JP2013248820A - Molded article, and multilayer laminated film - Google Patents
Molded article, and multilayer laminated film Download PDFInfo
- Publication number
- JP2013248820A JP2013248820A JP2012125737A JP2012125737A JP2013248820A JP 2013248820 A JP2013248820 A JP 2013248820A JP 2012125737 A JP2012125737 A JP 2012125737A JP 2012125737 A JP2012125737 A JP 2012125737A JP 2013248820 A JP2013248820 A JP 2013248820A
- Authority
- JP
- Japan
- Prior art keywords
- laminated film
- layer
- multilayer laminated
- film
- layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 238000006073 displacement reaction Methods 0.000 claims abstract description 17
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 9
- 239000010432 diamond Substances 0.000 claims abstract description 9
- 230000009477 glass transition Effects 0.000 claims description 24
- 230000000630 rising effect Effects 0.000 claims description 6
- 239000005001 laminate film Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 238000003825 pressing Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 151
- -1 polyethylene Polymers 0.000 description 39
- 229920001577 copolymer Polymers 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 18
- 239000005020 polyethylene terephthalate Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 238000010030 laminating Methods 0.000 description 15
- 238000003475 lamination Methods 0.000 description 15
- 238000009826 distribution Methods 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 14
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 11
- 239000011112 polyethylene naphthalate Substances 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 238000013461 design Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 229920006127 amorphous resin Polymers 0.000 description 5
- 229920006038 crystalline resin Polymers 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000012943 hotmelt Substances 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
- 238000005259 measurement Methods 0.000 description 4
- 229920001230 polyarylate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 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
- 230000003287 optical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 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
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000009823 thermal lamination Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 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
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VPXSRGLTQINCRV-UHFFFAOYSA-N dicesium;dioxido(dioxo)tungsten Chemical compound [Cs+].[Cs+].[O-][W]([O-])(=O)=O VPXSRGLTQINCRV-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000009824 pressure lamination Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は、意匠性の改良された成形品に関する。 The present invention relates to a molded article having improved design properties.
携帯電話やパソコンの筐体や電化製品や家具や自動車など外装に対する意匠性が要求される用途は多く、また、意匠性に対する要求も高まっている。意匠性の付与には塗装や印刷を施したり、着色されたフィルムを貼着したり、印刷されたフィルムの印刷面を基材上に転写したりする方法が知られている。また最近、２種の樹脂を厚み方向に交互に積層し、その干渉反射現象を利用して発色や光線の反射を行う多層積層フィルムは成形体に意匠性を付与する１つの手段として知られている。例えば、干渉反射を利用し金属光沢調を持つもの（特許文献１、特許文献２）や、飛散防止機能（特許文献３）を持つもの等が知られている。これらの多層積層フィルムを硬い支持体に加熱加圧ラミネートされて成形される成形品は、化粧版等の装飾材や、各種家電製品、建築部材、自動車関係の部品等に使われている。 There are many applications that require design for exteriors such as mobile phone and personal computer casings, electrical appliances, furniture, and automobiles, and the demand for design is also increasing. For imparting design properties, methods are known in which painting or printing is performed, a colored film is attached, or a printed surface of the printed film is transferred onto a substrate. Recently, a multilayer laminated film in which two kinds of resins are alternately laminated in the thickness direction, and the interference reflection phenomenon is used for color development and light reflection is known as one means for imparting design properties to a molded product. Yes. For example, those having a metallic luster tone using interference reflection (Patent Documents 1 and 2) and those having a scattering prevention function (Patent Document 3) are known. Molded articles formed by heating and pressure laminating these multilayer laminated films on a hard support are used for decorative materials such as decorative plates, various home appliances, building members, automobile-related parts, and the like.
これらの成形品は、人の目に触れる場所に使われるため外観が重要となる。しかし、耐印刷層が剥がれたり、鋭利なものでひっかかれたときなどキズが付いたりして、その耐久性やキズに対する耐性に対する要求が高まっている。先述のフィルムを貼着する態様にあっても同様の要求があるが、フィルム特有の問題としては、貼着時に異物を噛み混むと表面に凹凸が発生し外観を損なうという問題があった。特に、多層積層フィルムにあっては、層厚みの制御による干渉反射現象を利用するものであることからこうした凹凸は光学的な欠点として目立ち易くなるという点が指摘されていた。 The appearance of these molded products is important because they are used in places where people can see them. However, when the printing-resistant layer is peeled off or scratched with a sharp object, there is an increasing demand for durability and resistance to scratches. Although there is a similar request even in the above-described embodiment of attaching the film, a problem peculiar to the film is that when a foreign object is bitten and mixed at the time of application, irregularities are generated on the surface and the appearance is impaired. In particular, it has been pointed out that in a multilayer laminated film, such irregularities are easily noticeable as optical defects because they utilize an interference reflection phenomenon by controlling the layer thickness.
本発明は、多層積層フィルムが支持体上に配置された成形体において、加熱加圧による凹凸を抑制し、外観に優れた成形体を提供することを課題とする。 This invention makes it a subject to provide the molded object which suppressed the unevenness | corrugation by heat pressurization in the molded object by which the multilayer laminated film has been arrange | positioned on the support body, and was excellent in the external appearance.
上記課題を解決するために本発明は次のような構成を有する。 In order to solve the above problems, the present invention has the following configuration.
すなわち、支持体上に熱可塑性樹脂Ａからなる層（Ａ層）とＡ層を構成する樹脂とは異なる性質を有する熱可塑性樹脂Ｂからなる層（Ｂ層）とが交互に５１層以上積層された多層積層フィルムが配置された成形品であって、該多層積層フィルムは、フィルムを７０℃まで温めたときの稜線間の角度が１１５°のダイヤモンド製正三角錐圧子をフィルム面に対して垂直に負荷速度７．７４７ｍＮ／ｓ、荷重５０ｍＮにて押し込んだ際の変位量が５μｍ以下であることを特徴とする成形品。 That is, 51 layers or more of layers made of thermoplastic resin A (layer A) and layers of thermoplastic resin B having different properties from the resin constituting layer A (layer B) are alternately laminated on the support. The multilayer laminated film has a diamond regular triangular pyramid indenter whose angle between the ridges is 115 ° when the film is heated to 70 ° C. perpendicular to the film surface. A molded article characterized by having a displacement amount of 5 μm or less when pushed in at a load speed of 7.747 mN / s and a load of 50 mN.
本発明によって、外観および意匠性に優れた成形体を得ることができる。 By this invention, the molded object excellent in the external appearance and the designability can be obtained.
本発明者らは、支持体と多層積層フィルムが加熱加圧ラミネートされ成形される成形品において、多層積層フィルムの優れた意匠性を損なうことなく、該多層積層フィルムとして加熱後にフィルム面方向に加えた荷重に対する変位量が少ないものを用いることで外観にも優れた成形体とできることを発見した。以下、これについて詳説する。 In the molded product in which the support and the multilayer laminated film are laminated by heating and pressurizing, the present inventors added the multilayer laminated film in the film surface direction after heating without impairing the excellent design properties of the multilayer laminated film. It was discovered that a molded product having an excellent appearance can be obtained by using a material having a small displacement with respect to a load. This will be described in detail below.
支持体と多層積層フィルムをラミネートする場合、密着性を高めるために加熱と加圧を行なう。ラミネートの際、支持体と多層積層フィルムとの間に異物などがあると、加熱によって柔らかくなった多層積層フィルムが異物に押されることで、多層フィルムに凹凸が発生し、その凹凸によって光が散乱、乱反射を起こし、成形品の外観が悪く見える。また、支持体と多層積層フィルムの間に、接着剤層やフィルム等の中間層などが存在すると、接着剤層や中間層の形状（うねり、凹凸等）が多層積層フィルムに転写することで、多層積層フィルムに凹凸が発生し成形品の外観が悪くなる。いずれの場合においても、支持体はほとんど変形しないため、異物や、接着剤層や中間層の形状は支持体によって緩和することは無い。多層積層フィルムは、その中に異種の樹脂から形成される界面が存在するため、フィルム表面による光の散乱、乱反射以外に界面による散乱、反射が加わるため、一種類の樹脂からなるフィルムよりも凹凸が目立ち易くなる。したがって、凹凸が発生し難い多層積層フィルムを用いることができれば、成形品の外観不良問題を解消することができる。本発明は、支持体と多層積層フィルムとが加熱加圧ラミネート成形される成形品において発生する外観不良は、多層積層フィルムの凹凸に起因するものであり、かかる凹凸をどのようにすれば解消できるかを探求した結果到達されたものである。 When laminating a support and a multilayer laminated film, heating and pressurization are performed in order to improve adhesion. When laminating, if there is a foreign object between the support and the multi-layer film, the multi-layer film softened by heating will be pressed by the foreign object, resulting in unevenness in the multi-layer film, and the unevenness will scatter light. It causes irregular reflection and the appearance of the molded product looks bad. In addition, when an intermediate layer such as an adhesive layer or a film is present between the support and the multilayer laminated film, the shape of the adhesive layer or the intermediate layer (swell, unevenness, etc.) is transferred to the multilayer laminated film, Unevenness occurs in the multilayer laminated film, and the appearance of the molded product is deteriorated. In any case, since the support is hardly deformed, the shape of the foreign matter, the adhesive layer or the intermediate layer is not relaxed by the support. Multilayer laminated film has an interface formed from different types of resin in it, so scattering and reflection by the interface are added in addition to light scattering and irregular reflection on the film surface, so it is more uneven than a film made of one type of resin. Becomes more noticeable. Therefore, if a multilayer laminated film in which unevenness does not easily occur can be used, the appearance defect problem of the molded product can be solved. In the present invention, the appearance defect that occurs in a molded product in which the support and the multilayer laminated film are heat-press laminated is caused by the irregularities of the multilayer laminated film, and how these irregularities can be eliminated. It was achieved as a result of the search.
以下に本発明について詳細に述べるが、本発明は以下の実施例を含む具体的な実施の形態に限定して解釈されるものではなく、発明の目的を達成できて、かつ、発明の要旨を逸脱しない範囲内においての種々の態様は当然本発明の範囲に含まれる。 The present invention will be described in detail below. However, the present invention is not construed as being limited to the specific embodiments including the following examples, and the object of the invention can be achieved. Various embodiments within the scope not departing from the present invention are naturally included in the scope of the present invention.
本発明の成形品は、支持体上に熱可塑性樹脂Ａからなる層（Ａ層）とＡ層を構成する樹脂とは異なる性質を有する熱可塑性樹脂Ｂからなる層（Ｂ層）とが交互に５１層以上積層された多層積層フィルムが配置された成形品であって、該多層積層フィルムは、フィルムを７０℃まで温めたときの稜線間の角度が１１５°のダイヤモンド製正三角錐圧子をフィルム面に対して垂直に負荷速度７．７４７ｍＮ／ｓ、荷重５０ｍＮにて押し込んだ際の変位量が５μｍ以下であることが必要である。 In the molded product of the present invention, the layer (A layer) made of the thermoplastic resin A and the layer (B layer) made of the thermoplastic resin B having properties different from the resin constituting the A layer are alternately formed on the support. A molded article in which a multilayer laminated film laminated with 51 or more layers is disposed, and the multilayer laminated film has a diamond regular triangular pyramid indenter having an angle between ridges of 115 ° when the film is heated to 70 ° C. However, it is necessary that the displacement amount when pushed in at a load speed of 7.747 mN / s and a load of 50 mN is 5 μm or less.
本発明に係る多層積層フィルムに用いうる熱可塑性樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリ（４−メチルペンテン−１）などのポリオレフィン、シクロオレフィンとしては、ノルボルネン類の開環メタセシス重合，付加重合，他のオレフィン類との付加共重合体である脂環族ポリオレフィン、ポリ乳酸、ポリブチルサクシネートなどの生分解性ポリマー、ナイロン６、ナイロン１１、ナイロン１２、ナイロン６６などのポリアミド、アラミド、ポリメチルメタクリレート、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、ポリビニルブチラール、エチレン酢酸ビニルコポリマー、ポリアセタール、ポリグルコール酸、ポリスチレン、スチレン共重合ポリメタクリル酸メチル、ポリカーボネート、ポリプロピレンテレフタレート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン−２，６−ナフタレートなどのポリエステル、ポリエーテルサルフォン、ポリエーテルエーテルケトン、変性ポリフェニレンエーテル、ポリフェニレンサルファイド、ポリエーテルイミド、ポリイミド、ポリアリレート、４フッ化エチレン樹脂、３フッ化エチレン樹脂、３フッ化塩化エチレン樹脂、４フッ化エチレン−６フッ化プロピレン共重合体、ポリフッ化ビニリデンなどが挙げられる。これらの中で、強度・耐熱性・透明性の観点から、特にポリエステルを用いることが好ましく、ポリエステルとしては芳香族ジカルボン酸または脂肪族ジカルボン酸とジオールあるいはそれらの誘導体を用いて得られるポリエステルが好ましい。ここで、芳香族ジカルボン酸として、例えば、テレフタル酸、イソフタル酸、フタル酸、１,4-ナフタレンジカルボン酸、1,5−ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、4,4′-ジフェニルジカルボン酸、4,4′-ジフェニルエーテルジカルボン酸、4,4′-ジフェニルスルホンジカルボン酸などを挙げることができる。脂肪族ジカルボン酸としては、例えば、アジピン酸、スベリン酸、セバシン酸、ダイマー酸、ドデカンジオン酸、シクロヘキサンジカルボン酸とそれらのエステル誘導体などが挙げられる。中でも好ましくはテレフタル酸と2,6-ナフタレンジカルボン酸を挙げることができる。これらの酸成分は１種のみ用いてもよく、２種以上併用してもよく、さらには、ヒドロキシ安息香酸等のオキシ酸などを一部共重合してもよい。 Examples of the thermoplastic resin that can be used in the multilayer laminated film according to the present invention include polyolefins such as polyethylene, polypropylene, and poly (4-methylpentene-1), and cycloolefins include ring-opening metathesis polymerization and addition polymerization of norbornenes. , Biodegradable polymers such as alicyclic polyolefin, polylactic acid, polybutyl succinate and the like, addition copolymers with other olefins, polyamides such as nylon 6, nylon 11, nylon 12, nylon 66, aramid, poly Methyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl acetate copolymer, polyacetal, polyglycolic acid, polystyrene, styrene copolymer polymethyl methacrylate, polycarbonate, polypro Polyester such as terephthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polyethersulfone, polyetheretherketone, modified polyphenylene ether, polyphenylene sulfide, polyetherimide, polyimide, polyarylate, tetrafluoride Examples thereof include ethylene resins, trifluorinated ethylene resins, trifluorinated ethylene chloride resins, tetrafluoroethylene-6 fluoropropylene copolymers, and polyvinylidene fluoride. Among these, from the viewpoint of strength, heat resistance and transparency, it is particularly preferable to use a polyester, and as the polyester, a polyester obtained by using an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid and a diol or a derivative thereof is preferable. . Here, as the aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyl Examples include dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, and the like. Examples of the aliphatic dicarboxylic acid include adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedioic acid, cyclohexanedicarboxylic acid and ester derivatives thereof. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferred. These acid components may be used alone or in combination of two or more thereof, and further may be partially copolymerized with oxyacids such as hydroxybenzoic acid.
また、ジオール成分としては、例えば、エチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、ネオペンチルグリコール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、1,4-シクロヘキサンジメタノール、ジエチレングリコール、トリエチレングリコール、ポリアルキレングリコール、2,2-ビス（4-ヒドロキシエトキシフェニル）プロパン、イソソルベート、スピログリコールなどを挙げることができる。中でもエチレングリコールが好ましく用いられる。これらのジオール成分は１種のみ用いてもよく、２種以上併用してもよい。 Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4- Hydroxyethoxyphenyl) propane, isosorbate, spiroglycol and the like. Of these, ethylene glycol is preferably used. These diol components may be used alone or in combination of two or more.
上記ポリエステルのうち、ポリエチレンテレフタレートおよびその共重合体、ポリエチレンナフタレートおよびその共重合体、ポリブチレンテレフタレートおよびその共重合体、ポリブチレンナフタレートおよびその共重合体、さらにはポリヘキサメチレンテレフタレートおよびその共重合体並びにポリヘキサメチレンナフタレートおよびその共重合体の中から選択されるポリエステルを用いることが好ましい。 Among the above polyesters, polyethylene terephthalate and copolymers thereof, polyethylene naphthalate and copolymers thereof, polybutylene terephthalate and copolymers thereof, polybutylene naphthalate and copolymers thereof, and polyhexamethylene terephthalate and copolymers thereof. Preference is given to using polymers and polyesters selected from polyhexamethylene naphthalate and copolymers thereof.
本発明の成形品に用いる多層積層フィルムには、少なくとも２種の熱可塑性樹脂が用いられ、該２種の熱可塑性樹脂は異なる性質を有する。ここでいう性質とは、結晶性・非晶性、光学的性質、熱的性質、もしくは物理的性質が異なることをいう。異なる性質を持つ熱可塑性樹脂を積層することで、それぞれの熱可塑性樹脂の単一の層のフィルムではなし得ない機能をフィルムに与えることができる。層間密着性や、高精度で積層構造が実現しやすい観点から、前記２種類の熱可塑性樹脂は同一の繰り返し単位を含むことが好ましい。繰り返し単位とは、例えば、ポリエチレンテレフタレートの場合は、エチレンテレフタレート単位であり、ポリエチレンの場合、エチレン単位が繰り返し単位である。 The multilayer laminated film used in the molded article of the present invention uses at least two types of thermoplastic resins, and the two types of thermoplastic resins have different properties. The property here means that crystallinity / amorphous property, optical property, thermal property, or physical property is different. By laminating thermoplastic resins having different properties, it is possible to give the film a function that cannot be achieved by a single layer film of each thermoplastic resin. From the viewpoint of interlaminar adhesion and easy to realize a laminated structure with high accuracy, the two types of thermoplastic resins preferably contain the same repeating unit. For example, in the case of polyethylene terephthalate, the repeating unit is an ethylene terephthalate unit, and in the case of polyethylene, the ethylene unit is a repeating unit.
同じ繰り返し単位を有し、しかし、異なる性質を具備させるには、共重合体とすることが望ましい。すなわち、例えば、一方の樹脂がポリエチレンテレフタレートの場合、他方の樹脂は、エチレンテレフタレート単位と他のエステル結合を持った繰り返し単位とで構成された樹脂を用いるような態様である。他の繰り返し単位を入れる割合（共重合量ということがある）としては、異なる性質を獲得する必要性から１％以上が好ましく、一方、層間の密着性や、熱流動特性の差が小さいため各層の厚みの精度や厚みの均一性に優れることから９０％以下が好ましい。さらに好ましくは１０％以上、８０％以下である。また、Ａ層とＢ層はそれぞれ、複数種の熱可塑性樹脂がブレンド又はアロイされ用いられることも望ましい。複数種の熱可塑性樹脂をブレンド又はアロイさせることで、1種類の熱可塑性樹脂では得られない性能を得ることができる。 In order to have the same repeating unit but to have different properties, it is desirable to use a copolymer. That is, for example, when one resin is polyethylene terephthalate, the other resin is an embodiment using a resin composed of an ethylene terephthalate unit and another repeating unit having an ester bond. The proportion of other repeating units (sometimes referred to as the amount of copolymerization) is preferably 1% or more because of the need to obtain different properties. On the other hand, the difference in adhesion between layers and heat flow characteristics is small, so each layer The thickness is preferably 90% or less because of excellent thickness accuracy and thickness uniformity. More preferably, it is 10% or more and 80% or less. It is also desirable that the A layer and the B layer are used by blending or alloying a plurality of types of thermoplastic resins. By blending or alloying a plurality of types of thermoplastic resins, performance that cannot be obtained with one type of thermoplastic resin can be obtained.
本発明の成形品に用いる多層積層フィルムは熱可塑性樹脂からなる層（Ａ層）と少なくともＡ層を構成する樹脂とは異なる性質を有する熱可塑性樹脂からなる層（Ｂ層）が交互に５１層以上積層した構造を含んでいることが必要である。異なる性質を持つ熱可塑性樹脂を積層することで、それぞれの熱可塑性樹脂１層のみではなし得ない機能をフィルムに与えることができる。好ましくは１０１層以上、より好ましくは４０１層以上、さらに好ましくは６０１層以上であり、積層装置の大型化の観点から上限としては５０００層程度である。 The multilayer laminated film used in the molded product of the present invention has 51 layers alternately composed of a layer made of a thermoplastic resin (A layer) and a layer made of a thermoplastic resin having a property different from at least the resin constituting the A layer (B layer). It is necessary to include the laminated structure. By laminating thermoplastic resins having different properties, it is possible to give the film a function that cannot be achieved with only one thermoplastic resin layer. Preferably it is 101 layers or more, More preferably, it is 401 layers or more, More preferably, it is 601 layers or more, and it is about 5000 layers as an upper limit from a viewpoint of the enlargement of a lamination apparatus.
本発明の成形品に用いる多層積層フィルムは、フィルムを７０℃まで温めたときの、稜線間の角度が１１５°のダイヤモンド製正三角錐圧子をフィルム面に対して垂直に負荷速度７．７４７ｍＮ／ｓ、荷重５０ｍＮにて押し込んだ際の変位量が５μｍ以下であることが必要であり、好ましくは４μｍ以下である。成形品に発生する外観不良は、多層積層フィルムのフィルム面方向に加えられた荷重に対して、フィルム面方向の変位量が大きいことが原因である。従って、係る多層積層フィルムを用いることで、加熱加圧ラミネート成形の際に異物に押されることや、接着剤層やフィルム等の中間層の形状が多層積層フィルムに転写することが発生しなくなり、外観に優れた成形品を得ることができる。また、フィルムを１００℃まで温めたときの、稜線間の角度が１１５°のダイヤモンド製正三角錐圧子をフィルム面に対して垂直に負荷速度７．７４７ｍＮ／ｓ、荷重５０ｍＮにて押し込んだ際の変位量が５μｍ以下であることが好ましく、より好ましくは４μｍ以下である。このような多層積層フィルムを用いることで、より高い温度でラミネート成形を行なうことができ加工条件の幅が広がる。フィルム温度７０℃のときに、正三角錐圧子をフィルム面に対して荷重５０ｍＮにて押し込んだ際の変位量が５μｍ以下となる多層積層フィルムとしては、７０℃において硬度の高い樹脂を用いることが挙げられる。例えば、二軸延伸され配向結晶化したポリエチレンテレフタレート及びその共重合体、ポリエチレンナフタレート及びその共重合体が挙げられる。また、例えフィルム単体ではフィルム温度７０℃のときに、正三角錐圧子をフィルム面に対して荷重５０ｍＮにて押し込んだ際の変位量が５μｍ以上であっても、二軸延伸され配向結晶化したポリエチレンテレフタレート及びその共重合体、ポリエチレンナフタレート及びその共重合体が多層積層フィルムの表面側となるように積層し、正三角錐圧子をフィルム面に対して荷重５０ｍＮにて押し込んだ際の変位量が５μｍ以下となるように、二軸延伸され配向結晶化したポリエチレンテレフタレート及びその共重合体、ポリエチレンナフタレート及びその共重合体の積層比を調整することも挙げられる。二軸延伸以外の方法としては、ガラス転移点温度の高い樹脂を用いることである。好ましい樹脂として、ポリカーボネート、ポリアリレート、ポリエチレンナフタレート、スピログリコールを１５ｍｏｌ％以上共重合したポリエチレンテレフタレート、ナフタレンジカルボン酸を２０ｍｏｌ％以上共重合したポリエチレンテレフタレート等が挙げられる。また、これらの樹脂に他の成分を共重合させることや、他の樹脂とコンパウンドすることも好ましい。 The multilayer laminated film used in the molded product of the present invention is a diamond regular triangular pyramid indenter whose angle between ridges is 115 ° when the film is heated to 70 ° C., and the load speed is 7.747 mN / s perpendicular to the film surface. The amount of displacement when pushed in with a load of 50 mN is required to be 5 μm or less, and preferably 4 μm or less. The appearance defect occurring in the molded product is caused by a large amount of displacement in the film surface direction with respect to the load applied in the film surface direction of the multilayer laminated film. Therefore, by using such a multilayer laminated film, it does not occur that it is pressed by foreign matter during the heat and pressure laminate molding, or that the shape of the intermediate layer such as an adhesive layer or film is transferred to the multilayer laminated film, A molded product having an excellent appearance can be obtained. Displacement when a diamond regular triangular pyramid indenter with an angle between the ridges of 115 ° is pushed perpendicularly to the film surface at a load speed of 7.747 mN / s and a load of 50 mN when the film is heated to 100 ° C. The amount is preferably 5 μm or less, more preferably 4 μm or less. By using such a multilayer laminated film, laminate molding can be performed at a higher temperature, and the range of processing conditions is expanded. When the film temperature is 70 ° C., as the multilayer laminated film in which the displacement amount when the regular triangular pyramid indenter is pushed into the film surface with a load of 50 mN is 5 μm or less, a resin having high hardness at 70 ° C. is used. It is done. For example, biaxially stretched and oriented crystallized polyethylene terephthalate and its copolymer, polyethylene naphthalate and its copolymer are mentioned. For example, when the film itself is a film temperature of 70 ° C., even if the displacement amount when the regular triangular pyramid indenter is pushed into the film surface with a load of 50 mN is 5 μm or more, the biaxially stretched polyethylene is oriented and crystallized. When the terephthalate and its copolymer, polyethylene naphthalate and its copolymer are laminated so as to be on the surface side of the multilayer laminated film, the displacement amount when the regular triangular pyramid indenter is pushed into the film surface with a load of 50 mN is 5 μm. Examples include adjusting the lamination ratio of polyethylene terephthalate biaxially stretched and oriented crystallized and its copolymer, polyethylene naphthalate and its copolymer, as follows. As a method other than biaxial stretching, a resin having a high glass transition temperature is used. Preferable resins include polycarbonate, polyarylate, polyethylene naphthalate, polyethylene terephthalate copolymerized by 15 mol% or more of spiroglycol, polyethylene terephthalate copolymerized by 20 mol% or more of naphthalenedicarboxylic acid, and the like. It is also preferable to copolymerize these resins with other components or to compound with other resins.
本発明の成形品は、支持体上に多層積層フィルムが配置されている。配置する手段としては貼着圧力のもとラミネートすることが一般的であり、加熱加圧ラミネートが好ましい方法である。本発明の成形品に用いうる支持体としては、例えば、樹脂製の支持体、金属やガラスやセラミックによる支持体等があげられる。支持体の表面としては平面であっても曲面であっても任意の形状がとりうる。樹脂の例を挙げてみると、ポリカーボネート、環状ポリオレフィン、ポリアリレート、ポリエチレンテレフタレート、ポリメチルメタクリレート等のアクリル樹脂、ＡＢＳ、トリアセチルセルロース等が挙げられる。支持体は透明であることが好ましく、支持体の厚みは０．５ｍｍ〜５ｍｍであることが好ましい。 In the molded article of the present invention, a multilayer laminated film is disposed on a support. As a means for disposing, laminating is generally performed under a sticking pressure, and heat and pressure laminating is a preferable method. Examples of the support that can be used in the molded article of the present invention include a resin support, a support made of metal, glass, or ceramic. The surface of the support can have any shape, whether it is a flat surface or a curved surface. Examples of the resin include acrylic resins such as polycarbonate, cyclic polyolefin, polyarylate, polyethylene terephthalate, and polymethyl methacrylate, ABS, and triacetyl cellulose. The support is preferably transparent, and the thickness of the support is preferably 0.5 mm to 5 mm.
多層積層フィルムを支持体上に貼り合わせる方法としては、押出ラミネート、ホットメルトラミネート、サーマルラミネート、プレスラミネート、真空ラミネート、オートクレーブラミネート等がある。押出ラミネートとは、溶融状態の多層積層フィルムをダイからフィルム状に押し出して支持体に積層し、２本のロール間に成形品を通し成形する方法である。ホットメルトラミネートとは、多層積層フィルムまたは、支持体に熱で溶かした接着剤を塗布し、多層積層フィルムと支持体を積層する成形方法である。サーマルラミネートとは、多層積層フィルムと支持体を加熱ロールで加熱しつつ圧着して積層する成形方法である。プレスラミネートとは、多層積層フィルムと支持体を加熱し、プレス機にて圧着して積層する成形方法である。真空ラミネートとは、多層積層フィルムと支持体を加熱後、装置内を真空状態にしプレスして積層する成形方法である。オートクレーブラミネートとは、多層積層フィルムと支持体を加熱後、装置内をガス等で加圧して積層する成形方法である。 Examples of the method for laminating the multilayer laminated film on the support include extrusion lamination, hot melt lamination, thermal lamination, press lamination, vacuum lamination, autoclave lamination and the like. Extrusion laminating is a method in which a molten multilayer laminated film is extruded from a die into a film shape and laminated on a support, and a molded product is formed between two rolls. Hot melt lamination is a forming method in which a multilayer laminated film or an adhesive melted by heat is applied to a support, and the multilayer laminated film and the support are laminated. Thermal lamination is a molding method in which a multilayer laminated film and a support are pressed and laminated while being heated with a heating roll. Press laminating is a molding method in which a multilayer laminated film and a support are heated and pressed and laminated with a press. The vacuum lamination is a molding method in which a multilayer laminated film and a support are heated and then the inside of the apparatus is vacuumed and pressed to be laminated. Autoclave laminating is a molding method in which a multilayer laminated film and a support are heated and then the interior of the apparatus is pressurized with gas or the like and laminated.
支持体と多層積層フィルムを加熱加圧ラミネートする際に、接着剤を用いることも好ましい。接着剤としては、酢酸ビニル樹脂系、塩化ビニル・酢酸ビニル共重合体系、エチレン・酢酸ビニル共重合体系、ポリビニルアルコール、ポリビニルブチラール、ポリビニルアセタール、ポリビニルエーテル、ニトリルゴム系、スチレン・ブダジエンゴム系、天然ゴム系、クロロプレンゴム系、ポリアミド系、エポキシ樹脂系、ポリウレタン系、アクリル樹脂系、セルロース系、ポリ塩化ビニル、ポリアクリル酸エステル、ポリイソブチレン等が挙げられる。また、これら接着剤には、粘着性調整剤、可塑剤、熱安定剤、酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、着色剤、架橋剤等を添加しても良い。 It is also preferable to use an adhesive when laminating the support and the multilayer laminated film with heat and pressure. Adhesives include vinyl acetate resin, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl ether, nitrile rubber, styrene / budadiene rubber, natural Examples thereof include rubber, chloroprene rubber, polyamide, epoxy resin, polyurethane, acrylic resin, cellulose, polyvinyl chloride, polyacrylic acid ester, polyisobutylene, and the like. Moreover, you may add a tackiness modifier, a plasticizer, a heat stabilizer, antioxidant, a ultraviolet absorber, an antistatic agent, a lubricant, a coloring agent, a crosslinking agent, etc. to these adhesives.
本発明の成形品に用いる多層積層フィルムは、ｔａｎδの立ち上がり温度が７０℃以上であることが好ましい。ここでｔａｎδとは、動的粘弾性測定における損失弾性率と貯蔵弾性率の比であり、ｔａｎδの立ち上がり温度とは、横軸を温度（℃）縦軸をｔａｎδにとり、低温側のベースラインを高温側に延長した直線と、温度に対するｔａｎδの傾きが最大となる点で引いた接線との交点の温度である。ｔａｎδが立ち上がり始める温度以上にてフィルムの軟化が始まる。そのため、ｔａｎδの立ち上がり温度が７０℃以上であれば、加熱加圧ラミネート時にフィルムが軟化しづらくなる結果、フィルムの凹凸が出難くなり、外観に優れた成形品を得ることができる。ｔａｎδの立ち上がり温度は７５℃以上がより好ましく、さらに好ましくは８０℃以上である。ｔａｎδの立ち上がり温度を７０℃以上とする方法としては、熱結晶化、延伸による配向結晶化が挙げられる。好ましい樹脂として、ポリエチレンテレフタレート、ポリエチレンナフタレート及び、イソフタル酸、アジピン酸、ナフタレンジカルボン酸、シクロヘキサンジカルボン酸が１０ｍｏｌ％以下共重合したポリエチレンテレフタレート等が挙げられる。結晶化以外の方法としては、ガラス転移点温度の高い樹脂を用いることが挙げられる。 The multilayer laminated film used in the molded article of the present invention preferably has a tan δ rise temperature of 70 ° C. or higher. Here, tan δ is the ratio of loss elastic modulus to storage elastic modulus in dynamic viscoelasticity measurement. The rising temperature of tan δ is the temperature (° C.) on the horizontal axis and tan δ on the vertical axis, and the baseline on the low temperature side is This is the temperature at the intersection of the straight line extended to the high temperature side and the tangent drawn at the point where the slope of tan δ with respect to the temperature is maximum. The softening of the film starts at a temperature higher than the temperature at which tan δ starts to rise. Therefore, if the rising temperature of tan δ is 70 ° C. or higher, the film is difficult to soften during the heat and pressure lamination, so that the unevenness of the film is difficult to be produced and a molded product having an excellent appearance can be obtained. The rising temperature of tan δ is more preferably 75 ° C. or higher, and further preferably 80 ° C. or higher. Examples of the method for setting the rising temperature of tan δ to 70 ° C. or higher include thermal crystallization and orientation crystallization by stretching. Preferable resins include polyethylene terephthalate, polyethylene naphthalate, and polyethylene terephthalate copolymerized with 10 mol% or less of isophthalic acid, adipic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. As a method other than crystallization, a resin having a high glass transition temperature can be used.
本発明の成形品に用いる多層積層フィルムは観測されるガラス転移点温度の内、最も低いガラス転移点温度が８５℃以上であることが好ましい。最も低いガラス転移点温度とは、２つ以上のガラス転移点温度が観測された場合、そのうち最も低いガラス転移点温度である。当該ガラス転移点温度を８５℃以上とすることで、加熱加圧ラミネート時にフィルムが軟化しづらくなる結果、フィルムの凹凸が出難くなり、外観に優れた成形品を得ることができる。好ましい樹脂として、ポリカーボネート、ポリアリレート、ポリエチレンナフタレート、スピログリコールを１５ｍｏｌ％以上共重合したポリエチレンテレフタレート、ナフタレンジカルボン酸を２０ｍｏｌ％以上共重合したポリエチレンテレフタレート等が挙げられる。また、これらの樹脂にガラス転移点温度が８５℃以上になることを条件として、他の成分を共重合させることや、他の樹脂とコンパウンドすることも好ましい。ガラス転移点温度を高くする方法としては、配向結晶化によってガラス転移点温度が延伸温度まで高くなる樹脂を用いることである。好ましい樹脂として、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステルが挙げられる。 The multilayer laminated film used for the molded article of the present invention preferably has a lowest glass transition temperature of 85 ° C. or higher among the observed glass transition temperature. The lowest glass transition temperature is the lowest glass transition temperature when two or more glass transition temperatures are observed. By setting the glass transition point temperature to 85 ° C. or higher, the film is difficult to soften during heating and pressurizing lamination, and as a result, unevenness of the film is difficult to be produced, and a molded product having an excellent appearance can be obtained. Preferable resins include polycarbonate, polyarylate, polyethylene naphthalate, polyethylene terephthalate copolymerized by 15 mol% or more of spiroglycol, polyethylene terephthalate copolymerized by 20 mol% or more of naphthalenedicarboxylic acid, and the like. It is also preferable to copolymerize other components or to compound with other resins on the condition that the glass transition temperature of these resins is 85 ° C. or higher. A method for increasing the glass transition temperature is to use a resin whose glass transition temperature is increased to the stretching temperature by orientation crystallization. Preferred resins include polyesters such as polyethylene terephthalate and polyethylene naphthalate.
本発明の成形品に用いる多層積層フィルムは、Ａ層が結晶性の熱可塑性樹脂からなり、Ｂ層が非晶性の熱可塑性樹脂を主たる成分とする樹脂からなることが好ましい。ここで非晶性の熱可塑性樹脂を主たる成分とする樹脂とは、非晶性の熱可塑性樹脂の重量分率が６０％以上であることをいう。結晶性の樹脂層と非晶性の樹脂層を交互に積層することによって、それぞれの熱可塑性樹脂１層のみではなし得ない機能をフィルムに与えることができる。Ｂ層の非晶性樹脂はガラス転移点温度が高い樹脂が好ましいが、ガラス転移点温度が低い樹脂であっても、ガラス転移点温度が高い樹脂とコンパウンドしてガラス転移点温度を高くすることで、凹凸のつき難い多層積層フィルムを得ることができる。また、Ｂ層の非晶性樹脂に結晶性樹脂をコンパウンドすることも好ましい。多層積層フィルムを延伸した際に、Ｂ層の非晶性樹脂中の結晶性樹脂が配向結晶化することで、凹凸のつき難い多層積層フィルムを得ることができる。Ｂ層の非晶性樹脂にコンパウンドする好ましい結晶性樹脂として、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステルが挙げられる。 In the multilayer laminated film used in the molded article of the present invention, the A layer is preferably made of a crystalline thermoplastic resin, and the B layer is preferably made of a resin mainly composed of an amorphous thermoplastic resin. Here, the resin mainly composed of an amorphous thermoplastic resin means that the weight fraction of the amorphous thermoplastic resin is 60% or more. By alternately laminating the crystalline resin layer and the amorphous resin layer, it is possible to give the film a function that cannot be achieved with only one thermoplastic resin layer. The amorphous resin of layer B is preferably a resin having a high glass transition temperature, but even if it is a resin having a low glass transition temperature, it should be compounded with a resin having a high glass transition temperature to increase the glass transition temperature. Thus, it is possible to obtain a multilayer laminated film which is difficult to be uneven. It is also preferable to compound a crystalline resin with the amorphous resin of the B layer. When the multilayer laminated film is stretched, the crystalline resin in the amorphous resin of the B layer undergoes orientational crystallization, whereby a multilayer laminated film that is difficult to be uneven can be obtained. Examples of a preferable crystalline resin that is compounded with the amorphous resin of the B layer include polyesters such as polyethylene terephthalate and polyethylene naphthalate.
本発明の成形品に用いる多層積層フィルムは、波長４００ｎｍから８００ｎｍの範囲における平均反射率が１５％以上であることが好ましい。平均反射率が１５％以上であることにより、成形品に金属光沢感を持たせることが出来る。好ましくは２０％以上、より好ましくは４０％以上、さらに好ましくは６０％以上である。反射率スペクトルは、波長４００ｎｍから８００ｎｍの範囲に渡って、反射率が一定であるものでも、一部の波長範囲の反射率が高いものでも良い。 The multilayer laminated film used for the molded article of the present invention preferably has an average reflectance of 15% or more in the wavelength range of 400 nm to 800 nm. When the average reflectance is 15% or more, the molded product can have a metallic luster. Preferably it is 20% or more, More preferably, it is 40% or more, More preferably, it is 60% or more. The reflectance spectrum may have a constant reflectance over a wavelength range of 400 nm to 800 nm, or may have a high reflectance in a part of the wavelength range.
本発明の成形品に用いる多層積層フィルムは、波長４００ｎｍから７００ｎｍの範囲における平均反射率が１５％以下であり、波長８５０ｎｍから１２００ｎｍの範囲における平均反射率が７０％以上であることが好ましい。このような構成とすると、本発明の成形品を建物の窓ガラスや、自動車の窓ガラスとして用いた場合、室内や車内の温度上昇を防ぐことが出来る。好ましくは、波長４００ｎｍから７００ｎｍの範囲における平均反射率が１５％以下であり、波長８５０ｎｍから１２００ｎｍの範囲における平均反射率が８０％以上、さらに好ましくは、波長４００ｎｍから７００ｎｍの範囲における平均反射率が１５％以下であり、波長８５０ｎｍから１２００ｎｍの範囲における平均反射率が９０％以上である。 The multilayer laminated film used in the molded product of the present invention has an average reflectance in the wavelength range of 400 nm to 700 nm of 15% or less, and preferably has an average reflectance of 70% or more in the wavelength range of 850 nm to 1200 nm. If it is set as such a structure, when the molded article of this invention is used as a window glass of a building, or a window glass of a motor vehicle, the temperature rise in a room | chamber interior or a vehicle interior can be prevented. Preferably, the average reflectance in the wavelength range of 400 nm to 700 nm is 15% or less, the average reflectance in the wavelength range of 850 nm to 1200 nm is 80% or more, more preferably, the average reflectance in the wavelength range of 400 nm to 700 nm is It is 15% or less, and the average reflectance in the wavelength range of 850 nm to 1200 nm is 90% or more.
本発明の成形品に用いる多層積層フィルムは、波長４００ｎｍから７００ｎｍの範囲における平均反射率が４０％以下であり、波長８５０ｎｍから１４００ｎｍの範囲における平均反射率が７０％以上であることが好ましい。さらに好ましくは波長４００ｎｍから７００ｎｍの範囲における平均反射率が４０％以下であり、波長８５０ｎｍから１４００ｎｍの範囲における平均反射率が８０％以上、より好ましくは波長４００ｎｍから７００ｎｍの範囲における平均反射率が４０％以下であり、波長８５０ｎｍから１４００ｎｍの範囲における平均反射率が９０％以上である。このような構成とすると、より多くの熱エネルギーを遮断することができるため、本発明の成形品を建物の窓ガラスや、自動車の窓ガラスとして用いた場合、室内や車内の温度上昇を大いに防ぐことが出来る。別の好ましい反射率としては、波長４００ｎｍから７００ｎｍの範囲における平均反射率が２０％以下であり、波長８５０ｎｍから１４００ｎｍの範囲における平均反射率が７０％以上、別のさらに好ましい反射率としては、波長４００ｎｍから７００ｎｍの範囲における平均反射率が２０％以下であり、波長８５０ｎｍから１４００ｎｍの範囲における平均反射率が８０％以上、別のより好ましい反射率としては、波長４００ｎｍから７００ｎｍの範囲における平均反射率が２０％以下であり、波長８５０ｎｍから１４００ｎｍの範囲における平均反射率が９０％以上である。 The multilayer laminated film used for the molded article of the present invention preferably has an average reflectance in the wavelength range of 400 nm to 700 nm of 40% or less and an average reflectance in the wavelength range of 850 nm to 1400 nm of 70% or more. More preferably, the average reflectance in the wavelength range from 400 nm to 700 nm is 40% or less, the average reflectance in the wavelength range from 850 nm to 1400 nm is 80% or more, more preferably the average reflectance in the wavelength range from 400 nm to 700 nm is 40%. %, And the average reflectance in the wavelength range of 850 nm to 1400 nm is 90% or more. With such a configuration, more heat energy can be cut off. Therefore, when the molded product of the present invention is used as a window glass of a building or a window glass of an automobile, a temperature rise in the room or in the vehicle is greatly prevented. I can do it. As another preferable reflectance, the average reflectance in the wavelength range of 400 nm to 700 nm is 20% or less, the average reflectance in the wavelength range of 850 nm to 1400 nm is 70% or more, and another more preferable reflectance is the wavelength. The average reflectance in the range from 400 nm to 700 nm is 20% or less, the average reflectance in the wavelength range from 850 nm to 1400 nm is 80% or more, and another more preferable reflectance is an average reflectance in the wavelength range from 400 nm to 700 nm. Is 20% or less, and the average reflectance in the wavelength range of 850 nm to 1400 nm is 90% or more.
望ましい波長範囲における反射率を調整する方法は、Ａ層とＢ層の面内屈折率差、積層数、層厚み分布、製膜条件（例えば延伸倍率、延伸速度、延伸温度、熱処理温度、熱処理時間）の調整等が挙げられる。反射率が高くなり積層数が少なく済むことから、Ａ層とＢ層の面内屈折率差は０．０２以上が好ましく、より好ましくは０．０４以上、さらに好ましくは０．０８以上である。積層数は１０１層以上が好ましく、より好ましくは４０１層以上、さらに好ましくは６０１層以上であり、積層装置の大型化の観点から上限としては５０００層程度である。層厚み分布は隣接するＡ層とＢ層の光学厚みが下記（１）式を満たすことが好ましい。 The method for adjusting the reflectance in the desired wavelength range is the in-plane refractive index difference between layer A and layer B, the number of layers, the layer thickness distribution, and the film forming conditions (for example, the stretching ratio, stretching speed, stretching temperature, heat treatment temperature, heat treatment time). ) Adjustment and the like. Since the reflectivity increases and the number of stacked layers can be reduced, the in-plane refractive index difference between the A layer and the B layer is preferably 0.02 or more, more preferably 0.04 or more, and further preferably 0.08 or more. The number of stacked layers is preferably 101 layers or more, more preferably 401 layers or more, still more preferably 601 layers or more, and the upper limit is about 5000 layers from the viewpoint of increasing the size of the stacking apparatus. In the layer thickness distribution, it is preferable that the optical thicknesses of the adjacent A layer and B layer satisfy the following formula (1).
ここでλは反射波長、nAはA層の面内屈折率、dAはＡ層の厚み、nBはＢ層の面内屈折率、dBはＢ層の厚みである。 Where λ is the reflection wavelength, n A is the in-plane refractive index of the A layer, d A is the thickness of the A layer, n B is the in-plane refractive index of the B layer, and d B is the thickness of the B layer.
層厚み分布は式（１）と下記（２）式を同時に満たすことも好ましい。 It is also preferable that the layer thickness distribution satisfies the formula (1) and the following formula (2) simultaneously.
（１）と式（２）を同時に満たす層厚み分布を持つことで偶数次の反射を解消できる。そのため、波長８５０ｎｍから１２００ｎｍの範囲における平均反射率を高くしつつ、波長４００ｎｍから７００ｎｍの範囲における平均反射率を低くすることができ、透明でかつ、熱エネルギーの遮断性能の高い多層積層フィルムを得ることができる。 Even-order reflection can be eliminated by having a layer thickness distribution that satisfies (1) and (2) simultaneously. Therefore, while increasing the average reflectance in the wavelength range of 850 nm to 1200 nm, the average reflectance in the wavelength range of 400 nm to 700 nm can be lowered, and a transparent multilayer film having a high thermal energy blocking performance is obtained. be able to.
層厚み分布は式（１）、式（２）以外に７１１構成（米国特許第５３６０６５９号）を用いることも好ましい。７１１構成の層厚み分布とすることで、高次の反射を解消できる。そのため、波長８５０ｎｍから１４００ｎｍの範囲における平均反射率を高くしつつ、波長４００ｎｍから７００ｎｍの範囲における平均反射率を低くすることができ、透明でかつ、熱エネルギーの遮断性能のより高い多層積層フィルムを得ることができる。また、波長８５０ｎｍから１２００ｎｍの範囲の反射を式（１）と式（２）を同時に満たす層厚み分布によって、波長１２００ｎｍから１４００ｎｍの範囲の反射を７１１構成の層厚み分布とすることも好ましい。このような層厚み構成とすることで、少ない積層数で効率良く光を反射させることができる。 For the layer thickness distribution, it is also preferable to use a 711 configuration (US Pat. No. 5,360,659) in addition to the formulas (1) and (2). By adopting a layer thickness distribution of 711 configuration, higher-order reflection can be eliminated. Therefore, it is possible to reduce the average reflectance in the wavelength range from 400 nm to 700 nm while increasing the average reflectance in the wavelength range from 850 nm to 1400 nm, and to provide a multilayer laminated film that is transparent and has a higher thermal energy blocking performance. Can be obtained. It is also preferable that the reflection in the wavelength range from 850 nm to 1200 nm satisfies the expressions (1) and (2) at the same time, and the reflection in the wavelength range from 1200 nm to 1400 nm is changed to the layer thickness distribution of 711 configuration. With such a layer thickness configuration, light can be efficiently reflected with a small number of layers.
層厚みの分布はフィルム面の一方から反対側の面へ向かって増加または減少する層厚み分布や、フィルム面の一方からフィルム中心へ向かって層厚みが増加した後減少する層厚み分布や、フィルム面の一方からフィルム中心へ向かって層厚みが増加した後減少し、反対側の面からフィルム中心へ向かって増加する層厚み分布も好ましい。層厚み分布の変化の仕方としては、線形、等比、階差数列といった連続的に変化するものや、１０層から５０層程度の層がほぼ同じ層厚みを持ち、その層厚みがステップ状に変化するものが好ましい。 The layer thickness distribution increases or decreases from one side of the film surface to the opposite surface, the layer thickness distribution decreases after the layer thickness increases from one of the film surfaces toward the film center, and the film Also preferred is a layer thickness distribution that decreases after increasing the layer thickness from one of the faces toward the film center and increases from the opposite face toward the film center. Layer thickness distribution can be changed continuously, such as linear, geometric ratio, difference series, or 10 to 50 layers have almost the same layer thickness, and the layer thickness is stepped. Those that change are preferred.
多層積層フィルムの両表層に保護層として層厚み３μｍ以上の層を好ましく設けることができる、保護層の厚みは好ましくは５μｍ以上、より好ましくは１０μｍ以上である。保護層の厚みが厚くなることで、フローマークの抑制、透過率・反射率スペクトルのリップルの抑制、加熱加圧ラミネート時の多層積層フィルムの凹凸の抑制の効果が得られる。 A layer having a thickness of 3 μm or more can be preferably provided as a protective layer on both surface layers of the multilayer laminated film. The thickness of the protective layer is preferably 5 μm or more, more preferably 10 μm or more. By increasing the thickness of the protective layer, it is possible to obtain the effects of suppressing flow marks, suppressing ripples in the transmittance / reflectance spectrum, and suppressing unevenness of the multilayer laminated film during heating and pressing lamination.
本発明の成形品に用いる多層積層フィルムの厚みは、２０μｍ〜３００μｍであることが好ましい。 The thickness of the multilayer laminated film used for the molded article of the present invention is preferably 20 μm to 300 μm.
本発明の成形品に用いる多層積層フィルムは、フィルムの表面に易接着層、ハードコート層、耐磨耗性層、傷防止層、反射防止層、色補正層、紫外線吸収層、熱線吸収層、印刷層、ガスバリア層、粘着層などの機能性層が形成されることが好ましい。 The multilayer laminated film used for the molded product of the present invention has an easy-adhesion layer, a hard coat layer, an abrasion-resistant layer, an anti-scratch layer, an antireflection layer, a color correction layer, an ultraviolet absorption layer, a heat ray absorption layer on the film surface, It is preferable that functional layers such as a printing layer, a gas barrier layer, and an adhesive layer are formed.
本発明の成形品は多層積層フィルムと支持体との間に中間層が形成されることが好ましい。中間層としては、接着剤層やフィルム層が好ましい。中間層を設けることによって、支持体と多層積層フィルムの密着性、成形品の意匠性、耐久性、耐候性、耐衝撃性等の機能を高めることができる。意匠性を高める方法として、着色剤があり、アゾ系顔料、多環式系顔料、レーキ系顔料、ニトロ系顔料、ニトロソ系顔料、アニリンブラック、アルカリブルー、フタロシアニン系顔料、シアニン系顔料、アゾ系染料、アントラキノン系染料、キノフタロン系染料、メチン系染料、縮合多環系染料、反応染料、カチオン染料、六ホウ化ランタン、インジウムスズ酸化物、アンチモンスズ酸化物、セシウムタングステン酸化物等が挙げられる。 In the molded article of the present invention, an intermediate layer is preferably formed between the multilayer laminated film and the support. As the intermediate layer, an adhesive layer or a film layer is preferable. By providing the intermediate layer, functions such as adhesion between the support and the multilayer laminated film, designability of the molded product, durability, weather resistance, and impact resistance can be enhanced. As a method for improving the design, there are coloring agents, azo pigments, polycyclic pigments, lake pigments, nitro pigments, nitroso pigments, aniline black, alkali blue, phthalocyanine pigments, cyanine pigments, azo pigments. Examples include dyes, anthraquinone dyes, quinophthalone dyes, methine dyes, condensed polycyclic dyes, reactive dyes, cationic dyes, lanthanum hexaboride, indium tin oxide, antimony tin oxide, and cesium tungsten oxide.
本発明の成形品は多層積層フィルムの両側に支持体が加熱加圧ラミネートされていることが好ましい。多層積層フィルムの両側に支持体を積層することで成形品の意匠性、耐久性、耐候性、耐衝撃性等の機能を高めることができる。さらに、多層積層フィルムと支持体との間に中間層が形成されることが好ましい。 In the molded article of the present invention, the support is preferably laminated with heat and pressure on both sides of the multilayer laminated film. By laminating the support on both sides of the multilayer laminated film, functions such as designability, durability, weather resistance and impact resistance of the molded product can be enhanced. Furthermore, it is preferable that an intermediate layer is formed between the multilayer laminated film and the support.
以下、本発明の成形品を具体的な実施例をあげて説明する。なお、以下に具体的に例示した熱可塑性樹脂以外の熱可塑性樹脂を用いた場合でも下記実施例を含めた本明細書の記載を参酌すれば、同様にして本発明の多層積層フィルムを得ることができる。
[物性の測定方法ならびに効果の評価方法]
物性値の評価方法ならびに効果の評価方法は次の通りである。
Hereinafter, the molded article of the present invention will be described with specific examples. Even when a thermoplastic resin other than the thermoplastic resin specifically exemplified below is used, the multilayer laminated film of the present invention can be obtained in the same manner by referring to the description of the present specification including the following examples. Can do.
[Methods for measuring physical properties and methods for evaluating effects]
The physical property value evaluation method and the effect evaluation method are as follows.
（１）正三角錐圧子をフィルム面に対して荷重５０ｍＮにて押し込んだ際の変位量
島津製作所（株）製 微小圧縮試験機ＭＣＴＷ−５００を用いた。稜線間の角度が１１５°のダイヤモンド製正三角錐圧子を用い、負荷速度７．７４７ｍＮ／ｓにて圧子をフィルム面に押込み荷重５０ｍＮにおける変位量を測定した。フィルム温度７０℃又は１００℃において５回測定を行ない、その平均値を採用した。
(1) Displacement amount when the equilateral triangular pyramid indenter is pushed into the film surface with a load of 50 mN A micro compression tester MCTW-500 manufactured by Shimadzu Corporation was used. Using a diamond regular triangular pyramid indenter with an angle between ridges of 115 °, the indenter was pushed into the film surface at a load speed of 7.747 mN / s, and the displacement at a load of 50 mN was measured. The measurement was performed 5 times at a film temperature of 70 ° C. or 100 ° C., and the average value was adopted.
（２）ｔａｎδの立ち上がり温度
セイコーインスツルメント（株）製 ＥＸＳＴＡＲ ＤＭＳ６１００を用いた。引張モード、周波数１Ｈｚ、チャック間距離２０ｍｍ、歪振幅５．０μｍ、ゲイン１．５、力振幅初期値４００ｍＮ、昇温速度２℃／分の条件にて２５℃から２００℃の温度範囲でｔａｎδを測定した。得られたデータに対して、横軸を温度（℃）縦軸をｔａｎδにとり、低温側のベースラインを高温側に延長した直線と、温度に対するｔａｎδの傾きが最大となる点で引いた接線との交点の温度をｔａｎδの立ち上がり温度とした。
(2) Rise temperature of tan δ EXSTAR DMS6100 manufactured by Seiko Instruments Inc. was used. Tan δ in the temperature range from 25 ° C to 200 ° C under the conditions of tension mode, frequency 1 Hz, distance between chucks 20 mm, strain amplitude 5.0 µm, gain 1.5, force amplitude initial value 400 mN, and heating rate 2 ° C / min. It was measured. For the obtained data, the horizontal axis is the temperature (° C.), the vertical axis is tan δ, the low temperature side baseline is extended to the high temperature side, and the tangent line drawn at the point where the slope of tan δ with respect to the temperature is maximum. The temperature at the point of intersection was defined as the rising temperature of tan δ.
（３）ガラス転移点温度
セイコーインスツルメント（株）製ＥＸＳＴＡＲ ＤＳＣ６２２０を用いた。サンプルを電子天秤で５ｍｇ計量し、アルミパッキンで挟み込みサンプルを設置し、２５℃から３００℃まで２０℃／分で昇温した(１ｓｔＲｕｎ測定)。ガラス転移温度（Ｔｇ）として、ＪＩＳ−Ｋ−７１２１に記載の中間点ガラス転移温度を求めた。
(3) Glass transition temperature EXSTAR DSC6220 manufactured by Seiko Instruments Inc. was used. 5 mg of the sample was weighed with an electronic balance, sandwiched between aluminum packings, a sample was placed, and the temperature was raised from 25 ° C. to 300 ° C. at 20 ° C./min (1st Run measurement). As the glass transition temperature (Tg), the midpoint glass transition temperature described in JIS-K-7121 was determined.
（４）平均反射率
日立製作所製 分光光度計（Ｕ−４１００ Ｓｐｅｃｔｒｏｐｈｏｔｏｍａｔｅｒ）に付属の１２°正反射付属装置Ｐ／Ｎ１３４−０１０４を取り付け、入射角度φ＝１２度における波長２５０〜２６００ｎｍの絶対透過率及び反射率を測定した。測定条件：スリットは２ｎｍ（可視）／自動制御（赤外）とし、ゲインは２と設定し、走査速度を６００ｎｍ／分とした。サンプルをフィルム幅中央部から５ｃｍ×５ｃｍで切り出し測定した。これらの結果から、波長４００ｎｍ〜８００ｎｍ、波長４００ｎｍ〜７００ｎｍ、波長８５０ｎｍ〜１２００ｎｍ、波長８５０ｎｍ〜１４００ｎｍの平均反射率を求めた。
(4) Average reflectivity The spectrophotometer (U-4100 Spectrophotometer) manufactured by Hitachi, Ltd. is attached with a 12 ° specular reflection accessory P / N134-0104, and an absolute transmittance at a wavelength of 250 to 2600 nm at an incident angle φ = 12 degrees. And the reflectance was measured. Measurement conditions: The slit was 2 nm (visible) / automatic control (infrared), the gain was set to 2, and the scanning speed was 600 nm / min. A sample was cut out at 5 cm × 5 cm from the center of the film width and measured. From these results, average reflectances of wavelengths of 400 nm to 800 nm, wavelengths of 400 nm to 700 nm, wavelengths of 850 nm to 1200 nm, and wavelengths of 850 nm to 1400 nm were determined.
（５）成形品外観
蛍光灯下に設置した成形品に対して、評価部分の法線方向に対して６０°の角度から評価部分を目視にて評価を行った。評価基準は次のとおりである。
(5) Appearance of molded product With respect to a molded product installed under a fluorescent lamp, the evaluation part was visually evaluated from an angle of 60 ° with respect to the normal direction of the evaluation part. The evaluation criteria are as follows.
○：凹凸が見えない。 ○: Unevenness is not visible.
×：凹凸が見える。 X: Unevenness is visible.
（熱可塑性樹脂）
樹脂Ａ ＩＶ＝０．６５ ポリエチレンテレフタレート
樹脂Ｂ ＩＶ＝０．７５ アジピン酸を１６ｍｏｌ％共重合したポリエチレンテレフタレート
樹脂Ｃ ＩＶ＝０．６６ ポリエチレンナフタレート
樹脂Ｄ ＩＶ＝０．７７ テレフタル酸を５０ｍｏｌ％共重合したポリエチレンナフタレート
樹脂Ｅ ＩＶ＝０．６６ シクロヘキサンジカルボン酸を５ｍｏｌ％、スピログリコールを２５ｍｏｌ％共重合したポリエチレンテレフタレート
樹脂Ｆ 樹脂Ｅと樹脂Ａとを重量分率（８０ｗｔ％／２０ｗｔ％）にてコンパウンドした樹脂
樹脂Ｇ 三菱ガス化学社製スピログリコール共重合ポリエステル（アルテスタ４５）
樹脂Ｈ 樹脂Ｂと樹脂Ｇとを重量分率（５０ｗｔ％／５０ｗｔ％）にてコンパウンドした樹脂
（実施例１）
Ａ層を構成する熱可塑性樹脂（以下、熱可塑性樹脂Ａとも称する）として樹脂Ａを用い、またＢ層を構成する熱可塑性樹脂（以下、熱可塑性樹脂Ｂとも称する）として樹脂Ｂを用いた。熱可塑性樹脂Ａおよび熱可塑性樹脂Ｂを、それぞれ、押出機にて２８０℃で溶融させ、ＦＳＳタイプのリーフディスクフィルタを５枚介した後、ギアポンプにて吐出比（積層比）が熱可塑性樹脂Ａ／熱可塑性樹脂Ｂ＝４／１になるように計量しながら、５１層フィードブロックにて合流させて、層厚み分布一定、厚み方向に交互に５１層積層（Ａ層が２６層、Ｂ層が２５層）された積層体）とした。次いで、Ｔダイに供給し、シート状に成形した後、ワイヤーで８ｋＶの静電印可電圧をかけながら、表面温度２５℃に保たれたキャスティングドラム上で急冷固化し、未延伸フィルムを得た。この未延伸フィルムを、９０℃、延伸倍率３．３倍で縦延伸を行い、両端部をクリップで把持するテンターに導き１００℃、４．２倍横延伸した後、２００℃で熱処理を施し、約２％の幅方向リラックスを実施し、厚み５０μｍの多層積層フィルムを得た。厚さ３ｍｍ、１０ｃｍ角の環状オレフィン・コポリマー（ポリプラスチックス製 ＴＯＰＡＳ６０１７）を支持体として用い、３Ｍ社製ホットメルト接着剤Ｓｃｏｔｃｈ−Ｗｅｌｄ３７６４をホットメルトガンで約１２０℃に加熱した。多層積層フィルムと支持体をオーブンにて８０℃１分間加熱した後、多層積層フィルムと支持体間に接着剤を塗布し、富士プラスチック株式会社製、Ｆｕｊｉ ＬＡＭＩＰＡＣＫＥＲ ＬＰＰ６５０を用い、ロール温度を８０℃に加熱し、多層積層フィルムと支持体を圧着積層した。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。
(Thermoplastic resin)
Resin A IV = 0.65 Polyethylene terephthalate resin B IV = 0.75 Polyethylene terephthalate resin C copolymerized with 16 mol% adipic acid IV = 0.66 Polyethylene naphthalate resin D IV = 0.77 Copolymerized 50 mol% terephthalic acid Polyethylene naphthalate resin E IV = 0.66 Polyethylene terephthalate resin F copolymerized with 5 mol% of cyclohexanedicarboxylic acid and 25 mol% of spiroglycol Compound E and resin A are compounded at a weight fraction (80 wt% / 20 wt%). Resin Resin G Spiroglycol Copolymerized Polyester manufactured by Mitsubishi Gas Chemical Company (Artester 45)
Resin H Resin B and Resin G compounded at a weight fraction (50 wt% / 50 wt%) (Example 1)
Resin A was used as the thermoplastic resin constituting the A layer (hereinafter also referred to as thermoplastic resin A), and resin B was used as the thermoplastic resin constituting the B layer (hereinafter also referred to as thermoplastic resin B). The thermoplastic resin A and the thermoplastic resin B are each melted at 280 ° C. with an extruder, passed through 5 sheets of FSS type leaf disk filters, and then discharged with a gear pump (lamination ratio) of the thermoplastic resin A. / Merging with a 51-layer feed block while weighing so that the thermoplastic resin B = 4/1, the layer thickness distribution is constant, and 51 layers are laminated alternately in the thickness direction (A layer is 26 layers, B layer is 25 layers). Next, after supplying to a T-die and forming into a sheet shape, it was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. while applying an electrostatic applied voltage of 8 kV with a wire to obtain an unstretched film. This unstretched film is longitudinally stretched at 90 ° C. and a stretching ratio of 3.3 times, and both ends are led to a tenter gripped by a clip, 100 ° C. and 4.2 times laterally stretched, and then heat treated at 200 ° C., About 2% of width direction relaxation was implemented and the 50-micrometer-thick multilayer laminated film was obtained. A cyclic olefin copolymer (TOPAS6017 manufactured by Polyplastics) having a thickness of 3 mm and 10 cm square was used as a support, and hot melt adhesive Scotch-Weld 3764 manufactured by 3M was heated to about 120 ° C. with a hot melt gun. After the multilayer laminated film and the support are heated in an oven at 80 ° C. for 1 minute, an adhesive is applied between the multilayer laminated film and the support, and the roll temperature is set to 80 ° C. using Fuji LAMIPACKER LPP650 made by Fuji Plastic Co., Ltd. Heating was performed, and the multilayer laminated film and the support were pressure laminated. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product.
（実施例２）
熱可塑性樹脂Ａとして樹脂Ｃを用い、また熱可塑性樹脂Ｂとして樹脂Ｄを用いた。熱可塑性樹脂Ａおよび熱可塑性樹脂Ｂを、それぞれ、押出機にて２９０℃で溶融させ、ＦＳＳタイプのリーフディスクフィルタを５枚介した後、ギアポンプにて吐出比が熱可塑性樹脂Ａ／熱可塑性樹脂Ｂ＝１／１になるように計量しながら、５１層フィードブロックにて合流させて、層厚み分布一定、厚み方向に交互に５１層積層（Ａ層が２６層、Ｂ層が２５層）された積層体とした。次いで、Ｔダイに供給し、シート状に成形した後、ワイヤーで８ｋＶの静電印可電圧をかけながら、表面温度２５℃に保たれたキャスティングドラム上で急冷固化し、未延伸フィルムを得た。この未延伸フィルムを、１４０℃、延伸倍率４．０倍で縦延伸を行い、両端部をクリップで把持するテンターに導き１４０℃、４．０倍横延伸した後、２００℃で熱処理を施し、約２％の幅方向リラックスを実施し、厚み５０μｍの多層積層フィルムを得た。得られた多層積層フィルムから実施例１と同様の方法にて成形体を作成した。樹脂Ｃと樹脂Ｄはｔａｎδの立ち上がり温度とガラス転移点温度が高い樹脂であり、７０℃及び１００℃において、正三角錐圧子をフィルム面に対して荷重５０ｍＮにて押し込んだ際の変位量が非常に小さくなった。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例５のものよりも優れたものであった。
(Example 2)
Resin C was used as thermoplastic resin A, and resin D was used as thermoplastic resin B. The thermoplastic resin A and the thermoplastic resin B are each melted at 290 ° C. by an extruder, passed through 5 sheets of FSS type leaf disc filters, and the discharge ratio is thermoplastic resin A / thermoplastic resin by a gear pump. While weighing so that B = 1/1, they are merged in the 51-layer feed block, and the layer thickness distribution is constant and 51 layers are stacked alternately in the thickness direction (26 layers for A and 25 layers for B). A laminated body was obtained. Next, after supplying to a T-die and forming into a sheet shape, it was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. while applying an electrostatic applied voltage of 8 kV with a wire to obtain an unstretched film. This unstretched film is longitudinally stretched at 140 ° C. and a stretch ratio of 4.0 times, and both ends are guided to a tenter gripped by clips, and after 140 ° C. and 4.0 times transverse stretch, heat treatment is performed at 200 ° C., About 2% of width direction relaxation was implemented and the 50-micrometer-thick multilayer laminated film was obtained. A molded body was produced from the obtained multilayer laminated film in the same manner as in Example 1. Resin C and Resin D are resins having a high tan δ rise temperature and a glass transition point temperature, and the displacement amount when pressing a regular triangular pyramid indenter against the film surface with a load of 50 mN at 70 ° C. and 100 ° C. is very high. It has become smaller. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 5.
（実施例３）
熱可塑性樹脂Ｂとして樹脂Ｅを用い、ギアポンプにて吐出比が熱可塑性樹脂Ａ／熱可塑性樹脂Ｂ＝１／１になるように計量したこと以外は、実施例１と同様の条件にて多層積層フィルムを得た。得られた多層積層フィルムから実施例１と同様の方法にて成形体を作成した。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例１のものよりも優れたものであった。
(Example 3)
Multilayer lamination under the same conditions as in Example 1 except that resin E is used as thermoplastic resin B and the discharge ratio is measured with a gear pump such that thermoplastic resin A / thermoplastic resin B = 1/1 A film was obtained. A molded body was produced from the obtained multilayer laminated film in the same manner as in Example 1. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 1.
（実施例４）
熱可塑性樹脂Ｂとして樹脂Ｆを用い、ギアポンプにて吐出比が熱可塑性樹脂Ａ／熱可塑性樹脂Ｂ＝１／１になるように計量したこと以外は、実施例１と同様の条件にて多層積層フィルムを得た。得られた多層積層フィルムから実施例１と同様の方法にて成形体を作成した。樹脂Ｆは樹脂Ｅに結晶性樹脂である樹脂Ａをコンパウンドしたものであり、本例にて作成した多層積層フィルムは、実施例３にて作成した多層積層フィルムよりも７０℃及び１００℃において、正三角錐圧子をフィルム面に対して荷重５０ｍＮにて押し込んだ際の変位量が小さくなった。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例５のものよりも優れたものであった。
Example 4
Multilayer lamination under the same conditions as in Example 1 except that resin F is used as thermoplastic resin B and the discharge ratio is measured with a gear pump such that thermoplastic resin A / thermoplastic resin B = 1/1. A film was obtained. A molded body was produced from the obtained multilayer laminated film in the same manner as in Example 1. Resin F is obtained by compounding resin E, which is a crystalline resin, with resin E. The multilayer laminated film created in this example is 70 ° C. and 100 ° C. than the multilayer laminated film created in Example 3. The amount of displacement when the regular triangular pyramid indenter was pushed into the film surface with a load of 50 mN was reduced. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 5.
（実施例５）
熱可塑性樹脂Ｂとして樹脂Ｈを用い、ギアポンプにて吐出比が熱可塑性樹脂Ａ／熱可塑性樹脂Ｂ＝１／１になるように計量したこと以外は、実施例１と同様の条件にて多層積層フィルムを得た。樹脂Ｈはガラス転移点温度の低い樹脂Ｂに、ガラス転移点温度の高い樹脂Ｇをコンパウンドし、ガラス転移点温度を上げたものである。得られた多層積層フィルムから実施例１と同様の方法にて成形体を作成した。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例１のものよりも優れたものであった。
(Example 5)
Multilayer lamination under the same conditions as in Example 1 except that resin H is used as thermoplastic resin B and the discharge ratio is measured with a gear pump such that thermoplastic resin A / thermoplastic resin B = 1/1. A film was obtained. Resin H is obtained by compounding resin G having a high glass transition temperature to resin B having a low glass transition temperature to raise the glass transition temperature. A molded body was produced from the obtained multilayer laminated film in the same manner as in Example 1. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 1.
（比較例１）
ギアポンプにて吐出比が熱可塑性樹脂Ａ／熱可塑性樹脂Ｂ＝１／１になるように計量したこと以外は、実施例１と同様の条件にて多層積層フィルムを得た。得られた多層積層フィルムから実施例１と同様の方法にて成形体を作成した。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。
(Comparative Example 1)
A multilayer laminated film was obtained under the same conditions as in Example 1 except that the discharge ratio was measured with a gear pump so that the thermoplastic resin A / thermoplastic resin B = 1/1. A molded body was produced from the obtained multilayer laminated film in the same manner as in Example 1. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product.
（比較例２）
熱可塑性樹脂Ａとして樹脂Ａを用い、熱可塑性樹脂Ｂとして樹脂Ｂを用いた。熱可塑性樹脂Ａおよび熱可塑性樹脂Ｂを、それぞれ、押出機にて２８０℃で溶融させ、ＦＳＳタイプのリーフディスクフィルタを５枚介した後、ギアポンプにて吐出比が熱可塑性樹脂Ａ／熱可塑性樹脂Ｂ＝４／１になるように計量しながら、５１層フィードブロックにて合流させて、層厚み分布一定、厚み方向に交互に５１層積層（Ａ層が２６層、Ｂ層が２５層）された積層体とした。次いで、Ｔダイに供給し、シート状に成形した後、ワイヤーで８ｋＶの静電印可電圧をかけながら、表面温度２５℃に保たれたキャスティングドラム上で急冷固化し、厚み２００μｍの未延伸多層積層フィルムを得た。得られた多層積層フィルムから実施例１と同様の方法にて成形体を作成した。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例１のものよりも優れたものであった。
(Comparative Example 2)
Resin A was used as thermoplastic resin A, and resin B was used as thermoplastic resin B. The thermoplastic resin A and the thermoplastic resin B are each melted at 280 ° C. by an extruder, passed through 5 sheets of FSS type leaf disc filters, and the discharge ratio is thermoplastic resin A / thermoplastic resin by a gear pump. While weighing so that B = 4/1, they are merged in a 51-layer feed block, and the layer thickness distribution is constant and 51 layers are stacked alternately in the thickness direction (26 layers for A and 25 layers for B). A laminated body was obtained. Next, after feeding into a T-die and forming into a sheet, it was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. while applying an electrostatic application voltage of 8 kV with a wire, and an unstretched multilayer laminate having a thickness of 200 μm A film was obtained. A molded body was produced from the obtained multilayer laminated film in the same manner as in Example 1. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 1.
（実施例６）
熱可塑性樹脂Ｂとして樹脂Ｆを用い、フィルムの表面から反対側の面に向かって、Ａ層とＢ層の層厚みを、それぞれ６０ｎｍから１３０ｎｍの範囲で等比数列的に変化させ（但し、最表層のＡ層の層厚みは、最終的に５μｍの厚さとなるように厚くした。）厚み方向に交互に２５１層積層（Ａ層が１２６層、Ｂ層が１２５層）したこと以外は実施例１と同様の条件にて厚み３２μｍの多層積層フィルムを得た。厚さ３ｍｍ、１０ｃｍ角の板ガラスを支持体として用い、３Ｍ社製ホットメルト接着剤Ｓｃｏｔｃｈ−Ｗｅｌｄ３７６４をホットメルトガンで約１２０℃に加熱した。多層積層フィルムと支持体をオーブンにて８０℃１分間加熱した後、多層積層フィルムと支持体間に接着剤を塗布し、富士プラスチック株式会社製、Ｆｕｊｉ ＬＡＭＩＰＡＣＫＥＲ ＬＰＰ６５０を用い、ロール温度を８０℃に加熱し、多層積層フィルムと支持体を圧着積層した。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例１のものよりも優れたものであった。
(Example 6)
Resin F is used as the thermoplastic resin B, and the layer thicknesses of the A layer and the B layer are changed in a geometric progression from 60 nm to 130 nm, respectively, from the film surface to the opposite surface (however, the maximum The thickness of the surface A layer was increased to a final thickness of 5 μm.) Except that 251 layers were alternately stacked in the thickness direction (126 layers for A and 125 layers for B). A multilayer laminated film having a thickness of 32 μm was obtained under the same conditions as in 1. Using a plate glass having a thickness of 3 mm and a 10 cm square as a support, a hot melt adhesive Scotch-Weld 3764 manufactured by 3M was heated to about 120 ° C. with a hot melt gun. After the multilayer laminated film and the support are heated in an oven at 80 ° C. for 1 minute, an adhesive is applied between the multilayer laminated film and the support, and the roll temperature is set to 80 ° C. using Fuji LAMIPACKER LPP650 made by Fuji Plastic Co., Ltd. Heating was performed, and the multilayer laminated film and the support were pressure laminated. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 1.
（実施例７）
フィルムの表面から反対側の面に向かって、Ａ層とＢ層の層厚みを、それぞれ６０ｎｍから１３０ｎｍの範囲で等比数列的に変化させ（但し、最表層のＡ層の層厚みは、最終的に５μｍの厚さとなるように厚くした。）厚み方向に交互に１５１層積層（Ａ層が７６層、Ｂ層が７５層）したこと以外は実施例１と同様の条件にて厚み２４μｍの多層積層フィルムを得た。厚さ３ｍｍ、１０ｃｍ角の板ガラスを支持体として用い、支持体、０．４ｍｍのＥＶＡ（エチレン酢酸ビニル共重合体）シート、多層積層フィルムの順で重ね、オーブンにて８０℃１分間加熱した後、富士プラスチック株式会社製、Ｆｕｊｉ ＬＡＭＩＰＡＣＫＥＲ ＬＰＰ６５０を用い、ロール温度を８０℃に加熱し、多層積層フィルムと支持体を圧着積層した。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例５のものよりも優れたものであった。
(Example 7)
From the surface of the film toward the opposite surface, the layer thicknesses of the A layer and the B layer were changed in a geometric progression in the range of 60 nm to 130 nm, respectively (however, the layer thickness of the outermost layer A layer was The thickness was 24 μm under the same conditions as in Example 1 except that 151 layers were alternately laminated in the thickness direction (76 layers for A and 75 layers for B). A multilayer laminated film was obtained. After using a plate glass with a thickness of 3 mm and a 10 cm square as a support, the support, a 0.4 mm EVA (ethylene vinyl acetate copolymer) sheet, and a multilayer laminated film were stacked in this order and heated in an oven at 80 ° C. for 1 minute. The roll temperature was heated to 80 ° C. using Fuji Lamicker LPP650, manufactured by Fuji Plastics Co., Ltd., and the multilayer laminated film and the support were laminated by pressure bonding. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 5.
（実施例８）
熱可塑性樹脂Ｂとして樹脂Ｆを用い、フィルムの表面から反対側の面に向かって、Ａ層とＢ層の層厚みを、それぞれ１３０ｎｍから２００ｎｍの範囲で等比数列的に変化させ（但し、最表層のＡ層の層厚みは、最終的に５μｍの厚さとなるように厚くした。）厚み方向に交互に４０１層積層（Ａ層が２０１層、Ｂ層が２００層）したこと以外は実施例１と同様の条件にて厚み７５μｍの多層積層フィルムを得た。成形品の作成は日清紡 ＬＡＭＩＮＡＴＯＲ０３０３Ｓを用いた。多層積層フィルムの両側に支持体として、厚さ３ｍｍ、１０ｃｍ角の板ガラスを重ね、多層積層フィルムと支持体との間に中間層として厚さ０．４ｍｍのＰＶＢ（ポリビニルブチラール）を設置し、温度１００℃、５分間真空を引いた後、１０分間プレスした。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例１のものよりも優れたものであった。
(Example 8)
Resin F is used as the thermoplastic resin B, and the layer thicknesses of the A layer and the B layer are changed in a geometric progression from 130 nm to 200 nm from the surface of the film to the opposite surface (however, the maximum) The thickness of the surface A layer was increased to a final thickness of 5 μm.) Example 401 except that 401 layers were alternately laminated in the thickness direction (A layer was 201 layers and B layer was 200 layers). A multilayer laminated film having a thickness of 75 μm was obtained under the same conditions as in 1. Nisshinbo LAMINATOR0303S was used to make the molded product. 3 mm thick and 10 cm square plate glass is stacked on both sides of the multilayer laminated film, and 0.4 mm thick PVB (polyvinyl butyral) is installed as an intermediate layer between the multilayer laminated film and the support. A vacuum was applied at 100 ° C. for 5 minutes, followed by pressing for 10 minutes. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 1.
（実施例９）
熱可塑性樹脂Ｂとして樹脂Ｆを用い、フィルムの表面から反対側の面に向かって、Ａ層とＢ層の層厚みを、それぞれ１３０ｎｍから２３０ｎｍの範囲で等比数列的に変化させ（但し、最表層のＡ層の層厚みは、最終的に５μｍの厚さとなるように厚くした。）厚み方向に交互に６０１層積層（Ａ層が３０１層、Ｂ層が３００層）したこと以外は実施例１と同様の条件にて厚み１１０μｍの多層積層フィルムを得た。成形品の作成は日清紡 ＬＡＭＩＮＡＴＯＲ０３０３Ｓを用いた。多層積層フィルムの両側に支持体として、厚さ３ｍｍ、１０ｃｍ角の板ガラスを重ね、多層積層フィルムと支持体との間に中間層として厚さ０．４ｍｍのＰＶＢ（ポリビニルブチラール）を設置し、温度１００℃、５分間真空を引いた後、１０分間プレスした。多層積層フィルムの物性と成形品の外観評価結果を表１にまとめた。また、外観として実施例１のものよりも優れたものであった。
Example 9
Resin F is used as the thermoplastic resin B, and the layer thicknesses of the A layer and the B layer are changed in a geometric sequence in the range of 130 nm to 230 nm, respectively, from the surface of the film to the opposite side (however, The thickness of the surface A layer was increased to a final thickness of 5 μm.) Example except that 601 layers were alternately laminated in the thickness direction (A layer was 301 layers and B layer was 300 layers). A multilayer laminated film having a thickness of 110 μm was obtained under the same conditions as in 1. Nisshinbo LAMINATOR0303S was used to make the molded product. 3 mm thick and 10 cm square plate glass is stacked on both sides of the multilayer laminated film, and 0.4 mm thick PVB (polyvinyl butyral) is installed as an intermediate layer between the multilayer laminated film and the support. A vacuum was applied at 100 ° C. for 5 minutes, followed by pressing for 10 minutes. Table 1 summarizes the physical properties of the multilayer laminated film and the appearance evaluation results of the molded product. Further, the appearance was superior to that of Example 1.
本発明は、支持体と多層積層フィルムが加熱加圧ラミネートされて成形される成形品において、加熱加圧による凹凸ができがたい多層積層フィルムを用いること及び、その多層積層フィルムに関するものである。 The present invention relates to the use of a multilayer laminated film in which unevenness due to heat and pressure is difficult to be formed in a molded article formed by laminating a support and a multilayer laminated film by heat and pressure, and to the multilayer laminated film.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012125737A JP2013248820A (en) | 2012-06-01 | 2012-06-01 | Molded article, and multilayer laminated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012125737A JP2013248820A (en) | 2012-06-01 | 2012-06-01 | Molded article, and multilayer laminated film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2013248820A true JP2013248820A (en) | 2013-12-12 |
Family
ID=49847976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012125737A Pending JP2013248820A (en) | 2012-06-01 | 2012-06-01 | Molded article, and multilayer laminated film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2013248820A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000293113A (en) * | 1999-04-09 | 2000-10-20 | Teijin Ltd | Selectively light reflecting film for display |
| JP2004074764A (en) * | 2002-06-19 | 2004-03-11 | Teijin Ltd | Biaxially stretched multilayer laminated film and method for manufacturing the same |
| JP2006205729A (en) * | 1993-12-21 | 2006-08-10 | 3M Co | Multilayer optical film |
| JP2006303478A (en) * | 2005-03-24 | 2006-11-02 | Toray Ind Inc | Reflector for led |
| JP2007062081A (en) * | 2005-08-30 | 2007-03-15 | Teijin Dupont Films Japan Ltd | Multilayered laminated film |
| JP2008012877A (en) * | 2006-07-10 | 2008-01-24 | Toray Ind Inc | Stretched film and its molded article |
| JP2009037235A (en) * | 2007-07-09 | 2009-02-19 | Toray Ind Inc | Polarizing reflector and its manufacturing method |
| WO2013080987A1 (en) * | 2011-11-29 | 2013-06-06 | 帝人デュポンフィルム株式会社 | Biaxially stretched laminated polyester film, infrared-ray-shielding structure for laminated glass which comprises said film, and laminated glass comprising said film or said structure |
-
2012
- 2012-06-01 JP JP2012125737A patent/JP2013248820A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006205729A (en) * | 1993-12-21 | 2006-08-10 | 3M Co | Multilayer optical film |
| JP2000293113A (en) * | 1999-04-09 | 2000-10-20 | Teijin Ltd | Selectively light reflecting film for display |
| JP2004074764A (en) * | 2002-06-19 | 2004-03-11 | Teijin Ltd | Biaxially stretched multilayer laminated film and method for manufacturing the same |
| JP2006303478A (en) * | 2005-03-24 | 2006-11-02 | Toray Ind Inc | Reflector for led |
| JP2007062081A (en) * | 2005-08-30 | 2007-03-15 | Teijin Dupont Films Japan Ltd | Multilayered laminated film |
| JP2008012877A (en) * | 2006-07-10 | 2008-01-24 | Toray Ind Inc | Stretched film and its molded article |
| JP2009037235A (en) * | 2007-07-09 | 2009-02-19 | Toray Ind Inc | Polarizing reflector and its manufacturing method |
| WO2013080987A1 (en) * | 2011-11-29 | 2013-06-06 | 帝人デュポンフィルム株式会社 | Biaxially stretched laminated polyester film, infrared-ray-shielding structure for laminated glass which comprises said film, and laminated glass comprising said film or said structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6007903B2 (en) | Multilayer laminated film | |
| KR100994662B1 (en) | Biaxially oriented multi-layer laminated film and method for manufacture thereof | |
| JP5807466B2 (en) | Laminated film and automotive window glass using the same | |
| JP5966752B2 (en) | Head-up display and mobile device using the same | |
| JP6304028B2 (en) | Laminated film | |
| TWI464056B (en) | Laminated film and formed body, reflector | |
| JP2011528450A (en) | Multilayer optical film layer comprising a blend of methyl methacrylate polymer and styrene acrylonitrile polymer | |
| JP5994281B2 (en) | Multilayer film for surface decoration, method for producing the same, and surface decoration sheet | |
| TWI677436B (en) | Multilayer laminated film | |
| JP5418235B2 (en) | Laminated film | |
| JP2009262466A (en) | Molded body and laminated film | |
| JP6225495B2 (en) | Multilayer laminated film and glass window member using the same | |
| JP2012173374A (en) | Heat ray reflecting member | |
| JP2018127607A (en) | Film | |
| JP2013248820A (en) | Molded article, and multilayer laminated film | |
| JP2019155684A (en) | Laminate film | |
| JP4967486B2 (en) | Stretched film and its molded product | |
| JP4957305B2 (en) | Resin sheet | |
| US11772370B2 (en) | Laminated body, method of producing metal member, and method of producing resin member | |
| JP6291830B2 (en) | Multilayer laminated film | |
| WO2024062961A1 (en) | Film and method for producing same, laminated structure, laminated glass, and automobile | |
| JP2024072399A (en) | Laminated Polyester Film | |
| JP2017052273A (en) | Laminated film | |
| JP2011148198A (en) | Molded article | |
| JP2018164993A (en) | Laminated film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150527 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160315 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160316 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160419 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161011 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20170404 |