JP6705537B2 - Liquid crystal polyester resin for laminate, liquid crystal polyester resin composition, laminate and liquid crystal polyester resin film - Google Patents
Liquid crystal polyester resin for laminate, liquid crystal polyester resin composition, laminate and liquid crystal polyester resin film Download PDFInfo
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- JP6705537B2 JP6705537B2 JP2019141965A JP2019141965A JP6705537B2 JP 6705537 B2 JP6705537 B2 JP 6705537B2 JP 2019141965 A JP2019141965 A JP 2019141965A JP 2019141965 A JP2019141965 A JP 2019141965A JP 6705537 B2 JP6705537 B2 JP 6705537B2
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- Prior art keywords
- liquid crystal
- polyester resin
- crystal polyester
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 191
- 239000004645 polyester resin Substances 0.000 title claims description 190
- 229920001225 polyester resin Polymers 0.000 title claims description 190
- 239000000203 mixture Substances 0.000 title claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 61
- 239000002184 metal Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 32
- -1 aromatic diol Chemical class 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 11
- 238000005227 gel permeation chromatography Methods 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 238000000149 argon plasma sintering Methods 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 72
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 70
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 45
- 238000003756 stirring Methods 0.000 description 43
- 238000006116 polymerization reaction Methods 0.000 description 37
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 35
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 35
- 229920000642 polymer Polymers 0.000 description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 230000035484 reaction time Effects 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 16
- 229910001873 dinitrogen Inorganic materials 0.000 description 15
- 239000000835 fiber Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000155 melt Substances 0.000 description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 description 15
- 239000005020 polyethylene terephthalate Substances 0.000 description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- 230000008018 melting Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 239000000945 filler Substances 0.000 description 11
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000006640 acetylation reaction Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 125000004989 dicarbonyl group Chemical group 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001374 small-angle light scattering Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 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
- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QVLAWKAXOMEXPM-DICFDUPASA-N 1,1,1,2-tetrachloro-2,2-dideuterioethane Chemical compound [2H]C([2H])(Cl)C(Cl)(Cl)Cl QVLAWKAXOMEXPM-DICFDUPASA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- IKIUUOBVCBMFHU-UHFFFAOYSA-N 1,4-bis(4-hydroxyphenyl)butane-1,4-dione Chemical compound C1=CC(O)=CC=C1C(=O)CCC(=O)C1=CC=C(O)C=C1 IKIUUOBVCBMFHU-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- QXYLYYZZWZQACI-UHFFFAOYSA-N 2,3,4,5-tetrafluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1F QXYLYYZZWZQACI-UHFFFAOYSA-N 0.000 description 1
- IJGSULQFKYOYEU-UHFFFAOYSA-N 2,3,4-trifluorophenol Chemical compound OC1=CC=C(F)C(F)=C1F IJGSULQFKYOYEU-UHFFFAOYSA-N 0.000 description 1
- PBYIIRLNRCVTMQ-UHFFFAOYSA-N 2,3,5,6-tetrafluorophenol Chemical compound OC1=C(F)C(F)=CC(F)=C1F PBYIIRLNRCVTMQ-UHFFFAOYSA-N 0.000 description 1
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
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- ZRTWIJKGTUGZJY-UHFFFAOYSA-N 3,4,5-trifluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1 ZRTWIJKGTUGZJY-UHFFFAOYSA-N 0.000 description 1
- BWBGEYQWIHXDKY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC(O)=C1 BWBGEYQWIHXDKY-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
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- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004132 Calcium polyphosphate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
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- 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
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000000010 aprotic solvent Substances 0.000 description 1
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- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- 239000010951 brass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 238000007766 curtain coating Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 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
- 239000011490 mineral wool Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000007650 screen-printing Methods 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009423 ventilation Methods 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、積層体用液晶ポリエステル樹脂、液晶ポリエステル樹脂組成物、積層体および液晶ポリエステル樹脂フィルムに関する。より詳しくは、銅箔などの支持体と樹脂フィルムを貼り合わせた積層体の製造に適した液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物、ならびに、それを用いて得られる積層体および液晶ポリエステル樹脂フィルムに関する。 The present invention relates to a liquid crystal polyester resin for a laminate, a liquid crystal polyester resin composition, a laminate and a liquid crystal polyester resin film. More specifically, the present invention relates to a liquid crystal polyester resin and a liquid crystal polyester resin composition suitable for producing a laminate in which a support such as a copper foil and a resin film are bonded, and a laminate and a liquid crystal polyester resin film obtained by using the same. ..
液晶ポリエステル樹脂は、液晶構造を有するため、耐熱性、流動性および寸法安定性に優れる。このため、それらの特性が要求される電気・電子部品用途を中心に需要が拡大している。特に近年の機器の高性能化に伴い、上記部品の小型化や薄肉化が進んでいる。なかでも、フレキシブルプリント配線板などに使用される、銅箔などの金属と樹脂フィルムを貼り合わせた積層体は、極めて薄く、かつ、可とう性を有することから、空間的な自由度が大きく、立体的高密度の実装が可能であるため、スマートフォンに代表される携帯端末などの電子機器の小型軽量化に欠かせない存在であり、用途が拡大している。 Since the liquid crystal polyester resin has a liquid crystal structure, it has excellent heat resistance, fluidity and dimensional stability. For this reason, the demand is expanding mainly for electric/electronic component applications in which those characteristics are required. In particular, with the high performance of equipment in recent years, downsizing and thinning of the above-mentioned components are progressing. Among them, a laminate in which a metal such as a copper foil and a resin film are used for a flexible printed wiring board and the like is extremely thin and has flexibility, and thus has a large degree of spatial freedom. Since three-dimensional high-density mounting is possible, it is indispensable for reducing the size and weight of electronic devices such as mobile terminals typified by smartphones, and its applications are expanding.
液晶ポリエステル樹脂をこのような積層体に用いた例としては、例えば、芳香族アミン誘導体由来の構造単位を含む芳香族液晶ポリエステルと非プロトン性溶媒とを含有してなる溶液組成物を支持体に流延した後、溶媒を除去して得られる芳香族液晶ポリエステルフィルムが提案されている（例えば、特許文献１参照）。このような用途に用いられる液晶ポリエステル樹脂の要求特性として金属密着性がある。金属密着性を向上させた液晶ポリエステル樹脂としては、エチレングリコール単位を多く含む液晶ポリエステル樹脂を配合した液晶ポリエステル樹脂組成物（例えば、特許文献２参照）、高温雰囲気下でのガス量が一定以下である液晶性樹脂（例えば、特許文献３参照）などが提案されている。 As an example of using the liquid crystal polyester resin in such a laminate, for example, a solution composition containing an aromatic liquid crystal polyester containing a structural unit derived from an aromatic amine derivative and an aprotic solvent is used as a support. An aromatic liquid crystal polyester film obtained by casting and then removing the solvent has been proposed (see, for example, Patent Document 1). Metallic adhesion is a required characteristic of liquid crystal polyester resins used for such applications. As the liquid crystal polyester resin having improved metal adhesion, a liquid crystal polyester resin composition containing a liquid crystal polyester resin containing a large amount of ethylene glycol units (see, for example, Patent Document 2), a gas amount under a high temperature atmosphere is below a certain amount A certain liquid crystalline resin (see, for example, Patent Document 3) has been proposed.
前記特許文献１に記載された液晶ポリエステル樹脂からなるフィルムは、芳香族アミン誘導体由来の構造単位に由来する発生ガスが多いことなどから、金属密着性や引張特性が不十分であった。また、前記特許文献２に記載された液晶ポリエステル樹脂組成物や、前記特許文献３に記載された液晶性樹脂は、金属密着性が向上するもののなお十分ではなく、さらに引張特性についても十分ではなかった。 The film made of the liquid crystal polyester resin described in Patent Document 1 had insufficient metal adhesion and tensile properties because, for example, a large amount of generated gas was derived from the structural unit derived from the aromatic amine derivative. Further, the liquid crystal polyester resin composition described in Patent Document 2 and the liquid crystalline resin described in Patent Document 3 improve metal adhesion, but are still insufficient, and tensile properties are also insufficient. It was
本発明の課題は、金属密着性および引張特性に優れるフィルムを得ることのできる積層体用液晶ポリエステル樹脂、液晶ポリエステル樹脂組成物、それからなる液晶ポリエステル樹脂フィルムおよび該樹脂組成物を用いた積層体の製造方法を提供することを課題とする。 An object of the present invention is to provide a liquid crystal polyester resin for a laminate capable of obtaining a film having excellent metal adhesion and tensile properties, a liquid crystal polyester resin composition, a liquid crystal polyester resin film comprising the same, and a laminate using the resin composition. It is an object to provide a manufacturing method.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、特定の分子量分布を有する積層体用液晶ポリエステル樹脂により、金属密着性および引張特性に優れるフィルムを得ることのできることを見出し、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors have found that a liquid crystal polyester resin for a laminate having a specific molecular weight distribution can provide a film having excellent metal adhesion and tensile properties. The present invention has been reached.
すなわち本発明は、以下のとおりである：
（１）ゲル浸透クロマトグラフ／光散乱法により測定される絶対分子量の分子量分布において、全ピーク面積１００％に対する絶対分子量１００００以下の部分の面積分率が１２〜４０％であり、かつ絶対分子量５００００以上の部分の面積分率が３〜１７％である積層体用液晶ポリエステル樹脂。
（２）上記の液晶ポリエステル樹脂および溶媒を含有する液晶ポリエステル樹脂組成物であって、前記液晶ポリエステル樹脂１００重量部に対し、前記溶媒を１００〜１００００重量部含有する液晶ポリエステル樹脂組成物。
（３）上記の液晶ポリエステル樹脂からなる液晶ポリエステル樹脂フィルム。
（４）支持体および樹脂層が積層された積層体であって、上記の液晶ポリエステル樹脂からなる樹脂層の少なくとも一方の面に、支持体が積層された積層体。
（５）上記の液晶ポリエステル樹脂組成物を、支持体上に塗布した後、溶媒を除去する、積層体の製造方法。
（６）上記の方法によって得られた積層体から、支持体を除去することにより液晶ポリエステル樹脂フィルムを得る、液晶ポリエステル樹脂フィルムの製造方法。
That is, the present invention is as follows:
(1) In the molecular weight distribution of the absolute molecular weight measured by gel permeation chromatography/light scattering method, the area fraction of the portion having an absolute molecular weight of 10,000 or less is 12 to 40%, and the absolute molecular weight is 50,000. A liquid crystal polyester resin for a laminate, wherein the area fraction of the above portion is 3 to 17 %.
(2) A liquid crystal polyester resin composition containing the above liquid crystal polyester resin and a solvent, wherein 100 to 10,000 parts by weight of the solvent is contained in 100 parts by weight of the liquid crystal polyester resin.
(3) A liquid crystal polyester resin film comprising the above liquid crystal polyester resin.
(4) A laminate in which a support and a resin layer are laminated, and the support is laminated on at least one surface of the resin layer made of the above liquid crystal polyester resin.
(5) A method for producing a laminate, which comprises applying the above-mentioned liquid crystal polyester resin composition on a support and then removing the solvent.
(6) A method for producing a liquid crystal polyester resin film, wherein a liquid crystal polyester resin film is obtained by removing the support from the laminate obtained by the above method.
本発明の積層体用液晶ポリエステル樹脂によれば、金属密着性および引張特性に優れるフィルムを得ることができる。かかる樹脂は、電気・電子部品や機械部品内のフレキシブルプリント配線板や半導体パッケージなどに使用される積層体に好適である。 According to the liquid crystal polyester resin for a laminate of the present invention, a film having excellent metal adhesion and tensile properties can be obtained. Such a resin is suitable for a laminate used for a flexible printed wiring board in an electric/electronic component or a mechanical component, a semiconductor package, or the like.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
＜積層体用液晶ポリエステル樹脂＞
本発明の液晶ポリエステル樹脂は、異方性溶融相を形成するポリエステルである。このようなポリエステル樹脂としては、例えば、後述するオキシカルボニル単位、ジオキシ単位、ジカルボニル単位などから異方性溶融相を形成するよう選ばれた構造単位から構成されるポリエステルなどが挙げられる。
<Liquid crystal polyester resin for laminate>
The liquid crystal polyester resin of the present invention is a polyester that forms an anisotropic molten phase. Examples of such a polyester resin include polyesters composed of structural units selected from an oxycarbonyl unit, a dioxy unit, a dicarbonyl unit and the like described below so as to form an anisotropic molten phase.
次に、液晶ポリエステル樹脂を構成する構造単位について説明する。 Next, the structural units constituting the liquid crystal polyester resin will be described.
オキシカルボニル単位の具体例としては、ｐ−ヒドロキシ安息香酸、ｍ−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸などの芳香族ヒドロキシカルボン酸などに由来する構造単位が挙げられる。金属密着性および引張特性に優れるフィルムを得ることができる観点から、オキシカルボニル単位としては、芳香族ヒドロキシカルボン酸から生成した構造単位が好ましく、ｐ−ヒドロキシ安息香酸または６−ヒドロキシ−２−ナフトエ酸に由来する構造単位がより好ましく、ｐ−ヒドロキシ安息香酸から生成した構造単位が特に好ましい。 Specific examples of the oxycarbonyl unit include structural units derived from aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid, m-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. From the viewpoint of being able to obtain a film having excellent metal adhesion and tensile properties, the oxycarbonyl unit is preferably a structural unit formed from an aromatic hydroxycarboxylic acid, such as p-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid. Are more preferred, and structural units formed from p-hydroxybenzoic acid are particularly preferred.
ジオキシ単位の具体例としては、４，４’−ジヒドロキシビフェニル、ハイドロキノン、レゾルシノール、ｔ−ブチルハイドロキノン、フェニルハイドロキノン、クロロハイドロキノン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、３，４’−ジヒドロキシビフェニル、２，２−ビス（４−ヒドロキシフェニル）プロパン、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシベンゾフェノンなどの芳香族ジオールから生成した構造単位；エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコールなどの脂肪族ジオールから生成した構造単位；１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノールなどの脂環式ジオールから生成した構造単位などが挙げられる。金属密着性および引張特性に優れるフィルムが得られる観点から、ジオキシ単位としては、エチレングリコール、４，４’−ジヒドロキシビフェニルまたはハイドロキノンから生成した構造単位が好ましく、エチレングリコールまたは４，４’−ジヒドロキシビフェニルから生成した構造単位が特に好ましい。 Specific examples of the dioxy unit include 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, t-butylhydroquinone, phenylhydroquinone, chlorohydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4′- Dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, etc. Structural unit formed from an aromatic diol; a structural unit formed from an aliphatic diol such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol; 1,4-cyclohexanediol , A structural unit formed from an alicyclic diol such as 1,4-cyclohexanedimethanol. From the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, the dioxy unit is preferably a structural unit formed from ethylene glycol, 4,4′-dihydroxybiphenyl or hydroquinone, and ethylene glycol or 4,4′-dihydroxybiphenyl is preferable. Structural units produced from are particularly preferred.
ジカルボニル単位の具体例としては、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、４，４’−ジフェニルジカルボン酸、３，３’−ジフェニルジカルボン酸、２，２’−ジフェニルジカルボン酸、１，２−ビス（フェノキシ）エタン−４，４’−ジカルボン酸、１，２−ビス（２−クロロフェノキシ）エタン−４，４’−ジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸などの芳香族ジカルボン酸から生成した構造単位；アジピン酸、アゼライン酸、セバシン酸、ドデカンジオン酸、ヘキサヒドロテレフタル酸などの脂肪族ジカルボン酸から生成した構造単位；１，４−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸などの脂環式ジカルボン酸から生成した構造単位などが挙げられる。金属密着性および引張特性に優れるフィルムが得られる観点から、ジカルボニル単位としては、芳香族ジカルボン酸から生成した構造単位が好ましく、中でもテレフタル酸またはイソフタル酸から生成した構造単位が特に好ましい。 Specific examples of the dicarbonyl unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 3,3′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, Aroma such as 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid Structural units formed from group dicarboxylic acids; structural units formed from aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and hexahydroterephthalic acid; 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include structural units formed from alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. From the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, the dicarbonyl unit is preferably a structural unit formed from an aromatic dicarboxylic acid, and particularly preferably a structural unit formed from terephthalic acid or isophthalic acid.
また、液晶ポリエステル樹脂には、上記構造単位に加えて、ｐ−アミノ安息香酸、ｐ−アミノフェノールなどから生成した構造単位を、液晶性や特性を損なわない程度の範囲でさらに有することができる。 In addition to the above structural units, the liquid crystal polyester resin may further include structural units formed from p-aminobenzoic acid, p-aminophenol, etc., within a range that does not impair the liquid crystallinity and characteristics.
上記の各構造単位を構成する原料となるモノマーは、各構造単位を形成しうる構造であれば特に限定されない。また、そのようなモノマーの水酸基のアシル化物、カルボキシル基のエステル化物、酸ハロゲン化物、酸無水物などのカルボン酸誘導体などが使用されてもよい。 The raw material monomer that constitutes each structural unit is not particularly limited as long as it is a structure that can form each structural unit. In addition, a carboxylic acid derivative such as an acylated product of a hydroxyl group of such a monomer, an esterified product of a carboxyl group, an acid halide, or an acid anhydride may be used.
本発明の液晶ポリエステル樹脂は、液晶性を発現したうえで、金属密着性および引張特性に優れるフィルムが得られる観点から、液晶ポリエステル樹脂の全構造単位１００モル％に対して、芳香族ヒドロキシカルボン酸に由来する構造単位を１５モル％以上含むことが好ましい。より好ましくは３０モル％以上、さらに好ましくは４０モル％以上である。一方、不融物の生成を抑制し、金属密着性および引張特性に優れるフィルムが得られる観点から、芳香族ヒドロキシカルボン酸に由来する構造単位を８０モル％以下含むことが好ましい。より好ましくは７５モル％以下、さらに好ましくは７０モル％以下である。 The liquid crystal polyester resin of the present invention exhibits aromaticity of aromatic hydroxycarboxylic acid based on 100 mol% of all structural units of the liquid crystal polyester resin from the viewpoint that a film having excellent liquid crystallinity and excellent metal adhesion and tensile properties can be obtained. It is preferable that the content of the structural unit derived from is 15 mol% or more. It is more preferably 30 mol% or more, still more preferably 40 mol% or more. On the other hand, it is preferable that the structural unit derived from the aromatic hydroxycarboxylic acid is contained in an amount of 80 mol% or less from the viewpoint of suppressing the formation of an infusible substance and obtaining a film having excellent metal adhesion and tensile properties. It is more preferably 75 mol% or less, still more preferably 70 mol% or less.
本発明の液晶ポリエステル樹脂は、液晶性を発現したうえで、金属密着性および引張特性に優れるフィルムが得られる観点から、液晶ポリエステル樹脂の全構造単位１００モル％に対して、芳香族ジオールに由来する構造単位を３モル％以上含むことが好ましい。より好ましくは４モル％以上、さらに好ましくは５モル％以上である。一方、金属密着性および引張特性に優れるフィルムが得られる観点から、芳香族ジオールに由来する構造単位を２０モル％以下含むことが好ましい。より好ましくは１５モル％以下、さらに好ましくは１０モル％以下である。 The liquid crystal polyester resin of the present invention is derived from an aromatic diol based on 100 mol% of all structural units of the liquid crystal polyester resin from the viewpoint that a film having excellent liquid crystallinity and excellent metal adhesion and tensile properties can be obtained. It is preferable that the content of the structural unit is 3 mol% or more. It is more preferably 4 mol% or more, still more preferably 5 mol% or more. On the other hand, from the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, it is preferable that the structural unit derived from an aromatic diol be contained in an amount of 20 mol% or less. It is more preferably 15 mol% or less, still more preferably 10 mol% or less.
本発明の液晶ポリエステル樹脂は、液晶性を発現したうえで、金属密着性および引張特性に優れるフィルムが得られる観点から、液晶ポリエステル樹脂の全構造単位１００モル％に対して、芳香族ジカルボン酸に由来する構造単位を７モル％以上含むことが好ましい。より好ましくは１０モル％以上、さらに好ましくは１２モル％以上である。一方、金属密着性および引張特性に優れるフィルムが得られる観点から、芳香族ジカルボン酸に由来する構造単位を４０モル％以下含むことが好ましい。より好ましくは３５モル％以下、さらに好ましくは３０モル％以下である。 The liquid crystal polyester resin of the present invention has an aromatic dicarboxylic acid content based on 100 mol% of all structural units of the liquid crystal polyester resin, from the viewpoint that a film having excellent liquid crystallinity and excellent metal adhesion and tensile properties can be obtained. It is preferable that the derived structural unit is contained in an amount of 7 mol% or more. It is more preferably 10 mol% or more, still more preferably 12 mol% or more. On the other hand, from the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, it is preferable that the content of the structural unit derived from an aromatic dicarboxylic acid be 40 mol% or less. It is more preferably 35 mol% or less, still more preferably 30 mol% or less.
本発明の液晶ポリエステル樹脂は、後述する溶媒への溶解性に優れ、金属密着性および引張特性に優れるフィルムが得られる観点から、液晶ポリエステル樹脂の全構造単位１００モル％に対して、炭素数２〜４の脂肪族ジオールに由来する構造単位を３モル％以上含むことが好ましい。より好ましくは５モル％以上、さらに好ましくは７モル％以上である。一方、液晶性を発現したうえで、金属密着性および引張特性に優れるフィルムが得られる観点から、炭素数２〜４の脂肪族ジオールに由来する構造単位を４０モル％以下含むことが好ましい。より好ましくは３５モル％以下、さらに好ましくは３０モル％以下である。 The liquid crystal polyester resin of the present invention has a carbon number of 2 per 100 mol% of all structural units of the liquid crystal polyester resin from the viewpoint of obtaining a film having excellent solubility in a solvent described below and excellent metal adhesion and tensile properties. It is preferable to contain 3 mol% or more of the structural units derived from the aliphatic diol of 4 to 4. It is more preferably 5 mol% or more, and further preferably 7 mol% or more. On the other hand, from the viewpoint of obtaining a film having excellent liquid crystallinity and excellent metal adhesion and tensile properties, it is preferable to contain 40 mol% or less of a structural unit derived from an aliphatic diol having 2 to 4 carbon atoms. It is more preferably 35 mol% or less, still more preferably 30 mol% or less.
本発明の液晶ポリエステル樹脂は、金属密着性および引張特性に優れるフィルムが得られる観点から、前記液晶ポリエステル樹脂の全構造単位１００モル％に対する、芳香族ヒドロキシカルボン酸に由来する構造単位とテレフタル酸に由来する構造単位との合計が６０モル％以上であることが好ましい。より好ましくは６５モル％以上、さらに好ましくは６８モル％以上である。一方、芳香族ヒドロキシカルボン酸に由来する構造単位とテレフタル酸に由来する構造単位との合計の上限は１００モル％であるが、液晶ポリエステル樹脂の結晶性を制御することで、金属密着性および引張特性に優れるフィルムが得られる観点から、９０モル％以下であることが好ましい。より好ましくは８５モル％以下である。また、芳香族ヒドロキシカルボン酸に由来する構造単位とテレフタル酸に由来する構造単位は、いずれか一方の構造単位を有し、もう一方の構造単位が０モル％であってもよいが、それぞれが０モル％を超えることが好ましい。 The liquid crystal polyester resin of the present invention contains a structural unit derived from an aromatic hydroxycarboxylic acid and terephthalic acid based on 100 mol% of all structural units of the liquid crystal polyester resin from the viewpoint of obtaining a film having excellent metal adhesion and tensile properties. It is preferable that the total amount of the structural units derived from it is 60 mol% or more. It is more preferably 65 mol% or more, and further preferably 68 mol% or more. On the other hand, the upper limit of the total of the structural units derived from aromatic hydroxycarboxylic acid and the structural units derived from terephthalic acid is 100 mol %, but by controlling the crystallinity of the liquid crystal polyester resin, metal adhesion and tensile strength can be improved. From the viewpoint of obtaining a film having excellent characteristics, it is preferably 90 mol% or less. It is more preferably 85 mol% or less. The structural unit derived from an aromatic hydroxycarboxylic acid and the structural unit derived from terephthalic acid may have one of the structural units and the other structural unit may be 0 mol %, but It is preferably more than 0 mol %.
また、液晶ポリエステル樹脂の分子量分布を後述する好適な範囲に制御し、金属密着性および引張特性に優れるフィルムが得られる観点から、ジオール単位に由来する構造単位の割合が、ジカルボニル単位に由来する構造単位に対し、１．０１〜１．０７であることが好ましい。 Further, from the viewpoint of controlling the molecular weight distribution of the liquid crystal polyester resin to a suitable range described later and obtaining a film having excellent metal adhesion and tensile properties, the proportion of structural units derived from diol units is derived from dicarbonyl units. It is preferably 1.01 to 1.07 with respect to the structural unit.
本発明の液晶ポリエステル樹脂について、各構造単位の含有量の算出法を以下に示す。まず、液晶ポリエステル樹脂をＮＭＲ（核磁気共鳴）試料管に量りとり、液晶ポリエステル樹脂が可溶な溶媒（例えば、ペンタフルオロフェノール／重テトラクロロエタン−ｄ２混合溶媒）に溶解する。次に、得られた溶液について、１Ｈ−ＮＭＲスペクトル測定を行い、各構造単位由来のピークの面積比から算出することができる。 The method of calculating the content of each structural unit in the liquid crystal polyester resin of the present invention is shown below. First, the liquid crystal polyester resin is weighed in an NMR (nuclear magnetic resonance) sample tube and dissolved in a solvent in which the liquid crystal polyester resin is soluble (for example, a pentafluorophenol/heavy tetrachloroethane-d 2 mixed solvent). Next, 1 H-NMR spectrum measurement is performed on the obtained solution, and it can be calculated from the area ratio of peaks derived from each structural unit.
本発明の液晶ポリエステル樹脂の融点（Ｔｍ）は、耐熱性の観点から２００℃以上が好ましく、２５０℃以上がより好ましく、２８０℃以上がさらに好ましく、３００℃以上が特に好ましい。一方、溶解性に優れ、金属密着性および引張特性に優れる観点から、液晶ポリエステル樹脂の融点（Ｔｍ）は、３６０℃以下が好ましく、３５０℃以下がより好ましく、３４０℃以下がさらに好ましい。 From the viewpoint of heat resistance, the liquid crystal polyester resin of the present invention has a melting point (Tm) of preferably 200° C. or higher, more preferably 250° C. or higher, further preferably 280° C. or higher, particularly preferably 300° C. or higher. On the other hand, the melting point (Tm) of the liquid crystal polyester resin is preferably 360° C. or lower, more preferably 350° C. or lower, and even more preferably 340° C. or lower from the viewpoint of excellent solubility, metal adhesion and tensile properties.
融点（Ｔｍ）の測定は、示差走査熱量測定により行う。具体的には、まず、重合を完了したポリマーを室温から２０℃／分の昇温条件で加熱することにより吸熱ピーク温度（Ｔｍ１）を観測する。吸熱ピーク温度（Ｔｍ１）の観測後、吸熱ピーク温度（Ｔｍ１）＋２０℃の温度でポリマーを５分間保持する。その後、２０℃／分の降温条件で室温までポリマーを冷却する。そして、２０℃／分の昇温条件でポリマーを加熱することにより吸熱ピーク温度（Ｔｍ２）を観測する。本発明における融点（Ｔｍ）とは、２回目の昇温過程における該吸熱ピーク温度（Ｔｍ２）を指す。 The melting point (Tm) is measured by differential scanning calorimetry. Specifically, first, the endothermic peak temperature (Tm 1 ) is observed by heating the polymer that has completed the polymerization from room temperature under a temperature rising condition of 20° C./min. After observation of an endothermic peak temperature (Tm 1), holding the polymer for 5 minutes at a temperature of the endothermic peak temperature (Tm 1) + 20 ℃. Then, the polymer is cooled to room temperature under a temperature lowering condition of 20° C./min. Then, the endothermic peak temperature (Tm 2 ) is observed by heating the polymer under a temperature rising condition of 20° C./min. The melting point (Tm) in the present invention refers to the endothermic peak temperature (Tm 2 ) in the second heating process.
本発明の液晶ポリエステル樹脂の溶融粘度は、強度に優れることで、金属密着性および引張特性に優れるフィルムが得られる観点から、１Ｐａ・ｓ以上が好ましく、３Ｐａ・ｓ以上がより好ましく、５Ｐａ・ｓ以上がさらに好ましい。一方、後述する組成物とする際に、液晶ポリエステル樹脂の溶解性に優れる観点や、金属密着性および引張特性に優れるフィルムが得られる観点から、液晶ポリエステル樹脂の溶融粘度は、３５Ｐａ・ｓ以下が好ましく、２０Ｐａ・ｓ以下が好ましく、１０Ｐａ・ｓ以下がさらに好ましい。 The liquid crystal polyester resin of the present invention has a melt viscosity of preferably 1 Pa·s or more, more preferably 3 Pa·s or more, and more preferably 5 Pa·s, from the viewpoint that a film having excellent metal adhesion and tensile properties can be obtained due to its excellent strength. The above is more preferable. On the other hand, when the composition described below is used, the melt viscosity of the liquid crystal polyester resin is 35 Pa·s or less from the viewpoint of excellent solubility of the liquid crystal polyester resin and the viewpoint of obtaining a film having excellent metal adhesion and tensile properties. It is preferably 20 Pa·s or less, more preferably 10 Pa·s or less.
なお、この溶融粘度は、液晶ポリエステル樹脂の融点（Ｔｍ）＋１０℃の温度で、かつ、せん断速度１０００／秒の条件下で、高化式フローテスターによって測定した値である。 The melt viscosity is a value measured by a Koka flow tester at a melting point (Tm) of the liquid crystal polyester resin+10° C. and under a shear rate of 1000/sec.
発明者らは、液晶ポリエステル樹脂の分子量分布が、ある程度広いことによって、金属密着性および引張特性に優れるフィルムを得ることができることを見出した。 The inventors have found that a liquid crystal polyester resin having a relatively wide molecular weight distribution can provide a film having excellent metal adhesion and tensile properties.
具体的には、本発明の液晶ポリエステル樹脂は、ゲル浸透クロマトグラフ／光散乱法により測定される絶対分子量の分子量分布の全ピーク面積１００％に対する絶対分子量１００００以下の部分の面積分率が１０〜４０％である。絶対分子量１００００以下の面積分率が１０％未満であると、後述する組成物とする際に、液晶ポリエステル樹脂の溶解性が大幅に低下する。液晶ポリエステル樹脂の末端基が減少することで、フィルムにした場合の金属密着性が大幅に低下する。金属密着性に優れたフィルムが得られることから、絶対分子量１００００以下の部分の面積分率は、１２％以上がより好ましく、１３％以上がさらに好ましい。一方、絶対分子量１００００以下の面積分率が４０％より大きいと、フィルムにした場合に脆くなり、金属密着性および引張特性が大幅に低下する。金属密着性および引張特性に優れるフィルムが得られる観点から、３５％以下がより好ましく、３０％以下がさらに好ましい。 Specifically, the liquid crystal polyester resin of the present invention has an area fraction of a portion having an absolute molecular weight of 10,000 or less with respect to 100% of the total peak area of the molecular weight distribution of absolute molecular weight measured by gel permeation chromatography/light scattering method is 10 to 10. 40%. If the area fraction with an absolute molecular weight of 10,000 or less is less than 10%, the solubility of the liquid crystal polyester resin is significantly reduced in the case of the composition described later. The reduction in the terminal groups of the liquid crystal polyester resin significantly reduces the metal adhesion when formed into a film. Since a film having excellent metal adhesion is obtained, the area fraction of the portion having an absolute molecular weight of 10,000 or less is more preferably 12% or more, further preferably 13% or more. On the other hand, when the area fraction having an absolute molecular weight of 10,000 or less is larger than 40%, the film becomes brittle and the metal adhesion and the tensile properties are significantly lowered. From the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, it is more preferably 35% or less, still more preferably 30% or less.
また、本発明の液晶ポリエステル樹脂は、ゲル浸透クロマトグラフ／光散乱法により測定される絶対分子量の分子量分布の全ピーク面積１００％に対し、絶対分子量５００００以上の部分の面積分率が３〜２０％である。絶対分子量５００００以上の面積分率が３％未満であると、フィルムにした場合に脆くなり、金属密着性および引張特性が大幅に低下する。金属密着性および引張特性に優れるフィルムが得られる観点から、絶対分子量５００００以上の部分の面積分率は、５％以上がより好ましく、７％以上がさらに好ましい。一方、絶対分子量５００００以上の面積分率が２０％より大きいと、後述する組成物とする際に、液晶ポリエステル樹脂の溶解性が大幅に低下する。また、液晶ポリエステル樹脂の末端基が減少することで、フィルムにした場合の金属密着性が大幅に低下するほか、特に引張伸度における引張特性が大幅に低下する。金属密着性に優れたフィルムが得られることから、絶対分子量５００００以上の部分の面積分率は、１７％以下がより好ましく、１５％以下がさらに好ましい。 Further, the liquid crystal polyester resin of the present invention has an area fraction of 3 to 20 in a portion having an absolute molecular weight of 50,000 or more based on 100% of the total peak area of the molecular weight distribution of the absolute molecular weight measured by gel permeation chromatography/light scattering method. %. If the area fraction with an absolute molecular weight of 50,000 or more is less than 3%, the film becomes brittle and the metal adhesion and tensile properties are significantly reduced. From the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, the area fraction of the portion having an absolute molecular weight of 50,000 or more is more preferably 5% or more, further preferably 7% or more. On the other hand, when the area fraction having an absolute molecular weight of 50,000 or more is greater than 20%, the solubility of the liquid crystal polyester resin is significantly reduced when the composition described later is prepared. In addition, the reduction in the terminal groups of the liquid crystal polyester resin significantly reduces the metal adhesion when formed into a film, and also significantly reduces the tensile properties particularly in the tensile elongation. Since a film having excellent metal adhesion is obtained, the area fraction of the portion having an absolute molecular weight of 50,000 or more is more preferably 17% or less, further preferably 15% or less.
本発明の液晶ポリエステル樹脂の絶対数平均分子量は、フィルムの強度が向上するため、金属密着性および引張特性に優れるフィルムが得られる観点から、３０００以上が好ましく、５０００以上がより好ましく、７０００以上がさらに好ましい。また、液晶ポリエステル樹脂の溶解性が向上する観点や、金属密着性および引張特性に優れるフィルムが得られる観点から、絶対数平均分子量は、１７０００以下が好ましく、１５０００以下がより好ましく、１３０００以下がさらに好ましい。 The absolute number average molecular weight of the liquid crystal polyester resin of the present invention is preferably 3,000 or more, more preferably 5,000 or more, and more preferably 7,000 or more from the viewpoint that a film having excellent metal adhesion and tensile properties can be obtained because the strength of the film is improved. More preferable. Further, from the viewpoint of improving the solubility of the liquid crystal polyester resin and the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, the absolute number average molecular weight is preferably 17,000 or less, more preferably 15,000 or less, and further preferably 13,000 or less. preferable.
本発明の液晶ポリエステル樹脂の絶対重量平均分子量は、フィルムの強度が向上するため、金属密着性および引張特性に優れるフィルムが得られる観点から、１００００以上が好ましく、１３０００以上がより好ましく、１５０００以上がさらに好ましい。また、液晶ポリエステル樹脂の溶解性が向上する観点や、金属密着性および引張特性に優れるフィルムが得られる観点から、絶対重量平均分子量は、４００００以下が好ましく、３７０００以下がより好ましく、３５０００以下がさらに好ましい。 The absolute weight average molecular weight of the liquid crystal polyester resin of the present invention is preferably 10,000 or more, more preferably 13,000 or more, and more preferably 15,000 or more from the viewpoint that a film having excellent metal adhesion and tensile properties can be obtained because the strength of the film is improved. More preferable. Further, from the viewpoint of improving the solubility of the liquid crystal polyester resin and from the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, the absolute weight average molecular weight is preferably 40,000 or less, more preferably 37,000 or less, and even more preferably 35,000 or less. preferable.
本発明の液晶ポリエステル樹脂の絶対重量平均分子量を、絶対数平均分子量で除した値である多分散度は、金属密着性および引張特性に優れるフィルムが得られる観点から、２．２以上が好ましく、２．３以上がより好ましく、２．４以上がさらに好ましい。また、金属密着性および引張特性に優れるフィルムが得られる観点から、多分散度は、３．５以下が好ましく、３．３以下がより好ましく、３．０以下がさらに好ましい。 The polydispersity, which is a value obtained by dividing the absolute weight average molecular weight of the liquid crystal polyester resin of the present invention by the absolute number average molecular weight, is preferably 2.2 or more from the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, 2.3 or more is more preferable, and 2.4 or more is further preferable. From the viewpoint of obtaining a film having excellent metal adhesion and tensile properties, the polydispersity is preferably 3.5 or less, more preferably 3.3 or less, and further preferably 3.0 or less.
なお、絶対分子量は、液晶ポリエステル樹脂が可溶な溶媒を溶離液として使用してＧＰＣ／光散乱法（ゲル浸透クロマトグラフ／光散乱法）により測定することが可能である。液晶ポリエステルが可溶な溶媒としては、例えば、ハロゲン化フェノール類、ハロゲン化フェノールと一般有機溶媒との混合溶媒が挙げられる。好ましくはペンタフルオロフェノール、またはペンタフルオロフェノールとクロロホルムの混合溶媒であり、なかでもハンドリング性の観点からペンタフルオロフェノール／クロロホルム混合溶媒が特に好ましい。 The absolute molecular weight can be measured by GPC/light scattering method (gel permeation chromatography/light scattering method) using a solvent in which the liquid crystal polyester resin is soluble as an eluent. Examples of the solvent in which the liquid crystal polyester is soluble include halogenated phenols and a mixed solvent of halogenated phenol and a general organic solvent. Pentafluorophenol or a mixed solvent of pentafluorophenol and chloroform is preferable, and among them, a pentafluorophenol/chloroform mixed solvent is particularly preferable from the viewpoint of handleability.
なお、本発明の液晶ポリエステル樹脂が、絶対分子量１００００以下や５００００以上の面積分率を上記の好適な範囲に制御するには、以下の（Ａ）〜（Ｃ）の方法が挙げられる。 The following methods (A) to (C) can be used to control the area fraction of the liquid crystal polyester resin of the present invention having an absolute molecular weight of 10,000 or less or 50,000 or more within the above preferable range.
（Ａ）液晶ポリエステル樹脂を製造する際のフェノール性水酸基のアセチル化反応において、内温１４０℃〜１４５℃でのアセチル化反応時間を４０〜１００分とする方法。 (A) A method in which the acetylation reaction time at an internal temperature of 140° C. to 145° C. is 40 to 100 minutes in the acetylation reaction of a phenolic hydroxyl group when producing a liquid crystal polyester resin.
（Ｂ）液晶ポリエステル樹脂を製造する際に、無水酢酸の量を、液晶ポリエステル樹脂原料のフェノール性水酸基の合計の１．００〜１．０８モル当量とする方法。 (B) A method in which, when the liquid crystal polyester resin is produced, the amount of acetic anhydride is 1.00 to 1.08 molar equivalent of the total amount of phenolic hydroxyl groups of the liquid crystal polyester resin raw material.
（Ｃ）液晶ポリエステル樹脂のジオール単位に由来する構造単位の割合を、ジカルボニル単位に由来する構造単位に対し、１．０１〜１．０７とする方法。 (C) A method in which the ratio of the structural unit derived from the diol unit of the liquid crystal polyester resin is 1.01 to 1.07 with respect to the structural unit derived from the dicarbonyl unit.
上記の方法により、重合速度を制御することで分子量分布を制御することができ、絶対分子量１００００以下や５００００以上の面積分率を上記の好適な範囲に制御できる。なかでも、（Ａ）の方法が好ましい。 By the method described above, the molecular weight distribution can be controlled by controlling the polymerization rate, and the area fraction with an absolute molecular weight of 10,000 or less or 50,000 or more can be controlled within the above preferable range. Of these, the method (A) is preferable.
＜積層体用液晶ポリエステル樹脂の製造方法＞
本発明で使用する液晶ポリエステル樹脂を製造する方法は、特に制限がなく、公知のポリエステルの重縮合法に準じて製造できる。具体的には、ｐ−ヒドロキシ安息香酸に由来する構造単位、４，４’−ジヒドロキシビフェニルに由来する構造単位、テレフタル酸に由来する構造単位、およびエチレングリコールに由来する構造単位からなる液晶ポリエステル樹脂を例にすると、以下の方法が挙げられる。
<Method for producing liquid crystal polyester resin for laminate>
The method for producing the liquid crystal polyester resin used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method. Specifically, a liquid crystal polyester resin composed of a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 4,4′-dihydroxybiphenyl, a structural unit derived from terephthalic acid, and a structural unit derived from ethylene glycol. For example, the following method can be given.
（１）ｐ−アセトキシ安息香酸、４，４’−ジアセトキシビフェニルとテレフタル酸、およびポリエチレンテレフタレ―トのポリマーもしくはオリゴマーまたはビス（β−ヒドロキシエチル）テレフタレートから脱酢酸重縮合反応によって液晶ポリエステル樹脂を製造する方法。 (1) Liquid crystal polyester resin by deacetic acid polycondensation reaction from p-acetoxybenzoic acid, 4,4′-diacetoxybiphenyl and terephthalic acid, and a polymer or oligomer of polyethylene terephthalate or bis(β-hydroxyethyl)terephthalate. A method of manufacturing.
（２）ｐ−ヒドロキシ安息香酸、４，４’−ジヒドロキシビフェニル、テレフタル酸、およびポリエチレンテレフタレ―トなどのポリエステルのポリマーもしくはオリゴマーまたはビス（β−ヒドロキシエチル）テレフタレートに無水酢酸を反応させて、フェノール性水酸基をアセチル化した後、脱酢酸重縮合反応によって液晶ポリエステル樹脂を製造する方法。 (2) A polymer or oligomer of polyester such as p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, terephthalic acid, and polyethylene terephthalate or bis(β-hydroxyethyl)terephthalate is reacted with acetic anhydride, A method for producing a liquid crystal polyester resin by deacetylation polycondensation reaction after acetylating a phenolic hydroxyl group.
（３）（１）または（２）の製造方法において出発原料の一部に特開平３−５９０２４号公報のように１，２−ビス（４−ヒドロキシベンゾイル）エタンを用いる方法。 (3) A method of using 1,2-bis(4-hydroxybenzoyl)ethane as a part of the starting material in the production method of (1) or (2), as described in JP-A-3-59024.
なかでも（２）の方法が、液晶ポリエステル樹脂の重合度の制御に工業的に優れる点から、好ましく用いられる。 Among them, the method (2) is preferably used because it is industrially excellent in controlling the degree of polymerization of the liquid crystal polyester resin.
上記（２）の方法で製造する場合、液晶ポリエステル樹脂の分子量分布を上述の好適な範囲に制御することが容易であり、金属密着性および引張特性に優れる観点から、無水酢酸の量は、液晶ポリエステル樹脂原料のフェノール性水酸基の合計の１．００〜１．０８モル当量であることが好ましく、１．０２〜１．０８モル当量であることがより好ましい。 When the method (2) is used for production, it is easy to control the molecular weight distribution of the liquid crystal polyester resin within the above-mentioned preferred range, and from the viewpoint of excellent metal adhesion and tensile properties, the amount of acetic anhydride is not The total amount of phenolic hydroxyl groups of the polyester resin raw material is preferably 1.00 to 1.08 molar equivalent, and more preferably 1.02 to 1.08 molar equivalent.
また、フェノール性水酸基のアセチル化反応において、重合速度が遅くなるように制御することで、得られる液晶ポリエステル樹脂の分子量分布を広くなるように制御することができる。重合速度を適度に遅く制御することで、得られる液晶ポリエステル樹脂における絶対分子量１００００以下の部分や絶対分子量５００００以上の部分の面積分率を上記の好適な範囲に制御する観点から、内温１４０℃〜１４５℃でのアセチル化反応時間を１１０分以下とすることが好ましい。より好ましくは１００分以下、さらに好ましくは９０分以下である。一方で、重合速度が過度に遅くなりすぎない程度に制御することで、得られる液晶ポリエステル樹脂における絶対分子量１００００以下の部分や絶対分子量５００００以上の部分の面積分率を上記の好適な範囲に制御する観点から、内温１４０〜１４５℃でのアセチル化反応時間を４０分以上とすることが好ましい。より好ましくは４５分以上、さらに好ましくは５０分以上である。なお、アセチル化反応が効率よく進行する温度が内温１４０℃以上であり、副生成物である酢酸が留出しはじめる温度が内温１４５℃であることから、内温１４０〜１４５℃でのアセチル化反応に着目した。 Further, in the acetylation reaction of the phenolic hydroxyl group, by controlling the polymerization rate to be slow, the molecular weight distribution of the obtained liquid crystal polyester resin can be controlled to be wide. From the viewpoint of controlling the area fraction of the portion having an absolute molecular weight of 10,000 or less or the portion having an absolute molecular weight of 50,000 or more in the obtained liquid crystal polyester resin by controlling the polymerization rate to an appropriately low temperature, an internal temperature of 140° C. The acetylation reaction time at ˜145° C. is preferably 110 minutes or less. It is more preferably 100 minutes or less, still more preferably 90 minutes or less. On the other hand, by controlling the polymerization rate so as not to be excessively slow, the area fraction of the portion having an absolute molecular weight of 10,000 or less or the portion having an absolute molecular weight of 50,000 or more in the obtained liquid crystal polyester resin is controlled within the above-mentioned preferable range. From this viewpoint, the acetylation reaction time at an internal temperature of 140 to 145° C. is preferably 40 minutes or longer. It is more preferably 45 minutes or more, and further preferably 50 minutes or more. The temperature at which the acetylation reaction proceeds efficiently is 140° C. or higher, and the temperature at which acetic acid, which is a by-product, begins to distill is 145° C., so the acetylation at 140-145° C. Focused on the chemical reaction.
本発明で使用する液晶ポリエステル樹脂の製造方法として、固相重合法により重縮合反応を完了させることも可能である。固相重合法による処理としては、例えば、以下の方法が挙げられる。まず、液晶ポリエステル樹脂のポリマーまたはオリゴマーを粉砕機で粉砕する。粉砕したポリマーまたはオリゴマーを、窒素気流下、または、減圧下において加熱し、所望の重合度まで重縮合することで、反応を完了させる。上記加熱は、液晶ポリエステルの融点−５０℃〜融点−５℃（例えば、２００〜３００℃）の範囲で１〜５０時間行うことが好ましい。 As a method for producing the liquid crystal polyester resin used in the present invention, it is also possible to complete the polycondensation reaction by a solid phase polymerization method. Examples of the treatment by the solid-state polymerization method include the following methods. First, a polymer or oligomer of liquid crystal polyester resin is pulverized by a pulverizer. The reaction is completed by heating the pulverized polymer or oligomer under a nitrogen stream or under reduced pressure to polycondense to a desired degree of polymerization. The above heating is preferably performed for 1 to 50 hours within a range of the melting point of the liquid crystal polyester of -50°C to the melting point of -5°C (for example, 200 to 300°C).
液晶ポリエステル樹脂の重縮合反応は、無触媒でも進行するが、酢酸第一錫、テトラブチルチタネート、酢酸カリウムおよび酢酸ナトリウム、三酸化アンチモン、金属マグネシウムなどを触媒として使用することもできる。 Although the polycondensation reaction of the liquid crystal polyester resin proceeds without a catalyst, stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metallic magnesium and the like can be used as a catalyst.
＜液晶ポリエステル樹脂組成物＞
本発明の液晶ポリエステル樹脂は、溶媒に対する溶解性に優れる点から、液晶ポリエステル樹脂および溶媒を含有する液晶ポリエステル樹脂組成物として種々の用途に用いることができる。液晶ポリエステル樹脂組成物は、液晶ポリエステル樹脂が溶け残っている状態、液晶ポリエステル樹脂が完全に溶解して液状となっている状態、および液晶ポリエステル樹脂が溶解した後に溶液が冷却されることにより固化した状態のいずれの状態であってもよい。
<Liquid crystal polyester resin composition>
The liquid crystal polyester resin of the present invention can be used in various applications as a liquid crystal polyester resin composition containing a liquid crystal polyester resin and a solvent because of its excellent solubility in a solvent. The liquid crystal polyester resin composition was solidified by a state in which the liquid crystal polyester resin remained undissolved, a state in which the liquid crystal polyester resin was completely dissolved into a liquid state, and a state in which the solution was cooled after the liquid crystal polyester resin was dissolved. It may be any of the states.
かかる組成物を製造する方法について説明する。液晶ポリエステル樹脂組成物の製造に用いる溶媒としては、液晶ポリエステル樹脂を溶解できるものであれば特に限定されないが、例えば、ハロゲン化フェノール類、ハロゲン化アルコール、および上記溶媒と一般有機溶媒との混合溶媒が挙げられる。ハロゲン化フェノールとしては、２−クロロフェノール、３−クロロフェノール、４−クロロフェノール、２，４，６−トリクロロフェノール、２−フルオロフェノール、３−フルオロフェノール、４−フルオロフェノール、２，４，６−トリフルオロフェノール、３，４，５−トリフルオロフェノール、２，３，４−トリフルオロフェノール、２，３，５，６−テトラフルオロフェノール、２，３，４，５−テトラフルオロフェノール、ペンタフルオロフェノールなどが挙げられ、ハロゲン化アルコールとしては、ヘキサフルオロイソプロパノールが挙げられる。溶解性の点から、ベンゼン環に結合した水素原子が３つ以上フッ素原子に置換されたフェノールを最も多く含むことが好ましく、ペンタフルオロフェノールを最も多く含むことがより好ましい。 A method for producing such a composition will be described. The solvent used for producing the liquid crystal polyester resin composition is not particularly limited as long as it can dissolve the liquid crystal polyester resin, for example, halogenated phenols, halogenated alcohols, and a mixed solvent of the above solvent and a general organic solvent. Is mentioned. Examples of the halogenated phenol include 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4,6-trichlorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4,6. -Trifluorophenol, 3,4,5-trifluorophenol, 2,3,4-trifluorophenol, 2,3,5,6-tetrafluorophenol, 2,3,4,5-tetrafluorophenol, penta Examples thereof include fluorophenols, and examples of halogenated alcohols include hexafluoroisopropanol. From the viewpoint of solubility, it is preferable that the number of hydrogen atoms bonded to the benzene ring is 3 or more, and the number of phenol atoms substituted with fluorine atoms is the largest, and the amount of pentafluorophenol is the largest.
本発明の液晶ポリエステル樹脂組成物は、溶液粘度を高すぎない程度に制御し、支持体等に塗布する際に均一に塗布でき、フィルムとした場合に金属密着性および引張特性に優れるフィルムが得られる観点から、液晶ポリエステル樹脂１００重量部に対して溶媒１００重量部以上を含有することが好ましい。より好ましくは１５０重量部以上、さらに好ましくは２００重量部以上である。一方、溶液粘度を確保することで、支持体等に塗布する際に均一に塗布でき、フィルムとした場合に金属密着性および引張特性に優れるフィルムが得られる観点から、液晶ポリエステル樹脂１００重量部に対して溶媒１００００重量部以下を含有することが好ましい。より好ましくは５０００重量部以下、さらに好ましくは２０００重量部以下である。 The liquid crystal polyester resin composition of the present invention controls the solution viscosity not to be too high, and can be uniformly applied when applied to a support or the like, and when formed into a film, a film having excellent metal adhesion and tensile properties can be obtained. From this viewpoint, it is preferable to contain 100 parts by weight or more of the solvent with respect to 100 parts by weight of the liquid crystal polyester resin. The amount is more preferably 150 parts by weight or more, and further preferably 200 parts by weight or more. On the other hand, by ensuring the solution viscosity, 100 parts by weight of the liquid crystal polyester resin can be obtained from the viewpoint that it can be uniformly applied when applied to a support and the like, and a film having excellent metal adhesion and tensile properties can be obtained when formed into a film. On the other hand, it is preferable to contain 10,000 parts by weight or less of the solvent. The amount is more preferably 5000 parts by weight or less, still more preferably 2000 parts by weight or less.
前記の液晶ポリエステル樹脂組成物を必要に応じて、フィルターなどによってろ過し、組成物中に含まれる微細な異物を除去してもよい。 If necessary, the liquid crystal polyester resin composition may be filtered with a filter or the like to remove fine foreign matters contained in the composition.
＜充填材＞
本発明の効果を損なわない範囲で、本発明の積層体用液晶ポリエステル樹脂、または液晶ポリエステル樹脂組成物に公知の充填材、添加剤等を含有させてもよい。
<Filling material>
The liquid crystal polyester resin for a laminate or the liquid crystal polyester resin composition of the present invention may contain known fillers, additives and the like within a range that does not impair the effects of the present invention.
充填材としては、例えば、繊維状充填材、ウィスカー状充填材、板状充填材、粉末状充填材、粒状充填材などの充填材を挙げることができる。具体的には、繊維状充填材またはウィスカー状充填材としては、ガラス繊維、ＰＡＮ系やピッチ系の炭素繊維、ステンレス繊維、アルミニウム繊維や黄銅繊維などの金属繊維、芳香族ポリアミド繊維や液晶ポリエステル繊維などの有機繊維、石膏繊維、セラミック繊維、アスベスト繊維、ジルコニア繊維、アルミナ繊維、シリカ繊維、酸化チタン繊維、炭化ケイ素繊維、ロックウール、チタン酸カリウムウィスカー、チタン酸バリウムウィスカー、ホウ酸アルミニウムウィスカー、窒化ケイ素ウィスカー、および針状酸化チタンなどが挙げられる。板状充填材としては、マイカ、タルク、カオリン、ガラスフレーク、クレー、二硫化モリブデン、およびワラステナイトなどが挙げられる。粉状または粒状の充填材としては、シリカ、ガラスビーズ、酸化チタン、酸化亜鉛、ポリリン酸カルシウムおよび黒鉛などが挙げられる。上記の充填材は、その表面を公知のカップリング剤（例えば、シラン系カップリング剤、チタネート系カップリング剤など）、その他の表面処理剤で処理されていてもよい。また、充填材は２種以上を併用してもよい。 Examples of the filler include fibrous filler, whisker-shaped filler, plate-shaped filler, powdered filler, granular filler and the like. Specifically, examples of the fibrous filler or whisker-like filler include glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber and brass fiber, aromatic polyamide fiber and liquid crystal polyester fiber. Organic fiber such as gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, nitriding Silicon whiskers, acicular titanium oxide and the like can be mentioned. Examples of the plate-like filler include mica, talc, kaolin, glass flakes, clay, molybdenum disulfide, and wollastonite. Examples of the powdery or granular filler include silica, glass beads, titanium oxide, zinc oxide, calcium polyphosphate and graphite. The surface of the above-mentioned filler may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or another surface treatment agent. Two or more fillers may be used in combination.
添加剤としては、例えば、酸化防止剤、熱安定剤（例えば、ヒンダードフェノール、ハイドロキノン、ホスファイト、チオエーテル類およびこれらの置換体など）、紫外線吸収剤（例えば、レゾルシノール、サリシレート）、亜リン酸塩、次亜リン酸塩などの着色防止剤、滑剤および離型剤（モンタン酸およびその金属塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミドおよびポリエチレンワックスなど）、染料または顔料を含む着色剤、導電剤あるいは着色剤としてのカーボンブラック、結晶核剤、可塑剤、難燃剤（臭素系難燃剤、燐系難燃剤、赤燐、シリコーン系難燃剤など）、難燃助剤、および帯電防止剤から選択される通常の添加剤を配合することができる。 Examples of the additive include an antioxidant, a heat stabilizer (eg, hindered phenol, hydroquinone, phosphite, thioethers and their substitution products), an ultraviolet absorber (eg, resorcinol, salicylate), phosphorous acid. Colorants including salts, anti-coloring agents such as hypophosphite, lubricants and mold release agents (such as montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax), dyes or pigments , Carbon black as conductive agent or colorant, crystal nucleating agent, plasticizer, flame retardant (bromine flame retardant, phosphorus flame retardant, red phosphorus, silicone flame retardant, etc.), flame retardant aid, and antistatic agent Ordinary additives selected from can be blended.
＜液晶ポリエステル樹脂フィルムおよび積層体＞
本発明の積層体用液晶ポリエステル樹脂や液晶ポリエステル樹脂組成物は、液晶ポリエステル樹脂フィルムや積層体を製造するための原料として用いることができる。
<Liquid crystal polyester resin film and laminate>
The liquid crystal polyester resin for a laminate or the liquid crystal polyester resin composition of the present invention can be used as a raw material for producing a liquid crystal polyester resin film or a laminate.
本発明の液晶ポリエステル樹脂フィルムは、本発明の液晶ポリエステル樹脂からなるものである。液晶ポリエステル樹脂フィルムは、例えば、下記（Ｉ）または（ＩＩ）の方法で製造することができる。 The liquid crystal polyester resin film of the present invention comprises the liquid crystal polyester resin of the present invention. The liquid crystal polyester resin film can be produced, for example, by the following method (I) or (II).
（Ｉ）本発明の液晶ポリエステル樹脂を、例えば一軸押出機、二軸押出機、ベント押出機、タンデム押出機などにより支持体上に溶融押出して積層体を得た後、得られた積層体から支持体を除去する方法。 (I) The liquid crystal polyester resin of the present invention is melt-extruded onto a support by, for example, a single-screw extruder, a twin-screw extruder, a vent extruder, or a tandem extruder to obtain a laminate, and then the obtained laminate is used. Method of removing the support.
（ＩＩ）本発明の液晶ポリエステル樹脂組成物を、支持体上に塗布し、溶媒を除去して積層体を得た後、得られた積層体から支持体を除去する方法。 (II) A method of applying the liquid crystal polyester resin composition of the present invention on a support, removing the solvent to obtain a laminate, and then removing the support from the obtained laminate.
液晶ポリエステル樹脂特有の異方性を低減し、フィルムの金属密着性および引張特性に優れるフィルムが得られる観点や、簡便な操作で本発明の液晶ポリエステル樹脂フィルムを得ることができる観点から、（ＩＩ）の方法が好ましい。 From the viewpoint that the anisotropy peculiar to the liquid crystal polyester resin is reduced and a film having excellent metal adhesion and tensile properties of the film can be obtained and that the liquid crystal polyester resin film of the present invention can be obtained by a simple operation (II Method) is preferred.
また、本発明の積層体は、支持体および樹脂層が積層された積層体であって、本発明の液晶ポリエステル樹脂からなる樹脂層の少なくとも一方の面に、支持体が積層された積層体である。積層体は、例えば、下記（ＩＩＩ）〜（ＶＩ）の方法で製造することができる。 Further, the laminate of the present invention is a laminate in which a support and a resin layer are laminated, and the support is laminated on at least one surface of the resin layer made of the liquid crystal polyester resin of the present invention. is there. The laminate can be produced, for example, by the following methods (III) to (VI).
（ＩＩＩ）本発明の液晶ポリエステル樹脂組成物を、支持体上に塗布した後に、溶媒を除去する方法。 (III) A method of removing the solvent after coating the liquid crystal polyester resin composition of the present invention on a support.
（ＩＶ）上記（Ｉ）または（ＩＩ）の方法により製造されたフィルムを加熱圧着により支持体に貼付する方法。 (IV) A method in which the film produced by the above method (I) or (II) is attached to a support by thermocompression bonding.
（Ｖ）上記（Ｉ）または（ＩＩ）の方法により製造されたフィルムと支持体とを接着剤により貼付する方法。 (V) A method of adhering the film produced by the method (I) or (II) and the support with an adhesive.
（ＶＩ）上記（Ｉ）または（ＩＩ）の方法により製造されたフィルム上に支持体を蒸着により形成する方法。 (VI) A method of forming a support on the film produced by the method (I) or (II) by vapor deposition.
容易に、均一な膜厚の樹脂層を形成することができ、かつ支持体が金属箔である場合に樹脂層と金属箔との密着性が高い積層体を得ることができ、引張特性にも優れる観点から、（ＩＩＩ）の方法が好ましい。 It is possible to easily form a resin layer having a uniform film thickness, and when the support is a metal foil, it is possible to obtain a laminate having high adhesion between the resin layer and the metal foil, and also in tensile properties. From the viewpoint of being excellent, the method (III) is preferable.
上記（ＩＩ）〜（ＶＩ）の方法に使用する支持体としては、特に制約は無く、金属箔、ガラス基板、高分子フィルムなどから選ばれる。（ＩＩ）および（ＩＩＩ）の方法に用いられる支持体においては、使用する溶媒に対して耐性があることが重要である。支持体は金属箔、ガラス基板、高分子フィルムなどの単体であっても、これらの複合素材であってもよい。高分子フィルムとしては、絶縁性を有するポリイミドフィルム、液晶ポリエステルフィルム、シクロオレフィンポリマーフィルム、ポリプロピレンフィルムなどが挙げられる。 The support used in the above methods (II) to (VI) is not particularly limited and is selected from metal foils, glass substrates, polymer films and the like. It is important that the support used in the methods (II) and (III) is resistant to the solvent used. The support may be a simple substance such as a metal foil, a glass substrate, a polymer film or the like, or a composite material thereof. Examples of the polymer film include an insulating polyimide film, a liquid crystal polyester film, a cycloolefin polymer film, and a polypropylene film.
上記（ＩＩＩ）〜（Ｖ）の方法において、支持体が金属箔である場合や、上記（ＶＩ）の方法において、支持体が金属層である場合に使用される金属としては、例えば、金、銀、銅、ニッケル、アルミニウムなどが挙げられる。フレキシブルプリント配線板用途などでは銅が好ましい。 Examples of the metal used when the support is a metal foil in the methods (III) to (V) or when the support is a metal layer in the method (VI) include gold, Examples thereof include silver, copper, nickel and aluminum. Copper is preferred for applications such as flexible printed wiring boards.
以下、上記（ＩＩＩ）の方法により積層体を製造する方法を説明する。 Hereinafter, a method for producing a laminate by the method (III) will be described.
支持体上に液晶ポリエステル樹脂組成物を塗布する方法としては、例えば、ローラーコート法、ディップコート法、スプレイコーター法、スピナーコート法、カーテンコート法、スロットコート法、スクリーン印刷法等の各種手段が挙げられる。これらの手段によって液晶ポリエステル樹脂組成物を、支持体上に平坦かつ均一に流延して塗膜を形成する。 Examples of the method for applying the liquid crystal polyester resin composition on the support include various means such as a roller coating method, a dip coating method, a spray coater method, a spinner coating method, a curtain coating method, a slot coating method and a screen printing method. Can be mentioned. By these means, the liquid crystal polyester resin composition is flatly and uniformly cast on a support to form a coating film.
続いて、塗膜中の溶媒を除去することにより、支持体の表面に液晶ポリエステル樹脂層が形成される。溶媒の除去方法は、溶媒の蒸発により行うことが好ましい。溶媒を蒸発する方法としては、加熱、減圧、通風などの方法が挙げられる。溶媒の急激な蒸発を抑制し、クラックがなく膜厚が均一なフィルムが得られる観点から、加熱により溶媒を除去することが好ましい。加熱温度は、溶媒が揮発する温度であれば特に限定されないが、溶媒の急激な蒸発を抑制し、クラックがなく膜厚が均一なフィルムが得られる観点から、溶媒の沸点より低い温度であることが好ましい。したがって、室温より高く、溶媒の沸点より低い温度で加熱することが好ましい。 Then, the solvent in the coating film is removed to form a liquid crystal polyester resin layer on the surface of the support. The solvent is preferably removed by evaporation of the solvent. Examples of the method for evaporating the solvent include methods such as heating, depressurization, and ventilation. From the viewpoint of suppressing rapid evaporation of the solvent and obtaining a film having no crack and a uniform film thickness, it is preferable to remove the solvent by heating. The heating temperature is not particularly limited as long as it is a temperature at which the solvent volatilizes, but from the viewpoint of suppressing rapid evaporation of the solvent and obtaining a film having a uniform film thickness without cracks, the temperature is lower than the boiling point of the solvent. Is preferred. Therefore, it is preferable to heat at a temperature higher than room temperature and lower than the boiling point of the solvent.
このようにして積層体を形成した後、引張特性を向上させる観点から、必要に応じて、さらに熱処理を行ってもよい。熱処理の方法は特に限定されるものではなく、熱風オーブン、減圧オーブン、ホットプレート等の装置を用いて行うことができる。また、熱処理は、大気圧下、あるいは支持体や液晶ポリエステル樹脂が劣化しない範囲で、加圧下や減圧下で行ってもよい。また、液晶ポリエステル樹脂の劣化を抑制する観点から、熱処理を不活性ガスの雰囲気下で行うことが好ましい。例えば、窒素気流下、液晶ポリエステル樹脂の融点−５０℃〜融点−５℃の範囲から、融点＋５℃〜融点＋５０℃の範囲まで、１〜５０時間かけて昇温することで行うことができる。 After forming the laminated body in this manner, a heat treatment may be further performed, if necessary, from the viewpoint of improving the tensile properties. The method of heat treatment is not particularly limited, and it can be performed using an apparatus such as a hot air oven, a reduced pressure oven, or a hot plate. Further, the heat treatment may be carried out under atmospheric pressure or under pressure or under reduced pressure within a range where the support and the liquid crystal polyester resin are not deteriorated. Further, from the viewpoint of suppressing the deterioration of the liquid crystal polyester resin, it is preferable to perform the heat treatment in an atmosphere of an inert gas. For example, it can be carried out by raising the temperature from a range of −50° C. to −5° C. of melting point of the liquid crystal polyester resin to a range of +5° C. to 50° C. of melting point in a nitrogen stream for 1 to 50 hours.
このようにして得られる積層体の構造としては、例えば、フィルムと支持体との二層構造、フィルムの両面に支持体を積層させた三層構造、支持体の両面にフィルムを積層させた三層構造、さらにはフィルムと支持体を交互に四層以上積層させた多層構造などが挙げられる。 Examples of the structure of the laminate thus obtained include a two-layer structure of a film and a support, a three-layer structure in which the support is laminated on both sides of the film, and a three-layer structure in which the film is laminated on both sides of the support. Examples thereof include a layer structure and a multilayer structure in which a film and a support are alternately laminated in four or more layers.
上記の方法により得られた積層体は、例えば、各種コンピュータ、ＯＡ機器、ＡＶ機器などに代表される電気・電子部品や電気・電子部品を実装したフレキシブルプリント配線板、リジットプリント配線板などの回路基板；車載用半導体、産業用半導体などに用いられる半導体パッケージ；透明導電性フィルムの基材、偏光フィルムの基材、各種調理食品用および電子レンジ加熱用の包装フィルム、電磁波シールド用フィルム、抗菌性フィルム、気体分離用フィルムなどに用いることができる。均一な膜厚で金属密着性が高く、フィルムの引張特性にも優れる積層体を容易に得ることができるため、積層体を用いる、電気・電子部品や機械部品内のフレキシブルプリント配線板およびリジットプリント配線板などの回路基板や半導体パッケージに好適に使用される。 The laminated body obtained by the above method is, for example, a circuit such as a flexible printed wiring board or a rigid printed wiring board on which electric/electronic components typified by various computers, OA equipment, AV equipment and the like, and electric/electronic components are mounted. Substrates: Semiconductor packages used for in-vehicle semiconductors, industrial semiconductors, etc.; base materials for transparent conductive films, base materials for polarizing films, packaging films for various cooked foods and microwave oven heating, electromagnetic wave shielding films, antibacterial properties It can be used as a film, a gas separation film, and the like. A flexible printed wiring board and rigid print in electric/electronic parts and mechanical parts that use a laminate because a laminate with a uniform film thickness and high metal adhesion and excellent film tensile properties can be easily obtained. It is preferably used for circuit boards such as wiring boards and semiconductor packages.
以下、実施例を用いて本発明を説明するが、本発明が実施例により限定されるものではない。実施例中、液晶ポリエステル樹脂の組成および特性評価は以下の方法により測定した。ただし、実施例７、８は現在は比較例であり、実施例１〜６、９〜１１が本発明の実施例である。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples. In the examples, the composition and characteristics of the liquid crystal polyester resin were measured by the following methods. However, Examples 7 and 8 are currently comparative examples, and Examples 1 to 6 and 9 to 11 are examples of the present invention.
（１）液晶ポリエステル樹脂の組成分析
液晶ポリエステル樹脂の組成分析は、１Ｈ−核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）測定により実施した。液晶ポリエステル樹脂をＮＭＲ試料管に５０ｍｇ秤量し、溶媒（ペンタフルオロフェノール／１，１，２，２−テトラクロロエタン−ｄ２＝６５／３５（重量比）混合溶媒）８００μＬに溶解して、ＵＮＩＴＹ ＩＮＯＶＡ５００型ＮＭＲ装置（バリアン社製）を用いて観測周波数５００ＭＨｚ、温度８０℃で１Ｈ−ＮＭＲ測定を実施した。７〜９．５ｐｐｍ付近に観測される各構造単位に由来するピークの面積比から組成を分析した。
(1) Composition analysis of the liquid crystal polyester resin composition analysis LCP was carried out by 1 H- nuclear magnetic resonance spectrum (1 H-NMR) measurement. 50 mg of the liquid crystal polyester resin was weighed in an NMR sample tube, dissolved in 800 μL of a solvent (pentafluorophenol/1,1,2,2-tetrachloroethane-d 2 =65/35 (weight ratio) mixed solvent), and UNITY INOVA500 was dissolved. 1 H-NMR measurement was carried out at an observation frequency of 500 MHz and a temperature of 80° C. using a type NMR apparatus (manufactured by Varian). The composition was analyzed from the area ratio of peaks derived from each structural unit observed in the vicinity of 7 to 9.5 ppm.
（２）液晶ポリエステル樹脂の絶対分子量測定
液晶ポリエステル樹脂の絶対分子量分布は、下記条件に示したゲル浸透クロマトグラフ（ＧＰＣ）／ＬＡＬＬＳ法により測定し、絶対数平均分子量、絶対重量平均分子量、絶対分子量１００００以下の部分の面積分率、および絶対分子量５００００以上の部分の面積分率を求めた。
(2) Absolute molecular weight measurement of liquid crystal polyester resin The absolute molecular weight distribution of the liquid crystal polyester resin is measured by gel permeation chromatography (GPC)/LALLS method shown under the following conditions, and the absolute number average molecular weight, absolute weight average molecular weight, and absolute molecular weight are measured. The area fraction of the portion of 10,000 or less and the area fraction of the portion of absolute molecular weight of 50,000 or more were obtained.
（ＧＰＣ）
ＧＰＣ装置：Ｗａｔｅｒｓ製
検出器：示差屈折率検出器ＲＩ２４１０（Ｗａｔｅｒｓ製）
カラム：Ｓｈｏｄｅｘ Ｋ−８０６Ｍ（２本）、Ｋ−８０２（１本）（昭和電工製）
溶離液：ペンタフルオロフェノール／クロロホルム（３５／６５ｗ／ｗ％）
測定温度：２３℃
流速：０．８ｍＬ／ｍｉｎ
試料注入量：２００μＬ （濃度：０．１％）。
(GPC)
GPC device: Waters
Detector: differential refractive index detector RI2410 (manufactured by Waters)
Column: Shodex K-806M (2), K-802 (1) (Showa Denko)
Eluent: pentafluorophenol/chloroform (35/65w/w%)
Measurement temperature: 23 ℃
Flow rate: 0.8 mL/min
Sample injection volume: 200 μL (concentration: 0.1%).
（ＬＡＬＬＳ）
装置：低角度レーザー光散乱光度計ＫＭＸ−６（Ｃｈｒｏｍａｔｉｘ製）
検出器波長：６３３ｎｍ（Ｈｅ−Ｎｅ）
検出器温度：２３℃。
(LALLS)
Device: Low angle laser light scattering photometer KMX-6 (made by Chromatix)
Detector wavelength: 633 nm (He-Ne)
Detector temperature: 23°C.
（３）液晶ポリエステル樹脂の融点（Ｔｍ）
示差走査熱量計ＤＳＣ−７（パーキンエルマー製）を用いて、液晶ポリエステル樹脂を室温から２０℃／分の昇温条件で加熱した際に観測される吸熱ピーク温度（Ｔｍ１）の観測後、Ｔｍ１＋２０℃の温度で５分間保持した。その後、２０℃／分の降温条件で室温までいったん冷却し、再度２０℃／分の昇温条件で加熱した際に観測される吸熱ピーク温度（Ｔｍ２）を観測した。本発明においては、吸熱ピーク温度（Ｔｍ２）を融点（Ｔｍ）と記載する。
(3) Melting point (Tm) of liquid crystal polyester resin
After observing the endothermic peak temperature (Tm 1 ) observed when the liquid crystal polyester resin was heated from room temperature under a temperature rising condition of 20° C./min using a differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer), Tm was measured. Hold at a temperature of 1 +20° C. for 5 minutes. Then, the endothermic peak temperature (Tm 2 ) observed when the material was once cooled to room temperature under the temperature lowering condition of 20° C./min and heated again under the temperature rising condition of 20° C./min was observed. In the present invention, the endothermic peak temperature (Tm 2 ) is described as the melting point (Tm).
（４）液晶ポリエステル樹脂の溶融粘度
高化式フローテスターＣＦＴ−５００Ｄ（オリフィス０．５φ×１０ｍｍ）（島津製作所製）を用いて、Ｔｍ＋１０℃、せん断速度１０００／ｓの条件で液晶ポリエステル樹脂の溶融粘度を測定した。
(4) Melt Viscosity of Liquid Crystal Polyester Resin Melting of the liquid crystal polyester resin under the conditions of Tm+10° C. and shear rate of 1000/s using a high-performance flow tester CFT-500D (orifice 0.5φ×10 mm) (manufactured by Shimadzu Corporation) The viscosity was measured.
［実施例１］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で８０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は７５分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に２０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−１）を得た。
[Example 1]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4′-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) were charged and reacted at 145° C. for 80 minutes while stirring under a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 75 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 20 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-1) was obtained.
この液晶ポリエステル樹脂（Ａ−１）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、テレフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１３℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は１００００、絶対重量平均分子量は２６０００であった。 Composition analysis of this liquid crystal polyester resin (A-1) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from terephthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 313° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 10,000, and the absolute weight average molecular weight was 26,000.
［実施例２］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９４３重量部（フェノール性水酸基合計の１．０８当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で８０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は７５分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に３０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−２）を得た。
この液晶ポリエステル樹脂（Ａ−２）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、テレフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１３℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は９５００、絶対重量平均分子量は２６５００であった。
[Example 2]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4′-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 943 parts by weight of acetic anhydride (1.08 equivalents of total phenolic hydroxyl groups) were charged and reacted for 80 minutes at 145° C. with stirring under a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 75 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 30 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-2) was obtained.
Composition analysis of this liquid crystal polyester resin (A-2) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from terephthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 313° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 9500, and the absolute weight average molecular weight was 26500.
［実施例３］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１３４重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で８０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は７５分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に３０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−３）を得た。
[Example 3]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4'-dihydroxybiphenyl 134 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) were charged and reacted at 145° C. for 80 minutes while stirring under a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 75 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 30 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-3) was obtained.
この液晶ポリエステル樹脂（Ａ−３）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．４モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．６モル％、テレフタル酸に由来する構造単位は１６．６モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１３℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は９５００、絶対重量平均分子量は２６５００であった。 Composition analysis of this liquid crystal polyester resin (A-3) revealed that the structural units derived from p-hydroxybenzoic acid were 66.4 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.6. Mol%, the structural unit derived from terephthalic acid was 16.6 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 313° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 9500, and the absolute weight average molecular weight was 26500.
［実施例４］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９７６重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２４２重量部および無水酢酸９４５重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で７５分反応させた後、１４５℃から３１０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は７０分であった。その後、重合温度を３１０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に２０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−４）を得た。
[Example 4]
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 976 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl/g. 242 parts by weight of polyethylene terephthalate and 945 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) were charged and reacted at 145° C. for 75 minutes while stirring under a nitrogen gas atmosphere, then from 145° C. to 310° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 70 minutes. Then, the polymerization temperature was maintained at 310° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 20 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged into a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-4) was obtained.
この液晶ポリエステル樹脂（Ａ−４）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６４．６モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．２モル％、テレフタル酸に由来する構造単位は１７．７モル％、エチレングリコールに由来する構造単位は１１．５モル％であった。また、Ｔｍは３００℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は１００００、絶対重量平均分子量は２５５００であった。 Composition analysis of this liquid crystal polyester resin (A-4) revealed that the structural units derived from p-hydroxybenzoic acid were 64.6 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.2. Mol%, the structural unit derived from terephthalic acid was 17.7 mol%, and the structural unit derived from ethylene glycol was 11.5 mol%. The Tm was 300° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 10,000, and the absolute weight average molecular weight was 25500.
［実施例５］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９０１重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート３４６重量部および無水酢酸８８４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で８５分反応させた後、１４５℃から２９０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は８０分であった。その後、重合温度を２９０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に２０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−５）を得た。
[Example 5]
901 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl/g were placed in a 5 L reaction vessel equipped with a stirring blade and a distillation tube. Charge 346 parts by weight of polyethylene terephthalate and 884 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups), react under a nitrogen gas atmosphere with stirring at 145° C. for 85 minutes, then from 145° C. to 290° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 80 minutes. Then, the polymerization temperature was maintained at 290° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 20 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-5) was obtained.
この液晶ポリエステル樹脂（Ａ−５）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は５６．９モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は５．９モル％、テレフタル酸に由来する構造単位は２１．６モル％、エチレングリコールに由来する構造単位は１５．７モル％であった。また、Ｔｍは２６３℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は１０５００、絶対重量平均分子量は２５０００であった。 Composition analysis of this liquid crystal polyester resin (A-5) revealed that the structural units derived from p-hydroxybenzoic acid were 56.9 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 5.9. Mol%, the structural unit derived from terephthalic acid was 21.6 mol%, and the structural unit derived from ethylene glycol was 15.7 mol%. The Tm was 263° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 10500, and the absolute weight average molecular weight was 25,000.
［実施例６］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸５２８重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート８６５重量部および無水酢酸５８１重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で９０分反応させた後、１４５℃から２９０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は８５分であった。その後、重合温度を２９０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に３０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−６）を得た。
[Example 6]
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 528 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl/g. 865 parts by weight of polyethylene terephthalate and 581 parts by weight of acetic anhydride (1.10 equivalent of the total of phenolic hydroxyl groups) were charged and reacted for 90 minutes at 145° C. under stirring in a nitrogen gas atmosphere, then from 145° C. to 290° C. 4 The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 85 minutes. Then, the polymerization temperature was maintained at 290° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 30 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-6) was obtained.
この液晶ポリエステル樹脂（Ａ−６）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は２７．０モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は４．８モル％、テレフタル酸に由来する構造単位は３６．５モル％、エチレングリコールに由来する構造単位は３１．７モル％であった。また、Ｔｍは２１０℃、溶融粘度は５０Ｐａ・ｓ、絶対数平均分子量は１２８００、絶対重量平均分子量は３６０００であった。 Composition analysis of this liquid crystal polyester resin (A-6) revealed that the structural units derived from p-hydroxybenzoic acid were 27.0 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 4.8. The structural unit derived from terephthalic acid was 36.5 mol %, and the structural unit derived from ethylene glycol was 31.7 mol %. The Tm was 210° C., the melt viscosity was 50 Pa·s, the absolute number average molecular weight was 12800, and the absolute weight average molecular weight was 36000.
［実施例７］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１１０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は１０５分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に１０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−７）を得た。
[Example 7]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4′-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) were charged and reacted for 110 minutes at 145° C. under stirring in a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 105 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 10 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-7) was obtained.
この液晶ポリエステル樹脂（Ａ−７）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、テレフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１３℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は１１０００、絶対重量平均分子量は２５２００であった。 A composition analysis of the liquid crystal polyester resin (A-7) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from terephthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 313° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 11,000, and the absolute weight average molecular weight was 25200.
［実施例８］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で５０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は４３分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に６０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−８）を得た。
[Example 8]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4′-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) were charged and reacted at 145° C. for 50 minutes while stirring under a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 43 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 60 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-8) was obtained.
この液晶ポリエステル樹脂（Ａ−８）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、テレフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１３℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は８２００、絶対重量平均分子量は２５５００であった。 Composition analysis of this liquid crystal polyester resin (A-8) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from terephthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 313° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 8200, and the absolute weight average molecular weight was 25500.
［実施例９］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で８０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は４３分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に１０分反応を続け、撹拌に要するトルクが１０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−９）を得た。
[Example 9]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4′-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) were charged and reacted at 145° C. for 80 minutes while stirring under a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 43 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 10 minutes, and the polymerization was completed when the torque required for stirring reached 10 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-9) was obtained.
この液晶ポリエステル樹脂（Ａ−９）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、テレフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１０℃、溶融粘度は３Ｐａ・ｓ、絶対数平均分子量は５５００、絶対重量平均分子量は１６０００であった。 A composition analysis of this liquid crystal polyester resin (A-9) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from terephthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 310° C., the melt viscosity was 3 Pa·s, the absolute number average molecular weight was 5500, and the absolute weight average molecular weight was 16000.
［実施例１０］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、イソフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で８０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は７５分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に２０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−１０）を得た。
[Example 10]
In a 5 L reactor equipped with a stirring blade and a distillation tube, 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of isophthalic acid, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) were charged and reacted at 145° C. for 80 minutes while stirring under a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 75 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 20 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-10) was obtained.
この液晶ポリエステル樹脂（Ａ−１０）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、イソフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３０５℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は９５００、絶対重量平均分子量は２６０００であった。 Composition analysis of this liquid crystal polyester resin (A-10) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from isophthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 305° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 9500, and the absolute weight average molecular weight was 26000.
［実施例１１］
攪拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸８７０重量部、４，４’−ジヒドロキシビフェニル３５２重量部、ハイドロキノン８９重量部、テレフタル酸２９２重量部、イソフタル酸１５７重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で攪拌しながら１４５℃で９０分反応させた後、１４５℃から３３０℃までを４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は８５分であった。その後、重合温度を３３０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に１０分反応を続け、トルクが１０ｋｇ・ｃｍに到達したところで重縮合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−１１）を得た。
[Example 11]
870 parts by weight of p-hydroxybenzoic acid, 352 parts by weight of 4,4′-dihydroxybiphenyl, 89 parts by weight of hydroquinone, 292 parts by weight of terephthalic acid, 157 parts by weight of isophthalic acid were placed in a 5 L reaction vessel equipped with a stirring blade and a distillation tube. And 1314 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) were charged and reacted at 145° C. for 90 minutes while stirring under a nitrogen gas atmosphere, then the temperature was raised from 145° C. to 330° C. over 4 hours. Warmed. At this time, the reaction time at an internal temperature of 140 to 145° C. was 85 minutes. Then, the polymerization temperature was maintained at 330° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was further continued for 10 minutes, and polycondensation was completed when the torque reached 10 kg·cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-11) was obtained.
この液晶ポリエステル樹脂（Ａ−１１）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は５３．８モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は１６．２モル％、ハイドロキノンに由来する構造単位は６．９％、テレフタル酸に由来する構造単位は１５．０モル％、イソフタル酸に由来する構造単位は８．１モル％であった。また、Ｔｍは３１０℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は９５００、絶対重量平均分子量は２１０００であった。 Composition analysis of this liquid crystal polyester resin (A-11) revealed that the structural units derived from p-hydroxybenzoic acid were 53.8 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 16.2. Mol%, the structural unit derived from hydroquinone was 6.9%, the structural unit derived from terephthalic acid was 15.0 mol%, and the structural unit derived from isophthalic acid was 8.1 mol%. Further, Tm was 310° C., melt viscosity was 13 Pa·s, absolute number average molecular weight was 9500, and absolute weight average molecular weight was 21,000.
［比較例１］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は１１５分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に２分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−１２）を得た。
[Comparative Example 1]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4′-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) were charged and reacted for 120 minutes at 145° C. under stirring in a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 115 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for 2 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-12) was obtained.
この液晶ポリエステル樹脂（Ａ−１２）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、テレフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１３℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は１２５００、絶対重量平均分子量は２５５００であった。 Composition analysis of this liquid crystal polyester resin (A-12) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from terephthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. Further, Tm was 313° C., melt viscosity was 13 Pa·s, absolute number average molecular weight was 12,500, and absolute weight average molecular weight was 25500.
［比較例２］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸９９４重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート２１６重量部および無水酢酸９６０重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３２０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は１１５分であった。その後、重合温度を３２０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に１５分反応を続け、撹拌に要するトルクが４０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−１３）を得た。
[Comparative example 2]
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, p-hydroxybenzoic acid 994 parts by weight, 4,4′-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112 parts by weight, and an intrinsic viscosity of about 0.6 dl/g. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) were charged and reacted for 120 minutes at 145° C. under stirring in a nitrogen gas atmosphere, then from 145° C. to 320° C. The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 115 minutes. Then, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued for further 15 minutes, and the polymerization was completed when the torque required for stirring reached 40 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-13) was obtained.
この液晶ポリエステル樹脂（Ａ−１３）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は６６．７モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は６．３モル％、テレフタル酸に由来する構造単位は１６．７モル％、エチレングリコールに由来する構造単位は１０．４モル％であった。また、Ｔｍは３１３℃、溶融粘度は４０Ｐａ・ｓ、絶対数平均分子量は１９２００、絶対重量平均分子量は３８５００であった。 Composition analysis of this liquid crystal polyester resin (A-13) revealed that the structural units derived from p-hydroxybenzoic acid were 66.7 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 6.3. Mol%, the structural unit derived from terephthalic acid was 16.7 mol%, and the structural unit derived from ethylene glycol was 10.4 mol%. The Tm was 313° C., the melt viscosity was 40 Pa·s, the absolute number average molecular weight was 19200, and the absolute weight average molecular weight was 38500.
［比較例３］
攪拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸８７０重量部、４，４’−ジヒドロキシビフェニル３５２重量部、ハイドロキノン８９重量部、テレフタル酸２９２重量部、イソフタル酸１５７重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で攪拌しながら１４５℃で１２０分反応させた後、１４５℃から３３０℃までを４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は１１５分であった。その後、重合温度を３３０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧することを試みたが、１．０ｍｍＨｇに到達する前にトルクが１０ｋｇ・ｃｍに到達し、重縮合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ−１４）を得た。
[Comparative Example 3]
870 parts by weight of p-hydroxybenzoic acid, 352 parts by weight of 4,4′-dihydroxybiphenyl, 89 parts by weight of hydroquinone, 292 parts by weight of terephthalic acid, 157 parts by weight of isophthalic acid were placed in a 5 L reaction vessel equipped with a stirring blade and a distillation tube. And 1314 parts by weight of acetic anhydride (1.10 equivalents of the total of phenolic hydroxyl groups) were charged and reacted at 145°C for 120 minutes while stirring under a nitrogen gas atmosphere, then the temperature was raised from 145°C to 330°C over 4 hours. Warmed. At this time, the reaction time at an internal temperature of 140 to 145° C. was 115 minutes. After that, the polymerization temperature was maintained at 330° C., and it was tried to reduce the pressure to 1.0 mmHg (133 Pa) over 1.0 hour, but the torque reached 10 kg·cm before reaching 1.0 mmHg, and The condensation is complete. Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand shape through a die having one circular discharge port with a diameter of 10 mm, and was pelletized by a cutter to liquid crystal. A polyester resin (A-14) was obtained.
この液晶ポリエステル樹脂（Ａ−１４）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は５３．８モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は１６．２モル％、ハイドロキノンに由来する構造単位は６．９％、テレフタル酸に由来する構造単位は１５．０モル％、イソフタル酸に由来する構造単位は８．１モル％であった。また、Ｔｍは３１０℃、溶融粘度は１３Ｐａ・ｓ、絶対数平均分子量は１１５００、絶対重量平均分子量は２１５００であった。 Composition analysis of this liquid crystal polyester resin (A-14) revealed that the structural units derived from p-hydroxybenzoic acid were 53.8 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 16.2. Mol%, the structural unit derived from hydroquinone was 6.9%, the structural unit derived from terephthalic acid was 15.0 mol%, and the structural unit derived from isophthalic acid was 8.1 mol%. The Tm was 310° C., the melt viscosity was 13 Pa·s, the absolute number average molecular weight was 11500, and the absolute weight average molecular weight was 21500.
［比較例４］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ−ヒドロキシ安息香酸２１８重量部、４，４’−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレート１２９７重量部および無水酢酸３２８重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で８０分反応させた後、１４５℃から２９０℃まで４時間かけて昇温した。このとき、内温１４０〜１４５℃での反応時間は７５分であった。その後、重合温度を２９０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に６０分反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズしてポリエステル樹脂（Ａ−１５）を得たが、液晶性は観察されなかった。
[Comparative Example 4]
218 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl/g were placed in a 5 L reaction vessel equipped with a stirring blade and a distillation tube. 1297 parts by weight of polyethylene terephthalate and 328 parts by weight of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) were charged and reacted for 80 minutes at 145° C. with stirring under a nitrogen gas atmosphere, then from 145° C. to 290° C. 4 The temperature was raised over time. At this time, the reaction time at an internal temperature of 140 to 145° C. was 75 minutes. After that, the polymerization temperature was maintained at 290° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was further continued for 60 minutes, and the polymerization was completed when the torque required for stirring reached 20 kg·cm. It was Next, the inside of the reaction vessel was pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer was discharged in a strand form through a die having a circular discharge port with a diameter of 10 mm, and pelletized by a cutter to produce polyester. A resin (A-15) was obtained, but no liquid crystallinity was observed.
このポリエステル樹脂（Ａ−１５）について組成分析を行ったところ、ｐ−ヒドロキシ安息香酸に由来する構造単位は９．６モル％、４，４’−ジヒドロキシビフェニルに由来する構造単位は４．１モル％、テレフタル酸に由来する構造単位は４５．２モル％、エチレングリコールに由来する構造単位は４１．１モル％であった。また、Ｔｍは２０５℃、溶融粘度は５０Ｐａ・ｓ、絶対数平均分子量は１２５００、絶対重量平均分子量は３８５００であった。 A composition analysis of this polyester resin (A-15) revealed that the structural units derived from p-hydroxybenzoic acid were 9.6 mol% and the structural units derived from 4,4′-dihydroxybiphenyl were 4.1 mol. %, the structural unit derived from terephthalic acid was 45.2 mol %, and the structural unit derived from ethylene glycol was 41.1 mol %. Further, Tm was 205° C., melt viscosity was 50 Pa·s, absolute number average molecular weight was 12,500, and absolute weight average molecular weight was 38500.
続いて、以下の方法により金属密着性および引張特性評価を行った。 Subsequently, metal adhesion and tensile properties were evaluated by the following methods.
（５）金属密着性
得られた液晶ポリエステル樹脂（Ａ−１）〜（Ａ−１４）、およびポリエステル樹脂（Ａ−１５）について、粗粉砕機で粉砕して粉末とし、得られた粉末１００重量部に対し、（Ａ−１１）、（Ａ−１３）、（Ａ−１４）にはペンタフルオロフェノール２０００重量部、それ以外の樹脂にはペンタフルオロフェノール１３００重量部を加えた。１３０℃に加熱することで各液晶ポリエステル樹脂またはポリエステル樹脂を完全に溶解させた後、攪拌させて脱泡し、褐色透明な溶液を得た。得られた溶液を圧延銅箔（ＪＸ金属株式会社製、１２μｍ厚）上にフィルムアプリケーターを用いてキャストし、ホットプレート上で８０℃に加熱して溶媒を除去した後、各液晶ポリエステル樹脂またはポリエステル樹脂の融点−１０℃で１時間熱処理を行い、銅張積層板を得た。続いて、得られた銅張積層板を幅１０ｍｍの帯状に切出し、各液晶ポリエステル樹脂またはポリエステル樹脂層を両面テープで固定し、ＪＩＳＣ６４８１（１９９６）に準拠して、銅箔を各樹脂層に対して垂直となるように、５０ｍｍ／分の速度で引き剥がす際のピール強度（ｋｇｆ／ｃｍ）を測定した。ピール強度が大きいほど金属密着性に優れる。
(5) Metal Adhesion The obtained liquid crystal polyester resins (A-1) to (A-14) and the polyester resin (A-15) were crushed with a coarse crusher to give powder, and 100 parts by weight of the obtained powder 2000 parts by weight of pentafluorophenol for (A-11), (A-13), and (A-14), and 1300 parts by weight of pentafluorophenol for the other resins. Each liquid crystal polyester resin or polyester resin was completely dissolved by heating at 130° C., and then stirred and defoamed to obtain a brown transparent solution. The obtained solution was cast on a rolled copper foil (JX Metals Co., Ltd., 12 μm thick) using a film applicator, heated to 80° C. on a hot plate to remove the solvent, and then each liquid crystal polyester resin or polyester Heat treatment was carried out at a melting point of the resin of −10° C. for 1 hour to obtain a copper clad laminate. Subsequently, the obtained copper-clad laminate was cut into a strip having a width of 10 mm, each liquid crystal polyester resin or polyester resin layer was fixed with a double-sided tape, and a copper foil was attached to each resin layer in accordance with JIS C6481 (1996). The peel strength (kgf/cm) at the time of peeling at a speed of 50 mm/min was measured so as to be vertical. The greater the peel strength, the better the metal adhesion.
（６）引張特性
上記（５）で得た銅張積層板について、塩化第二鉄溶液を用いて銅箔を除去し、２０μｍ厚の液晶ポリエステル樹脂またはポリエステル樹脂フィルムを得た。フィルムをＪＩＳＫ６２５１（２０１０）に基づき平行部幅５ｍｍ、長さ２０ｍｍの引張試験３号ダンベルに切出し、ＪＩＳＫ７１６１（２０１４）に準拠して、５ｍｍ／分の引張速度にて引張試験を行い、引張伸度（％）を求めた。引張伸度が高いほど、引張特性に優れる。
実施例１〜１１および比較例１〜５で得られたペレットについて、上記の方法で各特性を測定した評価結果を表１に示す。
(6) Tensile Properties The copper foil was removed from the copper clad laminate obtained in (5) above using a ferric chloride solution to obtain a 20 μm thick liquid crystal polyester resin or polyester resin film. Based on JISK6251 (2010), the film is cut out into a dumbbell of tensile test No. 3 having a parallel part width of 5 mm and a length of 20 mm, and a tensile test is performed at a tensile speed of 5 mm/min in accordance with JISK7161 (2014) to determine the tensile elongation. (%) was calculated. The higher the tensile elongation, the better the tensile properties.
Table 1 shows the evaluation results obtained by measuring the properties of the pellets obtained in Examples 1 to 11 and Comparative Examples 1 to 5 by the methods described above.
表１の結果から、本発明の液晶ポリエステル樹脂からなるフィルムは、金属密着性および引張特性に優れることがわかる。 From the results in Table 1, it can be seen that the film made of the liquid crystal polyester resin of the present invention has excellent metal adhesion and tensile properties.
本発明の積層体用液晶ポリエステル樹脂は、フィルムとした場合の金属密着性や引張特性に優れる。本発明の積層体は、電気・電子部品や機械部品内のフレキシブルプリント配線板やリジットプリント配線板などの回路基板、および半導体パッケージなどに使用される積層体への使用に好適である。 The liquid crystal polyester resin for laminates of the present invention is excellent in metal adhesion and tensile properties when formed into a film. INDUSTRIAL APPLICABILITY The laminated body of the present invention is suitable for use in circuit boards such as flexible printed wiring boards and rigid printed wiring boards in electric/electronic parts and mechanical parts, and in laminated bodies used for semiconductor packages and the like.
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