JP6955768B2 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP6955768B2 JP6955768B2 JP2018512058A JP2018512058A JP6955768B2 JP 6955768 B2 JP6955768 B2 JP 6955768B2 JP 2018512058 A JP2018512058 A JP 2018512058A JP 2018512058 A JP2018512058 A JP 2018512058A JP 6955768 B2 JP6955768 B2 JP 6955768B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- acid
- copolymerized polyester
- glycol
- mol
- 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.)
- Active
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- 239000000853 adhesive Substances 0.000 title claims description 94
- 230000001070 adhesive effect Effects 0.000 title claims description 94
- 239000000203 mixture Substances 0.000 title claims description 87
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 61
- 229920000728 polyester Polymers 0.000 claims description 59
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 20
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 description 25
- -1 polyethylene terephthalate Polymers 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 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 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000007787 solid Substances 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
- PAZZVPKITDJCPV-UHFFFAOYSA-N 10-hydroxyoctadecanoic acid Chemical compound CCCCCCCCC(O)CCCCCCCCC(O)=O PAZZVPKITDJCPV-UHFFFAOYSA-N 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-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
- 150000008064 anhydrides Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RPBCDDTWDKYNQY-UHFFFAOYSA-N o-dodecyl propanethioate Chemical compound CCCCCCCCCCCCOC(=S)CC RPBCDDTWDKYNQY-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- OQLRBFNNEQUJPK-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 OQLRBFNNEQUJPK-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BVDAXFBFXWOHHU-UHFFFAOYSA-N 2-(4-hydroxyphenyl)octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C1=CC=C(O)C=C1 BVDAXFBFXWOHHU-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- WVQHODUGKTXKQF-UHFFFAOYSA-N 2-ethyl-2-methylhexane-1,1-diol Chemical compound CCCCC(C)(CC)C(O)O WVQHODUGKTXKQF-UHFFFAOYSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZQIKIVHRXXOLOA-UHFFFAOYSA-N 3-[3-(18-dodecyltriacontoxy)-3-oxopropyl]sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCC(CCCCCCCCCCCC)CCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)O ZQIKIVHRXXOLOA-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
- H01B7/0208—Cables with several layers of insulating material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/04—Flexible cables, conductors, or cords, e.g. trailing cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/08—Flat or ribbon cables
Description
本発明は、接着剤組成物およびそれからなる層を有する積層体に関する。 The present invention relates to an adhesive composition and a laminate having a layer comprising the adhesive composition.
ポリエチレンテレフタレート、ポリブチレンテレフタレートに代表されるポリエステル樹脂は、その優れた機械的強度、熱安定性、疎水性、耐薬品性を活かし、繊維、フィルム、成形材料等として各種分野で広く利用されている。 Polyester resins typified by polyethylene terephthalate and polybutylene terephthalate are widely used in various fields as fibers, films, molding materials, etc. by taking advantage of their excellent mechanical strength, thermal stability, hydrophobicity, and chemical resistance. ..
ポリエステル樹脂は、その構成成分であるジカルボン酸およびグリコールの種類を変更することにより、種々の特徴を有する共重合ポリエステル樹脂を得ることが可能である。
共重合ポリエステル樹脂は、一般的に、ポリエステル、ポリカーボネート、ポリ塩化ビニル樹脂等のプラスチック類、あるいはアルミニウム、銅等の金属に優れた密着性を有していることから、接着剤、コーティング剤、インキバインダー、塗料等に広く使用されている。たとえば、特許文献１には、特定のアルキレングリコールを共重合してなる、接着性に優れるポリエステル樹脂が開示されている。As the polyester resin, it is possible to obtain a copolymerized polyester resin having various characteristics by changing the types of dicarboxylic acids and glycols which are the constituents thereof.
Copolymerized polyester resins generally have excellent adhesion to plastics such as polyesters, polycarbonates and polyvinyl chloride resins, and metals such as aluminum and copper, so they are adhesives, coating agents and inks. Widely used in binders, paints, etc. For example, Patent Document 1 discloses a polyester resin having excellent adhesiveness, which is obtained by copolymerizing a specific alkylene glycol.
また、共重合ポリエステル系接着剤は、電気絶縁性、難燃性、柔軟性（屈曲部での耐剥離性）などの特性に優れることから、例えば、デジタル家電あるいは自動車用の配線材として広く利用されるフレキシブルフラットケーブル等に広く用いられている。
フレキシブルフラットケーブルは、基材フィルムと接着剤層の２層からなるインシュレーションフィルムの２枚を、互いに接着剤層側同士を向かいあわせ、その間に導線を挟みこんで貼り合わせた構造を有する。基材フィルムとしてポリエチレンテレフタレートフィルムが多く用いられ、導線として、銅、または錫で表面がメッキされた銅等の金属が用いられている。In addition, copolymerized polyester adhesives are widely used as wiring materials for digital home appliances or automobiles, for example, because they have excellent properties such as electrical insulation, flame retardancy, and flexibility (peeling resistance at bent parts). It is widely used for flexible flat cables and the like.
The flexible flat cable has a structure in which two sheets of an insulation film composed of two layers, a base film and an adhesive layer, are bonded to each other with the adhesive layer sides facing each other and a lead wire sandwiched between them. A polyethylene terephthalate film is often used as the base film, and a metal such as copper or copper whose surface is plated with tin is used as the conducting wire.
特に近年、薄型化、小型化が進行する小型家電や車載用部品で使用されるフレキシブルフラットケーブルにおいては、液晶のバックライトや、ＣＰＵなどからの放熱の影響が無視できなくなり、熱に対する耐性が必須要件となりつつあり、また、屋外で使用される場合もあるため、フレキシブルフラットケーブルを構成する接着剤は、高温高湿下でも接着界面が剥離せず接着性を維持できる耐湿熱性を有することも求められている。 In particular, in flexible flat cables used in small household appliances and in-vehicle parts, which are becoming thinner and smaller in recent years, the effects of heat dissipation from the LCD backlight and CPU cannot be ignored, and heat resistance is essential. Since it is becoming a requirement and may be used outdoors, the adhesive constituting the flexible flat cable is also required to have moisture and heat resistance that can maintain the adhesiveness without peeling off the adhesive interface even under high temperature and high humidity. Has been done.
本発明は、金属への接着性に優れるとともに、優れた耐熱性と耐湿熱性を備えた接着剤組成物、およびそれからなる層を有する積層体を提供することを目的とする。 An object of the present invention is to provide an adhesive composition having excellent adhesiveness to a metal and also having excellent heat resistance and moisture heat resistance, and a laminate having a layer made of the adhesive composition.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、特定の構造を有する共重合ポリエステルと架橋剤とを含有する接着剤組成物が、金属への接着性に優れるとともに、耐熱性と耐湿熱性にも優れることを見出し、本発明に到達した。
すなわち、本発明の要旨は下記の通りである。As a result of diligent research to solve the above problems, the present inventors have found that an adhesive composition containing a copolymerized polyester having a specific structure and a cross-linking agent has excellent adhesiveness to metals and has excellent adhesiveness to metals. We have found that it is also excellent in heat resistance and moisture heat resistance, and have reached the present invention.
That is, the gist of the present invention is as follows.
（１）共重合ポリエステル１００質量部と硬化剤０．２〜１５質量部を含有する接着剤組成物であって、
共重合ポリエステルの酸成分におけるイソフタル酸の含有量が３０モル％以上であり、
共重合ポリエステルのグリコール成分における、側鎖を有するグリコールの含有量が３０モル％以上であり、また繰り返し単位の炭素数が２〜４であるポリアルキレングリコールの含有量が１〜２０モル％であり、
前記繰り返し単位の炭素数が２〜４であるポリアルキレングリコールが２種類以上からなり、少なくとも１種類は数平均分子量が２００以上であることを特徴とする接着剤組成物。
（２）上記（１）記載の接着剤組成物からなる層を有することを特徴とする積層体。
（３）上記（２）記載の積層体を含むことを特徴とするフレキシブルフラットケーブル。
(1) An adhesive composition containing 100 parts by mass of a copolymerized polyester and 0.2 to 15 parts by mass of a curing agent.
The content of isophthalic acid in the acid component of the copolymerized polyester is 30 mol% or more, and the content is 30 mol% or more.
The content of glycol having a side chain in the glycol component of the copolymerized polyester is 30 mol% or more, and the content of polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit is 1 to 20 mol%. ,
An adhesive composition comprising two or more types of polyalkylene glycols having 2 to 4 carbon atoms in the repeating unit, and at least one type having a number average molecular weight of 200 or more .
(2) laminate characterized by having a layer comprising the above (1) Symbol mounting adhesive composition.
( 3 ) A flexible flat cable comprising the laminate described in (2 ) above.
本発明によれば、金属への接着性に優れるとともに、優れた耐熱性と耐湿熱性を備えた接着剤組成物を提供することができる。この接着剤組成物からなる層を有する積層体は、フレキシブルフラットケーブルの構成部材として使用することができる。 According to the present invention, it is possible to provide an adhesive composition having excellent adhesiveness to a metal and also having excellent heat resistance and moisture heat resistance. The laminate having a layer made of this adhesive composition can be used as a constituent member of a flexible flat cable.
本発明の接着剤組成物は、共重合ポリエステルと硬化剤とを含有し、軟化点が９０℃以上であり、共重合ポリエステルは、酸成分としてイソフタル酸を、またグリコール成分として、側鎖を有するグリコールと繰り返し単位の炭素数が２〜４であるポリアルキレングリコールを含有する。 The adhesive composition of the present invention contains a copolymerized polyester and a curing agent, has a softening point of 90 ° C. or higher, and the copolymerized polyester has an isophthalic acid as an acid component and a side chain as a glycol component. It contains glycol and a polyalkylene glycol having 2 to 4 carbon atoms as a repeating unit.
本発明の接着剤組成物を構成する共重合ポリエステルにおいて、酸成分は、イソフタル酸を３０モル％以上含有することが必要であり、４０モル％以上含有することが好ましく、中でも５０〜８０モル％含有することがより好ましい。酸成分におけるイソフタル酸の含有量が３０モル％未満であると、得られる接着剤組成物は、接着性が低下し、また有機溶剤への溶解性も低下する傾向にある。
イソフタル酸以外の酸成分としては、テレフタル酸、ナフタレンジカルボン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ヘキサヒドロテレフタル酸、フタル酸、４，４′−ジカルボキシビフェニル、５−ナトリウムスルホイソフタル酸、５−ヒドロキシ−イソフタル酸、フマル酸、マレイン酸、イタコン酸、メサコン酸、シトラコン酸、１，３，４−ベンゼントリカルボン酸、１，２，４，５−ベンゼンテトラカルボン酸、シュウ酸、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、２，５−ノルボルネンジカルボン酸等が挙げられる。これらは、無水物をモノマー原料として用いてもよく、組み合わせて使用してもよい。中でも、耐熱性維持の観点から、イソフタル酸以外の酸成分として、テレフタル酸、ナフタレンジカルボン酸、ヘキサヒドロテレフタル酸を用いることが好ましい。In the copolymerized polyester constituting the adhesive composition of the present invention, the acid component needs to contain 30 mol% or more of isophthalic acid, preferably 40 mol% or more, and particularly 50 to 80 mol%. It is more preferable to contain it. When the content of isophthalic acid in the acid component is less than 30 mol%, the obtained adhesive composition tends to have low adhesiveness and also low solubility in organic solvents.
Acid components other than isophthalic acid include terephthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, hexahydroterephthalic acid, phthalic acid, 4,4'-dicarboxybiphenyl, 5-sodium sulfoisophthal. Acid, 5-hydroxy-isophthalic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, 1,3,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, oxalic acid, Examples thereof include 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and 2,5-norbornenedicarboxylic acid. These may use an anhydride as a monomer raw material, or may be used in combination. Above all, from the viewpoint of maintaining heat resistance, it is preferable to use terephthalic acid, naphthalenedicarboxylic acid, and hexahydroterephthalic acid as an acid component other than isophthalic acid.
共重合ポリエステルにおいて、グリコール成分は、側鎖を有するグリコールを３０モル％以上含有することが必要であり、４０モル％以上含有することがより好ましく、５０〜８０モル％含有することがさらに好ましい。グリコール成分における、側鎖を有するグリコールの含有量が３０モル％未満であると、得られる接着剤組成物は接着性が低下し、また有機溶剤への溶解性も低下する傾向にある。一方、側鎖を有するグリコールの含有量が８０モル％を超えると、接着剤組成物は接着性が低下する傾向がある。
側鎖を有するグリコールとしては、１，２−プロパンジオール、２，２−ジメチル−１，３−プロパンジオール（ネオペンチルグリコール）、２−メチルプロパンジオール、３−メチル−１，５−ペンタンジオール、２−エチル−２−ブチルプロパンジオール、ビスフェノールＡのエチレンオキシド付加体、ビスフェノールＡのプロピレンオキシド付加体、トリメチロールプロパン等が挙げられ、これらを組み合わせて使用してもよい。中でも、接着性を向上させる観点から、側鎖を有するグリコールは、２，２−ジメチル−１，３−プロパンジオール（ネオペンチルグリコール）、ビスフェノールＡのエチレンオキシド付加体が好ましい。In the copolymerized polyester, the glycol component needs to contain 30 mol% or more of glycol having a side chain, more preferably 40 mol% or more, and further preferably 50 to 80 mol%. When the content of glycol having a side chain in the glycol component is less than 30 mol%, the resulting adhesive composition tends to have low adhesiveness and also low solubility in an organic solvent. On the other hand, when the content of glycol having a side chain exceeds 80 mol%, the adhesive composition tends to have low adhesiveness.
Glycols having a side chain include 1,2-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methylpropanediol, 3-methyl-1,5-pentanediol, and the like. Examples thereof include 2-ethyl-2-butylpropanediol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, and trimethylolpropane, and these may be used in combination. Among them, from the viewpoint of improving the adhesiveness, the glycol having a side chain is preferably an ethylene oxide adduct of 2,2-dimethyl-1,3-propanediol (neopentyl glycol) or bisphenol A.
共重合ポリエステルにおいて、グリコール成分は、繰り返し単位の炭素数が２〜４であるポリアルキレングリコールを１〜２０モル％含有することが必要であり、３〜１５モル％含有することが好ましく、４〜１０モル％含有することがより好ましい。グリコール成分における、繰り返し単位の炭素数が２〜４であるポリアルキレングリコールの含有量が１モル％未満であると、得られる接着剤組成物の耐湿熱性が低下する。また、共重合ポリエステルのガラス転移点が高くなる傾向があり、得られる接着剤組成物の接着性が低下する場合がある。一方、繰り返し単位の炭素数が２〜４であるポリアルキレングリコールの含有量が２０モル％を超えると、得られる接着剤組成物は、軟化点が低くなり、耐熱性に劣るものとなる。
繰り返し単位の炭素数が２〜４であるポリアルキレングリコールとしては、接着性と耐湿熱性の観点から、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリトリメチレングリコール、ポリテトラメチレングリコールが好ましい。In the copolymerized polyester, the glycol component needs to contain 1 to 20 mol% of polyalkylene glycol having 2 to 4 carbon atoms as a repeating unit, and preferably contains 3 to 15 mol%. It is more preferable to contain 10 mol%. When the content of the polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit in the glycol component is less than 1 mol%, the moist heat resistance of the obtained adhesive composition is lowered. In addition, the glass transition point of the copolymerized polyester tends to be high, and the adhesiveness of the obtained adhesive composition may be lowered. On the other hand, when the content of the polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit exceeds 20 mol%, the obtained adhesive composition has a low softening point and is inferior in heat resistance.
The polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit includes diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene from the viewpoint of adhesiveness and moisture heat resistance. Glycol is preferred.
共重合ポリエステルは、繰り返し単位の炭素数が２〜４であるポリアルキレングリコールとして、数平均分子量が２００以上であるものを用いることが好ましい。中でも、数平均分子量が５００〜１００００であるものを用いることがより好ましく、数平均分子量が８００〜５０００であるものを用いることがさらに好ましい。繰り返し単位の炭素数が２〜４であるポリアルキレングリコールの数平均分子量が２００以上であるものを用いることによって、得られる接着剤組成物は耐湿熱性が向上する。
さらに、共重合ポリエステルは、グリコール成分として、繰り返し単位の炭素数が２〜４であるポリアルキレングリコールを２種類以上含有することが好ましい。これにより、接着剤組成物の接着性を高めることができる。中でも２種類のものを用いる場合には、ポリテトラメチレングリコールとジエチレングリコールとを併用することが好ましく、また、ポリテトラメチレングリコールとトリエチレングリコールとを併用することが好ましい。As the copolymerized polyester, it is preferable to use a polyalkylene glycol having 2 to 4 carbon atoms as a repeating unit and having a number average molecular weight of 200 or more. Among them, those having a number average molecular weight of 500 to 10000 are more preferable, and those having a number average molecular weight of 800 to 5000 are further preferable. By using a polyalkylene glycol having 2 to 4 carbon atoms as a repeating unit and having a number average molecular weight of 200 or more, the obtained adhesive composition has improved moist heat resistance.
Further, the copolymerized polyester preferably contains two or more kinds of polyalkylene glycols having 2 to 4 carbon atoms as a repeating unit as a glycol component. Thereby, the adhesiveness of the adhesive composition can be enhanced. Among them, when two types are used, it is preferable to use polytetramethylene glycol and diethylene glycol in combination, and it is preferable to use polytetramethylene glycol and triethylene glycol in combination.
上記以外のグリコール成分としては、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジメタノールなどが挙げられ、これらを２種類以上併用してもよい。 Examples of glycol components other than the above include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and the like. , These may be used in combination of two or more.
また、共重合ポリエステルを構成する他の成分として、テトラヒドロフタル酸、乳酸、オキシラン、グリコール酸、２−ヒドロキシ酪酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、２−ヒドロキシイソ酪酸、２−ヒドロキシ−２−メチル酪酸、２−ヒドロキシ吉草酸、３−ヒドロキシ吉草酸、４−ヒドロキシ吉草酸、５−ヒドロキシ吉草酸、６−ヒドロキシカプロン酸、１０−ヒドロキシステアリン酸、４−（β−ヒドロキシ）エトキシ安息香酸等のヒドロキシカルボン酸、リンゴ酸、および、β−プロピオラクトン、β−ブチロラクトン、γ−ブチロラクトン、δ−バレロラクトン、ε−カプロラクトン等の脂肪族ラクトン等が挙げられ、これらを含有してもよい。 In addition, as other components constituting the copolymerized polyester, tetrahydrophthalic acid, lactic acid, oxylane, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2. -Methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, 4- (β-hydroxy) ethoxybenzoic acid Hydrocarboxylic acids such as, malic acid, and aliphatic lactones such as β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone may be contained. ..
また、共重合ポリエステルは、必要に応じて、モノカルボン酸、モノアルコールが共重合されていてもよい。モノカルボン酸としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、安息香酸、ｐ−ｔｅｒｔ−ブチル安息香酸、シクロヘキサン酸、４−ヒドロキシフェニルステアリン酸等が挙げられ、モノアルコールとしては、オクチルアルコール、デシルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、２−フェノキシエタノール等が挙げられる。 Further, the copolymerized polyester may be copolymerized with a monocarboxylic acid or a monoalcohol, if necessary. Examples of the monocarboxylic acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid, 4-hydroxyphenylstearic acid and the like. Examples of the monoalcohol include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-phenoxyethanol and the like.
共重合ポリエステルを構成する上記モノマーは、付与したい特性に応じて、複数種混合して用いてもよい。
また共重合ポリエステルも、２種以上を混合して用いてもよく、相分離していても、均一に混合されていてもよい。A plurality of types of the above-mentioned monomers constituting the copolymerized polyester may be mixed and used depending on the characteristics to be imparted.
Further, the copolymerized polyester may be used as a mixture of two or more kinds, and may be phase-separated or uniformly mixed.
共重合ポリエステルは、ガラス転移点が５０℃以下であることが好ましく、４０℃以下であることがより好ましく、３０℃以下であることがさらに好ましい。共重合ポリエステルのガラス転移点が５０℃を超えると、得られる接着剤組成物は、金属への接着性が低下することがある。
また、ガラス転移点は、−４０℃以上であることが好ましく、−２０℃以上であることがより好ましく、０℃以上であることがさらに好ましい。共重合ポリエステルは、ガラス転移点が−４０℃未満では、粘着性が強く、取り扱いにくいことがある。The copolymerized polyester preferably has a glass transition point of 50 ° C. or lower, more preferably 40 ° C. or lower, and even more preferably 30 ° C. or lower. When the glass transition point of the copolymerized polyester exceeds 50 ° C., the obtained adhesive composition may have a reduced adhesiveness to a metal.
The glass transition point is preferably −40 ° C. or higher, more preferably −20 ° C. or higher, and even more preferably 0 ° C. or higher. When the glass transition point of the copolymerized polyester is less than −40 ° C., the copolymerized polyester has strong adhesiveness and may be difficult to handle.
本発明の接着剤組成物は、硬化剤を含有することが必要であり、その含有量は、共重合ポリエステル１００質量部に対して、０．２〜１５質量部であることが必要であり、中でも０．４〜１０質量部であることが好ましく、０．４〜５．０質量部であることがより好ましい。硬化剤を添加することにより、耐熱性や耐湿熱性を向上させることができる。硬化剤の含有量が０．２質量部未満であると、得られる接着剤組成物は、耐熱性や耐湿熱性が低下し、一方、含有量が１５質量部を超えると、得られる接着剤組成物は接着性が低下する。
なお、本発明の接着剤組成物は、液状もしくはペースト状の接着剤を被着体１に塗布し、同種もしくは異種の被着体２を接着後、溶剤もしくは水を飛散させることによって、接着成分を固化（硬化）させて接着剤組成物からなる層を形成する。用途によって、接着剤組成物からなる層を被着体１に形成した後、熱処理を行い、被着体２を接着させる場合（パターン１）と、接着剤組成物からなる層を被着体１に形成した後、熱処理を行うことなく被着体２を接着させた後に熱処理を行う場合（パターン２）とがある。本発明の接着剤組成物は、特にパターン２で使用する場合において、接着性が優れている。パターン１で使用する場合においては、硬化剤の含有量は、共重合ポリエステル１００質量部に対して、０．４〜５．０質量部とすることが好ましい。The adhesive composition of the present invention needs to contain a curing agent, and the content thereof needs to be 0.2 to 15 parts by mass with respect to 100 parts by mass of the copolymerized polyester. Above all, it is preferably 0.4 to 10 parts by mass, and more preferably 0.4 to 5.0 parts by mass. By adding a curing agent, heat resistance and moisture heat resistance can be improved. When the content of the curing agent is less than 0.2 parts by mass, the obtained adhesive composition has reduced heat resistance and moist heat resistance, while when the content exceeds 15 parts by mass, the obtained adhesive composition is obtained. The adhesiveness of the object is reduced.
The adhesive composition of the present invention is an adhesive component obtained by applying a liquid or paste-like adhesive to an adherend 1, adhering an adherend 2 of the same type or a different type, and then scattering a solvent or water. Is solidified (cured) to form a layer composed of an adhesive composition. Depending on the application, there are cases where a layer made of the adhesive composition is formed on the adherend 1 and then heat-treated to bond the adherend 2 (pattern 1), and a layer made of the adhesive composition is formed on the adherend 1. There is a case (Pattern 2) in which the adherend 2 is adhered and then the heat treatment is performed without performing the heat treatment. The adhesive composition of the present invention has excellent adhesiveness, especially when used in pattern 2. When used in Pattern 1, the content of the curing agent is preferably 0.4 to 5.0 parts by mass with respect to 100 parts by mass of the copolymerized polyester.
また、硬化剤の含有量は、共重合ポリエステルの官能基（カルボキシ基、水酸基）の合計に対して、硬化剤の官能基の当量比が０．２〜２であることが好ましく、０．４〜１．５であることがより好ましく、０．５〜０．９であることがさらに好ましい。接着剤組成物は、上記当量比が０．２未満であると耐熱性が低下し、当量比が２を超えると接着性が低下することがある。 The content of the curing agent is preferably such that the equivalent ratio of the functional groups of the curing agent to the total of the functional groups (carboxy group, hydroxyl group) of the copolymerized polyester is 0.2 to 2, and is 0.4. It is more preferably ~ 1.5, and even more preferably 0.5 to 0.9. The heat resistance of the adhesive composition may decrease when the equivalent ratio is less than 0.2, and the adhesiveness may decrease when the equivalent ratio exceeds 2.
硬化剤は、共重合ポリエステルの水酸基またはカルボキシ基と反応しうる官能基を含有するものであり、イソシアネート化合物、エポキシ化合物、カルボジイミド化合物、オキサゾリン化合物などが挙げられ、これら化合物を適宜組み合わせてもよいが、反応性と取り扱い性の観点から、イソシアネート化合物が好ましく用いられる。
イソシアネート化合物としては、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）などの芳香族ジイソシアネート、水添ＴＤＩ、水添ＭＤＩ、水添ＸＤＩ、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）などの脂肪族または脂環族ジイソシナネートが、金属への接着性と耐熱性を両立するために有用である。これらのジイソシアネートにイソシアヌレート、ビューレット、アダクト構造を有するポリイソシアネート、あるいは、ポリメチレンポリフェニルポリイソシアネート、カルボジイミド変性体などの誘導体を使用してもよい。
中でも、トリレンジイソシアネート（ＴＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）が好ましく用いられ、これらは２種以上を併用して用いてもよい。The curing agent contains a functional group capable of reacting with a hydroxyl group or a carboxy group of the copolymerized polyester, and examples thereof include an isocyanate compound, an epoxy compound, a carbodiimide compound, and an oxazoline compound, and these compounds may be appropriately combined. From the viewpoint of reactivity and handleability, an isocyanate compound is preferably used.
Examples of the isocyanate compound include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and xylylene diisocyanate (XDI), hydrogenated TDI, hydrogenated MDI, hydrogenated XDI, hexamethylene diisocyanate (HDI), and isophorone. An aliphatic or alicyclic diisocyanate such as diisocyanate (IPDI) is useful for achieving both adhesion to a metal and heat resistance. As these diisocyanates, isocyanurate, burette, polyisocyanate having an adduct structure, or derivatives such as polymethylenepolyphenylpolyisocyanate and carbodiimide modified product may be used.
Of these, toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are preferably used, and two or more of these may be used in combination.
本発明の接着剤組成物は、軟化点が９０℃以上であることが必要であり、中でも１００℃以上であることが好ましく、１１０℃以上であることがさらに好ましく、１２０℃以上であることが最も好ましい。接着剤組成物は、軟化点が９０℃未満では、耐熱性が低下する。耐熱性が低下した接着剤組成物を含有するフレキシブルフラットケーブルでは、高温環境下において、樹脂が流動し始めて金属が剥離し、絶縁破壊を起す場合がある。一方、軟化点の上限は、共重合ポリエステル樹脂の熱分解が生じない温度とすることが好ましく、４００℃未満であることが好ましい。 The adhesive composition of the present invention needs to have a softening point of 90 ° C. or higher, particularly preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and more preferably 120 ° C. or higher. Most preferred. The heat resistance of the adhesive composition decreases when the softening point is less than 90 ° C. In a flexible flat cable containing an adhesive composition having reduced heat resistance, the resin may start to flow and the metal may peel off, causing dielectric breakdown in a high temperature environment. On the other hand, the upper limit of the softening point is preferably a temperature at which thermal decomposition of the copolymerized polyester resin does not occur, and is preferably less than 400 ° C.
本発明の接着剤組成物の軟化点を上記範囲のものとするには、接着剤組成物の数平均分子量を２０，０００〜１００，０００とすることが好ましく、中でも数平均分子量を３０，０００〜１００,０００とすることが好ましく、４０，０００〜１００，０００とすることがより好ましい。接着剤組成物の数平均分子量が２０，０００未満であると、軟化点が低下して耐熱性が低下しやすい。一方、接着剤組成物の数平均分子量が１００，０００を超えると、接着性が低下する傾向があり、好ましくない。 In order to keep the softening point of the adhesive composition of the present invention in the above range, the number average molecular weight of the adhesive composition is preferably 20,000 to 100,000, and the number average molecular weight is 30,000 to 100. It is preferably 000, more preferably 40,000 to 100,000. When the number average molecular weight of the adhesive composition is less than 20,000, the softening point is lowered and the heat resistance is likely to be lowered. On the other hand, if the number average molecular weight of the adhesive composition exceeds 100,000, the adhesiveness tends to decrease, which is not preferable.
また、本発明の接着剤組成物の数平均分子量を上記範囲のものとするには、本発明における共重合ポリエステルの数平均分子量を５，０００〜３０，０００とすることが好ましく、中でも１０，０００〜２５，０００とすることが好ましい。 Further, in order to keep the number average molecular weight of the adhesive composition of the present invention in the above range, the number average molecular weight of the copolymerized polyester in the present invention is preferably 5,000 to 30,000, and more preferably 10,000 to 30,000. It is preferably 25,000.
本発明の接着剤組成物は、必要に応じて、熱安定剤、酸化防止剤、難燃剤等を含有してもよい。
熱安定剤としては、リン酸、リン酸エステル、ジブチルヒドロキシトルエンテトラキス［３−（３′，５′−ジ−ｔ−ブチル−４′−ヒドロキシフェニル）プロピオン酸］ペンタエリトリトール、３−（３′，５′−ジ−ｔ−ブチル−４′−ヒドロキシフェニル）プロピオン酸ｎ−オクタデシル、３，３′，３″，５，５′，５″−ヘキサ−ｔｅｒｔ−ブチル−ａ，ａ′，ａ″−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾール、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、３，９−ビス｛２−［３−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］−１，１−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、１，３，５−トリス（４−ｔｅｒｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンゼン）イソフタル酸、トリエチルグリコール−ビス［３−（３−ｔｅｒｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、２，２−チオ−ジエチレン−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ジエチル［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスフェート等のリン系またはヒンダードフェノール系熱安定剤が挙げられる。
酸化防止剤としては、ヒンダードアミン化合物、ジオクチルチオジプロピオネート、ジドデシルチオジプロピオネート、ジドデシルステアリルチオジプロピオネート、ジステアリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジデシルチオジプロピオネート、ジドデシル−β，β′−チオジブチレート、ジステアリル−β，β′−チオジブチレート、ペンタエリスリトール−テトラキス（ドデシルチオプロピオネート）、ペンタエリスリトール−テトラキス（ドデシルチオアセテート）、ペンタエリスリトール−テトラキス（ドデシルチオブチレート）、ペンタエリスリトール−テトラキス（オクタデシルチオプロピオネート）、ペンタエリスリトール−テトラキス（ラウリルチオプロピオネート）、ジラウリル−３，３′−チオジプロピオネート、ジステアリル−３，３′−チオジプロピオネート、ジトリデシル３，３′−チオジプロピオネート、テトラキス［メチレン−３−（ドデシルチオ）プロピオネート］等の酸化防止剤が挙げられる。
難燃剤としては、デカブロモジフェニルエーテル、ビス（ペンタブロモフェニル）エタン、テトラブロモビスフェノール、ヘキサブロモシクロドデカン、ヘキサブロモベンゼン等のハロゲン化物、トリフェニルホスフェート、トリクレジルホスフェート、１，３−フェニレンビス（ジフェニルホスフェート）、ポリ燐酸アンモニウム、ポリ燐酸アミド、燐酸グアニジン等の燐化合物、トリス（クロロエチル）ホスフェート、トリス（ジクロロプロピル）ホスフェート等の含ハロゲン燐酸エステル、赤燐、また、トリアジン、メラミンシアヌレート、エチレンジメラミン等の窒素系難燃剤、二酸化スズ、五酸化アンチモン、三酸化アンチモン等が挙げられる。
その他、タルクやシリカ等の滑剤、酸化チタンやカーボンブラック等の顔料、充填剤、帯電防止剤、発泡剤等の従来公知の添加剤を含有してもよい。The adhesive composition of the present invention may contain a heat stabilizer, an antioxidant, a flame retardant and the like, if necessary.
Examples of heat stabilizers include phosphoric acid, phosphoric acid ester, dibutylhydroxytoluethanetetrax [3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionic acid] pentaerythritol, 3- (3'). , 5'-di-t-butyl-4'-hydroxyphenyl) n-octadecyl propionate, 3,3', 3 ", 5,5', 5" -hexa-tert-butyl-a, a', a "-(Mesitylen-2,4,6-triyl) tri-p-cresol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-tris (4-tert-butyl-3-3) Hydroxy-2,6-dimethylbenzene) isophthalic acid, triethylglycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3-( 3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl Phosphores such as -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphate. Examples include system or hindered phenolic heat stabilizers.
Antioxidants include hindered amine compounds, dioctylthiodipropionate, didodecylthiodipropionate, didodecylstearylthiodipropionate, distearylthiodipropionate, dimyristylthiodipropionate, didecylthiodipropionate. , Didodecyl-β, β'-thiodibutyrate, distearyl-β, β'-thiodibutyrate, pentaerythritol-tetrakis (dodecylthiopropionate), pentaerythritol-tetrakis (dodecylthioacetate), pentaerythritol-tetrakis (Dodecylthiobutyrate), pentaerythritol-tetrakis (octadecylthiopropionate), pentaerythritol-tetrakis (laurylthiopropionate), dilauryl-3,3'-thiodipropionate, distearyl-3,3' Antioxidants such as -thiodipropionate, ditridecyl3,3'-thiodipropionate, tetrakis [methylene-3- (dodecylthio) propionate] and the like can be mentioned.
Flame retardants include decabromodiphenyl ether, bis (pentabromophenyl) ethane, tetrabromobisphenol, hexabromocyclododecane, halides such as hexabromobenzene, triphenyl phosphate, tricresyl phosphate, 1,3-phenylene bis ( Diphenyl phosphate), phosphoric acid compounds such as ammonium polyphosphate, polyphosphate amide, guanidine phosphate, halogen-containing phosphoric acid esters such as tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, red phosphorus, and triazine, melamine cyanurate, ethylene. Examples thereof include nitrogen-based flame retardants such as dimelamine, tin dioxide, antimony pentoxide, and antimony trioxide.
In addition, conventionally known additives such as lubricants such as talc and silica, pigments such as titanium oxide and carbon black, fillers, antistatic agents, and foaming agents may be contained.
次に本発明の接着剤組成物の製造方法について説明する。
接着剤組成物を構成する共重合ポリエステルの製造においては、必要な原料を反応缶に投入し、１８０℃以上の温度でエステル化反応を３時間以上行った後、ポリアルキレングリコールを加え、公知の方法によりエステル化反応させる。ついで、例えば、１３０Ｐａ以下の減圧下に２２０〜２８０℃の温度で所望の分子量に達するまで重縮合反応を進めることにより、共重合ポリエステルを得ることができる。
エステル化反応および重縮合反応の際には、テトラブチルチタネ−トなどのチタン化合物、酢酸亜鉛、酢酸マグネシウム、酢酸亜鉛などの金属の酢酸塩、三酸化アンチモン、ヒドロキシブチルスズオキサイド、オクチル酸スズなどの有機スズ化合物を用いて重合をおこなうことができる。その際の触媒使用量は、酸成分１モルに対し、０．１〜２０×１０−４モルであることが好ましい。
また、前述の重縮合反応を終了後、多塩基酸成分やその無水物等を所定量添加し反応させることで、末端水酸基をカルボキシ基に変性したり、エステル交換反応により分子中鎖にカルボキシ基を導入することで適度の酸価を付与することができる。Next, a method for producing the adhesive composition of the present invention will be described.
In the production of the copolyester constituting the adhesive composition, necessary raw materials are put into a reaction can, an esterification reaction is carried out at a temperature of 180 ° C. or higher for 3 hours or longer, and then polyalkylene glycol is added to be known. The esterification reaction is carried out by the method. Then, for example, the copolymerized polyester can be obtained by proceeding the polycondensation reaction at a temperature of 220 to 280 ° C. under a reduced pressure of 130 Pa or less until a desired molecular weight is reached.
During esterification and polycondensation reactions, titanium compounds such as tetrabutyl titanate, acetates of metals such as zinc acetate, magnesium acetate, zinc acetate, antimony trioxide, hydroxybutyltin oxide, tin octylate, etc. The polymerization can be carried out using the organic tin compound of. The amount of the catalyst used at that time is preferably 0.1 to 20 × 10 -4 mol with respect to 1 mol of the acid component.
Further, after the above-mentioned polycondensation reaction is completed, a predetermined amount of a polybasic acid component or an anhydride thereof is added and reacted to modify the terminal hydroxyl group to a carboxy group, or a carboxy group is added to the middle chain of the molecule by a transesterification reaction. By introducing the above, an appropriate acid value can be imparted.
次に、共重合ポリエステルを適当な有機溶剤に溶解し、固形分の濃度が２０〜６０質量％程度の溶液を調製し、硬化剤を添加することにより、接着剤組成物の溶液を製造することができる。接着剤組成物の溶液から有機溶剤を除去することにより、接着剤組成物を得ることができる。 Next, the copolymerized polyester is dissolved in an appropriate organic solvent to prepare a solution having a solid content concentration of about 20 to 60% by mass, and a curing agent is added to produce a solution of the adhesive composition. Can be done. The adhesive composition can be obtained by removing the organic solvent from the solution of the adhesive composition.
有機溶剤としては、たとえば、トルエン、キシレン、ソルベントナフサ、ソルベッソなどの芳香族系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶剤、メチルアルコール、エチルアルコール、イソプロピルアルコール、イソブチルアルコールなどのアルコール系溶剤、酢酸エチル、酢酸ノルマルブチルなどのエステル系溶剤、セロソルブアセテート、メトキシアセテートなどのアセテート系溶剤、またはこれらの２種類以上からなる混合溶剤（たとえば、トルエンとメチルエチルケトンの混合溶剤）などが挙げられる。取り扱い性と環境面から、有機溶剤は、沸点の低いメチルエチルケトン、酢酸エチルが好ましい。 Examples of the organic solvent include aromatic solvents such as toluene, xylene, solvent naphtha and sorbesso, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol. Examples thereof include a solvent, an ester solvent such as ethyl acetate and normal butyl acetate, an acetate solvent such as cellosolve acetate and methoxy acetate, and a mixed solvent composed of two or more of these (for example, a mixed solvent of toluene and methyl ethyl ketone). From the viewpoint of handleability and the environment, the organic solvent is preferably methyl ethyl ketone or ethyl acetate having a low boiling point.
本発明の積層体は、接着剤組成物からなる層を有するものである。
本発明の接着剤組成物を使用して、接着剤組成物からなる層（以下、接着剤層と略することがある）を有する積層体を作製する方法として、接着剤組成物を有機溶剤に溶解した溶液（以下、接着剤溶液と略することがある）を基材フィルムに塗布、乾燥する方法が挙げられる。接着剤溶液として、前述の接着剤組成物の製造において、共重合ポリエステルの有機溶剤溶液に硬化剤を添加して調製した溶液を使用してもよい。接着剤溶液において、固形分の濃度は、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、３０質量％以上であることがさらに好ましい。
接着剤溶液を公知の塗布法で基材に塗布、乾燥することで、接着剤層が積層されてなる積層体を得ることができる。コーターとしては、例えば、バーコーター、コンマコーター、ダイコーター、ロールコーター、リバースロールコーター、グラビアコーター、グラビアリバースコーター、フローコーターなどを用いることができる。これらのコーターを使用した塗布法では、接着剤層の厚さを任意に制御することができる。また、複数回の塗布法で、基材に塗布してもよい。The laminate of the present invention has a layer made of an adhesive composition.
As a method for producing a laminate having a layer composed of an adhesive composition (hereinafter, may be abbreviated as an adhesive layer) using the adhesive composition of the present invention, the adhesive composition is used as an organic solvent. Examples thereof include a method in which a dissolved solution (hereinafter, may be abbreviated as an adhesive solution) is applied to a base film and dried. As the adhesive solution, a solution prepared by adding a curing agent to an organic solvent solution of a copolymerized polyester may be used in the production of the above-mentioned adhesive composition. In the adhesive solution, the solid content concentration is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.
By applying the adhesive solution to the base material by a known coating method and drying it, a laminated body in which the adhesive layers are laminated can be obtained. As the coater, for example, a bar coater, a comma coater, a die coater, a roll coater, a reverse roll coater, a gravure coater, a gravure reverse coater, a flow coater and the like can be used. In the coating method using these coaters, the thickness of the adhesive layer can be arbitrarily controlled. Further, it may be applied to the base material by a plurality of application methods.
本発明のフレキシブルフラットケーブルは、上記積層体を含むものであり、例えば、次の方法により作製することができる。
すなわち、ポリエチレンテレフタレートなどのポリエステルからなる厚さ２０〜５０μｍ程度の基材フィルムを使用し、このフィルムに、接着剤溶液を１〜５０μｍ程度の乾燥厚になるように塗布し、８０〜１５０℃で乾燥して、基材フィルム上に接着剤層が積層された積層体（インシュレーションフィルム）を作成する。厚み２０〜１００μｍ、線幅０．１〜１ｍｍの銅線を、２枚のインシュレーションフィルムの接着剤層面で挟み込んで、ヒートシーラーで温度１５０〜１８０℃、線圧２０〜４０Ｎ／ｃｍの条件で積層することで、フレキシブルフラットケーブルを作製することができる。
得られた積層体および／またはフレキシブルフラットケーブルは、４０〜８０℃で１２〜９６ｈ程度加熱エージングしてもよい。また、必要に応じ、インシュレーションフィルムにプライマー層を設けてもよい。The flexible flat cable of the present invention includes the above-mentioned laminate, and can be produced, for example, by the following method.
That is, a base film having a thickness of about 20 to 50 μm made of polyester such as polyethylene terephthalate is used, and an adhesive solution is applied to this film so as to have a dry thickness of about 1 to 50 μm, and at 80 to 150 ° C. It is dried to prepare a laminated body (insulation film) in which an adhesive layer is laminated on a base film. A copper wire with a thickness of 20 to 100 μm and a wire width of 0.1 to 1 mm is sandwiched between the adhesive layer surfaces of two insulation films, and a heat sealer is used under the conditions of a temperature of 150 to 180 ° C. and a linear pressure of 20 to 40 N / cm. By laminating, a flexible flat cable can be manufactured.
The obtained laminate and / or flexible flat cable may be heat-aged at 40 to 80 ° C. for about 12 to 96 hours. Further, if necessary, a primer layer may be provided on the insulation film.
以下に実施例によって本発明を具体的に説明する。
１．使用原料
（１）ポリアルキレングリコール
ＰＴＭＧ：ポリテトラメチレングリコール（数平均分子量１０００）
ＰＥＧ：ポリエチレングリコール（数平均分子量１０００）
ＴＥＧ：トリエチレングリコール（分子量１５０．１７）
ＤＥＧ：ジエチレングリコール（分子量１０６．１２）
（２）硬化剤
ＴＤＩ：トリレン−２，４−ジイソシアネート／トリレン−２，６−ジイソシアネート（８／２）（イソシアネート４８％含有）
ＴＤＩ−Ａ：トリレンジイソシアネートアダクト（イソシアネート１３％含有）
ＩＰＤＩ：イソホロンジイソシアネート（イソシアネート３８％含有）
ＩＰＤＩ−Ｎ：イソホロンジイソシアネートイソシアヌレート（イソシアネート１２％含有）
ＨＤＩ：ヘキサメチレン−１，６−ジイソシアネート（イソシアネート５０％含有）
ＨＤＩ−Ｎ：ヘキサメチレン−１，６−ジイソシアネートイソシアヌレート（イソシアネート２２％含有）
（３）有機溶剤
溶剤１：トルエン／メチルエチルケトン（８／２（質量比））混合溶剤
溶剤２：メチルエチルケトン
溶剤３：酢酸エチルHereinafter, the present invention will be specifically described with reference to Examples.
1. 1. Raw materials used (1) Polyalkylene glycol PTMG: polytetramethylene glycol (number average molecular weight 1000)
PEG: Polyethylene glycol (number average molecular weight 1000)
TEG: Triethylene glycol (molecular weight 150.17)
DEG: Diethylene glycol (molecular weight 106.12)
(2) Hardener TDI: Toluene-2,4-diisocyanate / Toluene-2,6-diisocyanate (8/2) (containing 48% isocyanate)
TDI-A: Tolylene diisocyanate adduct (containing 13% isocyanate)
IPDI: Isophorone diisocyanate (containing 38% isocyanate)
IPDI-N: Isophorone diisocyanate isocyanurate (containing 12% isocyanate)
HDI: Hexamethylene-1,6-diisocyanate (containing 50% isocyanate)
HDI-N: Hexamethylene-1,6-diisocyanate isocyanurate (containing 22% isocyanate)
(3) Organic solvent Solvent 1: Toluene / methyl ethyl ketone (8/2 (mass ratio)) Mixed solvent Solvent 2: Methyl ethyl ketone Solvent 3: Ethyl acetate
２．測定方法
（１）共重合ポリエステルの組成
ＮＭＲ測定装置（日本電子社製 ＪＮＭ−ＬＡ４００型）を用いて、１Ｈ−ＮＭＲ測定を行い、それぞれの共重合成分のピーク強度から組成を求めた。測定溶媒としては、重水素化トリフルオロ酢酸を用いた。2. Measuring method (1) Composition of copolymerized polyester 1 H-NMR measurement was carried out using an NMR measuring device (JNM-LA400 type manufactured by JEOL Ltd.), and the composition was determined from the peak intensity of each copolymerized component. Trifluoroacetic acid deuterated was used as the measurement solvent.
（２）共重合ポリエステルと接着剤組成物の数平均分子量
ＧＰＣ分析装置（島津製作所社製 送液ユニットＬＣ−１０ＡＤｖｐ型および紫外−可視分光光度計ＳＰＤ−６ＡＶ型、検出波長：２５４ｎｍ、溶媒：テトラヒドロフラン、ポリスチレン換算）により、数平均分子量を求めた。接着剤組成物がテトラヒドロフランに溶解せず数平均分子量が測定できない場合は「不溶」と示した。(2) Number average molecular weight of copolymerized polyester and adhesive composition GPC analyzer (Shimadzu liquid transfer unit LC-10ADvp type and ultraviolet-visible spectrophotometer SPD-6AV type, detection wavelength: 254 nm, solvent: tetrahydrofuran, polystyrene The number average molecular weight was determined by conversion). When the adhesive composition was insoluble in tetrahydrofuran and the number average molecular weight could not be measured, it was indicated as "insoluble".
（３）共重合ポリエステルのガラス転移点（Ｔｇ）
入力補償型示差走査熱量測定装置（パーキンエルマー社製 ダイヤモンドＤＳＣ）を用いて、ＪＩＳ−Ｋ７１２１に準拠して、ガラス転移点（補外ガラス転移開始温度）を求めた。(3) Glass transition point (Tg) of copolymerized polyester
The glass transition point (external glass transition start temperature) was determined in accordance with JIS-K7121 using an input compensation type differential scanning calorimetry device (Diamond DSC manufactured by PerkinElmer).
（４）軟化点
実施例、比較例で得られた積層体を、５０℃、９６時間熱処理した後、熱機械分析装置（ＴＡインスツルメンツ社製ＴＭＡ）を用い、ＪＩＳ−Ｋ７１９６に準拠して、軟化点を測定し、耐熱性を評価した。(4) Softening points The laminates obtained in Examples and Comparative Examples are heat-treated at 50 ° C. for 96 hours and then softened in accordance with JIS-K7196 using a thermomechanical analyzer (TMA manufactured by TA Instruments). The points were measured and the heat resistance was evaluated.
（５）接着性
（接着性１）
実施例、比較例で得られた積層体を、５０℃、９６時間熱処理した後、積層体の接着剤組成物層上に、圧延銅箔を重ね、上ロール１７０℃、線圧４０Ｎ／ｃｍ、速度１ｍ／分の条件でラミネートして、ラミネートシート１を作製した。
得られたラミネートシート１から１５ｍｍ巾の試料を作製し、２０℃でＴ型剥離試験を行い、剥離強度を測定して接着性１を評価した。
（接着性２）
実施例、比較例で得られた積層体の接着剤組成物層上に、圧延銅箔を重ね、上ロール１７０℃、線圧４０Ｎ／ｃｍ、速度１ｍ／分の条件でラミネートした後、５０℃、９６時間熱処理してラミネートシート２を作製した。
得られたラミネートシート２から１５ｍｍ巾の試料を作製し、２０℃でＴ型剥離試験を行い、剥離強度を測定して接着性２を評価した。
なお、接着性１および２の評価のいずれかで剥離強度が１３Ｎ／１５ｍｍ以上であれば実用上問題ないと判断し合格とした。(5) Adhesiveness (Adhesiveness 1)
After heat-treating the laminates obtained in Examples and Comparative Examples at 50 ° C. for 96 hours, a rolled copper foil was laminated on the adhesive composition layer of the laminate, and the upper roll was 170 ° C. and the linear pressure was 40 N / cm. Laminated sheet 1 was produced by laminating under the condition of a speed of 1 m / min.
A sample having a width of 15 mm was prepared from the obtained laminate sheet 1, a T-type peeling test was performed at 20 ° C., and the peeling strength was measured to evaluate the adhesiveness 1.
(Adhesiveness 2)
Rolled copper foil was laminated on the adhesive composition layer of the laminates obtained in Examples and Comparative Examples, and laminated under the conditions of an upper roll of 170 ° C., a linear pressure of 40 N / cm, and a speed of 1 m / min, and then 50 ° C. , 96 hours heat treatment to prepare a laminated sheet 2.
A sample having a width of 15 mm was prepared from the obtained laminate sheet 2, a T-type peeling test was performed at 20 ° C., and the peeling strength was measured to evaluate the adhesiveness 2.
In any of the evaluations of adhesiveness 1 and 2, if the peel strength was 13 N / 15 mm or more, it was judged that there was no practical problem and the result was passed.
（６）耐湿熱性
上記（５）の接着性２に記載の方法で作製したラミネートシート２を、恒温恒湿槽（ナカツ科学機械製作所製 型式ＬＨ−３０−１３Ｍ）を用い、温度８５℃、相対湿度８５％の条件下に１０００時間保持することにより、湿熱処理を行った。
湿熱処理後のラミネートシート２から１５ｍｍ巾の試料を作製し、２０℃でＴ型剥離試験を行い、剥離強度を測定して耐湿熱性を評価した。剥離強度が６Ｎ／１５ｍｍ以上であれば実用上問題ないと判断し合格とした。(6) Moisture and heat resistance The laminated sheet 2 produced by the method described in Adhesive 2 of (5) above is used in a constant temperature and humidity chamber (model LH-30-13M manufactured by Nakatsu Kagaku Kikai Seisakusho) at a temperature of 85 ° C. and relative to each other. Wet heat treatment was performed by holding for 1000 hours under the condition of humidity of 85%.
A sample having a width of 15 mm was prepared from the laminated sheet 2 after the moist heat treatment, a T-type peeling test was performed at 20 ° C., and the peeling strength was measured to evaluate the moist heat resistance. If the peel strength is 6N / 15mm or more, it is judged that there is no practical problem and the result is accepted.
（７）耐熱性
上記（５）の接着性２に記載の方法で作製したラミネートシート２から１５ｍｍ巾の試料を作製し、８０℃でＴ型剥離試験を行い、剥離強度を測定して耐熱性を評価した。剥離強度が３Ｎ／１５ｍｍ以上であれば実用上問題ないと判断し合格とした。(7) Heat resistance A sample having a width of 15 mm is prepared from the laminate sheet 2 prepared by the method described in Adhesiveness 2 of (5) above, a T-type peeling test is performed at 80 ° C., and the peeling strength is measured to obtain heat resistance. Was evaluated. If the peel strength is 3N / 15mm or more, it is judged that there is no practical problem and the result is passed.
実施例１
酸成分が、テレフタル酸５０モル％、イソフタル酸５０モル％になるように、またグリコール成分が、エチレングリコール４４モル％、ネオペンチルグリコール５０モル％、数平均分子量１０００のポリテトラメチレングリコール（ＰＴＭＧ）５モル％、ジエチレングリコール（ＤＥＧ）１モル％になるように、原料をエステル化反応缶に投入し、アンカー翼の攪拌機で１００ｒｐｍの回転数で攪拌しながら、０．２５ＭＰａの制圧下で、２５０℃で５時間エステル化を行い、エステル化物を作製した。その後、重縮合缶へ移送し、重合触媒を投入し、６０分かけて徐々に１．３ｈＰａになるまで減圧し、所定の分子量に到達するまで２５０℃で重縮合反応を行い、共重合ポリエステルＡを得た。得られた共重合ポリエステルＡは、数平均分子量２００００、水酸基価５ｍｇＫＯＨ／ｇ、ガラス転移点１５℃であった。
共重合ポリエステルＡを１００質量部用い、トルエン／メチルエチルケトン（８／２（質量比））の混合溶媒（溶剤１）に、固形分濃度が３０質量％になるように溶解し、硬化剤（ＴＤＩ）０．６質量部を添加して接着剤組成物の溶液を製造した。
溶液を、圧延銅箔（膜厚３０μｍ）にバーコーターを用いて塗布し、１２０℃で１分間熱処理し、銅箔上に、乾燥膜厚２０μｍの接着剤組成物層が積層された積層体を得た。Example 1
Polytetramethylene glycol (PTMG) having an acid component of 50 mol% terephthalic acid and 50 mol% isophthalic acid, and a glycol component of 44 mol% ethylene glycol, 50 mol% neopentyl glycol, and a number average molecular weight of 1000. The raw materials were put into an esterification reaction can so as to be 5 mol% and 1 mol% of diethylene glycol (DEG), and while stirring at a rotation speed of 100 rpm with an anchor blade stirrer, 250 ° C. under a suppression of 0.25 MPa. Esterification was carried out for 5 hours to prepare an esterified product. Then, it is transferred to a polycondensation can, a polymerization catalyst is added, the pressure is gradually reduced to 1.3 hPa over 60 minutes, and a polycondensation reaction is carried out at 250 ° C. until a predetermined molecular weight is reached. Got The obtained copolymerized polyester A had a number average molecular weight of 20000, a hydroxyl value of 5 mgKOH / g, and a glass transition point of 15 ° C.
Using 100 parts by mass of copolymerized polyester A, it was dissolved in a mixed solvent (solvent 1) of toluene / methyl ethyl ketone (8/2 (mass ratio)) so that the solid content concentration became 30% by mass, and a curing agent (TDI) was used. A solution of the adhesive composition was prepared by adding 0.6 parts by mass.
The solution was applied to a rolled copper foil (thickness 30 μm) using a bar coater, heat-treated at 120 ° C. for 1 minute, and a laminate in which an adhesive composition layer having a dry thickness of 20 μm was laminated on the copper foil was formed. Obtained.
実施例２〜３
エステル化物を用いて重縮合反応を行う際の重合時間を変更し、表１に示す数平均分子量に到達するように調整した以外は、実施例１と同様にして共重合ポリエステルＢ、共重合ポリエステルＣを得た。
得られた共重合ポリエステルＢ、Ｃを用い、硬化剤（ＴＤＩ）の添加量を表１に示すものに変更した以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Examples 2-3
Copolymerized polyester B and copolymerized polyester in the same manner as in Example 1 except that the polymerization time when the polycondensation reaction was carried out using the esterified product was changed and adjusted to reach the number average molecular weight shown in Table 1. C was obtained.
Using the obtained copolymerized polyesters B and C, a solution of the adhesive composition was obtained in the same manner as in Example 1 except that the amount of the curing agent (TDI) added was changed to that shown in Table 1. Then, a laminated body was obtained in the same manner as in Example 1.
実施例４、６〜７、９〜１６、比較例４〜７、参考例１〜２
共重合ポリエステルの組成を表１、２、４に示すように変更し、また、数平均分子量が表１、２、４に示す値に到達するようにエステル化物を用いて重縮合反応を行う際の重合時間を変更した以外は、実施例１と同様にして共重合ポリエステルＤ〜Ｐ、Ｒ〜Ｕを得た。
得られた共重合ポリエステルＤ〜Ｐ、Ｒ〜Ｕを用いた以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。
Examples 4 , 6 to 7, 9 to 16, Comparative Examples 4 to 7 , Reference Examples 1 to 2.
When the composition of the copolymerized polyester is changed as shown in Tables 1, 2 and 4, and the polycondensation reaction is carried out using the esterified product so that the number average molecular weight reaches the values shown in Tables 1, 2 and 4. Copolymerized polyesters D to P and R to U were obtained in the same manner as in Example 1 except that the polymerization time of the above was changed.
A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the obtained copolymerized polyesters D to P and RU were used. Then, a laminated body was obtained in the same manner as in Example 1.
実施例１７
共重合ポリエステルとして、実施例１で得られた共重合ポリエステルＡ（８０質量部）と比較例４で得られた共重合ポリエステルＲ（２０質量部）を用いた以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Example 17
The same as in Example 1 except that the copolymerized polyester A (80 parts by mass) obtained in Example 1 and the copolymerized polyester R (20 parts by mass) obtained in Comparative Example 4 were used as the copolymerized polyester. Obtained a solution of the adhesive composition. Then, a laminated body was obtained in the same manner as in Example 1.
実施例１８〜１９
接着剤組成物の溶液を得る際の溶剤の種類を、表３に示すものに変更した以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Examples 18-19
A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the type of solvent used to obtain the solution of the adhesive composition was changed to that shown in Table 3. Then, a laminated body was obtained in the same manner as in Example 1.
実施例２０〜２３、比較例１〜２
共重合ポリエステルＡに対する硬化剤の添加量を表３、４に示すものに変更した以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Examples 20-23, Comparative Examples 1-2
A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the amount of the curing agent added to the copolymerized polyester A was changed to that shown in Tables 3 and 4. Then, a laminated body was obtained in the same manner as in Example 1.
実施例２４、比較例３
共重合ポリエステルＢに対する硬化剤の添加量を表３、４に示すものに変更した以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Example 24, Comparative Example 3
A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the amount of the curing agent added to the copolymerized polyester B was changed to that shown in Tables 3 and 4. Then, a laminated body was obtained in the same manner as in Example 1.
実施例２５
共重合ポリエステルの組成を表３に示すように変更し、また、数平均分子量が表３に示す値に到達するようにエステル化物を用いて重縮合反応を行う際の重合時間を変更した以外は、実施例１と同様にして共重合ポリエステルＱを得た。
共重合ポリエステルＱに対する硬化剤の添加量を表３に示すものに変更した以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Example 25
Except that the composition of the copolymerized polyester was changed as shown in Table 3, and the polymerization time when the polycondensation reaction was carried out using the esterified product was changed so that the number average molecular weight reached the value shown in Table 3. , A copolymerized polyester Q was obtained in the same manner as in Example 1.
A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the amount of the curing agent added to the copolymerized polyester Q was changed to that shown in Table 3. Then, a laminated body was obtained in the same manner as in Example 1.
実施例２６〜２８
接着剤組成物の溶液を得る際の硬化剤の種類と添加量を、表３に示すものに変更した以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Examples 26-28
A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the type and amount of the curing agent added when obtaining the solution of the adhesive composition were changed to those shown in Table 3. Then, a laminated body was obtained in the same manner as in Example 1.
実施例２９〜３２
接着剤組成物の溶液を得る際に２種類の硬化剤を使用し、種類と添加量を表４に示すものに変更した以外は、実施例１と同様にして接着剤組成物の溶液を得た。そして、実施例１と同様にして積層体を得た。Examples 29-32
Two types of curing agents were used to obtain a solution of the adhesive composition, and a solution of the adhesive composition was obtained in the same manner as in Example 1 except that the types and the addition amounts were changed to those shown in Table 4. rice field. Then, a laminated body was obtained in the same manner as in Example 1.
実施例、比較例、参考例で得られた共重合ポリエステル、接着剤組成物、および積層体の特性を表１〜４に示す。 The properties of the copolymerized polyester, the adhesive composition, and the laminate obtained in Examples, Comparative Examples , and Reference Examples are shown in Tables 1 to 4.
実施例１〜４、６〜７、９〜３２で得られた接着剤組成物は、本発明で規定する構成を満足するものであるため、金属への接着性に優れるとともに、耐熱性と耐湿熱性にも優れていた。このため、これらの接着剤組成物を用いて得られた積層体は、これらの性能の評価結果に優れていた。
Since the adhesive compositions obtained in Examples 1 to 4, 6 to 7, 9 to 32 satisfy the constitution specified in the present invention, they are excellent in adhesiveness to metals, and have heat resistance and moisture resistance. It was also excellent in heat resistance. Therefore, the laminates obtained by using these adhesive compositions were excellent in the evaluation results of these performances.
比較例１の接着剤組成物は、硬化剤の含有量が０．１質量部と少ないため、軟化点が５５℃と低く、耐熱性に劣るものであった。
比較例２の接着剤組成物は、硬化剤の含有量が１５．７質量部と多いため、接着性に劣るものであった。
比較例３の接着剤組成物は、数平均分子量が１６，０００と低く、軟化点が８５℃と低いため、耐熱性に劣るものであった。
比較例４の接着剤組成物は、共重合ポリエステルのグリコール成分における、繰り返し単位の炭素数が２〜４であるポリアルキレングリコールの含有量が０．５モル％と少なく、また、共重合ポリエステルのガラス転移点が６５℃と高いため、接着性、耐湿熱性ともに劣るものであった。
比較例５の接着剤組成物は、共重合ポリエステルのグリコール成分における、繰り返し単位の炭素数が２〜４であるポリアルキレングリコールの含有量が２５モル％と多いため、軟化点が８０℃と低くなり、耐熱性に劣るものであった。
比較例６の接着剤組成物は、共重合ポリエステル中の、側鎖を有するグリコールであるネオペンチルグリコールの含有量がグリコール成分中２０モル％と少ないため、また比較例７の接着剤組成物は、共重合ポリエステル中の、イソフタル酸の含有量が酸成分中２０モル％と少ないため、いずれも接着性に劣るものであった。また、いずれの接着剤組成物も有機溶剤への溶解性に劣るものであった。
The adhesive composition of Comparative Example 1 had a low softening point of 55 ° C. and was inferior in heat resistance because the content of the curing agent was as small as 0.1 parts by mass.
The adhesive composition of Comparative Example 2 was inferior in adhesiveness because the content of the curing agent was as large as 15.7 parts by mass.
The adhesive composition of Comparative Example 3 was inferior in heat resistance because the number average molecular weight was as low as 16,000 and the softening point was as low as 85 ° C.
The adhesive composition of Comparative Example 4 has a low content of polyalkylene glycol having 2 to 4 carbon atoms as a repeating unit in the glycol component of the copolymerized polyester as low as 0.5 mol%, and the copolymerized polyester has a low content of 0.5 mol%. Since the glass transition point was as high as 65 ° C., both adhesiveness and moisture heat resistance were inferior.
The adhesive composition of Comparative Example 5 has a low softening point of 80 ° C. because the content of polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit is as high as 25 mol% in the glycol component of the copolymerized polyester. Therefore, it was inferior in heat resistance.
In the adhesive composition of Comparative Example 6, the content of neopentyl glycol, which is a glycol having a side chain, in the copolymerized polyester is as small as 20 mol% in the glycol component, and therefore, the adhesive composition of Comparative Example 7 is Since the content of isophthalic acid in the copolymerized polyester was as low as 20 mol% in the acid component, all of them were inferior in adhesiveness. In addition, all the adhesive compositions were inferior in solubility in organic solvents.
Claims (3)
共重合ポリエステルの酸成分におけるイソフタル酸の含有量が３０モル％以上であり、
共重合ポリエステルのグリコール成分における、側鎖を有するグリコールの含有量が３０モル％以上であり、また繰り返し単位の炭素数が２〜４であるポリアルキレングリコールの含有量が１〜２０モル％であり、
前記繰り返し単位の炭素数が２〜４であるポリアルキレングリコールが２種類以上からなり、少なくとも１種類は数平均分子量が２００以上であることを特徴とする接着剤組成物。 An adhesive composition containing 100 parts by mass of a copolymerized polyester and 0.2 to 15 parts by mass of a curing agent.
The content of isophthalic acid in the acid component of the copolymerized polyester is 30 mol% or more, and the content is 30 mol% or more.
The content of glycol having a side chain in the glycol component of the copolymerized polyester is 30 mol% or more, and the content of polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit is 1 to 20 mol%. ,
An adhesive composition comprising two or more types of polyalkylene glycols having 2 to 4 carbon atoms in the repeating unit, and at least one type having a number average molecular weight of 200 or more.
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| DE4121703A1 (en) * | 1991-07-01 | 1993-01-07 | Huels Chemische Werke Ag | FILM-FORMING, RADIATION-HARDENABLE AND HUMIDITY-HARDENING LAMINATING ADHESIVE, METHOD FOR LAMINATING TEXTILE LAYERS WITH THIS LAMINATING ADHESIVE, AND TEXTILE MATERIAL FROM TEXTILE LAYERS AND FOILS OF THE CASE |
| JPH07268308A (en) * | 1994-03-30 | 1995-10-17 | Toyobo Co Ltd | Polyester-based adhesive |
| JP2000063643A (en) * | 1998-08-20 | 2000-02-29 | Mitsubishi Rayon Co Ltd | Metal laminating polyester resin composition, metal laminating polyester film using same and laminated metallic material |
| JP4409023B2 (en) | 2000-01-17 | 2010-02-03 | ユニチカ株式会社 | Copolymerized polyester resin for adhesive and adhesive using the same |
| JP2004250484A (en) * | 2003-02-18 | 2004-09-09 | Nippon Ester Co Ltd | Polyester resin for adhesive, adhesive, and laminate |
| JP5124903B2 (en) * | 2005-02-04 | 2013-01-23 | 東洋紡株式会社 | Polyester resin, aqueous dispersion and adhesive using the same |
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| JP5187468B1 (en) * | 2011-09-30 | 2013-04-24 | 東洋紡株式会社 | Adhesive composition, laminate and polyester polyol |
| WO2014103994A1 (en) * | 2012-12-26 | 2014-07-03 | Dic株式会社 | Polyester resin composition, adhesive, and film |
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