JP2013199645A - Polyimide-based adhesive composition, cured product, adhesive sheet, laminate, and flexible printed board - Google Patents
Polyimide-based adhesive composition, cured product, adhesive sheet, laminate, and flexible printed board Download PDFInfo
- Publication number
- JP2013199645A JP2013199645A JP2013034797A JP2013034797A JP2013199645A JP 2013199645 A JP2013199645 A JP 2013199645A JP 2013034797 A JP2013034797 A JP 2013034797A JP 2013034797 A JP2013034797 A JP 2013034797A JP 2013199645 A JP2013199645 A JP 2013199645A
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- JP
- Japan
- Prior art keywords
- polyimide
- component
- adhesive composition
- resin
- bis
- 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
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- 239000000853 adhesive Substances 0.000 title claims abstract description 94
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 94
- 229920001721 polyimide Polymers 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000004642 Polyimide Substances 0.000 title claims abstract description 25
- -1 aromatic tetracarboxylic acids Chemical class 0.000 claims abstract description 62
- 150000004985 diamines Chemical class 0.000 claims abstract description 46
- 239000009719 polyimide resin Substances 0.000 claims abstract description 33
- 239000000539 dimer Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000003063 flame retardant Substances 0.000 claims abstract description 12
- 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 claims abstract description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 36
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 19
- 239000004643 cyanate ester Substances 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 239000012456 homogeneous solution Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 24
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 150000001412 amines Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 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 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 10
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000003949 imides Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 4
- 229910016847 F2-WS Inorganic materials 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 150000005130 benzoxazines Chemical class 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases 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
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical class NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- HFBHOAHFRNLZGN-LURJTMIESA-N (2s)-2-formamido-4-methylpentanoic acid Chemical compound CC(C)C[C@@H](C(O)=O)NC=O HFBHOAHFRNLZGN-LURJTMIESA-N 0.000 description 1
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- QBFWREVBCAJCJJ-UHFFFAOYSA-N (4-hydroxyphenyl) cyanate Chemical compound OC1=CC=C(OC#N)C=C1 QBFWREVBCAJCJJ-UHFFFAOYSA-N 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
電化製品や電子機器に用いるプリント回路基板(ビルドアップ基板)の作製に用いる接着剤としては従来、耐熱性や柔軟性、回路基板への密着性等に優れる芳香族系のポリイミド樹脂が賞用されてきた。また、芳香族系ポリイミド樹脂は、エポキシ樹脂等の熱硬化性樹脂と組み合わせることにより、半導体素子等の電子部品を搬送するための仮固定手段であるキャリアテープないしシートの接着剤としても汎用されており、電化製品や電子機器を製造するうえで欠かせない材料となっている。 Conventionally, aromatic polyimide resins with excellent heat resistance, flexibility, adhesion to circuit boards, etc. have been used as adhesives for the production of printed circuit boards (build-up boards) used in electrical appliances and electronic devices. I came. Aromatic polyimide resins are also widely used as adhesives for carrier tapes or sheets, which are temporary fixing means for transporting electronic components such as semiconductor elements, by combining with thermosetting resins such as epoxy resins. Therefore, it is an indispensable material for manufacturing electrical appliances and electronic devices.
ところで芳香族系ポリイミド樹脂の多くは有機溶剤に溶解し難く、ワニスとしての利用が困難とされているため、古くはその前駆体(ポリアミック酸)のワニスを回路基板に塗工した後、加熱下に閉環反応を行うことによって、基板上にポリイミド樹脂の皮膜を形成していた。しかしこの方法では基板自体が熱劣化しかねないため、有機溶剤への溶解性を高めた芳香族系ポリイミド樹脂として、例えばジアミン成分としてジアミノポリシロキサンを使用したものが種々提案されている。 By the way, most of the aromatic polyimide resins are difficult to dissolve in organic solvents and are difficult to use as varnishes. In the old days, the precursor (polyamic acid) varnish was applied to a circuit board and then heated. In this way, a polyimide resin film was formed on the substrate. However, since the substrate itself may be thermally deteriorated by this method, various aromatic polyimide resins having improved solubility in organic solvents, for example, using diaminopolysiloxane as a diamine component have been proposed.
例えば特許文献1には、ビフェニルテトラカルボン酸、ジアミノポリシロキサンおよびジアミノ安息香酸を反応させて得られる芳香族系ポリイミドシロキサンが開示されており、このものは有機溶剤に対して高い溶解性を有し、エポキシ樹脂との相溶性に優れ、耐熱性や柔軟性等も良好であるとされる。 For example, Patent Document 1 discloses an aromatic polyimidesiloxane obtained by reacting biphenyltetracarboxylic acid, diaminopolysiloxane and diaminobenzoic acid, which has high solubility in organic solvents. It is said that it is excellent in compatibility with the epoxy resin and has good heat resistance and flexibility.
また、特許文献2には、オキシジフタル酸二無水物(ビフェニルテトラカルボン酸類二無水物)、ビスアミノプロピルポリジメチルシロキサンおよびビスアミノフェノキシベンゼンを所定の割合で反応させて得られるガラス転移温度が350℃以下の芳香族系ポリイミドシロキサンが開示されており、半導体実装用の接着テープとして有用であるとされる。 Patent Document 2 discloses that a glass transition temperature obtained by reacting oxydiphthalic dianhydride (biphenyltetracarboxylic dianhydride), bisaminopropylpolydimethylsiloxane and bisaminophenoxybenzene at a predetermined ratio is 350 ° C. The following aromatic polyimide siloxane is disclosed and is useful as an adhesive tape for semiconductor mounting.
また、特許文献3には、各種テトラカルボン酸及びジアミンより得られる、有機溶剤に可溶であって且つ所定の粘度を有する芳香族系ポリイミドシロキサンと、エポキシ樹脂とからなる組成物を塗工したフレキシブル配線基板が開示されており、保護膜の耐熱性や密着性、基板の非カール性等が良好であるとされる。 In Patent Document 3, a composition composed of an aromatic polyimidesiloxane obtained from various tetracarboxylic acids and diamines, soluble in an organic solvent and having a predetermined viscosity, and an epoxy resin was applied. A flexible wiring board is disclosed, and the heat resistance and adhesion of the protective film, the non-curling property of the board, and the like are considered good.
また、特許文献4には、ビフェニルテトラカルボン酸、ジアミノポリシロキサンおよび芳香族ジアミンを反応させて得られる芳香族系ポリイミドシロキサンとエポキシ化合物より得られる組成物を基材に積層してなるTAB(Tape Automated Bonding)用キャリアテープが開示されており、耐熱性や加工性、接着性等に優れるとされる。 Further, Patent Document 4 discloses a TAB (Tape formed by laminating a composition obtained from an aromatic polyimidesiloxane obtained by reacting biphenyltetracarboxylic acid, diaminopolysiloxane and an aromatic diamine and an epoxy compound on a base material. A carrier tape for (Automated Bonding) is disclosed, and it is said to be excellent in heat resistance, workability, adhesiveness and the like.
しかしながら、それら芳香族系ポリイミドシロキサンを用いた接着剤組成物は、高温時の接着性ないし粘着性(以下、耐熱接着性という)が必ずしも十分ではない。また、それらをキャリアテープやシートの接着剤層として使用した場合には、糊残りが発生し易い問題もある。糊残りとは、キャリアテープないしシートの接着面より電子部品を剥離した際、部品表面に接着剤層の一部が付着するトラブルをいい、製品の歩留まりや生産性を低下させる要因となる。 However, an adhesive composition using these aromatic polyimide siloxanes does not necessarily have sufficient adhesiveness or tackiness (hereinafter referred to as heat resistant adhesiveness) at high temperatures. Further, when they are used as an adhesive layer of a carrier tape or a sheet, there is a problem that adhesive residue is likely to occur. The adhesive residue refers to a trouble that a part of the adhesive layer adheres to the surface of the component when the electronic component is peeled off from the adhesive surface of the carrier tape or sheet, and becomes a factor that decreases the yield and productivity of the product.
一方、キャリアテープないしシートの接着剤としては、芳香族系ポリイミドシロキサンに代えてアクリロニトリルブタジエンゴム(NBR)を使用したものも知られているが(特許文献5を参照)、耐熱接着性が不十分であり、また接着剤層のタックが強い等の問題もある。 On the other hand, as an adhesive for a carrier tape or a sheet, an adhesive using acrylonitrile butadiene rubber (NBR) instead of aromatic polyimide siloxane is known (see Patent Document 5), but the heat resistant adhesiveness is insufficient. There are also problems such as strong tackiness of the adhesive layer.
本発明は、均質な有機溶剤の溶液(樹脂ワニス)として利用でき、無機基材および有機基材に対する初期接着性ならびに耐熱接着性に優れ、硬化物状態で低タックであり、かつ糊残りも少ない新規なポリイミド系接着剤組成物を提供することを主たる課題とする。 INDUSTRIAL APPLICABILITY The present invention can be used as a homogeneous organic solvent solution (resin varnish), is excellent in initial adhesion and heat-resistant adhesion to inorganic and organic substrates, has low tack in a cured product, and has little adhesive residue The main object is to provide a novel polyimide-based adhesive composition.
本発明者は鋭意検討の結果、ジアミン成分として所定量のダイマージアミンを用いたポリイミド樹脂を用いることによって前記課題を解決可能な接着剤組成物が得られることを見出した。 As a result of intensive studies, the present inventors have found that an adhesive composition capable of solving the above problems can be obtained by using a polyimide resin using a predetermined amount of dimer diamine as a diamine component.
すなわち本発明は、芳香族テトラカルボン酸類(a1)およびダイマージアミンを30モル%以上含むジアミン類(a2)を反応させてなるポリイミド樹脂(A)、熱硬化性樹脂(B)、難燃剤(C)、ならびに有機溶剤(D)を含むポリイミド系接着剤組成物、ならびに、芳香族テトラカルボン酸類(a1)およびダイマージアミンを30モル%以上含むジアミン類(a2)を反応させてなるポリイミド樹脂(A)を更に(a2)成分で鎖伸長してなるポリイミド樹脂(A’)、熱硬化性樹脂(B)、難燃剤(C)、ならびに有機溶剤(D)を含むポリイミド系接着剤組成物、に関する。 That is, the present invention relates to a polyimide resin (A), a thermosetting resin (B), a flame retardant (C) obtained by reacting a diamine (a2) containing 30 mol% or more of an aromatic tetracarboxylic acid (a1) and dimer diamine. ), And a polyimide-based adhesive composition containing an organic solvent (D), and a polyimide resin (A2) obtained by reacting a diamine (a2) containing 30 mol% or more of aromatic tetracarboxylic acids (a1) and dimer diamine (A2) And (a2) a polyimide-based adhesive composition containing a polyimide resin (A '), a thermosetting resin (B), a flame retardant (C), and an organic solvent (D). .
また本発明は、当該接着剤組成物を硬化させることにより得られる硬化物、ならびに当該接着剤組成物をシート基材に塗布し乾燥させることによって得られる接着シート、当該接着シートの接着面に更にシート基材を熱圧着させることにより得られる積層体、当該積層体を更に加熱させることによって得られる積層体、および当該積層体を用いてなるフレキシブルプリント基板、に関する。 The present invention further provides a cured product obtained by curing the adhesive composition, an adhesive sheet obtained by applying the adhesive composition to a sheet substrate and drying, and an adhesive surface of the adhesive sheet. The present invention relates to a laminate obtained by thermocompression bonding a sheet base material, a laminate obtained by further heating the laminate, and a flexible printed board using the laminate.
本発明の接着剤組成物は、有機溶剤の均質な溶液(樹脂ワニス)として利用可能であり、無機基材および有機基材の双方に対する初期接着性のみならず、耐熱接着性も良好である。 また、当該接着剤組成物より得られる硬化物(接着剤層)は低タックであり、加熱時に発泡が生じず、かつ糊残りを生じ難いため、プリント回路基板(ビルドアップ基板、フレキシブルプリント基板等)やフレキシブルプリント基板用銅張り板の製造に用いる接着剤としてのみならず、TABテープやCOFテープ等のキャリアテープ、あるいはキャリアシートの接着剤、半導体層間材料、コーティング剤、レジストインキ、導電ペースト等の電気絶縁材料等としても有用である。ャリアテープ、あるいはキャリアシートの接着剤、半導体層間材料等としても有用である。 The adhesive composition of the present invention can be used as a homogeneous solution (resin varnish) of an organic solvent, and has good heat adhesion as well as initial adhesion to both inorganic and organic substrates. In addition, since a cured product (adhesive layer) obtained from the adhesive composition has a low tack, foaming does not occur during heating, and adhesive residue is hardly generated, printed circuit boards (build-up boards, flexible printed boards, etc.) ) And adhesives used in the manufacture of copper-clad boards for flexible printed circuit boards, as well as carrier tapes such as TAB tapes and COF tapes, carrier sheet adhesives, semiconductor interlayer materials, coating agents, resist inks, conductive pastes, etc. It is also useful as an electrical insulating material. It is also useful as a carrier tape, carrier sheet adhesive, semiconductor interlayer material, or the like.
<ポリイミド系接着剤組成物>
本発明のポリイミド系接着剤組成物は、芳香族テトラカルボン酸類(a1)(以下、(a1)成分という。)およびダイマージアミンを30モル%以上含むジアミン類(a2)(以下、(a2)成分という。)を反応させてなるポリイミド樹脂(A)(以下、(A)成分という。)、熱硬化性樹脂(B)(以下、(B)成分という。)、難燃剤(C)(以下、(C)成分という。)、ならびに有機溶剤(D)(以下、(D)成分という。)を含むポリイミド系接着剤組成物、ならびに、前記(A)成分を更に前記(a2)成分で鎖伸長してなるポリイミド樹脂(A’)(以下、(A’)成分という。)、(B)成分、(C)成分ならびに(D)成分を含むポリイミド系接着剤組成物、に関する。
<Polyimide-based adhesive composition>
The polyimide-based adhesive composition of the present invention includes diamines (a2) (hereinafter referred to as (a2) component) containing 30 mol% or more of aromatic tetracarboxylic acids (a1) (hereinafter referred to as (a1) component) and dimer diamine. Polyimide resin (A) (hereinafter referred to as “component (A)”), thermosetting resin (B) (hereinafter referred to as “component (B)”), flame retardant (C) (hereinafter referred to as “component”). (C) component)) and an organic solvent (D) (hereinafter referred to as component (D)) polyimide adhesive composition, and the component (A) is further chain-extended with the component (a2). The polyimide resin (A ') (hereinafter referred to as (A') component), the (B) component, the (C) component and the (D) component-based polyimide adhesive composition.
(a1)成分としては、ポリイミドの原料として公知のものを使用できる。具体的には、例えばピロメリット酸二無水物や下記一般式(1)で表される化合物が挙げられる。 As the component (a1), a known material for polyimide can be used. Specific examples include pyromellitic dianhydride and compounds represented by the following general formula (1).
式(1)で表される化合物としては、例えば、4,4’−オキシジフタル酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ジフェニルエーテルテトラカルボン酸二無水物、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物、1,2,3,4−ベンゼンテトラカルボン酸無水物、1,4,5,8−ナフタレンテトラカルボン酸無水物、2,3,6,7−ナフタレンテトラカルボン酸無水物、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,2’,3,3’−ビフェニルテトラカルボン酸二無水物、2,3,3’,4’−ビフェニルテトラカルボン酸二無水物、2,3,3’,4’−ベンゾフェノンテトラカルボン酸二無水物、2,3,3’,4’−ジフェニルエーテルテトラカルボン酸二無水物、2,3,3’,4’−ジフェニルスルホンテトラカルボン酸二無水物、2,2−ビス(3,3’,4,4’−テトラカルボキシフェニル)テトラフルオロプロパン二無水物、2,2’−ビス(3,4−ジカルボキシフェノキシフェニル)スルホン二無水物、2,2−ビス(2,3−ジカルボキシフェニル)プロパン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物、シクロペンタンテトラカルボン酸無水物、ブタン−1,2,3,4−テトラカルボン酸、2,3,5−トリカルボキシシクロペンチル酢酸無水物、4,4’−[プロパン−2,2−ジイルビス(1,4−フェニレンオキシ)]ジフタル酸二無水物などが挙げられ、これらは2種以上組み合わせてもよい。 Examples of the compound represented by the formula (1) include 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4, 4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,4,5 , 8-Naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3 3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3 , 3 ', 4'-Diff Nyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,3 ′, 4,4′-tetracarboxyphenyl) tetrafluoro Propane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, cyclopentanetetracarboxylic anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic anhydride, 4 , 4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride, and the like may be used in combination.
(a2)成分をなすダイマージアミンは、例えば特開平9−12712号公報に記載されているように、オレイン酸等の不飽和脂肪酸の二量体であるダイマー酸から誘導される化合物である。本発明では、公知のダイマージアミンを特に制限なく使用できるが、例えば下記一般式(2)および/または一般式(2’)で表されるものが好ましい。 The dimer diamine constituting the component (a2) is a compound derived from dimer acid which is a dimer of unsaturated fatty acid such as oleic acid, as described in, for example, JP-A-9-12712. In the present invention, known dimer diamines can be used without any particular limitation. For example, those represented by the following general formula (2) and / or general formula (2 ') are preferable.
ダイマージアミンとしては、本発明に係る接着剤組成物の有機溶剤溶解性や初期接着性、耐熱接着性、低タック性、低糊残り性等の観点より、前記一般式(2’)で表されるものが好ましく、特に下記構造のものが好ましい。 The dimer diamine is represented by the general formula (2 ′) from the viewpoint of the organic solvent solubility, initial adhesiveness, heat resistant adhesiveness, low tackiness, low adhesive residue, etc. of the adhesive composition according to the present invention. The thing of the following structure is especially preferable.
ダイマージアミンの市販品としては、例えばバーサミン551(BASFジャパン(株)製)、バーサミン552(コグニクスジャパン(株)製;バーサミン551の水添物)、PRIAMINE1075、PRIAMINE1074(いずれもクローダジャパン(株)製)等が挙げられる。 Examples of commercially available dimeramines include Versamine 551 (manufactured by BASF Japan), Versamine 552 (manufactured by Cognics Japan, Inc .; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all of which are Croda Japan). Manufactured) and the like.
(a2)成分におけるダイマージアミンの含有量は、耐熱接着性や低タック性、低糊残り性等の観点より、(a2)成分の全体100モル%を基準として、通常30モル%以上、好ましくは45〜100モル%である。 The content of dimerized amine in the component (a2) is usually 30 mol% or more based on the total 100 mol% of the component (a2) from the viewpoint of heat-resistant adhesiveness, low tackiness, low adhesive residue, etc., preferably It is 45-100 mol%.
また、(a2)成分には必要に応じて他のジアミンを通常70モル%未満、好ましくは55〜0モル%の範囲で含めることができる。 In addition, the component (a2) may contain other diamines as necessary in an amount of usually less than 70 mol%, preferably 55 to 0 mol%.
当該他のジアミンとしては、各種公知のものを特に制限なく使用することができる。具体的には、例えばジアミノポリシロキサンが挙げられ、なかでも下記一般式(3)で表されるものが好ましい。 As the other diamines, various known diamines can be used without particular limitation. Specifically, for example, diaminopolysiloxane is exemplified, and among them, one represented by the following general formula (3) is preferable.
一般式(3)で表されるジアミノポリシロキサンとしては、例えば、α,ω−ビス(2−アミノエチル)ポリジメチルシロキサン、α,ω−ビス(3−アミノプロピル)ポリジメチルシロキサン、α,ω−ビス(4−アミノブチル)ポリジメチルシロキサン、α,ω−ビス(5−アミノペンチル)ポリジメチルシロキサン、α,ω−ビス[3−(2−アミノフェニル)プロピル]ポリジメチルシロキサン、α,ω−ビス[3−(4−アミノフェニル)プロピル]ポリジメチルシロキサンなどが挙げられ、これらは2種以上組み合わせてもよい。 Examples of the diaminopolysiloxane represented by the general formula (3) include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω. -Bis (4-aminobutyl) polydimethylsiloxane, α, ω-bis (5-aminopentyl) polydimethylsiloxane, α, ω-bis [3- (2-aminophenyl) propyl] polydimethylsiloxane, α, ω -Bis [3- (4-aminophenyl) propyl] polydimethylsiloxane and the like may be mentioned, and these may be used in combination of two or more.
当該他のジアミンとしては、他にも例えば、2,2−ビス[4−(3−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン等のビスアミノフェノキシフェニルプロパン類;
3,3’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルエーテル等のジアミノジフェニルエーテル類;p−フェニレンジアミン、m−フェニレンジアミン等のフェニレンジアミン類;3,3’−ジアミノジフェニルスルフィド、3,4’−ジアミノジフェニルスルフィド、4,4’−ジアミノジフェニルスルフィド等のジアミノジフェニルスルフィド類;3,3’−ジアミノジフェニルスルホン、3,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン等のジアミノジフェニルスルホン類;3,3’−ジアミノベンゾフェノン、4,4’−ジアミノベンゾフェノン、3,4’−ジアミノベンゾフェノン等のジアミノベンゾフェノン類;3,3’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、3,4’−ジアミノジフェニルメタン等のジアミノジフェニルメタン類;2,2−ジ(3−アミノフェニル)プロパン、2,2−ジ(4−アミノフェニル)プロパン、2−(3−アミノフェニル)−2−(4−アミノフェニル)プロパン等のジアミノフェニルプロパン類;2,2−ジ(3−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ジ(4−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン、2−(3−アミノフェニル)−2−(4−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン等のジアミノフェニルヘキサフルオロプロパン類;
1,1−ジ(3−アミノフェニル)−1−フェニルエタン、1,1−ジ(4−アミノフェニル)−1−フェニルエタン、1−(3−アミノフェニル)−1−(4−アミノフェニル)−1−フェニルエタン等のジアミノフェニルフェニルエタン類;1,3−ビス(3−アミノフェノキシ)ベンゼン、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,4−ビス(3−アミノフェノキシ)ベンゼン、1,4−ビス(4−アミノフェノキシ)ベンゼン等のビスアミノフェノキシベンゼン類;1,3−ビス(3−アミノベンゾイル)ベンゼン、1,3−ビス(4−アミノベンゾイル)ベンゼン、1,4−ビス(3−アミノベンゾイル)ベンゼン、1,4−ビス(4−アミノベンゾイル)ベンゼン等のビスアミノベンゾイルベンゼン類;1,3−ビス(3−アミノ−α,α−ジメチルベンジル)ベンゼン、1,3−ビス(4−アミノ−α,α−ジメチルベンジル)ベンゼン、1,4−ビス(3−アミノ−α,α−ジメチルベンジル)ベンゼン、1,4−ビス(4−アミノ−α,α−ジメチルベンジル)ベンゼン等のビスアミノジメチルベンゼン類;1,3−ビス(3−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン、1,3−ビス(4−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン、1,4−ビス(3−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン、1,4−ビス(4−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン等のビスアミノジトリフルオロメチルベンジルベンゼン類;2,6−ビス(3−アミノフェノキシ)ベンゾニトリル、2,6−ビス(3−アミノフェノキシ)ピリジン、4,4’−ビス(3−アミノフェノキシ)ビフェニル、4,4’−ビス(4−アミノフェノキシ)ビフェニル等のアミノフェノキシビフェニル類;ビス[4−(3−アミノフェノキシ)フェニル]ケトン、ビス[4−(4−アミノフェノキシ)フェニル]ケトン等のアミノフェノキシフェニルケトン類;ビス[4−(3−アミノフェノキシ)フェニル]スルフィド、ビス[4−(4−アミノフェノキシ)フェニル]スルフィド等のアミノフェノキシフェニルスルフィド類;ビス[4−(3−アミノフェノキシ)フェニル]スルホン、ビス[4−(4−アミノフェノキシ)フェニル]スルホン等のアミノフェノキシフェニルスルホン類;ビス[4−(3−アミノフェノキシ)フェニル]エーテル、ビス[4−(4−アミノフェノキシ)フェニル]エーテル等のアミノフェノキシフェニルエーテル類;2,2−ビス[4−(3−アミノフェノキシ)フェニル]プロパン、2,2−ビス[3−(3−アミノフェノキシ)フェニル]−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]−1,1,1,3,3,3−ヘキサフルオロプロパン等のアミノフェノキシフェニルプロパン類;その他、1,3−ビス[4−(3−アミノフェノキシ)ベンゾイル]ベンゼン、1,3−ビス[4−(4−アミノフェノキシ)ベンゾイル]ベンゼン、1,4−ビス[4−(3−アミノフェノキシ)ベンゾイル]ベンゼン、1,4−ビス[4−(4−アミノフェノキシ)ベンゾイル]ベンゼン、1,3−ビス[4−(3−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,3−ビス[4−(4−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(3−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(4−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、4,4’−ビス[4−(4−アミノフェノキシ)ベンゾイル]ジフェニルエーテル、4,4’−ビス[4−(4−アミノ−α,α−ジメチルベンジル)フェノキシ]ベンゾフェノン、4,4’−ビス[4−(4−アミノ−α,α−ジメチルベンジル)フェノキシ]ジフェニルスルホン、4,4’−ビス[4−(4−アミノフェノキシ)フェノキシ]ジフェニルスルホン、3,3’−ジアミノ−4,4’−ジフェノキシベンゾフェノン、3,3’−ジアミノ−4,4’−ジビフェノキシベンゾフェノン、3,3’−ジアミノ−4−フェノキシベンゾフェノン、3,3’−ジアミノ−4−ビフェノキシベンゾフェノン、6,6’−ビス(3−アミノフェノキシ)3,3,3,’3,’−テトラメチル−1,1’−スピロビインダン6,6’−ビス(4−アミノフェノキシ)3,3,3,’3,’−テトラメチル−1,1’−スピロビインダン、1,3−ビス(3−アミノプロピル)テトラメチルジシロキサン、1,3−ビス(4−アミノブチル)テトラメチルジシロキサン、ビス(アミノメチル)エーテル、ビス(2−アミノエチル)エーテル、ビス(3−アミノプロピル)エーテル、ビス(2−アミノメトキシ)エチル]エ−テル、ビス[2−(2−アミノエトキシ)エチル]エーテル、ビス[2−(3−アミノプロトキシ)エチル]エーテル、1,2−ビス(アミノメトキシ)エタン、1,2−ビス(2−アミノエトキシ)エタン、1,2−ビス[2−(アミノメトキシ)エトキシ]エタン、1,2−ビス[2−(2−アミノエトキシ)エトキシ]エタン、エチレングリコ−ルビス(3−アミノプロピル)エーテル、ジエチレングリコ−ルビス(3−アミノプロピル)エーテル、トリエチレングリコ−ルビス(3−アミノプロピル)エーテル、エチレンジアミン、1,3−ジアミノプロパン、1,4−ジアミノブタン、1,5−ジアミノペンタン、1,6−ジアミノヘキサン、1,7−ジアミノヘプタン、1,8−ジアミノオクタン、1,9−ジアミノノナン、1,10−ジアミノデカン、1,11−ジアミノウンデカン、1,12−ジアミノドデカン、1,2−ジアミノシクロヘキサン、1,3−ジアミノシクロヘキサン、1,4−ジアミノシクロヘキサン、1,2−ジ(2−アミノエチル)シクロヘキサン、1,3−ジ(2−アミノエチル)シクロヘキサン、1,4−ジ(2−アミノエチル)シクロヘキサン、ビス(4−アミノシクロへキシル)メタン、2,6−ビス(アミノメチル)ビシクロ[2.2.1]ヘプタン、2,5−ビス(アミノメチル)ビシクロ[2.2.1]ヘプタン、1,3−ビス(アミノメチル)シクロヘキサン等が挙げられる。
Other examples of the diamine include bis such as 2,2-bis [4- (3-aminophenoxy) phenyl] propane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane. Aminophenoxyphenylpropanes;
Diaminodiphenyl ethers such as 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3′-diamino Diamino diphenyl sulfides such as diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide; 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'- Diaminodiphenyl sulfones such as diaminodiphenyl sulfone; diaminobenzophenones such as 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone; 3,3′-diaminodiphenylmethane, Diaminodiphenylmethanes such as 4,4′-diaminodiphenylmethane and 3,4′-diaminodiphenylmethane; 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- ( Diaminophenylpropanes such as 3-aminophenyl) -2- (4-aminophenyl) propane; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane; 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1, Diaminophenyl hexafluoropropanes such as 1,3,3,3-hexafluoropropane;
1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) ) Diaminophenylphenylethanes such as 1-phenylethane; 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) ) Bisaminophenoxybenzenes such as benzene and 1,4-bis (4-aminophenoxy) benzene; 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1 Bisaminobenzoylbenzenes such as 1,4-bis (3-aminobenzoyl) benzene and 1,4-bis (4-aminobenzoyl) benzene; (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) Bisaminodimethylbenzenes such as benzene and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene; 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1 , 3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino) -Α, α-ditrifluoromethylbenzyl) benzene and other bisaminoditrifluoromethylbenzylbenzenes; 2,6-bis (3-aminophenoxy) benzonitrile, 2,6- Aminophenoxybiphenyls such as bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl; bis [4- (3- Aminophenoxyphenyl ketones such as aminophenoxy) phenyl] ketone and bis [4- (4-aminophenoxy) phenyl] ketone; bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-amino Aminophenoxyphenyl sulfides such as phenoxy) phenyl] sulfide; aminophenoxyphenylsulfones such as bis [4- (3-aminophenoxy) phenyl] sulfone and bis [4- (4-aminophenoxy) phenyl] sulfone; bis [ 4- (3-aminophenoxy) phenyl] ether, bis [ Aminophenoxyphenyl ethers such as-(4-aminophenoxy) phenyl] ether; 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Aminophenoxyphenylpropanes such as propane; 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4 -Bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [ 4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4′-bis [4- ( 4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybe Zophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6,6′-bis ( 3-Aminophenoxy) 3,3,3,3,3 ','-tetramethyl-1,1'-spirobiindane 6,6'-bis (4-aminophenoxy) 3,3,3,3,3'-tetramethyl -1,1'-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, bis (aminomethyl) ether, bis (2 -Aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether Ter, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- ( Aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene Glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundeca 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2 -Aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2 , 5-bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane and the like.
(A)成分は、各種公知の方法により製造できる。例えば、先ず、(a1)成分と(a2)成分を、通常60〜120℃程度、好ましくは80〜100℃の温度において、通常0.1〜2時間程度、好ましくは0.1〜0.5時間重付加反応させる。次いで、得られた重付加物を更に80〜250℃程度、好ましくは100〜200℃の温度において、0.5〜50時間程度、好ましくは1〜20時間イミド化反応、即ち脱水閉環反応させることにより、目的とする(A)成分が得られる。 The component (A) can be produced by various known methods. For example, first, the (a1) component and the (a2) component are usually about 60 to 120 ° C., preferably about 80 to 100 ° C., usually about 0.1 to 2 hours, preferably 0.1 to 0.5. Time polyaddition reaction. Next, the obtained polyaddition product is further subjected to an imidization reaction, that is, a dehydration ring closure reaction, at a temperature of about 80 to 250 ° C., preferably 100 to 200 ° C., for about 0.5 to 50 hours, preferably 1 to 20 hours. Thus, the target component (A) can be obtained.
なお、イミド化反応においては、各種公知の反応触媒、脱水剤、および後述する有機溶剤を使用できる。反応触媒としては、トリエチルアミン等の脂肪族第3級アミン類、ジメチルアニリン等の芳香族第3級アミン類、ピリジン、ピコリン、イソキノリン等の複素環式第3級アミン類等が挙げられる。また、脱水剤としては、例えば無水酢酸等の脂肪族酸無水物や無水安息香酸等の芳香族酸無水物などが挙げられる。 In the imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents described later can be used. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride.
(A)成分のイミド閉環率は特に限定されないが、通常70%以上、好ましくは85〜100%である。ここに「イミド閉環率」とは、(A)成分における環状イミド結合の含有量を意味し、例えばNMRやIR分析等の各種分光手段により決定できる。そして、(A)成分のイミド閉環率を70%以上とすることにより、本発明の接着剤組成物の初期接着性や耐熱接着性がいっそう良好となり、また、本発明の硬化物に、前記イミド化反応において生じた水分に由来する発泡が生じ難くなる。 The imide ring closure rate of the component (A) is not particularly limited, but is usually 70% or more, preferably 85 to 100%. Here, the “imide ring closure rate” means the content of the cyclic imide bond in the component (A), and can be determined by various spectroscopic means such as NMR and IR analysis. And by making the imide cyclization rate of (A) component 70% or more, the initial adhesiveness and heat-resistant adhesiveness of the adhesive composition of the present invention are further improved, and the cured product of the present invention contains the imide. Foam derived from moisture generated in the chemical reaction is less likely to occur.
(a1)成分と(a2)成分の使用量は特に限定されないが、(A)成分の(D)成分への溶解性や、初期接着性および耐熱接着性等の観点より、〔(a1)成分の使用モル数/(a2)成分の使用モル数〕が通常0.6〜1.4程度、好ましくは0.8〜1.2となる範囲である。 Although the usage-amount of (a1) component and (a2) component is not specifically limited, From viewpoints, such as the solubility to (D) component of (A) component, initial stage adhesiveness, and heat-resistant adhesiveness, [(a1) component The number of moles used / the number of moles of component (a2)] is generally in the range of about 0.6 to 1.4, preferably 0.8 to 1.2.
(A’)成分は、前記方法で得た(A)成分を更に前記(a2)成分で鎖伸長してなるポリイミド樹脂である。 The component (A ′) is a polyimide resin obtained by further chain-extending the component (A) obtained by the above method with the component (a2).
(A)成分と(a2)成分の反応条件は特に限定されないが、通常は60℃以下、好ましくは50℃以下の温度において、1〜6時間程度、好ましくは1〜3時間重付加反応させればよい。また、反応の際には後述の有機溶剤を用いることもできる。 The reaction conditions for the component (A) and the component (a2) are not particularly limited, but are usually polyaddition reaction at a temperature of 60 ° C. or lower, preferably 50 ° C. or lower, for about 1 to 6 hours, preferably 1 to 3 hours. That's fine. Moreover, the below-mentioned organic solvent can also be used in the case of reaction.
鎖伸長剤としての(a2)成分の使用量は特に制限されないが、本発明の効果を達成し易くする目的において、通常、〔(A)成分中の残存カルボキシル基のモル数〕/〔鎖伸長剤としての(a2)成分のモル数〕が0.6/1〜1.4/1程度となる範囲である。 The amount of the component (a2) used as the chain extender is not particularly limited. However, for the purpose of easily achieving the effect of the present invention, it is usually [number of moles of residual carboxyl groups in component (A)] / [chain extension]. The number of moles of the component (a2) as an agent] is in the range of about 0.6 / 1 to 1.4 / 1.
なお、(A’)成分におけるイミド閉環率も特に限定されず、通常70%以上、好ましくは85〜100%である。 The imide ring closure rate in the component (A ′) is not particularly limited, and is usually 70% or more, preferably 85 to 100%.
(B)成分は、本発明のポリイミド系接着剤組成物の硬化剤であり、各種公知のものを特に制限なく使用することができる。具体的には、例えば、エポキシ樹脂、ベンゾオキサジン樹脂、ビスマレイミド樹脂及びシアネートエステル樹脂からなる群より選ばれる少なくとも1種が好ましい。 (B) A component is a hardening | curing agent of the polyimide-type adhesive composition of this invention, and can use various well-known things without a restriction | limiting in particular. Specifically, for example, at least one selected from the group consisting of epoxy resins, benzoxazine resins, bismaleimide resins, and cyanate ester resins is preferable.
前記エポキシ樹脂としては、例えばフェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、水添ビスフェノールF型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン型エポキシ樹脂、トリフェノールフェノ−ルメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン骨格含有エポキシ樹脂、ナフタレン骨格含有エポキシ樹脂、アリールアルキレン型エポキシ樹脂、これらエポキシ樹脂をダイマー酸で変性してなる変性エポキシ樹脂、ダイマー酸ジグリシジルエステル等が挙げられ、当該接着剤組成物の透明性や耐熱性等の観点よりビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂および脂環式エポキシ樹脂からなる群より選ばれる少なくとも1種が好ましい。また、市販品としては例えば、三菱化学(株)製の「jER828」や「jER834」、「jER807」、新日鐵化学(株)製の「ST−3000」、ダイセル化学工業(株)製の「セロキサイド2021P」、新日鐵化学(株)製の「YD−172−X75」等が挙げられ、これらは2種以上を組み合わせてもよい。 Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type. Epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, triphenolphenol methane type epoxy resin, alkyl modified Triphenolmethane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, arylalkylene type epoxy resin, Modified epoxy resins obtained by modifying these epoxy resins with dimer acid, diglycidyl esters of dimer acid, and the like. From the viewpoints of transparency and heat resistance of the adhesive composition, bisphenol A type epoxy resin, bisphenol F type At least one selected from the group consisting of epoxy resins, hydrogenated bisphenol A type epoxy resins and alicyclic epoxy resins is preferred. Examples of commercially available products include “jER828”, “jER834”, “jER807” manufactured by Mitsubishi Chemical Corporation, “ST-3000” manufactured by Nippon Steel Chemical Co., Ltd., and manufactured by Daicel Chemical Industries, Ltd. “Celoxide 2021P”, “YD-172-X75” manufactured by Nippon Steel Chemical Co., Ltd. and the like may be mentioned, and these may be used in combination of two or more.
なお、熱硬化性樹脂としてエポキシ樹脂を用いる場合には、各種公知のエポキシ樹脂用硬化剤を併用できる。具体的には、例えば、無水コハク酸、無水フタル酸、無水マレイン酸、無水トリメリット酸、無水ピロメリット酸、ヘキサヒドロ無水フタル酸、3−メチル−ヘキサヒドロ無水フタル酸、4−メチル−ヘキサヒドロ無水フタル酸、あるいは4−メチル−ヘキサヒドロ無水フタル酸とヘキサヒドロ無水フタル酸との混合物、テトラヒドロ無水フタル酸、メチル−テトラヒドロ無水フタル酸、無水ナジック酸、無水メチルナジック酸、ノルボルナン−2,3−ジカルボン酸無水物、メチルノルボルナン−2,3−ジカルボン酸無水物、メチルシクロヘキセンジカルボン酸無水物、3−ドデセニル無水コハク酸、オクテニルコハク酸無水物等の酸無水物系硬化剤;ジシアンジアミド(DICY)、芳香族ジアミン(商品名「LonzacureM−DEA」、「LonzacureM−DETDA」等。いずれもロンザジャパン(株)製。)、脂肪族アミン等のアミン系硬化剤;フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールA型ノボラック樹脂、トリアジン変性フェノールノボラック樹脂、フェノール性水酸基含有ホスファゼン(大塚化学(株)製の商品名「SPH−100」等)等のフェノール系硬化剤、環状ホスファゼン系化合物等が挙げられる。これらの中でもフェノール系硬化剤、特にフェノール性水酸基含有ホスファゼン系硬化剤は、本発明に係る硬化物及び積層体に難燃性を付与しやすくなるため好ましい。これら硬化剤の使用量は特に制限されないが、通常、本発明の接着剤組成物の固形分を100重量%とした場合において0.1〜120重量%程度であり、好ましくは10〜40重量%程度である。 In addition, when using an epoxy resin as a thermosetting resin, various well-known hardening | curing agents for epoxy resins can be used together. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride Acid, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride Acid anhydride-based curing agents such as methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine ( Product name "Lonacure M-" EA "," Lonzacure M-DETDA "etc., all manufactured by Lonza Japan Co., Ltd.), amine-based curing agents such as aliphatic amines; phenol novolac resins, cresol novolac resins, bisphenol A type novolac resins, triazine modified phenol novolac resins And phenolic curing agents such as phenolic hydroxyl group-containing phosphazenes (trade name “SPH-100” manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene compounds, and the like. Among these, a phenolic curing agent, particularly a phenolic hydroxyl group-containing phosphazene-based curing agent is preferable because it easily imparts flame retardancy to the cured product and the laminate according to the present invention. The amount of these curing agents used is not particularly limited, but is usually about 0.1 to 120% by weight, preferably 10 to 40% by weight when the solid content of the adhesive composition of the present invention is 100% by weight. Degree.
また、エポキシ樹脂とその硬化剤の反応を促進するための触媒として、例えば、1,8−ジアザ−ビシクロ[5.4.0]ウンデセン−7、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノールなどの三級アミン類;2−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、2−ヘプタデシルイミダゾールなどのイミダゾ−ル類;トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィンなどの有機ホスフィン類;テトラフェニルホスホニウム・テトラフェニルボレート、2−エチル−4−メチルイミダゾール・テトラフェニルボレート、N−メチルモルホリン・テトラフェニルボレートなどのテトラフェニルボロン塩等を使用することができ、これらは2種以上を組み合わせてもよい。また、当該触媒の使用量は特に制限されないが、通常、本発明の接着剤組成物の固形分を100重量%とした場合において0.01〜5重量%程度である。 Further, as a catalyst for promoting the reaction between the epoxy resin and its curing agent, for example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethyl Tertiary amines such as aminoethanol and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; tributylphosphine , Organic phosphines such as methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate It can be used tetraphenyl boron salts such as N- methylmorpholine-tetraphenyl borate, which may be in combination of two or more. The amount of the catalyst used is not particularly limited, but is usually about 0.01 to 5% by weight when the solid content of the adhesive composition of the present invention is 100% by weight.
前記ベンゾオキサジン樹脂としては、例えば、6,6−(1−メチルエチリデン)ビス(3,4−ジヒドロ−3−フェニル−2H−1,3−ベンゾオキサジン)、6,6−(1−メチルエチリデン)ビス(3,4−ジヒドロ−3−メチル−2H−1,3−ベンゾオキサジン)等が挙げられる。なお、オキサジン環の窒素にはフェニル基、メチル基、シクロヘキシル基等が結合していてもよい。また、市販品としては例えば、四国化成工業(株)社製の「ベンゾオキサジンF−a型」や「ベンゾオキサジンP−d型」、エア・ウォ−タ−社製の「RLV−100」等が挙げられ、これらは2種以上を組み合わせてもよい。 Examples of the benzoxazine resin include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6- (1-methylethylidene). ) Bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. Note that a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to nitrogen of the oxazine ring. In addition, examples of commercially available products include “benzoxazine Fa type” and “benzoxazine Pd type” manufactured by Shikoku Kasei Kogyo Co., Ltd., “RLV-100” manufactured by Air Water Co., etc. These may be used in combination of two or more.
前記ビスマレイミド樹脂としては、例えば、4,4’−ジフェニルメタンビスマレイミド、m−フェニレンビスマレイミド、ビスフェノールAジフェニルエーテルビスマレイミド、3,3’−ジメチル−5,5’−ジエチル−4,4’−ジフェニルメタンビスマレイミド、4−メチル−1,3−フェニレンビスマレイミド、1,6’−ビスマレイミド−(2,2,4−トリメチル)ヘキサン、4,4’−ジフェニルエーテルビスマレイミド、4,4’−ジフェニルスルフォンビスマレイミド等が挙げられる。また、市販品としては例えば、JFEケミカル(株)社製の「BAF−BMI」等が挙げられ、これらは2種以上を組み合わせてもよい。 Examples of the bismaleimide resin include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane. Bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone Examples thereof include bismaleimide. Moreover, as a commercial item, "BAF-BMI" by JFE Chemical Co., Ltd. etc. are mentioned, for example, These may combine 2 or more types.
前記シアネートエステル樹脂としては、例えば、2−アリルフェノールシアネートエステル、4−メトキシフェノールシアネートエステル、2,2−ビス(4−シアナトフェノール)−1,1,1,3,3,3−ヘキサフルオロプロパン、ビスフェノールAシアネートエステル、ジアリルビスフェノールAシアネートエステル、4−フェニルフェノールシアネートエステル、1,1,1−トリス(4−シアナトフェニル)エタン、4−クミルフェノールシアネートエステル、1,1−ビス(4−シアナトフェニル)エタン、4,4’−ビスフェノールシアネートエステル、および2,2‐ビス(4‐シアナトフェニル)プロパン等が挙げられ、例えば「PRIMASET BTP−6020S(ロンザジャパン(株)製)」等の市販品を使用できる。これらは2種以上を組み合わせてもよい。 Examples of the cyanate ester resin include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoro. Propane, bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate ester, 1,1-bis ( 4-Cyanatophenyl) ethane, 4,4′-bisphenol cyanate ester, 2,2-bis (4-cyanatophenyl) propane, and the like, for example, “PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)” Use a commercial product such as Yes. Two or more of these may be combined.
(B)成分の使用量は特に制限されないが、通常、(A)成分または(A’)成分100重量部(固形分換算)に対して1〜150重量部程度、好ましくは3〜100重量部程度、いっそう好ましくは3〜75重量部である。 Although the usage-amount of (B) component is not restrict | limited, Usually, about 1-150 weight part with respect to 100 weight part (solid content conversion) of (A) component or (A ') component, Preferably it is 3-100 weight part Degree, more preferably 3 to 75 parts by weight.
(C)成分は、ポリイミド系接着剤組成物に使用可能な難燃剤であれば各種公知のものを特に限定なく使用できるが、難燃効果の点より特にリン系難燃剤および/または無機フィラーが好ましい。 As the component (C), various known flame retardants can be used without particular limitation as long as they are flame retardants usable for the polyimide-based adhesive composition. However, in view of the flame retardant effect, phosphorous flame retardants and / or inorganic fillers are used. preferable.
前記リン系難燃剤としては、例えば、ポリリン酸やリン酸エステル、フェノール性水酸基を含有しないホスファゼン誘導体等が挙げられ、特に当該ホスファゼン誘導体、中でも環状ホスファゼン誘導体(伏見製薬所(株)製の「ラビトルFP−300」等)は、難燃性、耐熱性、耐ブリードアウト性等の点で好ましい。 Examples of the phosphorus-based flame retardant include polyphosphoric acid, phosphoric acid ester, phosphazene derivatives that do not contain phenolic hydroxyl groups, and the like. In particular, the phosphazene derivatives, especially cyclic phosphazene derivatives (“Rabitol” manufactured by Fushimi Pharmaceutical Co., Ltd.) FP-300 "etc.) is preferable in terms of flame retardancy, heat resistance, bleed out resistance and the like.
前記無機フィラーとしては、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、窒化アルミニウム、ほう酸アルミウイスカ、窒化ほう素、結晶性シリカ、非晶性シリカ、黒鉛粉、ベーマイト等が挙げられる。これらの中でも特に水酸化アルミニウム(ベーマイト)が、本発明の接着剤組成物中での分散性に優れ、また難燃性も良好であるため好ましい。 Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, boron nitride, Examples thereof include crystalline silica, amorphous silica, graphite powder, boehmite and the like. Among these, aluminum hydroxide (boehmite) is particularly preferable because of its excellent dispersibility in the adhesive composition of the present invention and good flame retardancy.
(C)成分の使用量は特に制限されないが、(A)成分または(A’)成分100重量部(固形分換算)に対して通常0〜200重量部程度、好ましくは25〜150重量部程度となる範囲である。 Although the usage-amount of (C) component is not restrict | limited, About 0-200 weight part normally with respect to 100 weight part (solid content conversion) of (A) component or (A ') component, Preferably it is about 25-150 weight part. This is the range.
(D)成分としては、例えば、N−メチル−2−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、N−メチルカプロラクタム、メチルトリグライム、メチルジグライム等の非プロトン性極性溶剤や、シクロヘキサノン、メチルシクロヘキサン等の脂環式溶剤、メタノール、エタノール、プロパノール、ベンジルアルコール、クレゾ−ル等のアルコール系溶剤が挙げられ、2種以上を組み合わせてもよい。 Examples of the component (D) include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyltriglyme, and methyldiglyme, cyclohexanone, methyl Examples thereof include alicyclic solvents such as cyclohexane, and alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol, and cresol, and two or more kinds may be combined.
(D)成分の使用量は特に限定されないが、通常、本発明の接着剤組成物の不揮発分が20〜60重量%程度となる範囲で用いればよい。 Although the usage-amount of (D) component is not specifically limited, Usually, what is necessary is just to use in the range from which the non volatile matter of the adhesive composition of this invention will be about 20 to 60 weight%.
また、本発明の接着剤組成物には他にも、必要に応じ、前記開環エステル化反応触媒や脱水剤、可塑剤、耐候剤、酸化防止剤、熱安定剤、滑剤、帯電防止剤、増白剤、着色剤、導電剤、離型剤、表面処理剤、粘度調節剤等の添加剤を配合できる。 In addition to the adhesive composition of the present invention, if necessary, the ring-opening esterification reaction catalyst and dehydrating agent, plasticizer, weathering agent, antioxidant, thermal stabilizer, lubricant, antistatic agent, Additives such as a brightener, a colorant, a conductive agent, a release agent, a surface treatment agent, and a viscosity modifier can be blended.
<硬化物>
本発明の硬化物は、本発明の接着剤組成物を硬化させたものである。具体的には、当該接着剤組成物を一旦、通常70〜200℃程度に加熱し、1〜10分間程度かけて硬化反応させる。次いで、(B)成分(熱硬化性樹脂)の硬化反応を進行させるために、更に通常150℃〜250℃程度、10分〜3時間程度加熱処理する。このように反応を二段階にすることによって、得られる硬化物の収縮を緩やかにすることができるため、基材に対する密着性を確保でき、また、前記脱水閉環反応において副生する水を原因とする発泡を抑制することもできる。なお、これら硬化反応には、(A)成分または(A’)成分に由来するポリアミック酸の脱水閉環反応が含まれる。
<Hardened product>
The cured product of the present invention is obtained by curing the adhesive composition of the present invention. Specifically, the adhesive composition is once heated usually to about 70 to 200 ° C. and cured for about 1 to 10 minutes. Subsequently, in order to advance the curing reaction of the component (B) (thermosetting resin), it is further heat-treated usually at about 150 ° C. to 250 ° C. for about 10 minutes to 3 hours. By making the reaction in two stages in this way, it is possible to moderate the shrinkage of the resulting cured product, so that it is possible to ensure adhesion to the base material, and due to water by-produced in the dehydration cyclization reaction. It is also possible to suppress foaming. These curing reactions include a dehydrating cyclization reaction of polyamic acid derived from the component (A) or the component (A ′).
本発明の硬化物の形状は特に限定されないが、基材シートの接着用途に供する場合には、膜厚が通常1〜100μm程度、好ましくは3〜50μm程度であり、用途に応じて適宜調整できる。 Although the shape of the hardened | cured material of this invention is not specifically limited, When using for the adhesion | attachment use of a base sheet, a film thickness is about 1-100 micrometers normally, Preferably it is about 3-50 micrometers, and can be suitably adjusted according to a use. .
本発明の接着シートは、本発明の接着剤組成物をシート基材に塗布し、乾燥させることによって得られる。当該シート基材としては、例えば、ポリイミド、ポリイミド−シリカハイブリッド、ポリエチレン(PE)、ポリプロピレン(PP)、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリメタクリル酸メチル樹脂(PMMA)、ポリスチレン樹脂(PSt)、ポリカーボネート樹脂(PC)、アクリロニトリル−ブタジエン−スチレン樹脂(ABS)、エチレンテレフタレートやフェノール、フタル酸、ヒドロキシナフトエ酸等とパラヒドロキシ安息香酸とから得られる芳香族系ポリエステル樹脂(所謂液晶ポリマー;(株)クラレ製、「ベクスター」等)などの有機基材が挙げられ、これらの中でも耐熱性や寸法安定性等の点より、ポリイミドフィルム、特にポリイミド−シリカハイブリッドフィルムが好ましい。また、当該シート基材の厚みは用途に応じて適宜設定すればよい。かかる接着シートはキャリアシートやキャリアテープとして使用することができる。 The adhesive sheet of the present invention is obtained by applying the adhesive composition of the present invention to a sheet substrate and drying it. Examples of the sheet base material include polyimide, polyimide-silica hybrid, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate resin (PMMA), and polystyrene resin. (PSt), polycarbonate resin (PC), acrylonitrile-butadiene-styrene resin (ABS), aromatic polyester resin (so-called liquid crystal polymer) obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid and the like and parahydroxybenzoic acid ; Organic base materials such as “Kuraray Co., Ltd.,“ Bexter ”, etc.) are mentioned. Among these, polyimide films, particularly polyimide-silica hybrid films are used from the viewpoint of heat resistance and dimensional stability. Masui. Moreover, what is necessary is just to set the thickness of the said sheet | seat base material suitably according to a use. Such an adhesive sheet can be used as a carrier sheet or a carrier tape.
本発明の積層体は、前記接着シートの接着面に更にシート基材を熱圧着させることにより得られる。当該シート基材としては、ガラス、鉄、アルミ、42アロイ、銅等の金属や、ITO、シリコンおよびシリコンカーバイド等の無機基材が好適でありその厚みは用途に応じて適宜設定できる。また、当該積層体は、更に加熱処理したものであってよい。 The laminate of the present invention can be obtained by further thermocompression bonding a sheet substrate to the adhesive surface of the adhesive sheet. As the sheet substrate, metals such as glass, iron, aluminum, 42 alloy, and copper, and inorganic substrates such as ITO, silicon, and silicon carbide are suitable, and the thickness can be appropriately set according to the application. Moreover, the said laminated body may be what heat-processed further.
本発明のフレキシブルプリント基板は、前記積層体を用いたものであり、当該積層体の無機基材面に更に前記接着シートの接着面を貼りあわせることにより得られる。当該フレキシブルプリント基板としては、有機基材としてポリイミドフィルムを、無機基材として金属箔(特に銅箔)を用いたものが好ましい。そして、かかるフレキシブルプリント基板の金属表面をソフトエッチング処理して回路を形成し、そのうえに更に前記接着シートを貼りあわせて熱プレスすることにより、フレキシブルプリント配線基板が得られる。 The flexible printed board of the present invention uses the laminate, and is obtained by further bonding the adhesive surface of the adhesive sheet to the inorganic base material surface of the laminate. As the said flexible printed circuit board, what used the polyimide film as an organic base material and the metal foil (especially copper foil) as an inorganic base material is preferable. And the flexible printed wiring board is obtained by carrying out the soft etching process of the metal surface of this flexible printed circuit board, forming a circuit, further bonding the said adhesive sheet on it, and carrying out the hot press.
以下、実施例及び比較例をあげて本発明を具体的に説明するが、それらによって本発明の範囲が制限されないことはもとよりである。なお、各例中、部及び%は特記しない限り重量基準である。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, naturally the scope of the present invention is not restrict | limited by them. In each example, parts and% are based on weight unless otherwise specified.
製造例1
撹拌機、分水器、温度計及び窒素ガス導入管を備えた反応容器に、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(商品名「BTDA」、ダイセル化学工業(株)製。以下、単にベンゾフェノンテトラカルボン酸二無水物という。)53.00g、シクロヘキサノン185.50g、メチルシクロヘキサン37.10gを仕込み、溶液を60℃まで加熱した。ついで、ダイマージアミン(商品名「PRIAMINE1075」、クローダジャパン(株)製。以下、単にダイマージアミンという。)85.40gを滴下した後、140℃で1時間かけてイミド化反応させることにより、ポリイミド樹脂(A−1)の溶液(不揮発分38.0%)を得た。なお、酸成分/アミン成分のモル比は1.04であった。
Production Example 1
In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (trade name “BTDA”, Daicel Chemical Industries, Ltd.) Hereinafter, simply referred to as benzophenone tetracarboxylic dianhydride.) 53.00 g, cyclohexanone 185.50 g, and methylcyclohexane 37.10 g were charged, and the solution was heated to 60 ° C. Next, 85.40 g of dimer diamine (trade name “PRIAMINE 1075”, manufactured by Croda Japan Co., Ltd., hereinafter simply referred to as dimer diamine) was dropped, and then the polyimide resin was subjected to an imidization reaction at 140 ° C. over 1 hour. A solution of (A-1) (non-volatile content: 38.0%) was obtained. The molar ratio of acid component / amine component was 1.04.
製造例2
製造例1と同様の反応容器に、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物(新日本理化(株)製、商品名「リカシッドDSDA」。以下、単にジフェニルスルホンテトラカルボン酸二無水物という。)53.00g、シクロヘキサノン185.50g、メチルシクロヘキサン37.10gを仕込み、溶液を60℃まで加熱した。ついで、ダイマージアミンを76.82g、徐々に添加した後、140℃で1時間かけてイミド化反応させることにより、不揮発分36.0%のポリイミド樹脂(A−2)の溶液を得た。なお、酸成分/アミン成分のモル比は1.04であった。
Production Example 2
In a reaction vessel similar to Production Example 1, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name “Licacid DSDA”. Hereinafter, simply diphenylsulfonetetra Carboxylic dianhydride) 53.00 g, cyclohexanone 185.50 g, methylcyclohexane 37.10 g were charged, and the solution was heated to 60 ° C. Next, 76.82 g of dimeramine amine was gradually added, and then an imidization reaction was performed at 140 ° C. over 1 hour, to obtain a solution of polyimide resin (A-2) having a nonvolatile content of 36.0%. The molar ratio of acid component / amine component was 1.04.
製造例3
製造例1と同様の反応容器に、ベンゾフェノンテトラカルボン酸二無水物を53.00g、シクロヘキサノンを185.50g、メチルシクロヘキサンを37.10g仕込み、溶液を60℃まで加熱した。ついで、ダイマージアミンを85.40g、徐々に添加した後、140℃で1時間かけてイミド化反応させることにより、不揮発分37.0%のポリイミド樹脂溶液を得た。なお、酸成分/アミン成分のモル比は1.04であった。次いで、当該ポリイミド樹脂溶液を室温まで冷却した後、更に鎖伸長剤として2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン(和歌山精化(株)製、商品名「BAPP」)1.78gを仕込み、温度が40℃以下に保たれるように少量ずつ添加し、添加終了後も引き続き室温で30分攪拌し、鎖伸長反応を進行させることによって、ポリイミド樹脂(A’−1)の溶液(不揮発分38.0%)を得た。
Production Example 3
A reaction vessel similar to Production Example 1 was charged with 53.00 g of benzophenone tetracarboxylic dianhydride, 185.50 g of cyclohexanone, and 37.10 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 85.40 g of dimer diamine was gradually added, and then an imidization reaction was performed at 140 ° C. for 1 hour to obtain a polyimide resin solution having a nonvolatile content of 37.0%. The molar ratio of acid component / amine component was 1.04. Next, after the polyimide resin solution was cooled to room temperature, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Co., Ltd., trade name “BAPP”) was further used as a chain extender. 1.78 g was charged and added little by little so that the temperature was kept at 40 ° C. or less. After the addition was completed, the mixture was continuously stirred at room temperature for 30 minutes to allow the chain extension reaction to proceed. ) Solution (non-volatile content: 38.0%).
製造例4
製造例1と同様の反応容器に、ベンゾフェノンテトラカルボン酸二無水物を53.00g、シクロヘキサノンを212.00g、メチルシクロヘキサンを42.40g仕込み、溶液を60℃まで加熱した。ついで、ダイマージアミンを42.70g、およびα,ω−ビス(3−アミノプロピル)ポリジメチルシロキサン(商品名「KF−8010」、信越化学工業(株)製。以下、単にビスアミノプロピルポリジメチルシロキサンという。)を69.59g、徐々に添加した後、140℃で1時間かけてイミド化反応させることにより、ポリイミド樹脂(A−3)の溶液(不揮発分39.0%)を得た。なお、ジアミン成分中のダイマージアミンは50モル%であり、酸成分/アミン成分のモル比は1.04であった。
Production Example 4
A reaction vessel similar to Production Example 1 was charged with 53.00 g of benzophenone tetracarboxylic dianhydride, 212.00 g of cyclohexanone, and 42.40 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 42.70 g of dimer diamine and α, ω-bis (3-aminopropyl) polydimethylsiloxane (trade name “KF-8010”, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter simply referred to as bisaminopropylpolydimethylsiloxane) 69.59 g was gradually added, and then an imidization reaction was performed at 140 ° C. over 1 hour to obtain a polyimide resin (A-3) solution (nonvolatile content: 39.0%). In addition, the dimer diamine in a diamine component was 50 mol%, and the molar ratio of an acid component / amine component was 1.04.
製造例5
製造例1と同様の反応容器にベンゾフェノンテトラカルボン酸二無水物53.00g、シクロヘキサノン159.00g、およびメチルシクロヘキサン31.80gを仕込み、60℃になるまで加熱した。ついで、ダイマージアミン80.74gを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂の溶液を得た。なお、酸成分/アミン成分のモル比は1.10であった。 次いで、当該ポリイミド樹脂溶液を室温まで冷却した後、更に鎖伸長剤としてダイマージアミン6.73gを少量ずつ添加し、室温で1時間撹拌することによって鎖伸長反応を実施しすることにより、ポリイミド樹脂(A’−2)の溶液(不揮発分が42.0%)を得た。
Production Example 5
A reaction vessel similar to Production Example 1 was charged with 53.00 g of benzophenone tetracarboxylic dianhydride, 159.00 g of cyclohexanone, and 31.80 g of methylcyclohexane, and heated to 60 ° C. Next, 80.74 g of dimer diamine was gradually added, and then heated to 140 ° C., and an imidization reaction was carried out over 1 hour to obtain a polyimide resin solution. The molar ratio of acid component / amine component was 1.10. Next, after the polyimide resin solution is cooled to room temperature, 6.73 g of dimer diamine is further added little by little as a chain extender, and the chain extension reaction is carried out by stirring at room temperature for 1 hour. A solution of A′-2) (nonvolatile content: 42.0%) was obtained.
製造例6
製造例1と同様の反応容器に4,4’−[プロパン−2,2−ジイルビス(1,4−フェニレンオキシ)]ジフタル酸二無水物(商品名「BisDA‐2000」、SABICイノベーティブプラスチックスジャパン合同会社製。以下、単にジイルビスフェニレンオキシジフタル酸二無水物という。)を70.00g、シクロヘキサノンを175.00g、メチルシクロヘキサンを35.00g仕込み、溶液を60℃まで加熱した。ついで、ダイマージアミン69.90gを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施する事により、ポリイミド樹脂(A−4)の溶液(不揮発分40.5%)を得た。なお、酸成分/アミン成分のモル比は1.04であった。
Production Example 6
In the same reaction vessel as in Production Example 1, 4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride (trade name “BisDA-2000”, SABIC Innovative Plastics Japan) 70.00 g of diylbisphenyleneoxydiphthalic acid dianhydride), 175.00 g of cyclohexanone, and 35.00 g of methylcyclohexane were prepared, and the solution was heated to 60 ° C. Next, after gradually adding 69.90 g of dimer diamine, heating to 140 ° C. and carrying out an imidization reaction over 1 hour, a solution of polyimide resin (A-4) (nonvolatile content: 40.5%) Got. The molar ratio of acid component / amine component was 1.04.
製造例7
製造例1と同様の反応容器に4,4’−オキシジフタル酸無水物(商品名「ODPA‐1000」、SABICイノベーティブプラスチックスジャパン合同会社製。以下、単にオキシジフタル酸無水物という。)を50.00g、シクロヘキサノンを226.50g、メチルシクロヘキサンを25.00g仕込み、溶液を60℃まで加熱した。ついで、ダイマージアミン84.56gを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施する事により、不揮発分35.0%のポリイミド樹脂(A−5)の溶液を得た。なお、酸成分/アミン成分のモル比は1.03であった。
Production Example 7
50.00 g of 4,4′-oxydiphthalic anhydride (trade name “ODPA-1000”, manufactured by SABIC Innovative Plastics Japan LLC. Hereinafter, simply referred to as oxydiphthalic anhydride) in the same reaction vessel as in Production Example 1. 226.50 g of cyclohexanone and 25.00 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, after 84.56 g of dimeramine amine was gradually added, the solution was heated to 140 ° C. and subjected to an imidization reaction over 1 hour, whereby a polyimide resin (A-5) solution having a nonvolatile content of 35.0% was obtained. Obtained. The molar ratio of acid component / amine component was 1.03.
製造例8
製造例1と同様の反応容器にジイルビスフェニレンオキシジフタル酸二無水物を65.00g、シクロヘキサノンを266.50g、メチルシクロヘキサンを44.42g仕込み、溶液を60℃まで加熱した。ついで、ダイマージアミン43.71gと、1,3−ビス(アミノメチル)シクロヘキサン((商品名「1,3−BAC」、三菱ガス化学製。)5.42gを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施する事により、ポリイミド樹脂(A−6)の溶液(不揮発分29.5%)を得た。なお、酸成分/アミン成分のモル比は1.05であった。
Production Example 8
A reaction vessel similar to Production Example 1 was charged with 65.00 g of diylbisphenyleneoxydiphthalic dianhydride, 266.50 g of cyclohexanone, and 44.42 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, after gradually adding 43.71 g of dimer diamine and 5.42 g of 1,3-bis (aminomethyl) cyclohexane (trade name “1,3-BAC”, manufactured by Mitsubishi Gas Chemical), the temperature was increased to 140 ° C. By heating and carrying out an imidization reaction over 1 hour, a polyimide resin (A-6) solution (nonvolatile content: 29.5%) was obtained, wherein the molar ratio of acid component / amine component was 1. 05.
比較製造例1
製造例1と同様の反応容器にベンゾフェノンテトラカルボン酸二無水物を53.00g、シクロヘキサノンを185.50g、メチルシクロヘキサンを37.10g仕込み、溶液を60℃まで加熱した。ついでダイマージアミンに代えてビスアミノプロピルポリジメチルシロキサンを139.17g、徐々に添加した後、溶液を140℃まで加熱し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂(イ)の溶液(不揮発分46.2%)を得た。なお、酸成分/アミン成分のモル比は1.04であった。
Comparative production example 1
A reaction vessel similar to Production Example 1 was charged with 53.00 g of benzophenone tetracarboxylic dianhydride, 185.50 g of cyclohexanone and 37.10 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 139.17 g of bisaminopropyl polydimethylsiloxane was gradually added instead of dimeramine amine, and then the solution was heated to 140 ° C. and subjected to an imidization reaction over 1 hour. A solution (non-volatile content: 46.2%) was obtained. The molar ratio of acid component / amine component was 1.04.
比較製造例2
製造例1と同様の反応容器にベンゾフェノンテトラカルボン酸二無水物53.00g、シクロヘキサノン212.00g、メチルシクロヘキサン42.40gを仕込み、溶液を60℃になるまで加熱した。ついで、ダイマージアミン21.35gおよびビスアミノプロピルポリジメチルシロキサン104.38gを徐々に添加し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂(ロ)の溶液(不揮発分41.0%)を得た。なお、酸成分/アミン成分のモル比は1.04であった。
Comparative production example 2
A reaction vessel similar to Production Example 1 was charged with 53.00 g of benzophenonetetracarboxylic dianhydride, 212.00 g of cyclohexanone, and 42.40 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 21.35 g of dimeramine amine and 104.38 g of bisaminopropylpolydimethylsiloxane were gradually added, and an imidization reaction was carried out over 1 hour, whereby a solution of polyimide resin (b) (non-volatile content: 41.0%) ) The molar ratio of acid component / amine component was 1.04.
BTDA:3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物
DSDA:3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物
ODPA:4,4’−オキシジフタル酸無水物
BISDA:4,4’−[プロパン−2,2−ジイルビス(1,4−フェニレンオキシ)]ジフタル酸二無水物
PRIAMINE:ダイマージアミン
KF8010:α,ω−ビス(3−アミノプロピル)ポリジメチルシロキサン
BAPP:2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン
1,3−BAC:1,3−ビス(アミノメチル)シクロヘキサン
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride ODPA: 4,4′-oxydiphthalic anhydride BISDA: 4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride PRIAMINE: dimer diamine KF8010: α, ω-bis (3-aminopropyl) polydimethylsiloxane BAPP : 2,2-bis [4- (4-aminophenoxy) phenyl] propane 1,3-BAC: 1,3-bis (aminomethyl) cyclohexane
実施例1
(A)成分として製造例1のポリイミド樹脂(A−1)の溶液100.0g、(B)成分としてビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン(株)製、商品名「jER828」、エポキシ当量190g/eq)4.23gおよびフェノールノボラック樹脂(荒川化学工業(株)製、商品名「タマノルT759」、水酸基当量106g/eq)2.18g、ならびに2−エチル−4−メチルイミダゾール(四国化成工業(株)製、商品名「2E4MZ」)0.06gを混合した。次いで、(C)成分としてベーマイト(河合石灰工業(株)製、商品名「セラシュールBMT−3LV」)25.66gおよび環状シアノフェノキシフォスファゼン誘導体((株)伏見製薬所製、商品名「ラビトルFP−300」)12.00g、ならびに有機溶剤としてシクロヘキサノンを49.33gおよびメタノールを8.55g加え、よく撹拌することによって、不揮発分40.7%の接着剤組成物を得た。
Example 1
(A) Component 100.0 g of the polyimide resin (A-1) of Production Example 1 as component (B) Component bisphenol A type epoxy resin (product of Japan Epoxy Resin Co., Ltd., trade name “jER828”, epoxy equivalent 190 g) / Eq) 4.23 g and phenol novolak resin (Arakawa Chemical Industries, trade name “Tamanor T759”, hydroxyl group equivalent 106 g / eq) 2.18 g, and 2-ethyl-4-methylimidazole (Shikoku Chemical Industries ( Co., Ltd., trade name “2E4MZ”) 0.06 g was mixed. Next, as component (C), boehmite (manufactured by Kawai Lime Industry Co., Ltd., trade name “Cerasur BMT-3LV”) 25.66 g and cyclic cyanophenoxyphosphazene derivative (manufactured by Fushimi Pharmaceutical Co., Ltd., trade name “ 12.00 g of Ravitor FP-300 ") and 49.33 g of cyclohexanone and 8.55 g of methanol as organic solvents were added and stirred well to obtain an adhesive composition having a nonvolatile content of 40.7%.
実施例2〜13
(A)成分、(B)成分、(C)成分および有機溶剤として、表2で示す種類のものをそれぞれの使用量で使用した他は実施例1と同様にして、各接着剤組成物を得た。
Examples 2-13
(A) Component, (B) component, (C) component and organic solvent were used in the same manner as in Example 1 except that the types shown in Table 2 were used in their respective amounts. Obtained.
比較例1〜2
実施例1において、(A−1)成分の溶液に代えて、前記(イ)成分の溶液または前記(ロ)成分の溶液を表3で示す量で用い、かつ(B)成分、(C)成分および有機溶剤として、表3で示す種類のものをそれぞれの使用量で使用した他は同様にして、各接着剤組成物を得た。
Comparative Examples 1-2
In Example 1, instead of the solution of component (A-1), the solution of component (a) or the solution of component (b) was used in the amounts shown in Table 3, and component (B), (C) Each adhesive composition was obtained in the same manner except that the components and organic solvents used in the respective amounts shown in Table 3 were used.
比較例3
実施例1において、(A−1)成分の溶液に代えてカルボキシル基含有NBR(JSR(株)製、商品名「XER−32C」)を表3で示す量で用い、かつ(B)成分、(C)成分および有機溶剤として、表3で示す種類のものをそれぞれの使用量で使用した他は同様にして、各接着剤組成物を得た。
Comparative Example 3
In Example 1, instead of the solution of the component (A-1), a carboxyl group-containing NBR (manufactured by JSR Corporation, trade name “XER-32C”) was used in the amount shown in Table 3, and the component (B), Each adhesive composition was obtained in the same manner as the component (C) and the organic solvent except that the types shown in Table 3 were used in their respective amounts.
jER828(商品名):ビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン(株)製、エポキシ当量190g/eq)
タマノルT759(商品名):フェノールノボラック樹脂(荒川化学工業(株)製、水酸基当量106g/eq)
2E4MZ(商品名):2−エチル−4−メチルイミダゾール(四国化成工業(株)製)
BMI−TMH(商品名):1,6’−ビスマレイミド−(2,2,4−トリメチル)ヘキサン(大和化成工業(株)製)
パークミルD(商品名):ジクミルパーオキサイド(日油(株)製)
PRIMASET BTP−6020S(商品名):シアネートエステル樹脂(ロンザジャパン(株)製)
セラシュールBMT−3LV(商品名):ベーマイト(河合石灰工業(株)製)
ラビトルFP−300:フェノキシフォスファゼン誘導体((株)伏見製薬所製)
jER828 (trade name): bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 190 g / eq)
Tamanoru T759 (trade name): phenol novolac resin (Arakawa Chemical Industries, Ltd., hydroxyl group equivalent 106 g / eq)
2E4MZ (trade name): 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)
BMI-TMH (trade name): 1,6′-bismaleimide- (2,2,4-trimethyl) hexane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Park mill D (trade name): Dicumyl peroxide (manufactured by NOF Corporation)
PRIMASET BTP-6020S (trade name): Cyanate ester resin (manufactured by Lonza Japan Co., Ltd.)
Cerasur BMT-3LV (trade name): Boehmite (manufactured by Kawai Lime Industry Co., Ltd.)
Ravitor FP-300: Phenoxyphosphazene derivative (Fushimi Pharmaceutical Co., Ltd.)
<接着シートの作製>
実施例1の接着剤組成物を、ブロック共重合ポリイミド−シリカハイブリッドフィルム(商品名「ポミランN25」、荒川化学工業(株)製;熱膨張係数=18ppm、引張弾性率=5.9GPa、膜厚25μm)に、乾燥後の厚みが30μmとなるようギャップコーターにて塗布した後、180℃で3分間乾燥させることによって接着シートを得た。他の実施例および比較例の接着剤組成物についても同様にして接着シートを得た。
<Preparation of adhesive sheet>
The adhesive composition of Example 1 was prepared from a block copolymerized polyimide-silica hybrid film (trade name “Pomilan N25”, manufactured by Arakawa Chemical Industries, Ltd .; thermal expansion coefficient = 18 ppm, tensile modulus = 5.9 GPa, film thickness 25 μm) was applied with a gap coater so that the thickness after drying was 30 μm, and then dried at 180 ° C. for 3 minutes to obtain an adhesive sheet. Adhesive sheets were obtained in the same manner for the adhesive compositions of other examples and comparative examples.
次いで、各接着シートの接着面に18μm厚の電解銅箔(商品名「F2−WS」、古河サーキットフォイル(株)製)の処理面(鏡面)を重ね、これを水平方向に動かした。その際、粘着性があり電解銅箔を動かせなかった場合をタック性有りと、水平方向に動かせた場合をタック性無しと判断した。結果を表4に示す。 Subsequently, the processing surface (mirror surface) of 18-micrometer-thick electrolytic copper foil (Brand name "F2-WS", Furukawa Circuit Foil Co., Ltd. product) was piled up on the adhesive surface of each adhesive sheet, and this was moved to the horizontal direction. At that time, it was judged that there was tackiness when there was stickiness and the electrolytic copper foil could not be moved, and there was no tackiness when it could be moved in the horizontal direction. The results are shown in Table 4.
<積層体(1)の作製>
実施例1に係る接着シートの接着面に、18μm厚の電解銅箔(商品名「F2−WS」、古河サーキットフォイル(株)製)の処理面を重ね合わせ、圧力10MPa、180℃及び1分間の条件で加熱プレスした後、更に200℃で1時間加熱することにより、積層体(1)を作製した。他の実施例および比較例の接着剤組成物についても同様にして積層体(1)のそれぞれを得た。なお、積層体(1)はFPC基板としての使用を想定している。
<Preparation of laminate (1)>
The treatment surface of 18 μm thick electrolytic copper foil (trade name “F2-WS”, manufactured by Furukawa Circuit Foil Co., Ltd.) is overlaid on the adhesion surface of the adhesive sheet according to Example 1, and the pressure is 10 MPa, 180 ° C. and 1 minute. Then, the laminate (1) was produced by heating and pressing at 200 ° C. for 1 hour. Each of the laminates (1) was obtained in the same manner for the adhesive compositions of other examples and comparative examples. The laminate (1) is assumed to be used as an FPC board.
<積層体(2)の作製>
実施例1に係る接着剤組成物を、ポミランN25に乾燥後の厚みが30μmとなるようギャップコーターにて塗布し、200℃で30分間加熱することにより接着シートを得た。次いで、当該接着シートの接着剤面に、前記電解銅箔(F2−WS)の処理面を重ね合わせた後、圧力10MPaおよび200℃の条件で1分間加熱プレスすることにより積層体を作製した。他の実施例および比較例についても同様にして積層体(2)をそれぞれ得た。なお、積層体(2)はキャリアシートやキャリアテープとしての使用を想定している。
<Preparation of laminate (2)>
The adhesive composition according to Example 1 was applied to Pomilan N25 with a gap coater so that the thickness after drying was 30 μm, and heated at 200 ° C. for 30 minutes to obtain an adhesive sheet. Next, after superposing the treated surface of the electrolytic copper foil (F2-WS) on the adhesive surface of the adhesive sheet, a laminate was produced by hot pressing for 1 minute under conditions of a pressure of 10 MPa and 200 ° C. The laminates (2) were obtained in the same manner for other examples and comparative examples. The laminate (2) is assumed to be used as a carrier sheet or carrier tape.
<接着性試験>
実施例および比較例の各積層体について、JIS C−6481に準じて剥離強度を測定した。結果を表3に示す。
<Adhesion test>
About each laminated body of an Example and a comparative example, peel strength was measured according to JIS C-6482. The results are shown in Table 3.
<はんだ耐熱性試験:高温域>
実施例および比較例の積層体(1)のそれぞれを120℃で5分間加熱した後、プラスチック基材面を上にして340℃のはんだ浴に1分間浮かべた後、接着剤層の発泡や金属基材の剥がれを確認し、ついでJIS C−6481に準じて銅箔の剥離強度を測定した。結果を表4に示す。なお、積層体(1)はFPC基板としての利用が想定されているため、剥離強度の数値が大きいほど接着性が良好である。
<Solder heat resistance test: High temperature range>
Each of the laminates (1) of Examples and Comparative Examples was heated at 120 ° C. for 5 minutes, then floated in a solder bath at 340 ° C. for 1 minute with the plastic substrate surface facing upward, and foaming of the adhesive layer or metal The peeling of the base material was confirmed, and then the peel strength of the copper foil was measured according to JIS C-6481. The results are shown in Table 4. Since the laminate (1) is assumed to be used as an FPC board, the larger the peel strength value, the better the adhesiveness.
<難燃性>
実施例および比較例の積層体(1)のそれぞれについて、UL94規格に準拠して難燃性を評価した。積層体(1)が、UL94規格のV−0クラスに相当する場合を難燃性有りと、燃焼した場合を難燃性無しとした。
<Flame retardance>
About each of the laminated body (1) of an Example and a comparative example, the flame retardance was evaluated based on UL94 specification. When the laminate (1) corresponds to the UL94 V-0 class, the flame retardancy was regarded as having flame retardancy, and when it was burned, the flame retardancy was absent.
<はんだ耐熱性:低温域>
実施例および比較例の積層体(2)のそれぞれを120℃で5分間加熱した後、プラスチック基材面を下にして260℃のはんだ浴に5分間浮かべた後、接着剤層の発泡や金属基材の剥がれを確認し、ついでJIS C−6481に準じて電解銅箔の剥離強度を測定した。その際、解銅箔の鏡面の表面状態を観察するとともに、当該基材の糊残り(付着硬化物)の有無を確認した。結果を表4に示す。なお、積層体(2)はキャリアシートやキャリアテープとしての利用を想定したものであり、仮固着した半導体素子等の電子部品を剥がす必要性があるため、剥離強度の数値が小さいほど良好とみなす。
<Solder heat resistance: low temperature range>
Each of the laminates (2) of Examples and Comparative Examples was heated at 120 ° C. for 5 minutes, then floated in a solder bath at 260 ° C. for 5 minutes with the plastic substrate face down, and then foaming of the adhesive layer or metal The peeling of the base material was confirmed, and then the peel strength of the electrolytic copper foil was measured according to JIS C-6481. At that time, the surface state of the mirror surface of the copper-removed foil was observed, and the presence or absence of adhesive residue (adhered cured product) of the substrate was confirmed. The results are shown in Table 4. The laminate (2) is assumed to be used as a carrier sheet or a carrier tape, and there is a need to peel off electronic components such as temporarily bonded semiconductor elements. Therefore, the smaller the peel strength value is, the better it is. .
<フレキシブルプリント配線板の作製>
実施例1に係る接着剤組成物を、ポミランN25に乾燥後の厚みが30μmとなるようギャップコーターにて塗布し、180℃で3分間乾燥させることによって、接着シートを得た。次いで、該接着シートの接着剤面に前記電解銅箔(F2−WS)の処理面を重ね合わせ、180℃のラミネートロールで圧着した後、200℃,2時間処理することによってフレキシブル銅張積層板を得た。この銅張積層板の銅表面をソフトエッチング処理し、銅回路を形成し、その上にさらに前記方法で得た積層体(1)(実施例1に係る本発明の接着剤組成物の使用)を重ねあわせ、圧力10MPa、180℃及び1分間の条件で加熱プレスした後、更に200℃で1時間加熱することにより、フレキシブルプリント配線板を作製することができた。また、他の実施例の接着剤組成物についても同様にしてフレキシブルプリント配線板を作製できたことを確認した。
<Production of flexible printed wiring board>
The adhesive composition according to Example 1 was applied to Pomilan N25 with a gap coater so that the thickness after drying was 30 μm, and dried at 180 ° C. for 3 minutes to obtain an adhesive sheet. Next, a flexible copper-clad laminate is obtained by superposing the treated surface of the electrolytic copper foil (F2-WS) on the adhesive surface of the adhesive sheet, pressing with a laminating roll at 180 ° C., and then treating at 200 ° C. for 2 hours. Got. The copper surface of this copper-clad laminate is subjected to a soft etching process to form a copper circuit, and a laminate (1) obtained by the above-described method (use of the adhesive composition of the present invention according to Example 1). After being heated and pressed under conditions of a pressure of 10 MPa, 180 ° C. and 1 minute, a flexible printed wiring board could be produced by further heating at 200 ° C. for 1 hour. Moreover, it confirmed that the flexible printed wiring board was able to be produced similarly about the adhesive composition of another Example.
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