JP4880945B2 - Flame-retardant polyester film and method for producing the same - Google Patents
Flame-retardant polyester film and method for producing the same Download PDFInfo
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- JP4880945B2 JP4880945B2 JP2005235854A JP2005235854A JP4880945B2 JP 4880945 B2 JP4880945 B2 JP 4880945B2 JP 2005235854 A JP2005235854 A JP 2005235854A JP 2005235854 A JP2005235854 A JP 2005235854A JP 4880945 B2 JP4880945 B2 JP 4880945B2
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- 239000003063 flame retardant Substances 0.000 title claims description 54
- 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 title claims description 51
- 229920006267 polyester film Polymers 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920005989 resin Polymers 0.000 claims description 75
- 239000011347 resin Substances 0.000 claims description 75
- -1 polyethylene naphthalene dicarboxylate Polymers 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 29
- 229920001601 polyetherimide Polymers 0.000 claims description 21
- 239000004697 Polyetherimide Substances 0.000 claims description 20
- 230000004580 weight loss Effects 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 95
- 239000010408 film Substances 0.000 description 87
- 239000007789 gas Substances 0.000 description 34
- 239000002245 particle Substances 0.000 description 18
- 238000002411 thermogravimetry Methods 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 229920000728 polyester Polymers 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 239000011888 foil Substances 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012792 core layer Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000013585 weight reducing agent Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 5
- 239000011112 polyethylene naphthalate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 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 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 229920004748 ULTEM® 1010 Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 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 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 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
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ZYZYQCACSQDPSB-UHFFFAOYSA-N 12,15-dioxatricyclo[8.6.0.02,7]hexadeca-1(10),2,4,6,8-pentaene-11,16-dione Chemical compound O=C1OCCOC(=O)C2=C1C=CC1=CC=CC=C21 ZYZYQCACSQDPSB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- XFEGRFIENDJTCK-UHFFFAOYSA-N 2-phenyl-2,3-dihydroindene-1,1-dicarboxylic acid Chemical compound C1C2=CC=CC=C2C(C(=O)O)(C(O)=O)C1C1=CC=CC=C1 XFEGRFIENDJTCK-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical class C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MHKBNMVNEQRFFF-UHFFFAOYSA-N cyclohexane;methanediol Chemical compound OCO.C1CCCCC1 MHKBNMVNEQRFFF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 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
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000000691 measurement method Methods 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
- 229930014626 natural product Natural products 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
本発明は難燃性ポリエステルフィルムおよびその製造方法に関する。更に詳しくは、難燃性に優れ、高温下での耐熱寸法安定性及び製膜性が良好な難燃性ポリエステルフィルムおよびその製造方法に関する。 The present invention relates to a flame retardant polyester film and a method for producing the same. More specifically, the present invention relates to a flame retardant polyester film excellent in flame retardancy, excellent in heat-resistant dimensional stability and film forming property at high temperatures, and a method for producing the same.
ポリエステルフィルム、特にポリエチレンテレフタレートやポリエチレンナフタレートの二軸延伸フィルムは、優れた機械的性質、耐熱性、耐薬品性を有するため、磁気テープ、強磁性薄膜テープ、写真フィルム、包装用フィルム、電子部品用フィルム、電気絶縁フィルム、金属ラミネート用フィルム、ガラスディスプレイ等の表面に貼るフィルム、各種部材の保護用フィルム等の素材として広く用いられている。 Polyester films, especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate, have excellent mechanical properties, heat resistance, and chemical resistance. Therefore, magnetic tape, ferromagnetic thin film tape, photographic film, packaging film, electronic parts It is widely used as a material such as a film for electrical use, an electrical insulation film, a film for metal lamination, a film attached to the surface of a glass display, and a protective film for various members.
近年、製造物責任法の施行に伴い、火災に対する安全性を確保するため、樹脂の難燃化が強く要望されている。従来用いられている有機ハロゲン化合物、ハロゲン含有有機リン化合物等のハロゲン系難燃剤は、難燃効果は高いものの、成形・加工時にハロゲンが遊離し、腐食性のハロゲン化水素ガスを発生して、成形・加工機器を腐食させ、また作業環境を悪化させる可能性が指摘されている。また、前記難燃剤は、火災などの燃焼に際して、ハロゲン化水素等のガスを発生するという報告もある。そのため、近年ハロゲン系難燃剤に替わり、ハロゲンを含まない難燃剤を用いることが強く要望されている。 In recent years, with the enforcement of the Product Liability Act, there has been a strong demand for flame retarding of resins in order to ensure safety against fire. Halogen-based flame retardants such as organic halogen compounds and halogen-containing organophosphorus compounds that have been used in the past have a high flame-retardant effect, but halogen is liberated during molding and processing, generating corrosive hydrogen halide gas, It has been pointed out that it may corrode molding and processing equipment and worsen the working environment. There is also a report that the flame retardant generates a gas such as hydrogen halide during combustion such as a fire. Therefore, in recent years, there has been a strong demand for using a flame retardant containing no halogen in place of the halogen flame retardant.
ハロゲンを含まない難燃剤による難燃化方法としては、水酸化マグネシウムに代表される無機化合物、赤リンに代表される無機リン化合物、リン酸エステルやホスホン酸化合物およびホスフィン酸化合物などに例示されるリン化合物等が知られている。しかしながら、これらのハロゲンを含まない難燃剤をポリエステルに適用した場合、十分な難燃性を得るためには多量の添加量を必要とすることから、ポリエステルフィルムが本来有する耐熱性や機械特性などが低下することが指摘されており、また、これら難燃剤が原因となって発生するガス成分が各種電気機器に影響を与える可能性もあることから、さらなる新しい難燃化方法が求められている。 Examples of the flame retardant method using a flame retardant containing no halogen include inorganic compounds typified by magnesium hydroxide, inorganic phosphorus compounds typified by red phosphorus, phosphate esters, phosphonic acid compounds, and phosphinic acid compounds. Phosphorus compounds and the like are known. However, when these flame retardants containing no halogen are applied to polyester, a large amount of addition is required to obtain sufficient flame retardancy. Since it is pointed out that the gas component generated due to these flame retardants may affect various electric devices, further new flame retardant methods are required.
例えば特開２００４−２４３７６０号公報には、ポリエステルフィルムの両面に特定の熱分解特性を有し、かつ１８０〜４５０℃における非可燃性ガス発生率が３〜４０％である樹脂層が積層された難燃性ポリエステルフィルムが提案されており、ポリエステルとしてポリエチレンテレフタレートが具体的に用いられている。該公報によれば、燃焼熱によって非可燃性ガスを発生させる化合物を配合して難燃性を高める発明であり、非可燃性ガスを発生する化合物として無機水酸化物および／またはトリアジン化合物が配合されている。しかしながらこのような化合物はポリエステルの熱分解が本格化する前に非可燃性ガスを発生させることでポリエステルの熱分解を抑制することから、用いるポリエステルの種類によっては加工温度域で非可燃性ガスが発生してしまい十分な製膜性が得られない場合がある。 For example, in Japanese Patent Application Laid-Open No. 2004-243760, a resin layer having specific thermal decomposition characteristics on both sides of a polyester film and having a nonflammable gas generation rate of 3 to 40% at 180 to 450 ° C. is laminated. Flame retardant polyester films have been proposed, and polyethylene terephthalate is specifically used as the polyester. According to the publication, it is an invention to increase the flame retardancy by compounding a compound that generates non-flammable gas by heat of combustion, and an inorganic hydroxide and / or triazine compound is blended as a compound that generates non-flammable gas. Has been. However, since such a compound suppresses the thermal decomposition of the polyester by generating a non-flammable gas before the thermal decomposition of the polyester becomes serious, depending on the type of polyester used, the non-flammable gas may be present in the processing temperature range. It may occur and sufficient film-forming property may not be obtained.
また特開２００４−２８５３３８号公報において、ポリエステルとポリイミドとを構成成分として含み、燃焼指数が１２５未満である単層または積層の二軸配向ポリエステルフィルムが提案されており、ポリエステルとして具体的にポリエチレンテレフタレートが用いられている。しかしながら、該公報に開示されるように単層または積層体の芯層としてポリエチレンテレフタレートとポリイミドとのブレンド物を用いた場合、２００℃近辺の高温条件下における寸法安定性が求められる用途には展開できないのが現状である。 Japanese Patent Application Laid-Open No. 2004-285338 proposes a monolayer or laminated biaxially oriented polyester film containing polyester and polyimide as constituent components and having a combustion index of less than 125. Specifically, the polyester may be polyethylene terephthalate. Is used. However, as disclosed in the publication, when a blend of polyethylene terephthalate and polyimide is used as the core layer of a single layer or a laminate, it is developed for applications that require dimensional stability under high temperature conditions around 200 ° C. The current situation is not possible.
本発明の目的は、上述の従来技術の課題を解決し、難燃性に優れ、２００℃近辺の高温下での耐熱寸法安定性及び製膜性が良好な難燃性ポリエステルフィルム及びその製造方法を提供することにある。本発明の他の目的は、難燃性に優れ、２００℃近辺の高温下での耐熱寸法安定性及び製膜性が良好な、比較的安価なフレキシブル回路基板の基材フィルムおよび太陽電池の基材フィルムを提供することにある。 The object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a flame-retardant polyester film excellent in flame retardancy and having good heat-resistant dimensional stability and film-forming property at a high temperature around 200 ° C. Is to provide. Another object of the present invention is to provide a relatively inexpensive base film for a flexible circuit board and a solar cell base, which are excellent in flame retardancy and have good heat-resistant dimensional stability and film-forming properties at high temperatures around 200 ° C. It is to provide a material film.
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、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層の両面に、ポリエチレンナフタレンジカルボキシレートおよびそれよりも高温側に変曲点を有する樹脂、すなわち熱分解開始温度がポリエチレンナフタレンジカルボキシレートよりも高い樹脂からなり、しかも７５０℃まで昇温した時の重量減少率が比較的小さく、残炭率が高い熱分解特性を有する樹脂層を積層させることによって、優れた難燃性を付与でき、しかも２００℃近辺の高温下での耐熱寸法安定性にも優れ、製膜性も良好であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have polyethylene naphthalene dicarboxylate and an inflection point on the higher temperature side than that on both sides of the layer mainly composed of polyethylene naphthalene dicarboxylate. Resin, that is, a resin layer having a thermal decomposition characteristic that is made of a resin having a higher thermal decomposition start temperature than polyethylene naphthalene dicarboxylate, has a relatively small weight loss rate when heated to 750 ° C., and has a high residual carbon ratio. By laminating, it has been found that excellent flame retardancy can be imparted, heat resistance dimensional stability at high temperatures around 200 ° C. is excellent, and film forming properties are also good, 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、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層Ａの両面に、下記（ａ）及び（ｂ）で表される特性
（ａ）ＴＧ曲線の４５０〜７５０℃の範囲に、ポリエチレンナフタレンジカルボキシレートに由来する変曲点（ａ１）、および（ａ１）よりも高温側に位置するポリエーテルイミドに由来の少なくとも１つの変曲点（ａ２）が存在し、
（ｂ）ＴＧ曲線の４０〜７５０℃の範囲における重量減少率が３０〜７０％
を同時に満たす、樹脂層Ｂの重量を基準としてポリエチレンナフタレンジカルボキシレートを２０〜６０重量％およびポリエーテルイミドを４０〜８０重量％含む樹脂層Ｂが積層されてなる難燃性ポリエステルフィルムによって達成される。
That is, according to the present invention, the object of the present invention is to provide on both sides of the layer A mainly composed of polyethylene naphthalene dicarboxylate, with the characteristics (a) represented by the following (a) and (b): In the range of 750 ° C., there exists an inflection point (a1) derived from polyethylene naphthalene dicarboxylate , and at least one inflection point (a2) derived from polyetherimide located on the higher temperature side than (a1). ,
(B) The weight loss rate in the range of 40 to 750 ° C. of the TG curve is 30 to 70%.
Is achieved by a flame retardant polyester film in which a resin layer B containing 20 to 60% by weight of polyethylene naphthalene dicarboxylate and 40 to 80% by weight of polyetherimide is laminated based on the weight of the resin layer B. The
また、本発明の二軸配向エステルフィルムは、その好ましい態様として、変曲点（ａ２）を有する樹脂がポリエーテルイミドであること、樹脂層Ｂの重量を基準としてポリエーテルイミドを４０〜８０重量％含むこと、樹脂層Ｂの合計厚みが１．５〜１０．０μｍであること、ポリエステルフィルム全層の厚みが５〜２００μｍであること、ポリエステルフィルム全層の厚みに対する樹脂層Ｂの合計厚みの割合が１０〜４０％の範囲内であること、樹脂層Ｂの１８０〜４５０℃における非可燃性ガス発生率が０．０１％以上３％未満であること、の少なくともいずれか一つを具備するものも包含する。
また本発明の難燃性ポリエステルフィルムは、フレキシブル回路基板の基材フィルムまたは太陽電池の基材フィルムのいずれかに用いられることを包含する。
Moreover, as for the biaxially oriented ester film of the present invention, as a preferred embodiment, the resin having the inflection point (a2) is a polyetherimide, and the polyetherimide is 40 to 80 weight based on the weight of the resin layer B. %, The total thickness of the resin layer B is 1.5 to 10.0 μm, the thickness of the entire polyester film layer is 5 to 200 μm, the total thickness of the resin layer B with respect to the thickness of the entire polyester film layer. It has at least any one of a ratio being in a range of 10 to 40% and a non-combustible gas generation rate at 180 to 450 ° C. of the resin layer B being 0.01% or more and less than 3%. Also included.
Moreover, the flame-retardant polyester film of this invention includes being used for either the base film of a flexible circuit board, or the base film of a solar cell.
さらに本発明は、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層Ａの両面に、下記の（ａ）及び（ｂ）で表される特性
（ａ）ＴＧ曲線の４５０〜７５０℃の範囲に、ポリエチレンナフタレンジカルボキシレートに由来する変曲点（ａ１）、および（ａ１）よりも高温側に位置するポリエーテルイミドに由来の少なくとも１つの変曲点（ａ２）が存在し、
（ｂ）ＴＧ曲線の４０〜７５０℃の範囲における重量減少率が３０〜７０％
を同時に満たす、樹脂層Ｂの重量を基準としてポリエチレンナフタレンジカルボキシレートを２０〜６０重量％およびポリエーテルイミドを４０〜８０重量％含む樹脂層Ｂが積層されてなる難燃性ポリエステルフィルムの製造方法であり、
層Ａを構成するポリエチレンナフタレンジカルボキシレートおよび層Ｂを構成する樹脂それぞれが共押出法により溶融状態でダイ内部で積層されてからシート状に押出された後、縦延伸倍率および横延伸倍率それぞれ２．５〜５．０倍の範囲で二軸延伸して得られる難燃性ポリエステルフィルムの製造方法も包含される。
Furthermore, the present invention relates to the properties represented by the following (a) and (b) (a) in the range of 450 to 750 ° C. of the TG curve on both sides of the layer A mainly composed of polyethylene naphthalene dicarboxylate. There is an inflection point (a1) derived from naphthalene dicarboxylate , and at least one inflection point (a2) derived from a polyetherimide located on the higher temperature side than (a1),
(B) The weight loss rate in the range of 40 to 750 ° C. of the TG curve is 30 to 70%.
Of flame retardant polyester film in which resin layer B containing 20 to 60% by weight of polyethylene naphthalene dicarboxylate and 40 to 80% by weight of polyetherimide is laminated based on the weight of resin layer B at the same time der is,
The polyethylene naphthalene dicarboxylate constituting layer A and the resin constituting layer B are each laminated in the die in a molten state by a coextrusion method and then extruded into a sheet, and then the longitudinal draw ratio and the transverse draw ratio are 2 respectively. Also included is a method for producing a flame retardant polyester film obtained by biaxial stretching in a range of 0.5 to 5.0 times.
本発明によれば、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層の両面に特定の熱分解特性を有する樹脂層を積層させることによって、優れた難燃性を付与でき、しかも２００℃近辺の高温下での耐熱寸法安定性にも優れ、製膜性も良好であることから、難燃性及び耐熱性が必要とされる各種用途に広く用いることができ、例えばフレキシブル回路基板の基材フィルムや太陽電池の基材フィルムとして有用である。 According to the present invention, excellent flame retardancy can be imparted by laminating a resin layer having specific thermal decomposition characteristics on both sides of a layer containing polyethylene naphthalene dicarboxylate as a main component, and high temperature around 200 ° C. Since it has excellent heat-resistant dimensional stability and good film-forming properties, it can be widely used in various applications that require flame retardancy and heat resistance. It is useful as a base film for solar cells.
以下、本発明を詳しく説明する。
＜ポリエチレンナフタレンジカルボキシレート層Ａ＞
本発明のフィルムの層Ａを構成するポリエチレンナフタレンジカルボキシレートは、主たるジカルボン酸成分としてナフタレンジカルボン酸が用いられ、主たるグリコール成分としてエチレングリコールが用いられる。ナフタレンジカルボン酸としては、たとえば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、１，５−ナフタレンジカルボン酸を挙げることができ、これらの中で２，６−ナフタレンジカルボン酸が好ましい。ここで「主たる」とは、層Ａを形成するポリマーの構成成分において全繰返し単位の少なくとも９０ｍｏｌ％、好ましくは少なくとも９５ｍｏｌ％を意味する。ポリエチレンナフタレートがコポリマーである場合、コポリマーを構成する共重合成分としては、例えば蓚酸、アジピン酸、フタル酸、セバシン酸、ドデカンジカルボン酸、イソフタル酸、テレフタル酸、１，４−シクロヘキサンジカルボン酸、４，４’−ジフェニルジカルボン酸、フェニルインダンジカルボン酸、２，７−ナフタレンジカルボン酸、テトラリンジカルボン酸、デカリンジカルボン酸、ジフェニルエーテルジカルボン酸等の如きジカルボン酸；ｐ−オキシ安息香酸、ｐ−オキシエトキシ安息香酸の如きオキシカルボン酸；或いはトリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、シクロヘキサンメチレングリコール、ネオペンチルグリコール、ビスフェノールスルホンのエチレンオキサイド付加物、ビスフェノールＡのエチレンオキサイド付加物、ジエチレングリコール、ポリエチレンオキシドグリコールの如きジオールを好ましく用いることができる。これらの共重合成分は、１種または２種以上用いてもよい。これらの共重合成分の中で、好ましい酸成分としては、イソフタル酸、テレフタル酸、４，４’−ジフェニルジカルボン酸、２，７−ナフタレンジカルボン酸、ｐ−オキシ安息香酸であり、好ましいジオール成分としては、トリメチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、ビスフェノールスルホンのエチレンオキサイド付加物である。
The present invention will be described in detail below.
<Polyethylene naphthalene dicarboxylate layer A>
In the polyethylene naphthalene dicarboxylate constituting the layer A of the film of the present invention, naphthalene dicarboxylic acid is used as the main dicarboxylic acid component, and ethylene glycol is used as the main glycol component. Examples of naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Among these, 2,6-naphthalenedicarboxylic acid is preferable. Here, “main” means at least 90 mol%, preferably at least 95 mol% of all repeating units in the constituent components of the polymer forming the layer A. When polyethylene naphthalate is a copolymer, examples of copolymer components constituting the copolymer include oxalic acid, adipic acid, phthalic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4 , 4′-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, tetralindicarboxylic acid, decalindicarboxylic acid, diphenyletherdicarboxylic acid and the like; p-oxybenzoic acid, p-oxyethoxybenzoic acid Or trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexane methylene glycol, neopentyl glycol, bisphenol sulfone with ethylene oxide Additives, bisphenol A ethylene oxide adducts, diols such as diethylene glycol and polyethylene oxide glycol can be preferably used. These copolymer components may be used alone or in combination of two or more. Among these copolymer components, preferred acid components are isophthalic acid, terephthalic acid, 4,4′-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-oxybenzoic acid, and preferred diol components. Is an ethylene oxide adduct of trimethylene glycol, hexamethylene glycol, neopentyl glycol, bisphenol sulfone.
ポリエチレンナフタレートがポリマーブレンドである場合、ブレンド成分としては、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリトリメチレンテレフタレート、ポリエチレン４，４’−テトラメチレンジフェニルジカルボキシレート、ポリエチレン−２，７−ナフタレンジカルボキシレート、ポリトリメチレン−２，６−ナフタレンジカルボキシレート、ポリネオペンチレン−２，６−ナフタレンジカルボキシレート、ポリ（ビス（４−エチレンオキシフェニル）スルホン）−２，６−ナフタレンジカルボキシレート等のポリエステルを挙げることができる。これらのブレンド成分は、１種または２種以上用いてもよい。 When polyethylene naphthalate is a polymer blend, the blend components include polyethylene terephthalate, polyethylene isophthalate, polytrimethylene terephthalate, polyethylene 4,4′-tetramethylene diphenyl dicarboxylate, polyethylene-2,7-naphthalene dicarboxylate , Polytrimethylene-2,6-naphthalene dicarboxylate, polyneopentylene-2,6-naphthalene dicarboxylate, poly (bis (4-ethyleneoxyphenyl) sulfone) -2,6-naphthalene dicarboxylate, etc. Can be mentioned. These blend components may be used alone or in combination of two or more.
また、本発明のポリエチレンナフタレンジカルボキシレートは、例えば安息香酸、メトキシポリアルキレングリコールなどの一官能性化合物によって末端の水酸基および／またはカルボキシル基の一部または全部を封鎖したものであってよく、極く少量の例えばグリセリン、ペンタエリスリトール等の如き三官能以上のエステル形成性化合物で実質的に線状のポリマーが得られる範囲内で共重合したものであってもよい。 Further, the polyethylene naphthalene dicarboxylate of the present invention may be one in which a terminal hydroxyl group and / or a carboxyl group is partially or entirely blocked with a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. It may be copolymerized with a small amount of a trifunctional or higher functional ester-forming compound such as glycerin or pentaerythritol within a range where a substantially linear polymer is obtained.
本発明のポリエチレンナフタレンジカルボキシレートは、従来公知の方法で、例えばジカルボン酸とグリコールの反応で直接低重合度ポリエステルを得る方法や、ジカルボン酸の低級アルキルエステルとグリコールとをエステル交換触媒を用いて反応させた後、重合触媒の存在下で重合反応を行う方法で得ることができる。 The polyethylene naphthalene dicarboxylate of the present invention is a conventionally known method, for example, a method of directly obtaining a low-polymerization degree polyester by reaction of dicarboxylic acid and glycol, or a transesterification catalyst of a lower alkyl ester of dicarboxylic acid and glycol. After the reaction, it can be obtained by a method of conducting a polymerization reaction in the presence of a polymerization catalyst.
本発明は、３層からなる難燃性ポリエステルフィルムの芯層である層Ａとしてポリエチレンナフタレンジカルボキシレートを用いることにより、２００℃近辺の高温条件下において良好な寸法安定性が得られ、また本発明の樹脂層Ｂとの共押出性および密着性を良好にすることが可能となる。 In the present invention, by using polyethylene naphthalene dicarboxylate as the layer A which is a core layer of a flame retardant polyester film consisting of three layers, good dimensional stability can be obtained under high temperature conditions around 200 ° C. Coextrudability and adhesion with the resin layer B of the invention can be improved.
＜樹脂層Ｂ＞
本発明のフィルムの層Ｂを構成する樹脂は、下記の（ａ）及び（ｂ）で表される特性
（ａ）ＴＧ曲線の４５０〜７５０℃の範囲に、ポリエチレンナフタレンジカルボキシレートに由来する変曲点（ａ１）および（ａ１）よりも高温側に位置する少なくとも１つの変曲点（ａ２）が存在し、
（ｂ）ＴＧ曲線の４０〜７５０℃の範囲における重量減少率が３０〜７０％
を同時に満たすことが必要である。
<Resin layer B>
The resin constituting layer B of the film of the present invention has a property derived from polyethylene naphthalene dicarboxylate within the range of 450 to 750 ° C. of the characteristics (a) TG curve represented by the following (a) and (b). There is at least one inflection point (a2) located on the higher temperature side than the inflection points (a1) and (a1),
(B) The weight loss rate in the range of 40 to 750 ° C. of the TG curve is 30 to 70%.
Must be satisfied at the same time.
樹脂層Ｂは、ポリエチレンナフタレンジカルボキシレートおよびそれよりも高温側に変曲点を有する樹脂、すなわち熱分解開始温度がポリエチレンナフタレンジカルボキシレートよりも高い樹脂からなり、しかも７５０℃まで昇温した時の重量減少率が比較的小さく、残炭率が高い熱分解特性を有することによって、３層からなる難燃性ポリエステルフィルムの両表面層を構成した場合に、燃焼時にチャー層（以下、炭化層と称することがある）が形成されて高い難燃性が得られ、また層Ａとの共押出性および密着性を良好にすることが可能となる。 The resin layer B is made of polyethylene naphthalene dicarboxylate and a resin having an inflection point on the higher temperature side, that is, a resin having a thermal decomposition start temperature higher than that of polyethylene naphthalene dicarboxylate, and when the temperature is raised to 750 ° C. When both surface layers of the flame retardant polyester film composed of three layers are formed by having a relatively small weight reduction rate and a high residual carbon rate, the char layer (hereinafter referred to as carbonized layer) during combustion. High flame retardancy can be obtained, and coextrudability and adhesion with the layer A can be improved.
樹脂層Ｂが、ＴＧ曲線の４５０〜７５０℃の範囲においてポリエチレンナフタレンジカルボキシレートに由来する変曲点（ａ１）を含まない場合、層Ａとの共押出性が乏しくなる。また、ポリエステルとしてポリエチレンナフタレンジカルボキシレート以外のポリエステル、例えばポリエチレンテレフタレートを用いた場合、変曲点（ａ２）を有する樹脂との融点差や熱分解開始温度差が大きいために、押出工程で粘度ムラがあり、また加工温度によってはポリエチレンテレフタレートが熱分解し、所望の配合比でブレンドすることが難しくなる。
また樹脂層Ｂが、ＴＧ曲線の４５０〜７５０℃の範囲において変曲点（ａ２）を含まない場合、難燃性ポリエステルフィルムの難燃性が不足する。また樹脂層Ｂが、ＴＧ曲線の４０〜７５０℃の範囲において３０％未満の重量減少率の場合、変曲点（ａ２）を有する樹脂の割合が高すぎるために層Ａとの共押出性が低下する。一方、かかる重量減少率が７０％を越える場合、燃焼時にチャー層が形成されないため高い難燃性が得られない。このように、本発明の難燃ポリエステルフィルムの難燃機構は、燃焼時にチャー層を形成しやすい樹脂層Ｂを両表面に積層することで、ポリエチレンナフタレンジカルボキシレート以外の樹脂の配合量が少なくても効率的に難燃性を高め、ポリエチレンナフタレンジカルボキシレートが本来有する機械的特性や耐熱寸法安定性の低下が少ない点に特徴を有するものである。
When the resin layer B does not contain the inflection point (a1) derived from polyethylene naphthalene dicarboxylate in the range of 450 to 750 ° C. of the TG curve, the coextrudability with the layer A becomes poor. In addition, when a polyester other than polyethylene naphthalene dicarboxylate, such as polyethylene terephthalate, is used as the polyester, there is a large difference in melting point and thermal decomposition starting temperature with the resin having the inflection point (a2). Depending on the processing temperature, polyethylene terephthalate is thermally decomposed, making it difficult to blend at a desired blending ratio.
Moreover, when the resin layer B does not contain an inflection point (a2) in the range of 450 to 750 ° C. of the TG curve, the flame retardancy of the flame retardant polyester film is insufficient. Further, when the resin layer B has a weight reduction rate of less than 30% in the range of 40 to 750 ° C. of the TG curve, the ratio of the resin having the inflection point (a2) is too high, and thus the coextrudability with the layer A is high. descend. On the other hand, when the weight reduction rate exceeds 70%, a char layer is not formed during combustion, so that high flame retardancy cannot be obtained. Thus, the flame retardant mechanism of the flame retardant polyester film of the present invention has a small amount of resin other than polyethylene naphthalene dicarboxylate by laminating the resin layer B that easily forms a char layer on combustion on both surfaces. However, it is characterized in that the flame retardancy is efficiently increased and the mechanical properties inherent to polyethylene naphthalene dicarboxylate and the reduction in heat-resistant dimensional stability are small.
なお、これらのＴＧ曲線特性は、熱重量分析（ＴＧ）装置を用い、サンプル重量１０ｍｇを昇温速度２０℃／分の条件で窒素流量２００ｍｌ／分の雰囲気下で測定し、温度変化に対するサンプルの重量減少を測定したものである。変曲点は、ＴＧ曲線を２次微分した曲線が０になるところを変曲点として求めたものである。また、重量減少率は加熱前の重量を１００％とした時の減少割合を表す。上記測定方法において、変曲点（ａ１）および変曲点（ａ２）は、それぞれＴＧ曲線の４５０〜７５０℃の範囲に存在し、かつ変曲点（ａ２）が変曲点（ａ１）よりも高温側に位置することが必要である。好ましくは、ポリエチレンナフタレンジカルボキシレートに由来する変曲点（ａ１）は４５０℃〜５００℃の範囲に存在し、また変曲点（ａ２）は５００℃〜７５０℃の範囲に存在する。変曲点（ａ２）は、５５０℃〜７００℃の範囲に存在することがより好ましい。 These TG curve characteristics were measured using a thermogravimetric analysis (TG) apparatus, and a sample weight of 10 mg was measured in a nitrogen flow rate of 200 ml / min at a temperature rising rate of 20 ° C./min. The weight loss is measured. The inflection point is obtained as an inflection point where the curve obtained by second-order differentiation of the TG curve becomes zero. The weight reduction rate represents the rate of reduction when the weight before heating is 100%. In the measurement method, the inflection point (a1) and the inflection point (a2) exist in the range of 450 to 750 ° C. of the TG curve, respectively, and the inflection point (a2) is more than the inflection point (a1). It must be located on the high temperature side. Preferably, the inflection point (a1) derived from polyethylene naphthalene dicarboxylate is in the range of 450 ° C to 500 ° C, and the inflection point (a2) is in the range of 500 ° C to 750 ° C. The inflection point (a2) is more preferably in the range of 550 ° C to 700 ° C.
樹脂層Ｂに含まれるポリエチレンナフタレンジカルボキシレートは、層Ａを構成するポリエチレンナフタレンジカルボキシレートに準ずる。ポリエステルとしてポリエチレンナフタレンジカルボキシレートを用いることにより、ポリエステルが熱分解することなく所望の配合比で変曲点（ａ２）を有する樹脂とのブレンドが可能になる。
変曲点（ａ２）を有する樹脂は、変曲点がＴＧ曲線の４５０〜７５０℃の範囲にあり、かつ変曲点（ａ１）よりも高温側に位置し、ポリエチレンナフタレンジカルボキシレートと配合して樹脂層（Ｂ）を形成した時に（ｂ）ＴＧ曲線の４０〜７５０℃の範囲における重量減少率が３０〜７０％、を満たすものであれば特に限定されないが、例えばポリエーテルイミドを用いることができる。変曲点（ａ２）を有する樹脂は１種または２種以上用いてもよい。かかるポリエーテルイミドとして、下記一般式（Ｉ）で表される繰り返し単位からなるものが挙げられる。
The polyethylene naphthalene dicarboxylate contained in the resin layer B conforms to the polyethylene naphthalene dicarboxylate constituting the layer A. By using polyethylene naphthalene dicarboxylate as the polyester, the polyester can be blended with a resin having an inflection point (a2) at a desired blending ratio without thermal decomposition.
The resin having the inflection point (a2) has an inflection point in the range of 450 to 750 ° C. of the TG curve and is located on the higher temperature side than the inflection point (a1), and is blended with polyethylene naphthalene dicarboxylate. When the resin layer (B) is formed, there is no particular limitation as long as the weight reduction rate in the range of 40 to 750 ° C. of the (b) TG curve satisfies 30 to 70%. For example, polyetherimide is used. Can do. You may use 1 type (s) or 2 or more types of resin which has an inflexion point (a2). Examples of the polyetherimide include those composed of repeating units represented by the following general formula (I).
これらの中でも特に好ましいポリエーテルイミドとして下記式（II）または下記式（III）で表される繰り返し単位からなるポリイミドが挙げられる。
樹脂層Ｂは、変曲点（ａ２）を有する樹脂としてポリエーテルイミドを用いた場合、樹脂層Ｂの重量を基準としてポリエチレンナフタレンジカルボキシレートが２０〜６０重量％、ポリエーテルイミドが４０〜８０重量％の範囲でそれぞれ配合されることが好ましい。樹脂層Ｂに含まれるポリエーテルイミドの比率が高ければ高いほど、フィルム両表面でのポリエーテルイミド比率が高くなり、より高い難燃性が得られる。一方、ポリエーテルイミドが上限を超える場合、延伸工程において破断が生じたり、層Ａとの共押出性および密着性が低下することがある。 When the resin layer B uses polyetherimide as the resin having the inflection point (a2), the polyethylene naphthalene dicarboxylate is 20 to 60% by weight and the polyetherimide is 40 to 80 based on the weight of the resin layer B. It is preferable to blend each in the range of% by weight. The higher the ratio of polyetherimide contained in the resin layer B, the higher the ratio of polyetherimide on both surfaces of the film, and higher flame retardancy can be obtained. On the other hand, when the polyetherimide exceeds the upper limit, breakage may occur in the stretching step, and coextrudability and adhesion with the layer A may be reduced.
本発明の難燃機構は、樹脂層Ｂが燃焼して形成されるチャー層が、燃焼過程で樹脂の熱分解ガスを気層に拡散するのを遮断することで発現されるものであり、樹脂層Ｂを燃焼させた際の非可燃性ガスの発生率は極めて低い。具体的には樹脂層Ｂの１８０〜４５０℃における非可燃性ガス発生率は０．０１％以上３％未満である。本発明は、非可燃性ガスを発生する化合物を樹脂層Ｂに含まないことがさらに好ましい。本発明における非可燃性ガス発生率とは、下記式（１）により定義される。
Ｗ1／Ｗ0×１００（％） ・・・（１）
（式中、Ｗ0は樹脂層Ｂの重量、Ｗ１は樹脂層を一定の昇温速度で昇温した場合に発生するガスのうち、１８０〜４５０℃の温度範囲で発生した非可燃性ガスの重量をそれぞれ示す）
The flame retardant mechanism of the present invention is manifested by blocking the diffusion of the pyrolysis gas of the resin into the gas layer during the combustion process of the char layer formed by burning the resin layer B. The generation rate of non-flammable gas when the layer B is burned is extremely low. Specifically, the nonflammable gas generation rate at 180 to 450 ° C. of the resin layer B is 0.01% or more and less than 3%. In the present invention, it is more preferable that the resin layer B does not contain a compound that generates a non-flammable gas. The non-combustible gas generation rate in the present invention is defined by the following formula (1).
W 1 / W 0 × 100 (%) (1)
(W 0 is the weight of the resin layer B, and W 1 is a non-combustible gas generated in the temperature range of 180 to 450 ° C. among the gases generated when the resin layer is heated at a constant heating rate. The weight of each)
非可燃性ガスを発生する化合物の代表例である無機水酸化物またはトリアジン系化合物を樹脂層Ｂに含めた場合、無機水酸化物によってポリエステルが分解することがあり、またトリアジン系化合物の熱分解開始温度が樹脂層Ｂに較べて低いために十分な難燃性が得られないばかりでなく、２００℃近辺の高温下でフィルムを使用する場合に非可燃性ガスが発生し、使用用途によっては好ましくないことがある。 When an inorganic hydroxide or a triazine compound, which is a representative example of a compound that generates a nonflammable gas, is included in the resin layer B, the polyester may be decomposed by the inorganic hydroxide, and the thermal decomposition of the triazine compound. Not only does the starting temperature be lower than that of the resin layer B, but sufficient flame retardancy is not obtained, and non-flammable gas is generated when the film is used at a high temperature around 200 ° C. It may not be preferable.
＜難燃性ポリエステルフィルム＞
本発明の難燃性ポリエステルフィルムは、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層Ａの両面に、樹脂層Ｂが積層される構成であることを必要とする。
本発明の難燃性ポリエステルフィルムにおいて、樹脂層Ｂの合計厚みは１．５〜１０．０μｍであることが好ましく、またポリエステルフィルム全層の厚みは５〜２００μｍであることが好ましい。さらに、ポリエステルフィルム全層の厚みに対する樹脂層Ｂの合計厚みの割合は１０〜４０％の範囲内であることが好ましい。
ポリエチレンナフタレンジカルボキシレートが本来有する耐熱寸法安定性および機械特性を維持するためには、上記の範囲内で樹脂層Ｂのフィルム厚みを薄肉化し、ポリエステルフィルム全層の厚みに対する樹脂層Ｂの合計厚みの割合を小さくする方向が好ましい。一方ポリエステルフィルム全層の厚みに対する樹脂層Ｂの合計厚みの割合が下限に満たない場合は十分な難燃性が得られないことがある。
また、ポリエステルフィルム全層の厚みが下限に満たない場合は、フィルムの絶縁性能が不足することがある。一方、フィルム全層の厚みが上限を超える場合、フィルムの耐屈曲性が不足することがあり、外力を加えられた場合、基板フィルムに割れが発生したり折れた状態のまま戻らなくなることがある。
<Flame retardant polyester film>
The flame-retardant polyester film of the present invention needs to have a structure in which the resin layer B is laminated on both surfaces of the layer A containing polyethylene naphthalene dicarboxylate as a main component.
In the flame-retardant polyester film of the present invention, the total thickness of the resin layer B is preferably 1.5 to 10.0 μm, and the thickness of the entire polyester film layer is preferably 5 to 200 μm. Furthermore, it is preferable that the ratio of the total thickness of the resin layer B with respect to the thickness of all the layers of a polyester film exists in the range of 10 to 40%.
In order to maintain the heat-resistant dimensional stability and mechanical properties inherent in polyethylene naphthalene dicarboxylate, the thickness of the resin layer B is reduced within the above range, and the total thickness of the resin layer B with respect to the total thickness of the polyester film. The direction in which the ratio is reduced is preferable. On the other hand, when the ratio of the total thickness of the resin layer B to the total thickness of the polyester film is less than the lower limit, sufficient flame retardancy may not be obtained.
Moreover, when the thickness of all the layers of a polyester film is less than a minimum, the insulation performance of a film may be insufficient. On the other hand, if the total thickness of the film exceeds the upper limit, the film may have insufficient bending resistance, and if an external force is applied, the substrate film may be cracked or may not return in a broken state. .
本発明の難燃性ポリエステルフィルムは、固有粘度が０．４７〜０．９０ｄｌ／ｇであることが好ましく、さらに好ましくは０．５０〜０．８０ｄｌ／ｇである。固有粘度が下限に満たない場合、フィルムが脆くなることがあり、例えばフィルムを所定の大きさに裁断したり、回路部品実装のための固定用の穴を穿孔する時に端面にバリが発生することがある。また、フィルムの固有粘度が上限を超える場合、通常の合成手法では重合に長時間を要し生産性が悪くなることがある。また特別な重合方法（固相重合等）を行うためには専用の設備が必要となるため生産コストが高くなることがある。 The flame-retardant polyester film of the present invention preferably has an intrinsic viscosity of 0.47 to 0.90 dl / g, more preferably 0.50 to 0.80 dl / g. If the intrinsic viscosity is less than the lower limit, the film may become brittle. For example, when the film is cut into a predetermined size or when a fixing hole for mounting circuit components is drilled, burrs will occur on the end face. There is. Moreover, when the intrinsic viscosity of a film exceeds an upper limit, a normal synthesis method may require a long time for polymerization, and productivity may be deteriorated. Moreover, in order to perform a special polymerization method (solid phase polymerization etc.), a dedicated facility is required, so that the production cost may increase.
＜添加剤＞
本発明の難燃性ポリエステルフィルムには、課題を損なわない範囲において、各層に添加剤、例えば安定剤、滑剤等を含有させることができる。
フィルムに滑り性を付与するためには、不活性粒子を少割合含有させることが好ましい。かかる不活性粒子としては、例えば球状シリカ、多孔質シリカ、炭酸カルシウム、アルミナ、二酸化チタン、カオリンクレー、硫酸バリウム、ゼオライトの如き無機粒子、或いはシリコン樹脂粒子、架橋ポリスチレン粒子の如き有機粒子を挙げることができる。無機粒子は粒径が均一であること等の理由で、天然品よりも合成品であることが好ましく、あらゆる結晶形態、硬度、比重、色の無機粒子を使用することができる。
<Additives>
In the flame-retardant polyester film of the present invention, additives such as a stabilizer and a lubricant can be contained in each layer as long as the problem is not impaired.
In order to impart slipperiness to the film, it is preferable to contain a small amount of inert particles. Examples of the inert particles include inorganic particles such as spherical silica, porous silica, calcium carbonate, alumina, titanium dioxide, kaolin clay, barium sulfate and zeolite, or organic particles such as silicon resin particles and crosslinked polystyrene particles. Can do. The inorganic particles are preferably a synthetic product rather than a natural product because the particle size is uniform, and inorganic particles having any crystal form, hardness, specific gravity, and color can be used.
かかる不活性粒子の平均粒径は０．０５〜５．０μｍの範囲であることが好ましく、０．１〜３．０μｍであることがさらに好ましい。また、不活性粒子の含有量は０．００１〜１．０重量％であることが好ましく、０．０３〜０．５重量％であることがさらに好ましい。フィルムに添加する不活性粒子は、上記に例示した中から選ばれた単一成分でもよく、あるいは二成分以上を含む多成分でもよい。
不活性粒子の添加時期は、製膜する迄の段階であれば特に制限はなく、例えば重合段階で添加してもよく、また製膜の際に添加してもよい。
The average particle size of the inert particles is preferably in the range of 0.05 to 5.0 μm, more preferably 0.1 to 3.0 μm. Further, the content of the inert particles is preferably 0.001 to 1.0% by weight, and more preferably 0.03 to 0.5% by weight. The inert particles added to the film may be a single component selected from those exemplified above, or may be a multi-component containing two or more components.
There is no particular limitation on the addition timing of the inert particles as long as it is a stage until film formation. For example, the inert particles may be added at the polymerization stage, or may be added at the time of film formation.
＜熱収縮率＞
本発明の難燃性ポリエステルフィルムは、２００℃の温度で１０分間加熱処理したときの熱収縮率がフィルムの長手方向（ＭＤ）、幅方向（ＴＤ）共それぞれ１．５％以下であり、好ましくはＭＤ、ＴＤ共それぞれ１．０％以下である。２００℃の温度で１０分間加熱処理したときの熱収縮率が１．５％を超えると、例えばフレキシブル基板として用いた場合に金属箔を貼りあわせた後のキュアリング時のフィルムの寸法変化や印刷後の乾燥処理でのフィルムの寸法変化が大きくなるため、回路基板に反りが発生することがある。なおフィルムの長手方向は、フィルム連続製膜方法、縦方向、ＭＤ方向と称することがあり、本発明においてはポリマーの主たる配向軸が観察される方向を表す。またフィルムの幅方向は、横方向、ＴＤ方向と称することがあり、発明においては主たる配向軸に直交する方向を表す。主たる配向軸は、フィルム面内の屈折率の分布を測定し、最も屈折率の高い方向により求められる。
<Heat shrinkage>
The flame-retardant polyester film of the present invention has a heat shrinkage rate of not more than 1.5% in each of the longitudinal direction (MD) and the width direction (TD) when heated at 200 ° C. for 10 minutes. Is 1.0% or less for both MD and TD. When the heat shrinkage rate when heated at 200 ° C. for 10 minutes exceeds 1.5%, for example, when used as a flexible substrate, dimensional change or printing of the film during curing after bonding metal foil Since the dimensional change of the film in the subsequent drying process becomes large, the circuit board may be warped. In addition, the longitudinal direction of a film may be called the film continuous film forming method, the longitudinal direction, and MD direction, and represents the direction where the main orientation axis of a polymer is observed in this invention. Moreover, the width direction of a film may be called a horizontal direction and a TD direction, and represents the direction orthogonal to the main orientation axis in this invention. The main orientation axis is obtained from the direction having the highest refractive index by measuring the refractive index distribution in the film plane.
＜製膜方法＞
本発明の難燃性ポリエステルフィルムは、層Ａを構成するポリエチレンナフタレンジカルボキシレートおよび層Ｂを構成する樹脂それぞれを共押出法により溶融状態でダイ内部で積層してからシート状に押出した後、テンター法、インフレーション法など公知の製膜方法を用いて製造することができる。
<Film forming method>
The flame-retardant polyester film of the present invention is formed by laminating the polyethylene naphthalene dicarboxylate constituting the layer A and the resin constituting the layer B in a molten state in a molten state by a coextrusion method, and then extruding the sheet. It can be manufactured using a known film forming method such as a tenter method or an inflation method.
具体的には、層Ａ用に調整したポリエチレンナフタレンジカルボキシレートを乾燥後、（Ｔｍａ）〜（Ｔｍａ＋７０）℃（ＴｍａはＰＥＮ樹脂の融点）の温度範囲内で溶融する。同時に、樹脂層Ｂ用に調整した樹脂組成物を乾燥し、（Ｔｍｂ）〜（Ｔｍｂ＋７０）℃（Ｔｍｂは樹脂組成物の融点）の温度範囲内で溶融する。続いて、両方の溶融樹脂をダイ内部で層Ｂ／層Ａ／層Ｂとなるように積層する方法、例えばマルチマニホールドダイを用いた共押出法（以下、同時積層押出法と称することがある）により、積層された未延伸フィルムが製造される。かかる共押出法によると、Ａ層を形成する樹脂の溶融物とＢ層を形成する樹脂の溶融物はダイ内部で交互に積層され、積層形態を維持した状態でダイよりシート状に成形される。 Specifically, after the polyethylene naphthalene dicarboxylate prepared for the layer A is dried, it is melted within a temperature range of (Tma) to (Tma + 70) ° C. (Tma is the melting point of the PEN resin). At the same time, the resin composition prepared for the resin layer B is dried and melted within a temperature range of (Tmb) to (Tmb + 70) ° C. (Tmb is the melting point of the resin composition). Subsequently, a method of laminating both molten resins so as to be layer B / layer A / layer B inside the die, for example, a co-extrusion method using a multi-manifold die (hereinafter sometimes referred to as a simultaneous lamination extrusion method) Thus, a laminated unstretched film is produced. According to this co-extrusion method, the melt of the resin forming the A layer and the melt of the resin forming the B layer are alternately laminated inside the die, and are formed into a sheet shape from the die while maintaining the laminated form. .
このようにして得られたシート状物を、キャスティングドラムで冷却固化させて未延伸フィルムとし、さらに該未延伸フィルムを一軸方向（縦方向または横方向）に（Ｔｇ-１０）〜（Ｔｇ＋７０）℃（ＴｇはＰＥＮ樹脂のガラス転移点）の温度で所定の倍率に延伸し、次いで上記延伸方向と直角方向（一段目が縦方向の場合には二段目は横方向となる）にＴｇ〜（Ｔｇ＋７０）℃の温度で所定の倍率に延伸し、必要に応じてさらに熱処理する方法を用いて製造することができる。縦延伸倍率は２．５倍以上５．０倍以下、好ましくは２．８倍以上４．０倍以下である。また、横延伸倍率は２．５倍以上５．０倍以下、好ましくは２．８倍以上４．０倍以下である。縦、横方向それぞれの延伸倍率が下限に満たない場合、十分な機械特性および耐熱寸法安定性が得られないことがある他、フィルムの厚み斑が悪くなり良好なフィルムが得られないことがある。一方上限を超える場合は製膜中に破断が発生しやすくなる。また面積延伸倍率は６〜３５倍が好ましく、より好ましくは６〜２５倍、さらには７〜１６倍にするのが好ましい。 The sheet-like material thus obtained is cooled and solidified with a casting drum to form an unstretched film, and the unstretched film is further uniaxially (longitudinal or transverse) (Tg-10) to (Tg + 70) ° C. (Tg is the glass transition point of the PEN resin) is stretched at a predetermined magnification, and then Tg to (in the case where the first stage is the longitudinal direction, the second stage is the transverse direction) in the direction perpendicular to the stretching direction ( It can be produced by a method of stretching at a predetermined magnification at a temperature of Tg + 70) ° C. and further heat-treating as necessary. The longitudinal draw ratio is 2.5 times or more and 5.0 times or less, preferably 2.8 times or more and 4.0 times or less. Further, the transverse draw ratio is 2.5 times or more and 5.0 times or less, preferably 2.8 times or more and 4.0 times or less. When the draw ratios in the longitudinal and transverse directions are less than the lower limit, sufficient mechanical properties and heat-resistant dimensional stability may not be obtained, and a good film may not be obtained due to poor film thickness unevenness. . On the other hand, if the upper limit is exceeded, breakage tends to occur during film formation. The area stretch ratio is preferably 6 to 35 times, more preferably 6 to 25 times, and even more preferably 7 to 16 times.
熱固定温度は１９０〜２５０℃の範囲内、また処理時間は１〜６０秒の範囲内であることが好ましい。特に、耐熱性が必要とされる場合、高温条件下での寸法安定性を向上させるために、２１０〜２４０℃の範囲で熱固定を行うことが好ましい。このような熱固定処理を行うことによって、得られた二軸配向フィルムの２００℃における熱収縮率をより小さくすることができる。また熱収縮を抑えるために、さらにオフライン工程において１５０〜２２０℃で１〜６０秒間熱処理した後、５０〜８０℃の温度雰囲気下で徐冷するアニール処理を施しても構わない。 The heat setting temperature is preferably in the range of 190 to 250 ° C., and the treatment time is preferably in the range of 1 to 60 seconds. In particular, when heat resistance is required, it is preferable to perform heat setting in the range of 210 to 240 ° C. in order to improve dimensional stability under high temperature conditions. By performing such a heat setting treatment, the thermal contraction rate at 200 ° C. of the obtained biaxially oriented film can be further reduced. Further, in order to suppress thermal shrinkage, an annealing process may be performed in which the heat treatment is performed at 150 to 220 ° C. for 1 to 60 seconds in the off-line process and then gradually cooled in a temperature atmosphere of 50 to 80 ° C.
かかる逐次二軸延伸法のほかに、同時二軸延伸法を用いることもできる。また逐次二軸延伸法において縦方向、横方向の延伸回数は１回に限られるものではなく、縦-横延伸を数回の延伸処理により行うことができ、その回数に限定されるものではない。 In addition to the sequential biaxial stretching method, a simultaneous biaxial stretching method can also be used. In the sequential biaxial stretching method, the number of stretching in the machine direction and the transverse direction is not limited to one, but the longitudinal-lateral stretching can be performed by several stretching processes, and the number of stretching is not limited thereto. .
本発明の難燃性ポリエステルフィルムは、層Ａ、層Ｂを構成する樹脂として既述の樹脂をそれぞれ用いることにより、溶融時の粘度ムラが小さいことから、それぞれの樹脂層を溶融状態で共押出法により製造することができ、しかも縦、横方向に、２．５倍以上５．０倍以下の範囲内で延伸が可能であることから、機械特性および耐熱寸法安定性に優れる難燃性ポリエステルフィルムが得られるものである。 Since the flame-retardant polyester film of the present invention uses the above-described resins as the resins constituting the layers A and B, the viscosity unevenness at the time of melting is small, so each resin layer is coextruded in a molten state. The flame-retardant polyester is excellent in mechanical properties and heat-resistant dimensional stability because it can be produced within a range of 2.5 to 5.0 times in the vertical and horizontal directions. A film is obtained.
＜用途＞
本発明によれば、本発明の難燃性ポリエステルフィルムは、高い難燃性を有し、しかも耐熱寸法安定性に優れることから、難燃性及び耐熱性が必要とされる各種用途に広く用いることができる。例えばフレキシブル回路基板用フィルムや太陽電池用基板用フィルムとして有用である。
<Application>
According to the present invention, the flame-retardant polyester film of the present invention has high flame retardancy and is excellent in heat-resistant dimensional stability, so that it is widely used in various applications where flame retardancy and heat resistance are required. be able to. For example, it is useful as a film for a flexible circuit board or a film for a solar cell substrate.
フレキシブル回路基板用フィルムとして用いる場合、難燃性ポリエステルフィルムの片面または両面に、金属箔を積層させることが好ましい。金属箔としては銅箔が例示される。金属箔の接合手段や形状の具体的手段としては特に制限はなく、例えば金属箔を難燃性ポリエステルフィルムに貼り合せた後、金属箔をパターンエッチングするいわゆるサブトラクティブ法、難燃性ポリエステルフィルム上に銅などをパターン状にメッキするアディティブ法、パターン状に打ち抜いた金属箔を難燃性ポリエステルフィルムに貼り合せるスタンピングホイルなどを利用することができる。 When used as a film for a flexible circuit board, it is preferable to laminate a metal foil on one or both sides of the flame retardant polyester film. An example of the metal foil is a copper foil. There are no particular restrictions on the means for joining and shape of the metal foil. For example, the so-called subtractive method in which the metal foil is bonded to the flame retardant polyester film and then the metal foil is subjected to pattern etching. For example, an additive method of plating copper or the like in a pattern, or a stamping foil in which a metal foil punched in a pattern is bonded to a flame-retardant polyester film can be used.
以下、実施例により本発明を詳述するが、本発明はこれらの実施例のみに限定されるものではない。なお、各特性値は以下の方法で測定した。また、実施例中の部および％は、特に断らない限り、それぞれ重量部および重量％を意味する。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited only to these Examples. Each characteristic value was measured by the following method. Moreover, unless otherwise indicated, the part and% in an Example mean a weight part and weight%, respectively.
（１）固有粘度
サンプルの固有粘度（［η］ｄｌ／ｇ）を、３５℃のｏ−クロロフェノール溶液で測定した。
(1) Intrinsic viscosity The intrinsic viscosity ([η] dl / g) of the sample was measured with an o-chlorophenol solution at 35 ° C.
（２）エチレンナフタレンジカルボキシレートの割合
フィルムの表層部分を採取したサンプルを用い、測定溶媒（ＣＤＣｌ３：ＣＦ３ＣＯＯＤ＝１：１）に溶解後、１Ｈ−ＮＭＲ測定を行い、得られた各シグナルの積分比をもって算出する。ブレンドからなる層が芯層に存在する場合は、表層を削り取った後の芯層のサンプルを用いて測定を行った。
(2) Ratio of ethylene naphthalene dicarboxylate Using a sample obtained by collecting the surface layer portion of the film, the sample was dissolved in a measurement solvent (CDCl 3 : CF 3 COOD = 1: 1), and then 1 H-NMR measurement was performed. Calculate with the integral ratio of each signal. When a layer composed of a blend was present in the core layer, the measurement was performed using a sample of the core layer after the surface layer was scraped.
（３）ＴＧ曲線測定
フィルムの表層部分を採取したサンプルを用い、セイコーインスツルメント製の熱重量分析装置ＳＳＣ５２００を用いて、サンプル重量１０ｍｇ、昇温速度２０℃/分の条件で窒素流量２００ｍｌ/分の雰囲気下でサンプル重量減量を測定した。変曲点については、図１に示すように、ＴＧ曲線を２次微分した曲線が０になるところを変曲点とした。また、重量減少率は加熱前の重量を１００％としたときの減少割合から算出した。
(3) TG curve measurement Using a sample from which the surface layer portion of the film was collected, using a thermogravimetric analyzer SSC5200 manufactured by Seiko Instruments Inc., a nitrogen flow rate of 200 ml / min under the conditions of a sample weight of 10 mg and a heating rate of 20 ° C / min. The weight loss of the sample was measured under an atmosphere of minutes. As for the inflection point, as shown in FIG. 1, the inflection point is a point where the curve obtained by second-order differentiation of the TG curve becomes zero. The weight reduction rate was calculated from the reduction rate when the weight before heating was 100%.
（４）フィルム厚み
アンリツ製打点式厚み計を用いて、打点法での厚み測定を行った。
(4) Film thickness Using an Anritsu dot-type thickness meter, the thickness was measured by the dot method.
（５）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２００℃の温度のオーブンで１０分間熱処理を実施し、熱処理後の標点間隔を測定して、フィルム連続製膜方向（ＭＤ方向）と、製膜方向に垂直な方向（ＴＤ方向）において、それぞれ下記式（２）にて熱収縮率を算出した。
熱収縮率（％）＝（（Ｌ０−Ｌ）／Ｌ０）×１００ ・・・（２）
（式中、Ｌ０は熱処理前の標点間距離、Ｌは熱処理後の標点間距離をそれぞれ示す。）
(5) Heat shrinkage rate Marks are applied to film samples at intervals of 30 cm, heat treatment is carried out for 10 minutes in an oven at a temperature of 200 ° C. without applying a load, and the intervals between the marks after heat treatment are measured. In the film direction (MD direction) and the direction perpendicular to the film forming direction (TD direction), the thermal contraction rate was calculated by the following formula (2).
Thermal contraction rate (%) = ((L 0 −L) / L 0 ) × 100 (2)
(In the formula, L 0 represents the distance between the gauge points before the heat treatment, and L represents the distance between the gauge points after the heat treatment.)
（６）平面安定性
フィルムサンプルと銅箔とを、汎用塩化ビニル系樹脂と可塑剤とからなる接着剤により貼り合わせて、温度１６０℃、圧力３０ｋｇ／ｃｍ２、時間３０分の条件で圧着ロールを用いて圧着した。試料寸法を２５ｃｍ×２５ｃｍとし、相対湿度８５％、６５℃の雰囲気下で１００時間定盤上に置いた状態で４隅のカール状態を観測した。４隅の反り量（ｍｍ）の平均を測定した。下記の基準に従って評価を行った。○が合格である。
○；１０ｍｍ未満の反り量
×；１０ｍｍ以上の反り量
(6) Plane stability A film sample and a copper foil are bonded together with an adhesive composed of a general-purpose vinyl chloride resin and a plasticizer, and a pressure-bonding roll under conditions of a temperature of 160 ° C., a pressure of 30 kg / cm 2 , and a time of 30 minutes. Crimped using The sample size was 25 cm × 25 cm, and the curled state at the four corners was observed in a state where the sample was placed on a surface plate for 100 hours in an atmosphere of 85% relative humidity and 65 ° C. The average of the amount of warping (mm) at the four corners was measured. Evaluation was performed according to the following criteria. ○ is a pass.
○: Warpage amount less than 10 mm ×: Warpage amount of 10 mm or more
（７）難燃性
フィルムサンプルを幅１２．７ｍｍ、長さ１２７ｍｍの短冊状に切り出して、長手方向が地面と垂直になるようにして、長手方向の上端を把持し、下端を約２０ｍｍの火炎に５秒間さらした後、離炎した。このときの離炎後のフィルムの燃焼時間を測定した。（１回目の接炎時の燃焼時間）。次にフィルムが燃え尽きずに消火された場合、消火後に１回目と同様にして２回目の接炎・離炎を行い、離炎後のフィルムの燃焼時間を測定した。（２回目接炎時の燃焼時間）難燃性は、１回目、２回目接炎時の燃焼時間の合計を次の４段階で評価した。
◎：３０秒未満で自己消火する
○：３０〜５０秒で自己消火する
△：５０秒以内にドリップして自己消火する
×：５０秒以内に自己消火しないか、または燃え尽きる
(7) Flame retardance A film sample is cut into a strip of width 12.7 mm and length 127 mm, the longitudinal direction is perpendicular to the ground, the upper end of the longitudinal direction is gripped, and the lower end is a flame of about 20 mm. After 5 seconds exposure, the flame broke out. The burning time of the film after flame separation at this time was measured. (Combustion time at the first flame contact). Next, when the film was extinguished without burning out, a second flame contact / flame-off was performed in the same manner as the first after the fire was extinguished, and the burning time of the film after the flame-off was measured. (Combustion time at the second flame contact) The flame retardancy was evaluated by the following four stages of the total combustion time at the first and second flame contact.
◎: Self-extinguishes in less than 30 seconds ○: Self-extinguishes in 30-50 seconds △: Drip within 50 seconds and self-extinguishes X: Does not self-extinguish within 50 seconds or burns out
（８）非可燃性ガス発生量
難燃性ポリエステルフィルムの樹脂層Ｂの部分を採取したサンプル１ｇを用い、管状炉に流速５０ｍｌ／分でヘリウムガスを流しながら６０℃〜４５０℃まで１０℃／分の昇温速度で加熱し、１８０℃〜４５０℃加熱中に発生するガスをフッ化ビニル製のテドラーバッグで回収した。このガスを試料ガスとし、ガステック（株）製の二酸化炭素検知管、水蒸気検知管、窒素酸化物検知管を用いて、試料ガス中のＣＯ2、Ｈ2ＯおよびＮＯ2の測定を行い、それぞれの試料ガス濃度を求めた。１８０℃〜４５０℃における総捕集ガス量（１３５０ｍｌ）におけるそれぞれのガス濃度より各ガスの換算質量（ｍｇ）の合計量（Ｗ１）を求め、下記式（１）により非可燃性ガス発生量を算出した。
Ｗ1／Ｗ0×１００（％） ・・・（１）
（式中、Ｗ0は樹脂層Ｂの重量、Ｗ１は樹脂層を一定の昇温速度で昇温した場合に発生するガスのうち、１８０〜４５０℃の温度範囲で発生した非可燃性ガスの重量をそれぞれ示す）
評価は以下の基準で行った。
○：１８０℃〜４５０℃の温度範囲における非可燃性ガスの発生量が０．０１以上３％未満
×：１８０℃〜４５０℃の温度範囲における非可燃性ガスの発生量が３％以上
(8) Amount of non-flammable gas generation Using 1 g of a sample of the resin layer B portion of the flame retardant polyester film, 10 ° C / 60 ° C to 450 ° C while flowing helium gas through the tubular furnace at a flow rate of 50 ml / min. The gas generated during heating at 180 ° C. to 450 ° C. was collected with a Tedlar bag made of vinyl fluoride. Using this gas as the sample gas, the CO 2 , H 2 O and NO 2 in the sample gas are measured using a carbon dioxide detector tube, a water vapor detector tube, and a nitrogen oxide detector tube manufactured by Gastec Corporation. Each sample gas concentration was determined. The total amount (W 1 ) of the converted mass (mg) of each gas is determined from the respective gas concentrations in the total collected gas amount (1350 ml) at 180 ° C. to 450 ° C., and the amount of non-flammable gas generated by the following formula (1) Was calculated.
W 1 / W 0 × 100 (%) (1)
(W 0 is the weight of the resin layer B, and W 1 is a non-combustible gas generated in the temperature range of 180 to 450 ° C. among the gases generated when the resin layer is heated at a constant heating rate. The weight of each)
Evaluation was performed according to the following criteria.
○: Generation amount of non-flammable gas in the temperature range of 180 ° C. to 450 ° C. is 0.01 or more and less than 3% ×: Generation amount of non-flammable gas in the temperature range of 180 ° C. to 450 ° C. is 3% or more
（９）製膜性
製膜時の状況を観察し、以下の基準でランク分けする。
○：製膜する上でネックダウンや切断の発生がない。
×：製膜する上でネックダウンや切断が生じる。
(9) Film-forming properties Observe the conditions during film-forming and rank them according to the following criteria.
○: Neck-down and cutting do not occur when forming a film.
X: Neck-down or cutting occurs during film formation.
［実施例１］
芯層（層Ａ）として平均粒径０．３μｍのシリカ粒子を０．２重量％含有し、固有粘度０．６０であるポリエチレン−２，６−ナフタレンジカルボキシレートを用い、押出機に投入して３００℃で溶融混練を行った。また、両表層（層Ｂ）として平均粒径０．３μｍのシリカ粒子を０．２重量％含有し、固有粘度０．６０であるポリエチレン−２，６−ナフタレンジカルボキシレート５０重量％とポリエーテルイミド（General Electric社製、Ｕｌｔｅｍ１０１０（登録商標））５０重量％との混合物を別の押出機に投入して３３０℃で溶融混練を行い、それぞれ溶融した状態で（層Ａの厚み：層Ｂの合計厚み）＝１９：６となるようにダイスリットより溶融共押出し、キャスティングドラム上で冷却固化させて未延伸フィルムを作成した。
この未延伸フィルムを、表１に示す条件で縦方向、横方向の順で逐次二軸延伸し、表１に示す条件で金枠で固定して熱処理を施し、総厚みが２５μｍのフィルムを作成した。
[Example 1]
Polyethylene-2,6-naphthalenedicarboxylate containing 0.2% by weight of silica particles having an average particle size of 0.3 μm as the core layer (Layer A) and having an intrinsic viscosity of 0.60 was put into an extruder. The mixture was melt kneaded at 300 ° C. Further, as both surface layers (layer B), 50% by weight of polyethylene-2,6-naphthalenedicarboxylate having an average viscosity of 0.60 and containing 0.2% by weight of silica particles having an average particle diameter of 0.3 μm and a polyether A mixture of 50% by weight of imide (manufactured by General Electric Co., Ultem 1010 (registered trademark)) was put into another extruder, melt kneaded at 330 ° C., and in a melted state (layer A thickness: layer B The film was melt-coextruded through a die slit so that the total thickness was 19: 6, and cooled and solidified on a casting drum to prepare an unstretched film.
This unstretched film was sequentially biaxially stretched in the order of the machine direction and the transverse direction under the conditions shown in Table 1, fixed with a metal frame under the conditions shown in Table 1, and subjected to heat treatment to produce a film having a total thickness of 25 μm. did.
さらに、このフィルムの片面に接着剤を塗布し、１／２ｏｚ厚みの銅箔（１８μｍ厚）を貼りつけ、この銅箔をエッチングすることで所定の回路を形成し、２００℃で１５分間乾燥を行いフレキシブル回路基板を得た。得られた難燃性フィルムの物性、フレキシブル回路基板の平面性の評価結果を表１に示す。製膜性については、未延伸工程、延伸工程ともにフィルム破断は発生しなかった。 Furthermore, an adhesive is applied to one side of the film, a 1/2 oz thickness copper foil (18 μm thickness) is applied, and this copper foil is etched to form a predetermined circuit, which is then dried at 200 ° C. for 15 minutes. A flexible circuit board was obtained. Table 1 shows the evaluation results of the physical properties of the obtained flame-retardant film and the flatness of the flexible circuit board. Regarding film forming property, film breakage did not occur in both the unstretched process and the stretched process.
［実施例２〜４、比較例１〜２］
両表層（層Ｂ）のポリエチレン−２，６−ナフタレンジカルボキシレートとポリエーテルイミドの配合比率、溶融混練温度、（層Ａの厚み／層Ｂの合計厚み）および延伸倍率を表１に記載したように変更した以外は実施例１と同様の操作を繰り返し、フィルムおよびフレキシブル回路基板を得た。得られた難燃性フィルムの物性、フレキシブル回路基板の平面性の評価結果を表１に示す。
[Examples 2-4, Comparative Examples 1-2]
Table 1 shows the blending ratio of polyethylene-2,6-naphthalenedicarboxylate and polyetherimide, melt kneading temperature, (thickness of layer A / total thickness of layer B), and draw ratio of both surface layers (layer B). Except for the above changes, the same operation as in Example 1 was repeated to obtain a film and a flexible circuit board. Table 1 shows the evaluation results of the physical properties of the obtained flame-retardant film and the flatness of the flexible circuit board.
［比較例３］
層Ａとして平均粒径０．３μｍのシリカ粒子を０．２重量％含有し、固有粘度０．６０であるポリエチレン−２，６−ナフタレンジカルボキシレートを用い、層Ｂを用いなかった以外は実施例１と同様の操作を繰り返し、総厚みが２５μｍの１層からなるフィルムおよびフレキシブル回路基板を得た。得られた難燃性フィルムの物性、フレキシブル回路基板の平面性の評価結果を表１に示す。
[Comparative Example 3]
Implemented with the exception of using polyethylene-2,6-naphthalenedicarboxylate having 0.2% by weight of silica particles with an average particle size of 0.3 μm as layer A and an intrinsic viscosity of 0.60, and not using layer B. The same operation as in Example 1 was repeated to obtain a single-layer film and a flexible circuit board having a total thickness of 25 μm. Table 1 shows the evaluation results of the physical properties of the obtained flame-retardant film and the flatness of the flexible circuit board.
［比較例４］
芯層に、平均粒径０．３μｍのシリカ粒子を０．２重量％含有し、固有粘度０．６０であるポリエチレン−２，６−ナフタレンジカルボキシレート５０重量％とポリエーテルイミド（General Electric社製、Ｕｌｔｅｍ１０１０（登録商標））５０重量％とをブレンドした樹脂を用い、両表層として平均粒径０．３μｍのシリカ粒子を０．２重量％含有し、固有粘度０．６０であるポリエチレン−２，６−ナフタレンジカルボキシレートを用い、それぞれの溶融混練温度を表１に記載したように変更した以外は実施例１と同様の操作を繰り返し、フィルムおよびフレキシブル回路基板を得た。得られた難燃性フィルムの物性、フレキシブル回路基板の平面性の評価結果を表１に示す。
[Comparative Example 4]
The core layer contains 0.2% by weight of silica particles having an average particle size of 0.3 μm and has an intrinsic viscosity of 0.60, 50% by weight of polyethylene-2,6-naphthalenedicarboxylate and polyetherimide (General Electric) Made of Ultem 1010 (registered trademark), 50% by weight, polyethylene-2 containing 0.2% by weight of silica particles having an average particle size of 0.3 μm as both surface layers, and having an intrinsic viscosity of 0.60 , 6-naphthalenedicarboxylate was used, and the same operation as in Example 1 was repeated except that each melt-kneading temperature was changed as described in Table 1 to obtain a film and a flexible circuit board. Table 1 shows the evaluation results of the physical properties of the obtained flame-retardant film and the flatness of the flexible circuit board.
［比較例５］
芯層（層Ａ）として平均粒径０．３μｍのシリカ粒子を０．２重量％含有し、固有粘度０．６２であるポリエチレンテレフタレートを用い、押出機に投入して２８０℃で溶融混練を行った。また両表層（層Ｂ）として平均粒径０．３μｍのシリカ粒子を０．２重量％含有し、固有粘度０．６０であるポリエチレンテレフタレート５０重量％とポリエーテルイミド（General Electric社製、Ｕｌｔｅｍ１０１０（登録商標））５０重量％との混合物を別の押出機に投入して３２０℃で溶融混練を行い、それぞれ溶融した状態で（層Ａの厚み：層Ｂの合計厚み）＝１９：６となるようにダイスリットより溶融共押出し、キャスティングドラム上で冷却固化させて未延伸フィルムを作成した。
この未延伸フィルムを、表１に示す条件で縦方向、横方向の順で逐次二軸延伸し、表１に示す条件で金枠で固定して熱処理を施し、総厚みが２５μｍのフィルムを作成した。
[Comparative Example 5]
Polyethylene terephthalate containing 0.2% by weight of silica particles having an average particle diameter of 0.3 μm as the core layer (layer A) and having an intrinsic viscosity of 0.62 is charged into an extruder and melt kneaded at 280 ° C. It was. Further, as both surface layers (layer B), 0.2% by weight of silica particles having an average particle diameter of 0.3 μm are contained, and 50% by weight of polyethylene terephthalate having an intrinsic viscosity of 0.60 and polyetherimide (manufactured by General Electric, Ultem 1010 ( (Registered trademark)) 50% by weight of the mixture is put into another extruder and melt kneaded at 320 ° C., and in the melted state (layer A thickness: layer B total thickness) = 19: 6 As described above, melt co-extrusion was performed from a die slit and cooled and solidified on a casting drum to prepare an unstretched film.
This unstretched film was sequentially biaxially stretched in the order of the machine direction and the transverse direction under the conditions shown in Table 1, fixed with a metal frame under the conditions shown in Table 1, and subjected to heat treatment to produce a film having a total thickness of 25 μm. did.
さらに、このフィルムの片面に接着剤を塗布し、１／２ｏｚ厚みの銅箔（１８μｍ厚）を貼りつけ、この銅箔をエッチングすることで所定の回路を形成し、２００℃で１５分間乾燥を行いフレキシブル回路基板を得た。得られた難燃性フィルムの物性、フレキシブル回路基板の平面性の評価結果を表１に示す。製膜性については、未延伸フィルムは作成できたが、延伸工程においてフィルム破断が発生した。 Furthermore, an adhesive is applied to one side of the film, a 1/2 oz thickness copper foil (18 μm thickness) is applied, and this copper foil is etched to form a predetermined circuit, which is then dried at 200 ° C. for 15 minutes. A flexible circuit board was obtained. Table 1 shows the evaluation results of the physical properties of the obtained flame-retardant film and the flatness of the flexible circuit board. Regarding film forming properties, an unstretched film could be prepared, but film breakage occurred in the stretching process.
本発明における難燃性ポリエステルフィルムは難燃性に優れ、しかも耐熱寸法安定性に優れることから、難燃性及び耐熱性が必要とされる各種用途に広く用いることができる。例えばフレキシブル回路基板用フィルムや太陽電池用基板用フィルムとして有用である。 Since the flame-retardant polyester film in the present invention is excellent in flame retardancy and excellent in heat-resistant dimensional stability, it can be widely used in various applications where flame retardancy and heat resistance are required. For example, it is useful as a film for a flexible circuit board or a film for a solar cell substrate.
１ 変曲点（ａ１）
２ 変曲点（ａ２）
1 Inflection point (a1)
2 Inflection point (a2)
Claims (8)
（ａ）ＴＧ曲線の４５０〜７５０℃の範囲に、ポリエチレンナフタレンジカルボキシレートに由来する変曲点（ａ１）、および（ａ１）よりも高温側に位置するポリエーテルイミドに由来の少なくとも１つの変曲点（ａ２）が存在し、
（ｂ）ＴＧ曲線の４０〜７５０℃の範囲における重量減少率が３０〜７０％
を同時に満たす、樹脂層Ｂの重量を基準としてポリエチレンナフタレンジカルボキシレートを２０〜６０重量％およびポリエーテルイミドを４０〜８０重量％含む樹脂層Ｂが積層されてなることを特徴とする難燃性ポリエステルフィルム。 Derived from polyethylene naphthalene dicarboxylate in the range of 450 to 750 ° C. of characteristics (a) TG curve expressed by the following (a) and (b) on both sides of layer A mainly composed of polyethylene naphthalene dicarboxylate inflection point (a1), and (a1) at least one inflection point from the polyetherimide positioned to the high temperature side than the (a2) is present to,
(B) The weight loss rate in the range of 40 to 750 ° C. of the TG curve is 30 to 70%.
Flame retardant, characterized in that a resin layer B containing 20 to 60% by weight of polyethylene naphthalene dicarboxylate and 40 to 80% by weight of polyetherimide based on the weight of the resin layer B is laminated. Polyester film.
（ａ）ＴＧ曲線の４５０〜７５０℃の範囲に、ポリエチレンナフタレンジカルボキシレートに由来する変曲点（ａ１）、および（ａ１）よりも高温側に位置するポリエーテルイミドに由来の少なくとも１つの変曲点（ａ２）が存在し、
（ｂ）ＴＧ曲線の４０〜７５０℃の範囲における重量減少率が３０〜７０％
を同時に満たす、樹脂層Ｂの重量を基準としてポリエチレンナフタレンジカルボキシレートを２０〜６０重量％およびポリエーテルイミドを４０〜８０重量％含む樹脂層Ｂが積層されてなる難燃性ポリエステルフィルムの製造方法であり、
層Ａを構成するポリエチレンナフタレンジカルボキシレートおよび層Ｂを構成する樹脂それぞれが共押出法により溶融状態でダイ内部で積層されてからシート状に押出された後、縦延伸倍率および横延伸倍率それぞれ２．５〜５．０倍の範囲で二軸延伸して得られることを特徴とする難燃性ポリエステルフィルムの製造方法。 On both sides of layer A containing polyethylene naphthalene dicarboxylate as the main component, the characteristics represented by the following (a) and (b) (a) in the range of 450 to 750 ° C. of the TG curve, the polyethylene naphthalene dicarboxylate derived inflection point (a1), and (a1) at least one inflection point from the polyetherimide located on the high temperature side (a2) exist than,
(B) The weight loss rate in the range of 40 to 750 ° C. of the TG curve is 30 to 70%.
Of flame retardant polyester film in which resin layer B containing 20 to 60% by weight of polyethylene naphthalene dicarboxylate and 40 to 80% by weight of polyetherimide is laminated based on the weight of resin layer B at the same time der is,
The polyethylene naphthalene dicarboxylate constituting layer A and the resin constituting layer B are each laminated in the die in a molten state by a coextrusion method and then extruded into a sheet, and then the longitudinal draw ratio and the transverse draw ratio are 2 respectively. A method for producing a flame-retardant polyester film obtained by biaxial stretching in a range of 0.5 to 5.0 times.
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