を増加させる方法、または
（ｅ）クリップの戻り部分が炉の外側を走行するタイプを用いてクリップの冷却を強化する方法、
を用いてクリップの近傍を冷却してから、テンター出口でクリップからフィルムを開放して得られる第１〜４のいずれかの発明に記載の成型用ポリエステルフィルムである。
第６の発明は、第１〜５のいずれかの発明に記載の成型用ポリエステルフィルムを成型してなる成型体である。
【発明を実施するための最良の形態】
【００１８】
本発明における成型用ポリエステルフィルムは、フィルムの長手方向及び幅方向における２５℃での１００％伸張時応力（Ｆ１００２５）がいずれも１０〜１０００ＭＰａであり、かつフィルムの長手方向及び幅方向における１００℃での１００％伸張時応力（Ｆ１００１００）がいずれも１〜１００ＭＰａであることが重要である。Ｆ１００２５またはＦ１００１００が前記範囲の上限を超えると成型性が低下するので好ましくない。一方、前記範囲の下限未満では、成型品を使用する際の弾性や形態安定性が低下するので好ましくない。
【００１９】
フィルムの長手方向及び幅方向におけるＦ１００２５は１０〜５００ＭＰａが好ましく、１０〜２００ＭＰａがより好ましく、１０〜１５０ＭＰａが特に好ましい。
【００２０】
また、フィルムの長手方向及び幅方向におけるＦ１００１００の上限は、成型性の点から、９０ＭＰａが好ましく、８０ＭＰａがより好ましく、７０ＭＰａが特に好ましい。一方、Ｆ１００１００の下限は、成型品を使用する際の弾性や形態安定性の点から、２ＭＰａが好ましく、３ＭＰａがより好ましく、５ＭＰａが特に好ましい。
【００２１】
本発明における成型用ポリエステルフィルムは、フィルムの長手方向及び幅方向における貯蔵粘弾性率（Ｅ′）が、いずれも１００℃において１０〜１０００ＭＰａで、かつ１８０℃において５〜４０ＭＰａであることが重要である。貯蔵粘弾性率（Ｅ′）を前記範囲内に制御することにより、成型性、特に低い温度および低い圧力での成型性が確保でき、未延伸シートでしか適用できなかった圧空成型法や真空成型法等の１０気圧以下の低い成型圧力の成型法でも仕上がり性の良好な成型品が得られ、かつ寸法安定性の良好な成型品を得ることができる。
【００２２】
前記の１００℃と１８０℃における貯蔵粘弾性率（Ｅ′）は、低温低圧下での成型性と、寸法安定性などに影響するパラメータである。特に、１００℃における貯蔵粘弾性率（Ｅ′）は低温低圧下での成型性と関連があり、１８０℃における貯蔵粘弾性率（Ｅ′）は寸法安定性と関連があることを本発明者らは新たに知見した。前記の特定の温度における貯蔵粘弾性率（Ｅ′）が前記のフィルム特性を発現させるための重要な指標になっている理由について、本発明者らは、それらのメカニズムを明確に解明できていないが、フィルムを構成するポリエステルに含まれる共重合成分の分子構造が寄与しているためであろうと推定している。
【００２３】
フィルムの長手方向及び幅方向における貯蔵粘弾性率（Ｅ′）は、フィルムの両方向とも１００℃において２０〜９００ＭＰａが好ましく、３０〜８００ＭＰａがより好ましく、４０〜７００ＭＰａが特に好ましい。また、１８０℃における貯蔵粘弾性率（Ｅ′）は７〜３８ＭＰａが好ましく、９〜３５ＭＰａがより好ましく、１０〜３０ＭＰａが特に好ましい。
【００２４】
また、本発明における成型用ポリエステルフィルムは、フィルムの長手方向における熱変形率（初期荷重４９ｍＮ）が、１７５℃において−３％〜＋３％であることが重要である。ここで、フィルムの熱変形率は、初期荷重４９ｍＮでのフィルムの変形率の温度依存性を、熱機械分析装置（ＴＭＡ）を用いて昇温速度５℃／分で測定し求めたものである。本特性を満たすことにより、成型品の耐溶剤性を改善することができる。例えば、圧空成型法や真空成型法等の１０気圧以下の低い成型圧力の成型法でも、仕上がり性の良好な成型品が得られる。しかしながら、ポリエステル、ポリカーボネートおよびアクリル系樹脂より得られた未延伸シートは本特性値が前記の範囲外となる。フィルムの微小張力（初期荷重４９ｍＮ）下での熱変形率と耐溶剤性という一見相互に無関係と考えられる特性が相関を示す理由は明確ではない。しかしながら、本発明の成型用ポリエステルフィルムは二軸配向されており、延伸による分子配向の発現により耐溶剤性や耐熱変形性が改善されたためと本発明者らは推察している。フィルムの長手方向における熱変形率（初期荷重４９ｍＮ）は、１８０℃において−３％〜＋３％であることが好ましく、１８５℃において−３％〜＋３％であることが特に好ましい。
【００２５】
前記の（１）フィルムの長手方向及び幅方向における１００％伸張時応力、（２）フィルムの長手方向及び幅方向における貯蔵粘弾性率（Ｅ′）、（３）フィルムの長手方向における微小張力下での熱変形率は、前記の範囲を同時に満足することが重要である。フィルムがこれらの特性を同時に満足することにより、前記の各種の市場要求を満足する効果を有する本発明の成型用ポリエステルフィルムを得ることができる。
【００２６】
本発明の成型用ポリエステルフィルムの基材は、共重合ポリエステルを含む二軸延伸ポリエステルフィルムである。
【００２７】
本発明の成型用ポリエステルフィルムは、芳香族ジカルボン酸成分と、エチレングリコール及び、分岐状脂肪族グリコール及び／又は脂環族グリコールを含むグリコール成分とから構成される共重合ポリエステルを、基材フィルム原料の一部あるいは全部に用いることが好ましい。
【００２８】
前記共重合ポリエステルは、芳香族ジカルボン酸成分がテレフタル酸からなる。
【００２９】
また、分岐状脂肪族グリコールとしては、ネオペンチルグリコールである。脂環族グリコールとしては、１，４−シクロヘキサンジメタノールである。
【００３０】
前記共重合ポリエステルを製造する際に用いる触媒としては、例えば、アルカリ土類金属化合物、マンガン化合物、コバルト化合物、アルミニウム化合物、アンチモン化合物、チタン化合物、チタン／ケイ素複合酸化物、ゲルマニウム化合物などが使用できる。これらのなかでも、チタン化合物、アンチモン化合物、ゲルマニウム化合物が触媒活性の点から好ましい。
【００３１】
前記共重合ポリエステルを製造する際に、熱安定剤としてリン化合物を添加することが好ましい。前記リン化合物としては、例えばリン酸、亜リン酸などが好ましい。
【００３２】
前記共重合ポリエステルは、成型性、接着性、製膜安定性の点から、固有粘度が０．５０ｄｌ／ｇ以上であることが好ましく、さらに好ましくは０．５５ｄｌ／ｇ以上、特に好ましくは０．６０ｄｌ／ｇ以上である。固有粘度が０．５０ｄｌ／ｇ未満では、成型性が低下する傾向がある。また、メルトラインに異物除去のためのフィルターを設けた場合、溶融樹脂の押出時における吐出安定性の点から、固有粘度の上限を１．０ｄｌ／ｇとすることが好ましい。
【００３３】
本発明の成型用ポリエステルフィルムは、前記共重合ポリエステルをそのままフィルム原料として用いてもよいし、共重合成分が多い共重合ポリエステルをホモポリエステルとブレンドして、共重合成分量を調整しても構わない。
【００３４】
特に、後者のブレンド法を用いてフィルムを製膜することによって、共重合ポリエステルのみを用いた場合と同等の柔軟性を維持しながら透明性と高い融点（耐熱性）を実現することができる。また、高融点のホモポリエステル（例えば、ポリエチレンテレフタレート）のみを用いた場合に対し、高い透明性を維持しながら柔軟性と実用上問題のない融点（耐熱性）を実現することができる。
【００３５】
また、前記共重合ポリエステルを２種以上ブレンドして、本発明の成型用ポリエステルフィルムの原料として使用することは、成型性の点から好ましい。
【００３６】
前記のポリエステルフィルムの融点は、耐熱性及び成型性の点から、２００〜２４５℃である。使用するポリマーの種類や組成、さらに製膜条件を前記融点の範囲内に制御することにより、成型性と仕上がり性とのバランスが取れ、高品位の成型品を経済的に生産することができる。ここで、融点とは、いわゆる示差走査熱量測定（ＤＳＣ）の１次昇温時に検出される融解時の吸熱ピーク温度のことである。該融点は、示差走査熱量分析装置（デュポン社製、Ｖ４．ＯＢ２０００型）を用いて、昇温速度２０℃／分で測定して求めた。融点の下限値は、２１０℃がさらに好ましく、特に好ましくは２３０℃である。融点が２００℃未満であると、耐熱性が悪化する傾向がある。そのため、成型時や成型品の使用時に高温にさらされた際に、問題となる場合がある。
【００３７】
前記融点の上限値は、耐熱性の点からは高いほうが良いが、ポリエチレンテレフタレート単位を主体とした場合、融点が２４５℃を超えるフィルムでは、成型性が悪化する傾向がある。また、透明性も悪化する傾向がある。さらに、高度な成型性や透明性を得るためには、融点の上限を２４０℃に制御することが好ましい。
【００３８】
また、フィルムの滑り性や巻き取り性などのハンドリング性を改善するために、フィルム表面に凹凸を形成させることが好ましい。フィルム表面に凹凸を形成させる方法としては、一般にフィルム中に粒子を含有させる方法が用いられる。
【００３９】
前記粒子としては、平均粒子径が０．０１〜１０μｍの内部析出粒子、無機粒子及び／又は有機粒子などの外部粒子が挙げられる。平均粒子径が１０μｍを越える粒子を使用すると、フィルムの欠陥が生じ易くなり、意匠性や透明性が悪化する傾向がある。一方、平均粒子径が０．０１μｍ未満の粒子では、フィルムの滑り性や巻き取り性などのハンドリング性が低下する傾向がある。前記粒子の平均粒子径は、滑り性や巻き取り性などのハンドリング性の点から、下限は０．１０μｍとすることがさらに好ましく、特に好ましくは０．５０μｍである。一方、前記粒子の平均粒子径は、透明性や粗大突起によるフィルム欠点の低減の点から、上限は５μｍとすることがさらに好ましく、特に好ましくは２μｍである。
【００４０】
なお、粒子の平均粒子径は、少なくとも２００個以上の粒子を電子顕微鏡法により複数枚写真撮影し、ＯＨＰフィルムに粒子の輪郭をトレースし、該トレース像を画像解析装置にて円相当径に換算して算出する。
【００４１】
前記外部粒子としては、例えば、湿式及び乾式シリカ、コロイダルシリカ、珪酸アルミ、酸化チタン、炭酸カルシウム、リン酸カルシウム、硫酸バリウム、アルミナ、マイカ、カオリン、クレー、ヒドロキシアパタイト等の無機粒子及びスチレン、シリコーン、アクリル酸類等を構成成分とする有機粒子等を使用することができる。なかでも、乾式、湿式及び乾式コロイド状シリカ、アルミナ等の無機粒子及びスチレン、シリコーン、アクリル酸、メタクリル酸、ポリエステル、ジビニルベンゼン等を構成成分とする有機粒子等が、好ましく使用される。これらの内部粒子、無機粒子及び／又は有機粒子は二種以上を、本願発明で規定した特性を損ねない範囲内で併用してもよい。
【００４２】
さらに、前記粒子のフィルム中での含有量は０．００１〜１０質量％の範囲であることが好ましい。０．００１質量％未満の場合、フィルムの滑り性が悪化したり、巻き取りが困難となったりするなどハンドリング性が低下しやすくなる。一方、１０質量％を越えると、粗大突起の形成、製膜性や透明性の悪化などの原因となりやすい。
【００４３】
また、フィルム中に含有させる粒子は、一般的には屈折率がポリエステルと異なるため、フィルムの透明性を低下させる要因となる。
【００４４】
成型品は意匠性を高めるために、フィルムを成型する前にフィルム表面に印刷が施される場合が多い。このような印刷層は、成型用フィルムの裏側に施されることが多いため、印刷鮮明性の点から、フィルムの透明性が高いことが要望されている。
【００４５】
そのため、フィルムのハンドリング性を維持しながら、高度な透明性を得るために、基材フィルム中に実質的に粒子を含有させず、厚みが０．０１〜５μｍの表面層にのみ粒子を含有させることが有効である。
【００４６】
なお、上記でいう「基材フィルム中に実質的に粒子を含有させず」とは、例えば無機粒子の場合、ケイ光Ｘ線分析で無機元素を定量した場合に検出限界以下となる含有量を意味する。これは意識的に粒子を基材フィルムに添加させなくても、外来異物由来のコンタミ成分などが混入する場合があるためである。
【００４７】
厚みの薄い表面層の形成は、コーティング法または共押出し法によって行うことができる。
【００４８】
なかでも、コーティング法の場合、粒子を含有する接着性改質樹脂からなる組成物を塗布層として用いることで、印刷層との密着性も改良することができるので好ましい方法である。前記の接着性改質樹脂としては、ポリエステル、ポリウレタン、アクリル系重合体および／またはそれらの共重合体から選ばれた少なくとも１種からなる樹脂が好ましい。
【００４９】
さらに、基材フィルムと接着性改質層との密着性をさらに向上させるために、予め基材フィルム表面を表面処理し、この表面処理面に接着性改質層を設けてもよい。表面処理の方法としては、例えば、（１）コロナ放電処理、プラズマ放電処理、紫外線（ＵＶ）照射処理、放射線（ＥＢ）照射処理などの活性エネルギー線照射による方法、（２）火炎処理、（３）ＰＶＤ、ＣＶＤなどのベーパーデポジット法、などが挙げられる。
【００５０】
このような積層構造とすることで、フィルムのハンドリング性を維持しながら、フィルムの厚みｄ（μｍ）に対するヘイズＨ（％）の比（Ｈ／ｄ）を０．０１０未満とすることができる。
【００５１】
前記成型用ポリエステルフィルムは、特に透明性が必要とされる用途に使用する場合には、フィルムの厚みｄ（μｍ）に対するヘイズＨ（％）の比（Ｈ／ｄ）を０．０１０未満とすることが、透明性及び印刷鮮明性の点から好ましい。前記Ｈ／ｄは、０を越え０．０１０未満であることがより好ましく、特に好ましくは０を越え０．００９以下である。なお、本願発明においては、前記Ｈ／ｄの数値は小数第３位で記載しているが、小数第４位以降は四捨五入せず、切り捨てる。例えば、０．００９９であっても０．００９とする。
【００５２】
前記Ｈ／ｄの下限値はゼロに近いほど透明性や印刷鮮明性の点から好ましい。しかしながら、重要最小限の凹凸をフィルム表面に形成しないと、滑り性や巻き性などのハンドリング性が悪化し、フィルム表面に傷がつく場合や生産性が悪化する場合がある。したがって、Ｈ／ｄの下限値を０．００１とすることが好ましく、特に好ましくは０．００５である。また、バックライトを用いる透光銘板の場合には、より高度な透明性が要求されるので、前記Ｈ／ｄはさらにゼロに近いほど好ましい。
【００５３】
前記表面層に含有させる粒子としては、前記で記載した粒子と同様のものを使用することができる。粒子のなかでも、シリカ粒子、ガラスフィラー、シリカ−アルミナ複合酸化物粒子は屈折率がポリエステルに比較的近いため、透明性の点から特に好適である。
【００５４】
また、前記表面層に平均粒子径が１０μｍを越える粒子を含有させると、フィルム表面に粗大突起が形成される頻度が増加し、意匠性が悪化する傾向がある。一方、平均粒子径が０．０１μｍ未満の粒子では、フィルムの滑り性や巻き取り性などのハンドリング性が低下する傾向がある。前記粒子の平均粒子径の好ましい範囲は、基材フィルム中に粒子を含有させる場合と同じである。
【００５５】
さらに、前記表面層における粒子含有量は、０．０１〜２５質量％の範囲であることが好ましい。０．０１質量％未満の場合、フィルムの滑り性が悪化したり、巻き取りが困難となったりするなどハンドリング性が低下しやすくなる。一方、２５質量％を越えると、透明性や塗布性が悪化しやすくなる。
【００５６】
本発明のポリエステルフィルムは、他の機能を付与するために、種類の異なるポリエステルを用い、公知の方法で積層構造とすることができる。かかる積層フィルムの形態は、特に限定されないが、例えば、Ａ／Ｂの２種２層構成、Ｂ／Ａ／Ｂ構成の２種３層構成、Ｃ／Ａ／Ｂの３種３層構成の積層形態が挙げられる
【００５７】
本発明の成型用ポリエステルフィルムは、二軸延伸フィルムであることが重要である。本発明においては、二軸延伸による分子配向により、前記のフィルムの微小張力（初期荷重４９ｍＮ）下での熱変形率を本発明の範囲内にすることができ、未延伸シートの欠点である耐溶剤性や寸法安定性が改善される。すなわち、未延伸シートの成型性の良さを維持しつつ、未延伸シートの欠点である耐溶剤性や耐熱性を改善したのが本発明の特徴の一つである。
【００５８】
前記ポリエステル基材フィルムの製造方法としては、特に限定されないが、例えばポリエステル樹脂を必要に応じて乾燥した後、公知の溶融押出機に供給し、スリット状のダイからシート状に押出し、静電印加などの方式によりキャスティングドラムに密着させ、冷却固化し、未延伸シートを得た後、かかる未延伸シートを二軸延伸する方法が例示される。
【００５９】
二軸延伸方法としては、未延伸シートをフィルムの長手方向（ＭＤ）及び幅方向（ＴＤ）に延伸、熱処理し、目的とする面内配向度を有する二軸延伸フィルムを得る方法が採用される。これらの方式の中でも、フィルム品質の点で、長手方向に延伸した後、幅方向に延伸するＭＤ／ＴＤ法、又は幅方向に延伸した後、長手方向に延伸するＴＤ／ＭＤ法などの逐次二軸延伸方式、長手方向及び幅方向をほぼ同時に延伸していく同時二軸延伸方式が望ましい。また、同時二軸延伸法の場合、リニアモーターで駆動するテンターを用いてもよい。さらに、必要に応じて、同一方向の延伸を多段階に分けて行う多段延伸法を用いても構わない。
【００６０】
二軸延伸する際のフィルム延伸倍率としては、長手方向と幅方向に１．６〜４．２倍とすることが好ましく、特に好ましくは１．７〜４．０倍である。この場合、長手方向と幅方向の延伸倍率はどちらを大きくしてもよいし、同一倍率としてもよい。長手方向の延伸倍率は２．８〜４．０倍、幅方向の延伸倍率は３．０〜４．５倍で行うことがより好ましい。
【００６１】
本発明の成型用ポリエステルフィルムを製造する際の延伸条件は、特に限定されるものではない。しかしながら、本発明で規定した上記特性を満足させるためには、例えば、下記の条件を採用することが選択することが好ましい。
【００６２】
縦延伸においては、後の横延伸がスムースにできるように、延伸温度は５０〜１１０℃、延伸倍率は１．６〜４．０倍とすることがさらに好ましい。
【００６３】
通常、ポリエチレンテレフタレートを延伸する際に、適切な条件に比べ延伸温度が低い場合は、横延伸の開始初期で急激に降伏応力が高くなるため、延伸ができない。また、たとえ延伸ができても厚みや延伸倍率が不均一になりやすいため好ましくない。
【００６４】
また、適切な条件に比べ延伸温度が高い場合は初期の応力は低くなるが、延伸倍率が高くなっても応力は高くならない。そのため、２５℃における１００％伸張時応力が小さいフィルムとなる。よって、最適な延伸温度をとることにより、延伸性を確保しながら配向の高いフィルムを得ることができる。
【００６５】
しかしながら、前記共重合ポリエステルが共重合成分を１〜４０モル％含む場合、降伏応力をなくすように延伸温度を高くしていくと、延伸応力は急激に低下する。特に、延伸の後半でも応力が高くならないため、配向が高くならず、２５℃における１００％伸張時応力が低下する。
【００６６】
このような現象は、フィルムの厚さが６０〜５００μｍで発生しやすく、特に厚みが１００〜３００μｍのフィルムで顕著に見られる。そのため、本発明の共重合したポリエステルを用いたフィルムの場合、横方向の延伸温度は、以下の条件とすることが好ましい。
【００６７】
まず、予熱温度は５０℃〜１５０℃とすることが好ましい。次いで、横延伸の前半部では延伸温度は予熱温度に対して−２０℃〜＋２５℃とすることが好ましく、特に好ましくは−１５℃〜＋２５℃とする。また、横延伸の後半部では、延伸温度は前半部の延伸温度に対して−１０℃〜−４０℃とすることが好ましい。このような条件を採用することにより、横延伸の前半では降伏応力が小さいため延伸しやすく、また後半では配向しやすくなる。なお、横方向の延伸倍率は、２．５〜５．０倍とすることが好ましい。その結果、本発明で規定したＦ１００２５やＦ１００１００を満足するフィルムを得ることが可能である。
【００６８】
さらに、二軸延伸後にフィルムの熱処理を行うが、この熱処理は、オーブン中、あるいは、加熱されたロール上など、従来公知の方法で行うことができる。また、熱処理温度及び熱処理時間は必要とされる熱収縮率のレベルによって任意に設定することができる。熱処理温度は１２０〜２４５℃の範囲が好ましく、特に好ましくは１５０〜２４０℃である。熱処理時間は、１〜６０秒間行うことが好ましい。なお、かかる熱処理はフィルムをその長手方向及び／又は幅方向に弛緩させつつ行ってもよい。
【００６９】
フィルムの長手方向及び横方向の１５０℃での熱収縮率を小さくするためには、熱処理温度を高くすること、熱処理時間を長くすること、弛緩処理を行うことが好ましい。具体的には、フィルムの長手方向及び幅方向における１５０℃での熱収縮率を６．０％以下とするためには、熱処理温度は２００〜２２０℃で、弛緩率１〜８％で弛緩させながら行うことが好ましい。さらに、再延伸を各方向に対して１回以上行ってもよく、その後熱処理を行ってもよい。
【００７０】
フィルムの長手方向及び横方向の１５０℃での熱収縮率を小さくするために、製造ラインを長くして熱処理時間を長くすることは設備上の制約により困難である。また、フィルムの送り速度を遅くすると、生産性が低下してしまう。このように、延伸区間までは区間温度を１００℃近傍とかなり低温にする必要がある一方で、熱固定では２００℃程度の高温に速やかに昇温する必要がある。したがって、該課題を解決する方策として熱処理ゾーンに遠赤外線ヒーターを設置し加熱を補強することが好ましい実施態様として推奨される。
【００７１】
さらに、延伸区間と熱固定区間の間に１ｍ以上の断熱区間を設け、断熱区間以後の加熱効率を上げる方法が挙げられる。具体的には、区間ごとの仕切りを強化して熱流の漏れを小さくすることで加熱効率を上げることができる。また、風量のバランス及び強さを調整することにより、風量を確保しつつ、オーブン内圧力を調整し、熱流の漏れを抑制する方法を用いてもよい。また、熱風加熱では不足する加熱に関しては強加熱区間に赤外線ヒーターを付加する方法も好適である。そのほかに、熱固定区間の長さ、区画数を増やすことで、加熱量を増加させる。などの方法も有効である。
【００７２】
本発明の成型用ポリエステルフィルムは、フィルムの長手方向及び幅方向における貯蔵粘弾性率（Ｅ′）が、いずれも１００℃において１０〜１０００ＭＰａで、かつ１８０℃において５〜４０ＭＰａである。このような貯蔵粘弾性率（Ｅ′）を達成するためには、基材として前記の共重合ポリエステルを含む二軸延伸フィルムを製造する際に、フィルムの面配向度を特定範囲に制御することも重要である。すなわち、フィルムの面配向度を０．１００以下と低くすることが好ましく、特に好ましくは０．００１〜０．０９０に制御する。このように面配向度を低くすることにより、前記のフィルムの貯蔵弾性率（Ｅ′）を小さくすることができる。
【００７３】
しかしながら、単にフィルムの面配向度を低くしただけでは、１８０℃におけるフィルムの貯蔵粘弾性率（Ｅ′）が小さくなりすぎる。本発明の好ましい実施態様である分岐状脂肪族グリコール及び／又は脂環族グリコールを共重合成分とする共重合ポリエステルをフィルム原料として用いることにより、該グリコール類の分子構造の嵩高さにより高温での分子運動性を抑制し、かつフィルムの面配向度を低くする特定の延伸条件を用いることによる相乗手段により、前記の１８０℃におけるフィルムの貯蔵粘弾性率（Ｅ′）を前記範囲に制御することができる。
【００７４】
上記のごとく基材フィルムの面配向度を低いレベルに設定することが好ましい実施態様の一つであるが、該特性を付与する手段も限定はされず任意である。一般に、面配向度を下げる手段としては延伸倍率を下げる方法と熱固定温度を上げる方法が知られているが、前者の方法はフィルムの厚み斑が悪化するので好ましくない。したがって、後者の方法が好ましい。後者の場合は前記の課題が生ずるが、好ましい実施態様として例示した方法等で回避できる。また、本発明においては基材フィルムとして共重合ポリエステルを用いる必要があり、融点が均一重合体に比して低いため、熱固定温度を高くすると、横延伸工程でフィルムを保持するクリップにフィルムが融着しやすくなる。したがって、テンター出口でクリップがフィルムを開放するときにクリップ近傍が充分に冷却することが重要である。具体的には、フィルムとクリップとの融着を防止するために、（１）クリップが加熱されにくいように、クリップ部分に熱遮蔽壁を設ける方法、（２）クリップ冷却機構をテンターに付加する方法、（３）冷却能力の強化を行うために熱固定後の冷却区間を長く設定し、フィルム全体の冷却を十分行う方法、（４）冷却区間の長さ、区画数を増やすことで、冷却効率を増加させる方法、（５）クリップの戻り部分が炉の外側を走行するタイプを用いてクリップの冷却を強化する方法、などを採用することが好ましい。
【００７５】
また、本発明においては、基材フィルムは波長３８０ｎｍ以下における光線透過率が９０％以下であることが好ましい。波長３９０ｎｍ以下における光線透過率が９０％以下であることがより好ましく、波長４００ｎｍ以下における光線透過率が９０％以下であることが特に好ましい。該特性の付与により成型用ポリエステルフィルム、特に、該フィルムに印刷を施した場合に印刷層の耐光性が向上する。
【００７６】
上記の波長３８０ｎｍ以下における光線透過率が９０％以下にする方法は限定なく任意であるが、基材フィルムの構成層のいずれかに紫外線吸収剤を配合する方法が推奨される。該方法において用いられる紫外線吸収剤は前記の特性を付与できるものであれば限定なく適宜選択すれば良い。無機系、有機系のどちらでも構わない。有機系紫外線吸収剤としては、ベンゾトアゾール系、ベンゾフェノン系、環状イミノエステル系等、及びその組み合わせが挙げられる。耐熱性の観点からはベンゾトアゾール系、環状イミノエステル系が好ましい。２種以上の紫外線吸収剤を併用した場合には、別々の波長の紫外線を同時に吸収させることができるので、いっそう紫外線吸収効果を改善することができる。
【００７７】
ベンゾトリアゾール系紫外線吸収剤としては、例えば、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシメチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシプロピル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシヘキシル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル−５′−（メタクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−ｔｅｒｔ−ブチル−３′−（メタクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシエチル）フェニル］−５−クロロ−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシエチル）フェニル］−５−メトキシ−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシエチル）フェニル］−５−シアノ−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシエチル）フェニル］−５−ｔｅｒｔ−ブチル−２Ｈ−ベンゾトリアゾール、２−［２′−ヒドロキシ−５′−（メタクリロイルオキシエチル）フェニル］−５−ニトロ−２Ｈ−ベンゾトリアゾールなどが挙げられるが、特にこれらに限定されるものではない。
【００７８】
環状イミノエステル系紫外線吸収剤としては、例えば、２，２′−（１，４−フェニレン）ビス（４Ｈ−３，１−ベンズオキサジノン−４−オン）、２−メチル−３，１−ベンゾオキサジン−４−オン、２−ブチル−３，１−ベンゾオキサジン−４−オン、２−フェニル−３，１−ベンゾオキサジン−４−オン、２−（１−又は２−ナフチル）−３，１−ベンゾオキサジン−４−オン、２−（４−ビフェニル）−３，１−ベンゾオキサジン−４−オン、２−ｐ−ニトロフェニル−３，１−ベンゾオキサジン−４−オン、２−ｍ−ニトロフェニル−３，１−ベンゾオキサジン−４−オン、２−ｐ−ベンゾイルフェニル−３，１−ベンゾオキサジン−４−オン、２−ｐ−メトキシフェニル−３，１−ベンゾオキサジン−４−オン、２−ｏ−メトキシフェニル−３，１−ベンゾオキサジン−４−オン、２−シクロヘキシル−３，１−ベンゾオキサジン−４−オン、２−ｐ−（又はｍ−）フタルイミドフェニル−３，１−ベンゾオキサジン−４−オン、２，２′−（１，４−フェニレン）ビス（４Ｈ−３，１−ベンズオキサジノン−４−オン）２，２′−ビス（３，１−ベンゾオキサジン−４−オン）、２，２′−エチレンビス（３，１−ベンゾオキサジン−４−オン）、２，２′−テトラメチレンビス（３，１−ベンゾオキサジン−４−オン）、２，２′−デカメチレンビス（３，１−ベンゾオキサジン−４−オン）、２，２′−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２′−ｍ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２′−（４，４′−ジフェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２′−（２，６−又は１，５−ナフタレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２′−（２−メチル−ｐ−フェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（２−ニトロ−ｐ−フェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２′−（２−クロロ−ｐ−フェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２′−（１，４−シクロヘキシレン）ビス（３，１−ベンゾオキサジン−４−オン）１，３，５−トリ（３，１−ベンゾオキサジン−４−オン−２−イル）ベンゼン、１，３，５−トリ（３，１−ベンゾオキサジン−４−オン−２−イル）ナフタレン、および２，４，６−トリ（３，１−ベンゾオキサジン−４−オン−２−イル）ナフタレン、２，８−ジメチル−４Ｈ，６Ｈ−ベンゾ（１，２−ｄ；５，４−ｄ′）ビス−（１，３）−オキサジン−４，６−ジオン、２，７−ジメチル−４Ｈ，９Ｈ−ベンゾ（１，２−ｄ；５，４−ｄ′）ビス−（１，３）−オキサジン−４，９−ジオン、２，８−ジフェニル−４Ｈ，８Ｈ−ベンゾ（１，２−ｄ；５，４−ｄ’）ビス−（１，３）−オキサジン−４，６−ジオン、２，７−ジフェニル−４Ｈ，９Ｈ−ベンゾ（１，２−ｄ；５，４−ｄ′）ビス−（１，３）−オキサジン−４，６−ジオン、６，６′−ビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−ビス（２−エチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−ビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−メチレンビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−メチレンビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−エチレンビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−エチレンビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−ブチレンビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−ブチレンビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−オキシビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−オキシビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−スルホニルビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−スルホニルビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−カルボニルビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，６′−カルボニルビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、７，７′−メチレンビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、７，７′−メチレンビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、７，７′−ビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、７，７′−エチレンビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、７，７′−オキシビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、７，７′−スルホニルビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、７，７′−カルボニルビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，７′−ビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，７′−ビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、６，７′−メチレンビス（２−メチル−４Ｈ，３，１−ベンゾオキサジン−４−オン）、および６，７′−メチレンビス（２−フェニル−４Ｈ，３，１−ベンゾオキサジン−４−オン）などが挙げられる。
【００７９】
上記の有機系紫外線吸収剤を基材フィルムに配合する場合は、押し出し工程で高温に晒されるので、紫外線吸収剤は分解開始温度が２９０℃以上の紫外線吸収剤を用いるのが製膜時の工程汚染を少なくする上で好ましい。分解開始温度が２９０℃以下の紫外線吸収剤を用いると製膜中に紫外線吸収剤の分解物が製造装置のロール群等に付着し、強いてはフィルムに再付着したり、キズを付けたりして光学的な欠点となるため好ましくない。
【００８０】
無機系紫外線吸収剤としては、酸化セリウム、酸化亜鉛、酸化チタン等の金属酸化物の超微粒子類が挙げられる。
【００８１】
上記の波長３８０ｎｍ以下における光線透過率が９０％以下にするもう一つの方法として、この波長域に吸収を有する、例えばナフタレンジカルボン酸等のポリエステルを形成する化合物をポリエステルの共重合成分として用いる方法を挙げることができる。
【００８２】
以上説明したように、本発明の成型用ポリエステルフィルムを用いることで、従来の二軸配向ポリエステルフィルムでは成型することが困難であった、成型時の成型圧力が１０気圧以下の低圧下での真空成型や圧空成型などの成型方法においても、仕上がり性の良好な成型品を得ることができる。また、これらの成型法は成型コストが安いので、成型品の製造における経済性において優位である。したがって、これらの成型法に適用することが本発明の成型用ポリエステルフィルムの特徴を最も有効に発揮することができる。
【００８３】
一方、金型成型は金型や成型装置が高価であり、経済性の点では不利であるが、前記の成型法よりも複雑な形状の成型品が高精度に成型されるという特徴がある。そのため、本発明に用いられる成型用ポリエステルフィルムを用いて金型成型した場合は、従来の二軸配向ポリエステルフィルムに比べて、より低い成型温度で成型が可能で、かつ成型品の仕上がり性が改善されるという顕著な効果が発現される。
【００８４】
さらに、このように成型された成型品は、常温雰囲気下で使用する際に、弾性および形態安定性（熱収縮特性、厚み斑）に優れ、そのうえ耐溶剤性や耐熱性に優れ、さらに環境負荷も小さいので、家電用銘板、自動車用銘板、ダミー缶、建材、化粧板、化粧鋼鈑、転写シートなどの成型部材として好適に使用することができる。
【００８５】
なお、本発明の成型用ポリエステルフィルムは、前記の成型方法以外にも、プレス成型、ラミネート成型、インモールド成型、絞り成型、折り曲げ成型などの成型方法を用いて成型する成型用材素材としても好適である。
【実施例】
【００８６】
以下、実施例によって本発明を詳細に説明する。なお、各実施例で得られたフィルム特性は以下の方法により測定、評価した。
【００８７】
（１）固有粘度
チップサンプル０．１ｇを精秤し、２５ｍｌのフェノール／テトラクロロエタン＝６／４（質量比）の混合溶媒に溶解し、オストワルド粘度計を用いて３０℃で測定した。なお、測定は３回行い、その平均値を求めた。
【００８８】
（２）厚みムラ
横延伸方向に３ｍ、縦延伸方向に５ｃｍの長さの連続したテープ状サンプルを巻き取り、フィルム厚み連続測定機（アンリツ株式会社製）にてフィルムの厚みを測定し、レコーダーに記録する。チャートより、厚みの最大値（Ｔｍａｘ）、最小値（Ｔｍｉｎ）、平均値（Ｔａｖ）を求め、下記式にて厚みムラ（％）を算出した。なお、測定は３回行い、その平均値を求めた。また、横延伸方向の長さが３ｍに満たない場合は、つなぎ合せて行う。なお、つなぎの部分における測定データは削除した。
厚みムラ（％）＝（（Ｔｍａｘ−Ｔｍｉｎ）／Ｔａｖ）×１００
【００８９】
（３）ヘイズ
ＪＩＳ−Ｋ７１３６に準拠し、ヘイズメータ（日本電色工業株式会社製、３００Ａ）を用いて測定した。なお、測定は２回行い、その平均値を求めた。
【００９０】
（４）フィルムの厚み
ミリトロンを用い、１枚当たり５点を計３枚の１５点を測定し、その平均値を求めた。
【００９１】
（５）１００％伸張時応力、破断伸度
二軸延伸フィルムの長手方向及び幅方向に対して、それぞれ長さ１８０ｍｍ及び幅１０ｍｍの短冊状に試料を片刃カミソリで切り出した。次いで、引っ張り試験機（東洋精機株式会社製）を用いて短冊状試料を引っ張り、得られた荷重−歪曲線から各方向の１００％伸張時応力（ＭＰａ）及び破断伸度（％）を求めた。
【００９２】
なお、測定は２５℃の雰囲気下で、初期長４０ｍｍ、チャック間距離１００ｍｍ、クロスヘッドスピード１００ｍｍ／ｍｉｎ、記録計のチャートスピード２００ｍｍ／ｍｉｎ、ロードセル２５ｋｇの条件にて行った。なお、この測定は１０回行い平均値を用いた。
【００９３】
また、１００℃の雰囲気下でも、上記と同様の条件で引っ張り試験を行った。この際、試料は１００℃の雰囲気下で３０秒保持した後、測定を行った。なお、測定は１０回行い平均値を用いた。
【００９４】
（６）１５０℃での熱収縮率
フィルムの長手方向及び幅方向に対し、それぞれ長さ２５０ｍｍ及び幅２０ｍｍの短冊状試料を切り出す。各試料の長さ方向に２００ｍｍ間隔で２つの印を付け、５ｇの一定張力（長さ方向の張力）下で２つの印の間隔Ａを測定する。続いて、短冊状の各試料の片側をカゴに無荷重下でクリップにて吊るし、１５０℃の雰囲気下のギアオーブンに入れると同時に時間を計る。３０分後、ギアオーブンからカゴを取り出し、３０分間室温で放置する。次いで、各試料について、５ｇの一定張力（長さ方向の張力）下で、２つの印の間隔Ｂを金指により０．２５ｍｍ単位で読み取る。読み取った間隔Ａ及びＢより、各試料の１５０℃での熱収縮率を下記式により算出する。
熱収縮率（％）＝（（Ａ−Ｂ）／Ａ）×１００
【００９５】
（７）貯蔵粘弾性率（Ｅ′）
動的粘弾性測定装置（アイティー計測制御（株）製、ＤＶＡ ２２５）を用い、下記の条件下で、フィルムの長手方向（ＭＤ）及び幅方向（ＴＤ）における１００℃及び１８０℃での貯蔵弾性率（Ｅ′）を求めた。
（ａ）サンプル幅：５ｍｍ
（ｂ）測定温度範囲：−５０〜２５０℃
（ｃ）周波数：１０Ｈｚ
（ｄ）昇温速度：５℃／分
【００９６】
（８）微小張力下での熱変形率
熱機械分析装置（セイコー電子（株）製、ＴＭＡ ＳＳ／１００）を用い、下記の条件下で、フィルムの長手方向における寸法変化の温度依存性を求めた。
（ａ）サンプル幅：２ｍｍ
（ｂ）測定温度範囲：３０〜２５０℃、
（ｃ）初期荷重：４９ｍＮ（５ｇｆ）
（ｄ）昇温速度：５℃／分
【００９７】
（９）面配向度（ΔＰ）
ナトリウムＤ線（波長５８９ｎｍ）を光源として、アッベ屈折計を用いて、フィルムの長手方向の屈折率（Ｎｚ）、幅方向の屈折率（Ｎｙ）、厚み方向の屈折率（Ｎｚ）を測定し下記式から算出した。
ΔＰ＝（（Ｎｘ＋Ｎｙ）／２）−Ｎｚ
【００９８】
（１０）波長３８０ｎｍにおける光線透過率
分光光度計（島津製作所（株）製、ＵＶ−１２００）を用いて、波長３８０ｎｍの紫外領域における光線透過率を測定した。
【００９９】
（１１）耐光性
暗箱中で蛍光灯ランプ（松下電器（株）社製、Ｕ型蛍光灯ＦＵＬ９ＥＸ）の直下３ｃｍの位置に、オフセット印刷した印刷サンプルを、印刷サンプルの印刷面が裏側になるように置いた。次いで、連続２０００時間の光照射を行い、印刷面側の光照射前後におけるカラー（ａ＊、ｂ＊、Ｌ＊）をもとに、ＪＩＳ Ｚ ８７３０に準拠し、色差（ΔＥ値）を測定した。色差（ΔＥ値）が小さいほど、光照射前後における色の変化が小さい、すなわち耐光性に優れていることを意味する。耐光性の合格レベルは、色差（ΔＥ値）で０．５以下である。なお、色差（ΔＥ値）は下記の式で算出される。
ΔＥ＝√（Δａ２＋Δｂ２＋ΔＬ２）
【０１００】
（１２）成型性
（ａ）真空成型性
フィルムに５ｍｍ四方のマス目印刷を施した後、５００℃に加熱した赤外線ヒーターでフィルムを１０〜１５秒加熱した後、金型温度３０〜１００℃で真空成型を行った。なお、加熱条件は各フィルムに対し、上記範囲内で最適条件を選択した。金型の形状はカップ型で、開口部は直径が５０ｍｍであり、底面部は直径が４０ｍｍで、深さが５０ｍｍであり、全てのコーナーは直径０．５ｍｍの湾曲をつけたものを用いた。
最適条件下で真空成型した成型品５個について成型性及び仕上がり性を評価し、下記基準にてランク付けを行った。なお、◎及び○を合格とし、×を不合格とした。
◎：（ｉ）成型品に破れがなく、
（ｉｉ）角の曲率半径が１ｍｍ以下で、かつ印刷ずれが０．１ｍｍ以下であり、
（ｉｉｉｉｉｉ）さらに×に該当する外観不良がないもの
○：（ｉ）成型品に破れがなく、
（ｉｉ）角の曲率半径が１ｍｍを超え１．５ｍｍ以下、または印刷ずれが０．１ｍｍを超え０．２ｍｍ以下で、
（ｉｉｉ）さらに×に該当する外観不良がなく、実用上問題ないレベルのもの
×：成型品に破れがあるもの、または破れがなくとも以下の項目（ｉ）〜（ｉｖ）のいずれかに該当するもの
（ｉ）角の曲率半径が１．５ｍｍを超えるもの
（ｉｉ）大きな皺が入り外観が悪いもの
（ｉｉｉ）フィルムが白化し透明性が低下したもの
（ｉｖ）印刷のずれが０．２ｍｍを超えるもの
【０１０１】
（ｂ）圧空成型性
フィルムに５ｍｍ四方のマス目印刷を施した後、５００℃に加熱した赤外線ヒーターでフィルムを１０〜１５秒加熱した後、金型温度３０〜１００℃で、４気圧の加圧下で圧空成型を行った。なお、加熱条件は各フィルムに対し、上記範囲内で最適条件を選択した。金型の形状はカップ型で、開口部は直径が６０ｍｍであり、底面部は直径が５５ｍｍで、深さが５０ｍｍであり、全てのコーナーは直径０．５ｍｍの湾曲をつけたものを用いた。
最適条件下で圧空成型した成型品５個について成型性及び仕上がり性を評価し、下記基準にてランク付けをした。なお、◎及び○を合格とし、×を不合格とした。
◎：（ｉ）成型品に破れがなく、
（ｉｉ）角の曲率半径が１ｍｍ以下で、かつ印刷ずれが０．１ｍｍ以下であり、
（ｉｉｉ）さらに×に該当する外観不良がないもの
○：（ｉ）成型品に破れがなく、
（ｉｉ）角の曲率半径が１ｍｍを超え１．５ｍｍ以下、または印刷ずれが０．１ｍｍを超え０．２ｍｍ以下で、
（ｉｉｉ）さらに×に該当する外観不良がなく、実用上問題ないレベルのもの
×：成型品に破れがあるもの、または破れがなくとも以下の項目（ｉ）〜（ｉｖ）のいずれかに該当するもの
（ｉ）角の曲率半径が１．５ｍｍを超えるもの
（ｉｉ）大きな皺が入り外観が悪いもの
（ｉｉｉ）フィルムが白化し透明性が低下したもの
（ｉｖ）印刷のずれが０．２ｍｍを超えるもの
【０１０２】
（ｃ）金型成型性
フィルムに印刷を施した後、１００〜１４０℃に加熱した熱板で４秒間接触加熱後、金型温度３０〜７０℃、保圧時間５秒にてプレス成型を行った。なお、加熱条件は各フィルムに対し、上記範囲内で最適条件を選択した。金型の形状はカップ型で、開口部は直径が５０ｍｍであり、底面部は直径が４０ｍｍで、深さが３０ｍｍであり、全てのコーナーは直径０．５ｍｍの湾曲をつけたものを用いた。
最適条件下で金型成型した成型品５個について成型性及び仕上がり性を評価し、下記基準にてランク付けをした。なお、◎及び○を合格とし、×を不合格とした。
◎：（ｉ）成型品に破れがなく、
（ｉｉ）角の曲率半径が１ｍｍ以下で、かつ印刷ずれが０．１ｍｍ以下であり、
（ｉｉｉ）さらに×に該当する外観不良がないもの
○：（ｉ）成型品に破れがなく、
（ｉｉ）角の曲率半径が１ｍｍを超え１．５ｍｍ以下、または印刷ずれが０．１ｍｍを超え０．２ｍｍ以下で、
（ｉｉｉ）さらに×に該当する外観不良がなく、実用上問題ないレベルのもの
×：成型品に破れがあるもの、または破れがなくとも以下の項目（ｉ）〜（ｉｖ）のいずれかに該当するもの
（ｉ）角の曲率半径が１．５ｍｍを超えるもの
（ｉｉ）大きな皺が入り外観が悪いもの
（ｉｉｉ）フィルムが白化し透明性が低下したもの
（ｉｖ）印刷のずれが０．２ｍｍを超えるもの
【０１０３】
（１３）耐溶剤性
２５℃に調温したトルエンに試料を３０分間浸漬し、浸漬前後の外観変化について下記の基準で判定し、○を合格とした。なお、ヘイズ値は前記の方法で測定した。
○：外観変化がほとんど無く、ヘイズ値の変化が１％未満
×：外観変化が認められる、あるいはヘイズ値の変化が１％以上
【０１０４】
（１４）印刷品位
印刷前のフィルムを９０℃で３０分熱処理し、次いで４色のスクリーン印刷を行った。
さらに、印刷層を設けたフィルムを８０℃で３０分乾燥した。印刷品位の評価は、下記のクリアー感、印刷適性、印刷ずれなどの印刷外観を、印刷面からではなく、裏側からフィルムを通して目視で判定した。判定基準は、全ての観点から問題無いものを○、少なくとも１つの点で問題あるものを×とした。
ａ．クリアー感：印刷した図柄が、基材フィルムや塗布層に遮られることなく、鮮明に見えること。
ｂ．印刷適性 ：印刷インキの転移不良による、色むらやヌケが生じないこと
ｃ．印刷のズレ：印刷のズレが目視で判別できないこと。
【０１０５】
［実施例１］
芳香族ジカルボン酸成分としてテレフタル酸単位１００モル％、ジオール成分としてエチレングリコール単位４０モル％及びネオペンチルグリコール単位６０モル％を構成成分とする、固有粘度が０．６９ｄｌ／ｇの共重合ポリエステルのチップ（Ａ）と、固有粘度が０．６９ｄｌ／ｇで、かつ平均粒子径（ＳＥＭ法）が１．５μｍの無定形シリカを４００ｐｐｍ含有するポリエチレンテレフタレートのチップ（Ｂ）をそれぞれ乾燥させた。さらに、チップ（Ａ）とチップ（Ｂ）を２５：７５の質量比となるように混合した。次いで、これらのチップ混合物を押出し機によりＴダイのスリットから２７０℃で溶融押出し、表面温度４０℃のチルロール上で急冷固化させ、同時に静電印加法を用いてチルロールに密着させながら無定形の未延伸シートを得た。
【０１０６】
得られた未延伸シートを加熱ロールと冷却ロールの間で縦方向に９０℃で３．３倍に延伸した。次いで、一軸延伸フィルムをテンターに導き、１２０℃で１０秒間予熱し、横延伸の前半部を１１０℃、後半部を１００℃で３．９倍延伸した。さらに、横方向に７％の弛緩処理を行いながら２３５℃で熱固定処理を行い、厚さ１００μｍの二軸延伸ポリエステルフィルムを得た。
【０１０７】
なお、熱固定処理ゾーンには、延伸区間との間に２ｍの中間区間を設け、熱固定ゾーンの加熱用区間には遠赤外線ヒーターを設置し、区間ごとの遮蔽板をフィルムに接触しない限界位置まで拡大し、設置した。加熱後の冷却区間においても区間遮蔽を強化し、クリップの戻り方法として外部リターン方式を用い、かつクリップ冷却装置を設置し、さらに２０℃の冷風で強制冷却し、テンター出口でのクリップ温度を４０℃以下とするクリップ融着防止対策を行った。
【０１０８】
（比較例１）
実施例１において、熱固定温度を２０５℃に変更すること以外は、実施例１と同様にして二軸延伸ポリエステルフィルムを得た。
【０１０９】
（比較例２）
市販のＡ−ＰＥＴの未延伸シート（東洋紡績（株）製、ＰＥＴＭＡＸ（Ｒ）Ａ５６０ＧＥ０Ｒ、厚み：２００μｍ）の特性評価を行った。
【０１１０】
（比較例３）
市販のポリカーボネートの未延伸シート（帝人化成（株）製、パンライトシート（Ｒ）ＰＣ２１５１、厚み：２００μｍ）の特性評価を行った。
【０１１１】
（比較例４）
アクリルの未延伸シート（三菱化成（株）製、アクリプレン（Ｒ）ＨＢＳ００６、厚み：１２５μｍ）の特性評価を行った。
【０１１２】
［実施例２］
芳香族ジカルボン酸成分としてテレフタル酸単位１００モル％、ジオール成分としてエチレングリコール単位７０モル％及びネオペンチルグリコール単位３０モル％を構成成分とする、固有粘度が０．７７ｄｌ／ｇの共重合ポリエステルのチップ（Ｃ）と、固有粘度が０．６３ｄｌ／ｇで、かつ平均粒子径（ＳＥＭ法）が１．５μｍの無定形シリカを４００ｐｐｍ含有するポリエチレンテレフタレートのチップ（Ｄ）、及び固有粘度が０．７５ｄｌ／ｇで、かつ平均粒子径（ＳＥＭ法）が１．５μｍの無定形シリカを４００ｐｐｍ含有するポリプロピレンテレフタレートのチップ（Ｅ）をそれぞれ乾燥させた。さらに、チップ（Ｃ）、チップ（Ｄ）、及びチップ（Ｅ）を５０：１０：４０の質量比となるように混合した。次いで、これらのチップ混合物を押出し機によりＴダイのスリットから２７０℃で溶融押出し、表面温度４０℃のチルロール上で急冷固化させ、同時に静電印加法を用いてチルロールに密着させながら無定形の未延伸シートを得た。
【０１１３】
得られた未延伸シートを加熱ロールと冷却ロールの間で縦方向に８３℃で３．５倍に延伸した。次いで、一軸延伸フィルムをテンターに導き、９５℃で１０秒予熱し、横延伸の前半部を８０℃、後半部を７５℃で３．９倍延伸した。さらに、横方向に７％の弛緩処理を行いながら２００℃で熱固定処理を行い、厚さ１００μｍの二軸延伸ポリエステルフィルムを得た。
【０１１４】
なお、熱固定処理ゾーンには、延伸区間との間に２ｍの中間区間を設け、熱固定ゾーンの加熱用区間には遠赤外線ヒーターを設置し、区間ごとの遮蔽板をフィルムに接触しない限界位置まで拡大し、設置した。加熱後の冷却区間においても区間遮蔽を強化し、クリップの戻り方法として外部リターン方式を用い、かつクリップ冷却装置を設置し、さらに２０℃の冷風で強制冷却し、テンター出口でのクリップ温度を４０℃以下とするクリップ融着防止対策を行った。
【０１１５】
［実施例３］
芳香族ジカルボン酸成分としてテレフタル酸単位１００モル％、ジオール成分としてエチレングリコール単位７０モル％及び１，４−シクロヘキサンジメタノール単位３０モル％を構成成分とする、固有粘度が０．７１ｄｌ／ｇの共重合ポリエステルのチップ（Ｆ）と、ポリエチレンテレフタレートのチップ（Ｂ）を５０：５０の質量比となるように混合し乾燥した。次いで、これらのチップ混合物を押出し機によりＴダイのスリットから２７０℃で溶融押出し、表面温度４０℃のチルロール上で急冷固化させ、同時に静電印加法を用いてチルロールに密着させながら無定形の未延伸シートを得た。
【０１１６】
得られた未延伸シートを加熱ロールと冷却ロールの間で縦方向に９０℃で３．５倍に延伸した。次いで、一軸延伸フィルムをテンターに導き、１２０℃で１０秒予熱し、横延伸の前半部を１０５℃、後半部を１００℃で３．９倍延伸した。さらに、横方向に７％の弛緩処理を行いながら２２０℃で熱固定処理を行い、厚さ１００μｍの二軸延伸ポリエステルフィルムを得た。
【０１１７】
なお、熱固定処理ゾーンには、延伸区間との間に２ｍの中間区間を設け、熱固定ゾーンの加熱用区間には遠赤外線ヒーターを設置し、区間ごとの遮蔽板をフィルムに接触しない限界位置まで拡大し、設置した。加熱後の冷却区間においても区間遮蔽を強化し、クリップの戻り方法として外部リターン方式を用い、かつクリップ冷却装置を設置し、さらに２０℃の冷風で強制冷却し、テンター出口でのクリップ温度を４０℃以下とするクリップ融着防止対策を行った。
【０１１８】
（比較例５）
実施例３において、熱固定温度を２０５℃に変更すること以外は実施例３と同様にして、厚さ１８８μｍの二軸延伸ポリエステルフィルムを得た。
【０１１９】
［実施例４］
芳香族ジカルボン酸成分としてテレフタル酸単位１００モル％、ジオール成分としてエチレングリコール単位４０モル％及びネオペンチルグリコール単位６０モル％を構成成分とする、固有粘度０．６９ｄｌ／ｇの共重合ポリエステルのチップ（Ａ）と、固有粘度が０．６９ｄｌ／ｇで、かつ平均粒子径（ＳＥＭ法）が１．５μｍの無定形シリカを４００ｐｐｍ含有するポリブチレンテレフタレートのチップ（Ｇ）を乾燥させた。次いで、チップ（Ａ）、チップ（Ｇ）、ベンゾトリアゾール系紫外線吸収剤（Ｉ）（チバ・スペシャルティ・ケミカルズ株式会社製、チヌビン３２６）を、２５．０：７４．５：０．５の質量比となるように混合した。次いで、これらの混合物を押出し機によりＴダイのスリットから２６５℃で溶融押出し、表面温度２０℃のチルロール上で急冷固化させ、同時に静電印加法を用いてチルロールに密着させながら無定形の未延伸シートを得た。
【０１２０】
得られた未延伸シートを加熱ロールと冷却ロールの間で縦方向に８０℃で３．３倍に延伸した。次いで、一軸延伸フィルムをテンターに導き、９５℃で１０秒予熱し、横延伸の前半部を８５℃、後半部を８０℃で３．８倍延伸した。さらに、横方向に７％の弛緩処理を行いながら２００℃で熱固定処理を行い、厚さ１００μｍの二軸延伸ポリエステルフィルムを得た。
【０１２１】
なお、熱固定処理ゾーンには、延伸区間との間に２ｍの中間区間を設け、熱固定ゾーンの加熱用区間には遠赤外線ヒーターを設置し、区間ごとの遮蔽板をフィルムに接触しない限界位置まで拡大し、設置した。加熱後の冷却区間においても区間遮蔽を強化し、クリップの戻り方法として外部リターン方式を用い、かつクリップ冷却装置を設置し、さらに２０℃の冷風で強制冷却し、テンター出口でのクリップ温度を４０℃以下とするクリップ融着防止対策を行った。
【０１２２】
（比較例６）
実施例４において、熱固定温度を１８５℃に変更すること以外は実施例４と同様にして、厚さ１００μｍの二軸延伸ポリエステルフィルムを得た。
【０１２７】
実施例１〜４及び比較例１、５、６に関しては、使用したポリマーの原料組成とポリマー特性を表１に、フィルムの製造条件と特性を表２〜４に示す。また、比較例２〜４のフィルム特性を表５に示す。
【０１２８】
実施例１〜４で得られた二軸配向ポリエステルフィルムは、成型時の成型圧力の低い真空成型法や圧空成型法で成型しても仕上がり性の良好な成型品が得られた。また、得られた成型品の耐溶剤性や寸法安定性も良好であった。また、実施例４で得られたフィルムは、紫外線吸収剤を含有しているため、波長３８０ｎｍにおける紫外線領域での光線透過率は０％であり、かつ連続２０００時間の光照射前後における印刷面側の色差は０．５以下であり、実施例１〜３で得られたフィルムより色差が小さく、耐光性に優れていた。
【０１２９】
一方、比較例１、５、６および７で得られたフィルムは、真空成型法や圧空成型法での成型性に劣り成型品の仕上がり性が良くなかった。さらに、これらの比較例で得られたフィルムは実施例１〜４で得られたフィルムに比べて、金型成型法での仕上がり性が劣っていた。また、比較例２〜４の未延伸シートは、成型性は良好であるが耐溶剤性や寸法安定性に劣っていた。
【０１３０】
【表１】
【表２】
【表３】
【表４】
【表５】
【０１３５】
本発明の成型用ポリエステルフィルムは、加熱成型時の成型性、特に低い温度および低い圧力での成型性に優れているので幅広い成型方法に適用ができ、かつ成型品として常温雰囲気下で使用する際に、弾性および形態安定性（熱収縮特性、厚み斑）に優れ、そのうえ耐溶剤性や耐熱性に優れ、さらに環境負荷が小さいという利点があり、家電、自動車の銘板用または建材用部材として好適であり、産業界への寄与は大きい。
【発明の効果】
【０１３６】
本発明の成型用ポリエステルフィルムは、加熱成型時の成型性、特に低い温度および低い圧力での成型性に優れているので幅広い成型方法に適用ができ、かつ成型品として常温雰囲気下で使用する際に、弾性および形態安定性（熱収縮特性、厚み斑）に優れ、そのうえ耐溶剤性や耐熱性に優れ、さらに環境負荷が小さいので、家電、自動車の銘板用または建材用部材として好適に用いることができるという利点がある。【Technical field】
[0001]
INDUSTRIAL APPLICABILITY The present invention is suitably used as a member for home appliances, automobile nameplates or building materials, which has excellent moldability, particularly moldability at low temperature and low pressure, excellent solvent resistance and heat resistance, and has low environmental impact. The present invention relates to a molding polyester film that can be used.
[Background]
[0002]
Conventionally, as a sheet | seat for shaping | molding, a polyvinyl chloride film is typical and has been preferably used at points, such as workability. On the other hand, the film has problems such as generation of toxic gas when the film burns due to a fire or the like, bleed-out of a plasticizer, and a new material with a small environmental load has been demanded due to recent environmental resistance needs. ing.
[0003]
In order to satisfy the above requirements, unstretched sheets made of polyester, polycarbonate and acrylic resin have been used in a wide range of fields as non-chlorine materials. In particular, unstretched sheets made of a polyester resin are attracting attention because they have good mechanical properties and transparency, and are excellent in economic efficiency. For example, an unstretched polyester-based sheet comprising substantially non-crystalline polyester-based resin in which about 30 mol% of ethylene glycol component in polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol is disclosed ( For example, see Patent Documents 1 to 5).
[0004]
[Patent Document 1]
Japanese Patent Laid-Open No. 9-156267
[Patent Document 2]
JP 2001-71669 A
[Patent Document 3]
JP 2001-80251 A
[Patent Document 4]
JP 2001-129951 A
[Patent Document 5]
JP 2002-249652 A
[0005]
The above-mentioned unstretched polyester sheet satisfies market demands regarding moldability and laminate suitability, but because it is an unstretched sheet, it does not have sufficient heat resistance and solvent resistance and satisfies high market demands. It has not yet reached.
[0006]
As a method for solving the above problems, a method using a biaxially stretched polyethylene terephthalate film is disclosed (for example, see Patent Documents 6 to 9).
[0007]
[Patent Document 6]
JP-A-9-187903
[Patent Document 7]
JP-A-10-296937
[Patent Document 8]
Japanese Patent Laid-Open No. 11-10816
[Patent Document 9]
JP-A-11-268215
[0008]
However, although the heat resistance and solvent resistance are improved, the above method has insufficient moldability and does not satisfy the market demand in terms of the balance of overall quality.
[0009]
As a method for solving the above-described problem, a method for specifying a stress at 100% elongation of a film is disclosed (for example, see Patent Document 10).
[0010]
[Patent Document 10]
JP 2001-347565 A
[0011]
Although this method has improved moldability as compared with the above-described method, it does not reach a level that can sufficiently meet the high demands of the market regarding moldability. In particular, there remains a problem in moldability that can be adapted to lowering the molding temperature and the finished quality of the obtained molded product.
[0012]
The inventors of the present invention have studied the solution of the above-mentioned problems, and have already developed a method for improving the above-mentioned problems by specifying a 100% elongation stress of the film using a copolymer polyester resin having the specified composition as a raw material. (For example, refer to Patent Documents 11 and 12).
[0013]
[Patent Document 11]
Japanese Patent Application No. 2002-233694
[Patent Document 12]
Japanese Patent Application No. 2003-309894
[0014]
With these methods, in a mold molding method with a high molding pressure at the time of molding, the moldability that can be adapted to the lowering of the molding temperature that satisfies the market demand and the finished product finished product can be greatly improved. However, in the case of a molding method having a low molding pressure at the time of molding, such as a compressed air molding method or a vacuum molding method, which has become increasingly demanding in the market, it is desired to further improve the finish of the molded product.
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0015]
The object of the present invention is to solve the above-mentioned problems in the prior art, and is excellent in moldability, particularly moldability at a low temperature and low pressure, excellent in solvent resistance and heat resistance, and has a small environmental load. It is to provide a polyester film for molding.
[Means for Solving the Problems]
[0016]
The polyester film for molding of the present invention capable of solving the above-mentioned problems has the following configuration.
[0017]
That is, the first invention of the present invention is a molding polyester film comprising a biaxially oriented polyester film, the film comprising a copolymer polyester as a constituent component,
(1) The copolymer polyester as a constituent component comprises terephthalic acid, ethylene glycol, and neopentyl glycol and / or 1,4-cyclohexanedimethanol as a copolymer component,
(2) In the copolymer polyester, the copolymer component is 1 to 40 mol%,
(3) The melting point of the film is 200 to 245 ° C,
(4) 100% elongation stress in the longitudinal and width directions of the film is 10 to 1000 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C.,
(5) The storage viscoelastic modulus (E ′) in the longitudinal and width directions of the film is 10 to 1000 MPa at 100 ° C. and 5 to 40 MPa at 180 ° C.,
(6) Thermal deformation rate in the longitudinal direction of the film (initial load 49 mN) is −3% to + 3% at 175 ° C.,
This is a polyester film for molding.
The second invention isThe film is a blend of the copolyester and homopolyester,
The homopolyester is polyethylene terephthalate, polytrimethylene terephthalate, or polybutylene terephthalate.A molding polyester film according to the first aspect of the invention.
First3In the first aspect of the invention, the molding polyester film has a heat shrinkage rate at 150 ° C. in the longitudinal and lateral directions of the film of 6.0% or less.Or 2It is the polyester film for a shaping | molding as described in invention.
First4The invention ofIn the transverse stretching performed after the longitudinal stretching, the film is obtained by a sequential biaxial stretching method. The molding polyester film according to any one of the first to third aspects, wherein the molding is performed in a range.
First5The invention ofThe film is heat-treated at 120 to 245 ° C.,
(A) a method of providing a heat shielding wall on the clip portion;
(B) a method of adding a clip cooling mechanism to the tenter;
(C) A method in which the cooling section after heat setting is set long and the entire film is sufficiently cooled,
(D) A method of increasing the cooling efficiency by increasing the length of the cooling section and the number of sections, or
(E) a method for enhancing cooling of the clip using a type in which the return portion of the clip travels outside the furnace,
It is the polyester film for shaping | molding in any one of the 1st-4th invention obtained by cooling the vicinity of a clip using, and releasing a film from a clip at a tenter exit.
First6The invention ofIt is a molding formed by molding the molding polyester film according to any one of the first to fifth inventions.
BEST MODE FOR CARRYING OUT THE INVENTION
[0018]
The polyester film for molding in the present invention has a stress at 100% elongation (F100) at 25 ° C. in the longitudinal direction and the width direction of the film.25) Is 10 to 1000 MPa, and the stress at 100% elongation (F100) at 100 ° C. in the longitudinal direction and the width direction of the film.100) Is important to be 1 to 100 MPa. F10025Or F100100If the value exceeds the upper limit of the above range, the moldability is lowered, which is not preferable. On the other hand, if it is less than the lower limit of the above range, the elasticity and shape stability when using a molded product are lowered, which is not preferable.
[0019]
F100 in the longitudinal direction and the width direction of the film25Is preferably 10 to 500 MPa, more preferably 10 to 200 MPa, and particularly preferably 10 to 150 MPa.
[0020]
Moreover, F100 in the longitudinal direction and the width direction of the film100From the viewpoint of moldability, the upper limit is preferably 90 MPa, more preferably 80 MPa, and particularly preferably 70 MPa. On the other hand, F100100The lower limit of is preferably 2 MPa, more preferably 3 MPa, and particularly preferably 5 MPa from the viewpoint of elasticity and shape stability when using a molded product.
[0021]
In the polyester film for molding in the present invention, it is important that the storage viscoelastic modulus (E ′) in the longitudinal direction and the width direction of the film is 10 to 1000 MPa at 100 ° C. and 5 to 40 MPa at 180 ° C. is there. By controlling the storage viscoelasticity (E ′) within the above range, the moldability, particularly the moldability at a low temperature and low pressure can be secured, and the compressed air molding method and the vacuum molding that can only be applied to unstretched sheets. Even a molding method with a low molding pressure of 10 atm or less, such as a method, can provide a molded product with good finish and a molded product with good dimensional stability.
[0022]
The storage viscoelastic modulus (E ′) at 100 ° C. and 180 ° C. is a parameter that affects the moldability under low temperature and low pressure, dimensional stability, and the like. In particular, the present inventor shows that the storage viscoelasticity (E ′) at 100 ° C. is related to moldability under low temperature and low pressure, and the storage viscoelasticity (E ′) at 180 ° C. is related to dimensional stability. Have newly found out. As for the reason why the storage viscoelastic modulus (E ′) at the specific temperature is an important index for developing the film characteristics, the present inventors have not clearly clarified their mechanism. However, it is assumed that the molecular structure of the copolymer component contained in the polyester constituting the film contributes.
[0023]
The storage viscoelastic modulus (E ′) in the longitudinal direction and the width direction of the film is preferably 20 to 900 MPa, more preferably 30 to 800 MPa, and particularly preferably 40 to 700 MPa in both directions of the film at 100 ° C. The storage viscoelastic modulus (E ′) at 180 ° C. is preferably 7 to 38 MPa, more preferably 9 to 35 MPa, and particularly preferably 10 to 30 MPa.
[0024]
Further, it is important that the polyester film for molding in the present invention has a thermal deformation rate (initial load 49 mN) in the longitudinal direction of the film of −3% to + 3% at 175 ° C. Here, the thermal deformation rate of the film is obtained by measuring the temperature dependence of the deformation rate of the film at an initial load of 49 mN using a thermomechanical analyzer (TMA) at a heating rate of 5 ° C./min. . By satisfying this characteristic, the solvent resistance of the molded product can be improved. For example, a molded product with good finish can be obtained even by a molding method with a molding pressure as low as 10 atm or less, such as a compressed air molding method or a vacuum molding method. However, an unstretched sheet obtained from polyester, polycarbonate, and acrylic resin has this characteristic value outside the above range. The reason why the seemingly unrelated characteristics of the thermal deformation rate and the solvent resistance under the micro tension (initial load 49 mN) of the film are correlated is not clear. However, the present inventors speculate that the polyester film for molding of the present invention is biaxially oriented and the solvent resistance and heat distortion resistance are improved by the expression of molecular orientation by stretching. The thermal deformation rate (initial load 49 mN) in the longitudinal direction of the film is preferably −3% to + 3% at 180 ° C., and particularly preferably −3% to + 3% at 185 ° C.
[0025]
(1) Stress at 100% elongation in the longitudinal direction and width direction of the film, (2) Storage viscoelastic modulus (E ′) in the longitudinal direction and width direction of the film, (3) Under micro tension in the longitudinal direction of the film It is important that the thermal deformation ratio in the above satisfies the above range at the same time. When the film satisfies these characteristics at the same time, the molding polyester film of the present invention having the effect of satisfying the above various market requirements can be obtained.
[0026]
The base material of the molding polyester film of the present invention is a biaxially stretched polyester film containing a copolymerized polyester.Ru.
[0027]
The polyester film for molding according to the present invention comprises a copolymer polyester composed of an aromatic dicarboxylic acid component and ethylene glycol and a glycol component containing a branched aliphatic glycol and / or an alicyclic glycol as a base film raw material. It is preferable to use it for a part or all of the above.
[0028]
The copolyester is an aromatic dicarboxylic acid componentButTerephthalic acidOrBecome.
[0029]
As branched aliphatic glycols,,Neopentyl glycolInThe As the alicyclic glycol, 1,4-cyclohexanedimethanolIt is.
[0030]
Examples of the catalyst used for producing the copolymer polyester include alkaline earth metal compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, titanium / silicon composite oxides, and germanium compounds. . Among these, titanium compounds, antimony compounds, and germanium compounds are preferable from the viewpoint of catalytic activity.
[0031]
When producing the copolymer polyester, it is preferable to add a phosphorus compound as a heat stabilizer. As said phosphorus compound, phosphoric acid, phosphorous acid, etc. are preferable, for example.
[0032]
The copolyester preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, and particularly preferably 0.00 from the viewpoint of moldability, adhesiveness, and film formation stability. 60 dl / g or more. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease. In addition, when a filter for removing foreign substances is provided in the melt line, the upper limit of the intrinsic viscosity is preferably 1.0 dl / g from the viewpoint of ejection stability during extrusion of the molten resin.
[0033]
In the molding polyester film of the present invention, the copolymerized polyester may be used as a film raw material as it is, or a copolymerized polyester having a large amount of copolymerized components may be blended with a homopolyester to adjust the amount of copolymerized components. Absent.
[0034]
In particular, by forming a film using the latter blending method, transparency and a high melting point (heat resistance) can be achieved while maintaining the same flexibility as when only the copolyester is used. In addition, when only a high melting point homopolyester (for example, polyethylene terephthalate) is used, it is possible to realize a melting point (heat resistance) having no flexibility and practical problem while maintaining high transparency.
[0035]
Moreover, it is preferable from the point of a moldability to blend 2 or more types of the said copolyester, and to use as a raw material of the polyester film for shaping | molding of this invention.
[0036]
The melting point of the polyester film is 200 to 245 ° C. from the viewpoint of heat resistance and moldability.Ru. By controlling the type and composition of the polymer to be used and the film forming conditions within the range of the melting point, a balance between moldability and finish can be achieved, and a high-quality molded product can be produced economically. Here, the melting point is an endothermic peak temperature at the time of melting, which is detected at the time of primary temperature rise in so-called differential scanning calorimetry (DSC). The melting point was determined by measuring with a differential scanning calorimeter (DuPont, V4.OB2000 type) at a heating rate of 20 ° C./min. The lower limit of the melting point is more preferably 210 ° C, particularly preferably 230 ° C. If the melting point is less than 200 ° C, the heat resistance tends to deteriorate. Therefore, it may become a problem when exposed to high temperature during molding or use of a molded product.
[0037]
The upper limit of the melting point is preferably high from the viewpoint of heat resistance. However, when the polyethylene terephthalate unit is a main component, a film having a melting point exceeding 245 ° C tends to deteriorate moldability. In addition, transparency tends to deteriorate. Furthermore, in order to obtain high moldability and transparency, it is preferable to control the upper limit of the melting point to 240 ° C.
[0038]
Moreover, in order to improve handling properties, such as the slipperiness and winding property of a film, it is preferable to form an unevenness | corrugation on the film surface. As a method for forming irregularities on the film surface, a method of incorporating particles in the film is generally used.
[0039]
Examples of the particles include internal particles having an average particle size of 0.01 to 10 μm, external particles such as inorganic particles and / or organic particles. When particles having an average particle diameter exceeding 10 μm are used, defects in the film are liable to occur, and the design and transparency tend to deteriorate. On the other hand, in the case of particles having an average particle diameter of less than 0.01 μm, handling properties such as film slipperiness and winding property tend to be lowered. The lower limit of the average particle diameter of the particles is more preferably 0.10 μm, particularly preferably 0.50 μm, from the viewpoint of handling properties such as slipping property and winding property. On the other hand, the average particle diameter of the particles is more preferably 5 μm, particularly preferably 2 μm, from the viewpoint of transparency and reduction of film defects due to coarse protrusions.
[0040]
The average particle size of the particles is taken by taking a plurality of photographs of at least 200 particles by electron microscopy, tracing the outline of the particles on an OHP film, and converting the trace image to an equivalent circle diameter with an image analyzer. To calculate.
[0041]
Examples of the external particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, hydroxyapatite and the like, and styrene, silicone, acrylic Organic particles or the like containing acids as constituent components can be used. Among these, inorganic particles such as dry, wet and dry colloidal silica and alumina, and organic particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components are preferably used. Two or more of these internal particles, inorganic particles and / or organic particles may be used in combination as long as the characteristics defined in the present invention are not impaired.
[0042]
Furthermore, the content of the particles in the film is preferably in the range of 0.001 to 10% by mass. When the amount is less than 0.001% by mass, the handling property is likely to be deteriorated, for example, the slipperiness of the film is deteriorated or winding becomes difficult. On the other hand, if it exceeds 10% by mass, it tends to cause formation of coarse protrusions, deterioration of film forming property and transparency.
[0043]
Moreover, since the particle | grains contained in a film generally differ in refractive index from polyester, it becomes a factor which reduces the transparency of a film.
[0044]
In many cases, the molded product is printed on the surface of the film before the film is molded in order to improve the design. Since such a printing layer is often applied to the back side of a molding film, it is desired that the transparency of the film is high from the viewpoint of printing clarity.
[0045]
Therefore, in order to obtain a high degree of transparency while maintaining the handleability of the film, the base film is substantially free of particles, and the particles are contained only in the surface layer having a thickness of 0.01 to 5 μm. It is effective.
[0046]
Note that “substantially no particles are contained in the base film” as used above means, for example, in the case of inorganic particles, the content that is below the detection limit when inorganic elements are quantified by fluorescent X-ray analysis. means. This is because contaminants derived from foreign substances may be mixed without intentionally adding particles to the base film.
[0047]
The thin surface layer can be formed by a coating method or a coextrusion method.
[0048]
Especially, in the case of the coating method, since the adhesiveness with a printing layer can also be improved by using the composition which consists of adhesive modification resin containing particle | grains as an application layer, it is a preferable method. As said adhesive property modification resin, resin which consists of at least 1 sort (s) chosen from polyester, a polyurethane, an acryl-type polymer, and those copolymers is preferable.
[0049]
Furthermore, in order to further improve the adhesion between the base film and the adhesive modified layer, the surface of the base film may be surface-treated in advance, and the adhesive modified layer may be provided on the surface-treated surface. Examples of the surface treatment method include: (1) a method using irradiation with active energy rays such as corona discharge treatment, plasma discharge treatment, ultraviolet (UV) irradiation treatment, radiation (EB) irradiation treatment, (2) flame treatment, (3 ) Vapor deposit methods such as PVD and CVD.
[0050]
By setting it as such a laminated structure, ratio (H / d) of haze H (%) with respect to the thickness d (micrometer) of a film can be made into less than 0.010, maintaining the handling property of a film.
[0051]
In particular, when the molding polyester film is used for applications requiring transparency, the ratio (H / d) of haze H (%) to film thickness d (μm) is less than 0.010. Is preferable from the viewpoint of transparency and print sharpness. The H / d is more preferably more than 0 and less than 0.010, particularly preferably more than 0 and 0.009 or less. In the present invention, the numerical value of H / d is described in the third decimal place, but it is not rounded off after the fourth decimal place. For example, even 0.0099 is set to 0.009.
[0052]
The lower limit of H / d is preferably closer to zero from the viewpoint of transparency and print sharpness. However, if the essential minimum unevenness is not formed on the film surface, the handling properties such as the slipping property and the winding property deteriorate, and the film surface may be damaged or the productivity may deteriorate. Therefore, the lower limit value of H / d is preferably 0.001, and particularly preferably 0.005. In the case of a translucent nameplate using a backlight, a higher degree of transparency is required. Therefore, the H / d is preferably closer to zero.
[0053]
As the particles to be contained in the surface layer, the same particles as those described above can be used. Among the particles, silica particles, glass fillers, and silica-alumina composite oxide particles are particularly suitable from the viewpoint of transparency because the refractive index is relatively close to that of polyester.
[0054]
Moreover, when the surface layer contains particles having an average particle diameter of more than 10 μm, the frequency with which coarse protrusions are formed on the film surface increases, and the design property tends to deteriorate. On the other hand, in the case of particles having an average particle diameter of less than 0.01 μm, handling properties such as film slipperiness and winding property tend to be lowered. The preferable range of the average particle diameter of the particles is the same as that when the particles are contained in the base film.
[0055]
Furthermore, the particle content in the surface layer is preferably in the range of 0.01 to 25% by mass. When the content is less than 0.01% by mass, handling properties are likely to deteriorate, for example, the slipperiness of the film is deteriorated or winding becomes difficult. On the other hand, when it exceeds 25 mass%, transparency and applicability tend to deteriorate.
[0056]
In order to impart other functions, the polyester film of the present invention can be made into a laminated structure by a known method using different types of polyester. The form of the laminated film is not particularly limited. For example, the laminated film has an A / B two-kind two-layer structure, a B / A / B two-kind three-layer structure, and a C / A / B three-kind three-layer structure. The form is mentioned
[0057]
It is important that the molding polyester film of the present invention is a biaxially stretched film. In the present invention, due to molecular orientation by biaxial stretching, the thermal deformation rate of the film under the micro tension (initial load 49 mN) can be within the range of the present invention, which is a disadvantage of the unstretched sheet. Solvent property and dimensional stability are improved. That is, it is one of the features of the present invention that the solvent resistance and heat resistance, which are defects of the unstretched sheet, are improved while maintaining the good formability of the unstretched sheet.
[0058]
The method for producing the polyester base film is not particularly limited. For example, after drying a polyester resin as necessary, the polyester base film is supplied to a known melt extruder, extruded into a sheet form from a slit die, and electrostatically applied. An example is a method in which the unstretched sheet is biaxially stretched after being brought into close contact with the casting drum by a method such as the above, solidified by cooling and obtaining an unstretched sheet.
[0059]
As the biaxial stretching method, a method is employed in which an unstretched sheet is stretched and heat-treated in the longitudinal direction (MD) and width direction (TD) of the film to obtain a biaxially stretched film having a desired in-plane orientation degree. . Among these methods, in terms of film quality, the MD / TD method in which the film is stretched in the longitudinal direction and then stretched in the width direction, or the TD / MD method in which the film is stretched in the width direction and then stretched in the longitudinal direction. An axial stretching method and a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are stretched almost simultaneously are desirable. In the case of the simultaneous biaxial stretching method, a tenter driven by a linear motor may be used. Furthermore, if necessary, a multistage stretching method in which stretching in the same direction is performed in multiple stages may be used.
[0060]
The film stretching ratio when biaxially stretching is preferably 1.6 to 4.2 times in the longitudinal direction and the width direction, particularly preferably 1.7 to 4.0 times. In this case, the stretching ratio in the longitudinal direction and the width direction may be either larger or the same ratio. More preferably, the stretching ratio in the longitudinal direction is 2.8 to 4.0 times, and the stretching ratio in the width direction is 3.0 to 4.5 times.
[0061]
The stretching conditions for producing the molding polyester film of the present invention are not particularly limited. However, in order to satisfy the characteristics defined in the present invention, it is preferable to select, for example, the following conditions.
[0062]
In the longitudinal stretching, it is more preferable that the stretching temperature is 50 to 110 ° C. and the stretching ratio is 1.6 to 4.0 times so that the subsequent lateral stretching can be performed smoothly.
[0063]
Usually, when stretching the polyethylene terephthalate, if the stretching temperature is lower than the appropriate conditions, the yield stress increases rapidly at the beginning of the lateral stretching, and therefore stretching cannot be performed. Moreover, even if it can extend | stretch, since thickness and a draw ratio become easy to become nonuniform, it is unpreferable.
[0064]
In addition, when the stretching temperature is higher than appropriate conditions, the initial stress is low, but the stress does not increase even when the stretch ratio is high. Therefore, the film has a small stress at 100% elongation at 25 ° C. Therefore, by taking the optimum stretching temperature, a highly oriented film can be obtained while ensuring stretchability.
[0065]
However, when the copolymerized polyester contains 1 to 40 mol% of a copolymer component, the stretching stress rapidly decreases as the stretching temperature is increased so as to eliminate the yield stress. In particular, since the stress does not increase even in the latter half of the stretching, the orientation does not increase and the stress at 100% elongation at 25 ° C. decreases.
[0066]
Such a phenomenon is likely to occur when the thickness of the film is 60 to 500 μm, and is particularly noticeable in a film having a thickness of 100 to 300 μm. Therefore, in the case of a film using the copolymerized polyester of the present invention, the stretching temperature in the transverse direction is preferably set as follows.
[0067]
First, the preheating temperature is preferably 50 ° C to 150 ° C. Next, in the first half of the transverse stretching, the stretching temperature is preferably −20 ° C. to + 25 ° C., particularly preferably −15 ° C. to + 25 ° C. with respect to the preheating temperature. Also, in the second half of transverse stretching, the stretching temperature is relative to the stretching temperature in the first half.-10Preferably between ℃ and -40 ℃No. By adopting such conditions, the first half of the transverse stretching is easy to stretch because the yield stress is small, and the second half is easily oriented. In addition, it is preferable that the draw ratio of a horizontal direction shall be 2.5 to 5.0 times. As a result, F100 defined in the present invention.25And F100100Can be obtained.
[0068]
Furthermore, the film is heat-treated after biaxial stretching, and this heat treatment can be performed by a conventionally known method such as in an oven or on a heated roll. Further, the heat treatment temperature and the heat treatment time can be arbitrarily set according to the required level of heat shrinkage. The heat treatment temperature is preferably in the range of 120 to 245 ° C, particularly preferably 150 to 240 ° C. The heat treatment time is preferably 1 to 60 seconds. In addition, you may perform this heat processing, relaxing a film to the longitudinal direction and / or the width direction.
[0069]
In order to reduce the thermal shrinkage rate at 150 ° C. in the longitudinal and lateral directions of the film, it is preferable to increase the heat treatment temperature, lengthen the heat treatment time, and perform relaxation treatment. Specifically, in order to set the heat shrinkage rate at 150 ° C. in the longitudinal direction and the width direction of the film to 6.0% or less, the heat treatment temperature is 200 to 220 ° C. and the relaxation rate is 1 to 8%. However, it is preferable to carry out. Furthermore, re-stretching may be performed once or more in each direction, and then heat treatment may be performed.
[0070]
In order to reduce the heat shrinkage rate at 150 ° C. in the longitudinal direction and the transverse direction of the film, it is difficult to lengthen the production line and lengthen the heat treatment time due to equipment limitations. Further, when the film feeding speed is slowed, productivity is lowered. Thus, while it is necessary to make the section temperature as low as about 100 ° C. until the stretching section, it is necessary to quickly raise the temperature to about 200 ° C. in heat setting. Therefore, it is recommended as a preferred embodiment that a far infrared heater is installed in the heat treatment zone to reinforce the heating as a measure for solving the problem.
[0071]
Furthermore, there is a method in which a heat insulating section of 1 m or more is provided between the extending section and the heat fixing section to increase the heating efficiency after the heat insulating section. Specifically, the heating efficiency can be increased by strengthening the partition for each section to reduce the leakage of heat flow. Moreover, you may use the method which adjusts the pressure in oven and suppresses the leakage of a heat flow, ensuring air volume by adjusting the balance and strength of an air volume. For heating that is insufficient with hot air heating, a method of adding an infrared heater to the strong heating section is also suitable. In addition, the heating amount is increased by increasing the length of the heat fixing section and the number of sections. Such a method is also effective.
[0072]
The polyester film for molding of the present invention has a storage viscoelastic modulus (E ′) in the longitudinal and width directions of the film of 10 to 1000 MPa at 100 ° C. and 5 to 40 MPa at 180 ° C. In order to achieve such storage viscoelastic modulus (E ′), when producing a biaxially stretched film containing the above-mentioned copolymerized polyester as a base material, the plane orientation degree of the film should be controlled within a specific range. It is also important. That is, the degree of plane orientation of the film is preferably as low as 0.100 or less, and particularly preferably controlled to 0.001 to 0.090. Thus, the storage elastic modulus (E ') of the said film can be made small by making plane orientation degree low.
[0073]
However, the storage viscoelastic modulus (E ′) of the film at 180 ° C. becomes too small simply by reducing the plane orientation of the film. By using a copolymerized polyester having a branched aliphatic glycol and / or alicyclic glycol as a copolymerization component, which is a preferred embodiment of the present invention, as a film material, the bulk of the molecular structure of the glycol can be increased at high temperatures. Controlling the storage viscoelastic modulus (E ′) of the film at 180 ° C. within the above range by synergistic means by using specific stretching conditions that suppress molecular mobility and lower the degree of plane orientation of the film. Can.
[0074]
As described above, it is one of the preferred embodiments that the surface orientation degree of the base film is set to a low level, but the means for imparting the characteristics is not limited and is arbitrary. In general, as means for lowering the degree of plane orientation, a method of lowering the draw ratio and a method of raising the heat setting temperature are known, but the former method is not preferred because the thickness unevenness of the film deteriorates. Therefore, the latter method is preferable. In the latter case, the above-mentioned problem occurs, but it can be avoided by the method exemplified as a preferred embodiment. Further, in the present invention, it is necessary to use a copolymerized polyester as a base film, and since the melting point is lower than that of a uniform polymer, when the heat setting temperature is increased, the film is attached to the clip that holds the film in the transverse stretching step. It becomes easy to fuse. Therefore, it is important that the vicinity of the clip is sufficiently cooled when the clip releases the film at the tenter outlet. Specifically, in order to prevent the film and the clip from being fused, (1) a method of providing a heat shielding wall on the clip portion so that the clip is hardly heated, and (2) a clip cooling mechanism is added to the tenter. Method, (3) A method of setting a long cooling section after heat setting to enhance cooling capacity and sufficiently cooling the entire film, (4) Cooling by increasing the length of the cooling section and the number of sections It is preferable to employ a method of increasing efficiency, (5) a method of enhancing the cooling of the clip using a type in which the return portion of the clip travels outside the furnace, and the like.
[0075]
In the present invention, the substrate film preferably has a light transmittance of 90% or less at a wavelength of 380 nm or less. The light transmittance at a wavelength of 390 nm or less is more preferably 90% or less, and the light transmittance at a wavelength of 400 nm or less is particularly preferably 90% or less. By imparting the characteristics, the light resistance of the polyester layer for molding, particularly when the film is printed, is improved.
[0076]
The method for adjusting the light transmittance at a wavelength of 380 nm or less to 90% or less is optional without limitation, but a method of blending an ultraviolet absorber in any of the constituent layers of the base film is recommended. The ultraviolet absorber used in the method may be appropriately selected without limitation as long as the above-described characteristics can be imparted. Either inorganic or organic may be used. Examples of organic ultraviolet absorbers include benzotoazole, benzophenone, cyclic imino ester, and combinations thereof. From the viewpoint of heat resistance, benzotoazole and cyclic imino ester are preferred. When two or more kinds of ultraviolet absorbers are used in combination, ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.
[0077]
Examples of the benzotriazole ultraviolet absorber include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl). ) Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyhexyl) phenyl ] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert -Butyl-3 '-(methacryloyloxyethyl) phenyl] -2 -Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-( Methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like. However, it is not particularly limited to these.
[0078]
Examples of the cyclic imino ester ultraviolet absorber include 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), 2-methyl-3,1-benzo. Oxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1 -Benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitro Phenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2 -O-metoki Phenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p- (or m-) phthalimidophenyl-3,1-benzoxazin-4-one 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one) 2,2'-bis (3,1-benzoxazin-4-one), 2, 2'-ethylenebis (3,1-benzoxazin-4-one), 2,2'-tetramethylenebis (3,1-benzoxazin-4-one), 2,2'-decamethylenebis (3 1-benzoxazin-4-one), 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazine-4 -On), 2,2 '-(4 '-Diphenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2,6- or 1,5-naphthalene) bis (3,1-benzoxazin-4-one), 2 , 2 '-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene) bis (3,1-benzoxazine- 4-one), 2,2 '-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene) bis (3 1-benzoxazin-4-one) 1,3,5-tri (3,1-benzoxazin-4-on-2-yl) benzene, 1,3,5-tri (3,1-benzoxazine-4 -On-2-yl) naphthalene and 2,4,6-tri (3,1- Nzooxazin-4-on-2-yl) naphthalene, 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,6 -Dione, 2,7-dimethyl-4H, 9H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,9-dione, 2,8-diphenyl- 4H, 8H-benzo (1,2-d; 5,4-d ′) bis- (1,3) -oxazine-4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2 -D; 5,4-d ') bis- (1,3) -oxazine-4,6-dione, 6,6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one) 6,6'-bis (2-ethyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2-phenyl- H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-phenyl- 4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2- Phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-butylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-butylenebis (2- Phenyl-4H, 3,1-benzoxazin-4-one), 6,6′-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-oxybis (2- Phenyl-4H, 3,1-benzoo Sazine-4-one), 6,6'-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-sulfonylbis (2-phenyl-4H, 3,1) -Benzoxazin-4-one), 6,6'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 7,7′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-methylenebis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 7,7′-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one) 7,7'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis (2-methyl-4H, 3,1-benzoxazin-4-one) ), 6,7'-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,7'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one) ), And 6,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one).
[0079]
When the above-mentioned organic ultraviolet absorber is blended into the base film, it is exposed to a high temperature in the extrusion process. Therefore, the ultraviolet absorber uses a UV absorber having a decomposition start temperature of 290 ° C. or more at the time of film formation. It is preferable in order to reduce contamination. If an ultraviolet absorber having a decomposition start temperature of 290 ° C. or lower is used, the decomposed product of the ultraviolet absorber adheres to the roll group of the manufacturing apparatus during film formation, and may reattach to the film or be damaged. Since it becomes an optical fault, it is not preferable.
[0080]
Examples of inorganic ultraviolet absorbers include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide.
[0081]
As another method for reducing the light transmittance at a wavelength of 380 nm or less to 90% or less, a method of using a compound that forms a polyester, such as naphthalenedicarboxylic acid, having absorption in this wavelength region, as a copolymerization component of the polyester. Can be mentioned.
[0082]
As described above, by using the molding polyester film of the present invention, it is difficult to mold with the conventional biaxially oriented polyester film, and the vacuum at a molding pressure of 10 atm or less is low. Also in molding methods such as molding and pressure molding, it is possible to obtain a molded product with good finish. In addition, these molding methods are advantageous in terms of economy in the production of molded products because the molding costs are low. Therefore, the characteristics of the molding polyester film of the present invention can be exhibited most effectively by applying to these molding methods.
[0083]
On the other hand, although the mold and the molding apparatus are expensive and disadvantageous in terms of economy, mold molding is characterized in that a molded product having a more complicated shape than that of the molding method is molded with high accuracy. Therefore, when molding using the molding polyester film used in the present invention, molding is possible at a lower molding temperature compared to conventional biaxially oriented polyester film, and the finished quality of the molded product is improved. The remarkable effect that it is done is expressed.
[0084]
Furthermore, the molded product thus molded has excellent elasticity and shape stability (heat shrinkage characteristics, thickness unevenness) when used in a room temperature atmosphere, and also has excellent solvent resistance and heat resistance, as well as environmental impact. Therefore, it can be suitably used as a molding member for home appliance nameplates, automobile nameplates, dummy cans, building materials, decorative plates, decorative steel plates, transfer sheets and the like.
[0085]
The molding polyester film of the present invention is also suitable as a molding material material to be molded using a molding method such as press molding, laminate molding, in-mold molding, draw molding, or bending molding, in addition to the above molding method. is there.
【Example】
[0086]
Hereinafter, the present invention will be described in detail by way of examples. The film properties obtained in each example were measured and evaluated by the following methods.
[0087]
(1) Intrinsic viscosity
0.1 g of the chip sample was precisely weighed and dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 6/4 (mass ratio) and measured at 30 ° C. using an Ostwald viscometer. In addition, the measurement was performed 3 times and the average value was calculated | required.
[0088]
(2) Thickness unevenness
A continuous tape sample having a length of 3 m in the transverse stretching direction and a length of 5 cm in the longitudinal stretching direction is taken up, and the film thickness is measured with a continuous film thickness measuring machine (manufactured by Anritsu Co., Ltd.) and recorded on a recorder. From the chart, the maximum value (Tmax), the minimum value (Tmin), and the average value (Tav) of the thickness were obtained, and the thickness unevenness (%) was calculated by the following formula. In addition, the measurement was performed 3 times and the average value was calculated | required. Moreover, when the length of a horizontal extending direction is less than 3 m, it joins and performs. In addition, the measurement data in the connection part was deleted.
Unevenness of thickness (%) = ((Tmax−Tmin) / Tav) × 100
[0089]
(3) Haze
Based on JIS-K7136, it measured using the haze meter (the Nippon Denshoku Industries Co., Ltd. make, 300A). In addition, the measurement was performed twice and the average value was calculated | required.
[0090]
(4) Film thickness
Using Millitron, a total of 15 points were measured, 5 points per sheet, and the average value was determined.
[0091]
(5) Stress at 100% elongation, elongation at break
With respect to the longitudinal direction and the width direction of the biaxially stretched film, the sample was cut into a strip shape having a length of 180 mm and a width of 10 mm, respectively, with a single-blade razor. Next, the strip-shaped sample was pulled using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the 100% elongation stress (MPa) and elongation at break (%) in each direction were determined from the obtained load-strain curve. .
[0092]
The measurement was performed in an atmosphere of 25 ° C. under the conditions of an initial length of 40 mm, a distance between chucks of 100 mm, a crosshead speed of 100 mm / min, a recorder chart speed of 200 mm / min, and a load cell of 25 kg. In addition, this measurement was performed 10 times and the average value was used.
[0093]
In addition, a tensile test was performed under the same conditions as described above even in an atmosphere at 100 ° C. At this time, the sample was held for 30 seconds in an atmosphere at 100 ° C. and then measured. In addition, the measurement was performed 10 times and the average value was used.
[0094]
(6) Thermal shrinkage at 150 ° C
A strip sample having a length of 250 mm and a width of 20 mm is cut out in the longitudinal direction and the width direction of the film, respectively. Two marks are marked at intervals of 200 mm in the length direction of each sample, and the distance A between the two marks is measured under a constant tension (tension in the length direction) of 5 g. Subsequently, one side of each strip-shaped sample is hung with a clip under no load on the basket, and placed in a gear oven under an atmosphere of 150 ° C., and time is taken. After 30 minutes, the basket is removed from the gear oven and left at room temperature for 30 minutes. Next, for each sample, under a constant tension of 5 g (tension in the length direction), the interval B between the two marks is read with a gold finger in units of 0.25 mm. From the read intervals A and B, the thermal shrinkage rate at 150 ° C. of each sample is calculated by the following formula.
Thermal contraction rate (%) = ((A−B) / A) × 100
[0095]
(7) Storage viscoelastic modulus (E ')
Storage at 100 ° C. and 180 ° C. in the longitudinal direction (MD) and width direction (TD) of the film using a dynamic viscoelasticity measuring apparatus (DVA 225, manufactured by IT Measurement Control Co., Ltd.) under the following conditions: The elastic modulus (E ′) was determined.
(A) Sample width: 5 mm
(B) Measurement temperature range: −50 to 250 ° C.
(C) Frequency: 10Hz
(D) Temperature rising rate: 5 ° C./min
[0096]
(8) Thermal deformation rate under micro tension
Using a thermomechanical analyzer (Seiko Electronics Co., Ltd., TMA SS / 100), the temperature dependence of the dimensional change in the longitudinal direction of the film was determined under the following conditions.
(A) Sample width: 2 mm
(B) Measurement temperature range: 30 to 250 ° C.
(C) Initial load: 49 mN (5 gf)
(D) Temperature rising rate: 5 ° C./min
[0097]
(9) Degree of plane orientation (ΔP)
Using a sodium D line (wavelength 589 nm) as a light source and using an Abbe refractometer, the refractive index (Nz) in the longitudinal direction of the film, the refractive index (Ny) in the width direction, and the refractive index (Nz) in the thickness direction are measured. Calculated from the formula.
ΔP = ((Nx + Ny) / 2) −Nz
[0098]
(10) Light transmittance at a wavelength of 380 nm
Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1200), the light transmittance in the ultraviolet region with a wavelength of 380 nm was measured.
[0099]
(11) Light resistance
In the dark box, the offset-printed print sample was placed at a position 3 cm directly below the fluorescent lamp lamp (manufactured by Matsushita Electric Co., Ltd., U-type fluorescent lamp FUL9EX) so that the printed surface of the printed sample was on the back side. Next, light was continuously irradiated for 2000 hours, and the color difference (ΔE value) was measured according to JIS Z 8730 based on the color (a *, b *, L *) before and after the light irradiation on the printing surface side. . The smaller the color difference (ΔE value), the smaller the color change before and after the light irradiation, that is, the better the light resistance. The acceptable level of light resistance is 0.5 or less in color difference (ΔE value). The color difference (ΔE value) is calculated by the following formula.
ΔE = √ (Δa2+ Δb2+ ΔL2)
[0100]
(12) Formability
(A) Vacuum formability
After 5 mm square printing was performed on the film, the film was heated with an infrared heater heated to 500 ° C. for 10 to 15 seconds, and then vacuum molded at a mold temperature of 30 to 100 ° C. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold was a cup shape, the opening had a diameter of 50 mm, the bottom part had a diameter of 40 mm, the depth was 50 mm, and all corners were curved with a diameter of 0.5 mm. .
Five molded products that were vacuum-molded under the optimum conditions were evaluated for moldability and finish, and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is 1 mm or less and the printing deviation is 0.1 mm or less,
(Iii) No appearance defect corresponding to x
○: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is more than 1 mm and 1.5 mm or less, or the printing deviation is more than 0.1 mm and 0.2 mm or less,
(Iii) Furthermore, there is no appearance defect corresponding to x, and there is no practical problem
X: The molded product is torn, or even if it is not torn, it falls under any of the following items (i) to (iv)
(I) Corner radius of curvature exceeds 1.5 mm
(Ii) A large bag with a bad appearance
(Iii) The film is whitened and the transparency is lowered
(Iv) Print deviation exceeds 0.2 mm
[0101]
(B) Pneumatic formability
After 5mm square printing on the film, the film is heated for 10-15 seconds with an infrared heater heated to 500 ° C, and then subjected to pressure molding at a mold temperature of 30-100 ° C under a pressure of 4 atm. It was. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold is a cup shape, the opening has a diameter of 60 mm, the bottom has a diameter of 55 mm, a depth of 50 mm, and all corners are curved with a diameter of 0.5 mm. .
The moldability and finish of five molded products that were pressure-molded under optimal conditions were evaluated and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is 1 mm or less and the printing deviation is 0.1 mm or less,
(Iii) Those having no appearance defect corresponding to ×
○: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is more than 1 mm and 1.5 mm or less, or the printing deviation is more than 0.1 mm and 0.2 mm or less,
(Iii) Furthermore, there is no appearance defect corresponding to x, and there is no practical problem
X: The molded product is torn, or even if it is not torn, it falls under any of the following items (i) to (iv)
(I) Corner radius of curvature exceeds 1.5 mm
(Ii) A large bag with a bad appearance
(Iii) The film is whitened and the transparency is lowered
(Iv) Print deviation exceeds 0.2 mm
[0102]
(C) Mold formability
After printing on the film, contact heating was performed with a hot plate heated to 100 to 140 ° C. for 4 seconds, and then press molding was performed at a mold temperature of 30 to 70 ° C. and a pressure holding time of 5 seconds. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold is a cup shape, the opening has a diameter of 50 mm, the bottom has a diameter of 40 mm, a depth of 30 mm, and all corners are curved with a diameter of 0.5 mm. .
The moldability and finish of the five molded products molded under optimal conditions were evaluated and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is 1 mm or less and the printing deviation is 0.1 mm or less,
(Iii) Those having no appearance defect corresponding to ×
○: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is more than 1 mm and 1.5 mm or less, or the printing deviation is more than 0.1 mm and 0.2 mm or less,
(Iii) Furthermore, there is no appearance defect corresponding to x, and there is no practical problem
X: The molded product is torn, or even if it is not torn, it falls under any of the following items (i) to (iv)
(I) Corner radius of curvature exceeds 1.5 mm
(Ii) A large bag with a bad appearance
(Iii) The film is whitened and the transparency is lowered
(Iv) Print deviation exceeds 0.2 mm
[0103]
(13) Solvent resistance
The sample was immersed in toluene adjusted to 25 ° C. for 30 minutes, and the appearance change before and after the immersion was determined according to the following criteria, and ○ was accepted. The haze value was measured by the method described above.
○: Almost no change in appearance, haze value change less than 1%
×: Appearance change is recognized or change in haze value is 1% or more
[0104]
(14) Print quality
The film before printing was heat-treated at 90 ° C. for 30 minutes, and then four-color screen printing was performed.
Furthermore, the film provided with the printing layer was dried at 80 ° C. for 30 minutes. Evaluation of printing quality was made by visually judging the printing appearance such as the following clear feeling, printing suitability, printing misalignment and the like through the film from the back side, not from the printing side. As the judgment criteria, “O” indicates that there is no problem from all viewpoints, and “X” indicates that there is a problem in at least one point.
a. Clear feeling: The printed design looks clear without being blocked by the base film or coating layer.
b. Printability: Color unevenness and missing due to poor transfer of printing ink
c. Printing misalignment: The misalignment of printing cannot be determined visually.
[0105]
[Example 1]
Copolymer polyester chip having an intrinsic viscosity of 0.69 dl / g, comprising 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 40 mol% of ethylene glycol units and 60 mol% of neopentyl glycol units as diol components. (A) and a polyethylene terephthalate chip (B) containing 400 ppm of amorphous silica having an intrinsic viscosity of 0.69 dl / g and an average particle diameter (SEM method) of 1.5 μm were dried. Furthermore, the chip (A) and the chip (B) were mixed so as to have a mass ratio of 25:75. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched sheet was obtained.
[0106]
The obtained unstretched sheet was stretched 3.3 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the uniaxially stretched film was guided to a tenter, preheated at 120 ° C. for 10 seconds, and the first half of the transverse stretching was stretched 3.9 times at 110 ° C. and the latter half at 100 ° C. Further, a heat setting treatment was performed at 235 ° C. while performing a relaxation treatment of 7% in the transverse direction to obtain a biaxially stretched polyester film having a thickness of 100 μm.
[0107]
In the heat setting zone, an intermediate section of 2 m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and the limit position where the shielding plate in each section does not contact the film Expanded and installed. Also in the cooling section after heating, section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C., and the clip temperature at the tenter outlet is set to 40. Measures were taken to prevent clip fusion to below ℃.
[0108]
(Comparative Example 1)
In Example 1, a biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the heat setting temperature was changed to 205 ° C.
[0109]
(Comparative Example 2)
Characteristic evaluation of a commercially available unstretched sheet of A-PET (Toyobo Co., Ltd., PETMAX® A560GE0R, thickness: 200 μm) was performed.
[0110]
(Comparative Example 3)
Characteristic evaluation of a commercially available polycarbonate unstretched sheet (manufactured by Teijin Chemicals Ltd., Panlite Sheet (R) PC2151, thickness: 200 μm) was performed.
[0111]
(Comparative Example 4)
Characteristic evaluation of an unstretched acrylic sheet (manufactured by Mitsubishi Kasei Co., Ltd., Acryprene (R) HBS006, thickness: 125 μm) was performed.
[0112]
[Example 2]
Copolymer polyester chip having an intrinsic viscosity of 0.77 dl / g, comprising 100 mol% terephthalic acid unit as the aromatic dicarboxylic acid component, 70 mol% ethylene glycol unit and 30 mol% neopentylglycol unit as the diol component (C), a polyethylene terephthalate chip (D) containing 400 ppm of amorphous silica having an intrinsic viscosity of 0.63 dl / g and an average particle diameter (SEM method) of 1.5 μm, and an intrinsic viscosity of 0.75 dl The polypropylene terephthalate chip (E) containing 400 ppm of amorphous silica having an average particle size (SEM method) of 1.5 μm / g was dried. Furthermore, the chip (C), the chip (D), and the chip (E) were mixed so as to have a mass ratio of 50:10:40. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched sheet was obtained.
[0113]
The obtained unstretched sheet was stretched 3.5 times at 83 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the uniaxially stretched film was guided to a tenter, preheated at 95 ° C. for 10 seconds, and the first half of the transverse stretching was stretched 3.9 times at 80 ° C. and the latter half at 75 ° C. Further, a heat setting treatment was performed at 200 ° C. while performing a relaxation treatment of 7% in the transverse direction to obtain a biaxially stretched polyester film having a thickness of 100 μm.
[0114]
In the heat setting zone, an intermediate section of 2 m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and the limit position where the shielding plate in each section does not contact the film Expanded and installed. Also in the cooling section after heating, section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C., and the clip temperature at the tenter outlet is set to 40. Measures were taken to prevent clip fusion to below ℃.
[0115]
[Example 3]
As an aromatic dicarboxylic acid component, a terephthalic acid unit of 100 mol%, a diol component of an ethylene glycol unit of 70 mol% and a 1,4-cyclohexanedimethanol unit of 30 mol% as constituent components, an intrinsic viscosity of 0.71 dl / g. The polymerized polyester chip (F) and the polyethylene terephthalate chip (B) were mixed at a mass ratio of 50:50 and dried. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched sheet was obtained.
[0116]
The obtained unstretched sheet was stretched 3.5 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the uniaxially stretched film was guided to a tenter, preheated at 120 ° C. for 10 seconds, and the first half of the transverse stretching was stretched 3.9 times at 105 ° C. and the latter half at 100 ° C. Furthermore, a heat setting treatment was performed at 220 ° C. while performing a relaxation treatment of 7% in the transverse direction to obtain a biaxially stretched polyester film having a thickness of 100 μm.
[0117]
In the heat setting zone, an intermediate section of 2 m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and the limit position where the shielding plate in each section does not contact the film Expanded and installed. Also in the cooling section after heating, section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C., and the clip temperature at the tenter outlet is set to 40. Measures were taken to prevent clip fusion to below ℃.
[0118]
(Comparative Example 5)
A biaxially stretched polyester film having a thickness of 188 μm was obtained in the same manner as in Example 3 except that the heat setting temperature was changed to 205 ° C. in Example 3.
[0119]
[Example 4]
Chip of copolymer polyester having an intrinsic viscosity of 0.69 dl / g, comprising 100 mol% of terephthalic acid unit as aromatic dicarboxylic acid component, 40 mol% of ethylene glycol unit and 60 mol% of neopentyl glycol unit as diol components A) and a polybutylene terephthalate chip (G) containing 400 ppm of amorphous silica having an intrinsic viscosity of 0.69 dl / g and an average particle diameter (SEM method) of 1.5 μm were dried. Next, chip (A), chip (G), benzotriazole-based ultraviolet absorber (I) (manufactured by Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) was added at a mass ratio of 25.0: 74.5: 0.5 It mixed so that it might become. Next, these mixtures were melt-extruded from the slit of the T die at 265 ° C. by an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 20 ° C., and at the same time, the amorphous unstretched film was adhered to the chill roll using an electrostatic application method. A sheet was obtained.
[0120]
The obtained unstretched sheet was stretched 3.3 times at 80 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the uniaxially stretched film was guided to a tenter, preheated at 95 ° C. for 10 seconds, and the first half of the transverse stretching was stretched 3.8 times at 85 ° C. and the latter half at 80 ° C. Further, a heat setting treatment was performed at 200 ° C. while performing a relaxation treatment of 7% in the transverse direction to obtain a biaxially stretched polyester film having a thickness of 100 μm.
[0121]
In the heat setting zone, an intermediate section of 2 m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and the limit position where the shielding plate in each section does not contact the film Expanded and installed. Also in the cooling section after heating, section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C., and the clip temperature at the tenter outlet is set to 40. Measures were taken to prevent clip fusion to below ℃.
[0122]
(Comparative Example 6)
In Example 4, a biaxially stretched polyester film having a thickness of 100 μm was obtained in the same manner as in Example 4 except that the heat setting temperature was changed to 185 ° C.
[0127]
Example 14As for Comparative Examples 1, 5, and 6, the raw material composition and polymer characteristics of the polymers used are shown in Table 1, and the production conditions and characteristics of the films are shown in Tables 2 to 4. Table 5 shows the film characteristics of Comparative Examples 2 to 4.
[0128]
Example 14The biaxially oriented polyester film obtained in (1) had a good finish even when molded by a vacuum molding method or a pressure molding method with a low molding pressure during molding. Moreover, the solvent resistance and dimensional stability of the obtained molded product were also good. Moreover, since the film obtained in Example 4 contains an ultraviolet absorber, the light transmittance in the ultraviolet region at a wavelength of 380 nm is 0%, and the printed surface side before and after light irradiation for 2000 hours is continuous. The color difference was 0.5 or less, the color difference was smaller than the films obtained in Examples 1 to 3, and the light resistance was excellent..
[0129]
On the other hand, the films obtained in Comparative Examples 1, 5, 6 and 7 were inferior in moldability by the vacuum forming method or the pressure forming method, and the finished quality of the molded product was not good. Furthermore, the film obtained by these comparative examples was inferior in the finish property by the metal mold method compared with the film obtained in Examples 1-4. In addition, the unstretched sheets of Comparative Examples 2 to 4 had good moldability but poor solvent resistance and dimensional stability.
[0130]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[0135]
The molding polyester film of the present invention is excellent in moldability at the time of heat molding, particularly at low temperature and low pressure, so it can be applied to a wide range of molding methods and used as a molded product in a room temperature atmosphere. In addition, it has the advantages of excellent elasticity and shape stability (heat shrinkage characteristics, thickness unevenness), excellent solvent resistance and heat resistance, and low environmental impact, and is suitable as a member for home appliances, automobile nameplates or building materials. And the contribution to the industry is great.
【Effect of the invention】
[0136]
The molding polyester film of the present invention is excellent in moldability at the time of heat molding, particularly at low temperature and low pressure, so it can be applied to a wide range of molding methods and used as a molded product in a room temperature atmosphere. In addition, it is excellent in elasticity and shape stability (heat shrinkage characteristics, thickness unevenness), in addition, excellent in solvent resistance and heat resistance, and also has a small environmental load, so it is suitable for use as a member for home appliances, automobile nameplates or building materials. There is an advantage that can be.
Claims (6)
（１）構成成分となる共重合ポリエステルは、テレフタル酸と、エチレングリコールと、共重合成分としてネオペンチルグリコール及び／または１、４−シクロヘキサンジメタノールからなり、
（２）前記共重合ポリエステル中、共重合成分は１〜４０モル％であり、
（３）前記フィルムの融点が２００〜２４５℃であり、
（４）フィルムの長手方向及び幅方向における１００％伸張時応力が、いずれも２５℃において１０〜１０００ＭＰａ及び１００℃において１〜１００ＭＰａであり、
（５）フィルムの長手方向及び幅方向における貯蔵粘弾性率（Ｅ′）が、いずれも１００℃において１０〜１０００ＭＰａで、かつ１８０℃において５〜４０ＭＰａであり、
（６）フィルムの長手方向における熱変形率（初期荷重４９ｍＮ）が、１７５℃において−３％〜＋３％である、
ことを特徴とする成型用ポリエステルフィルム。It is a polyester film for molding made of a biaxially oriented polyester film, and the film has a copolymer polyester as a constituent component,
(1) The copolymer polyester as a constituent component comprises terephthalic acid, ethylene glycol, and neopentyl glycol and / or 1,4-cyclohexanedimethanol as a copolymer component,
(2) In the copolymer polyester, the copolymer component is 1 to 40 mol%,
(3) The melting point of the film is 200 to 245 ° C,
( 4 ) 100% elongation stress in the longitudinal and width directions of the film is 10 to 1000 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C.,
( 5 ) The storage viscoelastic modulus (E ′) in the longitudinal and width directions of the film is 10 to 1000 MPa at 100 ° C. and 5 to 40 MPa at 180 ° C.,
( 6 ) The thermal deformation rate (initial load 49 mN) in the longitudinal direction of the film is −3% to + 3% at 175 ° C.
A polyester film for molding characterized by that.
前記ホモポリエステルが、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、もしくはポリブチレンテレフタレートであることを特徴とする請求項１記載の成型用ポリエステルフィルム。The polyester film for molding according to claim 1, wherein the homopolyester is polyethylene terephthalate, polytrimethylene terephthalate, or polybutylene terephthalate.
（ａ）クリップ部分に熱遮蔽壁を設ける方法、(A) a method of providing a heat shielding wall on the clip portion;
（ｂ）クリップ冷却機構をテンターに付加する方法、(B) a method of adding a clip cooling mechanism to the tenter;
（ｃ）熱固定後の冷却区間を長く設定し、フィルム全体の冷却を十分行う方法、(C) A method in which the cooling section after heat setting is set long and the entire film is sufficiently cooled,
（ｄ）冷却区間の長さ、区画数を増やして、冷却効率を増加させる方法、または(D) A method of increasing the cooling efficiency by increasing the length of the cooling section and the number of sections, or
（ｅ）クリップの戻り部分が炉の外側を走行するタイプを用いてクリップの冷却を強化する方法、(E) a method for enhancing cooling of the clip using a type in which the return portion of the clip travels outside the furnace,
を用いてクリップの近傍を冷却してから、テンター出口でクリップからフィルムを開放して得られる請求項１〜４のいずれかに成型用ポリエステルフィルム。The polyester film for molding according to any one of claims 1 to 4, which is obtained by cooling the vicinity of the clip using a film and then releasing the film from the clip at the tenter outlet.
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| WO2015156638A1 (en) * | 2014-04-11 | 2015-10-15 | 코오롱인더스트리 주식회사 | Polyester film and manufacturing method therefor, and polyester mold product using same and manufacturing method therefor |
| KR20150117871A (en) * | 2014-04-11 | 2015-10-21 | 코오롱인더스트리 주식회사 | Manufacturing method of polyester film and manufacturing method of polyester product |
| WO2023003180A1 (en) * | 2021-07-19 | 2023-01-26 | 코오롱인더스트리 주식회사 | Polyester film having enhanced durability and method for evaluating durability of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4529072B2 (en) * | 2003-09-02 | 2010-08-25 | 東洋紡績株式会社 | Polyester film for molding and molded member formed by molding the same |
| JP4631271B2 (en) * | 2003-11-07 | 2011-02-16 | 東洋紡績株式会社 | Polyester film for molding and molding member for dummy container |
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| JP2011057850A (en) * | 2009-09-10 | 2011-03-24 | Toyobo Co Ltd | Polyester film for forming |
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| JP2014185245A (en) * | 2013-03-23 | 2014-10-02 | Mitsubishi Plastics Inc | Easily stretchable polyester film |
| JP6307896B2 (en) * | 2014-01-27 | 2018-04-11 | 東レ株式会社 | Laminated film |
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| JP7010218B2 (en) * | 2017-04-24 | 2022-01-26 | 東レ株式会社 | Film and film manufacturing method |
| KR102036418B1 (en) | 2017-12-26 | 2019-10-24 | 도레이첨단소재 주식회사 | Polyester film for molding and manufacturing method thereof |
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- 2004-02-06 WO PCT/JP2004/001245 patent/WO2005023521A1/en active Application Filing
- 2004-02-06 JP JP2005513581A patent/JP5191097B2/en not_active Expired - Fee Related
- 2004-08-30 KR KR1020067004323A patent/KR100757771B1/en not_active IP Right Cessation
- 2004-08-30 AT AT04772823T patent/ATE383390T1/en not_active IP Right Cessation
- 2004-09-01 TW TW093126301A patent/TWI297706B/en not_active IP Right Cessation
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2010
- 2010-05-24 JP JP2010118702A patent/JP5359992B2/en not_active Expired - Fee Related
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| JP2002097261A (en) * | 2000-07-17 | 2002-04-02 | Toray Ind Inc | Polyester film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015156638A1 (en) * | 2014-04-11 | 2015-10-15 | 코오롱인더스트리 주식회사 | Polyester film and manufacturing method therefor, and polyester mold product using same and manufacturing method therefor |
| KR20150117871A (en) * | 2014-04-11 | 2015-10-21 | 코오롱인더스트리 주식회사 | Manufacturing method of polyester film and manufacturing method of polyester product |
| KR102115026B1 (en) * | 2014-04-11 | 2020-05-26 | 코오롱인더스트리 주식회사 | Manufacturing method of polyester film and manufacturing method of polyester product |
| US10774189B2 (en) | 2014-04-11 | 2020-09-15 | Kolon Industries, Inc. | Polyester film and manufacturing method therefor, and polyester mold product using same and manufacturing method therefor |
| WO2023003180A1 (en) * | 2021-07-19 | 2023-01-26 | 코오롱인더스트리 주식회사 | Polyester film having enhanced durability and method for evaluating durability of same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005023521A1 (en) | 2005-03-17 |
| TWI297706B (en) | 2008-06-11 |
| KR20060063955A (en) | 2006-06-12 |
| JPWO2005023521A1 (en) | 2006-11-02 |
| JP5359992B2 (en) | 2013-12-04 |
| TW200512235A (en) | 2005-04-01 |
| JP2010229416A (en) | 2010-10-14 |
| KR100757771B1 (en) | 2007-09-12 |
| JP2013028816A (en) | 2013-02-07 |
| ATE383390T1 (en) | 2008-01-15 |
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