JP2005255752A - Resin composition and adhesive using the same - Google Patents
Resin composition and adhesive using the same Download PDFInfo
- Publication number
- JP2005255752A JP2005255752A JP2004066641A JP2004066641A JP2005255752A JP 2005255752 A JP2005255752 A JP 2005255752A JP 2004066641 A JP2004066641 A JP 2004066641A JP 2004066641 A JP2004066641 A JP 2004066641A JP 2005255752 A JP2005255752 A JP 2005255752A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polyester
- adhesive
- acid
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 239000000853 adhesive Substances 0.000 title claims description 69
- 230000001070 adhesive effect Effects 0.000 title claims description 69
- 229920000728 polyester Polymers 0.000 claims abstract description 94
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002253 acid Substances 0.000 claims abstract description 27
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000098 polyolefin Polymers 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- -1 polytetramethylene Polymers 0.000 description 20
- 239000010408 film Substances 0.000 description 19
- 238000002844 melting Methods 0.000 description 19
- 230000008018 melting Effects 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 238000010030 laminating Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 239000002985 plastic film Substances 0.000 description 8
- 229920006255 plastic film Polymers 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FAXWFCTVSHEODL-UHFFFAOYSA-N 2,4-dibromophenol Chemical compound OC1=CC=C(Br)C=C1Br FAXWFCTVSHEODL-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride 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
- 150000003839 salts Chemical class 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009864 tensile test Methods 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
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-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
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-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
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-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
- SUTCVRHWHOUKJP-UHFFFAOYSA-N 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetic acid Chemical compound C1C(CC(=O)O)CCC2OC21 SUTCVRHWHOUKJP-UHFFFAOYSA-N 0.000 description 1
- WKJICCKTDQDONB-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCC1OC1 WKJICCKTDQDONB-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-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
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- WCAIBHQZNOQYAG-UHFFFAOYSA-N 3-hydroxy-2,2,5,5-tetramethylhexanoic acid Chemical compound CC(C)(C)CC(O)C(C)(C)C(O)=O WCAIBHQZNOQYAG-UHFFFAOYSA-N 0.000 description 1
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 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
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-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
- 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
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、接着性や加工性に優れた樹脂組成物に関するものである。さらに詳細には、本樹脂組成物は、フレキシブルフラットケーブル、フレキシブルプリント配線基板などの接着剤として用いた場合、プラスチックフィルムや金属に対する接着性が経時的に保持される信頼性の高い接着剤であり、さらに融点近傍の低温・高温でも接着が可能であるため、ラインスピードアップや省エネルギーといった加工性にも優れた接着剤を提供することができる。 The present invention relates to a resin composition excellent in adhesiveness and workability. More specifically, the resin composition is a highly reliable adhesive that maintains its adhesion to plastic films and metals over time when used as an adhesive for flexible flat cables, flexible printed wiring boards, and the like. Furthermore, since it can be bonded at low and high temperatures near the melting point, it is possible to provide an adhesive excellent in workability such as line speed up and energy saving.
プラスチックフィルムや金属の接着・積層するための接着剤としてポリエステルが幅広く用いられている。このような接着剤組成物の具体的な使用例として、家電製品や自動車部品の回路基板同士の配線に用いられるフレキシブルフラットケーブル（以下ＦＦＣと略す。）がある。ＦＦＣは錫メッキ銅箔をはじめとする金属導箔を、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／金属導箔／接着剤／絶縁フィルムの構造を有している。また、そのケーブル末端は、コネクター接続のために厚手の絶縁フィルム／接着剤／金属導箔といった補強用フィルムの接着も行われる。 Polyester is widely used as an adhesive for bonding and laminating plastic films and metals. A specific use example of such an adhesive composition is a flexible flat cable (hereinafter abbreviated as FFC) used for wiring between circuit boards of home appliances and automobile parts. The FFC has a structure in which a metal conductive foil such as a tin-plated copper foil is bonded to an insulating film via an adhesive, that is, an insulating film / adhesive / metal conductive foil / adhesive / insulating film structure. . The cable end is also bonded to a reinforcing film such as a thick insulating film / adhesive / metal conductive foil for connector connection.
最近、このような用途には結晶性ポリエステルを使用したホットメルト接着剤が使用されるようになり、接着力が経時的に保持される信頼性の高い接着性、かつラインスピードアップや低温加工性といった加工性にも優れた接着剤が求められている。接着性を高める従来の技術としては、特許文献１において、ポリテトラメチレングリコール（以下ＰＴＭＧと略す）を反応させた結晶性ポリエーテルエステルエラストマーとエポキシ樹脂を用いた接着剤を提案しているが、ここで用いられているポリエステル樹脂は結晶性が高い傾向にあり、接着後、非晶状態から結晶状態になる際のひずみエネルギーの緩和がうまく行われず、初期の接着性は良好だが、経時的に接着強度が大幅に低下する傾向があった。また、特許文献２の実施例でも、いくつかのポリエステル樹脂に低密度ポリエチレン等をブレンドしたものが検討されているが、特に金属接着性に関しては、ポリエステルの結晶化進行に伴い金属界面からの剥離が起こり経時的に接着強度が低下するような傾向が見られた。また、融点近傍では溶融粘度が高い傾向にあるため被着体に対する濡れ性が不十分となり十分な接着性を得ることは難しい。一般的には十分な接着性を得るために、融点より非常に高い温度でラミネートするか、もしくは低温で長時間加熱し続けるといった手法が取られるが、このような手法をとった場合、高エネルギーが必要である場合や、ラインスピードの低下を引き起こす場合があり加工性といった点で好まれない。また、高温でラミネートした場合、樹脂の流動特性の調節が困難であるため、樹脂が被着体間からはみ出し、外観や信頼性といった点でも不十分なものとなってしまう。したがって、低温でラミネートが可能であり、かつ高温でラミネートした場合でも樹脂のはみ出しが少ない接着剤が求められる。このような低温ラミネート性に関する対策としては低分子量化合物を添加することが有効である。例えば上記特許文献１で示したようなエポキシ化合物等を添加した場合には低温接着性は改善する。しかしながら、低分子量化合物は経時的に表面にブリードアウトする可能性もあり接着性の長期安定性といった点で懸念が残る。 Recently, hot-melt adhesives using crystalline polyester have been used for such applications, providing reliable adhesives that maintain adhesive strength over time, line speedup, and low-temperature processability. There is a demand for an adhesive having excellent processability. As a conventional technique for improving adhesiveness, Patent Document 1 proposes an adhesive using a crystalline polyetherester elastomer and an epoxy resin obtained by reacting polytetramethylene glycol (hereinafter abbreviated as PTMG). The polyester resin used here tends to have high crystallinity, and after bonding, the strain energy when changing from the amorphous state to the crystalline state is not well relaxed, the initial adhesiveness is good, but over time There was a tendency for the adhesive strength to drop significantly. Also, in Examples of Patent Document 2, some polyester resins blended with low-density polyethylene or the like have been studied. Particularly, regarding metal adhesion, peeling from a metal interface with the progress of crystallization of polyester. Tended to occur and the adhesive strength decreased with time. In addition, since the melt viscosity tends to be high near the melting point, the wettability with respect to the adherend becomes insufficient and it is difficult to obtain sufficient adhesion. In general, in order to obtain sufficient adhesion, a method such as laminating at a temperature much higher than the melting point or continuing to heat at a low temperature for a long time is taken. Is not preferable in terms of workability because it may cause a decrease in line speed. In addition, when laminating at a high temperature, it is difficult to adjust the flow characteristics of the resin, so that the resin protrudes from the adherend, and the appearance and reliability are insufficient. Therefore, there is a demand for an adhesive that can be laminated at a low temperature and that has little protrusion of resin even when laminated at a high temperature. Addition of a low molecular weight compound is effective as a countermeasure for such low temperature laminating properties. For example, when an epoxy compound or the like as shown in Patent Document 1 is added, the low-temperature adhesiveness is improved. However, low molecular weight compounds may bleed out to the surface over time, and there is concern over the long-term stability of adhesion.
このように、プラスチックフィルムや金属に対する接着力が経時的に保持される信頼性の高い接着剤であり、かつ融点近傍の低温でも接着が可能な加工性にも優れた接着剤は提案されていない。 Thus, no adhesive has been proposed that is a highly reliable adhesive that maintains its adhesive strength to plastic films and metals over time, and that has excellent workability that allows bonding even at low temperatures near the melting point. .
本発明は、接着性や加工性に優れた樹脂組成物を提供することにある。さらに詳細には、プラスチックフィルムや金属に対する接着性が経時的に保持される信頼性の高い接着剤であり、さらに融点近傍の低温でも接着が可能であるため、ラインスピードアップや省エネルギーといった加工性にも優れる接着剤を提供することにある。また、このような樹脂を用いた積層体、およびフレキシブルフラットケーブル、フレキシブルプリント配線基板を提供することにある。 An object of the present invention is to provide a resin composition excellent in adhesiveness and workability. More specifically, it is a highly reliable adhesive that maintains its adhesiveness to plastic films and metals over time, and can be bonded even at low temperatures near the melting point, thus improving workability such as line speedup and energy saving. Is to provide an excellent adhesive. Moreover, it is providing the laminated body using such resin, a flexible flat cable, and a flexible printed wiring board.
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、以下の樹脂組成物、接着剤組成物、積層体およびフレキシブルフラットケーブル、フレキシブルプリント配線基板に関する。 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, the present invention relates to the following resin composition, adhesive composition, laminate, flexible flat cable, and flexible printed wiring board.
（１）結晶性ポリエステル（Ａ）、酸成分として脂肪族多価カルボン酸または脂環族多価カルボン酸が４０モル％以上含むポリエステル（Ｂ）、ポリオレフィン（Ｃ）を含んでなることを特徴とする樹脂組成物。 (1) Crystalline polyester (A), polyester (B) containing 40 mol% or more of aliphatic polycarboxylic acid or alicyclic polycarboxylic acid as an acid component, and polyolefin (C) Resin composition.
（２）結晶性ポリエステル（Ａ）、ジオール成分として数平均分子量が４００〜１００００のポリエーテルグリコールを１モル％以上含むポリエステル（Ｂ）、ポリオレフィン（Ｃ）を含んでなることを特徴とする樹脂組成物。 (2) Resin composition comprising crystalline polyester (A), polyester (B) containing 1 mol% or more of polyether glycol having a number average molecular weight of 400 to 10,000 as a diol component, and polyolefin (C) Stuff.
（３）結晶性ポリエステル（Ａ）、酸成分として脂肪族多価カルボン酸または脂環族多価カルボン酸が４０モル％以上含み、かつジオール成分として数平均分子量が４００〜１００００のポリエーテルグリコールを１モル％以上含むポリエステル（Ｂ）、ポリオレフィン（Ｃ）を含んでなることを特徴とする樹脂組成物。 (3) Crystalline polyester (A), polyether glycol having 40 mol% or more of aliphatic polycarboxylic acid or alicyclic polycarboxylic acid as an acid component and a number average molecular weight of 400 to 10,000 as a diol component A resin composition comprising polyester (B) and polyolefin (C) containing 1 mol% or more.
（４）結晶性ポリエステル（Ａ）の酸成分として芳香族多価カルボン酸が６０モル％以上であり、かつジオール成分としてエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオールおよび１，６−ヘキサンジオールからなる群のうち少なくとも二つの成分を含有し、その合計量が５０モル％以上であることを特徴とする（１）〜（３）のいずれかに記載の樹脂組成物。 (4) The aromatic polyvalent carboxylic acid is 60 mol% or more as the acid component of the crystalline polyester (A), and the diol component is ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1, The resin composition according to any one of (1) to (3), wherein the resin composition contains at least two components of a group consisting of 6-hexanediol, and the total amount thereof is 50 mol% or more.
（５）結晶性ポリエステル（Ａ）のジオール成分として数平均分子量が４００〜１００００のポリエーテルグリコールを含有することを特徴とする（１）〜（４）のいずれかに記載の樹脂組成物。 (5) The resin composition according to any one of (1) to (4), wherein the diol component of the crystalline polyester (A) contains a polyether glycol having a number average molecular weight of 400 to 10,000.
（６）ポリエステル（Ｂ）の環球法による軟化点が結晶性ポリエステル（Ａ）の軟化点より低いことを特徴とする請求項１〜５のいずれかに記載の樹脂組成物。 (6) The resin composition according to any one of claims 1 to 5, wherein the softening point of the polyester (B) by the ring and ball method is lower than the softening point of the crystalline polyester (A).
（７）ポリエステル（Ｂ）の２００℃、せん断速度５０ｓｅｃ-1における溶融粘度が、結晶性ポリエステル（Ａ）の２００℃、せん断速度５０ｓｅｃ-1における溶融粘度より低いことを特徴とする（１）〜（６）のいずれかに記載の樹脂組成物。 (7) The melt viscosity of polyester (B) at 200 ° C. and a shear rate of 50 sec −1 is lower than the melt viscosity of crystalline polyester (A) at 200 ° C. and a shear rate of 50 sec −1 (1) to (6) The resin composition in any one of.
（８）ポリオレフィン（Ｃ）の密度が０．９１ｇ／ｃｍ3以下であることを特徴とする（１）〜（７）のいずれかに記載の樹脂組成物。 (8) The resin composition according to any one of (1) to (7), wherein the density of the polyolefin (C) is 0.91 g / cm 3 or less.
（９）エポキシ化合物（Ｄ）をさらに含有することを特徴とする（１）〜（８）のいずれかに記載の樹脂組成物。 (9) The resin composition according to any one of (1) to (8), further comprising an epoxy compound (D).
（１０）（１）〜（９）のいずれかに記載の樹脂組成物を含有する接着剤。 (10) An adhesive containing the resin composition according to any one of (1) to (9).
（１１）（１０）に記載の接着剤を用いた積層体。 (11) A laminate using the adhesive according to (10).
（１２）（１０）に記載の接着剤を用いたフレキシブルフラットケーブル。 (12) A flexible flat cable using the adhesive according to (10).
（１３）（１０）に記載の接着剤を用いたフレキシブルプリント配線基板。 (13) A flexible printed wiring board using the adhesive according to (10).
本発明の樹脂組成物は、フレキシブルフラットケーブルなどの接着剤として用いた場合、プラスチックフィルムや金属に対する接着性が経時的に保持される信頼性の高い接着剤であり、さらに融点近傍の低温でも接着が可能であるため、ラインスピードアップや省エネルギーといった加工性にも優れた接着剤を提供することができる。 The resin composition of the present invention is a highly reliable adhesive that maintains its adhesiveness to plastic films and metals over time when used as an adhesive for flexible flat cables, etc., and further adheres even at low temperatures near the melting point. Therefore, it is possible to provide an adhesive excellent in processability such as line speed up and energy saving.
本発明の樹脂組成物に用いられる結晶性ポリエステル（Ａ）、ポリエステル（Ｂ）の構成成分としては、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ジカルボン酸、フマル酸、マレイン酸、コハク酸、イタコン酸、アジピン酸、アゼライン酸、セバシン酸、１，１２−ドデカン二酸、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、等があげられる。 As the constituent components of the crystalline polyester (A) and the polyester (B) used in the resin composition of the present invention, the following polyvalent carboxylic acids, alkyl esters thereof, or acid anhydrides 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. Dicarboxylic acids, aromatic dicarboxylic acids such as 4,4′-diphenyl ether dicarboxylic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,4 -Aliphatic and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, trimellitic acid, Pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic , Ethylene glycol bis (anhydrotrimellitate), aromatic polycarboxylic acids such as glycerol tris (anhydrotrimellitate), and the like.
結晶性ポリエステル（Ａ）、ポリエステル（Ｂ）のポリオール成分としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、１，３−プロパンジオール、２−メチル−１，３−プロパンジオール、１，２−ブタンジオ−ル、１，３−ブタンジオ−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−ル、ジプロピレングリコ−ル、２，２，４−トリメチル−１，５−ペンタンジオ−ル、ネオペンチルヒドロキシピバリン酸エステル、ビスフェノ−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−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、２−ブチル−２−エチル−１，３−プロパンジオール、１，４−シクロヘキサンジメタノール、トリシクロデカンジメタノール、ダイマージオール、ポリカーボネートグリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジメチロールブタン酸、ジメチロールプロピオン酸、ポリエーテルグリコール等が挙げられる。ポリエーテルグリコールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのポリアルキレングリコール、およびそれらの共重合体、さらにはこれらアルキレングリコールにネオペンチルグリコールやビスフェノールＡなどのジオールなどを共重合したものもあてはまる。 Examples of the polyol component of the crystalline polyester (A) and the polyester (B) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1 , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, neopentylhydroxypivalate, bisphenol A ethylene oxide adduct and propylene oxide adduct, hydrogen Bisphenol A ethylene oxide adduct and pro Renoxide adduct, 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, tricyclo Examples include decanedimethanol, dimer diol, polycarbonate glycol, glycerin, trimethylolpropane, pentaerythritol, dimethylolbutanoic acid, dimethylolpropionic acid, and polyether glycol. Polyether glycols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and copolymers thereof, and those obtained by copolymerizing diols such as neopentyl glycol and bisphenol A with these alkylene glycols. Also applies.
結晶性ポリエステル（Ａ）の酸成分のうち好ましくは６０モル％以上が上記記載の芳香族多価カルボン酸から選ばれる少なくとも一つ以上成分から共重合されることが好ましい。さらには、結晶性が高いテレフタル酸、２，６−ナフタレンジカルボンル酸が共重合されていることが好ましい。ポリエステル（Ａ）の芳香族ジカルボン酸成分が６０モル％未満であると、耐加水分解性、耐薬品性、耐熱性、機械的特性が不十分となることがあり、接着剤として用いた場合には凝集力が低く、高い接着性が得られないおそれがある。また、芳香族ジカルボン酸成分が６０モル％以上であると、融点以上の温度でも急激な粘度低下が起こらず高温で接着した場合でも、被着体から樹脂がはみ出すことなく加工性が良好である。 Of the acid component of the crystalline polyester (A), preferably 60 mol% or more is preferably copolymerized from at least one component selected from the aromatic polycarboxylic acids described above. Furthermore, it is preferable that terephthalic acid and 2,6-naphthalenedicarboxylic acid having high crystallinity are copolymerized. When the aromatic dicarboxylic acid component of the polyester (A) is less than 60 mol%, the hydrolysis resistance, chemical resistance, heat resistance, and mechanical properties may be insufficient. When used as an adhesive Has a low cohesive force, and there is a possibility that high adhesiveness cannot be obtained. In addition, when the aromatic dicarboxylic acid component is 60 mol% or more, the processability is good without causing the resin to protrude from the adherend even when the viscosity is not drastically lowered even at a temperature higher than the melting point and the adhesive adheres at a high temperature. .
また、結晶性ポリエステル（Ａ）のポリオール成分とのうち好ましくは５０モル％以上がエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオールおよび１，６−ヘキサンジオールからなる群のうち少なくとも一つを５０モル％以上含有することが好ましい。さらに、好ましくは、結晶サイズを小さくし、結晶化に伴う結晶化ひずみを小さくするためにはこれらポリオールを２成分以上使用することが好ましい。５０モル％未満であると樹脂の耐熱性、機械的特性、ひいては接着性が不十分になる場合がある。また、結晶性ポリエステル（Ａ）のポリオール成分として数平均分子量が４００〜１００００のポリエーテルグリコールを共重合することが好ましい。ポリエーテルグリコールの共重合は適度な柔軟性を付与すると共に、その他の長鎖グリコールや長鎖カルボン酸を共重合するのとは異なり、結晶化時の体積収縮による接着性低下が起こりにくくなる。理由としてはポリエステル樹脂がソフトセグメントとハードセグメントのブロック状になることより、結晶歪みエネルギーがソフトセグメントによって効果的に緩和されるためである。また、ガラス転移点が低下するため、冬場の低温環境下でも十分な柔軟性を有し、接着剤として使用した場合も低温環境下の接着性が良好である。さらに、ポリエーテルグリコールを共重合することにより樹脂中のエステル基濃度が低下し耐湿熱性も大幅に改善される。ポリエーテルグリコールの数平均分子量としては４００〜１００００のものが望ましい。好ましい下限は６００、より好ましくは８００である。また、好ましい上限は４０００、より好ましくは３０００、さらに好ましくは２５００である。数平均分子量が４００未満であると、接着性の経時的な低下を抑えられないことがあり、一方１００００を超えるとポリエステルの主骨格との相溶性が低下し、接着性に悪影響の出る場合がある。ポリエーテルグリコールの共重合量は１モル％以上、好ましくは２モル％以上である。好ましい上限は２５モル％以下である。尚、本発明において数平均分子量とはゲルパーミネーションクロマトグラフィにおいて測定されるポリスチレン換算値である。 Preferably, at least 50 mol% of the polyol component of the crystalline polyester (A) is at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. One is preferably contained in an amount of 50 mol% or more. Further, it is preferable to use two or more of these polyols in order to reduce the crystal size and the crystallization strain accompanying crystallization. If it is less than 50 mol%, the heat resistance, mechanical properties, and thus the adhesiveness of the resin may be insufficient. Moreover, it is preferable to copolymerize polyether glycol having a number average molecular weight of 400 to 10,000 as the polyol component of the crystalline polyester (A). The copolymerization of polyether glycol gives moderate flexibility, and unlike the copolymerization of other long-chain glycols or long-chain carboxylic acids, it is difficult to cause a decrease in adhesion due to volume shrinkage during crystallization. The reason is that the crystal strain energy is effectively relieved by the soft segment because the polyester resin has a soft segment and hard segment block shape. Further, since the glass transition point is lowered, the glass transition point is sufficiently flexible even in a low temperature environment in winter, and the adhesiveness in a low temperature environment is good even when used as an adhesive. Furthermore, by copolymerizing polyether glycol, the ester group concentration in the resin is lowered, and the heat and moisture resistance is greatly improved. The number average molecular weight of the polyether glycol is preferably 400 to 10,000. A preferred lower limit is 600, more preferably 800. Moreover, a preferable upper limit is 4000, More preferably, it is 3000, More preferably, it is 2500. If the number average molecular weight is less than 400, the deterioration of adhesiveness over time may not be suppressed. On the other hand, if the number average molecular weight exceeds 10,000, the compatibility with the main skeleton of the polyester may be reduced, and the adhesiveness may be adversely affected. is there. The copolymerization amount of polyether glycol is 1 mol% or more, preferably 2 mol% or more. A preferable upper limit is 25 mol% or less. In the present invention, the number average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography.
本発明においてポリエステル（Ｂ）は、その酸成分のうち脂肪族多価カルボン酸もしくは脂環族多価カルボン酸が４０モル％以上含むか、あるいは数平均分子量が４００〜１００００のポリエーテルグリコールを１モル％以上含むことが望ましい。また、その両者を満足するものがさらに望ましい。ポリエステル（Ｂ）の結晶性、非晶性は限定しないが、酸成分として特にアジピン酸、アゼライン酸、セバシン酸、ダイマー酸などの脂肪族ジカルボン酸を共重合した樹脂は、分子量が高くても、融点もしくは軟化点以上では温度の増加に伴い溶融粘度が大幅に低下するため、この樹脂を接着剤として用いた場合、低温での被着体への濡れ性が優れており、低温での接着が可能となる。一方、脂肪族および／または脂環族多価カルボン酸成分が４０モル％未満であると、温度上昇に伴う溶融粘度の低下が不十分であるため被着体への濡れ性が悪く接着力の得られないことがある。数平均分子量が４００〜１００００のポリエーテルグリコールを１モル％以上共重合した樹脂も、その屈曲性ゆえ、分子量が高くても融点もしくは軟化点以上では温度の増加に伴い溶融粘度が大幅に低下するため、この樹脂を接着剤として用いた場合、低温での接着が可能となる。ポリエーテルグリコールの共重合量は１モル％以上、好ましくは２モル％以上である。上限は特に限定されないが２５モル％以下が好ましい。ポリエーテルグリコールの数平均分子量の下限としては、好ましくは６００、より好ましくは８００である。また、好ましい上限は４０００、より好ましくは３０００、さらに好ましくは２５００である。数平均分子量が４００未満であると、低温での接着に効果が見られないことがあり、一方１００００を超えるとポリエステルの主骨格との相溶性が低下し、接着性に悪影響をおよぼす場合がある。ポリエーテルグリコールとしては接着性の観点からポリテトラメチレングリコールが好ましい。 In the present invention, the polyester (B) contains 40 mol% or more of aliphatic polycarboxylic acid or alicyclic polycarboxylic acid among the acid components, or 1 polyether glycol having a number average molecular weight of 400 to 10,000. It is desirable to contain more than mol%. Moreover, what satisfies both of them is more desirable. Although the crystallinity and non-crystallinity of the polyester (B) are not limited, a resin obtained by copolymerizing an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid or dimer acid as an acid component may have a high molecular weight. Above this melting point or softening point, the melt viscosity decreases significantly with increasing temperature, so when this resin is used as an adhesive, it has excellent wettability to adherends at low temperatures, and adhesion at low temperatures. It becomes possible. On the other hand, when the aliphatic and / or alicyclic polyvalent carboxylic acid component is less than 40 mol%, the decrease in melt viscosity accompanying an increase in temperature is insufficient, resulting in poor wettability to the adherend and poor adhesive strength. It may not be obtained. A resin obtained by copolymerizing 1 mol% or more of a polyether glycol having a number average molecular weight of 400 to 10000, due to its flexibility, the melt viscosity greatly decreases with an increase in temperature above the melting point or softening point even if the molecular weight is high. Therefore, when this resin is used as an adhesive, bonding at a low temperature is possible. The copolymerization amount of polyether glycol is 1 mol% or more, preferably 2 mol% or more. Although an upper limit is not specifically limited, 25 mol% or less is preferable. The lower limit of the number average molecular weight of the polyether glycol is preferably 600, more preferably 800. Moreover, a preferable upper limit is 4000, More preferably, it is 3000, More preferably, it is 2500. If the number average molecular weight is less than 400, the effect of adhesion at low temperature may not be seen. On the other hand, if the number average molecular weight exceeds 10,000, the compatibility with the main skeleton of the polyester may be lowered, and the adhesion may be adversely affected. . As the polyether glycol, polytetramethylene glycol is preferable from the viewpoint of adhesiveness.
結晶性ポリエステル（Ａ）としては融点が５０℃〜１９０℃、好ましくは６０℃〜１８０℃、さらに好ましくは７０℃〜１５０℃であるものが望ましい。融点が５０℃未満であると、耐熱性が不十分であるとともに、室温でブロッキングを起こす場合がある。一方融点が１９０℃を超えると、樹脂を加工する際、高温を必要とするため加工性に劣る。結晶性ポリエステル（Ａ）のガラス転移点としては４０℃以下、好ましくは２０℃以下、さらに好ましくは０℃以下、最も好ましくは−２０℃以下である。ガラス転移点が４０℃を超えると、この樹脂を接着剤として用いた場合、室温付近における弾性率が高くなりすぎて、特に室温領域での接着性が低下するおそれがある。また、柔軟性に劣るため高い耐屈曲性を必要とするＦＦＣなどにおいては、屈曲時に接着剤と被着体間で剥離が生じることがある。下限は特に限定されないが高温領域の接着性を考慮すると−７０℃以上である。ここで融点やガラス転移温度は示差走査型熱量計を用いて測定した値である。 The crystalline polyester (A) has a melting point of 50 ° C to 190 ° C, preferably 60 ° C to 180 ° C, more preferably 70 ° C to 150 ° C. When the melting point is less than 50 ° C., the heat resistance is insufficient and blocking may occur at room temperature. On the other hand, if the melting point exceeds 190 ° C., the processability is inferior because a high temperature is required when processing the resin. The glass transition point of the crystalline polyester (A) is 40 ° C. or less, preferably 20 ° C. or less, more preferably 0 ° C. or less, and most preferably −20 ° C. or less. When the glass transition point exceeds 40 ° C., when this resin is used as an adhesive, the elastic modulus in the vicinity of room temperature becomes too high, and the adhesiveness particularly in the room temperature region may be lowered. Moreover, in FFC etc. which require high bending resistance because of poor flexibility, peeling may occur between the adhesive and the adherend during bending. Although a minimum is not specifically limited, if the adhesiveness of a high temperature area is considered, it will be -70 degreeC or more. Here, melting point and glass transition temperature are values measured using a differential scanning calorimeter.
また、ポリエステル（Ｂ）としては、非晶性ポリエステル、結晶性ポリエステルのどちらを使用しても良いが、耐熱性、力学特性の点から結晶性ポリエステルを使用することが好ましい。ポリエステル（Ｂ）により、ポリエステル（Ａ）の低温ラミネート性を改善するためには、ポリエステル（Ｂ）の環球法による軟化点が、結晶性ポリエステル（Ａ）の軟化点＋２０℃以下であることが好ましい。さらに好ましくはポリエステル（Ｂ）の軟化点が結晶性ポリエステル（Ａ）の軟化点より低いことが好ましい。軟化点の測定は、ＪＩＳ Ｋ ６８６３に準じて行うことが出来る。ただし媒体としてグリセリンを用い、５℃／分で昇温を行うものとする。ポリエステル（Ｂ）のガラス転移点としては、４０℃以下、好ましくは２０℃以下、さらに好ましくは０℃以下、最も好ましくは−２０℃以下である。下限は−７０℃以上が好ましい。 Further, as the polyester (B), either amorphous polyester or crystalline polyester may be used, but it is preferable to use crystalline polyester from the viewpoint of heat resistance and mechanical properties. In order to improve the low temperature laminating property of the polyester (A) with the polyester (B), the softening point of the polyester (B) by the ring-and-ball method is preferably the softening point of the crystalline polyester (A) + 20 ° C. or less. . More preferably, the softening point of the polyester (B) is lower than the softening point of the crystalline polyester (A). The softening point can be measured according to JIS K 6863. However, glycerin is used as a medium, and the temperature is increased at 5 ° C./min. As a glass transition point of polyester (B), it is 40 degrees C or less, Preferably it is 20 degrees C or less, More preferably, it is 0 degrees C or less, Most preferably, it is -20 degrees C or less. The lower limit is preferably −70 ° C. or higher.
尚、本発明において言う非晶性とは示差走査型熱量計（ＤＳＣ）を用いて、−１００℃〜３００℃まで２０℃／ｍｉｎで昇温し、次に−１００℃まで５０℃／ｍｉｎで降温し、続いて−１００℃〜３００℃まで２０℃／ｍｉｎで昇温する二度の昇温過程においてどちらにも融解ピークを示さないものを指す。逆に結晶性とはどちらかの昇温過程に明確な融解ピークを示すものを指す。 In the present invention, the term “amorphous” means that the temperature is raised from −100 ° C. to 300 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and then to −100 ° C. at 50 ° C./min. The temperature does not show a melting peak in either of the two temperature raising processes in which the temperature is lowered and subsequently raised from −100 ° C. to 300 ° C. at 20 ° C./min. On the other hand, crystallinity refers to those showing a clear melting peak in either temperature rising process.
本発明の樹脂組成物の構成成分として用いられる結晶性ポリエステル（Ａ）、ポリエステル（Ｂ）は２００℃、せん断速度５０ｓｅｃ-1における溶融粘度が１００ｄＰａ・ｓ以上２００００ｄＰａ・ｓ以下であることが望ましい。より好ましくは２００ｄＰａ・ｓ以上１５０００ｄＰａ・ｓ未満である。溶融粘度が１００ｄＰａ・ｓ未満であると、ラミネートしたとき樹脂がはみ出すことがあり、本来の接着力を発現することが困難となるおそれがある。一方２００００ｄＰａ・ｓを超えるとラミネート時の濡れ性が不十分となり高い接着力を得ることは困難になることがある。ポリエステル（Ｂ）により、結晶性ポリエステル（Ａ）の低温ラミネート性を改善するためには、ポリエステル（Ｂ）の２００℃、せん断速度５０ｓｅｃ-1における溶融粘度が、結晶性ポリエステル（Ａ）の２００℃における溶融粘度より低いことが好ましい。 The crystalline polyester (A) and polyester (B) used as the constituent components of the resin composition of the present invention preferably have a melt viscosity of 100 dPa · s or more and 20000 dPa · s or less at 200 ° C. and a shear rate of 50 sec −1 . More preferably, it is 200 dPa · s or more and less than 15000 dPa · s. If the melt viscosity is less than 100 dPa · s, the resin may protrude when laminated, and it may be difficult to develop the original adhesive force. On the other hand, if it exceeds 20000 dPa · s, the wettability at the time of lamination becomes insufficient, and it may be difficult to obtain a high adhesive force. In order to improve the low temperature laminating property of the crystalline polyester (A) with the polyester (B), the melt viscosity of the polyester (B) at 200 ° C. and a shear rate of 50 sec −1 is 200 ° C. of the crystalline polyester (A). It is preferably lower than the melt viscosity at.
本発明の樹脂組成物は、結晶性ポリエステル（Ａ）の低温ラミネート性を改善するためにポリエステル（Ｂ）を添加しているので、結晶性ポリエステル（Ａ）とポリエステル（Ｂ）の配合比は、重量比で（Ａ）／（Ｂ）＝２０／８０〜９９／１が好ましい。より好ましくは５０／５０〜９５／３、さらに好ましくは７０／３０〜９０／５である。結晶性ポリエステル樹脂（Ａ）成分が２０重量％より少ないと、機械的特性が劣り接着性や耐熱性が低下することがある。一方、結晶性ポリエステル樹脂（Ａ）成分が９９重量％以上を超えるとポリエステル（Ｂ）による低温ラミネート性の改善効果が見られないことがある。
上記のように、機械的特性が良好な結晶性ポリエステル（Ａ）と、ある特定組成の濡れ性の良好なポリエステル（Ｂ）を組み合わせることで、良好な接着性を示すとともに、低温でのラミネート性が良好な樹脂組成物および接着剤組成物となる。このような特性は一方の樹脂だけでは得られず、上記の特性の大きく異なる２種の樹脂ブレンドによる効果である。
In the resin composition of the present invention, the polyester (B) is added in order to improve the low-temperature laminating property of the crystalline polyester (A), so the compounding ratio of the crystalline polyester (A) and the polyester (B) The weight ratio (A) / (B) = 20/80 to 99/1 is preferable. More preferably, it is 50 / 50-95 / 3, More preferably, it is 70 / 30-90 / 5. If the amount of the crystalline polyester resin (A) component is less than 20% by weight, the mechanical properties may be inferior and the adhesiveness and heat resistance may be lowered. On the other hand, when the crystalline polyester resin (A) component exceeds 99% by weight or more, the effect of improving the low temperature laminating property by the polyester (B) may not be seen.
As described above, by combining the crystalline polyester (A) with good mechanical properties and the polyester (B) with good wettability of a specific composition, it exhibits good adhesiveness and can be laminated at low temperatures. Is a good resin composition and adhesive composition. Such a characteristic cannot be obtained with only one resin, but is an effect of two kinds of resin blends having greatly different characteristics.
本発明の樹脂組成物はさらにポリオレフィン（Ｃ）を有することが必要である。ポリオレフィンとして、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、超低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、エチレンプロピレンエラストマー、オレフィン系熱可塑性エラストマー、α−オレフィン共重合体、エチレン−α−オレフィン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エチル共重合体、エチレン−酢酸ビニル−無水マレイン酸三元共重合体、エチレン−アクリル酸エチル−無水マレイン酸三元共重合体、エチレン−メタクリル酸グリシジル共重合体、エチレン−酢酸ビニル−メタクリル酸グリシジル三元共重合体、エチレン−アクリル酸メチル−メタクリル酸グリシジル三元共重合体、マレイン酸変性ポリオレフィン、また、これらポリオレフィンを他成分のグラフトにより変性した樹脂などが使用できる。中でも、密度が０．８５〜０．９１ｇ／ｃｍ3のポリオレフィンは柔軟性に富んでおり、結晶性ポリエステル（Ａ）の結晶化進行に伴うひずみエネルギーを効果的に緩和することができ、経時的な接着強度低下をさらに抑制することができる。一方、密度が０．８５ｇ／ｃｍ3未満のポリオレフィンを使用した場合、樹脂組成物の力学的な特性を低下させる場合があり、密度が０．９１ｇ／ｃｍ3を超えると、ひずみエネルギーの緩和が不十分であり接着力が経時的に低下する傾向にある。また、ＡＳＴＭ Ｄ２２４０に従って測定したショアＤ硬度としては１０以上７０未満、好ましくは２０以上４８未満、さらに好ましくは２５以上４２未満であるものでも良い。好ましいポリオレフィンとしてはα−オレフィン共重合体であり、最も好ましくは、エチレン−α−オレフィン共重合体である。オレフィンの密度は例えば密度勾配管を用いることによって測定することが出来る。但し温度は３０℃で測定するものとする。 The resin composition of the present invention further needs to have a polyolefin (C). As polyolefin, high density polyethylene, medium density polyethylene, low density polyethylene, ultra low density polyethylene, linear low density polyethylene, polypropylene, ethylene propylene elastomer, olefin thermoplastic elastomer, α-olefin copolymer, ethylene-α- Olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate-maleic anhydride terpolymer, ethylene-ethyl acrylate-maleic anhydride terpolymer , Ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate terpolymer, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, maleic acid-modified polyolefin, and other polyolefins Completion Resins modified by grafting of a minute can be used. Among them, the polyolefin having a density of 0.85 to 0.91 g / cm 3 is rich in flexibility, and can effectively relax the strain energy accompanying the crystallization of the crystalline polyester (A), It is possible to further suppress a decrease in adhesive strength. On the other hand, when a polyolefin having a density of less than 0.85 g / cm 3 is used, the mechanical properties of the resin composition may be lowered. When the density exceeds 0.91 g / cm 3 , strain energy is alleviated. It is insufficient and the adhesive strength tends to decrease with time. The Shore D hardness measured in accordance with ASTM D2240 may be 10 or more and less than 70, preferably 20 or more and less than 48, and more preferably 25 or more and less than 42. Preferred polyolefins are α-olefin copolymers, most preferably ethylene-α-olefin copolymers. The density of the olefin can be measured, for example, by using a density gradient tube. However, the temperature shall be measured at 30 ° C.
本発明におけるポリオレフィンの配合量は、結晶性ポリエステル（Ａ）＋ポリエステル（Ｂ）を１００重量部とした場合、０．５〜８０重量部である。ポリオレフィン（Ｃ）が０．５重量部未満の場合、ポリエステルの結晶化によるひずみエネルギーの緩和が難しいため、接着強度が経時的に低下する傾向にある。また、ポリオレフィン（Ｃ）を８０重量部を超えて配合した場合、ポリエステルがもつ接着特性を打ち消してしまう傾向がある。 The blending amount of the polyolefin in the present invention is 0.5 to 80 parts by weight when the crystalline polyester (A) + the polyester (B) is 100 parts by weight. When the polyolefin (C) is less than 0.5 parts by weight, it is difficult to relax the strain energy due to crystallization of the polyester, so that the adhesive strength tends to decrease with time. Moreover, when blending more than 80 parts by weight of the polyolefin (C), there is a tendency to cancel the adhesive properties of the polyester.
本発明の樹脂組成物には必要に応じてさらにエポキシ樹脂（Ｄ）を併用しても良い。用いるエポキシ樹脂（Ｄ）とは、好ましくは数平均分子量４５０〜４００００の範囲にある分子中に少なくとも１．１個以上のグリシジル基を有するエポキシ樹脂であって、例えばビスフェノールＡジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、ノボラックグリシジルエーテル、ブロム化ビスフェノールＡジグリシジルエーテル等のグリシジルエーテルタイプ、ヘキサヒドロフタル酸グリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステルタイプ、トリグリシジルイソシアヌレート、グリシジルヒンダントイン、テトラグリシジルジアミノジフェニルメタン、トリグリシジルパラアミノフェノール、トリグリシジルメタアミノフェノール、ジグリシジルアニリン、ジグリシジルトルイジン、テトラグリシジルメタキシレンジアミン、ジグリシジルトリブロムアニリン、テトラグリシジルビスアミノメチルシクロヘキサン等のグリシジルアミン、あるいは３，４−エポキシシクロヘキシルメチルカルボキシレート、エポキシ化ポリブタジエン、エポキシ化大豆油等の脂環族あるいは脂肪族エポキサイドなどが挙げられる。これらのうち、特に、接着力を大幅に向上させるためには熱可塑性結晶性ポリエステルに対して相溶性が良いものが好ましい。ここでエポキシ樹脂の好ましい数平均分子量が、４５０〜４００００としたのは、４５０未満では接着剤組成物が極めて軟化し易く、機械的物性が劣ることがあり、４００００以上では、成分（Ａ）との相溶性が低下し、接着性への効果が損なわれるおそれがあるからである。 If necessary, the resin composition of the present invention may further contain an epoxy resin (D). The epoxy resin (D) used is preferably an epoxy resin having at least 1.1 glycidyl groups in a molecule having a number average molecular weight of 450 to 40,000, such as bisphenol A diglycidyl ether, bisphenol S. Diglycidyl ether, novolac glycidyl ether, glycidyl ether type such as brominated bisphenol A diglycidyl ether, glycidyl ester type such as hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, triglycidyl isocyanurate, glycidylhindantoin, tetraglycidyl Diaminodiphenylmethane, triglycidyl paraaminophenol, triglycidyl metaaminophenol, diglycidyl aniline, diglycidyl toluidine, tetrag Glycidylamines such as sidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisaminomethylcyclohexane, or alicyclic or aliphatic epoxides such as 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, epoxidized soybean oil Etc. Among these, in particular, those having good compatibility with the thermoplastic crystalline polyester are preferable in order to greatly improve the adhesive strength. Here, the preferable number average molecular weight of the epoxy resin is set to 450 to 40,000. If the adhesive resin composition is less than 450, the adhesive composition is very soft and mechanical properties may be inferior. This is because there is a possibility that the compatibility of the resin may be reduced and the effect on adhesiveness may be impaired.
本発明におけるエポキシ樹脂（Ｄ）の配合量は、結晶性ポリエステル（Ａ）＋ポリエステル（Ｂ）を１００重量部とした場合０〜８０重量部が好ましい。エポキシ樹脂（Ｄ）が８０重量％を超えると、機械的特性が劣り接着性、耐熱性が低下することがある。 The blending amount of the epoxy resin (D) in the present invention is preferably 0 to 80 parts by weight when the crystalline polyester (A) + the polyester (B) is 100 parts by weight. If the epoxy resin (D) exceeds 80% by weight, the mechanical properties may be inferior and the adhesion and heat resistance may be lowered.
また、本発明の樹脂組成物には、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、ペンタジブロモトルエン、臭素化フェニルメタクリル酸エステル、２，４−ジブロモフェノール等の臭素系難燃剤や臭素系難燃助剤である三酸化アンチモンやリン酸エステル、リン酸アミド、有機フォスフィンオキサイド等の有機リン系難燃剤や赤燐やポリリン酸アンモニウム、フォスファゼン、トリアジン、メラミンシアヌレート等の窒素系難燃剤、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等の水和金属系難燃剤、その他無機系難燃剤等が挙げられる。 Moreover, a flame retardant can be used together with the resin composition of the present invention as necessary. Examples of the flame retardant include bromine-based flame retardants such as pentadibromotoluene, brominated phenylmethacrylate, 2,4-dibromophenol, and bromine-based flame retardants such as antimony trioxide, phosphate esters, and phosphate amides. Organic phosphorus flame retardants such as organic phosphine oxide, nitrogen-based flame retardants such as red phosphorus, ammonium polyphosphate, phosphazene, triazine, melamine cyanurate, metal salt flame retardants such as polystyrene sulfonate alkali metal salts, hydroxylation Examples include hydrated metal flame retardants such as aluminum and magnesium hydroxide, and other inorganic flame retardants.
本発明の樹脂組成物には、各種の添加剤を配合することができる。添加剤としては、本発明以外の樹脂、無機フィラー、安定剤、紫外線吸収剤、及び老化防止剤を熱可塑性接着剤への添加剤として広く用いられているものを本発明の特徴を損なわない範囲で添加することができる。 Various additives can be blended in the resin composition of the present invention. As additives, resins, inorganic fillers, stabilizers, UV absorbers, and anti-aging agents other than those of the present invention that are widely used as additives for thermoplastic adhesives are within the range that does not impair the characteristics of the present invention. Can be added.
本発明の樹脂組成物には結晶性ポリエステル（Ａ）、ポリエステル（Ｂ）、ポリオレフィン（Ｃ）、エポキシ化合物（Ｄ）以外の樹脂を配合しても良い。それ以外の樹脂としては、ポリスチレン、ポリウレタン、ポリアミド、ポリ塩化ビニル、ポリ（メタ）アクリル酸、ポリ（メタ）アクリル酸エステル、スチレン系エラストマー、アクリロニトリル−ブタジエンゴム、シリコン系樹脂、フッ素樹脂、フェノール樹脂、フェノキシ樹脂、石油樹脂、水添石油樹脂、テルペン樹脂、ロジン、および変性ロジン等を添加することができる。 You may mix | blend resin other than crystalline polyester (A), polyester (B), polyolefin (C), and an epoxy compound (D) with the resin composition of this invention. Other resins include polystyrene, polyurethane, polyamide, polyvinyl chloride, poly (meth) acrylic acid, poly (meth) acrylic ester, styrene elastomer, acrylonitrile-butadiene rubber, silicon resin, fluororesin, phenol resin. Phenoxy resin, petroleum resin, hydrogenated petroleum resin, terpene resin, rosin, modified rosin and the like can be added.
無機フィラーとしては、タルク、炭酸カルシウム、酸化亜鉛、酸化チタン、クレー、ベントナント、フュ−ムドシリカ、シリカ粉末、雲母等を本発明の樹脂組成物の全体量１００重量部に対して４０重量部以下配合することができる。 As the inorganic filler, talc, calcium carbonate, zinc oxide, titanium oxide, clay, bentonant, fumed silica, silica powder, mica and the like are 40 parts by weight or less based on 100 parts by weight of the total amount of the resin composition of the present invention. Can be blended.
また、その他の添加剤として、各種金属塩等の結晶核剤、着色顔料、無機、有機系の充填剤、タック性向上剤、フェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、クエンチャー、金属不活性化剤、銅害防止剤、紫外線吸収剤、ヒンダードアミン光安定剤、加水分解安定剤等の安定剤、シランカップリング剤、チタンカップリング剤等を添加することもできる。 Other additives include crystal nucleating agents such as various metal salts, coloring pigments, inorganic and organic fillers, tackiness improvers, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants. Further, a quencher, a metal deactivator, a copper damage inhibitor, a UV absorber, a hindered amine light stabilizer, a stabilizer such as a hydrolysis stabilizer, a silane coupling agent, a titanium coupling agent and the like can be added.
本発明の樹脂組成物の製造方法としては、結晶性ポリエステル（Ａ）、ポリエステル（Ｂ）、ポリオレフィン（Ｃ）を単軸もしくは二軸のスクリュー式溶融混錬機、または、ニーダー式加熱機に代表される通常の熱可塑性樹脂の混合機を用いて製造し、引き続き造粒工程によりペレット化するか、もしくは直接被着材に塗布することが可能である。 As the method for producing the resin composition of the present invention, the crystalline polyester (A), the polyester (B), and the polyolefin (C) are represented by a single or biaxial screw-type melt kneader or a kneader-type heater. Can be produced using a conventional thermoplastic resin mixer and subsequently pelletized by a granulation process or directly applied to an adherend.
本発明の樹脂組成物を接着剤として用いる方法として、好ましくは、前述の製造方法により造粒されたペレットをＴ−ダイ方式、インフレーション方式、カレンダー方式、紡糸方式と称するダイス部分を有したスクリュー式押出し機により接着剤単体をシート状、フィルム状、不織布状に成形し、積層接着する被着材の中間に固定し、加熱接着するか、またはシート状に成形した接着剤を一方の被着材上で加熱溶融し、そのままもう一方の被着体を冷却しながら圧着する接着方法がある。
また、ペレットを前述のスクリュー式押出し機により溶融し、直接積層する被着材間に挿入して熱接着する方法や、一方の被着材が熱可塑性プラスチックの場合、共押出しにより直接接着するか、直接一方の被着材に塗布し、改めて加熱接着する方法がある。
As a method of using the resin composition of the present invention as an adhesive, preferably a screw type having a die part called a T-die method, an inflation method, a calendar method, and a spinning method, pellets granulated by the above-described manufacturing method Adhesive unit is formed into a sheet, film, or non-woven fabric by an extruder, fixed in the middle of an adhesive to be laminated and bonded, and then heated or bonded to one of the adhesives. There is an adhering method in which the above-mentioned adherend is heated and melted, and the other adherend is cooled as it is.
In addition, the pellets are melted by the above-described screw extruder and inserted between the substrates to be directly laminated and thermally bonded, or if one substrate is a thermoplastic, is it directly bonded by coextrusion? There is a method in which it is directly applied to one of the adherends and is again heat-bonded.
本発明の樹脂組成物を、プラスチック、金属、繊維、ガラス、セラミック、木材、紙いずれにも強い接着力を示す。特にプラスチックフィルムと金属の接着には有効である。プラスチックフィルムとしてはポリエチレンテレフタレートなどのポリエステルフィルム、全芳香族ポリエステルフィルム、ナイロンフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリスチレンフィルム、ポリ乳酸フィルム、ポリアミドイミドフィルム、ポリイミドフィルム、エチレン−ビニルアルコールフィルムを含む各種バリア性フィルム、およびこれらを席相したフィルムなどに使用できる。また、金属としては、銅、スズメッキ銅、アルミ、鋼板、ステンレス等に使用できる。 The resin composition of the present invention exhibits strong adhesion to any of plastic, metal, fiber, glass, ceramic, wood and paper. It is especially effective for bonding plastic film and metal. As plastic films, polyester films such as polyethylene terephthalate, wholly aromatic polyester films, nylon films, polyvinyl chloride films, polyvinylidene chloride films, polyethylene films, polypropylene films, polystyrene films, polylactic acid films, polyamideimide films, polyimide films, It can be used for various barrier films including an ethylene-vinyl alcohol film, and a film in which these films are used. Moreover, as a metal, it can use for copper, tin plating copper, aluminum, a steel plate, stainless steel, etc.
本発明の樹脂組成物は、この樹脂単独をフィルム化し使用することが可能であるが、非着体と接着剤を積層することもできる。構成としては、被着体／接着剤、被着体／接着剤／被着体、また、これら構成のものをさらに重ね合わせたものなどが挙げられる。 In the resin composition of the present invention, the resin alone can be used as a film, but a non-adherent and an adhesive can be laminated. Examples of the structure include an adherend / adhesive, an adherend / adhesive / adherent, and those obtained by further superimposing these structures.
特に本発明の樹脂組成物は高い接着信頼性、易加工性を有することから、電子材料などの接着剤として有効である。電子材料としては、フレキシブルフラットケーブル、フレキシブルプリント配線基板への使用が特に有効である。使用部位としては、特に限定されないが、絶縁フィルムと導体間の接着、カバーフィルムの接着、補強板の接着、多層化用の接着として使用できる。 In particular, since the resin composition of the present invention has high adhesion reliability and easy processability, it is effective as an adhesive for electronic materials and the like. As an electronic material, the use to a flexible flat cable and a flexible printed wiring board is especially effective. Although it does not specifically limit as a use site | part, It can use as adhesion | attachment between an insulating film and a conductor, adhesion | attachment of a cover film, adhesion | attachment of a reinforcement board, adhesion | attachment for multilayering.
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。実施例中に単に部とあるのは重量部を示す。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 the examples, “parts” means “parts by weight”. 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、1Ｈ−ＮＭＲにより定量した。 Resin composition: The resin was dissolved in deuterated chloroform and quantified by 1 H-NMR.
酸価：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当たりの当量（ｅｑ／１０6ｇ）を求めた。 Acid value: 0.2 g of polyester was dissolved in 20 ml of chloroform, and titrated with a 0.1 N potassium hydroxide ethanol solution to obtain an equivalent (eq / 10 6 g) per 10 6 g of resin.
溶融粘度：島津製作所製フローテスターを用い、２００℃、せん断速度５０ｓｅｃ-1の条件のもと、径１ｍｍ×長さ１０ｍｍのキャピラリーを用い測定した。樹脂サンプルは４０℃×２４時間の真空乾燥したものを用いた。 Melt viscosity: Measured using a flow tester manufactured by Shimadzu Corporation using a capillary having a diameter of 1 mm and a length of 10 mm under the conditions of 200 ° C. and a shear rate of 50 sec −1 . The resin sample used was vacuum-dried at 40 ° C. for 24 hours.
ガラス転移温度、融点：サンプル５ｍｇをアルミニウム製サンプルパンに入れて密封し、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、２００℃まで、昇温速度２０℃／分にて測定し、融解熱の最大ピーク温度を結晶融点として求めた。ガラス転移温度は、ガラス転移温度以下のベースラインの延長線と遷移部における最大傾斜を示す接線との交点の温度で求めた。 Glass transition temperature, melting point: 5 mg of sample was put in an aluminum sample pan and sealed, and a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc. was used. The maximum peak temperature of heat of fusion was determined as the crystalline melting point. The glass transition temperature was determined by the temperature at the intersection of the base line extension below the glass transition temperature and the tangent that indicates the maximum slope at the transition.
軟化点：ＪＩＳ Ｋ ６８６３に従い、環球型の軟化点測定装置を用い、媒体としてグリセリン、昇温速度５℃／分で測定を行った。金属球が落下した時の温度を軟化点とした。 Softening point: According to JIS K 6863, a ring-and-ball type softening point measuring device was used, and measurement was performed with glycerol as a medium and a heating rate of 5 ° C./min. The temperature at which the metal ball dropped was taken as the softening point.
＜結晶性ポリエステル（Ａ）の合成例１＞
撹拌機、温度計、溜出用冷却管を装備した反応缶内に、テレフタル酸１１６部、アジピン酸４４部、エチレングリコール８７部、１，４−ブタンジオール５４部、テトラブチルチタネート０．１０部を仕込み、１８０〜２４０℃で１時間エステル化反応を実施した。次いで、反応系を２４０℃から２５０℃に昇温する一方、系内を徐々に減圧していき、６０分かけて５００Ｐａとした。そして、さらに１３０Ｐａ以下で６５分間重縮合反応を行い、結晶性ポリエステル（Ａ−１）を得た。結晶性ポリエステル（Ａ−１）はＮＭＲ分析の結果、テレフタル酸７０モル％、アジピン酸３０モル％、エチレングリコール５０モル％、１，４−ブタンジオール５０モル％の組成を有しており、２００℃・せん断速度５０ｓｅｃ-1における溶融粘度が２５００ｄＰａ・ｓ、ガラス転移温度０℃、融点１１５℃、軟化点が１３０℃、酸価２５ｅｑ／１０6ｇであった。
<Synthesis example 1 of crystalline polyester (A)>
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube for distillation, 116 parts of terephthalic acid, 44 parts of adipic acid, 87 parts of ethylene glycol, 54 parts of 1,4-butanediol, 0.10 parts of tetrabutyl titanate The esterification reaction was carried out at 180 to 240 ° C. for 1 hour. Subsequently, while raising the temperature of the reaction system from 240 ° C. to 250 ° C., the pressure inside the system was gradually reduced to 500 Pa over 60 minutes. And polycondensation reaction was further performed for 65 minutes at 130 Pa or less, and crystalline polyester (A-1) was obtained. As a result of NMR analysis, the crystalline polyester (A-1) has a composition of terephthalic acid 70 mol%, adipic acid 30 mol%, ethylene glycol 50 mol%, 1,4-butanediol 50 mol%, and 200 The melt viscosity at 2500 ° C. and a shear rate of 50 sec −1 was 2500 dPa · s, the glass transition temperature was 0 ° C., the melting point was 115 ° C., the softening point was 130 ° C., and the acid value was 25 eq / 10 6 g.
＜結晶性ポリエステル（Ａ）の合成例２＞
結晶性ポリエステル樹脂（Ａ）の合成例１と同様の手法により、組成を変更させた結晶性ポリエステル（Ａ−２）、（Ａ−３）の作製を行った。
<Synthesis example 2 of crystalline polyester (A)>
Crystalline polyesters (A-2) and (A-3) with different compositions were prepared by the same method as in Synthesis Example 1 of the crystalline polyester resin (A).
＜ポリエステル（Ｂ）の合成例１〜４＞
結晶性ポリエステル樹脂（Ａ）の合成例１と同様の手法により、ポリエステル（Ｂ−１）〜（Ｂ−４）の作製を行った。
（Ａ−１）〜（Ａ−３）、（Ｂ−１）〜（Ｂ−４）の組成および諸特性の結果を表１に併せて示す。
<Synthesis Examples 1 to 4 of polyester (B)>
Polyesters (B-1) to (B-4) were prepared in the same manner as in Synthesis Example 1 of the crystalline polyester resin (A).
The results of the compositions (A-1) to (A-3) and (B-1) to (B-4) and various properties are also shown in Table 1.
＜実施例１＞
結晶性ポリエステル（Ａ−１）６５部、ポリエステル（Ｂ−１）２０部、エチレン−α−オレフィン（三井化学社製タフマーＰ０６８０）１０部、エポキシ樹脂ＹＤＣＮ７０３（東都化成社製、ノボラック型エポキシ樹脂）５部を２００℃にて二軸スクリュー式押出し機にて混練した。得られた接着剤を５０μｍの二軸延伸ＰＥＴ（ポリエチレンテレフタレート）フィルムの上に、スクリュー径４０ｍｍφの押し出し機を用いて、１７０℃の温度でＴダイを通して接着剤厚が３０μｍとなるように押し出し、接着テープを得た。この接着テープを用いて、下記の評価を行った。
<Example 1>
65 parts of crystalline polyester (A-1), 20 parts of polyester (B-1), 10 parts of ethylene-α-olefin (Tafmer P0680 manufactured by Mitsui Chemicals), epoxy resin YDCN703 (manufactured by Tohto Kasei Co., Ltd., novolak type epoxy resin) Five parts were kneaded at 200 ° C. with a twin screw extruder. The obtained adhesive was extruded onto a 50 μm biaxially stretched PET (polyethylene terephthalate) film using an extruder with a screw diameter of 40 mmφ through a T die at a temperature of 170 ° C. so that the adhesive thickness was 30 μm. An adhesive tape was obtained. The following evaluation was performed using this adhesive tape.
ＰＥＴ接着性：上記接着テープの接着剤面と、５０μｍの二軸延伸ＰＥＴフィルムを合わせ、テスター産業社製ロールラミネーターを用いて接着した。なお、ラミネートは温度１４０℃および１８０℃、圧力０．３ｍＰａ、速度０．５ｍ／ｍｉｎで行った。ラミネート後、室温にて１週間放置し、接着剤層を十分に結晶化させた後、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Ｔ型剥離接着力を測定した。 PET adhesiveness: The adhesive surface of the adhesive tape and a 50 μm biaxially stretched PET film were combined and bonded using a roll laminator manufactured by Tester Sangyo Co., Ltd. Lamination was performed at temperatures of 140 ° C. and 180 ° C., a pressure of 0.3 mPa, and a speed of 0.5 m / min. After laminating, it is allowed to stand at room temperature for 1 week to sufficiently crystallize the adhesive layer, and then a tensile test is performed in an atmosphere of 25 ° C. using RTM100 manufactured by Toyo Baldwin Co., Ltd., at a pulling speed of 50 mm / min. T-type peel adhesion was measured.
スズメッキ銅接着性：上記接着テープの接着剤面と、スズメッキ銅（厚み５０μｍ、幅１ｍｍ）を上記と同様の方法でラミネートした。ラミネート後、室温にて１週間放置し、接着剤層を十分に結晶化させた後、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１８０度剥離接着力を測定した。 Tin-plated copper adhesion: The adhesive surface of the adhesive tape and tin-plated copper (thickness 50 μm, width 1 mm) were laminated in the same manner as described above. After laminating, it is allowed to stand at room temperature for 1 week to sufficiently crystallize the adhesive layer, and then a tensile test is performed in an atmosphere of 25 ° C. using RTM100 manufactured by Toyo Baldwin Co., Ltd., at a pulling speed of 50 mm / min. The 180 degree peel adhesion was measured.
外観：上記接着テープの接着剤面と、スズメッキ銅（厚み５０μｍ、幅１ｍｍ）を上記と同様の方法でラミネートした時の外観を目視により評価を行った。樹脂のはみ出し、接着層の流動によるスズメッキ銅線のずれ、接着層厚みのばらつきが発生したものを×、発生しないものを○とした。 Appearance: The appearance when the adhesive surface of the adhesive tape and tin-plated copper (thickness 50 μm, width 1 mm) were laminated by the same method as described above was visually evaluated. The case where the protrusion of the resin, the displacement of the tin-plated copper wire due to the flow of the adhesive layer, and the variation in the thickness of the adhesive layer occurred was evaluated as x, and the case where it did not occur was evaluated as ◯.
＜実施例１〜５、比較例１〜４＞
以下同様にして実施例２〜５、比較例１〜４を作製し評価を行った。結果を表２に示した。
<Examples 1-5, Comparative Examples 1-4>
In the same manner, Examples 2 to 5 and Comparative Examples 1 to 4 were prepared and evaluated. The results are shown in Table 2.
本発明の樹脂組成物は、低温および高温でラミネートした時もＰＥＴやスズメッキ銅に対する接着性が良好であり、外観にも影響が無く加工性が良好であることがわかる。 It can be seen that the resin composition of the present invention has good adhesion to PET and tin-plated copper even when laminated at low and high temperatures, and has good workability without affecting the appearance.
それに対して、表２に見られるように、比較例１では、ポリエステル（Ｂ）が入っておらず、低温ラミネート時の接着性が悪い。一方、比較例２のポリエステル（Ｂ）単独では、接着剤強度が弱く十分な接着強度が得られない。比較例３のポリオレフィンが入っていない系では低温・高温ラミネート性に問題は無かったが、全体的に接着性が低くなる。比較例４では、ポリエステル（Ｂ）の脂肪族多価カルボン酸、脂環族多価カルボン酸の合計量が４０モル％以下であり、かつポリエーテルグリコールが共重合されていないため、低温ラミネート性の改善効果は見られなかった。 On the other hand, as seen in Table 2, in Comparative Example 1, the polyester (B) is not contained, and the adhesiveness at the time of low temperature lamination is poor. On the other hand, the polyester (B) of Comparative Example 2 alone has a weak adhesive strength and cannot provide a sufficient adhesive strength. In the system of Comparative Example 3 containing no polyolefin, there was no problem with the low temperature / high temperature laminating properties, but overall the adhesiveness was lowered. In Comparative Example 4, since the total amount of the aliphatic polyvalent carboxylic acid and the alicyclic polyvalent carboxylic acid of the polyester (B) is 40 mol% or less and the polyether glycol is not copolymerized, the low temperature laminating property The improvement effect was not seen.
本発明の樹脂組成物は、フレキシブルフラットケーブルなどの接着剤として用いた場合、プラスチックフィルムや金属に対する接着性が経時的に保持される信頼性の高い接着剤であり、さらに融点近傍の低温でも接着が可能であるため、ラインスピードアップや省エネルギーといった加工性にも優れた接着剤を提供することができる。 The resin composition of the present invention is a highly reliable adhesive that maintains its adhesiveness to plastic films and metals over time when used as an adhesive for flexible flat cables, etc., and further adheres even at low temperatures near the melting point. Therefore, it is possible to provide an adhesive excellent in processability such as line speed up and energy saving.
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| WO2007013461A1 (en) * | 2005-07-28 | 2007-02-01 | Mitsubishi Plastics, Inc. | Laminate film having adhesive for use in electrical material |
| JP2008019375A (en) * | 2006-07-14 | 2008-01-31 | Toyobo Co Ltd | Polyester resin composition and adhesive comprising the same |
| JP2009235183A (en) * | 2008-03-26 | 2009-10-15 | Unitika Ltd | Adhesive material of copolymerized polyester film and method for production thereof |
| JP2010150471A (en) * | 2008-12-26 | 2010-07-08 | Toyobo Co Ltd | Resin composition for sealing electric and electronic component, method for manufacturing electric and electronic component sealed object, and electric and electronic component sealed object |
| JP2011016947A (en) * | 2009-07-10 | 2011-01-27 | Nitto Shinko Kk | Thermoplastic resin composition and sealing material |
| WO2012020750A1 (en) * | 2010-08-10 | 2012-02-16 | 東洋紡績株式会社 | Resin composition, coated metal body using same, and adhesive |
| CN108587508A (en) * | 2018-03-29 | 2018-09-28 | 广东莱尔新材料科技股份有限公司 | A kind of hot melt adhesive film and preparation method thereof of high viscous metal power |
| CN109666434A (en) * | 2018-12-27 | 2019-04-23 | 苏州赛伍应用技术股份有限公司 | Adhesive and preparation method, glue film and preparation method and application comprising it |
| JP2019127581A (en) * | 2018-01-24 | 2019-08-01 | 東洋紡株式会社 | Hot-melt adhesive excellent in transparency and chemical resistance |
| JP2022170740A (en) * | 2016-10-21 | 2022-11-10 | 中国石油化工股▲ふん▼有限公司 | Polyester composition and preparation method therefor |
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| JP2000355091A (en) * | 1999-04-14 | 2000-12-26 | Toyobo Co Ltd | Container moldable improved polyester sheet and heat- resistant polyester molded article using the same |
| JP2002080813A (en) * | 2000-06-27 | 2002-03-22 | Tokai Rubber Ind Ltd | Adhesive composition and insulating tape for flat cable using this |
| JP2002358837A (en) * | 2001-06-01 | 2002-12-13 | Teijin Ltd | Flat cable and polyester resin component for coating |
| JP2004002592A (en) * | 2001-06-29 | 2004-01-08 | Sekisui Chem Co Ltd | Sheet |
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| JPS6143676A (en) * | 1985-08-08 | 1986-03-03 | Toray Ind Inc | Adhesive composition |
| JPS63264661A (en) * | 1986-04-15 | 1988-11-01 | Toyobo Co Ltd | Polyester resin composition |
| JPH0436342A (en) * | 1990-05-31 | 1992-02-06 | Nippon G Ii Plast Kk | Thermoplastic resin composition |
| JP2000355091A (en) * | 1999-04-14 | 2000-12-26 | Toyobo Co Ltd | Container moldable improved polyester sheet and heat- resistant polyester molded article using the same |
| JP2002080813A (en) * | 2000-06-27 | 2002-03-22 | Tokai Rubber Ind Ltd | Adhesive composition and insulating tape for flat cable using this |
| JP2002358837A (en) * | 2001-06-01 | 2002-12-13 | Teijin Ltd | Flat cable and polyester resin component for coating |
| JP2004002592A (en) * | 2001-06-29 | 2004-01-08 | Sekisui Chem Co Ltd | Sheet |
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| WO2007013461A1 (en) * | 2005-07-28 | 2007-02-01 | Mitsubishi Plastics, Inc. | Laminate film having adhesive for use in electrical material |
| JP2008019375A (en) * | 2006-07-14 | 2008-01-31 | Toyobo Co Ltd | Polyester resin composition and adhesive comprising the same |
| JP2009235183A (en) * | 2008-03-26 | 2009-10-15 | Unitika Ltd | Adhesive material of copolymerized polyester film and method for production thereof |
| JP2010150471A (en) * | 2008-12-26 | 2010-07-08 | Toyobo Co Ltd | Resin composition for sealing electric and electronic component, method for manufacturing electric and electronic component sealed object, and electric and electronic component sealed object |
| JP2011016947A (en) * | 2009-07-10 | 2011-01-27 | Nitto Shinko Kk | Thermoplastic resin composition and sealing material |
| WO2012020750A1 (en) * | 2010-08-10 | 2012-02-16 | 東洋紡績株式会社 | Resin composition, coated metal body using same, and adhesive |
| JPWO2012020750A1 (en) * | 2010-08-10 | 2013-10-28 | 東洋紡株式会社 | Resin composition, metal coating using the same, and adhesive |
| JP5786715B2 (en) * | 2010-08-10 | 2015-09-30 | 東洋紡株式会社 | Resin composition, metal coating using the same, and adhesive |
| JP7434450B2 (en) | 2016-10-21 | 2024-02-20 | 中国石油化工股▲ふん▼有限公司 | Polyester composition and method for its preparation |
| JP2022170740A (en) * | 2016-10-21 | 2022-11-10 | 中国石油化工股▲ふん▼有限公司 | Polyester composition and preparation method therefor |
| JP7151410B2 (en) | 2018-01-24 | 2022-10-12 | 東洋紡株式会社 | Hot melt adhesive with excellent transparency and chemical resistance |
| JP2019127581A (en) * | 2018-01-24 | 2019-08-01 | 東洋紡株式会社 | Hot-melt adhesive excellent in transparency and chemical resistance |
| CN108587508A (en) * | 2018-03-29 | 2018-09-28 | 广东莱尔新材料科技股份有限公司 | A kind of hot melt adhesive film and preparation method thereof of high viscous metal power |
| CN108587508B (en) * | 2018-03-29 | 2021-04-06 | 广东莱尔新材料科技股份有限公司 | High-viscosity metal hot-melt adhesive film and preparation method thereof |
| CN109666434B (en) * | 2018-12-27 | 2021-09-10 | 苏州赛伍应用技术股份有限公司 | Adhesive, preparation method, adhesive film containing adhesive, preparation method and application |
| CN109666434A (en) * | 2018-12-27 | 2019-04-23 | 苏州赛伍应用技术股份有限公司 | Adhesive and preparation method, glue film and preparation method and application comprising it |
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