JP5050429B2 - Polyester resin composition and adhesive containing the same - Google Patents
Polyester resin composition and adhesive containing the same Download PDFInfo
- Publication number
- JP5050429B2 JP5050429B2 JP2006193874A JP2006193874A JP5050429B2 JP 5050429 B2 JP5050429 B2 JP 5050429B2 JP 2006193874 A JP2006193874 A JP 2006193874A JP 2006193874 A JP2006193874 A JP 2006193874A JP 5050429 B2 JP5050429 B2 JP 5050429B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- adhesive
- acid
- resin composition
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001225 polyester resin Polymers 0.000 title claims description 51
- 239000004645 polyester resin Substances 0.000 title claims description 51
- 239000000853 adhesive Substances 0.000 title claims description 42
- 230000001070 adhesive effect Effects 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002985 plastic film Substances 0.000 claims description 5
- 229920006255 plastic film Polymers 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 36
- -1 polyethylene terephthalate Polymers 0.000 description 15
- 230000000903 blocking effect Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 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 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000005591 trimellitate group Chemical group 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-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
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 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
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 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
- 239000000243 solution Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- QIKSEZYONUMDRR-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-4,5-dicarboxylic acid Chemical compound OC(=O)C1C(C(=O)O)CCC2C(=O)OC(=O)C12 QIKSEZYONUMDRR-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LHOBKFFUEUQRQX-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,5-diol Chemical compound OCC(C)CC(C)(C)CO LHOBKFFUEUQRQX-UHFFFAOYSA-N 0.000 description 1
- QLVPICNVQBBOQP-UHFFFAOYSA-N 2-(4,6-diamino-1,3,5-triazin-2-yl)guanidine Chemical compound NC(N)=NC1=NC(N)=NC(N)=N1 QLVPICNVQBBOQP-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- BRSICLJIUFXBCB-UHFFFAOYSA-N 2-methyloctane-1,1-diol Chemical compound CCCCCCC(C)C(O)O BRSICLJIUFXBCB-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-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
- YWVFNWVZBAWOOY-UHFFFAOYSA-N 4-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1CCC(C(O)=O)C(C(O)=O)C1 YWVFNWVZBAWOOY-UHFFFAOYSA-N 0.000 description 1
- DGQOZCNCJKEVOA-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1CC(=O)OC1=O DGQOZCNCJKEVOA-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- ZUHMEUFBTDOKPX-UHFFFAOYSA-N 6-[2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl]-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(CCC=2N=C(N)N=C(N)N=2)=N1 ZUHMEUFBTDOKPX-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- IAANMKMHMYZVOC-UHFFFAOYSA-N aminomethyl dihydrogen phosphate Chemical compound NCOP(O)(O)=O IAANMKMHMYZVOC-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- PLUDEAUQZKPAIN-UHFFFAOYSA-N bis(4-methylphenyl) hydrogen phosphate Chemical compound C1=CC(C)=CC=C1OP(O)(=O)OC1=CC=C(C)C=C1 PLUDEAUQZKPAIN-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical class OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-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
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
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- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- HGJYOHAIVZXUML-UHFFFAOYSA-M potassium;3-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=CC=CC=2)=C1 HGJYOHAIVZXUML-UHFFFAOYSA-M 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
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- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Insulated Conductors (AREA)
Description
本発明は、電気、電子機器の配線などに使用されるフレキシブルフラットケーブル用接着剤に特に適したポリエステル樹脂組成物に関するものである。さらに詳細にはフレキシブルフラットケーブルの絶縁フィルムを接着するための接着剤として好適なものである。本発明の接着剤は、優れた耐ブロッキング性、ポリエステルフィルムや錫メッキ銅に対する接着性に優れた性能を発揮する。 The present invention relates to a polyester resin composition particularly suitable for an adhesive for flexible flat cables used for wiring of electric and electronic devices. More specifically, it is suitable as an adhesive for bonding an insulating film of a flexible flat cable. The adhesive of the present invention exhibits excellent blocking resistance and performance excellent in adhesion to polyester films and tin-plated copper.
近年、家電製品や自動車部品の軽薄短小化に伴い、回路基板同士の配線には多心平型のフレキシブルフラットケーブル(以下FFCと略することがある)が多用されるようになった。FFCは錫メッキ銅箔を、接着剤を介して絶縁フィルムと貼り合わせる構造、すなわち絶縁フィルム/接着剤/金属導線/接着剤/絶縁フィルムの構造を有している。絶縁基材としては、機械特性、電気特性の優れた2軸延伸ポリエチレンテレフタレート(PET)フィルム層が用いられていることが多い。 In recent years, with the miniaturization of home appliances and automobile parts, multi-core flat flexible flat cables (hereinafter sometimes abbreviated as FFC) have been frequently used for wiring between circuit boards. The FFC has a structure in which a tin-plated copper foil is bonded to an insulating film via an adhesive, that is, an insulating film / adhesive / metal conductor / adhesive / insulating film structure. As the insulating substrate, a biaxially stretched polyethylene terephthalate (PET) film layer having excellent mechanical properties and electrical properties is often used.
最近、フラットケーブルは可動部分の配線に使用されることが多くなっており、これに伴い、耐屈曲特性、耐熱性の要求も高まってきている。フラットケーブルの耐屈曲特性を向上させるには、一般に導体と絶縁基材の接着性を高める必要があるため、接着剤層には導体との接着性に優れる樹脂が選択され、熱可塑性飽和共重合体ポリエステルが主に用いられている(例えば特許文献1参照)。しかしながら従来知られてきたポリエステル系の接着剤では低温で接着させる際の接着性に劣り、耐屈曲特性、耐熱性、耐ブロッキング性に優れた接着剤は未だ提案されていない。 Recently, flat cables are often used for wiring of movable parts, and accordingly, demands for bending resistance and heat resistance are increasing. In order to improve the bending resistance of flat cables, it is generally necessary to improve the adhesion between the conductor and the insulating substrate. Therefore, a resin with excellent adhesion to the conductor is selected for the adhesive layer, and thermoplastic saturated copolymer A united polyester is mainly used (for example, see Patent Document 1). However, conventionally known polyester-based adhesives are inferior in adhesiveness at the time of bonding at low temperature, and an adhesive excellent in bending resistance, heat resistance and blocking resistance has not yet been proposed.
本発明の課題は、自動車部品、電化製品などに配線部品のFFCに用いられる接着剤に関して、錫メッキ銅に対する接着性とブロッキング性の両立、優れた耐熱性を得ることができるFFC用接着剤を提供することにある。 An object of the present invention is to provide an adhesive for FFC that can achieve both good adhesion and blocking property to tin-plated copper and excellent heat resistance with respect to an adhesive used for FFC of wiring parts in automobile parts, electrical appliances and the like. It is to provide.
本発明者等は、上記課題を達成すべく鋭意研究を重ねた結果、本発明に到達した。すなわち、本発明は以下の樹脂組成物、接着剤とそれを用いたFFCである。
数平均分子量が5000〜40000、ガラス転移温度が50℃以上、カルボキシル末端基が50〜300eq/106gである非晶性ポリエステル樹脂(A)と、数平均分子量が5000〜40000、ガラス転移温度が20℃未満である非晶性ポリエステル樹脂(B)を含み、かつその配合比が(A)/(B)=10/90〜50/50(重量比)であるポリエステル樹脂組成物、それを含む接着剤、その接着剤を用いたフレキシブルフラットケーブルである。
The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above-mentioned problems. That is, this invention is the following resin compositions and adhesives, and FFC using the same.
Amorphous polyester resin (A) having a number average molecular weight of 5000 to 40000, a glass transition temperature of 50 ° C. or higher, and a carboxyl end group of 50 to 300 eq / 10 6 g, a number average molecular weight of 5000 to 40000, a glass transition temperature A polyester resin composition comprising an amorphous polyester resin (B) having a temperature of less than 20 ° C. and a blending ratio of (A) / (B) = 10/90 to 50/50 (weight ratio), It is the flexible flat cable using the adhesive agent containing the adhesive agent.
本発明で得られた樹脂組成物は、錫メッキ銅への接着性と耐ブロッキング性に優れた接着剤として有用であり、特にFFC用接着剤として優れた効果を発揮する。 The resin composition obtained in the present invention is useful as an adhesive having excellent adhesion to tin-plated copper and anti-blocking property, and particularly exhibits an excellent effect as an adhesive for FFC.
本発明において用いられるポリエステル樹脂(A)のカルボキシル末端基は50〜300eq/106gである。より好ましくは50〜200eq/106g、さらに好ましくは80〜150eq/106gである。カルボキシル末端基がかかる範囲を越えると、金属への密着性、耐熱性、耐加水分解性などの特性に劣る場合がある。 The carboxyl end group of the polyester resin (A) used in the present invention is 50 to 300 eq / 10 6 g. More preferably, it is 50-200eq / 10 < 6 > g, More preferably, it is 80-150eq / 10 < 6 > g. When the carboxyl end group exceeds this range, the properties such as adhesion to metal, heat resistance, and hydrolysis resistance may be inferior.
本発明において用いられるポリエステル樹脂(A)およびポリエステル樹脂(B)の数平均分子量は5000〜40000が好ましい。より好ましくは10000〜35000である。数平均分子量が5000より低いと接着剤としての機械的特性が不足してしまい十分な接着性や耐熱性が得られない場合があり、40000を超えると加熱溶融時の溶融粘度が高くなり、接着時のラミネート温度が高くなる傾向にある。 The number average molecular weight of the polyester resin (A) and the polyester resin (B) used in the present invention is preferably 5000 to 40000. More preferably, it is 10000-35000. If the number average molecular weight is lower than 5,000, the mechanical properties as an adhesive may be insufficient and sufficient adhesiveness and heat resistance may not be obtained. If it exceeds 40,000, the melt viscosity at the time of heating and melting increases, The laminating temperature tends to increase.
本発明において用いられるポリエステル樹脂(A)のガラス転移温度は50℃以上である。好ましくは55℃以上、より好ましくは60℃以上である。ガラス転移温度が50℃以下であるとブロッキングが発生する場合があり、接着剤を塗布した後、フィルム等の基材の取り扱いが困難となる。上限は特に限定されないが接着性の観点から120℃未満であることが好ましい。一方、ポリエステル樹脂(B)のガラス転移温度は20℃未満である。好ましくは15℃未満、より好ましくは10℃未満である。ガラス転移温度が20℃以上であると、金属への密着性が劣る傾向にある。下限は特に限定されないがブロッキング性や接着性、樹脂の取り扱い性を考慮すると−30℃以上であることが好ましい。 The glass transition temperature of the polyester resin (A) used in the present invention is 50 ° C. or higher. Preferably it is 55 degreeC or more, More preferably, it is 60 degreeC or more. When the glass transition temperature is 50 ° C. or lower, blocking may occur, and it becomes difficult to handle a substrate such as a film after applying an adhesive. Although an upper limit is not specifically limited, It is preferable that it is less than 120 degreeC from an adhesive viewpoint. On the other hand, the glass transition temperature of the polyester resin (B) is less than 20 ° C. Preferably it is less than 15 degreeC, More preferably, it is less than 10 degreeC. When the glass transition temperature is 20 ° C. or higher, the adhesion to metal tends to be inferior. Although a minimum is not specifically limited, When blocking property, adhesiveness, and the handleability of resin are considered, it is preferable that it is -30 degreeC or more.
本発明において用いられるポリエステル樹脂(A)の重量平均分子量(Mw)/数平均分子量(Mn)の分散比(以下Mw/Mn)は2.5〜4.0が好ましい。より好ましくは2.7〜3.5である。Mw/Mnが2.5より小さいと接着剤としての耐熱性に劣る傾向にある。一方、4.0を越えると接着剤としての接着性が劣る場合がある。 The dispersion ratio (hereinafter Mw / Mn) of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the polyester resin (A) used in the present invention is preferably 2.5 to 4.0. More preferably, it is 2.7 to 3.5. When Mw / Mn is less than 2.5, the heat resistance as an adhesive tends to be inferior. On the other hand, if it exceeds 4.0, the adhesiveness as an adhesive may be inferior.
本発明において用いられるポリエステル樹脂(A)およびポリエステル樹脂(B)の二塩基酸成分としては、以下に示す多価カルボン酸、もしくはそのアルキルエステル、酸無水物を使用できる。多価カルボン酸としては、例えば、テレフタル酸、イソフタル酸、オルソフタル酸、1,5−ナフタレンジカルボン酸、2,6−ナフタレンジカルボンル酸、4,4’−ジフェニルジカルボン酸、2,2’−ジフェニルジカルボン酸、4,4’−ジフェニルエーテルジカルボン酸等の芳香族二塩基酸、アジピン酸、アゼライン酸、セバシン酸、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、1,2−シクロヘキサンジカルボン酸、4−メチル−1,2−シクロヘキサンジカルボン酸、ダイマー酸等の脂肪族や脂環族ジカルボン酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、エチレングリコールビス(アンヒドロトリメリテート)、グリセロールトリス(アンヒドロトリメリテート)等の芳香族多価カルボン酸等が挙げられる。耐熱性や屈曲性を考慮するとテレフタル酸および/またはイソフタル酸を全酸成分のうち、50モル%以上必須成分とするのがより好ましい。 As the dibasic acid component of the polyester resin (A) and the polyester resin (B) used in the present invention, the following polyvalent carboxylic acids, or alkyl esters or acid anhydrides thereof can be used. Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 2,2′-diphenyl. Aromatic dibasic acids such as dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid Acids, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid and other aliphatic and alicyclic dicarboxylic acids, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, ethylene glycol bis (amnes Hydrotrimellitate), glycerol tri And aromatic polycarboxylic acids (anhydrotrimellitate), and the like. In view of heat resistance and flexibility, it is more preferable that terephthalic acid and / or isophthalic acid is an essential component of 50 mol% or more of the total acid components.
また、グリコール成分としては特に制限されるものでは無いが、エチレングリコ−ル、1,2−プロピレングリコール、1,3−プロパンジオ−ル、2−メチル−1,3プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオ−ル、1,6−ヘキサンジオ−ル、3−メチル−1,5−ペンタンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、2,2,4−トリメチル−1,5−ペンタンジオール、ビスフェノールAのエチレンオキサイド付加物およびプロピレンオキサイド付加物、水素化ビスフェノールAのエチレンオキサイド付加物およびプロピレンオキサイド付加物、1,9−ノナンジオール、2−メチルオクタンジオール、1,10−デカンジオール、ポリテトラメチレングリコール、ポリプロピレングリコール、ポリエチレングリコール、ポリカーボネートグリコール等が挙げられる。これらのグリコール成分の中ではエチレングリコール、1,5−ペンタンジオ−ル、1,6−ヘキサンジオ−ル、3−メチル−1,5−ペンタンジオール、ネオペンチルグリコール、1,9−ノナンジオール、ポリテトラメチレングリコール、ポリプロピレングリコール、ポリエチレングリコール、ポリカーボネートグリコールが金属への密着性および溶解安定性の点から好ましい。 Further, the glycol component is not particularly limited, but ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, Dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, ethylene oxide adduct and propylene oxide adduct of bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, 1,9 -Nonanediol, 2-methyloctanediol, 1,1 - decanediol, polytetramethylene glycol, polypropylene glycol, polyethylene glycol, polycarbonate glycol. Among these glycol components, ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,9-nonanediol, polytetra Methylene glycol, polypropylene glycol, polyethylene glycol, and polycarbonate glycol are preferred from the viewpoint of adhesion to metal and dissolution stability.
ポリエステル樹脂にカルボキシル基を導入する方法は、ポリエステル樹脂を重合した後に、常圧、窒素雰囲気下で無水トリメリット酸、無水フタル酸、無水ピロメリット酸、無水コハク酸、無水マレイン酸、無水1,8−ナフタル酸、無水1,2−シクロヘキサンジカルボン酸、シクロヘキサン−1,2,3,4−テトラカルボン酸−3,4−無水物、エチレングリコールビスアンヒドロトリメリテート、5−(2,5−ジオキソテトラヒドロ−3−フラニル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸無水物、ナフタレン−1,8:4,5−テトラカルボン酸二無水物などから1種または2種以上を選択して添加し、付加反応させる方法や、ポリエステルを重縮合する前のオリゴマーにこれらの酸無水物を投入し、次いで減圧下の重縮合反応により高分子量化することで、ポリエステル樹脂にカルボキシル基を導入する方法などがあるが特に限定されない。効率的にカルボキシル基を導入するためには前者の方法が好ましい。好ましい酸無水物は、無水トリメリット酸やエチレングリコールビス(アンヒドロトリメリテート)、グリセロールトリスアンヒドロトリメリテートが挙げられる。 A method for introducing a carboxyl group into a polyester resin is that after polymerizing the polyester resin, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, maleic anhydride, anhydrous 1, 8-Naphthalic acid, 1,2-cyclohexanedicarboxylic anhydride, cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride, ethylene glycol bisanhydro trimellitate, 5- (2,5 -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, naphthalene-1,8: 4,5-tetracarboxylic dianhydride, etc. Add these selected anhydrides, add them, add these acid anhydrides to the oligomer before polycondensation of the polyester, By high molecular weight by polycondensation reaction pressure, but are not particularly limited and a method of introducing a carboxyl group into the polyester resin. The former method is preferred for efficiently introducing a carboxyl group. Preferred acid anhydrides include trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), and glycerol tris anhydro trimellitate.
本発明において用いられる非晶性ポリエステル樹脂(A)のMw/Mn(分散比)を2.5〜4に調整する方法としては、ポリエステル分子内に分岐構造を導入する方法が好ましい。分岐を導入するための共重合成分としては無水トリメリット酸、エチレングリコールビス(アンヒドロトリメリテート)、グリセロールトリスアンヒドロトリメリテート等の多官能カルボン酸やトリメチロールプロパンやペンタエリスリトール等の多官能グリコールを用いる方法がある。これらの成分の共重合量は0.01〜10モル%の範囲にあることが好ましい。 As a method for adjusting the Mw / Mn (dispersion ratio) of the amorphous polyester resin (A) used in the present invention to 2.5 to 4, a method of introducing a branched structure in the polyester molecule is preferable. Copolymerization components for introducing branching include polyfunctional carboxylic acids such as trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol trisanhydrotrimellitate, and other polyfunctional carboxylic acids such as trimethylolpropane and pentaerythritol. There is a method using a functional glycol. The copolymerization amount of these components is preferably in the range of 0.01 to 10 mol%.
本発明において非晶性ポリエステル樹脂(A)と非晶性ポリエステル樹脂(B)の配合比は重量比で(A)/(B)=10/90〜50/50ある。より好ましくは20/80〜30/70である。ポリエステル樹脂(A)成分が10重量%より少ないと、ブロッキング性が劣る場合がある。また、ポリエステル樹脂(B)が50重量%より少ないと、金属への接着性が低下することがある。 In the present invention, the blending ratio of the amorphous polyester resin (A) and the amorphous polyester resin (B) is (A) / (B) = 10/90 to 50/50 in weight ratio. More preferably, it is 20 / 80-30 / 70. When the polyester resin (A) component is less than 10% by weight, the blocking property may be inferior. On the other hand, when the amount of the polyester resin (B) is less than 50% by weight, the adhesion to metal may be lowered.
なお、本発明のポリエステル樹脂組成物には、必要に応じ難燃剤を併用することができる。難燃剤としては、例えば、トリフェニルフォスフェート、トリクレジルフォスフェート、トリキシレニルフォスフェート、トリエチルフォスフェート、クレジルジフェニルフォスフェート、キシレニルジフェニルフォスフェート、クレジルビス(2,6−キシレニル)フォスフェート、2−エチルヘキシルフォスフェート、ジメチルメチルフォスフェート、レゾルシノールビス(ジフェニル)フォスフェート、ビスフェノールAビス(ジフェニル)フォスフェート、ビスフェノールAビス(ジクレジル)フォスフェート、ジエチル−N,N―ビス(2−ヒドロキシエチル)アミノメチルフォスフェート、リン酸アミド、有機フォスフィンオキサイド、赤燐等のリン系難燃剤、ポリリン酸アンモニウム、フォスファゼン、シクロフォスファゼン、トリアジン、メラミンシアヌレート、サクシノグアナミン、エチレンジメラミン、トリグアナミン、シアヌル酸トリアジニル塩、メレム、メラム、トリス(β−シアノエチル)イソシアヌレート、アセトグアナミン、硫酸グアニルメラミン、硫酸メレム、硫酸メラム等の窒素系難燃剤、ジフェニルスルホン−3−スルホン酸カリウム、芳香族スルフォンイミド金属塩、ポリスチレンスルフォン酸アルカリ金属塩等の金属塩系難燃剤、水酸化アルミニウム、水酸化マグネシウム、ドロマイト、ハイドロタルサイト、水酸化バリウム、塩基性炭酸マグネシウム、水酸化ジルコニウム、酸化スズ等の水和金属系難燃剤、シリカ、酸化アルミニウム、酸化鉄、酸化チタン、酸化マンガン、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化コバルト、酸化ビスマス、酸化クロム、酸化スズ、酸化アンチモン、酸化ニッケル、酸化銅、酸化タングステン、ホウ酸亜鉛、メタホウ酸亜鉛、メタホウ酸バリウム、炭酸亜鉛、炭酸マグネシウム、炭酸カルシウム、炭酸バリウムスズ酸亜鉛等無機系難燃剤、シリコーンパウダー等のシリコン系難燃剤である。リン化合物含有樹脂自身の高い難燃性と難燃剤が持つ難燃機構の複合効果からより高い難燃効果が得られる。 In addition, a flame retardant can be used together with the polyester resin composition of the present invention as necessary. Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl bis (2,6-xylenyl) phosphate Fate, 2-ethylhexyl phosphate, dimethyl methyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, diethyl-N, N-bis (2-hydroxy) Ethyl) aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, phosphorous flame retardants such as red phosphorus, ammonium polyphosphate, phosphazene, cyclophosphazene Nitrogen such as triazine, melamine cyanurate, succinoguanamine, ethylene dimelamine, triguanamine, triazinyl cyanurate, melem, melam, tris (β-cyanoethyl) isocyanurate, acetoguanamine, guanylmelamine sulfate, melem sulfate, melam sulfate Flame retardant, potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide metal salt, polystyrene sulfonate alkali metal salt, etc., aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, hydroxylation Hydrated metal flame retardants such as barium, basic magnesium carbonate, zirconium hydroxide, tin oxide, silica, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide Den, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium stannic acid Inorganic flame retardants such as zinc and silicon flame retardants such as silicone powder. Higher flame retardant effect can be obtained from the combined effect of the flame retardant mechanism of the high flame retardancy of the phosphorus compound-containing resin itself and the flame retardant.
このポリエステル樹脂組成物には、必要に応じ、エポキシ樹脂、酸無水物、イソシアネート化合物等の硬化剤、スズ系、アミン系等の硬化触媒を使用することができる。特に、エポキシ樹脂は耐熱性を発現する上で非常に好ましい。 In this polyester resin composition, an epoxy resin, an acid anhydride, a curing agent such as an isocyanate compound, and a curing catalyst such as tin or amine can be used as necessary. In particular, an epoxy resin is very preferable in terms of developing heat resistance.
また、本発明のポリエステル樹脂組成物には、各種の添加剤を混合して接着剤、コーティング剤に用いることができる。添加剤としては、上記に示した難燃剤の他にタルク、雲母、ポリエチレン、各種金属塩等の結晶核剤、着色顔料、無機、有期系の充填剤、タック性向上剤等が挙げられる。 Moreover, various additives can be mixed with the polyester resin composition of this invention, and it can use for an adhesive agent and a coating agent. Examples of the additives include crystal nucleating agents such as talc, mica, polyethylene, and various metal salts, coloring pigments, inorganic and fixed fillers, and tackiness improvers in addition to the flame retardants described above.
例えば本発明の組成物を接着剤として用いる場合には、有機溶剤に溶解させ、プラスチックフィルム上に塗工、乾燥することにより接着用フィルムを得ることが出来る。乾燥膜厚としては、200μm〜3μmが好ましい。より好ましくは100μm以下、さらに好ましくは、70μm以下であり、10μm以上がより好ましい。 For example, when the composition of the present invention is used as an adhesive, an adhesive film can be obtained by dissolving in an organic solvent, coating on a plastic film, and drying. As a dry film thickness, 200 micrometers-3 micrometers are preferable. More preferably, it is 100 micrometers or less, More preferably, it is 70 micrometers or less, and 10 micrometers or more are more preferable.
プラスチックフィルムとしては、ポリエステルフィルム(以下PETフィルムと略す)、ポリアミドフィルム、ポリカーボネートフィルム、ポリプロピレンフィルム、ポリスチレンフィルム、ポリイミドフィルム、ポリアミドフィルム、ポリオキサベンザゾールフィルム等、任意のプラスチックフィルムが用いられるが、ポリエステルフィルムが経済性や汎用性の面で好ましい。プラスチックフィルムには、必要に応じコロナ処理や易接着層を設けることができる。 As the plastic film, an arbitrary plastic film such as a polyester film (hereinafter abbreviated as PET film), a polyamide film, a polycarbonate film, a polypropylene film, a polystyrene film, a polyimide film, a polyamide film, a polyoxabenzazole film is used. A film is preferable in terms of economy and versatility. The plastic film can be provided with a corona treatment or an easy adhesion layer as necessary.
本発明をさらに詳細に説明するために以下に実施例を挙げるが、本発明は実施例になんら限定されるものではない。なお、実施例に記載された測定値は以下の方法によって測定したものである。 In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to the examples. In addition, the measured value described in the Example is measured by the following method.
樹脂組成:樹脂を重クロロホルムに溶解し、ヴァリアン社製核磁気共鳴分析計(NMR)ジェミニ−200を用いて、1H−NMR分析を行ってその積分比より決定した。 Resin composition: The resin was dissolved in deuterated chloroform, and 1 H-NMR analysis was performed using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian Inc., and the integral ratio was determined.
ガラス転移温度:示差走査熱量計を用い、測定試料10mgをアルミパンに入れ、蓋を押さえて密封し、セイコーインスツルメンツ(株)製示差走査熱量分析計(DSC)DSC−220を用いて、20℃/minの昇温速度で測定することにより求めた。 Glass transition temperature: Using a differential scanning calorimeter, 10 mg of a measurement sample was put in an aluminum pan, sealed with a lid, and 20 ° C. using a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc. It was determined by measuring at a heating rate of / min.
数平均分子量:テトラヒドロフランを溶離液としたウォーターズ社製ゲルろ過浸透クロマトグラフィー(GPC)150cを用い、カラム温度30℃、流量1ml/分にてGPC測定を行った結果から計算して、ポリスチレン換算の測定値を得た。但し、カラムは昭和電工(株)shodex KF−802、804、806を用いた。 Number average molecular weight: Calculated from the results of GPC measurement at a column temperature of 30 ° C. and a flow rate of 1 ml / min using Waters Gel Filtration Permeation Chromatography (GPC) 150c with tetrahydrofuran as an eluent. Measurements were obtained. However, Showa Denko Co., Ltd. shodex KF-802, 804, 806 was used for the column.
酸価(カルボキシル末端基量):ポリエステル0.2gを20mlのクロロホルムに溶解し、0.1Nの水酸化カリウムエタノール溶液で滴定し、樹脂106gあたりの当量(eq/106g)を求めた。 Acid value (carboxyl end group amount): 0.2 g of polyester was dissolved in 20 ml of chloroform, and titrated with 0.1 N potassium hydroxide ethanol solution to obtain the equivalent (eq / 10 6 g) per 10 6 g of resin. It was.
<ポリエステル樹脂(A)の合成例1>
撹拌器、温度計、流出用冷却機を装備した反応缶内に、テレフタル酸83部、イソフタル酸81部、トリメリット酸2部、エチレングリコール77部、ネオペンチルグリコール79部を仕込み、加圧下4時間かけて230℃まで徐々に上昇し、留出する水を系外に除きつつエステル化反応を行った。続いて重合触媒を入れ、常圧で10分間攪拌した後、1時間かけて10mmHgまで減圧初期重合を行うと共に温度を250℃まで上昇し、更に1mmHg以下で30分後期重合を行った。その後、窒素雰囲気下中、200℃まで冷却した後、トリメリット酸2部を仕込み、30分間攪拌を行い、ポリエステル樹脂(A)合成例1を得た。この様にして得られたポリエステル樹脂の特性値を表1に示した。
<Synthesis example 1 of polyester resin (A)>
In a reaction vessel equipped with a stirrer, thermometer, and cooler for outflow, 83 parts of terephthalic acid, 81 parts of isophthalic acid, 2 parts of trimellitic acid, 77 parts of ethylene glycol, 79 parts of neopentyl glycol are charged under pressure. The temperature gradually increased to 230 ° C. over time, and the esterification reaction was carried out while removing distilled water out of the system. Subsequently, the polymerization catalyst was added, and the mixture was stirred at normal pressure for 10 minutes, and then the initial polymerization under reduced pressure was performed to 10 mmHg over 1 hour, the temperature was increased to 250 ° C., and the latter polymerization was further performed at 1 mmHg or less for 30 minutes. Then, after cooling to 200 degreeC in nitrogen atmosphere, 2 parts of trimellitic acid was prepared, and it stirred for 30 minutes, and obtained polyester resin (A) synthesis example 1. The characteristic values of the polyester resin thus obtained are shown in Table 1.
<ポリエステル樹脂(A)の合成例2および3>
合成例1と同様にして、ポリエステル樹脂(A)の合成例2および3の作成を行った。この様にして得られたポリエステル樹脂の特性値を表1に示した。
<Synthesis Examples 2 and 3 of polyester resin (A)>
In the same manner as in Synthesis Example 1, Synthesis Examples 2 and 3 of the polyester resin (A) were prepared. The characteristic values of the polyester resin thus obtained are shown in Table 1.
<ポリエステル樹脂(A)の合成例4>
撹拌器、温度計、流出用冷却機を装備した反応缶内に、テレフタル酸83部、イソフタル酸81部、エチレングリコール77部、ネオペンチルグリコール79部を仕込み、4時間かけて230℃まで徐々に上昇し、留出する水を系外に除きつつエステル化反応を行った。続いて重合触媒を入れ、常圧で10分間攪拌した後、1時間かけて10mmHgまで減圧初期重合を行うと共に温度を250℃まで上昇し、更に1mmHg以下で30分後期重合を行い、ポリエステル樹脂(A)合成例4を得た。この様にして得られたポリエステル樹脂の特性値を表1に示した。
<Synthesis example 4 of polyester resin (A)>
In a reaction vessel equipped with a stirrer, a thermometer, and an outflow cooler, 83 parts of terephthalic acid, 81 parts of isophthalic acid, 77 parts of ethylene glycol and 79 parts of neopentyl glycol were charged and gradually increased to 230 ° C. over 4 hours. The esterification reaction was carried out while removing the water that rose and distilled out of the system. Subsequently, a polymerization catalyst was added and stirred for 10 minutes at normal pressure. Then, initial polymerization was performed at a reduced pressure to 10 mmHg over 1 hour, the temperature was increased to 250 ° C., and the latter polymerization was further performed at 1 mmHg or less for 30 minutes to obtain a polyester resin ( A) Synthesis example 4 was obtained. The characteristic values of the polyester resin thus obtained are shown in Table 1.
<ポリエステル樹脂(B)の合成例5〜8>
ポリエステル樹脂(A)の合成例4と同様にポリエステル(B)の合成例5〜8の作成を行った。この様にして得られたポリエステル樹脂の特性値を表1に示した。
<Synthesis Examples 5 to 8 of polyester resin (B)>
Polyester (B) synthesis examples 5 to 8 were prepared in the same manner as in polyester resin (A) synthesis example 4. The characteristic values of the polyester resin thus obtained are shown in Table 1.
<実施例1>
錫メッキ銅接着性:合成例1〜8で得られた接着剤用ポリエステル樹脂を固形分濃度が30%となるように、メチルエチルケトン/トルエン=1/4(重量比)にて溶解した。この溶解した接着剤用ポリエステル樹脂を固形分量で100部、デカブロモジフェニルエーテルを50部、三酸化アンチモンを36部、二酸化チタンを14部、二酸化ケイ素を4部、ガラスビーズを100部、250mlマヨネーズ瓶に入れて、シェーカーで6時間分散した。この得られた分散溶液を25μmの二軸延伸PETフィルム上に乾燥後の厚みが25μmとなる様に塗布し、120℃で10分乾燥したものを作成した。これを用い、接着層と錫メッキ銅をテスター産業社製ロールラミネータを用いて接着した。なお、ラミネートは温度80〜120℃、圧力0.3MPa、速度1m/minで行った。接着強度は東洋ボールドウイン社製RTM100を用いて、25℃雰囲気下で引っ張り試験を行い、50mm/minの引っ張り速度で、90°剥離接着力を測定した。
<Example 1>
Tin-plated copper adhesiveness: The polyester resin for adhesive obtained in Synthesis Examples 1 to 8 was dissolved in methyl ethyl ketone / toluene = 1/4 (weight ratio) so that the solid content concentration was 30%. 100 parts of this dissolved polyester resin for adhesive, 50 parts of decabromodiphenyl ether, 36 parts of antimony trioxide, 14 parts of titanium dioxide, 4 parts of silicon dioxide, 100 parts of glass beads, 250 ml mayonnaise bottle And dispersed with a shaker for 6 hours. The obtained dispersion solution was applied onto a 25 μm biaxially stretched PET film so that the thickness after drying was 25 μm, and dried at 120 ° C. for 10 minutes to prepare. Using this, the adhesive layer and tin-plated copper were bonded using a roll laminator manufactured by Tester Sangyo Co., Ltd. The lamination was performed at a temperature of 80 to 120 ° C., a pressure of 0.3 MPa, and a speed of 1 m / min. The adhesive strength was determined by performing a tensile test in an atmosphere of 25 ° C. using RTM100 manufactured by Toyo Baldwin Co., Ltd., and measuring 90 ° peel adhesive strength at a tensile speed of 50 mm / min.
耐ブロッキング性:上記得られた接着フィルムを同方向に5枚重ね、接着層とPETフィルムが交互に重なるようにした。次いで、このようにして重ねた接着フィルムの上に20g/cm2の荷重をかけ、70℃雰囲気中に72時間保存した。この後、接着シートを取り出し、重ねたシート間の接着強度を測定し、下記の判定を行った。
(判定)○:0〜1N/cm △:1〜2N/cm
×:2N/cm以上
Blocking resistance: Five of the obtained adhesive films were stacked in the same direction so that the adhesive layer and the PET film overlapped alternately. Next, a load of 20 g / cm 2 was applied on the adhesive film thus piled up and stored in an atmosphere at 70 ° C. for 72 hours. Thereafter, the adhesive sheet was taken out, the adhesive strength between the stacked sheets was measured, and the following determination was performed.
(Judgment) ○: 0 to 1 N / cm Δ: 1 to 2 N / cm
X: 2 N / cm or more
耐熱性:上記得られた接着フィルム2枚を用い、接着層で錫メッキ銅線を挟み込んでロールラミネータで貼り合せてFFC(PETフィルム/接着剤層/錫メッキ銅線/接着剤層/PETフィルム)を作成した。なお、ラミネートは温度160℃、圧力0.3MPa、速度1m/minで行った。このFFCを90°に折り曲げて、85℃×90RH%×168hrの条件下に放置し、折り曲げ部分のFFCの外観を確認した。
(判定)○:接着剤層と錫メッキCu、または接着剤層とPETの間で剥離が生じなかった。
×:接着剤層と錫メッキCu、または接着剤層とPETの間で剥離が生じた。
Heat resistance: FFC (PET film / adhesive layer / tin-plated copper wire / adhesive layer / PET film) using two adhesive films obtained above, sandwiching a tin-plated copper wire with an adhesive layer and bonding with a roll laminator )created. Lamination was performed at a temperature of 160 ° C., a pressure of 0.3 MPa, and a speed of 1 m / min. This FFC was bent at 90 ° and allowed to stand under conditions of 85 ° C. × 90 RH% × 168 hr, and the appearance of the FFC in the bent portion was confirmed.
(Judgment) (circle): Peeling did not arise between an adhesive bond layer and tin plating Cu, or an adhesive bond layer and PET.
X: Peeling occurred between the adhesive layer and tin-plated Cu or between the adhesive layer and PET.
<実施例2〜8、比較例1〜8>
以下同様にして行った実施例2〜8の評価結果を表2に、比較実施例1〜8の評価結果を表3に示した。
<Examples 2-8, Comparative Examples 1-8>
The evaluation results of Examples 2 to 8 performed in the same manner are shown in Table 2, and the evaluation results of Comparative Examples 1 to 8 are shown in Table 3.
本発明の接着剤組成物は従来技術と比較して、金属接着性および耐ブロッキング性に優れている。 The adhesive composition of the present invention is superior in metal adhesion and blocking resistance as compared with the prior art.
それに対して、表3に示したように、比較例1および4では、酸価の低いポリエステル樹脂(A)を使用しているため、金属への密着性に劣る。また、ポリエステル樹脂(A)が分子中に分岐を有していないため、耐熱性も劣る。比較例2および3では、ガラス転移温度の高いポリエステル(B)を使用しているため、金属への密着性に劣る。比較例5および6では、ガラス転移温度の低いポリエステル(B)の配合量が多いため、金属への密着性は優れているが、耐ブロッキング性に劣る。比較例7では、ガラス転移温度の高いポリエステル(B)を使用しているため、金属への接着性が劣り、またポリエステル樹脂(B)の配合量が多いため、耐ブロッキング性に劣る。比較例8ではガラス転移温度の低いポリエステル樹脂(B)の配合量が少ないため、金属への密着性に劣る。表2から分かる様に、本発明のポリエステル接着剤は、接着性、耐ブロッキング性、耐熱性に優れた性能を有することがわかる。それに対して、表3に示したように、比較例1〜8は、錫メッキ銅への接着性、耐ブロッキング性、耐熱性が劣っている。 On the other hand, as shown in Table 3, in Comparative Examples 1 and 4, since the polyester resin (A) having a low acid value is used, the adhesion to metal is inferior. Moreover, since the polyester resin (A) does not have a branch in a molecule | numerator, heat resistance is also inferior. In Comparative Examples 2 and 3, since the polyester (B) having a high glass transition temperature is used, the adhesion to metal is inferior. In Comparative Examples 5 and 6, since the compounding amount of polyester (B) having a low glass transition temperature is large, the adhesion to metal is excellent, but the blocking resistance is poor. In Comparative Example 7, since the polyester (B) having a high glass transition temperature is used, the adhesion to metal is inferior, and since the blending amount of the polyester resin (B) is large, the blocking resistance is inferior. In Comparative Example 8, since the blending amount of the polyester resin (B) having a low glass transition temperature is small, the adhesion to metal is poor. As can be seen from Table 2, it can be seen that the polyester adhesive of the present invention has excellent performance in adhesion, blocking resistance and heat resistance. On the other hand, as shown in Table 3, Comparative Examples 1 to 8 are inferior in adhesion to tin-plated copper, blocking resistance, and heat resistance.
本発明で得られた接着剤は、錫メッキ銅への接着性と耐ブロッキング性に優れた接着剤であり、FFC用接着剤として有用である。 The adhesive obtained in the present invention is an adhesive excellent in adhesion to tin-plated copper and blocking resistance, and is useful as an adhesive for FFC.
Claims (7)
2.5 ≦ 重量平均分子量/数平均分子量 ≦ 4.0 (1) The polyester resin composition according to claim 1 or 2, wherein the amorphous polyester resin (A) satisfies the following formula (1).
2.5 ≦ weight average molecular weight / number average molecular weight ≦ 4.0 (1)
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JP2020077645A (en) * | 2020-01-29 | 2020-05-21 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, and joined body |
CN117651747A (en) * | 2021-07-29 | 2024-03-05 | 东洋纺Mc株式会社 | Adhesive composition, adhesive sheet, laminate, and printed wiring board |
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