JP6352034B2 - Multi-layer release film - Google Patents
Multi-layer release film Download PDFInfo
- Publication number
- JP6352034B2 JP6352034B2 JP2014088645A JP2014088645A JP6352034B2 JP 6352034 B2 JP6352034 B2 JP 6352034B2 JP 2014088645 A JP2014088645 A JP 2014088645A JP 2014088645 A JP2014088645 A JP 2014088645A JP 6352034 B2 JP6352034 B2 JP 6352034B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- release film
- multilayer
- release
- layer
- 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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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- RXPKHKBYUIHIGL-UHFFFAOYSA-L calcium;12-hydroxyoctadecanoate Chemical compound [Ca+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O RXPKHKBYUIHIGL-UHFFFAOYSA-L 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- LSFBQOPXRBJSSI-UHFFFAOYSA-L calcium;tetradecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O LSFBQOPXRBJSSI-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 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
- 239000012792 core layer Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- MFUGKPWEUBVBNA-UHFFFAOYSA-L dilithium;dibenzoate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 MFUGKPWEUBVBNA-UHFFFAOYSA-L 0.000 description 1
- RCRBCNZJGBTYDI-UHFFFAOYSA-L dilithium;terephthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 RCRBCNZJGBTYDI-UHFFFAOYSA-L 0.000 description 1
- OXDOANYFRLHSML-UHFFFAOYSA-N dimethoxyphosphorylbenzene Chemical compound COP(=O)(OC)C1=CC=CC=C1 OXDOANYFRLHSML-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical class [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 description 1
- QNFQYLRYCQTBEP-UHFFFAOYSA-L dipotassium;dibenzoate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QNFQYLRYCQTBEP-UHFFFAOYSA-L 0.000 description 1
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 description 1
- VVTXSHLLIKXMPY-UHFFFAOYSA-L disodium;2-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(C([O-])=O)C=CC=C1C([O-])=O VVTXSHLLIKXMPY-UHFFFAOYSA-L 0.000 description 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
- GFQOFGWPGYRLAO-UHFFFAOYSA-N dodecanamide;ethene Chemical compound C=C.CCCCCCCCCCCC(N)=O.CCCCCCCCCCCC(N)=O GFQOFGWPGYRLAO-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- VKLYZBPBDRELST-UHFFFAOYSA-N ethene;methyl 2-methylprop-2-enoate Chemical compound C=C.COC(=O)C(C)=C VKLYZBPBDRELST-UHFFFAOYSA-N 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- RKVQXYMNVZNJHZ-UHFFFAOYSA-N hexacosanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCC(N)=O RKVQXYMNVZNJHZ-UHFFFAOYSA-N 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- UADIOTAIECKQLQ-UHFFFAOYSA-M lithium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Li+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C UADIOTAIECKQLQ-UHFFFAOYSA-M 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 description 1
- 229960003629 potassium salicylate Drugs 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- PYJBVGYZXWPIKK-UHFFFAOYSA-M potassium;tetradecanoate Chemical compound [K+].CCCCCCCCCCCCCC([O-])=O PYJBVGYZXWPIKK-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- XTIVBOWLUYDHKE-UHFFFAOYSA-M sodium;cyclohexanecarboxylate Chemical compound [Na+].[O-]C(=O)C1CCCCC1 XTIVBOWLUYDHKE-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は接着剤を用いてフィルムまたはシート状の積層物を加圧成形する際などに使用するに好適な剥離性に優れる多層離型フィルムに関するものであり、より詳細には、電子機器、電気機器に用いられる電気回路を形成したフレキシブルプリント回路基板本体に、接着剤によってカバーレイフィルムを加圧接着する際に使用される剥離性に優れた多層離型フィルムに関する。 The present invention relates to a multilayer release film excellent in releasability suitable for use when pressure-forming a film or a sheet-like laminate using an adhesive, and more particularly to an electronic device, an electric The present invention relates to a multilayer release film excellent in releasability, which is used when a coverlay film is pressure-bonded with an adhesive to a flexible printed circuit board body on which an electric circuit used in an apparatus is formed.
プリント配線基板、フレキシブルプリント配線基板、多層プリント配線基板など（以下、「プリント配線基板等」と表記することがある。）の製造工程において、プリプレグ又は耐熱フィルムを介して銅張り積層板又は銅箔を熱プレスする際には配線基板の電極配線を保護するため離型フィルムが使用されている。また、フレキシブルプリント配線基板の製造工程において、電気回路を形成したフレキシブルプリント配線基板本体に、熱硬化型接着剤又は熱硬化性接着シートによってカバーレイフィルム又は補強板を熱プレス接着する際に、カバーレイフィルムとプレス熱板とが接着するのを防止するためにも、離型フィルムが用いられている。 In the manufacturing process of printed wiring boards, flexible printed wiring boards, multilayer printed wiring boards, etc. (hereinafter sometimes referred to as “printed wiring boards etc.”), a copper-clad laminate or copper foil via a prepreg or a heat-resistant film A release film is used in order to protect the electrode wiring of the wiring board when hot-pressing. In addition, in the manufacturing process of the flexible printed circuit board, when the cover lay film or the reinforcing plate is hot-press bonded to the flexible printed circuit board body on which the electric circuit is formed with a thermosetting adhesive or a thermosetting adhesive sheet, A release film is also used to prevent the lay film and the press hot plate from adhering to each other.
かかる用途に用いられる離型フィルムとしては、例えばポリブチレンテレフタレートを含む離型フィルム（特許文献１：特開２００９−７３１９５号公報）や比較的良好な埋め込み性、即ちカバーレイフィルムに覆われない回路パターン部分（凹凸部分）への段差追随性を示し、プリント配線基板等の製作時の電子回路を配置した回路露出フィルム（以下、「回路露出フィルム」と表記することがある。）と当該回路露出フィルムを選択的に保護するためのカバーレイフィルム（以下、「カバーレイフィルム」と表記することがある。）との間の接着剤がその回路パターン部分へ染み出す量を許容範囲内に止めることができる離型フィルム（特許文献２：国際公開第０５／０３０４６６号公報、特許文献３：特開２０１１−２３０３６３号公報）が提案されている。 As a release film used for such applications, for example, a release film containing polybutylene terephthalate (Patent Document 1: Japanese Patent Application Laid-Open No. 2009-73195) and a relatively good embedding property, that is, a circuit not covered by a coverlay film A circuit exposure film (hereinafter, also referred to as “circuit exposure film”) showing an electronic circuit at the time of production of a printed wiring board or the like, showing the step following to the pattern portion (uneven portion) and the circuit exposure. The amount of the adhesive between the coverlay film for selectively protecting the film (hereinafter sometimes referred to as “coverlay film”) to the circuit pattern portion is kept within an allowable range. Release film (Patent Document 2: International Publication No. 05/030466, Patent Document 3: JP 2011-230363 A) ) It has been proposed.
しかしながら、最近ではプリント配線基板等の生産性を上げるためにプレスする方式が自動化されたロールツーロール方式やステッピングロール方式（以下、「ロールツーロール方式等」と表記することがある。）でのプレス工程が増加してきており、特許文献１から３に記載の発明では不具合が起こる可能性があった。即ち、ロールツーロール方式等では、各フィルムに張力をかけた状態で加熱プレスが行われるため、特許文献１から３に記載の離型フィルムでは、フィルムに柔軟性をもたせていることで回路パターン部分（凹凸部分）への良好な追随性を得ているものの、逆にロールツーロール方式等においての耐熱性という観点からは充分とはいえず、加熱プレス時に離型フィルムが加熱によって軟化し伸びて弛み、フィルム長手方向にシワが複数発生した状態でプレスされ、これらシワがプリント配線基板等に転写されて不良品となって歩留まりの低下につながる恐れがあった。 However, recently, a roll-to-roll method or a stepping roll method (hereinafter, referred to as a “roll-to-roll method or the like”) in which the method of pressing to increase the productivity of a printed wiring board or the like is automated is sometimes used. The press process has been increasing, and the inventions described in Patent Documents 1 to 3 have a possibility of malfunction. That is, in the roll-to-roll method or the like, since the heat press is performed in a state where tension is applied to each film, in the release film described in Patent Documents 1 to 3, the circuit pattern is obtained by giving the film flexibility. Although good followability to the part (uneven part) is obtained, it is not sufficient from the viewpoint of heat resistance in the roll-to-roll method etc., and the release film is softened and stretched by heating at the time of hot pressing. There was a possibility that the film was pressed in a state where a plurality of wrinkles were generated in the longitudinal direction of the film, and these wrinkles were transferred to a printed wiring board or the like to become defective products, leading to a decrease in yield.
また、特許文献２においては、特定の粘弾性率のポリブチレンテレフタレートを含む離型層がクッション層の両方の表面に設けられた離型フィルムが、離型性や外観シワ、形状追従性が良好との記述がある。しかし、特許文献２に開示されている離型フィルムでは前記クッション層の樹脂がエチレンメチルメタクリレートや低密度ポリエチレンの単体から構成されているため、クッション層と離型層の層間接着強度が弱いという欠点があった。即ち、クッション層と離型層間の層間接着強度が弱いことにより、例えば、エンボスロールによりエンボス処理をして離型フィルムを形成する場合に、エンボスロールによる加熱のため剥離時にクッション層と離型層とが剥離してしまうことがあるという問題があった。 In Patent Document 2, a release film in which a release layer containing polybutylene terephthalate having a specific viscoelastic modulus is provided on both surfaces of the cushion layer has good release properties, appearance wrinkles, and shape following properties. There is a description. However, in the release film disclosed in Patent Document 2, since the resin of the cushion layer is composed of a single element of ethylene methyl methacrylate or low density polyethylene, the interlayer adhesion strength between the cushion layer and the release layer is weak. was there. That is, because the interlayer adhesion strength between the cushion layer and the release layer is weak, for example, when a release film is formed by embossing with an embossing roll, the cushion layer and the release layer are peeled off when heated due to the embossing roll. There was a problem that and may peel off.
本発明は、優れた離型性、耐熱性、埋め込み性、耐汚染性、および多層離型フィルムを構成する離型層とクッション層との安定した層間接着性を有し、さらには耐熱性を有することによりプリント配線基板等の製作時のロールツーロール方式やステッピングロール方式におけるカバーレイフィルムの接着工程で効果的にシワの発生を防止するという耐シワ性をも有する多層離型フィルムを得ることを目的とする。 The present invention has excellent releasability, heat resistance, embedding property, stain resistance, and stable interlayer adhesion between the release layer and the cushion layer constituting the multilayer release film. Obtaining a multilayer release film that also has wrinkle resistance that effectively prevents wrinkle generation in the cover-lay film adhesion process in the roll-to-roll method and stepping roll method when manufacturing printed circuit boards, etc. With the goal.
本発明は、離型層がクッション層の両面に積層された多層離型フィルムであって、前記離型層がポリブチレンテレフタレート（Ａ）を主成分とし、かつ厚みが３２〜７３μｍの範囲にあり、２３℃における引張弾性率が１１００〜１４００ＭＰａである多層離型フィルムを提供するものである。本発明の多層離型フィルムにより、従前のＰＢＴ（ポリブチレンテレフタレート）系離型フィルムと同様に離型層の回路露出フィルム及びカバーレイフィルムへの密着や離型層同士の密着を防ぐことができると共に、ロールツーロール方式等における加熱プレス時でも、離型フィルムが熱で弛むことなく、従前のＰＢＴ系離型フィルムよりも、配線基板にもシワ転写することなく歩留まりの低下を抑制でき、なおかつ回路露出フィルムとカバーレイフィルムとの間の接着剤がその回路パターン部分へ染み出す量を低減することができることを見出した。 The present invention is a multilayer release film in which a release layer is laminated on both sides of a cushion layer, wherein the release layer is mainly composed of polybutylene terephthalate (A) and has a thickness in the range of 32 to 73 μm. A multilayer release film having a tensile elastic modulus at 23 ° C. of 1100 to 1400 MPa is provided. The multilayer release film of the present invention can prevent adhesion of the release layer to the circuit-exposed film and the coverlay film and adhesion between the release layers as in the case of the conventional PBT (polybutylene terephthalate) release film. At the same time, even during the heat-pressing in the roll-to-roll method, the release film is not loosened by heat, and it is possible to suppress the decrease in yield without causing wrinkle transfer to the wiring board as compared with the conventional PBT release film, and It has been found that the amount of the adhesive between the circuit exposed film and the coverlay film can be reduced to the circuit pattern portion.
本発明の多層離型フィルムは、離型層がポリブチレンテレフタレートを主成分とし、かつ所定範囲の厚みと引張弾性率により優れた離型性、耐熱性、埋め込み性、耐汚染性および多層離型フィルムを構成する離型層とクッション層との安定した層間接着性を有する。また、プリント配線基板等のロールツーロール方式等による製造工程においては、離型性、耐熱性、埋め込み性、耐汚染性に加え、耐熱性に由来するシワを効果的に防止するといういわゆる耐シワ性に優れているため、特にカバーレイフィルムにエポキシ樹脂系接着剤が用いられるプリント配線基板、フレキシブルプリント配線基板、多層プリント配線基板などの製造に好適に使用し得る。 In the multilayer release film of the present invention, the release layer is mainly composed of polybutylene terephthalate, and has excellent release properties, heat resistance, embedding properties, stain resistance and multilayer release properties with a predetermined range of thickness and tensile modulus. It has stable interlayer adhesion between the release layer and the cushion layer constituting the film. In addition, in a manufacturing process using a roll-to-roll method such as a printed wiring board, in addition to releasability, heat resistance, embedding property, and contamination resistance, so-called wrinkle resistance that effectively prevents wrinkles derived from heat resistance. In particular, it can be suitably used for the production of printed wiring boards, flexible printed wiring boards, multilayer printed wiring boards and the like in which an epoxy resin adhesive is used for the coverlay film.
また、本発明の多層離型フィルムを構成するクッション層のビカット軟化温度が５０〜１５０℃であることにより、シワ発生の防止効果をより向上させることができる。 Moreover, the prevention effect of a wrinkle generation | occurrence | production can be improved more because the Vicat softening temperature of the cushion layer which comprises the multilayer release film of this invention is 50-150 degreeC.
また、本発明の多層離型フィルムを構成するクッション層が、ポリブチレンテレフタレート（Ａ）が０〜５０質量％、およびエチレン・（メタ）アクリル酸メチル共重合体（Ｂ）が５０〜１００質量％の範囲で含む組成物〔但し、（Ａ）＋（Ｂ）＝１００質量％とする。〕からなることにより離型層との層間接着力の観点から好ましく、ポリブチレンテレフタレート（Ａ）を含む方が、離型層との層間接着性のみならず、耐汚染性向上の観点からも好ましい。なお、本発明において、「エチレン・（メタ）アクリル酸メチル共重合体」とは、エチレン・アクリル酸メチル共重合体および／またはエチレン・メタクリル酸メチル共重合体をいうものとする。 Further, the cushion layer constituting the multilayer release film of the present invention is such that the polybutylene terephthalate (A) is 0 to 50% by mass and the ethylene / (meth) methyl acrylate copolymer (B) is 50 to 100% by mass. The composition included in the range [However, (A) + (B) = 100 mass%. It is preferable from the viewpoint of interlayer adhesive strength with the release layer, and it is preferable that polybutylene terephthalate (A) is included from the viewpoint of not only interlayer adhesion with the release layer but also improvement of stain resistance. . In the present invention, the term “ethylene / methyl methacrylate copolymer” means an ethylene / methyl acrylate copolymer and / or an ethylene / methyl methacrylate copolymer.
さらに、本発明の多層離型フィルムを構成する離型層の表面粗さ（Ｒａ）（ＪＩＳＢ０６０１（１９９４年）に準じて測定）が０．３〜１０μｍであることが、シワ発生防止効果のさらなる向上および離型性の向上の観点から好ましい。 Furthermore, the surface roughness (Ra) (measured according to JISB0601 (1994)) of the release layer constituting the multilayer release film of the present invention is 0.3 to 10 μm, so that the effect of preventing generation of wrinkles is further achieved. It is preferable from a viewpoint of improvement and improvement of mold release property.
＜多層離型フィルム＞
本発明の多層離型フィルムは、離型層がクッション層の両面に積層された多層離型フィルムであって、前記離型層がポリブチレンテレフタレート（Ａ）を主成分、即ち５０〜１００質量％であって、かつ厚みが３２〜７３μｍの範囲にあり、２３℃における引張弾性率（ＪＩＳＫ７１２７（１９９９年）に準じて測定）が１１００〜１４００ＭＰａであることを特徴とする。また、本発明の多層離型フィルムのクッション層の両面に積層された離型層の少なくとも一方の離型層の表面の表面粗さ（Ｒａ）（ＪＩＳ Ｂ０６０１（１９９４年）に準じて測定）が耐シワ性向上やプリント配線基板等への離型層の表面凹凸の転写防止の観点から、０．３〜１０μｍであることが好ましく、０．５〜１０μｍであることがより好ましく、１〜５μｍであることがさらに好ましく、１．５〜４μｍであることが最も好ましい。さらに、本発明の多層離型フィルムにおいて、クッション層の両面に積層された離型層の双方が前記表面粗さ（Ｒａ）を有することが耐シワ性の安定的な向上の観点から好ましい。
以下、本発明の多層離型フィルムの各構成層について詳述する。
<Multilayer release film>
The multilayer release film of the present invention is a multilayer release film in which a release layer is laminated on both sides of a cushion layer, and the release layer is mainly composed of polybutylene terephthalate (A), that is, 50 to 100% by mass. And having a thickness in the range of 32 to 73 μm and a tensile elastic modulus at 23 ° C. (measured according to JISK7127 (1999)) of 1100 to 1400 MPa. Moreover, the surface roughness (Ra) (measured according to JIS B0601 (1994)) of the surface of at least one of the release layers laminated on both surfaces of the cushion layer of the multilayer release film of the present invention is From the viewpoint of improving wrinkle resistance and preventing transfer of the surface irregularities of the release layer to a printed wiring board, it is preferably 0.3 to 10 μm, more preferably 0.5 to 10 μm, and 1 to 5 μm. More preferably, it is most preferable that it is 1.5-4 micrometers. Furthermore, in the multilayer release film of the present invention, it is preferable from the viewpoint of stable improvement of wrinkle resistance that both of the release layers laminated on both sides of the cushion layer have the surface roughness (Ra).
Hereinafter, each constituent layer of the multilayer release film of the present invention will be described in detail.
＜多層離型フィルムの構成層の詳細＞
１．離型層
離型層は、後述するポリブチレンテレフタレート（Ａ）を主成分として構成されている。本発明に係る離型層はクッション層の両側の表面に設けられるが、これら両側の離型層を構成する樹脂組成については双方の離型層の樹脂組成が同一であっても異なっていてもよい。本発明に係る離型層の厚みは３２〜７３μｍであり、好ましくは３７〜６８μｍ、さらに好ましくは４２〜６３μｍである。離型層の厚みが３２μｍ未満であると、プリント配線基板等の製作の際の加熱プレス時にフィルムが軟化し伸びて弛み、シワの原因となる可能性があり、一方、厚みが７３μｍを超えるといわゆる埋め込み性が低下し、カバーレイフィルムからの接着剤の浸み出しが防げずにプリント配線基板等の電極端子を毀損してしまう可能性がある。なお、明細書において、埋め込み性とは、プリント配線基板等の製作時にカバーレイフィルムの切欠き部の電極端子の露出部分に隙間なく密着する性質をいうものとする。また、離型層のＪＩＳＫ７１２７（１９９９年）に準じて測定した２３℃におけるＭＤ方向の引張弾性率が１１００〜１４００ＭＰａ、好ましくは１１５０〜１３５０ＭＰａ、より好ましくは１２００〜１３００ＭＰａである。離型層の引張弾性率が１１００ＭＰａ未満であるとプリント配線基板等の製作時にフィルムが軟化し伸びて弛み、シワが生じやすくなる可能性があり、一方１４００ＭＰａを超えると埋め込み性が低下してプリント配線基板等の製作時にカバーレイフィルムから接着剤が染み出して電極端子を毀損する恐れがある。ここで、ＭＤ方向とは離型層の原反フィルムのフィルム成形時における流れ方向をいう。
<Details of constituent layers of multilayer release film>
1. Release layer The release layer is composed mainly of polybutylene terephthalate (A) described later. The release layer according to the present invention is provided on the surfaces on both sides of the cushion layer, and the resin compositions constituting the release layers on both sides may be the same or different from each other. Good. The release layer according to the present invention has a thickness of 32 to 73 μm, preferably 37 to 68 μm, and more preferably 42 to 63 μm. When the thickness of the release layer is less than 32 μm, the film may soften and stretch during heating press in the production of a printed wiring board or the like, which may cause wrinkles, while when the thickness exceeds 73 μm. The so-called embedding property is lowered, and there is a possibility that an electrode terminal such as a printed wiring board is damaged without preventing the adhesive from seeping out from the coverlay film. In the specification, embeddability refers to the property of closely contacting the exposed portion of the electrode terminal in the cutout portion of the coverlay film when a printed wiring board or the like is manufactured. Moreover, the tensile elasticity modulus of MD direction in 23 degreeC measured according to JISK7127 (1999) of a mold release layer is 1100-1400 MPa, Preferably it is 1150-1350 MPa, More preferably, it is 1200-1300 MPa. If the release layer has a tensile modulus of less than 1100 MPa, the film may be softened and stretched during production of a printed wiring board or the like, and may be prone to wrinkles. When manufacturing a wiring board or the like, the adhesive may ooze out from the coverlay film and damage the electrode terminal. Here, the MD direction refers to the flow direction during film formation of the original film of the release layer.
１−２．ポリブチレンテレフタレート（Ａ）
本発明に係る離型層を構成するポリブチレンテレフタレート（Ａ）は、１．４−ブタンジオールとテレフタル酸から得られるエステルである。ポリブチレンテレフタレート（Ａ）は、フィルムの製膜性や低汚染性の観点から、好ましくは、固有粘度（ＩＶ）が１．０〜１．３、より好ましくは１．０〜１．２の範囲にある。なお、本発明に係るポリブチレンテレフタレート（Ａ）の固有粘度（ＩＶ）は、オルトクロロフェノール中、２５℃で測定した溶液粘度から下式によって計算される値を用いる。すなわち、ηｓｐ／Ｃ＝[η]＋Ｋ[η]2×Ｃ
ここで、ηｓｐ＝（溶液粘度／溶媒粘度）−１、Ｃは溶媒１００ｍｌあたりの溶解ポリマー質量（ｇ／１００ｍｌ）、Ｋはハギンス定数（０．３４３とする）である。また、溶液粘度、溶媒粘度はオストワルド粘度計を用いた測定により求められる。また、本発明に係るポリブチレンテレフタレート（Ａ）は、減圧下もしくは不活性ガス流通下で２００℃以上の温度で固相重合した原料を使用することが好ましい。固相重合することによりフィルム成形しやすい固有粘度に調整でき、さらに末端カルボン酸基量の減少、オリゴマーの減少が期待できる。
1-2. Polybutylene terephthalate (A)
The polybutylene terephthalate (A) constituting the release layer according to the present invention is an ester obtained from 1.4-butanediol and terephthalic acid. The polybutylene terephthalate (A) is preferably in the range of an intrinsic viscosity (IV) of 1.0 to 1.3, more preferably 1.0 to 1.2, from the viewpoint of film forming properties and low contamination. It is in. The intrinsic viscosity (IV) of the polybutylene terephthalate (A) according to the present invention uses a value calculated from the solution viscosity measured at 25 ° C. in orthochlorophenol by the following formula. That is, ηsp / C = [η] + K [η] 2 × C
Here, ηsp = (solution viscosity / solvent viscosity) −1, C is the dissolved polymer mass per 100 ml of solvent (g / 100 ml), and K is the Huggins constant (assuming 0.343). Further, the solution viscosity and the solvent viscosity are determined by measurement using an Ostwald viscometer. The polybutylene terephthalate (A) according to the present invention is preferably a raw material that is solid-phase polymerized at a temperature of 200 ° C. or higher under reduced pressure or under an inert gas flow. It can be adjusted to an intrinsic viscosity that is easy to form a film by solid phase polymerization, and a decrease in the amount of terminal carboxylic acid groups and a decrease in oligomers can be expected.
本発明に係るポリブチレンテレフタレート（Ａ）は、１，４−ブタンジオールとテレフタル酸との重合体を骨格に有する限り、１，４−ブタンジオールとテレフタル酸とからなる、所謂、ＰＢＴと称されるポリブチレンテレフタレートであっても、ポリブチレンテレフタレートとポリエーテル、ポリエステル、あるいはポリカプロラクタムなどとのブロック共重合体であってもよい。 The polybutylene terephthalate (A) according to the present invention is referred to as so-called PBT composed of 1,4-butanediol and terephthalic acid as long as it has a polymer of 1,4-butanediol and terephthalic acid in the skeleton. The polybutylene terephthalate may be a block copolymer of polybutylene terephthalate and polyether, polyester, or polycaprolactam.
本発明に係るポリブチレンテレフタレート（Ａ）は、例えば、ポリプラスチックス社から、商品名 ジュラネックス７００ＦＰ（ＩＶ：１．１）、三菱エンジニアリングプラスチック社から、商品名 ノバデュラン５０１０ＣＳ（ＩＶ：１．１）、長春社から、商品名 １１００−２１１Ｓ（ＩＶ：１．２）として、製造・販売されている。
本発明に係るポリブチレンテレフタレート（Ａ）のガラス転移点と融点は、示差走査型熱量計（ＤＳＣ）を用いて２８０℃で５分間加熱溶融した後、液体窒素で急冷して得たサンプル約１０ｍｇを精秤し、窒素気流中、１０℃／分の昇温速度で２８０℃まで昇温して熱融解曲線を得、得られた熱融解曲線から、ガラス転移点（Ｔｇ）（℃）と融点（Ｔｍ）（℃）が求められる。
The polybutylene terephthalate (A) according to the present invention is, for example, from Polyplastics Co., Ltd. under the trade name DURANEX 700FP (IV: 1.1), from Mitsubishi Engineering Plastics Co., Ltd. under the trade name NOVADURAN 5010CS (IV: 1.1). , Manufactured and sold by Changchun as the trade name 1100-211S (IV: 1.2).
The glass transition point and melting point of the polybutylene terephthalate (A) according to the present invention are about 10 mg of a sample obtained by heating and melting at 280 ° C. for 5 minutes using a differential scanning calorimeter (DSC) and then rapidly cooling with liquid nitrogen. Was precisely weighed and heated to 280 ° C. at a rate of 10 ° C./min in a nitrogen stream to obtain a thermal melting curve. From the obtained thermal melting curve, the glass transition point (Tg) (° C.) and melting point were obtained. (Tm) (° C.) is required.
また、本発明に係るポリブチレンテレフタレート（Ａ）には、本発明の目的を損なわない範囲で、慣用の添加剤などを配合することが出来る。斯かる添加剤としては、特に制限されず、例えば、酸化防止剤、耐熱安定剤などの安定剤の他、滑剤、紫外線吸収剤、触媒失活剤、結晶核剤などが挙げられる。これらの添加剤は、重合途中または重合後に添加することが出来る。更に、本発明に係るポリブチレンテレフタレート（Ａ）に、所望の性能を付与するため、難燃剤、染顔料などの着色剤、帯電防止剤、発泡剤、可塑剤、耐衝撃性改良剤などを配合することが出来る。 Moreover, a conventional additive etc. can be mix | blended with the polybutylene terephthalate (A) based on this invention in the range which does not impair the objective of this invention. Such additives are not particularly limited and include, for example, stabilizers such as antioxidants and heat stabilizers, lubricants, ultraviolet absorbers, catalyst deactivators, crystal nucleating agents, and the like. These additives can be added during or after the polymerization. Furthermore, in order to give the desired performance to the polybutylene terephthalate (A) according to the present invention, a flame retardant, a coloring agent such as a dye / pigment, an antistatic agent, a foaming agent, a plasticizer, and an impact resistance improving agent are blended. I can do it.
安定剤としては、２，６−ジ−ｔ−ブチル−４−オクチルフェノール、ペンタエリスリチル−テトラキス〔３−（３’，５’−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕等のフェノール化合物、ジラウリル−３，３’−チオジプロピオネート、ペンタエリスリチル−テトラキス（３−ラウリルチオジプロピオネート）等のチオエーテル化合物、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト等の燐化合物などの抗酸化剤、滑剤としては、パラフィンワックス、マイクロクリスタリンワックス、ポリエチレンワックス、モンタン酸やモンタン酸エステルに代表される長鎖脂肪酸およびそのエステルなどが挙げられる。 Stabilizers include phenol compounds such as 2,6-di-t-butyl-4-octylphenol and pentaerythrityl-tetrakis [3- (3 ′, 5′-t-butyl-4′-hydroxyphenyl) propionate]. , Thioether compounds such as dilauryl-3,3′-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiodipropionate), triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4 -Anti-oxidants such as phosphorus compounds such as -di-t-butylphenyl) phosphite and lubricants include paraffin wax, microcrystalline wax, polyethylene wax, long chain fatty acids represented by montanic acid and montanic acid ester, and esters thereof Etc.
結晶核剤としては、脂肪族エステル、脂肪族アミド、脂肪酸金属塩等が挙げられ、脂肪族エステルとしては、ステアリン酸モノグリセライド、ベヘニン酸モノグリセライド等の脂肪酸エステル、１２−ヒドロキシステアリン酸トリグリセライド等のヒドロキシ脂肪酸エステル；脂肪族アミドとしては１２−ヒドロキシステアリン酸モノエタノールアミド等のヒドロキシ脂肪酸モノアミド、エチレンビスラウリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスカプリル酸アミド等の脂肪族ビスアミド、エチレンビス１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス１２−ヒドロキシステアリン酸アミド等のヒドロキシ脂肪酸ビスアミド；脂肪酸金属塩としては、１２−ヒドロキシステアリン酸カルシウム等のヒドロキシ脂肪酸金属塩等が挙げられる。結晶化速度と耐熱性、感温性、さらには透明性の観点から、１２−ヒドロキシステアリン酸トリグリセライド、ベヘニン酸モノグリセライド、エチレンビス１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス１２−ヒドロキシステアリン酸アミド、１２−ヒドロキシステアリン酸モノエタノールアミド、エチレンビスカプリル酸アミド、エチレンビスカプリン酸アミドが好ましく、１２−ヒドロキシステアリン酸トリグリセライド、エチレビス１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス１２−ヒドロキシステアリン酸アミド、１２−ヒドロキシステアリン酸モノエタノールアミドがより好ましく、１２−ヒドロキシステアリン酸トリグリセライド、エチレンビス１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス１２−ヒドロキシステアリン酸アミドがさらに好ましく、エチレンビス１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス１２−ヒドロキシステアリン酸アミドが特に好ましい。 Examples of the crystal nucleating agent include aliphatic esters, aliphatic amides, fatty acid metal salts, etc., and aliphatic esters include fatty acid esters such as stearic acid monoglyceride and behenic acid monoglyceride, and hydroxy fatty acids such as 12-hydroxystearic acid triglyceride. Esters: aliphatic amides such as hydroxy fatty acid monoamides such as 12-hydroxystearic acid monoethanolamide, aliphatic bisamides such as ethylene bislauric acid amide, ethylene biscapric acid amide and ethylene biscaprylic acid amide, ethylene bis 12-hydroxy stearin Hydroxy fatty acid bisamides such as acid amide and hexamethylene bis 12-hydroxystearic acid amide; As fatty acid metal salts, hydroxy fats such as calcium 12-hydroxystearate Acid metal salts and the like. From the viewpoints of crystallization speed, heat resistance, temperature sensitivity, and transparency, 12-hydroxystearic acid triglyceride, behenic acid monoglyceride, ethylene bis 12-hydroxystearic acid amide, hexamethylene bis 12-hydroxystearic acid amide, 12 -Hydroxystearic acid monoethanolamide, ethylene biscaprylic acid amide, ethylene biscapric acid amide are preferred, 12-hydroxystearic acid triglyceride, ethylene bis 12-hydroxystearic acid amide, hexamethylene bis 12-hydroxystearic acid amide, 12-hydroxy More preferred is stearic acid monoethanolamide, 12-hydroxystearic acid triglyceride, ethylene bis 12-hydroxystearic acid amide, hexamethyle More preferably bis 12-hydroxystearic acid amide, ethylenebis 12-hydroxystearic acid amide, hexamethylene bis hydroxystearic acid amide are particularly preferred.
難燃剤としては、例えば、有機ハロゲン化合物、アンチモン化合物、リン化合物、その他の有機難燃剤、無機難燃剤などが挙げられる。有機ハロゲン化合物としては、例えば、臭素化ポリカーボネート、臭素化エポキシ樹脂、臭素化フェノキシ樹脂、臭素化ポリフェニレンエーテル樹脂、臭素化ポリスチレン樹脂、臭素化ビスフェノールＡ、ポリペンタブロモベンジルアクリレート等が挙げられる。アンチモン化合物としては、例えば、三酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダ等が挙げられる。リン化合物としては、例えば、リン酸エステル、ポリリン酸、ポリリン酸アンモニウム、赤リン等が挙げられる。その他の有機難燃剤としては、例えば、メラミン、シアヌール酸などの窒素化合物などが挙げられる。その他の無機難燃剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、ケイ素化合物、ホウ素化合物などが挙げられる。 Examples of the flame retardant include organic halogen compounds, antimony compounds, phosphorus compounds, other organic flame retardants, and inorganic flame retardants. Examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, polypentabromobenzyl acrylate and the like. Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, and the like. As a phosphorus compound, phosphate ester, polyphosphoric acid, ammonium polyphosphate, red phosphorus etc. are mentioned, for example. Examples of other organic flame retardants include nitrogen compounds such as melamine and cyanuric acid. Examples of other inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, silicon compound, and boron compound.
さらに、本発明に係るポリブチレンテレフタレート（Ａ）には、本発明の目的を損なわない範囲で、強化充填材を配合することが出来る。強化充填材としては、特に制限されないが、例えば、板状無機充填材、セラミックビーズ、アスベスト、ワラストナイト、タルク、クレー、マイカ、ゼオライト、カオリン、チタン酸カリウム、硫酸バリウム、酸化チタン、酸化ケイ素、酸化アルミニウム、水酸化マグネシウムや、ガラス繊維、カーボン繊維、シリカ・アルミナ繊維、ジルコニア繊維、ホウ素繊維、窒化ホウ素繊維、窒化ケイ素チタン酸カリウム繊維、金属繊維などの無機繊維、芳香族ポリアミド繊維、フッ素樹脂繊維などの有機繊維などが挙げられる。これらの強化充填材は、２種以上を組み合わせて使用することが出来る。上記の強化充填材の中では、無機充填材、特に酸化ケイ素からなる不定形粒子が好適に使用される。 Furthermore, a reinforcing filler can be blended with the polybutylene terephthalate (A) according to the present invention as long as the object of the present invention is not impaired. The reinforcing filler is not particularly limited. For example, plate-like inorganic filler, ceramic beads, asbestos, wollastonite, talc, clay, mica, zeolite, kaolin, potassium titanate, barium sulfate, titanium oxide, silicon oxide , Aluminum oxide, magnesium hydroxide, glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, metal fiber and other inorganic fibers, aromatic polyamide fiber, fluorine Examples thereof include organic fibers such as resin fibers. These reinforcing fillers can be used in combination of two or more. Among the above reinforcing fillers, inorganic fillers, particularly amorphous particles made of silicon oxide are preferably used.
強化充填材は、ポリブチレンテレフタレート（Ａ）との界面密着性を向上させるため、表面処理剤で表面処理して使用することが好ましい。表面処理剤としては、例えば、エポキシ系化合物、アクリル系化合物、イソシアネート系化合物、シラン系化合物、チタネート系化合物などの官能性化合物が挙げられる。強化充填材は、収束剤または表面処理剤により予め表面処理しておくことが出来、または、ポリブチレンテレフタレート（Ａ）の組成物の調製の際に、表面処理剤を添加して表面処理することも出来る。強化充填材の添加量は、ポリブチレンテレフタレート（Ａ）１００質量部に対し、通常、１５０質量部以下、好ましくは1〜５０質量部の範囲である。 In order to improve the interfacial adhesion with the polybutylene terephthalate (A), the reinforcing filler is preferably used after being surface-treated with a surface treatment agent. Examples of the surface treatment agent include functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds. The reinforcing filler can be surface-treated with a sizing agent or a surface treatment agent in advance, or the surface treatment agent can be surface-treated by adding a surface treatment agent when preparing the polybutylene terephthalate (A) composition. You can also. The addition amount of the reinforcing filler is usually 150 parts by mass or less, preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate (A).
本発明に係るポリブチレンテレフタレート（Ａ）には、必要に応じて、ポリエチレン、ポリプロピレン、ポリメチルペンテン、ポリスチレン、ポリアクリロニトリル、ポリメタクリル酸エステル、ＡＢＳ樹脂、ポリカーボネート、ポリアミド、ポリフェニレンサルファイド、ポリエチレンテレフタレート、液晶ポリエステル、ポリアセタール、ポリフェニレンオキサイド等の熱可塑性樹脂、フェノール樹脂、メラミン樹脂、シリコーン樹脂、エポキシ樹脂などの熱硬化性樹脂を配合することが出来る。これらの熱可塑性樹脂および熱硬化性樹脂は、２種以上を組み合わせて使用することも出来る。 The polybutylene terephthalate (A) according to the present invention includes polyethylene, polypropylene, polymethylpentene, polystyrene, polyacrylonitrile, polymethacrylic acid ester, ABS resin, polycarbonate, polyamide, polyphenylene sulfide, polyethylene terephthalate, and liquid crystal as necessary. Thermosetting resins such as thermoplastic resins such as polyester, polyacetal, and polyphenylene oxide, phenol resins, melamine resins, silicone resins, and epoxy resins can be blended. These thermoplastic resins and thermosetting resins can be used in combination of two or more.
本発明に係るポリブチレンテレフタレート（Ａ）に、更に、結晶核剤（Ｂ）を添加することが耐熱性、プリント配線基板等の製造時には耐シワ性および剥離性向上の観点から好ましい。結晶核剤（Ｂ）の添加量としては、ポリブチレンテレフタレート（Ａ）１００質量部に対して、好ましくは３質量部以下、より好ましくは０．０１〜０．５質量部含む、さらに好ましくは０．０５〜０．３質量部含むと、より剥離性に優れる剥離フィルムを得ることができる。 It is preferable to add a crystal nucleating agent (B) to the polybutylene terephthalate (A) according to the present invention from the viewpoints of heat resistance and improvement of wrinkle resistance and peelability during the production of a printed wiring board and the like. The amount of the crystal nucleating agent (B) added is preferably 3 parts by mass or less, more preferably 0.01 to 0.5 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the polybutylene terephthalate (A). When it is contained in an amount of 0.05 to 0.3 parts by mass, a release film having more excellent peelability can be obtained.
本発明に係るポリブチレンテレフタレート（Ａ）に配合して使用される結晶核剤（Ｂ）としては、公知の有機系結晶核剤や無機系結晶核剤を用いることができる。無機系結晶核剤としては、タルク、カオリン、モンモリロナイト、合成マイカ、クレー、ゼオライト、シリカ、グラファイト、カーボンブラック、酸化亜鉛、酸化マグネシウム、酸化チタン、硫化カルシウム、窒化ホウ素、炭酸カルシウム、硫酸バリウム、酸化アルミニウム、酸化ネオジウム、第２リン酸アルミニウム、第３リン酸カルシウム及びフェニルホスホネートの金属塩等を挙げることができる。これらの無機系結晶核剤は、組成物中での分散性を高めるために、有機物で修飾されていてもよい。 As the crystal nucleating agent (B) used by blending with the polybutylene terephthalate (A) according to the present invention, a known organic crystal nucleating agent or inorganic crystal nucleating agent can be used. Inorganic crystal nucleating agents include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, oxidation Examples thereof include aluminum, neodymium oxide, dibasic aluminum phosphate, tricalcium phosphate, and metal salts of phenylphosphonate. These inorganic crystal nucleating agents may be modified with an organic substance in order to enhance the dispersibility in the composition.
有機系結晶核剤としては、フェニルホスホン酸（塩）又はその誘導体、例えば、フェニルホスホン酸亜鉛、フェニルホスホン酸ジクロライド、フェニルホスホン酸ジメチル、リン酸メラミン、ビス(p-メチルペンジリデン)ソルビトール,ビス(p-トルイリデン)ソルビトール等が好ましい。その他の有機系結晶核剤としては、安息香酸ナトリウム、安息香酸カリウム、安息香酸リチウム、安息香酸カルシウム、安息香酸マグネシウム、安息香酸バリウム、テレフタル酸リチウム、テレフタル酸ナトリウム、テレフタル酸カリウム、シュウ酸カルシウム、ラウリン酸ナトリウム、ラウリン酸カリウム、ミリスチン酸ナトリウム、ミリスチン酸カリウム、ミリスチン酸カルシウム、オクタコサン酸ナトリウム、オクタコサン酸カルシウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸リチウム、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸バリウム、モンタン酸ナトリウム、モンタン酸カルシウム、トルイル酸ナトリウム、サリチル酸ナトリウム、サリチル酸カリウム、サリチル酸亜鉛、アルミニウムジベンゾエート、カリウムジベンゾエート、リチウムジベンゾエート、ナトリウムβ−ナフタレート、ナトリウムシクロヘキサンカルボキシレート等の有機カルボン酸金属塩、ｐ−トルエンスルホン酸ナトリウム、スルホイソフタル酸ナトリウム等の有機スルホン酸塩、ステアリン酸アミド、エチレンビスラウリン酸アミド、パルチミン酸アミド、ヒドロキシステアリン酸アミド、エルカ酸アミド、トリメシン酸トリス（ｔ−ブチルアミド）等のカルボン酸アミド、エチレン−アクリル酸又はメタクリル酸コポリマーのナトリウム塩、スチレン−無水マレイン酸コポリマーのナトリウム塩等のカルボキシル基を有する重合体のナトリウム塩又はカリウム塩（いわゆるアイオノマー）、ベンジリデンソルビトール及びその誘導体、ナトリウム−２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェート等のリン化合物金属塩、及び２，２−メチルビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム等を挙げることができる。これら結晶核剤の中では、ビス（４−メチルベンジリデン）ソルビトール、ナトリウム−２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェート、ステアリン酸マグネシウム、エチレン・ビスステアリン酸アミドなどが好ましい。 Organic crystal nucleating agents include phenylphosphonic acid (salts) or derivatives thereof, such as zinc phenylphosphonate, phenylphosphonic dichloride, dimethyl phenylphosphonate, melamine phosphate, bis (p-methylpentylidene) sorbitol, bis (p-Toluylidene) sorbitol and the like are preferable. Other organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate , Sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, etc., organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid amide , Carboxylic acid amides such as ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, styrene-maleic anhydride Sodium salt or potassium salt of polymer having carboxyl group such as sodium salt of acid copolymer (so-called ionomer), benzylidene sorbitol and its derivatives, nato Phosphorus compound metal salts such as lithium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) sodium Can be mentioned. Among these crystal nucleating agents, bis (4-methylbenzylidene) sorbitol, sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, magnesium stearate, ethylene bis-stearamide Etc. are preferable.
２．クッション層
本発明に係るクッション層により、多層離型フィルムを使用する際に、離型層の所定の厚みと引張弾性率に起因する効果と相まって加熱プレスの圧力を均一にかけることができ、プリント配線基板等の凹凸に追従できるといういわゆる埋め込み性を多層離型フィルムに付与することができる。また、前記クッション層のビカット軟化温度が５０〜１５０℃であることにより多層離型フィルムに剛性を付与し、プリント配線基板等の加工の際の加熱プレス時に弛みを減少させてシワの発生を抑止することおよび多層離型フィルム自体に発生するボイドを効果的に防止することができる。なお、クッション層のビカット軟化温度はＪＩＳＫ７２０６（１９９９年）に準じて測定された値である。また、クッション層のビカット軟化温度は多層離型フィルムに適切な剛性を付与し、プリント配線基板等の加工の際のシワ発生を防止するという観点から、７０〜１２０℃がより好ましい。また、クッション層の厚みは２０〜８０μｍが好ましく、２５〜６０μｍがさらに好ましく、３０〜５０μｍが最も好ましい。クッション層の厚みを２０〜８０μｍに範囲にすることにより、埋め込み性、耐汚染性、および離型性をより向上させることができる。
2. Cushion layer By using the cushion layer according to the present invention, when using a multilayer release film, the pressure of the heating press can be uniformly applied in combination with the effect due to the predetermined thickness and tensile elastic modulus of the release layer. A so-called embedding property that can follow the unevenness of a wiring board or the like can be imparted to the multilayer release film. Moreover, the Vicat softening temperature of the cushion layer is 50 to 150 ° C. to give rigidity to the multilayer release film, and to reduce wrinkles by reducing slack during heating press when processing printed circuit boards etc. And voids generated in the multilayer release film itself can be effectively prevented. The Vicat softening temperature of the cushion layer is a value measured according to JISK7206 (1999). Further, the Vicat softening temperature of the cushion layer is more preferably 70 to 120 ° C. from the viewpoint of imparting appropriate rigidity to the multilayer release film and preventing generation of wrinkles during processing of a printed wiring board or the like. The thickness of the cushion layer is preferably 20 to 80 μm, more preferably 25 to 60 μm, and most preferably 30 to 50 μm. By setting the thickness of the cushion layer in the range of 20 to 80 μm, embedding property, contamination resistance, and mold release property can be further improved.
本発明に係るクッション層を構成する樹脂として、具体的には低密度ポリエチレン、ポリプロピレン、エチレンメチルメタクリレート共重合体、エチレン酢酸ビニル共重合体、エチレンプロピレン共重合体、エチレンブテン共重合体、プロピレンブテン共重合体、などのポリオレフィン樹脂、エチレン・アクリル酸メチル共重合体、エチレン・メタクリル酸メチル共重合体などのアクリル系樹脂の共重合体、を単独で使用しても２種類以上が併用されてもよい。その中でもクッション層を構成する樹脂として埋め込み性およびクッション層と離型層との接着安定性の観点からエチレン・アクリル酸メチル共重合体、エチレン・メタクリル酸メチル共重合体が好ましい。さらに、クッション層を構成する樹脂として、エチレン・（メタ）アクリル酸メチル共重合体（Ｂ）に加え、ポリブチレンテレフタレート（Ａ）を含有していることがプリント配線基板等の製作の際の多層離型フィルムの剥離性向上や熱プレス時にクッション層を構成する軟化温度の低い樹脂が染み出して基板やプレス熱板を汚染することを抑制する観点から好ましい。クッション層でのポリブチレンテレフタレート（Ａ）の含有量としては多層離型フィルムの剥離性向上や低汚染性の観点から５０質量％を上限としてエチレン・（メタ）アクリル酸メチル共重合体とともに含有させることが好ましく、より好ましくは５〜４５質量％、さらに好ましくは１０〜４０質量％である〔但し、（Ａ）＋（Ｂ）＝１００質量％とする。〕。 Specifically, as the resin constituting the cushion layer according to the present invention, low density polyethylene, polypropylene, ethylene methyl methacrylate copolymer, ethylene vinyl acetate copolymer, ethylene propylene copolymer, ethylene butene copolymer, propylene butene Copolymers and other polyolefin resins, ethylene / methyl acrylate copolymers, and acrylic resin copolymers such as ethylene / methyl methacrylate copolymers can be used alone or in combination. Also good. Of these, ethylene / methyl acrylate copolymer and ethylene / methyl methacrylate copolymer are preferable as the resin constituting the cushion layer from the viewpoint of embedding property and adhesion stability between the cushion layer and the release layer. In addition to the ethylene / methyl (meth) acrylate copolymer (B) as a resin constituting the cushion layer, polybutylene terephthalate (A) is included in the multilayer for the production of printed wiring boards and the like. It is preferable from the viewpoint of suppressing the release property of the release film and preventing the resin having a low softening temperature that constitutes the cushion layer from exuding during hot pressing and contaminating the substrate and the press hot plate. The content of polybutylene terephthalate (A) in the cushion layer is 50% by mass with the ethylene / (meth) acrylate methyl copolymer from the viewpoint of improving the peelability of the multilayer release film and low contamination. It is preferably 5 to 45% by mass, more preferably 10 to 40% by mass [provided that (A) + (B) = 100% by mass. ].
２−１．エチレン・（メタ）アクリル酸メチル共重合体（Ｂ）
本発明の多層離型フィルムのクッション層を構成するエチレン・（メタ）アクリル酸メチル共重合体（Ｂ）は、エチレンと不飽和カルボン酸エステルであるアクリル酸エステルまたはメタクリル酸エステルからなる共重合体である。 本発明に係るエチレン・（メタ）アクリル酸メチル共重合体（Ｂ）のメルトフローレート（ＭＦＲ）は０．１〜２０ｇ／１０分であることが好ましく、より好ましくは０．５〜１５ｇ／１０分であり、さらに好ましくは１〜１０ｇ／１０分である。ＭＦＲが小さすぎると押出加工した時に押出機の負荷が高くなることがあり、ＭＦＲが大きすぎると押出加工時に押出し量が一定化しないいわゆるサージングが発生することがある。なお、エチレン・（メタ）アクリル酸メチル共重合体（Ｂ）のＭＦＲは、ＪＩＳ Ｋ ７２１０に従い、温度１９０℃ 、荷重２１．１８Ｎの条件で測定される。
2-1. Ethylene / methyl methacrylate copolymer (B)
The ethylene / (meth) methyl acrylate copolymer (B) constituting the cushion layer of the multilayer release film of the present invention is a copolymer comprising ethylene and an acrylic ester or methacrylic ester which is an unsaturated carboxylic ester. It is. The melt flow rate (MFR) of the ethylene / (meth) acrylic acid methyl copolymer (B) according to the present invention is preferably 0.1 to 20 g / 10 minutes, more preferably 0.5 to 15 g / 10. Minute, more preferably 1 to 10 g / 10 minutes. If the MFR is too small, the load on the extruder may increase when extrusion is performed, and if the MFR is too large, so-called surging that does not stabilize the extrusion amount during extrusion may occur. The MFR of the ethylene / methacrylic acid methyl copolymer (B) is measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N according to JIS K 7210.
本発明に係るエチレン・（メタ）アクリル酸メチル共重合体（Ｂ）は、公知の製造方法、例えば、有機過酸化物や酸素等の遊離基発生剤を使用するラジカル共重合反応等が挙げられる。ラジカル共重合反応は、通常１３０〜３００℃の重合温度、通常４０〜３００ＭＰａの重合圧力で実施される。
本発明に係るエチレン・（メタ）アクリル酸メチル共重合体（Ｂ）におけるアクリル酸エステル、メタクリル酸エステルから誘導される繰り返し単位の含有量は２〜３０重量％であることが好ましく、より好ましくは５〜２５重量％ である。当該含有量が少なすぎると、クッション性が低くなることがあり、該含有量が多すぎると、フィルムに加工する際に耐熱性が低下し、冷却ロールに巻き付く等の加工性に劣ることがある。
The ethylene / methyl (meth) acrylate copolymer (B) according to the present invention may be a known production method such as a radical copolymerization reaction using a free radical generator such as an organic peroxide or oxygen. . The radical copolymerization reaction is usually performed at a polymerization temperature of 130 to 300 ° C. and a polymerization pressure of 40 to 300 MPa.
The content of the repeating unit derived from the acrylate ester and methacrylate ester in the ethylene / (meth) acrylate methyl copolymer (B) according to the present invention is preferably 2 to 30% by weight, more preferably. 5 to 25% by weight. If the content is too small, the cushioning property may be lowered, and if the content is too large, the heat resistance is lowered when processed into a film, and the workability such as winding around a cooling roll may be inferior. is there.
本発明に係るエチレン・（メタ）アクリル酸メチル共重合体（Ｂ）のうち、エチレン・メタクリル酸メチル共重合体は、例えば、住友化学社から、商品名 アクリフトＷＤ２０１（ＭＦＲ：２ｇ／１０分、メタクリル酸メチル単量体単位含有量：１０質量％）、アクリフトＷＤ２０６（ＭＦＲ：２ｇ／１０分、メタクリル酸メチル単量体単位含有量：２０質量％）として、製造・販売されている。 Among the ethylene / methyl methacrylate copolymer (B) according to the present invention, an ethylene / methyl methacrylate copolymer is, for example, from Sumitomo Chemical Co., Ltd., trade name ACRIFT WD201 (MFR: 2 g / 10 min. Methyl methacrylate monomer unit content: 10% by mass), Acrift WD206 (MFR: 2 g / 10 min, methyl methacrylate monomer unit content: 20% by mass), manufactured and sold.
本発明に係るエチレン・（メタ）アクリル酸メチル共重合体（Ｂ）の融点は、示差走査型熱量計（ＤＳＣ）を用いて１６０℃で５分間加熱溶融した後、液体窒素で急冷して得たサンプル約１０ｍｇを精秤し、窒素気流中、１０℃／分の昇温速度で１６０℃まで昇温して熱融解曲線を得、得られた熱融解曲線から、融点（Ｔｍ）（℃）が求められる。 The melting point of the ethylene / (meth) acrylic acid methyl copolymer (B) according to the present invention is obtained by heating and melting at 160 ° C. for 5 minutes using a differential scanning calorimeter (DSC) and then rapidly cooling with liquid nitrogen. About 10 mg of the sample was precisely weighed and heated to 160 ° C. in a nitrogen stream at a rate of temperature increase of 10 ° C./min to obtain a thermal melting curve. From the obtained thermal melting curve, melting point (Tm) (° C.) Is required.
＜多層離型フィルムの製造方法＞
本発明の離型多層離型フィルムは、種々公知のフィルムの成形方法により製造できる。例えば、本発明の離型多層離型フィルムを製造する場合は、多層Ｔ−ダイあるいは多層環状ダイを用いて、共押出成形することにより製造することができ、その他の押出ラミネート法、ドライラミネート法などの公知のラミネート方法を用いても良い。その中でも上記多層Ｔ−ダイを用いてなる共押出成形法が各層の膜厚を均一にでき、また幅広化ができる点で優れており、幅広の積層体を製造した後、多種多様なＦＰＣの幅に合わせた幅にスリットすることが容易なため、ＦＰＣ製造用の多層離型フィルムの製造方法として好ましい。
<Method for producing multilayer release film>
The release multilayer release film of the present invention can be produced by various known film forming methods. For example, when producing the release multilayer release film of the present invention, it can be produced by coextrusion using a multilayer T-die or multilayer annular die, and other extrusion lamination methods and dry lamination methods. A known laminating method such as, for example, may be used. Among them, the coextrusion method using the multilayer T-die is excellent in that the thickness of each layer can be made uniform and widened, and after manufacturing a wide laminate, a wide variety of FPC Since it is easy to slit to the width | variety matched with the width | variety, it is preferable as a manufacturing method of the multilayer release film for FPC manufacture.
本発明の多層離型フィルムは、上記記載の製造方法で得られた多層離型フィルムを、さらに加熱処理すると離型性が向上するので好ましい。本発明の多層離型フィルムを加熱処理する方法は、種々公知の方法、具体的には、テンター法で成形して得たロール状の多層離型フィルムを加熱された熱風オーブンにロールツーロール方式で通す方法、または、ロールツーロール方式で通しているライン上に、赤外線ヒーターなどのヒーターを設置して多層離型フィルムを加熱する方法、ロール状の多層離型フィルムを所定の寸法にカットした枚葉状のフィルムで、熱風オーブンで加熱処理する方法、テンター法で成形したロール状の多層離型フィルムをロール巻取り方式で加熱したロールに接触させる方法などである。 The multilayer release film of the present invention is preferable because the release property is improved when the multilayer release film obtained by the production method described above is further heat-treated. The method for heat-treating the multilayer release film of the present invention may be any of various known methods, specifically, a roll-to-roll method in which a roll-shaped multilayer release film obtained by molding by a tenter method is heated in a heated hot air oven. Or a method of heating a multilayer release film by installing a heater such as an infrared heater on a line passing by a roll-to-roll method, or cutting a roll-shaped multilayer release film into a predetermined dimension For example, a sheet-like film is heated in a hot air oven, and a roll-shaped multilayer release film formed by a tenter method is brought into contact with a roll heated by a roll winding method.
多層離型フィルムを加熱する熱源としては特に限定はされないが、赤外線ヒーターである遠赤外線ヒーターや短波長赤外線ヒーター、中波長赤外線ヒーター、カーボンヒーターなどが好ましい。また、テンター法で成形したロール状の多層離型フィルムをロールツーロール方式で加熱したロールに接触させる方法は、加熱したロールに直接多層離型フィルムが接触するため、多層離型フィルム表面の熱伝達が早くて済むため、加熱処理時間が比較的短時間にできるため生産性を向上させることができる。 The heat source for heating the multilayer release film is not particularly limited, but a far infrared heater, a short wavelength infrared heater, a medium wavelength infrared heater, a carbon heater, or the like that is an infrared heater is preferable. In addition, the method in which a roll-shaped multilayer release film formed by the tenter method is brought into contact with a roll heated by a roll-to-roll method is such that the multilayer release film is in direct contact with the heated roll. Since the transmission is fast, the heat treatment time can be made relatively short, so that productivity can be improved.
多層離型フィルムを構成する離型層の表面に所定の表面粗さ（Ｒａ）を付与するための方法として、生産効率の観点からエンボスロールによりエンボス処理をすることが好ましい。エンボスロールによるエンボス処理の場合、製膜した多層離型フィルムを高温高圧下にて、マットロールにフィルムを通すことによって行う方法、多層離型フィルムを製膜しながらダイレクトにエンボスロールに押し当てて行う方法などが利用できる。当該エンボスロールによるエンボス処理を行う方法では、エンボスロールの温度によって多層離型フィルムの離型層の表面粗さ（Ｒａ）を制御することができ、エンボスロールの温度は、１５０〜２００℃でエンボス処理を行なうことにより所定の表面粗さ（Ｒａ）を得ることができる。エンボスロールの温度が２００℃を超えると、多層離型フィルムが軟化しすぎてエンボスロールへの密着が強くなりすぎ、エンボスロールからの離型が難しくなる。一方、エンボスロールの温度が１５０℃より低いとエンボスロールにて押圧後の多層離型フィルムの表面粗さ（Ｒａ）が小さくなることがある。 As a method for imparting a predetermined surface roughness (Ra) to the surface of the release layer constituting the multilayer release film, embossing with an embossing roll is preferred from the viewpoint of production efficiency. In the case of embossing with an embossing roll, a method of passing the formed multilayer release film by passing the film through a mat roll under high temperature and high pressure, directly pressing the multilayer release film on the embossing roll while forming the film The method of doing etc. can be used. In the method of embossing with the embossing roll, the surface roughness (Ra) of the release layer of the multilayer release film can be controlled by the temperature of the embossing roll, and the embossing roll is embossed at 150 to 200 ° C. A predetermined surface roughness (Ra) can be obtained by performing the treatment. When the temperature of the embossing roll exceeds 200 ° C., the multilayer release film becomes too soft and the adhesion to the embossing roll becomes too strong, making it difficult to release from the embossing roll. On the other hand, when the temperature of the embossing roll is lower than 150 ° C., the surface roughness (Ra) of the multilayer release film after being pressed by the embossing roll may be small.
また、エンボスロールの柄は、円形、方形等の規則性柄であってもサンドブラストの不規則柄であってもよく、特に制限されないが汎用のサンドブラスト模様が加熱されたフィルムの滑り性が良い点で適している。さらに、エンボスロールの表面粗さＲａは、１〜２０μｍ、好ましくは２〜１５μｍ、さらに好ましくは３〜１０μｍである。エンボスロールの表面粗さに対して、上述したようにエンボスロール温度を適宜選択することで、エンボスロールからフィルムへのエンボス転写率を制御することができるが、エンボス処理時のエンボスロールの線圧によってもエンボス転写率を制御することができ、好ましい線圧は２０〜１５０ｋｇ／ｃｍ、さらに好ましい線圧は５０〜１００ｋｇ／ｃｍである。 In addition, the pattern of the embossing roll may be a regular pattern such as a circle or a square, or an irregular pattern of sandblast, and is not particularly limited, but the slipperiness of a film heated with a general-purpose sandblast pattern is good. Suitable for. Furthermore, the surface roughness Ra of the embossing roll is 1 to 20 μm, preferably 2 to 15 μm, and more preferably 3 to 10 μm. By appropriately selecting the embossing roll temperature as described above for the surface roughness of the embossing roll, the embossing transfer rate from the embossing roll to the film can be controlled, but the linear pressure of the embossing roll during the embossing process Can also control the emboss transfer rate, and a preferable linear pressure is 20 to 150 kg / cm, and a more preferable linear pressure is 50 to 100 kg / cm.
また、多層離型フィルムの離型層の表面に効率よく凹凸を設ける為に、エンボスロール直前に予熱ロールを設けても良い。予熱ロールとは、フィルムを予め加熱するための加熱されたロールをいう。予熱ロール温度は、５０〜１８０℃、好ましくは９０〜１６０℃である。 Moreover, in order to provide unevenness efficiently on the surface of the release layer of the multilayer release film, a preheating roll may be provided immediately before the embossing roll. The preheating roll refers to a heated roll for preheating the film. The preheating roll temperature is 50 to 180 ° C, preferably 90 to 160 ° C.
（実施例）
本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。使用した樹脂組成物等は次の通りである。
本発明の実施例及び比較例で用いたポリブチレンテレフタレート及び結晶核剤、エチレン・（メタ）アクリル酸メチル共重合体を以下に示す。
（１）ポリブチレンテレフタレート（Ａ）（ＰＢＴ（Ａ））
（Ａ−１）Ｔｇ＝５２℃、Ｔｍ＝２２３℃、ＩＶ＝１．１
〔ポリプラスチックス（株）製、商品名：ジュラネックス７００ＦＰ〕
（Ａ−２）Ｔｇ＝５４℃、Ｔｍ＝２２７℃、ＩＶ＝１．２
〔長春製、商品名：１１００−２１１Ｓ〕
（Ａ−３）Ｔｇ＝４６℃、Ｔｍ＝２２３℃、ＩＶ＝１．１
〔三菱エンジニアリングプラスチック（株）製、商品名：ノバデュラン５０１０ＣＳ〕
（Ａ−４）Ｔｇ＝４６℃、Ｔｍ＝２１９℃、ＩＶ＝１．２
〔三菱エンジニアリングプラスチック（株）製、商品名：ノバデュラン５５０５Ｓ〕
（２）エチレン・（メタ）アクリル酸メチル共重合体（Ｂ）（ＥＭＭＡ（Ｂ））
（Ｂ−１）Ｔｍ＝１００℃、ＭＦＲ（ｇ／１０ｍｉｎ）＝２
〔住友化学（株）製、商品名：アクリフトＷＤ２０１〕
（３）結晶核剤（Ｃ）
（Ｃ−１）ビス（４−メチルベンジリデン）ソルビトール、Ｔｍ＝２６０℃
〔新日本理化（株）製、商品名：ゲルオールＭＤ〕
(Example)
Examples The present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The resin composition used is as follows.
The polybutylene terephthalate, crystal nucleating agent, and ethylene / methyl (meth) acrylate copolymer used in Examples and Comparative Examples of the present invention are shown below.
(1) Polybutylene terephthalate (A) (PBT (A))
(A-1) Tg = 52 ° C., Tm = 223 ° C., IV = 1.1
[Product name: DURANEX 700FP, manufactured by Polyplastics Co., Ltd.]
(A-2) Tg = 54 ° C., Tm = 227 ° C., IV = 1.2
[Product made in Changchun, trade name: 1100-211S]
(A-3) Tg = 46 ° C., Tm = 223 ° C., IV = 1.1
[Product name: NOVADURAN 5010CS, manufactured by Mitsubishi Engineering Plastics Co., Ltd.]
(A-4) Tg = 46 ° C., Tm = 219 ° C., IV = 1.2
[Made by Mitsubishi Engineering Plastics Co., Ltd., product name: Nova Duran 5505S]
(2) Ethylene / (meth) methyl acrylate copolymer (B) (EMMA (B))
(B-1) Tm = 100 ° C., MFR (g / 10 min) = 2
[Product name: ACLIFT WD201, manufactured by Sumitomo Chemical Co., Ltd.]
(3) Crystal nucleating agent (C)
(C-1) Bis (4-methylbenzylidene) sorbitol, Tm = 260 ° C.
[New Nippon Rika Co., Ltd., trade name: Gelall MD]
（結晶核剤のマスターバッチの作製方法）
上記記載のポリブチレンテレフタレート（Ａ）９５質量％と上記記載の結晶核剤（Ｃ）５質量％の組成比でブレンド後、二軸押出機を使用し、２５０℃のシリンダー温度で溶融混練しペレット化し、結晶核剤の濃度が５質量％である結晶核剤マスターバッチを作製した。
(Production method of master batch of crystal nucleating agent)
After blending at a composition ratio of 95% by mass of the polybutylene terephthalate (A) described above and 5% by mass of the crystal nucleating agent (C) described above, the mixture was melt-kneaded using a twin screw extruder at a cylinder temperature of 250 ° C. A crystal nucleating agent master batch having a concentration of 5% by mass of the crystal nucleating agent was produced.
（参考例１）
（多層離型フィルムの作製方法）
表１に示す配合量でポリブチレンテレフタレート（Ａ）（「ＰＢＴ（Ａ）」と表記）として（Ａ−１）、及び結晶核剤（Ｃ）として（Ｃ−１）、エチレン・（メタ）アクリル酸メチル（Ｂ）（「ＥＭＭＡ（Ｂ）」と表記）として（Ｂ−１）を原料として、シリンダー径が４０ｍｍφの押出機に投入して、原料の混練・均一化を行いそれぞれ樹脂温度２５０℃程度で３層共押出し法によりキャスティングロール温度８０℃程度にして、両外面の離型層（以下、それぞれ「離型層１」、「離型層２」と表記する。）の厚み３５μｍの層と、コア層のクッション層の厚み４０μｍの層とからなる３層構成の多層フィルムを得た。エンボス処理は、ロールツーロールで８０℃の予熱ロール温度に前記多層フィルムの離型層１面を接触させた後、同離型層１面を表面粗さＲａが４μｍのエンボスロールで、エンボスロール温度１６０℃、エンボス線圧５０ｋｇ／ｃｍで押圧して一旦ロール状で巻き取った。さらに離型層２面についても上記条件にてエンボス処理し両面エンボス多層離型フィルムを得た。
（参考例２）
クッション層の両表面に設けられた離型層１、２の厚みを４０μｍとした以外は参考例１と同様にして３層構成の多層離型フィルムを得た。
（実施例３）
クッション層の両表面に設けられた離型層１、２の厚みを５０μｍとした以外は参考例１と同様にして３層構成の多層離型フィルムを得た。
（実施例４）
クッション層の両表面に設けられた離型層１、２の厚みを７０μｍとした以外は参考例１と同様にして３層構成の多層離型フィルムを得た。
（参考例５）
クッション層の厚みを６０μｍとし、離型層１、２の厚みを４０μｍとした以外は参考例１と同様にして３層構成の多層離型フィルムを得た。
（参考例６）
離型層１、２のＰＢＴ（Ａ）の原料を（Ａ−２）に変更した以外は参考例２と同様にして３層構成の多層フィルムを得た。
（参考例７）
離型層１、２のＰＢＴ（Ａ）の原料を（Ａ−３）に変更した以外は参考例２と同様にして３層構成の多層フィルムを得た。
（参考例８）
クッション層の原料をＥＭＭＡ（Ｂ）１００質量％にした以外は参考例２と同様にして２種３層構成の多層フィルムを得た。
（参考例９）
離型層１、２のＰＢＴ（Ａ）の原料を（Ａ−１）１００質量％にし、結晶核剤（Ｃ）を使用しなかった以外は参考例２と同様にして３層構成の多層フィルムを得た。
( Reference Example 1)
(Method for producing multilayer release film)
(A-1) as polybutylene terephthalate (A) (denoted as “PBT (A)”), (C-1) as crystal nucleating agent (C), ethylene (meth) acrylic in the compounding amounts shown in Table 1 Methyl acid (B) (denoted as “EMMA (B)”) (B-1) as a raw material is introduced into an extruder having a cylinder diameter of 40 mmφ, and the raw material is kneaded and homogenized to a resin temperature of 250 ° C. A casting roll temperature of about 80 ° C. by a three-layer coextrusion method, and a layer having a thickness of 35 μm of release layers on both outer surfaces (hereinafter referred to as “release layer 1” and “release layer 2”, respectively). And a multilayer film having a three-layer structure comprising a cushion layer of the core layer and a thickness of 40 μm. The embossing treatment is performed by roll-to-roll with an embossing roll having a surface roughness Ra of 4 μm after bringing the release layer 1 side of the multilayer film into contact with a preheated roll temperature of 80 ° C. It was pressed at a temperature of 160 ° C. and an embossed linear pressure of 50 kg / cm and once wound up in a roll shape. Further, the two release layers were embossed under the above conditions to obtain a double-sided embossed multilayer release film.
( Reference Example 2)
A multilayer release film having a three-layer structure was obtained in the same manner as in Reference Example 1 except that the thickness of the release layers 1 and 2 provided on both surfaces of the cushion layer was 40 μm.
(Example 3)
A multilayer release film having a three-layer structure was obtained in the same manner as in Reference Example 1 except that the thicknesses of the release layers 1 and 2 provided on both surfaces of the cushion layer were 50 μm.
Example 4
A multilayer release film having a three-layer structure was obtained in the same manner as in Reference Example 1 except that the thicknesses of the release layers 1 and 2 provided on both surfaces of the cushion layer were 70 μm.
( Reference Example 5)
A multilayer release film having a three-layer structure was obtained in the same manner as in Reference Example 1 except that the thickness of the cushion layer was 60 μm and the thickness of the release layers 1 and 2 was 40 μm.
( Reference Example 6)
A multilayer film having a three-layer structure was obtained in the same manner as in Reference Example 2 except that the raw material of PBT (A) for the release layers 1 and 2 was changed to (A-2).
( Reference Example 7)
A multilayer film having a three-layer structure was obtained in the same manner as in Reference Example 2 except that the raw material of PBT (A) for the release layers 1 and 2 was changed to (A-3).
( Reference Example 8)
A multilayer film having two types and three layers was obtained in the same manner as in Reference Example 2 except that the material for the cushion layer was changed to 100% by mass of EMMA (B).
( Reference Example 9)
A multilayer film having a three-layer structure as in Reference Example 2 except that the PBT (A) raw material of the release layers 1 and 2 is (A-1) 100 mass% and the crystal nucleating agent (C) is not used. Got.
（比較例１）
クッション層の両表面に設けられた離型層１、２の厚みを３０μｍとし、クッション層の厚みを９０μｍとし、クッション層の原料をＥＭＭＡ（Ｂ）１００質量％にした以外は参考例１と同様にして３層構成の多層フィルムを得た。
（比較例２）
クッション層の両表面に設けられた離型層１、２の厚みを２５μｍとし、クッション層の厚みを７５μｍとした以外は比較例１と同様にして３層構成の多層フィルムを得た。
（比較例３）
クッション層の両表面に設けられた離型層１、２の厚みを１２μｍとし、クッション層の厚みを１００μｍとした以外は比較例１と同様にして３層構成の多層フィルムを得た。
（比較例４）
クッション層の両表面に設けられた離型層１、２の厚みを２５μｍとし、クッション層の厚さを１００μｍとした以外は参考例１と同様にして３層構成の多層フィルムを得た。
（比較例５）
クッション層の両表面に設けられた離型層１、２の厚みを両外層の離型層の厚さを８０μｍとし、クッション層の厚さを４０μｍとした以外は参考例１と同様にして３層構成の多層フィルムを得た。
（比較例６）
クッション層の両表面に設けられた離型層１、２のＰＢＴ（Ａ）の原料を（Ａ−４）に変更した以外は参考例２と同様にして３層構成の多層フィルムを得た。
(Comparative Example 1)
The same as Reference Example 1 except that the release layers 1 and 2 provided on both surfaces of the cushion layer have a thickness of 30 μm, the cushion layer has a thickness of 90 μm, and the cushion layer material is 100% by mass of EMMA (B). Thus, a multilayer film having a three-layer structure was obtained.
(Comparative Example 2)
A multilayer film having a three-layer structure was obtained in the same manner as in Comparative Example 1 except that the release layers 1 and 2 provided on both surfaces of the cushion layer had a thickness of 25 μm and the cushion layer had a thickness of 75 μm.
(Comparative Example 3)
A multilayer film having a three-layer structure was obtained in the same manner as in Comparative Example 1 except that the release layers 1 and 2 provided on both surfaces of the cushion layer had a thickness of 12 μm and the cushion layer had a thickness of 100 μm.
(Comparative Example 4)
A multilayer film having a three-layer structure was obtained in the same manner as in Reference Example 1 except that the thickness of the release layers 1 and 2 provided on both surfaces of the cushion layer was 25 μm and the thickness of the cushion layer was 100 μm.
(Comparative Example 5)
3 in the same manner as in Reference Example 1 except that the thicknesses of the release layers 1 and 2 provided on both surfaces of the cushion layer are 80 μm for the outer layers and 40 μm for the cushion layers. A multilayer film having a layer structure was obtained.
(Comparative Example 6)
A multilayer film having a three-layer structure was obtained in the same manner as in Reference Example 2 except that the raw material of PBT (A) of the release layers 1 and 2 provided on both surfaces of the cushion layer was changed to (A-4).
（評価項目）
上記の離型フィルムを以下の方法により、評価を行った。
（１）離型性評価および耐シワ性評価
図２に示すように、ポリイミドフィルム４-１とエポキシ樹脂系接着剤層４-２からなるカバーレイフィルム４〔ニッカン工業（株）製、商品名：ＣＩＳＶ２５３５）を用いた。このカバーレイフィルム４にはプリント配線基板５の電極端子部分に相当する部分が切欠き部６として打ち抜かれている。切欠き部６の大きさは４ｍｍ×２０ｍｍで、１枚のカバーレイフィルム４に複数箇所に形成されている。一方、プリント配線基板５は厚さ２５μｍのポリイミドフィルム上に厚さ１２μｍの銅箔（図示せず）で配線パターンが形成されている２４０ｍｍ×３００ｍｍの大きさのものを用いた。
プリント配線基板５とカバーレイフィルム４を位置決めして重ね合わせ、カバーレイフィルム側に多層離型フィルム１の離型層１の表面が重なるようにして、加熱プレス機にセットした。なお、多層離型フィルム１は、図２に示すようにフィルム長手方向の両端におもり７を固定し、テンションがかかった状態で加熱プレスすることで、多層離型フィルム１の耐シワ性の評価を行った。多層離型フィルム１の幅は２７０ｍｍとし、テンションは３．５ｋｇ／２７０ｍｍの荷重になるようにおもり７を取り付けた。
温度１８０℃、圧力４ＭＰａ、加圧時間１２０秒の条件で加熱プレスした後、プレス板を開放して多層離型フィルムのテンションを除荷した後、多層離型フィルム１をカバーレイフィルム４が接着したプリント配線基板５から手で剥がしてプリント配線基板５の表面に対しほぼ垂直な角度で離型させた。
離型性評価としては、多層離型フィルム１を手で離型させた際、離型が重い場合に発生するプリント配線基板への折れ跡痕の有無を調べた。
離型性の評価としては以下の基準に基づいて行った。
・折れ跡痕無し：判定○
・折れ跡痕あり：判定×
離型性評価において、折れ跡痕がなければプリント配線基板等の離型フィルムとして使用可能であるが、折れ跡痕があればプリント配線基板等の離型フィルムとしては使用することができない。
耐シワ性評価としては、離型フィルム離型後のプリント配線基板表面に入った長さ５ｍｍ以上のシワの数を数えた。
耐シワ性の評価は以下の基準に基づいて行った。
・３０本未満：判定◎
・３０本以上、４０本未満：判定○
・４０本以上、５０本未満：判定△
・５０本以上：判定×
耐シワ性評価において、上記シワの数で５０本未満がプリント配線基板等の製作時に離型フィルムとして使用できる範囲であり、シワの数が少ないほど好ましい。一方、上記シワの数が５０本以上（判定：×）となると離型フィルムの剥離後にプリント配線基板等にシワの転写により不良品となる可能性が高いため、離型フィルムとして使用できない。
（２）カバーレイフィルムの接着剤の流れだし長さ（埋め込み性）
「カバーレイフィルムの接着剤の流れだし長さ」が埋め込み性の指標となるため、本実施例では当該値を測定することにより埋め込み性の優劣を判断した。
ポリイミドフィルム４−１とエポキシ樹脂系接着剤層４-２からなるカバーレイフィルム４〔ニッカン工業（株）製、商品名：ＣＩＳＶ２５３５）を用いた。このカバーレイフィルム４にはプリント配線基材の端子部分に相当する窓６が打ち抜かれており、打ち抜き部の大きさは５０ｍｍ×５０ｍｍである。
このカバーレイフィルム４と厚さ１２μｍの銅箔８を重ね合わせ、さらにカバーレイフィルム側に離型フィルム１の離型層１の表面が重なるようにして、加熱プレス機にセットした。温度１８０℃、圧力４ＭＰａ、加圧時間１２０秒の条件で加熱プレスし、プレス板を開放し冷却した後、多層離型フィルム１をカバーレイフィルム４が接着した銅箔８から離型させた。その状態の断面を図４に示す。カバーレイフィルムの切欠き部６の端縁部から染み出したエポキシ樹脂系接着剤の染み出し部９のエポキシ接着剤成分の長さをフィルム面上部から光学顕微鏡で観察し測定した。測定はカバーレイフィルムの切欠き部６の端縁部の４辺に対し各辺２点ずつ測定し、これらの平均値を「カバーレイフィルムの接着剤の染み出し長さ」とした。
カバーレイフィルムの接着剤の染み出し長さの評価は、以下の基準に基づいて行った。
・５０μｍ未満：判定◎
・５０μｍ以上、１５０μｍ未満：判定○
・１５０μｍ以上、２００μｍ未満：判定△
・２００μｍ以上：判定×
カバーレイフィルムの接着剤の染み出し長さにおいて、２００μｍ未満がプリント配線基板等の製作時に離型フィルムとして使用できる範囲であり、当該長さは小さいほど好ましい。一方、上記染み出し長さが２００μｍ以上（判定：×）となるとプリント配線基板等の製造時にカバーレイフィルムの接着剤が電極端子に達して後のメッキ工程で不良品が発生しやすくなるので、離型フィルムとして使用できない。
（３）多層離型フィルム端部の染み出し長さ（耐汚染性）
「多層離型フィルム端部の染み出し長さ」が耐汚染性の指標となるため、本実施例では当該値を測定することにより耐汚染性の優劣を判断した。
多層離型フィルム（大きさ７０ｍｍ×７０ｍｍ）と厚さ１２μｍの銅箔（大きさ１００ｍｍ×１００ｍｍ）を重ね合わせ、更に、その外側にアルミ板とＳＵＳ板で挟みこみ、加熱プレス機にセットした。温度１８０℃、圧力４ＭＰａ、加圧時間１２０秒の条件で加熱プレスし、プレス圧を解放し冷却した後、多層離型フィルム端部から染み出したクッション層成分の長さをフィルム面上部から光学顕微鏡で観察し測定した。測定は多層離型フィルムの４辺に対し各辺２点ずつ測定し、これらの平均値を多層離型フィルム端部の染み出し長さとした。
多層離型フィルム端部の染み出し長さの評価は、以下の基準に基づいて行った。
・３００μｍ未満：判定◎
・３００μｍ以上、３５０μｍ未満：判定○
・３５０μｍ以上、４００μｍ未満：判定△
・４００μｍ以上：判定×
多層離型フィルム端部の染み出し長さの評価において、４００μｍ未満がプリント配線基板等の製作時に離型フィルムとして使用できる範囲であり、当該長さは小さいほど好ましい。一方、上記染み出し長さが４００μｍ以上（判定：×）となるとプリント配線基板等の製造時にハンドリング性の低下や製造装置を汚損の可能性があるため、離型フィルムとして使用できない。
（４）引張弾性率
多層離型フィルムから、離型層１のみを剥がしてフィルムの長手方向が縦方向（ＭＤ）となるようにして、幅１５ｍｍの短冊状の試験片を切出し、引張り試験機を用いてＪＩＳ Ｋ ７１２７（１９９９年）に準拠して２３℃でのＭＤの引張弾性率を測定した。
（５）ビカット軟化温度（℃）
多層離型フィルムとして厚さ３ｍｍに圧縮成形したものを試験片とし、ＪＩＳＫ７２０６（１９９９年）に準拠（荷重：１Ｋｇ、昇温速度：２℃／ｍｉｎ）して測定した。
（６）表面粗さ（Ｒａ）
ＪＩＳ Ｂ０６０１（１９９４年）に準拠して、多層離型フィルム１の離型層１表面の算術表面粗さＲａを求めた。
接触式粗さ計
株式会社小坂研究所製三次元表面粗さ測定器ＳＥ−３５００Ｋ
基準長さ：２．５ｍｍ
速度：０．３ｍｍ／ｓ
カットオフ：０．８ｍｍ
上記評価結果を表1に示す。
(Evaluation item)
The release film was evaluated by the following method.
(1) Evaluation of releasability and evaluation of wrinkle resistance As shown in FIG. 2, a coverlay film 4 comprising a polyimide film 4-1 and an epoxy resin adhesive layer 4-2 [trade name, manufactured by Nikkan Kogyo Co., Ltd. : CISV2535). In this coverlay film 4, a portion corresponding to the electrode terminal portion of the printed wiring board 5 is punched out as a notch portion 6. The size of the notch 6 is 4 mm × 20 mm, and is formed at a plurality of locations on one coverlay film 4. On the other hand, a printed wiring board 5 having a size of 240 mm × 300 mm in which a wiring pattern is formed of a 12 μm thick copper foil (not shown) on a 25 μm thick polyimide film was used.
The printed wiring board 5 and the coverlay film 4 were positioned and overlapped, and the surface of the release layer 1 of the multilayer release film 1 was overlapped on the coverlay film side, and set in a heating press. In addition, as shown in FIG. 2, the multilayer release film 1 fixes the weights 7 at both ends in the longitudinal direction of the film, and heat-presses in a state where tension is applied, thereby evaluating the wrinkle resistance of the multilayer release film 1. Went. The width of the multilayer release film 1 was 270 mm, and a weight 7 was attached so that the tension was 3.5 kg / 270 mm.
After heat-pressing under conditions of a temperature of 180 ° C., a pressure of 4 MPa, and a pressurization time of 120 seconds, the press release plate is opened to release the tension of the multilayer release film, and then the multilayer release film 1 is bonded to the coverlay film 4 The printed wiring board 5 was peeled off by hand and released from the surface of the printed wiring board 5 at an angle substantially perpendicular to the surface.
As the release property evaluation, when the multilayer release film 1 was released by hand, the presence or absence of fold marks on the printed wiring board that occurred when the release was heavy was examined.
Evaluation of releasability was performed based on the following criteria.
・ No fold marks: Judgment ○
-There is a fold mark: Judgment ×
In the releasability evaluation, if there is no crease trace, it can be used as a release film for a printed wiring board or the like, but if there is a crease trace, it cannot be used as a release film for a printed wiring board or the like.
For the evaluation of wrinkle resistance, the number of wrinkles having a length of 5 mm or more that entered the surface of the printed wiring board after releasing the release film was counted.
Evaluation of wrinkle resistance was performed based on the following criteria.
・ Less than 30: Judgment
・ 30 or more and less than 40: Judgment ○
・ 40 or more and less than 50: Judgment △
・ 50 or more: Judgment ×
In the evaluation of wrinkle resistance, the number of wrinkles is less than 50 in a range that can be used as a release film when producing a printed wiring board or the like, and the smaller the number of wrinkles, the better. On the other hand, when the number of wrinkles is 50 or more (judgment: x), it is not likely to be a defective product due to the transfer of wrinkles to a printed wiring board or the like after the release film is peeled off.
(2) Adhesive flow length of coverlay film (embeddability)
Since the “flow length of the adhesive of the coverlay film” is an index of embedding property, in this example, the superiority or inferiority of embedding property was determined by measuring the value.
A coverlay film 4 (made by Nikkan Kogyo Co., Ltd., trade name: CISV2535) comprising a polyimide film 4-1 and an epoxy resin adhesive layer 4-2 was used. A window 6 corresponding to the terminal portion of the printed wiring board is punched in the coverlay film 4, and the size of the punched portion is 50 mm × 50 mm.
This cover lay film 4 and a copper foil 8 having a thickness of 12 μm were overlapped, and the surface of the release layer 1 of the release film 1 was further overlapped on the cover lay film side, and set in a heating press. After heating and pressing under conditions of a temperature of 180 ° C., a pressure of 4 MPa, and a pressurization time of 120 seconds, the press plate was opened and cooled, the multilayer release film 1 was released from the copper foil 8 to which the coverlay film 4 was adhered. The cross section in this state is shown in FIG. The length of the epoxy adhesive component of the exuded portion 9 of the epoxy resin adhesive that exudes from the edge of the cutout portion 6 of the coverlay film was observed and measured from above the film surface with an optical microscope. The measurement was performed by measuring two points on each of the four sides of the edge of the cutout portion 6 of the cover lay film, and the average value of these was defined as “the length of the cover lay film that oozed out the adhesive”.
The evaluation of the length of the cover lay film with which the adhesive oozed out was performed based on the following criteria.
・ Less than 50μm: Judgment ◎
・ 50 μm or more and less than 150 μm: Judgment ○
・ 150 μm or more and less than 200 μm: Determination Δ
・ 200μm or more: Judgment ×
In the cover lay film, the adhesive oozing length is less than 200 μm within a range that can be used as a release film in the production of a printed wiring board or the like, and the smaller the length, the better. On the other hand, if the seepage length is 200 μm or more (judgment: ×), the adhesive of the coverlay film reaches the electrode terminal during the production of a printed wiring board and the like, and defective products are likely to occur in the subsequent plating process. Cannot be used as a release film.
(3) Permeation length at the edge of multilayer release film (contamination resistance)
Since “the exudation length of the end portion of the multilayer release film” is an index of the stain resistance, in this example, the superiority or inferiority of the stain resistance was determined by measuring the value.
A multilayer release film (size 70 mm × 70 mm) and a 12 μm-thick copper foil (size 100 mm × 100 mm) were superposed, and further sandwiched between an aluminum plate and a SUS plate, and set in a heating press. After heating and pressing under conditions of a temperature of 180 ° C., a pressure of 4 MPa, and a pressurization time of 120 seconds, releasing the press pressure and cooling, the length of the cushion layer component that exudes from the edge of the multilayer release film is optically measured from the upper part of the film surface. It was observed and measured with a microscope. The measurement was carried out by measuring two points on each side of the four sides of the multilayer release film, and the average of these values was taken as the bleeding length at the end of the multilayer release film.
The evaluation of the bleeding length at the end of the multilayer release film was performed based on the following criteria.
・ Less than 300 μm: Judgment
・ 300 μm or more and less than 350 μm: Judgment ○
・ 350 μm or more and less than 400 μm: Determination Δ
・ 400μm or more: Judgment ×
In the evaluation of the bleeding length at the end of the multilayer release film, less than 400 μm is a range that can be used as a release film when producing a printed wiring board or the like, and the smaller the length, the better. On the other hand, if the bleed length is 400 μm or more (judgment: x), the handling property may be deteriorated during the production of a printed wiring board or the like, and the production apparatus may be soiled, and therefore cannot be used as a release film.
(4) Tensile tester A strip test piece having a width of 15 mm is cut out from the multilayer release film so that only the release layer 1 is peeled off and the longitudinal direction of the film is the longitudinal direction (MD). Was used to measure the tensile modulus of MD at 23 ° C. in accordance with JIS K 7127 (1999).
(5) Vicat softening temperature (° C)
A multilayer release film compression-molded to a thickness of 3 mm was used as a test piece and measured in accordance with JIS K7206 (1999) (load: 1 kg, temperature increase rate: 2 ° C./min).
(6) Surface roughness (Ra)
Based on JIS B0601 (1994), the arithmetic surface roughness Ra of the release layer 1 surface of the multilayer release film 1 was determined.
Contact type roughness meter Kosaka Laboratory 3D surface roughness measuring instrument SE-3500K
Standard length: 2.5mm
Speed: 0.3mm / s
Cut-off: 0.8mm
The evaluation results are shown in Table 1.
参考例１では離型層１の厚みが３５μｍに対し、比較例１、２、３、４では離型層１の厚みはそれぞれ３０μｍ、２５μｍ、１２μｍ、２５μｍである。参考例１、および比較例１、２、３、４の耐シワ性を比較すると、参考例１が耐シワ性が使用可能である「△」の評価である一方、比較例１、２、３、４では耐シワ性が「×」の評価であり離型フィルムとして使用不可能なレベルであることがわかる。
また、実施例４では離型層１の厚みが７０μｍであり、比較例５は離型層１の厚みが８０μｍである。実施例４と比較例５の埋め込み性を比較すると、実施例４の埋め込み性が使用可能である「△」の評価である一方、比較例５の埋め込み性は「×」の評価であり、離型フィルムとして使用不可能なレベルであることがわかる。
さらに、参考例２、６、７、８、９の引張弾性率はそれぞれ１２５０ＭＰａ、１３５０ＭＰａ、１３００ＭＰａ、１２５０ＭＰａ、１１５０ＭＰａに対し、比較例６、７の引張弾性率は双方とも８００ＭＰａである。参考例２、６、７、８、９の耐シワ性を比較すると、参考例２、６、７、８、９の耐シワ性がそれぞれ「○」、「○」、「◎」、「◎」、「○」、「○」の評価でありきわめて良好であるのに対し、比較例６、７の耐シワ性は双方とも「×」の評価であり離型フィルムとして使用不可能なレベルであることがわかる。
In Reference Example 1, the thickness of the release layer 1 is 35 μm, whereas in Comparative Examples 1, 2, 3, and 4, the thickness of the release layer 1 is 30 μm, 25 μm, 12 μm, and 25 μm, respectively. Comparing the wrinkle resistance of Reference Example 1 and Comparative Examples 1, 2, 3, and 4, Reference Example 1 is an evaluation of “Δ” that the wrinkle resistance can be used, while Comparative Examples 1, 2, 3 4 indicates that the wrinkle resistance is evaluated as “x”, which is a level that cannot be used as a release film.
In Example 4, the release layer 1 has a thickness of 70 μm, and in Comparative Example 5, the release layer 1 has a thickness of 80 μm. Comparing the embeddability of Example 4 and Comparative Example 5, the embeddability of Example 4 is evaluated as “Δ”, while the embeddability of Comparative Example 5 is evaluated as “x”, and the embedding property of It turns out that it is a level which cannot be used as a mold film.
Further, the tensile elastic moduli of Reference Examples 2, 6, 7, 8, and 9 are 1250 MPa, 1350 MPa, 1300 MPa, 1250 MPa, and 1150 MPa, respectively, while the tensile elastic moduli of Comparative Examples 6 and 7 are both 800 MPa. Comparing the anti wrinkle of Reference Example 2,6,7,8,9, anti wrinkle resistance of Reference Example 2,6,7,8,9 are "○", "○", "◎", "◎ ”,“ ◯ ”and“ O ”, which are very good, whereas the wrinkle resistances of Comparative Examples 6 and 7 are both“ x ”and cannot be used as a release film. I know that there is.
本発明の多層離型フィルムは、耐シワ性に優れ、且つ、離型性、埋め込み性、染み出し性、耐熱性、耐汚染性を有するので、安全かつ容易に廃棄処理でき、プリント配線基板、フレキシブルプリント配線基板、又は、多層プリント配線板の製造工程において、プリプレグ又は耐熱フィルムを介して銅張積層板又は銅箔を熱プレス成形する際に、好適に用いられる。 The multilayer release film of the present invention is excellent in wrinkle resistance and has mold release property, embedding property, seepage property, heat resistance, and contamination resistance, and can be disposed of safely and easily. In the manufacturing process of a flexible printed wiring board or a multilayer printed wiring board, it is suitably used when hot-pressing a copper clad laminate or a copper foil via a prepreg or a heat-resistant film.
１：多層離型フィルム
２−１：離型層１
２−２：離型層２
３：クッション層
４：カバーレイフィルム（保護フィルム）
４−１：ポリイミドフィルム
４−２：エポキシ樹脂系接着剤層
５：プリント配線基板
６：切欠き部
７：おもり
８：銅箔
９：エポキシ樹脂系接着剤の染み出し部
１０：ロール
1: Multilayer release film 2-1: Release layer 1
2-2: Release layer 2
3: Cushion layer 4: Coverlay film (protective film)
4-1: Polyimide film 4-2: Epoxy resin adhesive layer 5: Printed wiring board 6: Notch portion 7: Weight 8: Copper foil 9: Exuded portion of epoxy resin adhesive 10: Roll
Claims (4)
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| KR20200135302A (en) * | 2018-03-19 | 2020-12-02 | 세키스이가가쿠 고교가부시키가이샤 | Release film |
| JP2019162874A (en) * | 2018-03-19 | 2019-09-26 | 積水化学工業株式会社 | Release film |
| CN108237761B (en) * | 2018-03-23 | 2024-01-12 | 东莞领益精密制造科技有限公司 | Processing technology and processing equipment for multilayer structure |
| US11114308B2 (en) | 2018-09-25 | 2021-09-07 | International Business Machines Corporation | Controlling of height of high-density interconnection structure on substrate |
| WO2022034834A1 (en) * | 2020-08-12 | 2022-02-17 | 住友ベークライト株式会社 | Mold release film and method for manufacturing molded product |
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| JP2006312263A (en) * | 2005-05-09 | 2006-11-16 | Mitsubishi Polyester Film Copp | Laminated mat-like polyester film |
| JP2007090644A (en) * | 2005-09-28 | 2007-04-12 | Sekisui Chem Co Ltd | Multilayer mold-releasing film |
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| JP2010208140A (en) * | 2009-03-10 | 2010-09-24 | Dainippon Printing Co Ltd | Mold release film and method for manufacturing the same |
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