JP2009079170A - Polyester film for in-mold transfer foil - Google Patents
Polyester film for in-mold transfer foil Download PDFInfo
- Publication number
- JP2009079170A JP2009079170A JP2007250821A JP2007250821A JP2009079170A JP 2009079170 A JP2009079170 A JP 2009079170A JP 2007250821 A JP2007250821 A JP 2007250821A JP 2007250821 A JP2007250821 A JP 2007250821A JP 2009079170 A JP2009079170 A JP 2009079170A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyester
- transfer foil
- polyester film
- molded
- 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.)
- Withdrawn
Links
- 238000012546 transfer Methods 0.000 title claims abstract description 147
- 239000011888 foil Substances 0.000 title claims abstract description 108
- 229920006267 polyester film Polymers 0.000 title claims abstract description 94
- 238000000465 moulding Methods 0.000 abstract description 30
- 239000010410 layer Substances 0.000 description 93
- 229920001225 polyester resin Polymers 0.000 description 53
- 239000004645 polyester resin Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 42
- 229920000728 polyester Polymers 0.000 description 41
- 239000002245 particle Substances 0.000 description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- 238000001816 cooling Methods 0.000 description 25
- 238000000576 coating method Methods 0.000 description 19
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 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 3
- 239000011146 organic particle Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 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 2
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 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
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本発明は、成型転写箔用ポリエステルフィルムに関するものである。さらに詳しく述べれば、本発明は、転写後の成型品表面の艶消し性、成形性に優れた、成型転写箔用ポリエステルフィルムに関するものである。 The present invention relates to a polyester film for molded transfer foil. More specifically, the present invention relates to a polyester film for molded transfer foil, which has excellent matte properties and moldability on the surface of the molded product after transfer.
一般に、転写箔は、基材であるポリエステルフィルムの片面（転写面）に、順次、易接着層、離型層、印刷層および接着層などを積層して構成される。これら転写箔の転写方法としては、転写装置を用いて加熱ロールで被転写物に転写する、いわゆるホットスタンピング方法や、射出成形機やブロー成形機の金型に接着層が成形樹脂と接するように転写材をセッティングした後、成形樹脂を射出またはブローし、成形と同時に転写し、冷却後金型より成形品を取り出す、インモールド成形に代表される、いわゆる成形同時転写方法などが一般的に知られている。インモールド成形法は、成形と転写を同時に行えるため、複雑な絵柄の付与に非常に有用であり、家庭用電化製品、自動車部材、台所用品、化粧容器、玩具類および文具類などに使用されるプラスチック成形品で広く用いられている。 In general, a transfer foil is formed by sequentially laminating an easy adhesion layer, a release layer, a printing layer, an adhesive layer, and the like on one surface (transfer surface) of a polyester film as a base material. As a transfer method of these transfer foils, a transfer device is used to transfer to a transfer object with a heating roll, or a so-called hot stamping method, or an adhesive layer is in contact with a mold resin of an injection molding machine or a blow molding machine. After setting the transfer material, injection molding or blowing of molding resin, transfer at the same time as molding, take out the molded product from the mold after cooling, generally known as so-called molding simultaneous transfer method represented by in-mold molding, etc. It has been. The in-mold molding method can be molded and transferred at the same time, so it is very useful for applying complex patterns, and is used for household appliances, automobile parts, kitchenware, cosmetic containers, toys and stationery. Widely used in plastic molded products.
従来、基材であるフィルムとしては、二軸延伸ポリエステルが用いられてきたが、近年では、インモールド成形に用いる基材フィルムに対する種々の要求が高まってきた。例えば、共重合ポリエステルを用いて深絞り追従性とラミネート性に優れた成形加工用ポリエステルフィルムなどが提案されている（例えば、特許文献１参照）。 Conventionally, biaxially stretched polyester has been used as a film as a base material, but in recent years, various demands for a base film used for in-mold molding have increased. For example, a polyester film for molding process using a copolyester and excellent in deep drawing followability and laminating properties has been proposed (for example, see Patent Document 1).
しかしながら、最近は、成形性や加工性のみに留まらず、金属感、パール調、光沢、艶消しなど多彩な意匠性を実現するための改良が求められている。例えば、艶消しを発現させるため、成形用フィルムの転写面側に表面凸凹意匠性を付与する必要がある。
本発明の目的は、上記した従来技術の問題点を解消することにあり、転写後の成型品表面の艶消し性、成形性に優れた成型転写箔用ポリエステルフィルムを提供することにある。 An object of the present invention is to eliminate the above-described problems of the prior art, and to provide a polyester film for molded transfer foil that is excellent in matteness and moldability of the surface of a molded product after transfer.
上記課題は、次に挙げる手段を採用することにより達成することができる。すなわち、
（１）少なくとも転写面側のフィルム表面において、光沢度が１００％未満で、
１２０℃における破断伸度が４００％以上、かつ１２０℃における４００％伸長時の応力が１５ＭＰａ以下であることを特徴とする成型転写箔用ポリエステルフィルム。
The above-mentioned subject can be achieved by adopting the following means. That is,
(1) The glossiness is less than 100% at least on the film surface on the transfer surface side,
A polyester film for molded transfer foil, wherein the breaking elongation at 120 ° C is 400% or more, and the stress at 400% elongation at 120 ° C is 15 MPa or less.
（２）１００℃で３０分加熱した場合の熱収縮率が−０．５〜０．５％であることを特徴とする前記（１）に記載の成型転写箔用ポリエステルフィルム。 (2) The polyester film for molded transfer foil as described in (1) above, which has a thermal shrinkage of −0.5 to 0.5% when heated at 100 ° C. for 30 minutes.
（３）面配向係数が０〜０．０５であることを特徴とする前記（１）または（２）のいずれかに記載の成型転写箔用ポリエステルフィルム。 (3) The polyester film for molded transfer foil according to any one of (1) and (2), wherein the plane orientation coefficient is 0 to 0.05.
（４）前記（１）〜（３）のいずれかに記載の成型転写箔用ポリエステルフィルムを用いてなることを特徴とする成型転写箔。 (4) A molded transfer foil comprising the polyester film for molded transfer foil according to any one of (1) to (3).
本発明によれば、転写後の成型品表面の艶消し性、成形性に優れた、成型転写箔用ポリエステルフィルムを得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the polyester film for shaping | molding transfer foil which was excellent in the mattness of the surface of the molded article after transcription | transfer and the moldability can be obtained.
以下、本発明の成型転写箔用ポリエステルフィルムについて、実施の形態を説明する。 Hereinafter, embodiments of the polyester film for molded transfer foil of the present invention will be described.
本発明で用いられるポリエステルは、エステル結合を主鎖の主要な結合鎖とする高分子化合物であり、ジカルボン酸とジオールの重縮合によって得ることができる。 The polyester used in the present invention is a polymer compound having an ester bond as the main bond chain of the main chain, and can be obtained by polycondensation of dicarboxylic acid and diol.
ジカルボン酸成分としては、例えば、テレフタル酸、イソフタル酸、ジフェニルカルボン酸、ジフェニルスルホンジカルボン酸、ジフェノキシエタンジカルボン酸、５−ナトリウムスルホイソフタル酸、フタル酸などの芳香族ジカルボン酸、シュウ酸、コハク酸、エイコ酸、アジピン酸、セバシン酸、ダイマー酸、ドデカンジオン酸、マレイン酸、フマル酸などの脂肪族ジカルボン酸、シクロヘキサンジカルボン酸などの脂環族ジカルボン酸、トリメリット酸、およびピロメリット酸などの多官能酸などを挙げることができ、これら成分を複数用いて共重合体とすることもできる。 Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, diphenylcarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid and other aromatic dicarboxylic acids, oxalic acid, and succinic acid. , Eicoic acid, adipic acid, sebacic acid, dimer acid, dodecanedioic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, trimellitic acid, and pyromellitic acid A polyfunctional acid etc. can be mentioned, It can also be set as a copolymer using two or more of these components.
一方、ジオール成分としては、例えば、エチレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール、ヘキサンジオール、ネオペンチルグリコールおよびトリエチレングリコールなどの脂肪族グリコール、ビスフェノールＡやビスフェノールＳなどの芳香族グリコール、ジエチレングリコール、およびポリテトラメチレングリコールなどを挙げることができ、これら成分を複数用いて共重合体とすることもできる。 On the other hand, examples of the diol component include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol and triethylene glycol, aromatic glycols such as bisphenol A and bisphenol S, diethylene glycol, And polytetramethylene glycol, and a plurality of these components can be used as a copolymer.
ポリエステル中には、各種添加剤、例えば、酸化防止剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、有機および無機の粒子、顔料、染料、充填剤、帯電防止剤および核剤などが、本発明の効果を損なわない範囲で添加されていてもよい。 In the polyester, there are various additives such as antioxidants, heat stabilizers, weathering stabilizers, UV absorbers, organic lubricants, organic and inorganic particles, pigments, dyes, fillers, antistatic agents and nuclei. An agent or the like may be added as long as the effects of the present invention are not impaired.
本発明の成型転写箔用ポリエステルフィルムは、転写後の成型品の艶消し性の観点から、少なくとも転写面側のフィルム表面において、光沢度が１００％未満であることが重要である。成型転写箔用ポリエステルフィルムの転写面側のフィルム表面において、光沢度が１００％以上の場合、転写後の被転写物表面が平滑となり、その結果として、成型品表面の艶消し性が悪くなるので好ましくない。また、より好ましくは、少なくとも転写面側のフィルム表面において、光沢度が８０％以下である。また、適度な艶消し性を成型品表面に与えるためには、光沢度は１％以上であることが好ましいが、特に限定されない。 In the polyester film for molded transfer foil of the present invention, it is important that the glossiness is less than 100% at least on the film surface on the transfer surface side, from the viewpoint of matteness of the molded product after transfer. When the glossiness is 100% or more on the film surface on the transfer surface side of the polyester film for molded transfer foil, the surface of the transferred material after transfer becomes smooth, and as a result, the matte property of the molded product surface becomes worse. It is not preferable. More preferably, the glossiness is 80% or less at least on the film surface on the transfer surface side. Further, in order to give an appropriate matte surface to the molded product surface, the glossiness is preferably 1% or more, but is not particularly limited.
上記の光沢度が１００％未満であるポリエステルフィルムを製造するには、例えば、加熱溶融した樹脂をＴダイから押し出し、冷却ロールに密着せしめて冷却固化する製造方法を採用し、その際において、冷却ロールの温度を４０〜９０℃で冷却固化することが好ましい。この方法によると、結晶化を進め、フィルム表面を粗くして、光沢度を低くすることができる。 In order to produce a polyester film having a glossiness of less than 100%, for example, a production method is adopted in which a heat-melted resin is extruded from a T-die and adhered to a cooling roll to be cooled and solidified. It is preferable to cool and solidify the roll at 40 to 90 ° C. According to this method, crystallization can be advanced, the film surface can be roughened, and glossiness can be lowered.
また上記の光沢度が１００％未満であるポリエステルフィルムを製造するには、冷却ロールの表面が粗い形状のものを用いる方法、ニップロールを用いてエンボスを付ける方法、フィルム中に不活性な無機または有機等の粒子を含有する方法も好ましい。 In addition, in order to produce a polyester film having a glossiness of less than 100%, a method using a chill roll having a rough surface, a method of embossing using a nip roll, an inert inorganic or organic film. A method containing particles such as is also preferred.
フィルム中に粒子を含有する方法において、用いる粒子としては、無機シリカ、アルミナ、炭酸カルシウム、カオリン、酸化チタン、硫酸バリウム、フッ化リチウム、タルク、カーボンブラック等の不活性外部粒子、ポリエステル樹脂の溶融製膜に際して不溶な高融点有機化合物、架橋高分子およびポリエステル合成時に使用する金属化合物触媒、例えば、アルカリ金属化合物、アルカリ土類金属化合物などによってポリエステル製造時にポリマー内部に形成される内部粒子を挙げることができる。これらの粒子は、単独あるいは２成分以上を同時に使用してもよいが、フィルム中の含有量は、本発明のポリエステルフィルムの全構成成分１００重量％において０．６〜１０．０重量％、好ましくは１．０〜５．０重量％の範囲である。粒子の含有量が０．６重量％未満の場合は、フィルム表面が平滑になりすぎ、光拡散性を得るために必要とする表面粗さが得られないことがある。また、フィルム中の全構成成分１００重量％における粒子含有量が１０．０重量％を越えると、フィルムの製造押出機において、凝集・粗大粒子のための濾過フィルターの寿命が短くなったり、再凝集粒子の詰まりによる口金リップ部でフィルム筋が発生したりすることがある。より有効な光拡散性、また、フィルム安定製膜性を得るためには、粒子含有量は１．０〜５．０重量％の範囲とすることがさらに望ましい。 In the method of containing particles in the film, the particles used are inorganic silica, alumina, calcium carbonate, kaolin, titanium oxide, barium sulfate, lithium fluoride, talc, carbon black and other inert external particles, polyester resin melting List internal particles formed in the polymer during the production of the polyester by the high melting point organic compound insoluble in the film formation, the cross-linked polymer and the metal compound catalyst used in the synthesis of the polyester, such as an alkali metal compound or an alkaline earth metal compound. Can do. These particles may be used alone or in combination of two or more components. However, the content in the film is preferably 0.6 to 10.0% by weight, preferably 100% by weight, based on 100% by weight of all the components of the polyester film of the present invention. Is in the range of 1.0 to 5.0% by weight. When the content of the particles is less than 0.6% by weight, the film surface becomes too smooth and the surface roughness required for obtaining light diffusibility may not be obtained. Moreover, if the content of particles in 100% by weight of all components in the film exceeds 10.0% by weight, the life of the filter for agglomerated and coarse particles will be shortened or reagglomerated in the film production extruder. Film streaks may occur at the base lip due to particle clogging. In order to obtain more effective light diffusibility and stable film-forming property, the particle content is more preferably in the range of 1.0 to 5.0% by weight.
フィルムに適正な表面粗さを与えて、光沢度が１００％未満とするためには、粒子の粒径も関与するので、用いる粒子の平均粒径は、０．３〜１０．０μｍの範囲、さらには１．０〜５．０μｍの範囲にすることが好ましい。平均粒径が０．３μｍ未満の粒子では、フィルムの表面粗さが小さくなりすぎ、十分な拡散反射効果が得られないことがある。また、平均粒径が１０．０μｍを越える粒子では、凝集・粗大粒子除去のための濾過フィルターを粗くする必要があり、フィルム中に異物が多くなる傾向がある。 In order to give an appropriate surface roughness to the film and the glossiness is less than 100%, the particle size of the particles is also involved, so the average particle size of the particles used is in the range of 0.3 to 10.0 μm, Furthermore, it is preferable to set it as the range of 1.0-5.0 micrometers. When the average particle size is less than 0.3 μm, the surface roughness of the film becomes too small, and a sufficient diffuse reflection effect may not be obtained. In addition, when the average particle size exceeds 10.0 μm, it is necessary to roughen the filter for removing aggregated and coarse particles, and there is a tendency that foreign matters increase in the film.
本発明において粒子の平均粒径とは、透過型電子顕微鏡ＨＵ−１２型（（株）日立製作所製）を用い、フィルムの断面を１０，０００倍に拡大観察した断面写真から求めた粒径の数平均値のことである。すなわち、断面写真の粒子部分をマーキングして、その粒子部分をハイビジョン画像解析処理装置ＰＩＡＳ−IV（（株）ピアス製）を用いて画像処理を行い、測定視野内の計１００個の粒子を真円に換算した時の平均径である。 In the present invention, the average particle diameter of the particles is a particle diameter determined from a cross-sectional photograph obtained by magnifying the cross section of the film 10,000 times using a transmission electron microscope HU-12 (manufactured by Hitachi, Ltd.). It is a number average value. That is, the particle portion of the cross-sectional photograph is marked, and the particle portion is subjected to image processing using a high-definition image analysis processing apparatus PIAS-IV (manufactured by Pierce Co., Ltd.), and a total of 100 particles in the measurement field of view are true. It is the average diameter when converted to yen.
またコーティングによって、転写箔を構成する離型層をフィルムの転写面側に設ける際、粒子を添加した離型剤をフィルムの転写面側に塗布する方法が好ましい。離型層を積層するプロセスとしては、オフラインコーティングとインラインコーティングの２種に大別することができ、プロセスは特に限定されない。 Moreover, when providing the release layer which comprises transfer foil on the transfer surface side of a film by coating, the method of apply | coating the release agent which added particle | grains to the transfer surface side of a film is preferable. The process for laminating the release layer can be broadly classified into two types, off-line coating and in-line coating, and the process is not particularly limited.
また他には、表面処理方法において、コロナ放電やプラズマ放電、 火炎(フレーム)処理や紫外線処理などの活性線照射処理、トリクロロ酢酸、アミン、クロム酸混液処理などによる化学的処理、エンボス加工、サンドマット加工（金属ブラシ・サンドブラスト法）、ヘアライン加工などによる物理的処理をすることが好ましい。 Other surface treatment methods include corona discharge, plasma discharge, active ray irradiation treatment such as flame treatment and ultraviolet treatment, chemical treatment such as trichloroacetic acid, amine and chromic acid mixed solution treatment, embossing, sand It is preferable to perform a physical treatment by mat processing (metal brush / sandblasting), hairline processing, or the like.
本発明の成型転写箔用ポリエステルフィルムは、フィルムの１２０℃における破断伸度が４００％以上であることが重要である。成型転写箔用ポリエステルフィルムの、１２０℃における破断伸度が４００％より小さい場合、成形性に劣り、成形中にフィルム破断が発生しやすくなるので好ましくない。成型転写箔用ポリエステルフィルムの、１２０℃における破断伸度は、好ましくは長さ方向および幅方向の直行する２方向で４００％以上の場合である。またより好ましくは、フィルムの１２０℃における破断伸度が長さ方向および幅方向で６００％以上であり、特に好ましくは、１２０℃における破断伸度が長さ方向および幅方向で８００％以上である。なお、１２０℃における破断伸度の上限値は特に限定されないが、現実的には２，０００％とすることは困難と考えられる。 It is important that the polyester film for molded transfer foil of the present invention has a breaking elongation at 120 ° C. of 400% or more. When the breaking elongation at 120 ° C. of the polyester film for molded transfer foil is less than 400%, the moldability is inferior, and film breakage tends to occur during molding, which is not preferable. The breaking elongation at 120 ° C. of the polyester film for molded transfer foil is preferably 400% or more in two directions perpendicular to the length direction and the width direction. More preferably, the breaking elongation at 120 ° C. of the film is 600% or more in the length direction and the width direction, and particularly preferably, the breaking elongation at 120 ° C. is 800% or more in the length direction and the width direction. . Note that the upper limit of the elongation at break at 120 ° C. is not particularly limited, but in practice, it is considered difficult to set it to 2,000%.
さらに本発明では、上述のようにフィルムの１２０℃における破断伸度を４００％以上と制御することと同時に、フィルムの１２０℃における４００％伸張時の応力が１５ＭＰａ以下であることが重要である。成型転写箔用ポリエステルフィルムの、１２０℃における４００％伸張時の応力が１５ＭＰａより大きい場合、成型加工において、フィルムが型に十分に追従しなくなり、成形性に劣るので好ましくない。成型転写箔用ポリエステルフィルムの、１２０℃における４００％伸張時の応力は、好ましくは長さ方向および幅方向の直行する２方向で１５ＭＰａより大きい場合である。またより好ましくは、フィルムの１２０℃における４００％伸張時の応力が長さ方向および幅方向で１０ＭＰａ以下である。なお、１２０℃における４００％伸張時の応力の下限値は特に限定されないが、成形性を考慮すると、下限値は１ＭＰａと考えられる。 Furthermore, in the present invention, it is important that the stress at 400% elongation at 120 ° C. of the film is 15 MPa or less at the same time as controlling the breaking elongation at 120 ° C. of 400% or more as described above. When the stress at 400% elongation at 120 ° C. of the polyester film for molded transfer foil is greater than 15 MPa, the film does not sufficiently follow the mold in the molding process, which is not preferable. The stress at 400% elongation at 120 ° C. of the polyester film for molded transfer foil is preferably greater than 15 MPa in two orthogonal directions in the length direction and width direction. More preferably, the stress at 400% elongation at 120 ° C. of the film is 10 MPa or less in the length direction and the width direction. The lower limit value of the stress at 400% elongation at 120 ° C. is not particularly limited, but the lower limit value is considered to be 1 MPa in consideration of formability.
また本発明では、本発明の成型転写箔用ポリエステルフィルムを１００℃において３０分加熱した場合の熱収縮率が−０．５〜０．５％であることが好ましい。成型転写箔用ポリエステルフィルムの熱収縮率が上記範囲から外れると、易接着層、離型層、印刷層および接着層を積層する際の乾燥工程において、フィルムが変形、収縮しやすく、しわなどが発生するので好ましくない。またより好ましくは、フィルムを１００℃において３０分加熱した場合の熱収縮率が−０．３〜０．３である。なお、本発明の成型転写箔用ポリエステルフィルムにおいて熱収縮率が−０．５〜０．５％となる方向は、フィルム面内の少なくとも一方向であることが重要であり、より好ましくは熱収縮率が−０．５〜０．５％である該一方向と同一面内にあるその直行方向であることが好ましい。なお、熱収縮率の値が「−」（マイナス）の値である場合、フィルムが伸びたことを示すものとする。 Moreover, in this invention, it is preferable that the heat shrink rate at the time of heating the polyester film for shaping | molding transfer foils of this invention for 30 minutes at 100 degreeC is -0.5 to 0.5%. When the thermal shrinkage rate of the polyester film for molded transfer foil is out of the above range, the film easily deforms and shrinks in the drying process when laminating the easy-adhesion layer, the release layer, the printing layer, and the adhesive layer, and wrinkles, etc. Since it occurs, it is not preferable. More preferably, the thermal shrinkage when the film is heated at 100 ° C. for 30 minutes is −0.3 to 0.3. In the polyester film for molded transfer foil of the present invention, it is important that the direction in which the heat shrinkage rate is −0.5 to 0.5% is at least one direction in the film plane, and more preferably heat shrinkage. It is preferable that it is the orthogonal direction which exists in the same plane as this one direction whose rate is -0.5 to 0.5%. In addition, when the value of thermal contraction rate is a value of “−” (minus), it indicates that the film is stretched.
本発明の成型転写箔用ポリエステルフィルムにおいて、少なくとも転写面側の表面において、１２０℃における破断伸度を長さ方向および幅方向で４００％以上、かつ１２０℃における４００％伸長時の応力を長さ方向および幅方向で１５ＭＰａ以下、１００℃において３０分加熱した場合の熱収縮率を−０．５〜０．５％とした成型転写箔用ポリエステルフィルムとする方法は、例えば以下に述べる方法で得ることができるが、本発明の成型転写箔用ポリエステルフィルムはこれに限定されない。 In the polyester film for molded transfer foil according to the present invention, at least at the surface on the transfer surface side, the elongation at break at 120 ° C. is 400% or more in the length direction and width direction, and the stress at 400% elongation at 120 ° C. is long. A method for forming a polyester film for molded transfer foil having a thermal shrinkage rate of −0.5 to 0.5% when heated at 100 ° C. for 30 minutes or less in the direction and width direction is obtained by, for example, the method described below. However, the polyester film for molded transfer foil of the present invention is not limited to this.
つまり、本発明の成型転写箔用ポリエステルフィルムは、
（１）ポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）の２層、もしくはポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）／ポリエステル樹脂層（Ａ）の３層からなること、
（２）前記ポリエステル樹脂層（Ａ）が、ポリエステルの全グリコール由来成分中の９０モル％以上１００モル％以下が１，４−ブタンジオール由来成分、ポリエステルの全ジカルボン酸由来成分中の９０モル％以上１００モル％以下がテレフタル酸由来成分であるポリエステルであること、
（３）前記ポリエステル樹脂層（Ａ）の１層の厚みが１〜３０μｍであること、
（４）前記ポリエステル樹脂層（Ｂ）が、ポリエステルの全グリコール由来成分中の６０モル％以上９９モル％以下がエチレングリコール由来成分、全グリコール由来成分中の１モル％以上４０モル％以下が１，４−ブタンジオール由来成分、ポリエステルの全ジカルボン酸由来成分中の９０モル％以上１００モル％以下がテレフタル酸および／またはナフタレンジカルボン酸由来成分であるポリエステルであること、
が本発明の成型転写箔用ポリエステルフィルムとして好ましい態様である。
That is, the polyester film for molded transfer foil of the present invention is
(1) Two layers of polyester resin layer (A) / polyester resin layer (B), or three layers of polyester resin layer (A) / polyester resin layer (B) / polyester resin layer (A),
(2) In the polyester resin layer (A), 90 mol% or more and 100 mol% or less in the total glycol-derived component of the polyester is 1,4-butanediol-derived component, and 90 mol% in the total dicarboxylic acid-derived component of the polyester. More than 100 mol% is a polyester which is a component derived from terephthalic acid,
(3) The thickness of one layer of the polyester resin layer (A) is 1 to 30 μm,
(4) In the polyester resin layer (B), 60 mol% or more and 99 mol% or less of the total glycol-derived component of the polyester is ethylene glycol-derived component, and 1 mol% or more and 40 mol% or less of the total glycol-derived component is 1 , 4-butanediol-derived component, and 90 mol% or more and 100 mol% or less of the total dicarboxylic acid-derived component of the polyester is terephthalic acid and / or naphthalenedicarboxylic acid-derived polyester,
Is a preferred embodiment as the polyester film for molded transfer foil of the present invention.
上記（２）について、前記ポリエステル樹脂層（Ａ）が、ポリエステルの全グリコール由来成分中の９０モル％以上１００モル％以下が１，４−ブタンジオール由来成分、ポリエステルの全ジカルボン酸由来成分中の９０モル％以上１００モル％以下がテレフタル酸由来成分であるポリエステルであることが好ましい。ポリエステル樹脂層（Ａ）の１，４−ブタンジオール由来成分が、ポリエステルの全ジカルボン酸由来成分中の９０モル％より小さく、かつ、テレフタル酸由来成分が、ポリエステルの全ジカルボン酸由来成分中の９０モル％より小さい場合、フィルム面内の少なくとも一方向の熱収縮率を−０．５〜０．５％の範囲のフィルムを得られ難いので好ましくない。 About said (2), the said polyester resin layer (A) is 90 mol% or more and 100 mol% or less in the component derived from all glycols of a polyester in a 1, 4- butanediol origin component, in all dicarboxylic acid origin components of polyester. It is preferable that 90 mol% or more and 100 mol% or less of the polyester is a terephthalic acid-derived component. The 1,4-butanediol-derived component of the polyester resin layer (A) is smaller than 90 mol% in the total dicarboxylic acid-derived component of the polyester, and the terephthalic acid-derived component is 90 in the total dicarboxylic acid-derived component of the polyester. When it is smaller than mol%, it is difficult to obtain a film having a thermal shrinkage ratio in at least one direction in the film plane of -0.5 to 0.5%, which is not preferable.
上記（３）について、前記ポリエステル樹脂層（Ａ）の１層の厚みが１〜３０μｍであることが好ましい。ポリエステル樹脂層（Ａ）の１層の厚みが１μｍより小さい場合、耐溶剤性が低下しやすくなり、かつ、熱収縮率が上記範囲のフィルムを得られ難いので好ましくない。また、ポリエステル樹脂層（Ａ）の１層の厚みが３０μｍより大きいと、１２０℃における４００％伸張時の応力が長さ方向および幅方向で１５ＭＰａ以下の範囲のフィルムを得られ難いので好ましくない。 About said (3), it is preferable that the thickness of 1 layer of the said polyester resin layer (A) is 1-30 micrometers. When the thickness of one layer of the polyester resin layer (A) is smaller than 1 μm, the solvent resistance is likely to be lowered, and it is difficult to obtain a film having a heat shrinkage rate within the above range, which is not preferable. Moreover, if the thickness of one layer of the polyester resin layer (A) is larger than 30 μm, it is difficult to obtain a film having a stress at 400% elongation at 120 ° C. in the range of 15 MPa or less in the length direction and the width direction.
上記（４）について、前記ポリエステル樹脂層（Ｂ）が、ポリエステルの全グリコール由来成分中の６０モル％以上９９モル％以下がエチレングリコール由来成分、全グリコール由来成分中の１モル％以上４０モル％以下が１，４−ブタンジオール由来成分、ポリエステルの全ジカルボン酸由来成分中の９０モル％以上１００モル％以下がテレフタル酸および／またはナフタレンジカルボン酸由来成分であるポリエステルであることが好ましい。上記以外のグリコール成分および／または上記範囲外であると、成形性および生産性が低下しやすくなり、かつ、１２０℃における破断伸度を４００％以上とすることが困難になり、また１２０℃における４００％伸張時の応力が長さ方向および幅方向で１５ＭＰａ以下とすることが困難になるので好ましくない。 About said (4), the said polyester resin layer (B) is 60 mol% or more and 99 mol% or less in all the glycol origin components of polyester from ethylene glycol origin components and 1 mol% or more and 40 mol% in all glycol origin components. It is preferable that the following is a polyester in which 90 mol% or more and 100 mol% or less of the 1,4-butanediol-derived component and the total dicarboxylic acid-derived component of the polyester is a terephthalic acid and / or naphthalenedicarboxylic acid-derived component. If the glycol component other than the above and / or the content is outside the above range, the moldability and productivity are likely to be lowered, and the elongation at break at 120 ° C becomes difficult to be 400% or more, and at 120 ° C. Since it becomes difficult for the stress at 400% elongation to be 15 MPa or less in the length direction and the width direction, it is not preferable.
また、本発明の成型転写箔用ポリエステルフィルムの製造方法として、
（５）加熱溶融した樹脂をＴダイから押し出し、４０〜９０℃に加熱した冷却ロールに、密着せしめて冷却固化する製造方法であることが好ましい。
Moreover, as a manufacturing method of the polyester film for molded transfer foil of the present invention,
(5) It is preferable that it is a manufacturing method which extrudes the heat-melted resin from the T-die and adheres it to a cooling roll heated to 40 to 90 ° C. to cool and solidify.
冷却ロールの温度を４０℃より低くすると、冷却ロールへの密着性が低下し、その結果として、生産性が低下しやすくなり、かつ、フィルム面内の少なくとも一方向の熱収縮率を−０．５〜０．５％と制御したフィルムを得られ難いので好ましくない。逆に、冷却ロールの温度を９０℃よりも高くすると、冷却ロールへの密着性が高くなりすぎ、冷却ロールからフィルムが剥がれにくく、フィルムの破断につながりやすく、また表面欠点が発生し、生産性が低下しやすくなり、かつ、１２０℃における４００％伸張時の応力が長さ方向および幅方向で１５ＭＰａ以下のフィルムが得られ難いので好ましくない。冷却ロールへの安定した密着方法として、生産性の観点から、シートの両端部に針状エッジピニング装置を用いる静電印加方式やシート全面にワイヤー装置を用いる静電印加方式が好ましい。 When the temperature of the cooling roll is lower than 40 ° C., the adhesion to the cooling roll is lowered, and as a result, the productivity is easily lowered, and the thermal shrinkage rate in at least one direction in the film plane is −0. It is not preferable because it is difficult to obtain a film controlled to 5 to 0.5%. On the contrary, if the temperature of the cooling roll is higher than 90 ° C., the adhesion to the cooling roll becomes too high, the film is not easily peeled off from the cooling roll, the film is easily broken, and surface defects occur, resulting in productivity. And a film having a stress at 400% elongation at 120 ° C. of 15 MPa or less in the length direction and the width direction is difficult to be obtained. From the viewpoint of productivity, an electrostatic application method using a needle-like edge pinning device at both ends of the sheet or an electrostatic application method using a wire device over the entire sheet is preferable as a method for stably adhering to the cooling roll.
なお、４０〜９０℃に加熱した冷却ロールに、密着せしめて冷却固化する製造方法を用いる場合において、本発明の成型転写箔用ポリエステルフィルムとして上記した好ましいポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）の２層からなるポリエステルフィルムを用いる場合は、ポリエステル樹脂層（Ａ）の面側を冷却ロールに密着させることが好ましい。 In addition, when using the manufacturing method which adheres to the cooling roll heated at 40-90 degreeC, and solidifies by cooling, preferable polyester resin layer (A) / polyester resin layer (as above-mentioned as a polyester film for shaping | molding transfer foils of this invention ( When using the polyester film which consists of two layers of B), it is preferable to make the surface side of a polyester resin layer (A) contact | adhere to a cooling roll.
また、４０〜９０℃に加熱した冷却ロールに、密着せしめて冷却固化する製造方法を用いて、樹脂に粒子を添加する場合において、上記した好ましいポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）の２層からなるポリエステルフィルムを用いる場合、およびポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）／ポリエステル樹脂層（Ａ）の３層からなるポリエステルフィルムを用いる場合は、ポリエステル樹脂層（Ａ）に粒子を添加させるのが好ましい。 In addition, in the case where particles are added to the resin by using a production method in which the particles are cooled and solidified by being adhered to a cooling roll heated to 40 to 90 ° C., the above-described preferable polyester resin layer (A) / polyester resin layer (B) When using a polyester film consisting of two layers, and when using a polyester film consisting of three layers of polyester resin layer (A) / polyester resin layer (B) / polyester resin layer (A), polyester resin layer (A) It is preferable to add the particles.
本発明の成型転写箔用ポリエステルフィルムは、成形性の観点から、面配向係数が０〜０．０５であることが好ましい。本発明の成型転写箔用ポリエステルフィルムにおいて、面配向係数を０〜０．０５とする方法は、本発明の成型転写箔用ポリエステルフィルムを無延伸フィルムとすることが好ましい。つまり、製膜時に長さ方向および幅方向への延伸工程を設けないことが好ましい。なお、通常のフィルムの製造方法においては、無延伸フィルムであっても製膜時にドラフトがかかり、機械（長手）方向にフィルムがやや配向する場合があるので、面配向係数を０．００〜０．０５とするためには無延伸の場合であっても配向を抑制することが重要である。 The polyester film for molded transfer foil of the present invention preferably has a plane orientation coefficient of 0 to 0.05 from the viewpoint of moldability. In the polyester film for molded transfer foil of the present invention, the method for setting the plane orientation coefficient to 0 to 0.05 is preferably such that the polyester film for molded transfer foil of the present invention is an unstretched film. That is, it is preferable not to provide a stretching process in the length direction and the width direction during film formation. In addition, in a normal film manufacturing method, even a non-stretched film is drafted during film formation, and the film may be slightly oriented in the machine (longitudinal) direction. In order to achieve .05, it is important to suppress orientation even in the case of non-stretching.
本発明の成型転写箔用ポリエステルフィルムの厚みは、２５〜３００μｍであることが好ましい。２５μｍ未満の場合、成形性、生産性が低下しやすくなるので好ましくない。また、３００μｍを超える場合も同様に、成形性、生産性が低下しやすくなるので好ましくない。 The polyester film for molded transfer foil of the present invention preferably has a thickness of 25 to 300 μm. If it is less than 25 μm, the moldability and productivity are likely to be lowered, which is not preferable. Similarly, when the thickness exceeds 300 μm, the moldability and productivity are likely to be lowered, which is not preferable.
本発明の成型転写箔用ポリエステルフィルムには、転写後の成型品の艶消し以外の目的や用途においても上述した以外の各種の粒子を添加することができる。添加する粒子は、ポリエステル樹脂に不活性なものであれば特に限定されないが、無機粒子、有機粒子、架橋高分子粒子、重合系内で生成させる内部粒子などを挙げることができる。 Various particles other than those described above can be added to the polyester film for molded transfer foil of the present invention for purposes and uses other than matting of the molded product after transfer. The particles to be added are not particularly limited as long as they are inert to the polyester resin, and examples thereof include inorganic particles, organic particles, crosslinked polymer particles, and internal particles generated in the polymerization system.
無機粒子の種類としては、特に限定されないが、炭酸カルシウム、炭酸マグネシウム、炭酸バリウムなどの各種炭酸塩、硫酸カルシウム、硫酸バリウムなどの各種硫酸塩、カオリン、タルクなどの各種複合酸化物、リン酸リチウム、リン酸カルシウム、リン酸マグネシウムなどの各種リン酸塩、酸化アルミニウム、酸化ケイ素、酸化チタン、酸化ジルコニウムなどの各種酸化物、フッ化リチウムなどの各種塩を使用することができる。 The type of inorganic particles is not particularly limited, but various carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, various sulfates such as calcium sulfate and barium sulfate, various composite oxides such as kaolin and talc, lithium phosphate Various phosphates such as calcium phosphate and magnesium phosphate, various oxides such as aluminum oxide, silicon oxide, titanium oxide and zirconium oxide, and various salts such as lithium fluoride can be used.
また有機粒子としては、蓚酸カルシウムや、カルシウム、バリウム、亜鉛、マンガン、マグネシウムなどのテレフタル酸塩などが使用される。 As the organic particles, calcium oxalate, terephthalate such as calcium, barium, zinc, manganese, magnesium, etc. are used.
架橋高分子粒子としては、ジビニルベンゼン、スチレン、アクリル酸、メタクリル酸のビニル系モノマーからの単独重合体または共重合体などが挙げられる。その他、ポリテトラフルオロエチレン、ベンゾグアナミン樹脂、熱硬化エポキシ樹脂、不飽和ポリエステル樹脂、熱硬化性尿素樹脂、熱硬化性フェノール樹脂などの有機微粒子も好ましく使用される。 Examples of the crosslinked polymer particles include homopolymers or copolymers of vinyl monomers such as divinylbenzene, styrene, acrylic acid, and methacrylic acid. In addition, organic fine particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used.
ポリエステル重合系内で生成させる内部粒子としては、アルカリ金属化合物、アルカリ土類金属化合物などをポリエステルの反応系内に添加して、さらにリン化合物も重合系内に添加する公知の方法によって生成される粒子が挙げられる。 The internal particles produced in the polyester polymerization system are produced by a known method in which an alkali metal compound, an alkaline earth metal compound or the like is added to the polyester reaction system, and a phosphorus compound is also added to the polymerization system. Particles.
本発明の成型転写箔用ポリエステルフィルムには各種の添加剤を含有することができる。つまり、ポリエステル樹脂以外の成分として、必要に応じて公知の添加剤、例えば、難燃剤、熱安定剤、酸化防止剤、紫外線吸収剤、帯電防止剤、可塑剤、粘着性付与剤、脂肪酸エステル、ワックスなどの有機滑剤またはポリシロキサンなどの消泡剤を適量配合することができる。 Various additives can be contained in the polyester film for molded transfer foil of the present invention. That is, as components other than the polyester resin, known additives as necessary, for example, flame retardants, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, plasticizers, tackifiers, fatty acid esters, An appropriate amount of an organic lubricant such as wax or an antifoaming agent such as polysiloxane can be blended.
本発明の成型転写箔用ポリエステルフィルムを構成するポリエステルには、必要に応じて公知のポリマーを添加することができる。例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン、ポリアクリレート、ポリメチルメタクリレートなどのアクリル、ポリカーボネートなどのポリマーを適量配合することができる。 A known polymer can be added to the polyester constituting the polyester film for molded transfer foil of the present invention, if necessary. For example, polyolefins such as polyethylene and polypropylene, acrylics such as polyacrylate and polymethyl methacrylate, and polymers such as polycarbonate can be blended in appropriate amounts.
本発明の成型転写箔用ポリエステルフィルムの転写面側には、ポリエステル樹脂を含む塗膜層により形成された易接着層を設けることができる。インモールド成形用フィルムは、その工程において、成型転写箔用ポリエステルフィルムの転写面側に順次、易接着層、離型層および印刷層などを積層させ機能を発現させるが、基材である成型転写箔用ポリエステルフィルムの製膜工程で易接着層を積層させることは、加工工程において易接着層を設ける工程を省略することができるので、製造コストや加工時間の点から好ましい態様である。 An easy-adhesion layer formed of a coating layer containing a polyester resin can be provided on the transfer surface side of the polyester film for molded transfer foil of the present invention. The film for in-mold molding has a function of laminating an easy-adhesion layer, a release layer, a printing layer, etc. sequentially on the transfer surface side of the polyester film for molded transfer foil in that process. Laminating the easy-adhesion layer in the process of forming the polyester film for foil is a preferable embodiment from the viewpoint of manufacturing cost and processing time because the step of providing the easy-adhesion layer in the processing process can be omitted.
成型転写箔用ポリエステルフィルムの転写面に易接着層を付与する方法としては、多層構成として外層に練りこむ方法、製膜時にインラインにてコートする方法、フィルム製膜後にオフラインにてコートする方法などがあるが、特に限定されない。塗液の塗布方法としては、各種の塗布方法、例えば、リバースコート法、グラビアコート法、ロッドコート法、バーコート法、ダイコート法およびスプレーコート法などを好ましく用いることができるが、これらに限定されるものではない。 Examples of methods for providing an easy-adhesion layer on the transfer surface of a polyester film for molded transfer foil include a method of kneading into an outer layer as a multilayer structure, a method of in-line coating during film formation, a method of offline coating after film formation, etc. There is no particular limitation. Various coating methods such as a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a die coating method, and a spray coating method can be preferably used as the coating method for the coating liquid, but are not limited thereto. It is not something.
易接着層の厚みは、１０〜２０００ｎｍが好ましく、より好ましくは５０〜１０００ｎｍである。易接着層の厚みが薄すぎると離型層との接着性や耐溶剤性が不足する場合があり、厚すぎると易滑性やフィルムロールとしたときの耐ブロッキング性、製膜安定性が低下する場合がある。 10-2000 nm is preferable and, as for the thickness of an easily bonding layer, More preferably, it is 50-1000 nm. If the thickness of the easy-adhesion layer is too thin, adhesion to the release layer and solvent resistance may be insufficient, and if it is too thick, the slip resistance and blocking resistance when used as a film roll will deteriorate. There is a case.
また、易接着層は、ポリエステル樹脂を含むことが好ましい。易接着層にポリエステル樹脂を用いると、基材である成型転写箔用ポリエステルフィルムとの親和性が高いため界面剥離や削れが発生しにくく、さらに水性塗布の場合には塗布外観が良くなる。また製造コストや離型層との接着力の観点からもポリエステル樹脂であることが好ましい。 Moreover, it is preferable that an easily bonding layer contains a polyester resin. When a polyester resin is used for the easy-adhesion layer, it has a high affinity with the polyester film for molded transfer foil that is a base material, so that interfacial peeling and scraping hardly occur, and in the case of aqueous coating, the coating appearance is improved. Moreover, it is preferable that it is a polyester resin also from a viewpoint of manufacturing cost or the adhesive force with a mold release layer.
易接着層に含有されるポリエステルは、また、共重合成分として、ジエチレングリコールを含有する共重合ポリエステルであることが好ましい。該成分を共重合成分とすることで、特にアルコールに対する易接着層の耐溶剤性が向上できるし、また、基材である成型転写箔用ポリエステルフィルムとの親和性を向上させることができる。その他の共重合成分として、公知のジカルボン酸およびジオールを用いることができ、その例として前記したジカルボン酸やジオールを挙げることができるが、本発明の成型転写箔用ポリエステルフィルムの転写面に形成される易接着層に含有されるポリエステルは、それらに限定されるものではない。また、前記したスルホン酸塩基を含む化合物や、カルボン酸塩基を含む化合物を共重合成分として含むこともできる。該共重合ポリエステルの好ましいガラス転移点の範囲は０〜６０℃であり、さらに好ましくは１０〜４５℃である。 The polyester contained in the easy-adhesion layer is preferably a copolymerized polyester containing diethylene glycol as a copolymerization component. By using this component as a copolymerization component, it is possible to improve the solvent resistance of the easy-adhesion layer particularly to alcohol, and it is possible to improve the affinity with the polyester film for molded transfer foil that is a substrate. As other copolymerization components, known dicarboxylic acids and diols can be used, and examples thereof include the above-mentioned dicarboxylic acids and diols, which are formed on the transfer surface of the polyester film for molded transfer foil of the present invention. The polyester contained in the easy-adhesion layer is not limited thereto. Moreover, the compound containing an above described sulfonate group and the compound containing a carboxylate group can also be included as a copolymerization component. The range of the preferable glass transition point of this copolyester is 0-60 degreeC, More preferably, it is 10-45 degreeC.
ジエチレングリコールを共重合成分として含む共重合ポリエステルの含有量は、易接着層を形成する樹脂の合計に対して１０〜６０重量％が好ましく、さらに好ましくは２０〜５０重量％である。該含有量が少なすぎると耐溶剤性や基材である成型転写箔用ポリエステルフィルムとの接着力に劣る場合があり、多すぎるとフィルムロールとしたときの耐ブロッキング性に劣る場合がある。 The content of the copolymerized polyester containing diethylene glycol as a copolymerization component is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, based on the total amount of resins forming the easy-adhesion layer. If the content is too small, the solvent resistance and the adhesive strength with the polyester film for molded transfer foil as the substrate may be inferior, and if it is too large, the blocking resistance may be inferior when used as a film roll.
易接着層を形成するジエチレングリコールを共重合成分とする共重合ポリエステル以外の樹脂としては、本発明の効果を損なわない範囲で特に限定されるものではないが、例えば、その他のポリエステル樹脂、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、シリコーン樹脂、尿素樹脂およびフェノール樹脂などを挙げることができ、なかでも特にその他のポリエステル樹脂を好ましく挙げることができる。 The resin other than the copolyester having a copolymer component of diethylene glycol that forms the easy-adhesion layer is not particularly limited as long as the effects of the present invention are not impaired, but other polyester resins, acrylic resins, A urethane resin, an epoxy resin, a silicone resin, a urea resin, a phenol resin, and the like can be exemplified. Among them, other polyester resins can be preferably exemplified.
また、本発明における易接着層中には、本発明の効果が損なわれない範囲内で、例えば、酸化防止剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、顔料、染料、有機または無機の微粒子、充填剤、耐電防止剤、核剤などを配合しても良い。 Further, in the easy-adhesion layer in the present invention, for example, an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, and a dye are within the range where the effects of the present invention are not impaired. Organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, and the like may be blended.
本発明の成型転写箔用ポリエステルフィルムは、コロナ放電処理などの表面処理を施すことにより、必要に応じて塗工性、印刷性などを向上させることが可能である。また、各種コーティングを施してもよく、その塗布化合物の種類、塗布方法や厚みは、本発明の効果を損なわない範囲であれば、特に限定されない。さらに、必要に応じてエンボス加工などの成形加工、印刷などを施して使用することもできる。 The polyester film for molded transfer foil of the present invention can be improved in coating properties, printability, and the like as necessary by performing surface treatment such as corona discharge treatment. Various coatings may be applied, and the type, coating method, and thickness of the coating compound are not particularly limited as long as the effects of the present invention are not impaired. Furthermore, it can be used after being subjected to molding processing such as embossing, printing, or the like, if necessary.
本発明の成型転写箔用ポリエステルフィルムを用いてなるインモールド成形用転写箔は、インモールド成形に用いられる転写箔であればいかなる形態でも構わないが、基材である本発明の成型転写箔用ポリエステルフィルムの転写面の上に順次離型層、保護層、印刷層、蒸着層、接着層などを有し、携帯電話、自動車部品、家電製品などのプラスチック部分の加飾に好適に用いられる転写箔であることが好ましい。またこのとき、離型層はメラミン樹脂成分、保護層はハードコート性を有するアクリル樹脂成分により形成されていることがより好ましい様態である。 The transfer foil for in-mold molding using the polyester film for molded transfer foil of the present invention may have any form as long as it is a transfer foil used for in-mold molding, but for the molded transfer foil of the present invention which is a substrate. Transfer that has a release layer, protective layer, printing layer, vapor deposition layer, adhesive layer, etc. on the transfer surface of the polyester film, and is suitable for decorating plastic parts such as mobile phones, automobile parts, and home appliances. A foil is preferred. In this case, it is more preferable that the release layer is formed of a melamine resin component and the protective layer is formed of an acrylic resin component having hard coat properties.
本発明の成型転写箔用ポリエステルフィルムは、Ｔダイ法またはインフレーション法などの溶融押出し法によって得られる。例えばＴダイ法によりフィルムを得る場合、押出されたフィルムを急冷し、冷却固化することは重要な条件である。 The polyester film for molded transfer foil of the present invention can be obtained by a melt extrusion method such as a T-die method or an inflation method. For example, when a film is obtained by the T-die method, it is an important condition that the extruded film is rapidly cooled and solidified by cooling.
次に、本発明の成型転写箔用ポリエステルフィルムの製造方法について説明するが、本発明はこれに限定されない。 Next, although the manufacturing method of the polyester film for shaping | molding transfer foil of this invention is demonstrated, this invention is not limited to this.
本発明の成型転写箔用ポリエステルフィルムは、例えば、ポリエステル樹脂層（Ａ）を構成するポリエステルＡ、およびポリエステル樹脂層（Ｂ）を構成するポリエステルＢを必要に応じて乾燥した後、公知の溶融押出機に供給する。なお前述のように、ポリエステル樹脂層（Ａ）を構成するポリエステルＡとしては、ポリエステルの全グリコール由来成分中の９０モル％以上１００モル％以下が１，４−ブタンジオール由来成分、ポリエステルの全ジカルボン酸由来成分中の９０モル％以上１００モル％以下がテレフタル酸由来成分であるポリエステル、であることが好ましい。さらに同様に前述のように、ポリエステル樹脂層（Ｂ）を構成するポリエステルＢとしては、ポリエステルの全グリコール由来成分中の６０モル％以上９９モル％以下がエチレングリコール由来成分、全グリコール由来成分中の１モル％以上４０モル％以下が１，４−ブタンジオール由来成分、ポリエステルの全ジカルボン酸由来成分中の９０モル％以上１００モル％以下がテレフタル酸および／またはナフタレンジカルボン酸由来成分であるポリエステルであることが好ましく用いられる。 The polyester film for molded transfer foil of the present invention may be prepared by, for example, drying the polyester A constituting the polyester resin layer (A) and the polyester B constituting the polyester resin layer (B) as necessary, followed by known melt extrusion. Supply to the machine. In addition, as mentioned above, as polyester A which comprises a polyester resin layer (A), 90 mol% or more and 100 mol% or less in the component derived from all the glycols of a polyester are 1, 4- butanediol origin components, all the dicarboxylic acids of polyester. It is preferable that 90 mol% or more and 100 mol% or less of the acid-derived component is a polyester which is a terephthalic acid-derived component. Furthermore, as mentioned above, as the polyester B constituting the polyester resin layer (B), 60 mol% or more and 99 mol% or less in the total glycol-derived component of the polyester is an ethylene glycol-derived component, in the total glycol-derived component. 1 to 40 mol% of the polyester is a component derived from 1,4-butanediol, and 90 to 100 mol% of the total dicarboxylic acid-derived component of the polyester is a component derived from terephthalic acid and / or naphthalenedicarboxylic acid. It is preferably used.
押出機は、一軸溶融押出機でもベント口を具備した二軸溶融押出機でも構わない。供給された樹脂は、それぞれのポリエステルの融点＋２０〜３０℃の温度で溶融させた後、濾過精度２０〜４０μｍのリーフディスクフィルターを通過させる。次に、ポリエステル樹脂層（Ｂ）／ポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）の３層またはポリエステル樹脂層（Ｂ）／ポリエステル樹脂層（Ａ）の２層ピノール管を通過させ、スリット状のＴダイ口金に導き、シート状に押出す。 The extruder may be a single screw melt extruder or a twin screw melt extruder provided with a vent port. The supplied resin is melted at a temperature of the melting point of each polyester + 20-30 ° C. and then passed through a leaf disk filter having a filtration accuracy of 20-40 μm. Next, three layers of polyester resin layer (B) / polyester resin layer (A) / polyester resin layer (B) or two-layer pinole tube of polyester resin layer (B) / polyester resin layer (A) are passed through and slitted. Into a T-die die and extruded into a sheet.
押出されたシートの両端部に針状エッジピニング装置を用いる静電印加の方式、エアーノズル、エアーチャンバーなどの方式、吸引チャンバーの方式などにより、表面温度４０〜９０℃に調整した冷却ロールに密着させ、溶融状態から冷却固化することで、成型転写箔用ポリエステルフィルムを得ることができる。なお前述したように、ポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）の２層構成の場合は、ポリエステル樹脂層（Ａ）側を冷却ロールに密着させることが好ましい。 Adhering to a cooling roll adjusted to a surface temperature of 40 to 90 ° C by electrostatic application method using a needle-like edge pinning device, air nozzle, air chamber method, suction chamber method, etc. at both ends of the extruded sheet The polyester film for molded transfer foil can be obtained by cooling and solidifying from a molten state. As described above, in the case of a two-layer configuration of polyester resin layer (A) / polyester resin layer (B), it is preferable that the polyester resin layer (A) side is in close contact with the cooling roll.
冷却ロールは、鏡面でも、梨地でも構わないが、フィルムの冷却ロールへの密着性、粘着性の観点から中心線平均粗さが０．１〜５μｍの梨地が好ましい。梨地を用いた場合、冷却ロールへの密着性が不十分となりやすく、透明性が劣るフィルムとなるので他の密着方式を併用することが好ましく、特に、０〜４０℃の温度の連続気流にて密着させる方法が好ましい。 The cooling roll may be a mirror surface or a satin finish, but a satin finish having a center line average roughness of 0.1 to 5 μm is preferable from the viewpoint of adhesion of the film to the cooling roll and adhesiveness. When using satin, the adhesion to the cooling roll tends to be insufficient, and it becomes a film with poor transparency, so it is preferable to use another adhesion method, particularly in a continuous air flow at a temperature of 0 to 40 ° C. The method of making it adhere | attach is preferable.
得られたフィルムは、面配向係数ｆｎが０．００〜０．０５の実質的に無配向の無延伸フィルムが得られる。１２０℃における４００％伸長時の応力を長さ方向および幅方向で１５ＭＰａ以下、１００℃において３０分加熱した場合のフィルム面内の少なくとも1方向の熱収縮率を−０．５〜０．５％とするためには、冷却ロールの温度を４０〜９０℃とすることが好ましい。冷却ロールの温度が９０℃を越えると、１２０℃における４００％伸長時の応力が長さ方向および幅方向で１５ＭＰａより大きくなりやすく、かつ、フィルムがキャストドラムに粘着しやすく生産性が劣るものとなる。また、冷却ロールの温度が９０℃を越えるとフィルムが白化し、透明性が劣る場合やフィルムの成形性が劣る場合があるので好ましくない。逆に冷却ロールの温度が４０℃未満であると、１００℃において３０分加熱した場合のフィルム面内の少なくとも1方向の熱収縮率を−０．５〜０．５％と制御することができず、かつ、耐溶剤性や耐熱性が劣るものとなるので好ましくない。 The obtained film is a substantially non-oriented unstretched film having a plane orientation coefficient fn of 0.00 to 0.05. When the stress at 400% elongation at 120 ° C. is 15 MPa or less in the length direction and width direction and the heat shrinkage rate in at least one direction in the film plane when heated at 100 ° C. for 30 minutes is −0.5 to 0.5% In order to achieve, it is preferable that the temperature of a cooling roll shall be 40-90 degreeC. When the temperature of the cooling roll exceeds 90 ° C., the stress at 400% elongation at 120 ° C. tends to be greater than 15 MPa in the length direction and width direction, and the film tends to stick to the cast drum, resulting in poor productivity. Become. Moreover, when the temperature of a cooling roll exceeds 90 degreeC, since a film whitens and transparency may be inferior or the moldability of a film may be inferior, it is unpreferable. Conversely, if the temperature of the cooling roll is less than 40 ° C, the heat shrinkage rate in at least one direction in the film plane when heated at 100 ° C for 30 minutes can be controlled to -0.5 to 0.5%. And the solvent resistance and heat resistance are inferior.
以下、実施例に沿って本発明を説明するが、本発明はこれらの実施例によって制限されるものではない。なお、諸特性は以下の方法により測定、評価した。
（１）総厚み
（株）ミツトヨ製デジマチックマイクロメータＭＤＣ−２５Ｓを用いて、フィルムの幅方向に等間隔に１０点測定し、その平均値を求めて測定結果とした。
（２）積層厚み
本発明の成型転写箔用ポリエステルフィルムを１０ｍｍ×５ｍｍに試料を採取し、ミクロトームを用いて氷中で断面方向に切断した。（株）日立製作所製透過型電子顕微鏡ＨＵ−１２を用いて、切断した試料の断面を３００倍に拡大して観察し、積層厚みを算出した。
（３）光沢度
本発明の成型転写箔用ポリエステルフィルムの転写面を、スガ試験機（株）製デジタル変角光沢度計ＵＧＶ−４Ｄを用いて、ＪＩＳ Ｚ ８７４１−１９９７に従って測定した。なお、入射角は６０°、受光角は６０°とした。
（４）１２０℃における破断伸度および１２０℃における４００％伸長時の応力
本発明の成型転写箔用ポリエステルフィルムを、（株）オリエンテック製引張試験器ＵＣＴ−１００を用いて、ＡＳＴＭ Ｄ−８８２に従って１２０℃雰囲気下で測定した。なお、引っ張り方向は成型転写箔用ポリエステルフィルムの製膜方向および幅方向の２方向とし、試料の幅は１０ｍｍ、初期長は２０ｍｍ、引っ張り速度は２００ｍｍ／分とした。
（５）熱収縮率
本発明の成型転写箔用ポリエステルフィルムを、１００ｍｍ×１０ｍｍの大きさに成型転写箔用ポリエステルフィルムの長さ方向および幅方向の２方向に切り出し、均一に一定荷重（３ｇ）をかけ、（株）テクノニーズ製の自動測長器で原長を測定した。続いて、３０分間、１００℃の雰囲気のオーブンに入れ、熱処理後、再び自動測長器にて処理後長を測定し、下記の数式より熱収縮率を求めた。
EXAMPLES Hereinafter, although this invention is demonstrated along an Example, this invention is not restrict | limited by these Examples. Various characteristics were measured and evaluated by the following methods.
(1) Total thickness Ten points were measured at equal intervals in the width direction of the film using a Mitsutoyo Digimatic Micrometer MDC-25S, and the average value was obtained as a measurement result.
(2) Lamination thickness A sample of the polyester film for molded transfer foil of the present invention was sampled to 10 mm x 5 mm, and cut in the cross-sectional direction in ice using a microtome. Using a transmission electron microscope HU-12 manufactured by Hitachi, Ltd., the cross section of the cut sample was magnified 300 times and observed, and the lamination thickness was calculated.
(3) Glossiness The transfer surface of the polyester film for molded transfer foil of the present invention was measured according to JIS Z 8741-1997 using a digital variable angle glossiness meter UGV-4D manufactured by Suga Test Instruments Co., Ltd. The incident angle was 60 ° and the light receiving angle was 60 °.
(4) Breaking elongation at 120 ° C. and stress at 400% elongation at 120 ° C. The polyester film for molded transfer foil of the present invention was subjected to ASTM D-882 using an orientec tensile tester UCT-100. The measurement was performed in an atmosphere at 120 ° C. The pulling direction was two directions, ie, the film forming direction and the width direction of the polyester film for molded transfer foil, the width of the sample was 10 mm, the initial length was 20 mm, and the pulling speed was 200 mm / min.
(5) Heat shrinkage rate The polyester film for molded transfer foil of the present invention was cut into a size of 100 mm × 10 mm in two directions of the polyester film for molded transfer foil in the length direction and the width direction, and the load was uniformly constant (3 g). The length was measured with an automatic length measuring device manufactured by Technonez Corporation. Subsequently, it was placed in an oven at 100 ° C. for 30 minutes, and after the heat treatment, the post-treatment length was measured again with an automatic length measuring device, and the heat shrinkage rate was obtained from the following formula.
熱収縮率（％）=｛（原長−処理後長）／原長｝×１００
（６）面配向係数
本発明の成型転写箔用ポリエステルフィルムの転写面を使用して測定した。装置はアッベ屈折計ＮＡＲ−４Ｔ（（株）アタゴ社製）を用い、ナトリウムＤ線（波長５８９ｎｍ）を光源とし、マウント液としてヨウ化メチレンを用いてＭＤ方向、ＴＤ方向および厚み方向の屈折率（それぞれｎｘ、ｎｙ、ｎｚ）を求め、下記の数式より面配向係数を求めた。
Thermal contraction rate (%) = {(original length−post-treatment length) / original length} × 100
(6) Plane orientation coefficient It measured using the transfer surface of the polyester film for shaping | molding transfer foils of this invention. The apparatus uses an Abbe refractometer NAR-4T (manufactured by Atago Co., Ltd.), a sodium D line (wavelength 589 nm) as a light source, and methylene iodide as a mount solution, and refractive indexes in the MD, TD, and thickness directions. (Respectively nx, ny, nz) were obtained, and the plane orientation coefficient was obtained from the following formula.
面配係数＝｛（ｎｘ＋ｎｙ）／２｝−ｎｚ
（７）ベースフィルムの耐溶剤性
本発明の成型転写箔用ポリエステルフィルムのヘイズを測定した後、本発明の成型転写箔用ポリエステルフィルムの転写面上に、酢酸エチル、メチルエチルケトン、メチルイソブチルケトン、トルエンを各々３ｍｌ滴下させて６時間放置した後、溶剤をきれいに拭き取って、上述した方法によりフィルムヘイズを測定した。そして溶剤滴下前後におけるヘイズの変化を測定して、下記の評価基準に従って判定した。○と△であれば合格レベルである。ここで本発明の成型転写箔用ポリエステルフィルムがポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）の２層積層体である場合は、ポリエステル樹脂層（Ａ）側に溶剤を滴下して試験を実施した。
○：すべての溶剤に対して、Δヘイズ（＝試験後のヘイズ値−試験前のヘイズ値）≦５％。
△：○および×ではない時。
×：いずれかの溶剤に対して、１０％＜Δヘイズ（＝試験後のヘイズ値−試験前のヘイズ値）
（８）成形品表面の艶消し性、成形性、コーティング適性
本発明の成型転写箔用ポリエステルフィルムの転写面側に、アクリル系樹脂を用いてグラビアコート法で剥離層を形成し、１００℃で乾燥させた。その上に図柄層として、ビニル樹脂系インキによるメタリック色（アルミニウム顔料２０％含有）のベタパターンと、黒色（カーボンブラック１５％含有）の文字パターンをグラビア印刷で形成し、８０℃で乾燥させた。次いで、４０℃の温水で洗浄、乾燥し、最後にアクリル系樹脂の接着層を図柄層上にグラビアコート法で形成し、８０℃で乾燥させ、転写箔を得た。
Plane distribution coefficient = {(nx + ny) / 2} -nz
(7) Solvent resistance of base film After measuring the haze of the polyester film for molded transfer foil of the present invention, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene on the transfer surface of the polyester film for molded transfer foil of the present invention 3 ml of each was dropped and allowed to stand for 6 hours, and then the solvent was wiped clean and the film haze was measured by the method described above. And the change of the haze before and behind solvent dripping was measured, and it determined in accordance with the following evaluation criteria. ○ and △ are acceptable levels. Here, when the polyester film for molded transfer foil of the present invention is a two-layer laminate of polyester resin layer (A) / polyester resin layer (B), a test was conducted by dropping a solvent on the polyester resin layer (A) side. Carried out.
○: Δhaze (= haze value after test−haze value before test) ≦ 5% for all solvents.
Δ: When it is not ○ or ×.
X: 10% <Δhaze (= haze value after test−haze value before test) for any solvent
(8) Matte surface of molded product, moldability, coating suitability On the transfer surface side of the polyester film for molded transfer foil of the present invention, a release layer is formed by gravure coating method using an acrylic resin at 100 ° C. Dried. On top of that, as a pattern layer, a solid pattern of metallic color (containing 20% aluminum pigment) and a character pattern of black (containing 15% carbon black) were formed by gravure printing and dried at 80 ° C. . Next, the substrate was washed with warm water at 40 ° C. and dried, and finally an acrylic resin adhesive layer was formed on the pattern layer by a gravure coating method and dried at 80 ° C. to obtain a transfer foil.
得られた転写箔を、直径５０ｍｍ、深さ５０ｍｍの深さ方向に直径が一定の円筒のカップ凹金型を用いて、金型温度１２０℃で金型内で接着層を内側にして真空成形したのち型締めを行い、その後アクリル樹脂を成形樹脂として２５ＭＰａの射出圧力条件で成形同時転写加工を行った。
（Ａ）成形品表面の艶消し性
得られた成形品に対し、スガ試験機（株）製デジタル変角光沢度計ＵＧＶ−４Ｄを用いて、ＪＩＳ Ｚ ８７４１−１９９７に従って測定した。なお、入射角は６０°、受光角は６０°とした。成形品の表面光沢度をＧＦ、標準金属試料の表面光沢度をＧＭとしたとき、以下の判定に従った。
○：ＧＦ＜ＧＭ−２０
△：ＧＭ−２０≦ＧＦ＜ＧＭ
×：ＧＦ≧ＧＭ
（Ｂ）成形性
真空成型後の転写箔に対し、最もコーナーがシャープに成形された転写箔の状態を以下の基準で目視にて観察し、判定した。
○：コーナーがシャープに成形され、成形後の厚みも均一であった。
△：コーナーにやや丸みがあり、成形後の厚みもやや不均一であった。
×：成形後の厚みが不均一であり、しわ、破れが発生した。
（Ｃ）コーティング適性
得られた転写箔に対し、欠点、濁り、しわなどの点から以下の基準で目視にて観察し、判定した。
○：非常にきれいであり、欠点、しわ、濁りなど全くない。
△：比較的良好であるが、かすかな濁りや、ごくわずかのしわなどが認められる。
×：品質が悪く、欠点または濁り、しわの発生が認められる。
［ポリブチレンテレフタレートＡ（ＰＢＴ−Ａ）］
東レ（株）製 “トレコン”（登録商標）１２００Ｓのポリブチレンテレフタレート（融点２２４℃、固有粘度１．２３ｄｌ／ｇ）を用いた。なお、固有粘度はオルトクロロフェノールを用いて２５℃で測定したものである（以下、同じ）。
［ポリブチレンテレフタレートＢ（ＰＢＴ−Ｂ）］
二酸化ケイ素（富士シリシア化学（株）製“サイリシア４４５”、平均粒子径２．５μｍ）６重量％を東レ（株）製 “トレコン”（登録商標）１２００Ｓのポリブチレンテレフタレート（融点２２４℃、固有粘度１．２３ｄｌ／ｇ）に添加し、得られた混合物を２５０℃に設定したベント式二軸押出機（Ｌ／Ｄ＝３５）に供給した。押出機にて溶融した溶融樹脂を口金に供給して直径５ｍｍの円状の穴から押出し、ただちに１０℃の冷却水にて急冷して得られたガット状樹脂を４ｍｍ間隔で切断し、二酸化ケイ素を６重量％含有したポリブチレンテレフタレートペレット（融点２２６℃、固有粘度１．１９ｄｌ／ｇ）を得た。
［ポリエチレンテレフタレートＡ（ＰＥＴ−Ａ）］
テレフタル酸ジメチル１００重量部、エチレングリコール６０重量部の混合物に、テレフタル酸ジメチル量に対して酢酸マグネシウム０．０９重量％、三酸化アンチモン０．０３重量部を添加して、常法により加熱昇温してエステル交換反応を行なった。次いで、該エステル交換反応生成物に、テレフタル酸ジメチル量に対して、リン酸８５％水溶液０．０２０重量部を添加した後、重縮合反応槽に移行する。次いで、加熱昇温しながら反応系を徐々に減圧して１ｍｍＨｇの減圧下、２９０℃で常法により重縮合反応を行い、融点２５７℃、固有粘度０．７１ｄｌ／ｇのポリエチレンテレフタレート樹脂を得た。
［イソフタル酸共重合ポリエチレンテレフタレートＢ（ＰＥＴ−Ｂ）］
ジカルボン酸成分をテレフタル酸ジメチル８２．５モル％、イソフタル酸ジメチル１７．５モル％としたこと以外は、ＰＥＴ−Ａと同様にしてイソフタル酸１７．５モル％共重合ポリエチレンテレフタレート（融点２２３℃、固有粘度０．５８ｄｌ／ｇ）を得た。
The resulting transfer foil is vacuum-formed using a cylindrical cup concave mold with a diameter of 50 mm and a depth of 50 mm with a constant diameter in the mold at a temperature of 120 ° C. with the adhesive layer inside. After that, mold clamping was performed, and thereafter, simultaneous molding and transfer processing was performed under an injection pressure condition of 25 MPa using an acrylic resin as a molding resin.
(A) Matte property of molded product surface The obtained molded product was measured according to JIS Z 8741-1997 using a digital variable angle gloss meter UGV-4D manufactured by Suga Test Instruments Co., Ltd. The incident angle was 60 ° and the light receiving angle was 60 °. When the surface glossiness of the molded product was GF and the surface glossiness of the standard metal sample was GM, the following judgment was followed.
○: GF <GM-20
Δ: GM-20 ≦ GF <GM
×: GF ≧ GM
(B) Formability With respect to the transfer foil after vacuum forming, the state of the transfer foil having the sharpest corner formed was visually observed and judged according to the following criteria.
A: The corner was sharply formed, and the thickness after forming was uniform.
Δ: Slightly rounded corners and slightly non-uniform thickness after molding.
X: The thickness after molding was uneven, and wrinkles and tears occurred.
(C) Coating suitability The transfer foil obtained was visually observed and judged according to the following criteria in terms of defects, turbidity, wrinkles and the like.
○: It is very clean and has no defects, wrinkles or turbidity.
(Triangle | delta): Although it is comparatively favorable, a slight turbidity, a slight wrinkle, etc. are recognized.
X: Poor quality, defects or turbidity, wrinkles are observed.
[Polybutylene terephthalate A (PBT-A)]
“Toraycon” (registered trademark) 1200S polybutylene terephthalate (melting point 224 ° C., intrinsic viscosity 1.23 dl / g) manufactured by Toray Industries, Inc. was used. The intrinsic viscosity is measured at 25 ° C. using orthochlorophenol (hereinafter the same).
[Polybutylene terephthalate B (PBT-B)]
6% by weight of silicon dioxide (“Silysia 445” manufactured by Fuji Silysia Chemical Co., Ltd., average particle size of 2.5 μm) is made of Toray Industries, Inc. “Trecon” (registered trademark) 1200S polybutylene terephthalate (melting point 224 ° C., intrinsic viscosity) 1.23 dl / g) and the resulting mixture was fed to a vented twin screw extruder (L / D = 35) set at 250 ° C. The molten resin melted by the extruder is supplied to the die, extruded from a circular hole having a diameter of 5 mm, and immediately cooled with 10 ° C. cooling water to cut the gut-shaped resin obtained at intervals of 4 mm. Of polybutylene terephthalate (melting point: 226 ° C., intrinsic viscosity: 1.19 dl / g) was obtained.
[Polyethylene terephthalate A (PET-A)]
To a mixture of 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.09% by weight of magnesium acetate and 0.03 part by weight of antimony trioxide are added to the amount of dimethyl terephthalate, and the temperature is raised by a conventional method. Then, a transesterification reaction was performed. Subsequently, 0.020 part by weight of 85% aqueous solution of phosphoric acid is added to the transesterification reaction product with respect to the amount of dimethyl terephthalate, and then transferred to a polycondensation reaction tank. Subsequently, the reaction system was gradually reduced in pressure while being heated, and a polycondensation reaction was performed at 290 ° C. under a reduced pressure of 1 mmHg by a conventional method to obtain a polyethylene terephthalate resin having a melting point of 257 ° C. and an intrinsic viscosity of 0.71 dl / g. .
[Isophthalic acid copolymerized polyethylene terephthalate B (PET-B)]
Except that the dicarboxylic acid component was 82.5 mol% dimethyl terephthalate and 17.5 mol% dimethyl isophthalate, 17.5 mol% copolymerized polyethylene terephthalate (melting point 223 ° C., 223 ° C. An intrinsic viscosity of 0.58 dl / g) was obtained.
（実施例１）
ポリエステル樹脂層（Ａ）のポリエステルとして、ＰＢＴ−Ａ（９６重量％）とＰＢＴ−Ｂ（４重量％）の混合物を用い、１５０℃で４時間減圧乾燥を行った後、押出温度２５５℃に設定した一軸押出機（Ｌ／Ｄ＝３６）に、ポリエステル樹脂層（Ｂ）のポリエステルとして、ＰＢＴ−Ａ（８重量％）とＰＥＴ−Ａ（９２重量％）の混合物を用い、１５０℃で４時間減圧乾燥を行った後、押出温度２８０℃に設定した一軸押出機（Ｌ／Ｄ＝３６）に、それぞれ投与し、ポリエステル樹脂層（Ａ）／ポリエステル樹脂層（Ｂ）／ポリエステル樹脂層（Ａ）の３層ピノールを通し、２８０℃に設定したスリット間隙０．８ｍｍのＴダイ口金に導きフィルム状に押出し、押し出されたシートの両端部に針状エッジピニング装置を用いて静電印加方式を使用して、温度６０℃の中心線平均粗さが１μｍの梨地冷却ロールに密着させて冷却固化し、厚み７５μｍの成型転写箔用ポリエステルフィルムを得た。
Example 1
As polyester of the polyester resin layer (A), a mixture of PBT-A (96% by weight) and PBT-B (4% by weight) was used, dried at 150 ° C. for 4 hours under reduced pressure, and then set to an extrusion temperature of 255 ° C. The mixture of PBT-A (8% by weight) and PET-A (92% by weight) was used as the polyester of the polyester resin layer (B) in a single screw extruder (L / D = 36) at 150 ° C. for 4 hours. After drying under reduced pressure, each was administered to a single screw extruder (L / D = 36) set at an extrusion temperature of 280 ° C., and polyester resin layer (A) / polyester resin layer (B) / polyester resin layer (A) Through a three-layer pinole, and led to a T die die with a slit gap of 0.8 mm set at 280 ° C., extruded into a film, and electrostatically applied using needle-like edge pinning devices at both ends of the extruded sheet Use, center line average roughness of the temperature 60 ° C. is cooled and solidified by close contact with 1μm satin cooling roll, to obtain a molding transfer foil for polyester film having a thickness of 75 [mu] m.
このようにして得られた、本発明の成型転写箔用ポリエステルフィルム、および本発明の成型転写箔用ポリエステルフィルムを用いた転写箔、ならびに転写箔を用いて成型同時転写加工を行った成型品は、表１に示すように転写後の成型品表面の艶消し性、成形性、耐熱性、に優れた特性を示した。 The polyester film for molded transfer foil of the present invention obtained in this way, the transfer foil using the polyester film for molded transfer foil of the present invention, and the molded product that has been subjected to molding simultaneous transfer processing using the transfer foil are as follows: As shown in Table 1, the surface of the molded article after transfer exhibited excellent matting properties, moldability, and heat resistance.
（実施例２）
平均粒径２．５μｍの無定形シリカ粒子を１．０重量％含有させたＰＢＴ−Ｂを用いた以外は、実施例１と同様の方法によって、本発明の成型転写箔用ポリエステルフィルムを得た。
(Example 2)
A polyester film for molded transfer foil of the present invention was obtained in the same manner as in Example 1 except that PBT-B containing 1.0% by weight of amorphous silica particles having an average particle diameter of 2.5 μm was used. .
（実施例３）
実施例１と同様の方法によって、得られたフィルムをサンドブラスト処理により、本発明の成型転写箔用ポリエステルフィルムを得た。
(Example 3)
The polyester film for molded transfer foil of the present invention was obtained by sandblasting the obtained film by the same method as in Example 1.
（比較例１）
本発明の成型転写箔用ポリエステルフィルムのフィルム積層構成、用いるポリマーを表１のとおりに変更し、エアーチャンバー方式を用いた以外は、実施例１と同様の方法によって、本発明の成型転写箔用ポリエステルフィルムを得た。
(Comparative Example 1)
The laminated film structure of the polyester film for molded transfer foil of the present invention, the polymer to be used are changed as shown in Table 1, and the air chamber method is used. A polyester film was obtained.
このようにして得られた、本発明の成型転写箔用ポリエステルフィルム、および本発明の成型転写箔用ポリエステルフィルムを用いた転写箔、ならびに転写箔を用いて成型同時転写加工を行った成型品は、表１に示すとおりであり、一部の特性に劣る点があった。
（比較例２）
本発明の成型転写箔用ポリエステルフィルムのフィルム積層構成、および用いるポリマーを、表１のとおりに変更し、実施例１と同様の方法によって、本発明の成型転写箔用ポリエステルフィルムを得た。
The polyester film for molded transfer foil of the present invention obtained in this way, the transfer foil using the polyester film for molded transfer foil of the present invention, and the molded product that has been subjected to molding simultaneous transfer processing using the transfer foil are as follows: As shown in Table 1, some characteristics were inferior.
(Comparative Example 2)
The film lamination constitution of the polyester film for molded transfer foil of the present invention and the polymer to be used were changed as shown in Table 1, and the polyester film for molded transfer foil of the present invention was obtained by the same method as in Example 1.
このようにして得られた、本発明の成型転写箔用ポリエステルフィルム、および本発明の成型転写箔用ポリエステルフィルムを用いた転写箔、ならびに転写箔を用いて成型同時転写加工を行った成型品は、表１に示すとおりであり、一部の特性に劣る点があった。 The polyester film for molded transfer foil of the present invention obtained in this way, the transfer foil using the polyester film for molded transfer foil of the present invention, and the molded product that has been subjected to molding simultaneous transfer processing using the transfer foil are as follows: As shown in Table 1, some characteristics were inferior.
（比較例３、４）
本発明の成型転写箔用ポリエステルフィルムのフィルム積層構成、用いるポリマーを表１のとおりに変更し、実施例１と同様の方法によって、本発明の成型転写箔用ポリエステルフィルムを得た。
(Comparative Examples 3 and 4)
The film lamination configuration of the polyester film for molded transfer foil of the present invention and the polymer used were changed as shown in Table 1, and the polyester film for molded transfer foil of the present invention was obtained in the same manner as in Example 1.
このようにして得られた、本発明の成型転写箔用ポリエステルフィルム、および本発明の成型転写箔用ポリエステルフィルムを用いた転写箔、ならびに転写箔を用いて成型同時転写加工を行った成型品は、表１に示すとおりであり、一部の特性に劣る点があった。 The polyester film for molded transfer foil of the present invention obtained in this way, the transfer foil using the polyester film for molded transfer foil of the present invention, and the molded product that has been subjected to molding simultaneous transfer processing using the transfer foil are as follows: As shown in Table 1, some characteristics were inferior.
（比較例５）
ポリエステル樹脂層（Ｂ）を構成するポリエステルＢとして、ＰＥＴ−Ｂを用い、１５０℃で４時間減圧乾燥を行った後、押出温度２６０℃に設定した一軸押出機に投与し、２６０℃に設定したスリット間隙０．８ｍｍのＴダイ口金に導き、フィルム状に押出し、静電印加させながら、２５℃に保った鏡面金属ドラムに巻き付けて冷却固化せしめ、未延伸フィルムを得た。次に、この未延伸フィルムを長手方向に９０℃で３．２倍に延伸し、幅方向に１１５℃で３．２倍に延伸し、２００℃で熱処理を行い、厚み２０μｍの二軸延伸ポリエステルフィルムを得た。
(Comparative Example 5)
As polyester B constituting the polyester resin layer (B), PET-B was used, and after drying under reduced pressure at 150 ° C. for 4 hours, it was administered to a single screw extruder set to an extrusion temperature of 260 ° C. and set to 260 ° C. The film was led to a T die die having a slit gap of 0.8 mm, extruded into a film shape, wound around a mirror surface metal drum kept at 25 ° C. while being electrostatically applied, and cooled and solidified to obtain an unstretched film. Next, this unstretched film is stretched 3.2 times at 90 ° C. in the longitudinal direction, stretched 3.2 times at 115 ° C. in the width direction, heat treated at 200 ° C., and biaxially stretched polyester having a thickness of 20 μm. A film was obtained.
このようにして得られた、本発明の成型転写箔用ポリエステルフィルム、および本発明の成型転写箔用ポリエステルフィルムを用いた転写箔、ならびに転写箔を用いて成型同時転写加工を行った成型品は、表１に示すとおりであり、一部の特性に劣る点があった。 The polyester film for molded transfer foil of the present invention obtained in this way, the transfer foil using the polyester film for molded transfer foil of the present invention, and the molded product that has been subjected to molding simultaneous transfer processing using the transfer foil are as follows: As shown in Table 1, some characteristics were inferior.
本発明は、転写後の成型品表面の艶消し性、成形性、耐熱性に優れた、成型転写箔用ポリエステルフィルムを得ることができる。 INDUSTRIAL APPLICABILITY The present invention can provide a polyester film for molded transfer foil that has excellent matteness, moldability, and heat resistance on the surface of a molded product after transfer.
Claims (4)
１２０℃における破断伸度が４００％以上、かつ１２０℃における４００％伸長時の応力が１５ＭＰａ以下であることを特徴とする、成型転写箔用ポリエステ ルフィルム。 At least on the film surface on the transfer surface side, the gloss is less than 100%,
A polyester film for molded transfer foil, wherein the elongation at break at 120 ° C. is 400% or more and the stress at 400% elongation at 120 ° C. is 15 MPa or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007250821A JP2009079170A (en) | 2007-09-27 | 2007-09-27 | Polyester film for in-mold transfer foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007250821A JP2009079170A (en) | 2007-09-27 | 2007-09-27 | Polyester film for in-mold transfer foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2009079170A true JP2009079170A (en) | 2009-04-16 |
Family
ID=40654174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007250821A Withdrawn JP2009079170A (en) | 2007-09-27 | 2007-09-27 | Polyester film for in-mold transfer foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2009079170A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012140498A (en) * | 2010-12-28 | 2012-07-26 | Mitsubishi Plastics Inc | Biaxially oriented polyester film for concurrent deep drawing and transfer |
| WO2014157652A1 (en) * | 2013-03-29 | 2014-10-02 | 凸版印刷株式会社 | Gas-barrier laminate and method for manufacturing gas-barrier laminate |
-
2007
- 2007-09-27 JP JP2007250821A patent/JP2009079170A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012140498A (en) * | 2010-12-28 | 2012-07-26 | Mitsubishi Plastics Inc | Biaxially oriented polyester film for concurrent deep drawing and transfer |
| WO2014157652A1 (en) * | 2013-03-29 | 2014-10-02 | 凸版印刷株式会社 | Gas-barrier laminate and method for manufacturing gas-barrier laminate |
| US10329658B2 (en) | 2013-03-29 | 2019-06-25 | Toppan Printing Co., Ltd. | Gas barrier laminate and method for producing the gas barrier laminate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5309564B2 (en) | Biaxially oriented polyester film for molded parts | |
| KR101276992B1 (en) | Polyester multilayer film and transfer foil | |
| JP5990983B2 (en) | Laminated film for simultaneous molding transfer | |
| JP5428337B2 (en) | Biaxially oriented polyester film for molded members, molded laminate using the same, and method for producing the same | |
| JPWO2007094382A1 (en) | Polyester film for molded parts | |
| JP5115079B2 (en) | Polyester film for molded transfer foil | |
| JP5127296B2 (en) | Polyester film for deep drawing molding simultaneous transfer foil | |
| JP5363176B2 (en) | Release film | |
| KR20130098152A (en) | Biaxially oriented polyester film for molding | |
| JP4955480B2 (en) | Biaxially stretched laminated polyester film for simultaneous decoration | |
| CN107529335A (en) | Mold release polyester film for simultaneous transfer printing | |
| WO2019139030A1 (en) | Film for holding metal layer, metal-toned decorative sheet intermediate, metal-toned decorative sheet, extrusion laminate body, metal-toned molded body, injection molded body, method for producing metal-toned molded body, method for producing injection molded body, and method for producing extrusion laminate body | |
| JP2008088410A (en) | Surface protective polyester film for molding | |
| JP2009220479A (en) | Biaxially oriented polyester film for molding member and laminate for molding | |
| JP2004091619A (en) | Polyester film for printing and molding | |
| JP2009208302A (en) | Polyester film for in-mold transfer | |
| JP2004188708A (en) | Laminated film for transfer foil | |
| JP2009079170A (en) | Polyester film for in-mold transfer foil | |
| JP2007203571A (en) | Polyester film for simultaneous decoration | |
| JP5531854B2 (en) | Molded laminate | |
| JP5223191B2 (en) | Decorative sheet for injection molding | |
| JP4765567B2 (en) | Laminated film for transfer foil and transfer foil using the same | |
| JP2010260275A (en) | Laminated polyester film for in-mold transfer foil | |
| JP2013022887A (en) | Polyester film for insert molding | |
| JP5225828B2 (en) | Polyester film for in-mold transfer foil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20100924 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A761 | Written withdrawal of application |
Effective date: 20101015 Free format text: JAPANESE INTERMEDIATE CODE: A761 |