JP5917979B2 - Laminate for laminated glass, laminated glass laminate comprising the same, and method for producing the same - Google Patents
Laminate for laminated glass, laminated glass laminate comprising the same, and method for producing the same Download PDFInfo
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- JP5917979B2 JP5917979B2 JP2012080699A JP2012080699A JP5917979B2 JP 5917979 B2 JP5917979 B2 JP 5917979B2 JP 2012080699 A JP2012080699 A JP 2012080699A JP 2012080699 A JP2012080699 A JP 2012080699A JP 5917979 B2 JP5917979 B2 JP 5917979B2
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- JP
- Japan
- Prior art keywords
- laminated
- layer
- film
- glass
- biaxially stretched
- 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.)
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- 239000005340 laminated glass Substances 0.000 title claims description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000010410 layer Substances 0.000 claims description 193
- 229920006267 polyester film Polymers 0.000 claims description 65
- 229920000728 polyester Polymers 0.000 claims description 59
- -1 polyethylene naphthalate Polymers 0.000 claims description 56
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 31
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 30
- 239000011241 protective layer Substances 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 22
- 230000009477 glass transition Effects 0.000 claims description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 10
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical group C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 125
- 238000000034 method Methods 0.000 description 33
- 230000000694 effects Effects 0.000 description 25
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 14
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 238000010030 laminating Methods 0.000 description 8
- 238000009998 heat setting Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
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- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 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 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
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- 239000011247 coating layer Substances 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
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- CVBWTNHDKVVFMI-LBPRGKRZSA-N (2s)-1-[4-[2-[6-amino-8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]purin-9-yl]ethyl]piperidin-1-yl]-2-hydroxypropan-1-one Chemical compound C1CN(C(=O)[C@@H](O)C)CCC1CCN1C2=NC=NC(N)=C2N=C1SC(C(=C1)Br)=CC2=C1OCO2 CVBWTNHDKVVFMI-LBPRGKRZSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 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 2
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-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
- 239000000049 pigment Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- 229960001860 salicylate Drugs 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- RZFMVZZLGKPQBN-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylbutan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(CC)C=2C=CC=CC=2)=CC=1C(C)(CC)C1=CC=CC=C1 RZFMVZZLGKPQBN-UHFFFAOYSA-N 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
- MPFAYMDFVULHEW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MPFAYMDFVULHEW-UHFFFAOYSA-N 0.000 description 1
- UZUNCLSDTUBVCN-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C(O)C=1C(C)(C)C1=CC=CC=C1 UZUNCLSDTUBVCN-UHFFFAOYSA-N 0.000 description 1
- ZSSVCEUEVMALRD-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 ZSSVCEUEVMALRD-UHFFFAOYSA-N 0.000 description 1
- AWEVLIFGIMIQHY-UHFFFAOYSA-N 2-ethylhexyl 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCC(CC)CCCC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O AWEVLIFGIMIQHY-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical compound C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000005487 naphthalate group Chemical group 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
- TWCBCCIODCKPGX-UHFFFAOYSA-N octyl 2-[4-[4,6-bis(4-phenylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoate Chemical compound OC1=CC(OC(C)C(=O)OCCCCCCCC)=CC=C1C1=NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=N1 TWCBCCIODCKPGX-UHFFFAOYSA-N 0.000 description 1
- DMFXLIFZVRXRRR-UHFFFAOYSA-N octyl 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O DMFXLIFZVRXRRR-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
Description
本発明は合わせガラス用構成体、それからなる合わせガラス積層体およびその製造方法に関し、さらに詳しくは、熱線遮蔽効果に優れ、しかも曲面を有する合わせガラスとの成形加工性に優れる合わせガラス用構成体、それからなる合わせガラス積層体およびその製造方法に関する。 The present invention relates to a laminated glass composition, a laminated glass laminate comprising the laminated glass, and a method for producing the same, more specifically, a laminated glass composition excellent in heat ray shielding effect and excellent in molding processability with a laminated glass having a curved surface, The present invention relates to a laminated glass laminate and a method for producing the same.
自動車や電車などの乗り物および建築物の窓に用いるガラスとして、熱線を遮蔽する機能を有する合わせガラスが検討されており、一部は既に実用化されている。このような合わせガラスは熱線の入射を防ぐので省エネルギーの観点から近年注目を集めている。
この合わせガラスは、全光線のうち可視光線は透過し、熱線を選択的に反射または吸収する。例えばこれを窓ガラスとして用いると、太陽光の強い時期には熱線の入射による室内の温度上昇を抑え、他方太陽光が弱く暖房を使用する時期には室内から屋外への熱の逃避を抑えることができる。そのため、この合わせガラスを用いることによってエネルギーの利用効率を大幅に向上させることができ、省エネルギーに役立たせることができる。
この合わせガラスは熱線遮蔽フィルムをガラスに積層することにより得ることができる。
Laminated glass having a function of shielding heat rays has been studied as glass used for vehicles such as automobiles and trains and windows of buildings, and some of them have already been put into practical use. In recent years, such laminated glass has attracted attention from the viewpoint of energy saving because it prevents the incidence of heat rays.
This laminated glass transmits visible light out of all light, and selectively reflects or absorbs heat rays. For example, when this is used as a window glass, it suppresses the rise in indoor temperature due to the incidence of heat rays when sunlight is strong, and suppresses the escape of heat from the room to the outdoors when sunlight is weak and heating is used. Can do. Therefore, the use efficiency of energy can be greatly improved by using this laminated glass, and it can be used for energy saving.
This laminated glass can be obtained by laminating a heat ray shielding film on glass.
特許文献１には、非金属ポリマー多層光学フィルムを含む透明光学シート、ボンディングシート、およびグレージングコンポーネントを含むラミネートが記載されており、多層フィルムの層間のデラミネーションを防止するためには多層フィルムのサイズをボンディングシートのサイズより小さくすることが好ましいことが開示されている。また、特許文献１には該透明光学シートの一例として、可視波長領域では高透明で赤外線を反射させるフィルムが記載されている。一方、特許文献１にはポリエチレンナフタレートを高屈折率層に用いる場合に曲面を有する合わせガラスに貼り合わせる際の成形加工性について検討されていない。 Patent Document 1 describes a transparent optical sheet including a non-metallic polymer multilayer optical film, a bonding sheet, and a laminate including a glazing component. In order to prevent delamination between layers of the multilayer film, the size of the multilayer film is described. Is preferably smaller than the size of the bonding sheet. Patent Document 1 describes, as an example of the transparent optical sheet, a film that is highly transparent and reflects infrared rays in the visible wavelength region. On the other hand, Patent Document 1 does not discuss molding processability when pasted on a laminated glass having a curved surface when polyethylene naphthalate is used for a high refractive index layer.
また特許文献２には、ポリエステルフィルムの片面に、金属および/または金属化合物から構成される熱線遮断層を積層してなる安全ガラス用積層体について、スパッタ加工や合わせガラス成形をする際にフィルムの平面性を維持するために、１５０℃、３０分間の熱処理での縦方向および横方向のフィルムの収縮率の和が１０％以下であることが好ましいことが開示されているが、ポリエチレンテレフタレートフィルムを平面ガラスに貼り合わせる際のフィルム平面性に関する。 Patent Document 2 discloses a laminated body for safety glass formed by laminating a heat ray blocking layer composed of a metal and / or a metal compound on one side of a polyester film, when the film is formed by sputtering or laminated glass molding. In order to maintain flatness, it is disclosed that the sum of the shrinkage ratios of the film in the longitudinal direction and the transverse direction in heat treatment at 150 ° C. for 30 minutes is preferably 10% or less. The present invention relates to film flatness when bonded to flat glass.
特許文献３には、耐引き裂き性を高めるために２種類のポリエステル層を有する多層フィルムを合わせガラス用に用い、該フィルムの縦方向と横方向の１００℃における熱収縮率が１．５％以下であることにより、エチレンビニルーアセテート膜と熱圧着する場合、しわなどが入りにくいことが開示されている。一方、特許文献３では多層の干渉機能を用いた熱線遮蔽効果とともに曲面を有する合わせガラスへの成形加工性を両立させること、およびポリエチレンナフタレート層を用いる場合の成形加工性について検討されていない。 In Patent Document 3, a multilayer film having two types of polyester layers is used for laminated glass in order to improve tear resistance, and the thermal shrinkage rate at 100 ° C. in the longitudinal and transverse directions of the film is 1.5% or less. Therefore, it is disclosed that when thermocompression bonding with an ethylene vinyl-acetate film, wrinkles and the like are difficult to enter. On the other hand, Patent Document 3 does not discuss the compatibility between the heat ray shielding effect using the multilayer interference function and the moldability of the laminated glass having a curved surface, and the moldability of the polyethylene naphthalate layer.
特許文献４にはポリエチレンテレフタレートフィルムをわん曲形状の合わせガラス中間膜として用いるに際し、合わせガラス加工後の外観にうねりやしわが発生しないよう１５０℃、３０分熱処理後のフィルムの長手方向の熱収縮率を０．６％以上１．２％以下、幅方向の熱収縮率を０．１５％以上１．０％以下とすることが記載されている。一方、特許文献４は中間膜として単層のポリエチレンテレフタレートフィルムを用いるものであり、ポリエチレンナフタレート層を含む多層ポリエステルフィルムを、曲面を有する合わせガラスに貼り合わせる際の成形加工性について検討されていない。 In Patent Document 4, when a polyethylene terephthalate film is used as a curved laminated glass intermediate film, heat shrinkage in the longitudinal direction of the film after heat treatment at 150 ° C. for 30 minutes is performed so that no waviness or wrinkle is generated in the appearance after the laminated glass processing. The rate is 0.6% or more and 1.2% or less, and the thermal shrinkage rate in the width direction is 0.15% or more and 1.0% or less. On the other hand, Patent Document 4 uses a single-layer polyethylene terephthalate film as an intermediate film, and has not been studied for moldability when a multilayer polyester film containing a polyethylene naphthalate layer is bonded to a laminated glass having a curved surface. .
このように、ポリエチレンテレフタレートを主とする単層あるいは積層フィルムを用いた合わせガラス用フィルムについて、目的に応じて熱収縮率を所望の範囲とすることは従来より検討がなされているものの、合わせガラス用フィルムとして超多層構成の干渉反射に着目した熱線遮蔽フィルムを用いる際、層間の屈折率差を大きくできるポリエチレンナフタレートを高屈折率層に用いると、曲面を有する合わせガラスに貼り合わせるときの成形加工性がポリエチレンテレフタレートと異なっており、単に熱収縮率を調整するだけでは十分な成形加工性が得られていないのが現状である。 As described above, regarding a laminated glass film using a single layer or a laminated film mainly composed of polyethylene terephthalate, it has been conventionally studied that the heat shrinkage rate is in a desired range depending on the purpose. When using a heat ray shielding film that focuses on interference reflection with a super multi-layer structure as a film for use, if polyethylene naphthalate, which can increase the difference in refractive index between layers, is used for the high refractive index layer, molding when pasting on laminated glass with a curved surface At present, the processability is different from that of polyethylene terephthalate, and sufficient molding processability cannot be obtained simply by adjusting the heat shrinkage rate.
本発明はかかる従来の課題を鑑みてなされたものであり、本発明の目的は、高い熱線遮蔽効果が得られるポリエチレンナフタレート層を含む多層積層構成のポリエステルフィルムを用いながら、曲面を有する合わせガラスとの成形加工性に優れる合わせガラス用構成体、およびそれからなる合わせガラス積層体、ならびにその製造方法を提供することにある。 The present invention has been made in view of such conventional problems, and an object of the present invention is to provide a laminated glass having a curved surface while using a polyester film having a multilayer laminated structure including a polyethylene naphthalate layer capable of obtaining a high heat ray shielding effect. And a laminated glass laminate comprising the same, and a method for producing the same.
本発明者らは前記課題を解決するために鋭意検討した結果、高い熱線遮蔽効果が得られるポリエチレンナフタレート層を含む多層積層構成のポリエステルフィルムを合わせガラス用フィルムとして用いる場合、合わせガラスのラミネート加工温度での熱収縮率挙動が従来のポリエチレンテレフタレートフィルムと異なっており、曲面の合わせガラスに加工する際に１２０℃で０．８％以下の熱収縮率の小さいフィルムではしわが発生しやすいこと、また熱収縮率を高めるとしわは解消するものの、反射率が低下し、十分な熱線遮蔽効果が得られないことを知見した。そして、熱収縮率の小さいポリエチレンナフタレート層を含む多層積層フィルムと中間膜とを予め貼り合わせた合わせガラス用構成体を作成し、その後、曲面を有する合わせガラスと貼り合わせることにより、高い熱線遮蔽効果を低下させることなく、同時に曲面を有する合わせガラスと貼り合わせた際にしわも発生せずに良好な外観性も得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention have used a laminated film of laminated glass when a polyester film having a multilayer laminated structure including a polyethylene naphthalate layer that can provide a high heat ray shielding effect is used as a laminated glass film. Thermal shrinkage behavior at temperature is different from conventional polyethylene terephthalate film, and when processed into a curved laminated glass, wrinkles are likely to occur in a film with a thermal shrinkage rate of 0.8% or less at 120 ° C, Moreover, although wrinkles were eliminated when the heat shrinkage rate was increased, it was found that the reflectance was lowered and a sufficient heat ray shielding effect could not be obtained. Then, a multilayer glass film including a polyethylene naphthalate layer having a low thermal shrinkage rate and an intermediate film are prepared in advance, and then laminated with a laminated glass having a curved surface, thereby high heat ray shielding. It has been found that a good appearance can be obtained without causing wrinkles when laminated with a laminated glass having a curved surface at the same time without reducing the effect, and the present invention has been completed.
すなわち本発明によれば、本発明の目的は、二軸延伸積層ポリエステルフィルムおよびその少なくとも片面に中間膜が積層された合わせガラス用構成体であり、前記二軸延伸積層ポリエステルフィルムは第１の層および第２の層が交互に積層された合計５１層以上の積層構成（Ｉ）を有し、前記第１の層を構成するポリエステル（Ａ）がポリエチレンナフタレートであり、前記二軸延伸積層ポリエステルフィルムの１２０℃、３０分熱処理したときの熱収縮率が０．８％以下であり、前記二軸延伸積層ポリエステルフィルムの４００〜７５０ｎｍの波長範囲における平均反射率が２５％以下であり、８００〜１２００ｎｍの波長範囲における平均反射率が５０％以上である、曲面を有する合わせガラス用構成体により達成される。 That is, according to the present invention, an object of the present invention is a biaxially stretched laminated polyester film and a laminated glass laminate in which an intermediate film is laminated on at least one surface thereof, and the biaxially stretched laminated polyester film is a first layer. And the polyester (A) constituting the first layer is polyethylene naphthalate, wherein the biaxially stretched laminated polyester 120 ° C. of the film state, and are heat shrinkage of not more than 0.8% when heat-treated for 30 minutes, the average reflectance in the wavelength range of 400~750nm of the biaxially oriented laminated polyester film is 25% or less, 800 It is achieved by a laminated glass structure having a curved surface having an average reflectance of 50% or more in a wavelength range of ˜1200 nm .
本発明の曲面を有する合わせガラス用構成体は、さらに好ましい態様として、前記中間膜が二軸延伸積層ポリエステルフィルムおよび合わせガラスとの接着層であること、
前記二軸延伸積層ポリエステルフィルムの第２の層が、該層の全繰り返し単位を基準としてエチレンテレフタレート単位の割合が５０〜９５モル％である共重合ポリエチレンテレフタレートからなり、該二軸延伸積層ポリエステルフィルムは該積層構成（Ｉ）の両側にガラス転移温度が９０℃以上のポリマーからなる保護層を有し、かつ各保護層の厚みが５μｍ以上２０μｍ以下であること、
前記二軸延伸積層ポリエステルフィルムの第２の層が、該層の全繰返し単位を基準としてのエチレンナフタレート単位の割合が４５〜９０モル％でガラス転移温度が９０℃以上の共重合ポリエチレンナフタレートからなること、
加熱圧着なされてなること、の少なくともいずれか１つの態様も包含される。
また本発明には、本発明の曲面を有する合わせガラス用構成体の前記中間膜上に曲面を有するガラスが積層された合わせガラス積層体も包含される。
For laminated glass structure having a mode of the invention, it further preferred embodiment, an adhesive layer with the previous SL intermediate film biaxially oriented laminated polyester film and laminated glass,
The second layer of the biaxially stretched laminated polyester film is made of a copolymerized polyethylene terephthalate in which the proportion of ethylene terephthalate units is 50 to 95 mol% based on all repeating units of the layer, and the biaxially stretched laminated polyester film Has a protective layer made of a polymer having a glass transition temperature of 90 ° C. or higher on both sides of the laminated structure (I), and the thickness of each protective layer is 5 μm or more and 20 μm or less,
The second layer of the biaxially stretched laminated polyester film is a copolymerized polyethylene naphthalate having a ratio of ethylene naphthalate units of 45 to 90 mol% based on all repeating units of the layer and a glass transition temperature of 90 ° C. or higher. Consisting of,
At least one embodiment of being thermocompression bonded is also included.
The present invention also includes a laminated glass laminate in which a glass having a curved surface is laminated on the intermediate film of the laminated glass having a curved surface of the present invention.
さらに本発明には、上記の合わせガラス積層体の製造方法であって、
ｉ）二軸延伸積層ポリエステルフィルムおよびその少なくとも片面に中間膜が積層された構成体を作成し、
ii）前記二軸延伸積層ポリエステルフィルムは第１の層および第２の層が交互に積層された合計５１層以上の積層構成（Ｉ）を有し、前記第１の層を構成するポリエステル（Ａ）がポリエチレンナフタレートであり、前記二軸延伸積層ポリエステルフィルムの１２０℃、３０分熱処理したときの熱収縮率が０．８％以下であって、
iii）作成された前記構成体を加熱圧着する工程を含み、
iv）加熱圧着工程の後に前記中間膜上に曲面を有するガラスが積層される、
合わせガラス積層体の製造方法も包含される。
Furthermore, the present invention is a method for producing the above laminated glass laminate,
i) Create a biaxially stretched laminated polyester film and a structure in which an intermediate film is laminated on at least one side thereof,
ii) The biaxially stretched laminated polyester film has a total of 51 or more laminated constitutions (I) in which the first layers and the second layers are alternately laminated, and the polyester (A ) Is polyethylene naphthalate, and the heat shrinkage rate when the biaxially stretched laminated polyester film is heat-treated at 120 ° C. for 30 minutes is 0.8% or less,
iii) including the step of thermocompression bonding the prepared structure,
iv) A glass having a curved surface is laminated on the intermediate film after the thermocompression bonding step,
A method for producing a laminated glass laminate is also included.
本発明によれば、本発明はポリエチレンナフタレート層を含む熱収縮率の小さい多層積層フィルムと中間膜とを予め貼り合わせた合わせガラス用構成体であることにより、曲面を有する合わせガラスと貼り合わせる際に高い熱線遮蔽効果を低下させることなく、同時にしわも発生せずに良好な外観性も得られることから、曲面を有し、優れた外観性と熱線遮蔽が求められる車のフロントガラスなどに好適に用いることができる。 According to the present invention, the present invention is a laminated glass structure in which a multilayer laminated film having a low thermal shrinkage rate including a polyethylene naphthalate layer and an intermediate film are laminated in advance, so that the laminated glass having a curved surface is laminated. It has a curved surface and has excellent appearance and heat ray shielding, because it does not reduce the high heat ray shielding effect at the same time, and at the same time it has good appearance without wrinkles. It can be used suitably.
本発明の二軸延伸積層ポリエステルフィルムは、以下に述べる第１の層と第２の層が交互に積層された合計５１層以上の積層構成（Ｉ）を有し、前記第１の層を構成するポリエステル（Ａ）がポリエチレンナフタレートであり、記二軸延伸積層ポリエステルフィルムの１２０℃、３０分熱処理したときの熱収縮率が０．８％以下である。 The biaxially stretched laminated polyester film of the present invention has a laminated structure (I) of a total of 51 or more layers in which the first layer and the second layer described below are alternately laminated, and constitutes the first layer. The polyester (A) to be used is polyethylene naphthalate, and the heat shrinkage rate when the biaxially stretched laminated polyester film is heat-treated at 120 ° C. for 30 minutes is 0.8% or less.
＜二軸延伸積層ポリエステルフィルム＞
（第１の層）
本発明における第１の層はポリエチレンナフタレート（以下、ポリエステル（Ａ）と称することがある）からなる。なおここでいうポリエチレンナフタレートには、ホモポリエステルだけでなく、共重合成分が全酸成分を基準として８モル％以下、好ましくは６モル％以下、より好ましくは４モル％以下共重合されたポリエチレンナフタレートも含まれるが、なかでもホモポリエステルが好ましい。共重合成分が８モル％を超える場合には、後述する第２の層との間に十分な屈折率差を付与しがたくなって、十分な近赤外線反射性能を発現させることが難しくなる。ポリエチレンナフタレートの中でも特にポリエチレン−２，６−ナフタレートが好ましい。
<Biaxially stretched laminated polyester film>
(First layer)
The first layer in the present invention is made of polyethylene naphthalate (hereinafter sometimes referred to as polyester (A)). The polyethylene naphthalate used herein includes not only homopolyester but also polyethylene copolymerized with a copolymerization component of 8 mol% or less, preferably 6 mol% or less, more preferably 4 mol% or less, based on the total acid components. Although naphthalate is also included, homopolyester is preferred. When the copolymerization component exceeds 8 mol%, it is difficult to give a sufficient refractive index difference to the second layer described later, and it becomes difficult to develop sufficient near infrared reflection performance. Among the polyethylene naphthalates, polyethylene-2,6-naphthalate is particularly preferable.
好ましく用いられる共重合成分としては、イソフタル酸、テレフタル酸、オルトフタル酸、主たる成分で用いられる成分以外のナフタレンジカルボン酸、ビフェニルジカルボン酸の如き芳香族カルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸等の如き脂肪族ジカルボン酸；シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸等の酸成分や、ジエチレングリコール、プロピレングリコール、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、ネオペンチルグリコール等の如き脂肪族ジオール；１，４−シクロヘキサンジメタノールの如き脂環族ジオール、ポリエチレングリコール、ポリテトラメチレングリコール等のグリコール成分を挙げることができる。中でもイソフタル酸、テレフタル酸、ネオペンチルグリコール、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好ましく、特にイソフタル酸、テレフタル酸が好ましい。これらの共重合成分は、単独で用いてもよく、また２成分以上併用することもできる。 Preferred copolymerization components include isophthalic acid, terephthalic acid, orthophthalic acid, aromatic carboxylic acids such as naphthalenedicarboxylic acid and biphenyldicarboxylic acid other than those used in the main components; succinic acid, adipic acid, azelaic acid, sebacin Acid, aliphatic dicarboxylic acid such as decanedicarboxylic acid, etc .; acid components such as alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, Examples thereof include aliphatic diols such as 6-hexanediol and neopentyl glycol; alicyclic diols such as 1,4-cyclohexanedimethanol, glycol components such as polyethylene glycol and polytetramethylene glycol. Of these, isophthalic acid, terephthalic acid, neopentyl glycol, 1,4-cyclohexanedimethanol and diethylene glycol are preferable, and isophthalic acid and terephthalic acid are particularly preferable. These copolymer components may be used alone or in combination of two or more components.
ポリエステル（Ａ）は、公知の方法を適用して製造することができる。例えば、主たる成分の酸成分、グリコール成分、および必要に応じて共重合成分をエステル化反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造することができる。また、これらの原料モノマーの誘導体をエステル交換反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造してもよい。さらに、２種以上のポリエステルを用いて押出機内で溶融混合してエステル交換反応（再分配反応）させて得る方法であってもよい。 The polyester (A) can be produced by applying a known method. For example, it can be produced by a method in which the main component acid component, glycol component, and if necessary, a copolymerization component are esterified, and then the resulting reaction product is polycondensed to give a polyester. Alternatively, these raw material monomer derivatives may be transesterified, and then the resulting reaction product may be subjected to a polycondensation reaction to obtain a polyester. Further, a method may be used in which two or more kinds of polyesters are melt-mixed in an extruder and transesterified (redistribution reaction).
第１の層を構成するポリエステル（Ａ）の固有粘度は、好ましくは０．４０〜０．８０ｄｌ／ｇであり、更には０．４５〜０．７５ｄｌ／ｇの範囲であることが好ましい。固有粘度がかかる範囲内にあれば、後述する第２の層との多層積層構造部を有するフィルムを形成する際の製膜性が良好となる。
本発明の第１の層には、本発明の目的を損なわない範囲で他のポリマーや添加剤を少量含有していてもよく、例えば不活性粒子などの滑剤、顔料、染料などの着色剤、安定剤、難燃剤、発泡剤、紫外線吸収剤などの添加剤が例示される。
The intrinsic viscosity of the polyester (A) constituting the first layer is preferably 0.40 to 0.80 dl / g, and more preferably in the range of 0.45 to 0.75 dl / g. If the intrinsic viscosity is within such a range, the film forming property when forming a film having a multilayer laminated structure with a second layer described later is good.
The first layer of the present invention may contain a small amount of other polymers and additives as long as the object of the present invention is not impaired. For example, lubricants such as inert particles, colorants such as pigments and dyes, Examples thereof include additives such as a stabilizer, a flame retardant, a foaming agent, and an ultraviolet absorber.
（第２の層）
本発明における第２の層は、第１の層との間に屈折率差を有しており、ポリエステル（Ａ）とともに二軸延伸可能な樹脂であれば特に限定されないが、第２の層もポリエステルで構成されることが好ましい。第１の層との屈折率差が大きくて積層数が小さくても近赤外線反射性能を付与しやすいといった点からは、第２の層の全繰り返し単位を基準としてエチレンテレフタレート単位の割合が５０〜９５モル％、特に６０〜９０モル％である（すなわち共重成分が５〜５０モル％、特に１０〜４０モル％共重合された）共重合ポリエチレンテレフタレート（以下、ポリエステル（Ｂ−１）と称することがある。）が好ましく、合わせガラスに加工する際にフィルムの平坦性が保たれて、細かな凹凸の発生がなく良好な外観が得られやすいといった点からは、第２の層の全繰返し単位を基準としてエチレンナフタレート単位の割合が４５〜９０モル％でガラス転移温度が９０℃以上の共重合ポリエチレンナフタレート（以下、ポリエステル（Ｂ−２）と称することがある。）が好ましい。
(Second layer)
The second layer in the present invention has a refractive index difference with the first layer, and is not particularly limited as long as it is a resin that can be biaxially stretched together with the polyester (A). It is preferably composed of polyester. The ratio of ethylene terephthalate units is 50 to 50% based on the total repeating units of the second layer from the viewpoint that near-infrared reflection performance is easily imparted even if the refractive index difference with the first layer is large and the number of stacked layers is small. Copolymerized polyethylene terephthalate (hereinafter referred to as polyester (B-1)) of 95 mol%, particularly 60 to 90 mol% (that is, copolymerized with 5 to 50 mol%, particularly 10 to 40 mol% copolymerized component). From the standpoint that the flatness of the film is maintained when processed into a laminated glass, and a good appearance is easily obtained without the occurrence of fine irregularities. Copolymerized polyethylene naphthalate having a proportion of ethylene naphthalate units of 45 to 90 mol% and a glass transition temperature of 90 ° C. or higher based on the units (hereinafter, polyester (B-2)) It is.) Is preferably referred to.
（ポリエステル（Ｂ−１））
上述のポリエステル（Ｂ−１）は、第２の層の全繰り返し単位を基準としてエチレンテレフタレート単位の割合が５０〜９５モル％、好ましくは６０〜９０モル％である共重合ポリエチレンテレフタレートからなる。共重合量が下限未満である場合には、製膜時に結晶、配向化しやすくなって第１の層との間に屈折率差がつきにくくなり、積層数を多くしなければ十分な近赤外線反射能を得ることが難しくなる。一方、共重合量が上限を超える場合には、製膜時（特に押出時）の耐熱性や製膜性が低下するだけでなく、共重合成分が高屈折率性を付与する成分である場合には、屈折率増加によって第１の層との屈折率差が小さくなるというという問題も起こる。共重合量が上記の範囲内にあることにより、良好な耐熱性、製膜性を維持しつつ、第１の層との屈折率差を確保することができ、十分な近赤外線反射性能を付与することができるようになる。
(Polyester (B-1))
The above-mentioned polyester (B-1) is composed of copolymerized polyethylene terephthalate in which the proportion of ethylene terephthalate units is 50 to 95 mol%, preferably 60 to 90 mol%, based on all repeating units of the second layer. If the copolymerization amount is less than the lower limit, it is easy to crystallize and orientate during film formation, making it difficult for the first layer to have a refractive index difference, and sufficient near-infrared reflection unless the number of layers is increased. It becomes difficult to obtain Noh. On the other hand, when the copolymerization amount exceeds the upper limit, not only the heat resistance and film forming property during film formation (particularly during extrusion) are deteriorated, but also the copolymer component is a component that imparts high refractive index properties. In addition, there arises a problem that a difference in refractive index from the first layer is reduced by increasing the refractive index. When the copolymerization amount is within the above range, the difference in refractive index from the first layer can be secured while maintaining good heat resistance and film-forming property, and sufficient near-infrared reflection performance is imparted. Will be able to.
なお、後述する製膜時の熱固定温度をポリエステル（Ｂ−１）の融点以上にして、第１の層の配向を維持しながら第２の層のポリエステル（Ｂ−１）を溶融し、第２の層の配向を低下させて第１の層と第２の層との屈折率差をより大きくすることが好ましいので、ポリエステル（Ｂ−１）の融点は前記のポリエステル（Ａ）の融点より１０℃以上、さらに３０℃以上低いことが好ましい。 The heat setting temperature at the time of film formation described later is set to be equal to or higher than the melting point of the polyester (B-1), and the second layer polyester (B-1) is melted while maintaining the orientation of the first layer. Since it is preferable to reduce the orientation of the second layer to increase the difference in refractive index between the first layer and the second layer, the melting point of the polyester (B-1) is higher than the melting point of the polyester (A). It is preferably 10 ° C. or higher, and more preferably 30 ° C. or lower.
好ましく用いられる共重合成分としては、イソフタル酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸等の芳香族ジカルボン酸、アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸等の脂肪族ジカルボン酸、シクロヘキサンジカルボン酸といった脂環族ジカルボン酸等の酸成分、ブタンジオール、ヘキサンジオール等の脂肪族ジオール、シクロヘキサンジメタノールといった脂環族ジオール、スピログリコール等のグリコール成分を挙げることができる。なかでもイソフタル酸、２，６−ナフタレンジカルボン酸、シクロヘキサンジメタノール、スピログリコールが好ましく、これら以外の共重合成分を含む場合には、その共重合量は１０モル％以下であることが好ましい。 Examples of the copolymer component preferably used include aliphatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and aliphatics such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid. Examples thereof include acid components such as alicyclic dicarboxylic acids such as dicarboxylic acid and cyclohexanedicarboxylic acid, aliphatic diols such as butanediol and hexanediol, alicyclic diols such as cyclohexanedimethanol, and glycol components such as spiroglycol. Of these, isophthalic acid, 2,6-naphthalenedicarboxylic acid, cyclohexanedimethanol, and spiroglycol are preferable. When a copolymerization component other than these is included, the copolymerization amount is preferably 10 mol% or less.
また、ポリエステル（Ｂ−１）のガラス転移温度が９０℃以下の場合には、第１の層のポリエステル（Ａ）が配向するような延伸条件で延伸した場合、第２の層のポリエステル（Ｂ−１）にとっては高い延伸温度となるために配向が進まず、第１の層と第２の層との間に屈折率差をつけやすくなる。
なおポリエステル（Ｂ−１）は、非晶性、結晶性のいずれであってもよい。ここで非晶性とは、ポリエステルフィルムを昇温速度２０℃／分でＤＳＣ測定したときに第２の層に由来する融点が観察されないことをいう。また結晶性とは前述のＤＳＣ測定で第２の層に由来する融点が観察されることをいう。
Further, when the glass transition temperature of the polyester (B-1) is 90 ° C. or lower, the second layer polyester (B) is stretched under stretching conditions such that the first layer polyester (A) is oriented. For -1), since the stretching temperature is high, the orientation does not advance, and a difference in refractive index between the first layer and the second layer is easily made.
The polyester (B-1) may be either amorphous or crystalline. Here, the term “amorphous” means that the melting point derived from the second layer is not observed when the polyester film is subjected to DSC measurement at a heating rate of 20 ° C./min. Crystallinity means that the melting point derived from the second layer is observed by the above-mentioned DSC measurement.
上述のポリエステル（Ｂ−１）も、公知の方法を適用して製造することができる。例えば、主たる成分の酸成分、グリコール成分、および必要に応じて共重合成分をエステル化反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造することができる。また、これらの原料モノマーの誘導体をエステル交換反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造してもよい。さらに、２種以上のポリエステルを用いて押出機内で溶融混合してエステル交換反応（再分配反応）させて得る方法であってもよい。
ポリエステル（Ｂ−１）の固有粘度は、好ましくは０．４０〜１．０ｄｌ／ｇであり、更には０．４５〜０．９５ｄｌ／ｇの範囲であることが好ましい。固有粘度がかかる範囲内にない場合には、第１の層を構成するポリエステル（Ａ）の固有粘度との差が大きくなることがあり、その結果交互積層構成とした場合に層構成が乱れたり、製膜はできたとしても製膜性が低下することがある。
The above-described polyester (B-1) can also be produced by applying a known method. For example, it can be produced by a method in which the main component acid component, glycol component, and if necessary, a copolymerization component are esterified, and then the resulting reaction product is polycondensed to give a polyester. Alternatively, these raw material monomer derivatives may be transesterified, and then the resulting reaction product may be subjected to a polycondensation reaction to obtain a polyester. Further, a method may be used in which two or more kinds of polyesters are melt-mixed in an extruder and transesterified (redistribution reaction).
The intrinsic viscosity of the polyester (B-1) is preferably 0.40 to 1.0 dl / g, and more preferably in the range of 0.45 to 0.95 dl / g. When the intrinsic viscosity is not within such a range, the difference from the intrinsic viscosity of the polyester (A) constituting the first layer may become large. Even if the film is formed, the film forming property may be lowered.
（ポリエステル（Ｂ−２））
上述のポリエステル（Ｂ−２）は、第２の層の全繰返し単位を基準としてのエチレンナフタレート単位の割合が４５〜９０モル％でガラス転移温度が９０℃以上の共重合ポリエチレンナフタレートからなる。エチレンナフタレート単位の割合の下限は、好ましくは５０モル％、特に好ましくは５５モル％である。また、エチレンナフタレート単位の割合の上限は好ましくは８５モル％、特に好ましくは８０モル％である。エチレンナフタレート単位の割合が４５モル％未満の場合には、９０℃以上のガラス転移温度を達成することが困難となり、一方、９０モル％を超える場合には、第１層の屈折率との屈折率差が得られ難くなり、十分な反射率特性を得ることが難しい。かかるエチレンナフタレート単位は、エチレン−２，６−ナフタレート単位であることが好ましい。
(Polyester (B-2))
The above-mentioned polyester (B-2) is composed of copolymer polyethylene naphthalate having a ratio of ethylene naphthalate units of 45 to 90 mol% based on all repeating units of the second layer and a glass transition temperature of 90 ° C. or higher. . The lower limit of the proportion of ethylene naphthalate units is preferably 50 mol%, particularly preferably 55 mol%. Further, the upper limit of the proportion of ethylene naphthalate units is preferably 85 mol%, particularly preferably 80 mol%. When the proportion of ethylene naphthalate units is less than 45 mol%, it becomes difficult to achieve a glass transition temperature of 90 ° C. or higher, whereas when it exceeds 90 mol%, the refractive index of the first layer is It becomes difficult to obtain a difference in refractive index, and it is difficult to obtain sufficient reflectance characteristics. Such ethylene naphthalate units are preferably ethylene-2,6-naphthalate units.
また、ポリエステル（Ｂ−２）のガラス転移温度が９０℃以上、好ましくは９５℃以上、特に好ましくは１００℃以上であることにより、合わせガラス加工工程において、ポリエステルフィルムに軟化による細かな凹凸や、しわなどが発生しにくくなるため、合わせガラス加工時のフィルムの平坦性を保つことができ、良好な外観を呈する合わせガラスが得られやすい。 In addition, when the glass transition temperature of the polyester (B-2) is 90 ° C. or higher, preferably 95 ° C. or higher, particularly preferably 100 ° C. or higher, in the laminated glass processing step, fine unevenness due to softening in the polyester film, Since wrinkles and the like are less likely to occur, the flatness of the film during processing of the laminated glass can be maintained, and a laminated glass exhibiting a good appearance can be easily obtained.
好ましく用いられる共重合成分としては、イソフタル酸、テレフタル酸、オルトフタル酸、ビフェニルジカルボン酸などの芳香族カルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸などの脂肪族ジカルボン酸；シクロヘキサンジカルボン酸などの脂環族ジカルボン酸といった酸成分や、ジエチレングリコール、プロピレングリコール、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、ネオペンチルグリコールなどの脂肪族ジオール；１，４−シクロヘキサンジメタノールなどの脂環族ジオール、ポリエチレングリコール、ポリテトラメチレングリコールなどのグリコール成分を好ましく挙げることができる。また、従たる共重合成分として、主たる成分以外のナフタレンジカルボン酸を用いてもよく、主たる酸成分が２，６−ナフタレンジカルボン酸の場合は、従たる共重合成分として２，７−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸が挙げられる。
これらの共重合成分の中でも、テレフタル酸、イソフタル酸が好ましく、テレフタル酸が特に好ましい。
Examples of the copolymer component preferably used include aromatic carboxylic acids such as isophthalic acid, terephthalic acid, orthophthalic acid, and biphenyldicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; Acid components such as cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, and aliphatic diols such as diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol; Preferable examples include alicyclic diols such as 1,4-cyclohexanedimethanol, and glycol components such as polyethylene glycol and polytetramethylene glycol. Further, naphthalene dicarboxylic acid other than the main component may be used as the secondary copolymer component. When the main acid component is 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid is used as the secondary copolymer component. 1,5-naphthalenedicarboxylic acid.
Among these copolymer components, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is particularly preferable.
ポリエステル（Ｂ−２）のガラス転移温度の上限は、用いられる共重合成分によっておのずと定まり、特に制限はないが、第１層のポリエステルのガラス転移温度よりも低くなる傾向にある。
なおポリエステル（Ｂ−２）も、非晶性、結晶性のいずれであってもよい。ここで非晶性とは、ポリエステルフィルムを昇温速度２０℃／分でＤＳＣ測定したときに第２の層に由来する融点が観察されないことをいう。また結晶性とは前述のＤＳＣ測定で第２の層に由来する融点が観察されることをいう。
The upper limit of the glass transition temperature of the polyester (B-2) is naturally determined by the copolymerization component used, and is not particularly limited, but tends to be lower than the glass transition temperature of the polyester of the first layer.
The polyester (B-2) may be either amorphous or crystalline. Here, the term “amorphous” means that the melting point derived from the second layer is not observed when the polyester film is subjected to DSC measurement at a heating rate of 20 ° C./min. Crystallinity means that the melting point derived from the second layer is observed by the above-mentioned DSC measurement.
上述のポリエステル（Ｂ−２）も、公知の方法を適用して製造することができる。例えば、主たる成分の酸成分、グリコール成分、および必要に応じて共重合成分をエステル化反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造することができる。また、これらの原料モノマーの誘導体をエステル交換反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造してもよい。さらに、２種以上のポリエステルを用いて押出機内で溶融混合してエステル交換反応（再分配反応）させて得る方法であってもよい。 The above-mentioned polyester (B-2) can also be produced by applying a known method. For example, it can be produced by a method in which the main component acid component, glycol component, and if necessary, a copolymerization component are esterified, and then the resulting reaction product is polycondensed to give a polyester. Alternatively, these raw material monomer derivatives may be transesterified, and then the resulting reaction product may be subjected to a polycondensation reaction to obtain a polyester. Further, a method may be used in which two or more kinds of polyesters are melt-mixed in an extruder and transesterified (redistribution reaction).
ポリエステル（Ｂ−２）の固有粘度は、好ましくは０．４０〜０．８０ｄｌ／ｇであり、さらには０．４５〜０．７５ｄｌ／ｇの範囲であることが好ましい。固有粘度がかかる範囲内にない場合には、第１の層を構成するポリエステル（Ａ）の固有粘度との差が大きくなることがあり、その結果交互積層構成とした場合に層構成が乱れたり、製膜はできたとしても製膜性が低下することがある。 The intrinsic viscosity of the polyester (B-2) is preferably 0.40 to 0.80 dl / g, and more preferably in the range of 0.45 to 0.75 dl / g. When the intrinsic viscosity is not within such a range, the difference from the intrinsic viscosity of the polyester (A) constituting the first layer may become large. Even if the film is formed, the film forming property may be lowered.
以上に述べた本発明の第２の層にも、前術の第１の層と同じく、本発明の目的を損なわない範囲で他のポリマーや添加剤を少量含有していてもよく、例えば不活性粒子などの滑剤、顔料、染料などの着色剤、安定剤、難燃剤、発泡剤、紫外線吸収剤などの添加剤が例示される。 Similarly to the first layer of the previous operation, the second layer of the present invention described above may contain a small amount of other polymers and additives as long as the purpose of the present invention is not impaired. Examples include additives such as lubricants such as active particles, colorants such as pigments and dyes, stabilizers, flame retardants, foaming agents, and UV absorbers.
（屈折率差）
第１の層と第２の層の屈折率差は、ＭＤ方向（長さ方向、製膜方向）およびＴＤ方向（幅方向、製膜方向に直角方向）のいずれも０．０９以上であることが好ましく、より好ましくは０．１３以上である。屈折率差がかかる範囲にあることにより、反射特性を効率よく高めることができるため、より少ない積層数で高い反射率を得ることができる。
(Refractive index difference)
The refractive index difference between the first layer and the second layer is 0.09 or more in both the MD direction (length direction, film forming direction) and the TD direction (width direction, direction perpendicular to the film forming direction). Is preferable, and more preferably 0.13 or more. When the refractive index difference is within such a range, the reflection characteristics can be improved efficiently, so that a high reflectance can be obtained with a smaller number of layers.
（積層構造部）
本発明における積層ポリエステルフィルムは、前述の第１の層と第２の層とを交互に合計５１層以上積層した積層構造部を有する。積層数の上限は、例えば１００１層といった層数であってもよいが、生産性の観点から高々９００層であることが好ましい。また、層数の下限はより好ましくは１００層以上、さらに好ましくは１５０層以上である。層数が下限未満である場合には、多重干渉による選択反射が小さく十分な近赤外線反射性能が得られない。
(Laminated structure)
The laminated polyester film in the present invention has a laminated structure part in which the above-mentioned first layer and second layer are alternately laminated in total 51 layers or more. The upper limit of the number of stacked layers may be, for example, 1001 layers, but is preferably at most 900 layers from the viewpoint of productivity. Further, the lower limit of the number of layers is more preferably 100 layers or more, and still more preferably 150 layers or more. When the number of layers is less than the lower limit, selective reflection due to multiple interference is small and sufficient near infrared reflection performance cannot be obtained.
（各層の層厚み）
本発明における第１層、第２層の各層厚みは、層間の光干渉によって選択的に近赤外光を反射する効果が得られる厚みであることが好ましい。
ここで、積層フィルムの反射波長は、隣り合った第１層と第２層の光学厚みの合計の２倍に対応する。かかる光学厚みは、屈折率と各層厚みの積で表され、使用する樹脂の屈折率と目的とする反射波長によって各層厚みを調整することが好ましい。
(Layer thickness of each layer)
The thicknesses of the first layer and the second layer in the present invention are preferably such thicknesses that an effect of selectively reflecting near-infrared light by optical interference between layers is obtained.
Here, the reflection wavelength of the laminated film corresponds to twice the total optical thickness of the adjacent first and second layers. Such optical thickness is represented by the product of the refractive index and the thickness of each layer, and the thickness of each layer is preferably adjusted according to the refractive index of the resin used and the target reflection wavelength.
また、ラドフォードらの「Ｒｅｆｌｅｃｔｉｖｉｔｙ ｏｆ Ｉｒｉｄｅｓｃｅｎｔ Ｃｏ ｅｘｔｒｕｄｅｄ Ｍｕｌｔｉｌａｙｅｒｅｄ Ｐｌａｓｔｉｃ Ｆｉｌｍｓ」や、Ｐｏｌｙｍｅｒ Ｅｎｇｉｎｅｅｒｉｎｇ ａｎｄ Ｓｃｉｅｎｃｅ、Ｖｏｌ．１３、Ｎｏ．３、１９７３年５月号にあるように、四分の一波長による多層干渉を利用した多層フィルムは、主反射ピークが可視光領域に生じない場合でも、高次反射ピークが可視光領域に生じると、高次反射による着色を示すことがあるため、高次反射を除くための適切な光学厚みとすることが好ましい。
多層干渉フィルムにおいて、主反射ピークの第１層の光学厚みに対する第２層の光学厚みの比が１．０の場合には、高次のピークのうち、２次（主反射ピークの１／２波長）、４次（主反射ピークの１／４波長）を除去することができる。
In addition, Radford et al., “Reflectivity of Irradient Co-extracted Multilayered Plastic Films”, Polymer Engineering and Science, Vol. 13, no. 3. As shown in the May, 1973 issue, a multilayer film using multilayer interference due to a quarter wavelength has a higher-order reflection peak in the visible light region even if the main reflection peak does not occur in the visible light region. In some cases, coloring due to higher-order reflection may be exhibited, and therefore, an appropriate optical thickness for removing higher-order reflection is preferable.
In the multilayer interference film, when the ratio of the optical thickness of the second layer to the optical thickness of the first layer of the main reflection peak is 1.0, the second order (1/2 of the main reflection peak) Wavelength), fourth order (1/4 wavelength of main reflection peak) can be removed.
高次反射を除くための適切な光学厚みを考慮した一例として、第１層にポリエチレン−２，６−ナフタレート（以下「ＰＥＮ」と称する）、第２層にイソフタル酸を１２ｍｏｌ％共重合した共重合ポリエチレンテレフタレート（以下「ＩＡ１２ＰＥＴ」と称する）を使用し、８００〜１２００ｎｍの波長を一次反射させる場合の各層厚みについて説明する。フィルムの製膜条件にもよるが、一般的にＰＥＮの延伸方向の屈折率は１．７４〜１．７８、ＩＡ１２ＰＥＴの延伸方向の屈折率は１．５８〜１．６５程度であるので、第１の層の各層厚みは０．１〜０．２μｍの範囲であることが好ましく、第２の層の各層厚みは０．０９〜０．２２μｍの範囲であること、特に０．１０〜０．２０μｍの範囲であることが好ましい。
第１の層および第２の層の各層がこの範囲の厚みを有することにより、近赤外領域の光を選択的に反射し、遮蔽することができる。第１の層または第２の層の各層の厚みが下限より薄い範囲では反射光が可視光線の領域となり、フィルムが着色し、視認性が低下することがある。一方上限を超えると、層間の光干渉によって３次ピーク（主反射ピークの１／３）が可視光域に生じるため着色が生じ、透明性が損なわれることがある。
As an example in consideration of an appropriate optical thickness for removing higher-order reflection, a copolymer obtained by copolymerizing polyethylene-2,6-naphthalate (hereinafter referred to as “PEN”) in the first layer and 12 mol% of isophthalic acid in the second layer. The thickness of each layer when using a polymerized polyethylene terephthalate (hereinafter referred to as “IA12PET”) to primarily reflect a wavelength of 800 to 1200 nm will be described. Although it depends on the film forming conditions of the film, the refractive index in the stretching direction of PEN is generally 1.74 to 1.78, and the refractive index in the stretching direction of IA12PET is about 1.58 to 1.65. Each layer thickness of the first layer is preferably in the range of 0.1 to 0.2 [mu] m, and each layer thickness of the second layer is in the range of 0.09 to 0.22 [mu] m, particularly 0.10 to 0.00. A range of 20 μm is preferable.
When each of the first layer and the second layer has a thickness in this range, light in the near infrared region can be selectively reflected and shielded. In the range where the thickness of each layer of the first layer or the second layer is thinner than the lower limit, the reflected light becomes a visible light region, the film is colored, and the visibility may be lowered. On the other hand, if the upper limit is exceeded, a third-order peak (1/3 of the main reflection peak) is generated in the visible light region due to light interference between layers, so that coloring may occur and transparency may be impaired.
本発明の積層ポリエステルフィルムの場合、上述した光学厚みの関係および各層の屈折率を考慮し、隣接する第１の層の厚みに対する第２の層の厚みの比（厚み比）が０．９〜１．１の範囲内となる組み合わせをより多くすることにより、可視光域に生じる高次のピークを減らすことができ、可視光域の平均反射率をより小さくすることができる。
この関係は、積層フィルムの層の大部分について成立していればよく、積層構造部の総層数の７０％以上、好ましくは８０％以上、さらに好ましくは９０％以上、特に好ましくは９５％以上について成立していればよい。
In the case of the laminated polyester film of the present invention, the ratio of the thickness of the second layer to the thickness of the adjacent first layer (thickness ratio) is 0.9 to 0.9 in consideration of the optical thickness relationship and the refractive index of each layer described above. By increasing the number of combinations within the range of 1.1, higher-order peaks generated in the visible light region can be reduced, and the average reflectance in the visible light region can be further reduced.
This relationship only needs to hold for most of the layers of the laminated film, and is 70% or more, preferably 80% or more, more preferably 90% or more, particularly preferably 95% or more of the total number of layers of the laminated structure. As long as it is true.
また、各層の厚みは、波長８００−１２００ｎｍの領域での反射率を向上させるため、第１層における最大厚みと最小厚みの比が最大／最小で１．２〜１．８で連続的に変化させることが好ましい。
また、第２の層の各層の厚みも波長８００−１２００ｎｍの領域での反射率を向上させるため、最大厚みと最小厚みの比が最大／最小で１．２〜１．６で連続的に変化させることが好ましい。
Moreover, in order to improve the reflectance in the wavelength range of 800 to 1200 nm, the thickness of each layer continuously changes from 1.2 to 1.8 at the maximum / minimum thickness ratio of the first layer. It is preferable to make it.
In addition, the thickness of each layer of the second layer is continuously changed from 1.2 to 1.6 at the maximum / minimum thickness ratio in order to improve the reflectance in the wavelength range of 800 to 1200 nm. It is preferable to make it.
（保護層）
本発明の二軸延伸積層ポリエステルフィルムは、積層構造部の両側にガラス転移温度が９０℃以上、好ましくは１１０℃以上のポリマーからなる、厚み２〜２０μｍ、好ましくは５〜２０μｍ、さらに好ましくは７〜１５μｍ、特に好ましくは７〜１３μｍの保護層を有することが好ましい。かくすることにより、合わせガラスに加工する際の加工条件でも保護層の強度が保たれ、その結果、フィルムの平坦性が保たれて、細かな凹凸の発生が認められない良好な外観の合わせガラスが得られる。特に、前述のポリエステル（Ｂ−１）を第２層に用いた場合には、細かな凹凸の発生が起こりやすいので、厚み５〜２０μｍ、さらに好ましくは７〜１５μｍ、特に好ましくは７〜１３μｍの保護層を設けるとその効果が大きいので好ましい。
(Protective layer)
The biaxially stretched laminated polyester film of the present invention comprises a polymer having a glass transition temperature of 90 ° C. or higher, preferably 110 ° C. or higher on both sides of the laminated structure, and has a thickness of 2 to 20 μm, preferably 5 to 20 μm, more preferably 7 It is preferable to have a protective layer of -15 μm, particularly preferably 7-13 μm. By doing so, the strength of the protective layer is maintained even under the processing conditions when processing into a laminated glass, and as a result, the flatness of the film is maintained and fine laminated glass with no appearance of fine irregularities is recognized. Is obtained. In particular, when the above-mentioned polyester (B-1) is used for the second layer, fine irregularities are likely to occur, so that the thickness is 5 to 20 μm, more preferably 7 to 15 μm, and particularly preferably 7 to 13 μm. Providing a protective layer is preferable because the effect is great.
保護層ポリマーのガラス転移温度が９０℃未満の場合や、保護層の厚さが下限に満たない場合には、合わせガラスに加工した際の細かな凹凸発生の抑制効果が低減することがある。一方、保護層の厚さが上限を超える場合には、細かな凹凸の発生抑制への効果はそれより薄いものと変わらない上、湾曲した形状の合わせガラスを成形する際に湾曲部分への追従性が低下する傾向にある。 When the glass transition temperature of the protective layer polymer is less than 90 ° C., or when the thickness of the protective layer is less than the lower limit, the effect of suppressing the occurrence of fine irregularities when processed into laminated glass may be reduced. On the other hand, when the thickness of the protective layer exceeds the upper limit, the effect of suppressing the occurrence of fine irregularities is not different from that of a thinner one, and it follows the curved part when forming a curved laminated glass. Tend to decrease.
好ましく用いられるガラス転移温度が９０℃以上のポリマーとしては、ポリエチレンナフタレート、ポリカーボネート、ポリスチレン、ポリメタクリル酸メチル、ポリフェニレンスルフィド、ポリエーテルサルフォン、ポリフェニレンオキシドなどが挙げられる。保護層の積層方法としては、共押出によって積層構造部分と保護層とを同時に作成してもよいし、保護層のみ後から貼り合わせてもよい。なかでも、保護層として第１層のポリマーであるポリエチレンナフタレートを使用し、共押出法によって保護層と積層構造部分とを同時に作成するのが好ましい。 Preferred examples of the polymer having a glass transition temperature of 90 ° C. or higher include polyethylene naphthalate, polycarbonate, polystyrene, polymethyl methacrylate, polyphenylene sulfide, polyether sulfone, and polyphenylene oxide. As a method for laminating the protective layer, the laminated structure portion and the protective layer may be formed simultaneously by coextrusion, or only the protective layer may be bonded later. Among these, it is preferable to use polyethylene naphthalate, which is a polymer of the first layer, as the protective layer, and simultaneously form the protective layer and the laminated structure portion by a coextrusion method.
（滑剤）
本発明の二軸延伸積層ポリエステルフィルムは、高い透明性を維持する観点から、フィルム中には不活性粒子を含まないことが好ましい。しかし、製造工程での微小なキズ防止や、フィルムの巻取り性を向上させるために、滑剤として不活性粒子を含有させてもよい。この場合、最外層に含有させることが好ましいが、表層に近い第１の層および／または第２の層にも含有させてもよい。不活性粒子は、例えば平均粒径０．０１〜２μｍ、さらには０．０５〜１μｍ、特に０．１〜０．３μｍのものを用いるとよい。配合割合としては、配合する層の重量を基準として、例えば０．００１〜１重量％の範囲が好ましい。
不活性粒子を配合する場合、不活性粒子の平均粒径が下限よりも小さいか、含有量が下限よりも少ないと、フィルムの巻取り性を向上させる効果が不十分になりやすく、他方、不活性粒子の含有量が上限を超えるか、平均粒径が上限を超えると、透明性が低下する傾向がある。
(Lubricant)
The biaxially stretched laminated polyester film of the present invention preferably contains no inert particles from the viewpoint of maintaining high transparency. However, in order to prevent minute scratches in the manufacturing process and to improve the winding property of the film, inert particles may be included as a lubricant. In this case, it is preferably contained in the outermost layer, but it may also be contained in the first layer and / or the second layer close to the surface layer. As the inert particles, for example, particles having an average particle diameter of 0.01 to 2 μm, further 0.05 to 1 μm, and particularly 0.1 to 0.3 μm may be used. The blending ratio is preferably in the range of 0.001 to 1% by weight, for example, based on the weight of the layer to be blended.
When blending inert particles, if the average particle size of the inert particles is smaller than the lower limit or the content is less than the lower limit, the effect of improving the winding property of the film tends to be insufficient, while When the content of the active particles exceeds the upper limit or the average particle diameter exceeds the upper limit, the transparency tends to decrease.
好ましく用いられる不活性粒子としては、例えばシリカ、アルミナ、炭酸カルシウム、燐酸カルシウム、カオリン、タルクのような無機不活性粒子、シリコーン、架橋ポリスチレン、スチレン−ジビニルベンゼン共重合体のような有機不活性粒子を挙げることができる。
これらの不活性粒子は、その長径と短径の比が１．２以下、さらには１．１以下である球状粒子（以下、真球状粒子ということがある）であることが、フィルムの滑り性と透明性とをできるかぎり維持する観点から好ましい。また、これらの不活性粒子の粒度分布はシャープであることが好ましい。
The inert particles preferably used include inorganic inert particles such as silica, alumina, calcium carbonate, calcium phosphate, kaolin, and talc, and organic inert particles such as silicone, crosslinked polystyrene, and styrene-divinylbenzene copolymer. Can be mentioned.
These inert particles are spherical particles whose ratio of major axis to minor axis is 1.2 or less, and further 1.1 or less (hereinafter sometimes referred to as true spherical particles). And transparency from the viewpoint of maintaining as much as possible. Moreover, it is preferable that the particle size distribution of these inert particles is sharp.
（紫外線吸収剤）
本発明の二軸延伸積層ポリエステルフィルムは、紫外線吸収剤を含有する層を少なくとも１層有することができる。
好ましく用いられる紫外線吸収剤は、波長３８０ｎｍにおける吸光係数εが２以上、さらに好ましくは３以上の紫外線吸収剤である。ここでいう吸光係数εは下記式（１）で表され、Ｌａｍｂｅｒｔ−Ｂｅｅｒの式をもとにし、テトラヒドロフラン中に溶解させた紫外線吸収剤の吸光度を測定し、濃度の値から算出した吸光係数である。
ε＝Ａ／（ｃ×ｂ） ・・・（１）
（上式（１）中、εは吸光係数、Ａは吸光度、ｃは濃度（ｇ／Ｌ）、ｂは試料中の光路長（ｃｍ）をそれぞれ表す）
(UV absorber)
The biaxially stretched laminated polyester film of the present invention can have at least one layer containing an ultraviolet absorber.
The ultraviolet absorber preferably used is an ultraviolet absorber having an extinction coefficient ε at a wavelength of 380 nm of 2 or more, more preferably 3 or more. The extinction coefficient ε here is expressed by the following formula (1). Based on the Lambert-Beer formula, the absorbance of the UV absorber dissolved in tetrahydrofuran is measured, and the extinction coefficient calculated from the concentration value is used. is there.
ε = A / (c × b) (1)
(In the above formula (1), ε is an extinction coefficient, A is absorbance, c is concentration (g / L), and b is optical path length (cm) in the sample)
かかる吸光特性を有する紫外線吸収剤を用いることにより、紫外線耐久性が比較的低いポリエチレンナフタレート層を含む積層ポリエステルフィルムでありながら、乗り物や建築物の窓などの熱線遮蔽用途に用いることのできる高い紫外線耐久性を付与することができる。
紫外線吸収剤として、例えばトリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ベンゾオキサジノン系紫外線吸収剤、サリシレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、サルチレート系紫外線吸収剤を挙げることができ、好ましくはトリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤を用いるが、これら全てが上述の吸光特性を満足するわけではなく、これら中から選択して用いる必要がある。
By using an ultraviolet absorber having such light absorption characteristics, it is a laminated polyester film including a polyethylene naphthalate layer having a relatively low ultraviolet durability, but it can be used for heat ray shielding applications such as vehicles and windows of buildings. UV durability can be imparted.
Examples of UV absorbers include triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, benzoxazinone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, and salicylate UV absorbers. Preferably, triazine-based UV absorbers and benzotriazole-based UV absorbers are used, but not all of them satisfy the above-mentioned light absorption characteristics, and it is necessary to select and use them.
波長３８０ｎｍにおける吸光係数εが２以上の特性を満足する紫外線吸収剤として、具体的には、２−（２−ヒドロキシ−４−［１−オクチロキシカルボニルエトキシ］フェニル）−４，６−ビス（４−フェニルフェニル）−１，３，５−トリアジン、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェニルエチル）フェノール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−６−（１−メチル−１−フェニルエチル）−４−（１，１，３，３−テトラメチルブチル）フェノール、オクチル−３−［３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル］プロピオネート、２−エチルヘキシル−３−［３−ｔｅｒｔ−ブチルー４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル］プロピオネート、２−（２Ｈ−ベンゾトリアゾール−２−イル）４，６−ビス（１−エチル−１−フェニルエチル）フェノール、フェノール，２−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）−６−（１，１−ジメチルエチル）４−メチル、２，２’−メチレンビス（６−（２Ｈ−ベンゾトリアゾール−２−イル）−４−１，１，３，３−テトラメチルブチル）フェノール）、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）ロキシ］フェノール、２，４−ビス（２−ヒドロキシ−４−ブチロキシフェニル）−６−（２，４−ビス−ブチロキシフェニシル）−１，３，５−トリアジン、ベンゼンプロパン酸，３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ−Ｃ７−９分岐及び鎖状アルキルエステル、２−（２−ヒドロキシ−５−ｔｅｒｔ−メチルフェニル）−２Ｈ−ベンゾトリアゾール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ジ−ｔｅｒｔ−ペンチルフェノール，２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２−［４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン−２−イル］−５−（オクチロキシ）フェノール、２−（２’−ヒドロキシ−５’−オクチルフェニル）ベンゾトリアゾールが例示される。 As an ultraviolet absorber satisfying the characteristic that the extinction coefficient ε at a wavelength of 380 nm satisfies 2 or more, specifically, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis ( 4-phenylphenyl) -1,3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzo Triazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, octyl-3- [3-tert-butyl-4- Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5 (5-Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- (2H-benzotriazol-2-yl) 4,6-bis (1-ethyl-1-phenylethyl) phenol, phenol, 2 -(5-Chloro-2H-benzotriazol-2-yl) -6- (1,1-dimethylethyl) 4-methyl, 2,2'-methylenebis (6- (2H-benzotriazol-2-yl)- 4-1,1,3,3-tetramethylbutyl) phenol), 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) loxy] phenol, 2 , 4-Bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bis-butyroxyphenicyl) -1,3,5-triazine, benzenepropanoic acid, 3- (2H-be Nzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-C7-9 branched and chain alkyl ester, 2- (2-hydroxy-5-tert-methylphenyl) -2H -Benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2,2'-dihydroxy-4-methoxybenzophenone, 2- [4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- (2′-hydroxy-5′-octylphenyl) benzotriazole.
紫外線吸収剤を含む層における紫外線吸収剤の濃度は、層の重量を基準として、例えば０．１重量％以上、好ましくは１〜８０重量％である。紫外線吸収剤の含有量が下限に満たないと十分な紫外線の吸収効果が得られないことがある。
本発明の二軸延伸積層ポリエステルフィルムは、かかる紫外線吸収剤を含有する層を有することによって、波長３００〜４００ｎｍの範囲内での該フィルムの平均光線透過率が１０％以下であることが好ましく、５％以下であることがさらに好ましい。
The concentration of the ultraviolet absorber in the layer containing the ultraviolet absorber is, for example, 0.1% by weight or more, preferably 1 to 80% by weight, based on the weight of the layer. If the content of the ultraviolet absorber is less than the lower limit, a sufficient ultraviolet absorption effect may not be obtained.
The biaxially stretched laminated polyester film of the present invention preferably has an average light transmittance of 10% or less within a wavelength range of 300 to 400 nm by having a layer containing such an ultraviolet absorber. More preferably, it is 5% or less.
紫外線吸収剤を含有させる層は、前述の第１の層（ＰＥＮ層）より表層側にあることが好ましく、前述の積層構造部上、または前述の保護層上に別途層を設けてもよく、また、前述の保護層に含有させてもよいが、特に保護層に含有させることが好ましい。
また、後述の中間膜中に紫外線吸収剤を含有させることも好ましい。このように紫外線がポリエチレンナフタレート層に到達する前の段階で紫外線を遮蔽することが好ましく、外側に位置する層に該紫外線吸収剤を含有させることが好ましい。
また紫外線吸収剤とともに、クエンチャーやＨＡＬＳといった光安定剤を併用してもよい。
The layer containing the ultraviolet absorber is preferably on the surface layer side from the first layer (PEN layer), and a separate layer may be provided on the laminated structure or the protective layer. Moreover, although you may make it contain in the above-mentioned protective layer, it is preferable to make it contain in a protective layer especially.
Moreover, it is also preferable to contain an ultraviolet absorber in the below-mentioned intermediate film. Thus, it is preferable to block the ultraviolet rays before the ultraviolet rays reach the polyethylene naphthalate layer, and the ultraviolet absorber is preferably contained in the layer located on the outside.
A light stabilizer such as a quencher or HALS may be used in combination with the ultraviolet absorber.
＜塗布層＞
本発明の二軸延伸積層ポリエステルフィルムは、高い透明性を維持する観点から、フィルム内部に粒子がほとんど存在しないことから、易滑性の機能を塗布層によって付与することが好ましい。また、中間膜との接着性を向上させるために易接着性の機能を塗布層によって付与することが好ましい。
<Coating layer>
From the viewpoint of maintaining high transparency, the biaxially stretched laminated polyester film of the present invention is preferably provided with a slippery function by a coating layer since there are almost no particles inside the film. Moreover, it is preferable to provide an easy-adhesive function by the coating layer in order to improve the adhesiveness with the intermediate film.
＜フィルム特性＞
（熱収縮率）
本発明の二軸延伸積層ポリエステルフィルムは、１２０℃、３０分熱処理したときの熱収縮率が、フィルム縦方向および横方向の両方において０．８％以下であり、好ましくは０．７％以下である。熱収縮率の下限は特に規定するものではないが、好ましくは０．３％以上、より好ましくは０．５％以上である。本発明の二軸延伸積層ポリエステルフィルムがこのような小さな熱収縮率特性を有し、かつ後述するように中間膜と予め積層された構成体を作成し、かかる構成体を曲面を有する合わせガラスと貼り合わせることにより、高い熱線遮蔽効果を発現する屈折率差を有する積層構成を維持しつつ、曲面を有する合わせガラスとの加工の際のしわ発生を低減することができる。
一方、二軸延伸積層ポリエステルフィルムの熱収縮率を上限を超えて高くすると、曲面を有する合わせガラスとの加工の際のしわ発生は低減するものの、層間の屈折率特性を十分に維持することができずに熱線遮蔽効果の低下につながる。かかる熱収縮率特性は、フィルム製造工程において、熱固定温度を２００℃〜２５０℃にすることにより得ることができる。
<Film characteristics>
(Heat shrinkage)
The biaxially stretched laminated polyester film of the present invention has a heat shrinkage rate of 0.8% or less, preferably 0.7% or less in both the longitudinal direction and the transverse direction when heat-treated at 120 ° C. for 30 minutes. is there. The lower limit of the heat shrinkage rate is not particularly specified, but is preferably 0.3% or more, more preferably 0.5% or more. The biaxially stretched laminated polyester film of the present invention has such a small heat shrinkage characteristic, and creates a structure laminated in advance with an intermediate film as will be described later. By bonding, wrinkle generation at the time of processing with a laminated glass having a curved surface can be reduced while maintaining a laminated structure having a refractive index difference that exhibits a high heat ray shielding effect.
On the other hand, when the heat shrinkage rate of the biaxially stretched laminated polyester film is increased beyond the upper limit, the generation of wrinkles during processing with a laminated glass having a curved surface is reduced, but the refractive index characteristics between the layers can be sufficiently maintained. Failure to do so leads to a decrease in the heat ray shielding effect. Such heat shrinkage characteristics can be obtained by setting the heat setting temperature to 200 ° C. to 250 ° C. in the film manufacturing process.
（反射率）
本発明の二軸延伸積層ポリエステルフィルムは、該フィルムの４００〜７５０ｎｍの波長範囲における平均反射率が２５％以下であり、８００〜１２００ｎｍの波長範囲における平均反射率が５０％以上であることが好ましい。また、該フィルムの４００〜７５０ｎｍの波長範囲における平均反射率は２０％以下であることが好ましい。可視光線波長域の平均反射率がより低いほど、可視光線透過率が高くなり、良好な視認性が得られる。８００〜１２００ｎｍの波長範囲における平均反射率は好ましくは５５％以上、特に好ましくは６０％以上であり、赤外波長領域の平均反射率が高いほど熱線遮熱性能が向上するので好ましい。
かかる反射率特性を有することにより、自動車や電車などの乗り物および建築物の窓に用いるガラスと貼り合わせて優れた外観性と熱線遮蔽効果を付与することができる。
(Reflectance)
In the biaxially stretched laminated polyester film of the present invention, the average reflectance in the wavelength range of 400 to 750 nm of the film is 25% or less, and the average reflectance in the wavelength range of 800 to 1200 nm is preferably 50% or more. . Moreover, it is preferable that the average reflectance in the wavelength range of 400-750 nm of this film is 20% or less. The lower the average reflectance in the visible light wavelength region, the higher the visible light transmittance and the better the visibility. The average reflectance in the wavelength range of 800 to 1200 nm is preferably 55% or more, particularly preferably 60% or more. The higher the average reflectance in the infrared wavelength region, the better the heat ray shielding performance.
By having such reflectance characteristics, it is possible to impart excellent appearance and heat ray shielding effect by bonding to glass used for vehicles such as automobiles and trains and windows of buildings.
（フィルム製造方法）
本発明の二軸延伸積層ポリエステルフィルムは、例えば次の方法で製造することができる。すなわち第１の押出機より供給された第１の層用ポリエステルと、第２の押出機より供給された第２の層用樹脂とを溶融状態で交互に少なくとも５１層以上重ね合わせ、さらに保護層を付与する場合は保護層用のポリマーを積層構造部の両側に重ね合わせて多層未延伸シートとする。
これを回転するドラム上にキャストすることにより、未延伸多層積層フィルムとする。このようにして得られた未延伸多層積層フィルムを、製膜方向とそれに直交する幅方向の二軸方向（フィルム面に沿った方向）に延伸する。延伸温度は、第１の層用のポリエステルのガラス転移点の温度（Ｔｇ）〜Ｔｇ＋５０℃の範囲とする。延伸の面積倍率は５〜５０倍とすることが好ましい。延伸倍率が大きい程、第１の層および第２の層の個々の層における面方向のバラツキが延伸による薄層化により小さくなり、得られるフィルムの光干渉が面方向に均一になるので、延伸倍率はこの範囲で大きいことが好ましい。延伸方法は、逐次二軸延伸、同時二軸延伸のいずれの方法であってもよい。
(Film production method)
The biaxially stretched laminated polyester film of the present invention can be produced, for example, by the following method. That is, at least 51 layers of the first layer polyester supplied from the first extruder and the second layer resin supplied from the second extruder are alternately superposed in a molten state, and further a protective layer. Is applied to both sides of the laminated structure portion to form a multilayer unstretched sheet.
By casting this on a rotating drum, an unstretched multilayer laminated film is obtained. The unstretched multilayer laminated film thus obtained is stretched in the biaxial direction (direction along the film surface) in the width direction perpendicular to the film forming direction. The stretching temperature is in the range of the glass transition temperature (Tg) to Tg + 50 ° C. of the polyester for the first layer. The stretching area ratio is preferably 5 to 50 times. The larger the draw ratio, the smaller the variation in the plane direction in the individual layers of the first layer and the second layer due to thinning by stretching, and the optical interference of the resulting film becomes uniform in the plane direction. The magnification is preferably large in this range. The stretching method may be either sequential biaxial stretching or simultaneous biaxial stretching.
得られた二軸延伸積層ポリエステルフィルムは、第１の層に使用するポリエステルの結晶化温度の範囲で熱固定するが、本発明の熱収縮率特性を得るため、２００℃〜２５０℃の温度範囲で熱固定を行う。熱固定温度が下限に満たない場合は十分に熱収縮率を小さくし難く、一方、上限を超える温度では第１層の結晶配向構造がくずれ、層間の屈折率差を十分なものとすることができず、熱線遮蔽効果の低下につながる。
第２の層用のポリエステルが融点を有する場合には、熱固定温度を該融点以上とすることにより、第１の層は結晶化し、第２の層は熱固定条件下で溶融して部分的に無配向状態となり、その結果、層間の屈折率差がさらに大きくなって赤外領域の反射率を高め、高い熱線遮蔽効果を得ることができる。
The obtained biaxially stretched laminated polyester film is heat-set within the range of the crystallization temperature of the polyester used for the first layer, but in order to obtain the heat shrinkage characteristics of the present invention, a temperature range of 200 ° C. to 250 ° C. Fix with heat. When the heat setting temperature is less than the lower limit, it is difficult to sufficiently reduce the heat shrinkage rate. On the other hand, when the temperature exceeds the upper limit, the crystal orientation structure of the first layer is broken, and the refractive index difference between the layers is sufficient. This is not possible, leading to a reduction in the heat ray shielding effect.
When the polyester for the second layer has a melting point, by setting the heat setting temperature to be equal to or higher than the melting point, the first layer is crystallized, and the second layer is melted under the heat setting condition and partially melted. As a result, the refractive index difference between the layers is further increased, the reflectance in the infrared region is increased, and a high heat ray shielding effect can be obtained.
＜合わせガラス用構成体＞
本発明の合わせガラス用構成体は、本発明の二軸延伸積層ポリエステルフィルムおよびその少なくとも片面に中間膜が積層された構成を有する。
本発明において用いられる中間膜は本発明の二軸延伸積層ポリエステルフィルムおよび合わせガラスとの接着性を有する接着層であることが好ましい。かかる中間膜として、エチレン−ビニルアセテート共重合体、ポリビニルブチラール、アイオノマー樹脂、ポリウレタンが例示され、ポリビニルブチラールが特に好ましい。
<Structure for laminated glass>
The laminate for laminated glass of the present invention has a configuration in which the biaxially stretched laminated polyester film of the present invention and an intermediate film are laminated on at least one surface thereof.
The intermediate film used in the present invention is preferably an adhesive layer having adhesiveness with the biaxially stretched laminated polyester film of the present invention and laminated glass. Examples of such an intermediate film include ethylene-vinyl acetate copolymer, polyvinyl butyral, ionomer resin, and polyurethane, and polyvinyl butyral is particularly preferable.
本発明の合わせガラス用構成体には、片面に中間膜が積層された構成、両面に中間膜が積層された構成が含まれる。
本発明の合わせガラス用構成体は、二軸延伸積層ポリエステルフィルムと中間膜を重ねた状態で予め熱と圧力を加えて接着（加熱圧着と称することがある）させる方法で製造することが好ましい。具体的な加熱圧着手法としては、二軸延伸積層ポリエステルフィルムと中間膜を重ねた状態で加熱しながら、ニップロールに通すことで圧力をかけて接着させる手法が挙げられる。加熱温度は中間膜が軟化する温度であれば特に制限されないが上限は１００℃以下が好ましい。
The structure for laminated glass of the present invention includes a structure in which an intermediate film is laminated on one side and a structure in which an intermediate film is laminated on both sides.
The structure for laminated glass of the present invention is preferably produced by a method in which heat and pressure are applied in advance in a state where the biaxially stretched laminated polyester film and the intermediate film are laminated (referred to as thermocompression bonding). As a specific thermocompression bonding method, there is a method in which pressure is applied by passing through a nip roll while heating in a state where the biaxially stretched laminated polyester film and the intermediate film are stacked. The heating temperature is not particularly limited as long as the intermediate film is softened, but the upper limit is preferably 100 ° C. or less.
二軸延伸積層ポリエステルフィルムと中間膜とを予め加熱圧着してまず合わせガラス用構成体を作成し、その後、該中間膜上に曲面を有するガラスを積層し、後述する方法で加熱加圧処理を行う方法を用いることにより、曲面を有する合わせガラスと貼り合わせる際に高い熱線遮蔽効果を低下させることなく、同時にしわの発生も抑制できるため、良好な熱線遮蔽効果と外観性を備える、曲面を有する合わせガラス積層体が得られる。一方、本発明の二軸延伸積層ポリエステルフィルムを用いて曲面を有する合わせガラスと貼り合わせるにあたり、従来のようなポリエステルフィルム、中間膜およびガラスを同時に加熱圧着させる方法ではしわが発生してしまい、外観性が低下する。なお、従来の同時に加熱圧着させる方法を用いる場合、本発明と同じ組成の積層ポリエステルフィルムであれば、本発明より高い熱収縮率とすれば曲面を有する合わせガラスと貼り合わせてもしわを低減させることが可能ではあるが、一方で熱線遮蔽効果の低下を引き起こす傾向にある。 A biaxially stretched laminated polyester film and an intermediate film are preliminarily heat-pressed to prepare a laminated glass structure, and then a glass having a curved surface is laminated on the intermediate film, followed by heat and pressure treatment by a method described later. By using the method, it is possible to suppress the generation of wrinkles at the same time without lowering the high heat ray shielding effect when laminating with a laminated glass having a curved surface, and thus has a curved surface having a good heat ray shielding effect and appearance. A laminated glass laminate is obtained. On the other hand, in laminating with a laminated glass having a curved surface using the biaxially stretched laminated polyester film of the present invention, wrinkles are generated by the method of simultaneously heat-pressing the polyester film, the intermediate film and the glass as in the past. Sex is reduced. In addition, when using the conventional method of heat-pressing simultaneously, if the laminated polyester film has the same composition as the present invention, the wrinkle can be reduced even if it is bonded to a laminated glass having a curved surface if the heat shrinkage rate is higher than that of the present invention. Although it is possible, it tends to cause a decrease in the heat ray shielding effect.
また、本発明の合わせガラス用構成体は、金属系の積層体を介して該二軸延伸積層ポリエステルフィルムと該中間膜が積層された構成であってもよい。金属系の積層体をさらに有することにより、さらに熱線遮蔽効果を高めることができる。金属系の積層体として、低屈折率層と高屈折率層とが交互に積層された積層構成を有する金属および／あるいは金属酸化物の積層体が例示される。
金属は低屈折率層に使用することができ、金属酸化物は低屈折率層と高屈折率層の両方に使用することができる。
Moreover, the structure by which this biaxially stretched laminated polyester film and this intermediate film were laminated | stacked through the metal-type laminated body may be sufficient as the structure for laminated glasses of this invention. By further including a metal-based laminate, the heat ray shielding effect can be further enhanced. Examples of the metal-based laminated body include a laminated body of metal and / or metal oxide having a laminated structure in which low refractive index layers and high refractive index layers are alternately laminated.
Metals can be used for the low refractive index layer and metal oxides can be used for both the low and high refractive index layers.
該金属系の積層体に用いられる金属としては、Ａｕ、Ａｇ、ＣｕまたはＡｌなどの金属が例示される。これらの中で特に好ましいのは可視光線の吸収がほとんどないＡｇである。なお、該金属層を形成する金属は、必要に応じて２種以上併用しても良い。
係る金属層を形成する方法としては、気相成長法が好ましく、特に真空蒸着法、スパッタ―法またはプラズマＣＶＤ法が好ましい。該金属層の厚みは、５〜１０００ｎｍ、好ましくは１０〜５００ｎｍの範囲である。該金属層厚みが下限に満たないと十分な熱線遮蔽性能が発現しにくい。また、該金属層厚みが上限を越えると、可視光の透過率が不十分なものとなりやすく、透明性が損なわれることがある。
Examples of the metal used in the metal-based laminate include metals such as Au, Ag, Cu, and Al. Among these, Ag is particularly preferable because it hardly absorbs visible light. In addition, you may use together 2 or more types of the metal which forms this metal layer as needed.
As a method for forming such a metal layer, a vapor phase growth method is preferable, and a vacuum deposition method, a sputtering method, or a plasma CVD method is particularly preferable. The thickness of the metal layer is in the range of 5 to 1000 nm, preferably 10 to 500 nm. If the thickness of the metal layer is less than the lower limit, sufficient heat ray shielding performance is hardly exhibited. On the other hand, if the thickness of the metal layer exceeds the upper limit, the visible light transmittance tends to be insufficient, and transparency may be impaired.
該金属酸化物としては、ＴｉＯ２、ＺｒＯ２、ＳｎＯ２、Ｉｎ２Ｏ３、ＳｉＯ２、ＩＴＯ、ＩＺＯ、ＡＺＯなどが挙げられる。
係る金属酸化物層の形成方法は、前述の金属層の形成方法と同様に、気相成長法が好ましく、特に真空蒸着法、スパッタ―法またはプラズマＣＶＤ法が好ましい。該金属酸化物層の厚みは、光干渉の面から他の金属層や金属酸化物層の屈折率および厚みとも関連するが、０．１〜７５０ｎｍ、好ましくは１０〜５００ｎｍの範囲である。該厚みが範囲外であると光干渉効果が得られず、可視光の反射率の増加や熱線反射性能の低下といった問題が生じることがある。
Examples of the metal oxide include TiO 2 , ZrO 2 , SnO 2 , In 2 O 3 , SiO 2 , ITO, IZO, and AZO.
The method for forming such a metal oxide layer is preferably a vapor phase growth method, particularly the vacuum layer deposition method, the sputtering method, or the plasma CVD method, as in the above-described method for forming a metal layer. The thickness of the metal oxide layer is related to the refractive index and thickness of other metal layers and metal oxide layers in terms of optical interference, but is in the range of 0.1 to 750 nm, preferably 10 to 500 nm. If the thickness is out of the range, the light interference effect cannot be obtained, and problems such as an increase in visible light reflectance and a decrease in heat ray reflection performance may occur.
該金属系の積層体をさらに有する場合、本発明の二軸延伸積層ポリエステルフィルム、該金属系の積層体および中間膜が積層された合わせガラス用構成体の４００〜７５０ｎｍの波長範囲における平均反射率は２５％以下であることが好ましく、また８００〜１２００ｎｍの波長範囲における平均反射率は５０％以上であることが好ましい。 When the metal-based laminate is further included, the average reflectance in the wavelength range of 400 to 750 nm of the biaxially stretched laminated polyester film of the present invention, and the laminated glass laminate in which the metal-based laminate and the intermediate film are laminated. Is preferably 25% or less, and the average reflectance in the wavelength range of 800 to 1200 nm is preferably 50% or more.
＜合わせガラス用積層体＞
本発明の合わせガラス用積層体は、本発明の曲面を有する合わせガラス用構成体の中間膜上に曲面を有するガラスが積層された構成を有することが好ましい。
合わせガラス積層体を製造方法する方法として、本発明の二軸延伸積層ポリエステルフィルムおよびその少なくとも片面に中間膜が積層された構成体を作成し、該構成体を加熱圧着する工程を含み、該加熱圧着工程の後に該中間膜上に曲面を有するガラスを積層する方法が挙げられる。２枚の曲面を有するガラスで該合わせガラス用構成体を挟持し、それ自体公知の合わせガラス製造条件で加熱加圧処理を行うことにより製造することができる。
<Laminated body for laminated glass>
The laminated body for laminated glass of the present invention preferably has a structure in which a glass having a curved surface is laminated on an intermediate film of the laminated glass having a curved surface of the present invention.
The method for producing a laminated glass laminate includes a step of preparing a biaxially stretched laminated polyester film of the present invention and a structure in which an intermediate film is laminated on at least one surface thereof, and thermocompression-bonding the structure. The method of laminating | stacking the glass which has a curved surface on this intermediate film after a crimping | compression-bonding process is mentioned. It can be manufactured by sandwiching the laminated glass structure with two curved glass and subjecting it to heat and pressure treatment under known laminated glass manufacturing conditions.
また、該合わせガラス用構成体において中間膜が二軸延伸積層ポリエステルフィルムの片面のみに貼り合わされている場合は、合わせガラスの作製工程で中間膜を貼り合わせていないフィルム面に新たな中間膜を積層してから２枚のガラスの間に挟持して、加熱加圧処理を行うことが好ましい。驚くべきことに、一方の面の中間膜が予め二軸延伸積層ポリエステルフィルムと貼り合されていれば、他方の面の中間膜が従来と同じく合わせガラスの作成工程で貼り合されても本発明の効果は発現される。
加熱加圧処理の条件は特に制限されないが、一例として、加熱加圧炉に入れ、１２０〜１５０℃、１４ａｔｍ以下で１０〜６０分間処理後、圧は維持したまま温度だけ室温まで低下させた後、常圧に戻し、加熱加圧炉から取り出す方法が挙げられる。
In addition, when the interlayer film is bonded to only one side of the biaxially stretched laminated polyester film in the laminated glass composition, a new interlayer film is added to the film surface where the interlayer film is not bonded in the laminated glass production process. It is preferable to perform the heating and pressurizing treatment by sandwiching between two glasses after lamination. Surprisingly, if the intermediate film on one side is preliminarily bonded to the biaxially stretched laminated polyester film, the present invention can be applied even if the intermediate film on the other side is bonded in the same process as the laminated glass. The effect of is expressed.
The conditions for the heat and pressure treatment are not particularly limited. For example, after being placed in a heat and pressure furnace and treated at 120 to 150 ° C. and 14 atm or less for 10 to 60 minutes, the pressure is maintained and the temperature is lowered to room temperature. The method of returning to normal pressure and taking out from a heating and pressurizing furnace can be mentioned.
以下、実施例をもって本発明をさらに詳細に説明する。なお、実施例中の物性や特性は下記の方法によって測定または評価した。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical property and characteristic in an Example were measured or evaluated by the following method.
（１）熱収縮率
フィルムサンプルに３０ｃｍ間隔で標点をつけ、荷重をかけずに１２０℃のオーブンで３０分間熱処理を実施し、熱処理後の標点間隔を測定して、下記式にて熱収縮率を算出した。
熱収縮率(％)＝((熱処理前標点間距離−熱処理後標点間距離)／熱処理前標点間距離)×１００
(1) Heat shrinkage rate Marks are applied to film samples at intervals of 30 cm, heat treatment is performed in an oven at 120 ° C. for 30 minutes without applying a load, the distance between the marks after heat treatment is measured, and heat is calculated according to the following formula. Shrinkage was calculated.
Thermal contraction rate (%) = ((distance between the pre-heat treatment gauge points−distance between the heat treatment gauge points) / distance between the heat treatment gauge points) × 100
（２）ポリエステルの組成
１Ｈ−ＮＭＲ測定を用いて特定した。
(2) Composition of polyester
Identified using 1 H-NMR measurements.
（３）フィルム厚み
電子マイクロメータ（アンリツ（株）製の商品名「Ｋ−３１２Ａ型」）を用いて針圧３０ｇにてフィルム厚みを測定した。
(3) Film thickness Film thickness was measured at 30 g of needle pressure using an electronic micrometer (trade name “K-312A type” manufactured by Anritsu Corporation).
（４）フィルムの平均反射率
分光光度計（島津製作所製、ＭＰＣ−３１００）を用い、波長３５０ｎｍから２１００ｎｍの範囲にわたり、アルミ蒸着したミラーとの相対鏡面反射率を測定した。得られたスペクトルのなかで８００〜１２００ｎｍの範囲、および４００〜７５０ｎｍの範囲における反射率を平均して、それぞれの平均反射率とした。
(4) Average reflectance of film Using a spectrophotometer (manufactured by Shimadzu Corporation, MPC-3100), relative specular reflectance with an aluminum-deposited mirror was measured over a wavelength range of 350 nm to 2100 nm. In the obtained spectrum, the reflectance in the range of 800 to 1200 nm and the range of 400 to 750 nm was averaged to obtain the average reflectance.
（５）ＤＳＣによる樹脂のガラス転移温度
各層を構成する樹脂１０ｍｇについて、ＤＳＣ（ＴＡインスツルメンツ社製、商品名：ＤＳＣ２９２０）を用い、２０℃／ｍｉｎの昇温速度でガラス転移温度を測定した。
(5) Glass transition temperature of resin by DSC About 10 mg of resin constituting each layer, the glass transition temperature was measured at a rate of temperature increase of 20 ° C./min using DSC (trade name: DSC2920, manufactured by TA Instruments).
（６）積層ポリエステルフィルムの各層厚み
サンプルを三角形に切り出し、包埋カプセルに固定後、エポキシ樹脂にて包埋した。そして、包埋されたサンプルをミクロトーム（ＵＬＴＲＡＣＵＴＳ、製造元：ライヘルト社）で製膜方向と厚み方向に沿って切断し、厚さ５０ｎｍの薄膜切片にした。得られた薄膜切片を、透過型電子顕微鏡（製造元：日本電子（株）、商品名：ＪＥＭ２０１０）を用いて、加速電圧１００ｋＶにて観察・撮影し、写真から各層の厚みを測定した。
(6) Layer thickness of laminated polyester film A sample was cut into a triangle, fixed to an embedding capsule, and then embedded with an epoxy resin. And the embedded sample was cut | disconnected along the film forming direction and thickness direction with the microtome (ULTRACUTS, manufacturer: Reichert), and it was set as the thin film slice | slice of thickness 50nm. The obtained thin film slices were observed and photographed at an accelerating voltage of 100 kV using a transmission electron microscope (manufacturer: JEOL Ltd., trade name: JEM2010), and the thickness of each layer was measured from the photograph.
（７）合わせガラス加工性評価
二軸延伸積層ポリエステルフィルムおよび中間膜からなる構成体サンプルを、厚さ２ｍｍ、５００ｍｍ（曲率１５０Ｒ）×４００ｍｍ（曲率１５００Ｒ）のガラス板２枚で挟み、その後、加熱加圧炉に入れ、１３０℃、１３ａｔｍで３０分間処理後、圧は維持したまま温度だけ４０℃まで低下させた後、常圧に戻し、加熱加圧炉から取り出し、ガラス板の周囲にはみでているフィルムを切り放し、合わせガラスを得た。この際、構成体サンプルが一方のみに中間膜を有している場合は、ガラス板２枚で挟みこむ際に中間膜を有していない側に反対面と同組成の中間膜を介してガラス板と貼り合わせた。
上記方法で得られた合わせガラスにおいて、目視にて３０Ｗ蛍光灯光源のもと、シワが発生しているものを×、シワは発生していないが微細凹凸が発生しているものを△、シワや凹凸といった外観上の問題がないものを○とした。
(7) Laminated glass processability evaluation A sample composed of a biaxially stretched laminated polyester film and an intermediate film is sandwiched between two glass plates having a thickness of 2 mm, 500 mm (curvature 150R) × 400 mm (curvature 1500R), and then heated. Place in a pressure furnace and treat at 130 ° C and 13 atm for 30 minutes, reduce the temperature to 40 ° C while maintaining the pressure, return to normal pressure, take out from the heating and pressure furnace, and stick around the glass plate The film was cut off to obtain a laminated glass. At this time, when the constituent sample has an intermediate film on only one side, the glass is interposed through the intermediate film having the same composition as the opposite surface on the side not having the intermediate film when sandwiched between two glass plates. Bonded to the board.
In the laminated glass obtained by the above-mentioned method, x is a wrinkle generated visually under a 30 W fluorescent light source, Δ is a wrinkle-free but fine unevenness is generated, and wrinkles are generated. And those having no appearance problems such as irregularities.
（８）日射透過率
分光光度計（島津製作所製、ＭＰＣ−３１００）を用い、合わせガラスの各波長での硫酸バリウム積分球に対する相対分光透過率を波長３００ｎｍから２１００ｎｍの範囲で測定した。得られた透過率曲線から、ＪＩＳ Ｒ ３１０６：１９９８に準じて、３４０〜１８００ｎｍの波長域より日射透過率を算出した。
(8) Solar transmittance Using a spectrophotometer (manufactured by Shimadzu Corporation, MPC-3100), the relative spectral transmittance with respect to the barium sulfate integrating sphere at each wavelength of the laminated glass was measured in the wavelength range of 300 nm to 2100 nm. From the obtained transmittance curve, the solar transmittance was calculated from the wavelength range of 340 to 1800 nm according to JIS R 3106: 1998.
［実施例１］
第１の層用でかつ保護層用であるポリエステルとして固有粘度（オルトクロロフェノール、３５℃）０．６２ｄｌ／ｇのポリエチレン−２，６−ナフタレート（以下「ＰＥＮ」という）、第２の層用のポリエステルとしてイソフタル酸を１２ｍｏｌ％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６５ｄｌ／ｇのイソフタル酸共重合ポリエチレンテレフタレート（以下「ＩＡ１２ＰＥＴ」という）をそれぞれ準備した。
そして、第１の層用でかつ保護層用であるポリエステルを１８０℃で５時間、第２の層用ポリエステルを１６０℃で３時間乾燥後、押出機に供給し、ＰＥＮは３００℃、ＩＡ１２ＰＥＴは２８０℃まで加熱して溶融状態とした。第１の層のポリエステルを９０層、第２の層のポリエステルを９１層に分岐させた後、第１の層のポリエステル層と第２の層のポリエステル層とが交互に積層され、かつ第１の層と第２の層におけるそれぞれの最大層厚みと最小層厚みの比が最大／最小で１．５倍まで連続的に変化するような積層構造部分と該積層構造部分の両面に保護層を積層させるような、多層フィードブロック装置を使用して積層し、その積層状態を保持したままダイへと導き、キャスティングドラム上にキャストした。そして、フィルム両面の最外層にＰＥＮ層からなる保護層を持ち、積層構造部の全層数が１８１層の未延伸多層積層フィルムを作成した。なお、積層構造部および保護層の厚みは、延伸後の厚みが表１記載のとおりとなるように供給量を調整した。
この未延伸多層積層フィルムを１５０℃の温度で製膜方向に４．５倍延伸した。続いてテンターに供給し、１５５℃の温度で幅方向に４．５倍に延伸し、次いで２０４℃で３秒間熱固定処理を行った。得られたフィルム（フィルム１）の特性を表１に示す。
得られた近赤外線遮蔽性を有する二軸延伸積層ポリエステルフィルムを、厚さ０．３８ｍｍのポリビニルブチラールシート（ＰＶＢ、積水化学（株）製、Ｓ−ＬＥＣ Ｆｉｌｍ（商品名））２枚の間にはさみ、ラミネート装置で９０℃で加熱圧着することで合わせガラス用構成体を作製した。得られた特性を表２に示す。
[Example 1]
Polyethylene-2,6-naphthalate (hereinafter referred to as “PEN”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.62 dl / g as a polyester for the first layer and for the protective layer, for the second layer As polyesters, isophthalic acid copolymerized polyethylene terephthalate (hereinafter referred to as “IA12PET”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.65 dl / g obtained by copolymerization of 12 mol% of isophthalic acid was prepared.
The polyester for the first layer and the protective layer is dried at 180 ° C. for 5 hours and the polyester for the second layer is dried at 160 ° C. for 3 hours, and then supplied to the extruder. PEN is 300 ° C., IA12PET is It heated to 280 degreeC and was made into the molten state. After the first layer polyester is branched into 90 layers and the second layer polyester is branched into 91 layers, the first layer polyester layer and the second layer polyester layer are alternately laminated, and the first layer And a protective layer on both sides of the laminated structure portion in which the ratio of the maximum layer thickness and the minimum layer thickness in each layer of the first layer and the second layer continuously changes up to 1.5 times at maximum / minimum. Lamination was performed using a multi-layer feed block apparatus such as laminating, and the laminated state was guided to a die and cast on a casting drum. And the protective layer which consists of a PEN layer was provided in the outermost layer of both surfaces of a film, and the unstretched multilayer laminated film whose total number of layers of a laminated structure part was 181 layers was created. The thicknesses of the laminated structure and the protective layer were adjusted so that the thickness after stretching was as shown in Table 1.
This unstretched multilayer laminated film was stretched 4.5 times in the film forming direction at a temperature of 150 ° C. Subsequently, the film was supplied to a tenter, stretched 4.5 times in the width direction at a temperature of 155 ° C., and then heat set at 204 ° C. for 3 seconds. Table 1 shows the properties of the obtained film (film 1).
The obtained biaxially stretched laminated polyester film having near-infrared shielding properties is placed between two sheets of polyvinyl butyral sheet (PVB, manufactured by Sekisui Chemical Co., Ltd., S-LEC Film (trade name)) having a thickness of 0.38 mm. A laminated glass construction was produced by scissoring and thermocompression bonding at 90 ° C. with a laminating apparatus. The obtained characteristics are shown in Table 2.
［実施例２］
ＰＶＢを片面のみに貼り合わせた以外は実施例１と同様にして構成体を得た。得られた構成体の特性を表２に示す。
[Example 2]
A structure was obtained in the same manner as in Example 1 except that PVB was bonded to only one side. Table 2 shows the characteristics of the obtained structure.
[実施例３]
中間膜に厚さ０．４０ｍｍのエチレンビニルアセテート（ＥＶＡ、積水化学（株）製、Ｓ−ＬＥＣ Ｆｉｌｍ−ＥＮ（商品名））を使用した以外は実施例１と同様にして構成体を得た。得られた構成体の特性を表２に示す。
[Example 3]
A structure was obtained in the same manner as in Example 1 except that ethylene vinyl acetate (EVA, manufactured by Sekisui Chemical Co., Ltd., S-LEC Film-EN (trade name)) having a thickness of 0.40 mm was used for the intermediate film. . Table 2 shows the characteristics of the obtained structure.
［実施例４，５］
二軸延伸積層ポリエステルフィルムの種類およびフィルム製造時の熱固定温度を表１、表２に示すとおりに変更した以外は実施例１と同様にして構成体を得た。得られた特性を表２に示す。
なお、フィルム２に使用しているＴＡ４４ＰＥＮはテレフタル酸を８ｍｏｌ％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６３ｄｌ／ｇの共重合ポリエチレンナフタレンジカルボキシレート（以下「ＴＡ８ＰＥＮ」という）と２，６-ナフタレンジカルボン酸を１１ｍｏｌ％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６３ｄｌ／ｇの共重合ポリエチレンテレフタレート（以下「ＮＤＣ１１ＰＥＴ」という）を重量比６：４でブレンドすることで得ている。
[Examples 4 and 5]
A structure was obtained in the same manner as in Example 1 except that the type of the biaxially stretched laminated polyester film and the heat setting temperature at the time of film production were changed as shown in Tables 1 and 2. The obtained characteristics are shown in Table 2.
The TA44PEN used for the film 2 is a copolymerized polyethylene naphthalene dicarboxylate (hereinafter referred to as “TA8PEN”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.63 dl / g obtained by copolymerizing 8 mol% of terephthalic acid. Blending a copolymerized polyethylene terephthalate (hereinafter referred to as “NDC11PET”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.63 dl / g obtained by copolymerizing 11 mol% of 2,6-naphthalenedicarboxylic acid at a weight ratio of 6: 4. It is gained in.
[比較例１〜４]
ガラスと貼り合わせる前に中間体と二軸延伸積層ポリエステルフィルムを加熱圧着させて構成体を作製する工程を経ずに、ガラスと貼り合わせる際に中間体とフィルムを同時に挟み込んで合わせガラスを作製した。使用したフィルム、中間膜およびその特性を表２に示す。
[Comparative Examples 1-4]
Prior to bonding with glass, the intermediate body and the biaxially stretched laminated polyester film were subjected to thermocompression bonding, and the laminated body was made by sandwiching the intermediate body and the film at the same time when bonding to the glass without going through the process of manufacturing the structure. . Table 2 shows the films used, the interlayer films, and their characteristics.
[比較例５]
二軸延伸積層ポリエステルフィルムの第１層および保護層の種類をポリエチレンテレフタレート（ＰＥＴ）に変更し、溶融温度を２８０℃、製膜方向の延伸温度を９５℃、幅方向の延伸温度を１１５℃、熱固定温度を２３５℃に変更した以外は実施例１におけるフィルム１と同じ操作を行い、フィルム４を作成した。
また、ガラスと貼り合わせる前に中間体と二軸延伸積層ポリエステルフィルムを加熱圧着させて構成体を作製する工程を経ずに、ガラスと貼り合わせる際に中間体とフィルムを同時に挟み込んで合わせガラスを作製した。使用したフィルム、中間膜およびその特性を表２に示す。
[Comparative Example 5]
The type of the first layer and the protective layer of the biaxially stretched laminated polyester film is changed to polyethylene terephthalate (PET), the melting temperature is 280 ° C, the stretching temperature in the film forming direction is 95 ° C, the stretching temperature in the width direction is 115 ° C, Except for changing the heat setting temperature to 235 ° C., the same operation as film 1 in Example 1 was performed to prepare film 4.
Also, before bonding with glass, the intermediate body and the biaxially stretched laminated polyester film are subjected to thermocompression bonding, and the intermediate body and the film are sandwiched at the same time when bonded to the glass, without passing through the process of preparing the structure. Produced. Table 2 shows the films used, the interlayer films, and their characteristics.
本発明はポリエチレンナフタレート層を含む熱収縮率の小さい多層積層フィルムと中間膜とを予め貼り合わせた合わせガラス用構成体であることにより、曲面を有する合わせガラスと貼り合わせる際に高い熱線遮蔽効果を低下させることなく、同時にしわも発生せずに良好な外観性も得られることから、曲面を有し、優れた外観性と熱線遮蔽が求められる車のフロントガラスなどに好適に用いることができる。 The present invention is a laminate for laminated glass in which a multilayer laminated film having a low thermal shrinkage rate including a polyethylene naphthalate layer and an intermediate film are laminated in advance, so that a high heat ray shielding effect can be obtained when laminated with laminated glass having a curved surface. Can be suitably used for a windshield of a vehicle that has a curved surface and requires excellent appearance and heat ray shielding. .
Claims (7)
前記二軸延伸積層ポリエステルフィルムの４００〜７５０ｎｍの波長範囲における平均反射率が２５％以下であり、８００〜１２００ｎｍの波長範囲における平均反射率が５０％以上である、ことを特徴とする曲面を有する合わせガラス用構成体。 A biaxially stretched laminated polyester film and a laminated glass laminate in which an intermediate film is laminated on at least one side thereof, and the biaxially stretched laminated polyester film has a total of 51 layers in which first layers and second layers are alternately laminated. Thermal shrinkage when the polyester (A) having a laminated structure (I) of at least one layer and the first layer is polyethylene naphthalate, and the biaxially stretched laminated polyester film is heat-treated at 120 ° C. for 30 minutes the rate is Ri der 0.8% or less,
The biaxially stretched laminated polyester film has a curved surface characterized in that an average reflectance in a wavelength range of 400 to 750 nm is 25% or less and an average reflectance in a wavelength range of 800 to 1200 nm is 50% or more. Laminate structure.
ｉ）二軸延伸積層ポリエステルフィルムおよびその少なくとも片面に中間膜が積層された構成体を作成し、
ii）前記二軸延伸積層ポリエステルフィルムは第１の層および第２の層が交互に積層された合計５１層以上の積層構成（Ｉ）を有し、前記第１の層を構成するポリエステル（Ａ）がポリエチレンナフタレートであり、前記二軸延伸積層ポリエステルフィルムの１２０℃、３０分熱処理したときの熱収縮率が０．８％以下であって、
iii）作成された前記構成体を加熱圧着する工程を含み、
iv）加熱圧着工程の後に前記中間膜上に曲面を有するガラスが積層される
ことを特徴とする合わせガラス積層体の製造方法。
It is a manufacturing method of the laminated glass laminated body of Claim 6 , Comprising:
i) Create a biaxially stretched laminated polyester film and a structure in which an intermediate film is laminated on at least one side thereof,
ii) The biaxially stretched laminated polyester film has a total of 51 or more laminated constitutions (I) in which the first layers and the second layers are alternately laminated, and the polyester (A ) Is polyethylene naphthalate, and the heat shrinkage rate when the biaxially stretched laminated polyester film is heat-treated at 120 ° C. for 30 minutes is 0.8% or less,
iii) including the step of thermocompression bonding the prepared structure,
iv) A method for producing a laminated glass laminate, wherein a glass having a curved surface is laminated on the intermediate film after the thermocompression bonding step.
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