TWI627639B - Electrical connecting material and manufacturing method thereof, and connecting body - Google Patents
Electrical connecting material and manufacturing method thereof, and connecting body Download PDFInfo
- Publication number
- TWI627639B TWI627639B TW103135171A TW103135171A TWI627639B TW I627639 B TWI627639 B TW I627639B TW 103135171 A TW103135171 A TW 103135171A TW 103135171 A TW103135171 A TW 103135171A TW I627639 B TWI627639 B TW I627639B
- Authority
- TW
- Taiwan
- Prior art keywords
- resin composition
- radical polymerizable
- polymerizable compound
- epoxy
- thermosetting resin
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 89
- 239000002245 particle Substances 0.000 claims abstract description 88
- 239000011342 resin composition Substances 0.000 claims abstract description 80
- 239000004593 Epoxy Substances 0.000 claims abstract description 64
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 54
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 17
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 17
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 9
- 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 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 101
- -1 acrylate compound Chemical class 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- SHJXSYJQBXYBGA-UHFFFAOYSA-N 2-cyclohexyl-2-hydroxy-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(O)C1CCCCC1 SHJXSYJQBXYBGA-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- ORJNLUXHBUSOKL-UHFFFAOYSA-N 6,7-dihydrodibenzo[2,1-b:1',2'-d][7]annulen-5-one Chemical compound O=C1CCC2=CC=CC=C2C2=CC=CC=C12 ORJNLUXHBUSOKL-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OTQHPLSTQPGTCX-UHFFFAOYSA-N C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C1=CC=CC1 Chemical compound C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C1=CC=CC1 OTQHPLSTQPGTCX-UHFFFAOYSA-N 0.000 description 1
- PHQSYHHLVVDIFC-UHFFFAOYSA-N CC1=C(C=P(C2=CC=CC=C2)C2=CC=CC=C2)C(=CC(=C1)C)C Chemical compound CC1=C(C=P(C2=CC=CC=C2)C2=CC=CC=C2)C(=CC(=C1)C)C PHQSYHHLVVDIFC-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MRNHCWNSIKGASF-UHFFFAOYSA-N OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1 Chemical compound OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1.C(C=C1)=CC=C1SC1=CC=CC=C1 MRNHCWNSIKGASF-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 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
- GKAZFNXELDRFNU-UHFFFAOYSA-N [O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 GKAZFNXELDRFNU-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- MUUZIDFBKZNXQS-UHFFFAOYSA-N oxido-phenyl-[(2,4,6-trimethylphenyl)methylidene]phosphanium Chemical compound CC1=C(C=P(C2=CC=CC=C2)=O)C(=CC(=C1)C)C MUUZIDFBKZNXQS-UHFFFAOYSA-N 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
本發明之抑制於各向異性導電連接部等電連接部產生翹曲,而且不會使藉由各向異性導電連接等電連接而獲得之連接體之導通可靠性降低的各向異性導電膜等電連接材料具有含導電粒子層被第1絕緣性熱硬化型樹脂組成物層與第2絕緣性熱硬化型樹脂組成物層夾持之構造。該含導電粒子層係藉由光照射使含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子之含導電粒子樹脂組成物層進行光自由基聚合而B階段化而成者。第1絕緣性熱硬化型樹脂組成物層及第2絕緣性熱硬化型樹脂組成物層分別含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑。
Description
本發明係關於一種各向異性導電膜等電連接材料、其製造方法及連接體。
於將IC晶片等電氣零件安裝於基板等時,廣泛使用由導電粒子與成為其分散介質之黏合劑樹脂組成物所構成之各向異性導電膜作為電連接材料。對於此種各向異性導電膜,要求較高接著強度,因此作為黏合劑樹脂組成物,廣泛使用可實現高於丙烯酸酯系接著劑組成物之接著強度之環氧系接著劑組成物。通常,此種環氧系接著劑組成物係於環氧系化合物中摻合陰離子系硬化劑或陽離子系硬化劑而成者。
但是,於將環氧系接著劑組成物用作黏合劑樹脂組成物之各向異性導電膜之情形時,環氧系接著劑組成物之硬化物無法充分緩和因該環氧系接著劑組成物之硬化收縮而於各向異性導電連接部產生之應力,因此有於各向異性導電連接部產生翹曲之問題。因此,提出於使用陽離子系硬化劑之環氧系接著劑組成物中摻合較其而言可提供應力緩和能相對優異之硬化物之丙烯酸酯系自由基聚合性組成物,欲不使環氧系接著劑組成物之較高之接著強度降低而賦予應力緩和能(專利文獻1)。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特開2006-127776號公報
然而,於專利文獻1之各向異性導電膜之情形時,可於某種程度上減少各向異性導電連接部之翹曲之產生,但於將使用各向異性導電膜而形成之連接體於高溫高濕下保管之情形時,有導通電阻增大,導通可靠性降低之問題。
本發明之目的在於解決以上習知技術之問題點,提供一種抑制於各向異性導電連接部等電連接部產生翹曲,而且不會使藉由各向異性導電連接等電連接而獲得之連接體之導通可靠性降低的各向異性導電膜等電連接材料。
本發明人發現將各向異性導電膜等電連接材料設為使含導電粒子層由絕緣性熱硬化型樹脂組成物層夾持之構造,且作為該含導電粒子層,採用使將環氧系非自由基聚合性化合物在不與環氧化合物用之硬化劑併用之情況下摻合於含有導電粒子之丙烯酸酯系自由基聚合性組成物中而成之樹脂組成物層進行光硬化而B階段化而成者,藉此可達成上述目的,從而完成本發明。
即,本發明提供一種電連接材料,其含導電粒子層被第1
絕緣性熱硬化型樹脂組成物層與第2絕緣性熱硬化型樹脂組成物層夾持之電連接材料、較佳為各向異性導電膜,其特徵在於:含導電粒子層係藉由光照射使含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子之含導電粒子樹脂組成物層進行光自由基聚合而B階段化而成者,第1絕緣性熱硬化型樹脂組成物層及第2絕緣性熱硬化型樹脂組成物層分別含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑。
又,本發明提供一種製造方法,其係上述本發明之電連接材料、較佳為各向異性導電膜之製造方法,且具有如下步驟:將含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子之含導電粒子樹脂組成物成膜,並對所獲得之膜照射光使其進行光自由基聚合而B階段化,藉此形成含導電粒子層;及於含導電粒子層之單面積層含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑之第1絕緣性熱硬化型樹脂組成物層,於另一面積層含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑之第2絕緣性熱硬化型樹脂組成物層。
進而,本發明提供一種連接體,其係將第1電氣零件之端子與第2電氣零件之端子經由上述本發明之電連接材料、較佳為各向異性導電膜藉由熱壓接而電連接、較佳為各向異性導電連接而成。
本發明之各向異性導電膜等電連接材料具有含導電粒子層由第1絕緣性熱硬化型樹脂組成物層與第2絕緣性熱硬化型樹脂組成物層夾持之構造。因此,例如若使第1絕緣性熱硬化型樹脂組成物層與第2絕緣性熱硬化型樹脂組成物層之硬化收縮率相互吻合為同水準,則可抑制使用各向異性導電膜等電連接材料而製成之連接體之翹曲之產生。
又,含導電粒子層係藉由光照射使含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子之含導電粒子樹脂組成物層進行光自由基聚合而B階段化而成。因此,於各向異性導電連接等電連接時,導電粒子變得不易自應連接之端子間(連接部)流動,從而可有助於導通可靠性之提昇。而且,可使各向異性導電膜等電連接材料整體表現應力緩和能,亦可有助於抑制使用各向異性導電膜等電連接材料而製成之連接體之翹曲之產生。
進而,於該含導電粒子層中不含使環氧系非自由基聚合性化合物聚合之聚合起始劑。因此,於經B階段化之含導電粒子層中含有未聚合之環氧系非自由基聚合性化合物,若使用液狀之環氧化合物,則可確保於各向異性導電連接等電連接時壓入導電粒子所必需之流動性。
又,含導電粒子層中所含有之環氧系非自由基聚合性化合物可利用各向異性導電連接等電連接時之熱壓接而於第1及第2絕緣性熱硬化型樹脂組成物層產生之熱陽離子聚合或熱陰離子聚合,藉此進行陽離子聚合或陰離子聚合。藉此,可使含導電粒子層充分地硬化,可抑制使用各向異性導電膜等電連接材料而製成之連接體之導通可靠性之降低。如此,本案發明之電連接材料作為各向異性導電膜有用,作為各向異性導電
膏、通常之導電膜或導電膏亦有用。
1‧‧‧含導電粒子層
2‧‧‧第1絕緣性熱硬化型樹脂組成物層
3‧‧‧第2絕緣性熱硬化型樹脂組成物層
圖1係本發明之電連接材料之較佳之一態樣之各向異性導電膜的剖面圖。
以下,以本發明之電連接材料之較佳之一態樣之各向異性導電膜為例對本發明進行詳細說明。
<各向異性導電膜>
如圖1所示,本發明之各向異性導電膜10具有含導電粒子層1由第1絕緣性熱硬化型樹脂組成物層2與第2絕緣性熱硬化型樹脂組成物層3夾持之構造。
(含導電粒子層1)
該含導電粒子層1係藉由光照射使含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子之含導電粒子樹脂組成物層進行光自由基聚合而B階段化而成者。此處,所謂“B階段”,意指使硬化型樹脂組成物半硬化之狀態,且藉由加熱而流動或軟化之狀態。
作為含導電粒子層1之光自由基聚合前之前驅物之含導電粒子樹脂組成物層含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子,但不含使環氧系非自
由基聚合性化合物聚合之聚合起始劑。其原因在於:藉由積層於含導電粒子層1之兩面之第1絕緣性熱硬化型樹脂組成物層2及第2絕緣性熱硬化型樹脂組成物層3的聚合,而使環氧系非自由基聚合性化合物聚合。
於含導電粒子層1中,藉由光照射而產生之光自由基聚合中之丙烯酸酯系自由基聚合性化合物之反應率較佳為70%以上。若反應率為70%以上,則可充分地獲得抑制連接時之粒子流動之效果。反應率之測定可藉由FT-IR等公知之手法而進行。再者,其反應率為100%之情形亦為本案發明之範圍,但由於含導電粒子層1含有未聚合之環氧系非自由基聚合性化合物,故而作為含導電粒子層1整體而言並非為正式硬化狀態,而可將其稱為B階段狀態。
再者,可適當設定光照射條件(光源、光波長、光強度、光量、溫度等)。
作為丙烯酸酯系自由基聚合性化合物,可列舉單官能或多官能(甲基)丙烯酸酯(此處,所謂(甲基)丙烯酸酯為包含丙烯酸酯與甲基丙烯酸酯之用語)化合物。作為單官能(甲基)丙烯酸酯化合物,可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正或異丙酯、(甲基)丙烯酸正、異、第二或三級丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苄酯、丙烯酸雙環戊酯化合物等。作為多官能(甲基)丙烯酸酯化合物,可例示:乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、1,2-環己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、二環戊二烯二甲基丙烯酸酯等2官
能(甲基)丙烯酸酯化合物,或甘油三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、異氰尿酸三(2-丙烯醯氧基乙基)酯等3官能(甲基)丙烯酸酯化合物。又,可使用環氧改性、胺酯(urethane)改性、環氧乙烷改性、環氧丙烷改性而成者。其中,就硬化後之連接穩定性之方面而言,可較佳地使用雙酚A型環氧丙烯酸酯。
作為光自由基聚合起始劑,可自公知之光自由基聚合起始劑中適當選擇而使用。例如可列舉:苯乙酮系光聚合起始劑、苯偶醯縮酮系光聚合起始劑、α-烷基胺基苯酮(α-allkylamino phenone)系光聚合起始劑、磷系光聚合起始劑等。具體而言,作為苯乙酮系光聚合起始劑,可列舉:2-羥基-2-環己基苯乙酮(IRGACURE 184,BASF JAPAN股份有限公司)、α-羥基-α,α'-二甲基苯乙酮(DAROCUR 1173,BASF JAPAN股份有限公司)、2,2-二甲氧基-2-苯基苯乙酮(IRGACURE 651,BASF JAPAN股份有限公司)、4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮(IRGACURE 2959,BASF JAPAN股份有限公司)、2-羥基-1-{4-[2-羥基-2-甲基-丙醯基]-苄基}苯基}-2-甲基-丙烷-1-酮(IRGACURE 127,BASF JAPAN股份有限公司)等。作為苯偶醯縮酮系光聚合起始劑,可列舉:二苯甲酮、茀酮、二苯并環庚酮、4-胺基二苯甲酮、4,4'-二胺基二苯甲酮、4-羥基二苯甲酮、4-氯二苯甲酮、4,4'-二氯二苯甲酮等。又,作為α-烷基胺基苯酮系光聚合起始劑,可使用2-苄基-2-二甲胺基-1-(4-口末啉基苯基)-丁酮-1(IRGACURE 369,BASF JAPAN股份有限公司)。作為磷系光聚合起始劑,可列舉:雙
(2,4,6-三甲基苯甲醯基)-苯基氧化膦(IRGACURE 819,BASF JAPAN股份有限公司)、(2,4,6-三甲基苯甲醯基)-二苯基氧化膦(DAROCURE TPO,BASF JAPAN股份有限公司)等。
光自由基聚合起始劑之摻合量相對於丙烯酸酯系自由基聚合性化合物100質量份,較佳為0.1~40質量份,更佳為0.5~30質量份。若為該範圍,則可使光自由基聚合充分地進行,可抑制含導電粒子層1之機械強度之降低。
作為丙烯酸酯系自由基聚合性化合物與光自由基聚合起始劑之較佳組合,可列舉雙酚A型環氧丙烯酸酯與α-烷基胺基苯酮系光聚合起始劑之組合。
作為環氧系非自由基聚合性化合物,液狀或固體狀均可,可列舉環氧當量通常為100~4000左右,於分子內不存在自由基聚合性之不飽和鍵,且具有2個以上之環氧基之化合物。例如可較佳地使用雙酚A型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、酯型環氧化合物、脂環型環氧化合物等。又,該等化合物包含單體或低聚物。
環氧系非自由基聚合性化合物之摻合量相對於丙烯酸酯系自由基聚合性化合物100質量份,較佳為3~250質量份,更佳為10~150質量份。若為該範圍,則可提昇接著力,可抑制過度之翹曲之變化。
再者,於含導電粒子層1中,除丙烯酸酯系自由基聚合性化合物與環氧系非自由基聚合性化合物以外,亦可含有作為膜形成用樹脂之苯氧基樹脂、環氧樹脂、不飽和聚酯樹脂、飽和聚酯樹脂、胺酯樹脂、
丁二烯樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚烯烴樹脂等。此種膜形成用樹脂成分之摻合量相對於丙烯酸酯系自由基聚合性化合物與環氧系非自由基聚合性化合物之合計100質量份,較佳為10~200質量份,更佳為20~150質量份。若為該範圍,則可提昇硬化前之使用性,可抑制亦成為翹曲之主要原因之硬化後之殘留應力。
作為導電粒子,可採用構成公知之各向異性導電膜之導電粒子。例如可列舉鎳等金屬粒子、於樹脂芯之表面形成有鎳等金屬鍍敷膜之金屬被覆樹脂粒子等。視需要亦可形成絕緣薄膜。
作為此種導電粒子之平均粒徑,就導通保持性之方面而言,較佳為1~20μm,更佳為2~10μm。
導電粒子之摻合量相對於丙烯酸酯系自由基聚合性化合物與環氧系非自由基聚合性化合物及視需要摻合之膜形成用樹脂之合計100質量份,較佳為2~200質量份,更佳為5~150質量份。若為該範圍,則可提昇導通可靠性,可抑制接著性之過度之降低或連接後之短路之產生。
就確保導通與防止短路之方面而言,含導電粒子層1中之導電粒子密度較佳為1000~150000個/mm2,更佳為2000~100000個/mm2。
再者,作為含導電粒子層1中之導電粒子之存在形態,可為於含導電粒子樹脂組成物中均勻地混合而成膜之形態,亦可為使用公知之手法、例如轉印模具以單層規則排列之形態。
含導電粒子層1之層厚較佳為1~20μm,更佳為2~10μm,進而更佳為3~8μm。若為該範圍,則不會使粒子捕捉效率降低至
必需以上,亦可抑制導通電阻之過度之上升。
(第1絕緣性熱硬化型樹脂組成物層2及第2絕緣性熱硬化型樹脂組成物層3)
該等樹脂組成物層分別獨立地含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑。
作為環氧系非自由基聚合性化合物,液狀或固體狀均可,可列舉環氧當量通常為100~4000左右,於分子內不存在自由基聚合性之不飽和鍵,且具有2個以上之環氧基之化合物。例如可較佳地使用雙酚A型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、酯型環氧化合物、脂環型環氧化合物等。又,該等化合物包含單體或低聚物。作為尤佳之環氧系非自由基聚合性化合物,就硬化後之連接穩定性之方面而言,為雙酚A型環氧化合物。
作為熱陽離子聚合起始劑,可使用使環氧化合物之陽離子聚合開始之公知之熱陽離子聚合起始劑,例如可使用公知之錪鹽、鋶鹽、鏻鹽、二茂鐵類等,可較佳地使用對溫度顯示良好之潛伏性之芳香族鋶鹽。作為熱陽離子系熱聚合起始劑之較佳例,可列舉:六氟銻酸二苯基錪、六氟磷酸二苯基錪、六氟硼酸二苯基錪、六氟銻酸三苯基鋶、六氟磷酸三苯基鋶、六氟硼酸三苯基鋶。具體而言,可列舉:ADEKA股份有限公司製造之SP-150、SP-170、CP-66、CP-77;日本曹達股份有限公司製造之CI-2855、CI-2639;三新化學工業股份有限公司製造之San-Aid SI-60、SI-80;Union Carbide公司製造之CYRACURE-UVI-6990、UVI-6974等。
關於熱陽離子聚合起始劑之摻合量,若過少,則有熱陽離子聚合不充分進行之傾向,若過多,則有成為剛性降低之原因之虞,因此相對於環氧系非自由基聚合性化合物100質量份,較佳為0.1~40質量份,更佳為0.5~30質量份。
作為熱陰離子聚合起始劑,可使用使環氧化合物之陰離子聚合開始之公知的熱陰離子聚合起始劑,例如可列舉:脂族胺系化合物、芳香族胺系化合物、二級或三級胺系化合物、咪唑系化合物、聚硫醇系化合物、三氟化硼-胺錯合物、雙氰胺、有機酸醯肼等,可較佳地使用對溫度顯示良好之潛伏性之膠囊化咪唑系化合物。具體而言,可列舉旭化成E-MATERIALS股份有限公司製造之Novacure HX3941HP等。
關於熱陰離子聚合起始劑之摻合量,若過少,則有熱陰離子聚合不充分進行之傾向,若過多,則有成為剛性降低之原因之虞,因此相對於環氧系非自由基聚合性化合物100質量份,較佳為0.1~200質量份,更佳為0.5~150質量份。
為了進一步抑制使用本發明之各向異性導電膜而製成之連接體之翹曲之產生,第1絕緣性熱硬化型樹脂組成物層2與第2絕緣性熱硬化型樹脂組成物層3之間之硬化收縮率差較佳為10%以下。再者,硬化收縮率可依據JISK6901而測定。各層各自之硬化收縮率較佳為10%以內,更佳為5%以內,進而更佳為3%以內。
第1絕緣性熱硬化型樹脂組成物層2及第2絕緣性熱硬化型樹脂組成物層3之層厚分別較佳為0.1~30μm,更佳為1~20μm。若為該範圍,則不會使粒子捕捉效率降低至必需以上,亦可抑制導通電阻之
過度上升。
以上,以各向異性導電膜為例對本發明之電連接材料進行了說明,但本發明之電連接材料除各向異性導電膜以外,亦可採用各向異性導電膏、導電膏、導電膜等態樣。
<電連接材料(較佳為各向異性導電膜)之製造方法>
本發明之各向異性導電膜等電連接材料可藉由包含以下說明之步驟1與步驟2之製造方法而製造。
(步驟1)
首先,將含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子之含導電粒子樹脂組成物成膜,並對所獲得之膜照射光使其進行光自由基聚合而B階段化,藉此形成含導電粒子層。
含導電粒子樹脂組成物可藉由將丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、導電粒子、及視需要摻合之膜形成成分等其他成分一併藉由公知之手法、例如行星式混合機等均勻地混合而製備。其成膜亦可藉由公知之手段、例如刮刀法而進行。於此情形時,可於經剝離處理之基底片材(例如經剝離處理之聚酯片材)上將含導電粒子樹脂組成物成膜,視需要使其乾燥,藉此形成未硬化之狀態之含導電粒子樹脂組成物層。對如此形成之含導電粒子樹脂組成物層照射紫外線等光,使丙烯酸酯系自由基聚合性化合物進行光自由基聚合,較佳為使丙烯酸酯系自由基聚合性化合物之反應率成為70%以上、較佳為90%以上。藉此形成經B階段化之含導電粒子層。
(步驟2)
繼而,於含導電粒子層之單面積層含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑之第1絕緣性熱硬化型樹脂組成物層,於另一面積層含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑之第2絕緣性熱硬化型樹脂組成物層。藉此,可獲得本發明之各向異性導電膜等電連接材料。
第1絕緣性熱硬化型樹脂組成物層及第2絕緣性熱硬化型樹脂組成物層可以如下方式製成。首先,將環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑及視需要摻合之膜形成成分等其他成分一併利用公知之手法、例如行星式混合機等均勻地混合,藉此分別製備絕緣性熱硬化型樹脂組成物。將該樹脂組成物藉由公知之手段、例如刮刀法等於經剝離處理之基底片材成膜,視需要使其乾燥,藉此製成未硬化之狀態之第1絕緣性熱硬化型樹脂組成物層及第2絕緣性熱硬化型樹脂組成物層。
其次,於上述形成之含導電粒子層重疊第1絕緣性熱硬化型樹脂組成物層,並進行壓接。繼而,將含導電粒子層側之剝離基底片材剝離,重疊第2絕緣性熱硬化型樹脂組成物層,對所獲得之積層物進行壓接,藉此可獲得本發明之各向異性導電膜等電連接材料。再者,使自經剝離處理之基底片材剝離之含導電粒子層由第1絕緣性熱硬化型樹脂組成物層與第2絕緣性熱硬化型樹脂組成物層夾持,對所獲得之積層物進行壓接,藉此亦可獲得本發明之各向異性導電膜等電連接材料。
<連接體>
本發明之各向異性導電膜等電連接材料係配置於第1電氣零件(例如IC晶片)之端子(例如凸塊)與第2電氣零件(例如配線基板)之端子(例如凸塊、焊墊)之間,自第1或第2電氣零件側藉由熱壓接而電連接、較佳為各向異性導電連接,藉此提供連接體。
[實施例]
以下,藉由實施例對本發明進行更具體之說明。
實施例1~7、比較例1~4
(第1絕緣性熱硬化型樹脂組成物層之形成)
依據表1所示之組成(單位:質量份),使用甲苯而製備50%固體成分之第1絕緣性熱硬化型樹脂組成物混合液,將該混合液以乾燥厚度成為8μm之方式塗佈於剝離PET基底片材上,於80℃乾燥5分鐘,藉此形成第1絕緣性熱硬化型樹脂組成物層。
(第2絕緣性熱硬化型樹脂組成物層之形成)
依據表1所示之組成(單位:質量份),使用甲苯而製備50%固體成分之第2絕緣性樹脂組成物混合液,將該混合液以乾燥厚度成為8μm之方式塗佈於剝離PET基底片材上,於80℃乾燥5分鐘,藉此形成第2絕緣性熱硬化型樹脂組成物層。
(含導電粒子層之形成)
依據表1所示之組成(單位:質量份),使用甲苯而製備50%固體成分之含導電粒子樹脂組成物混合液,將該混合液以乾燥厚度成為6μm之方式塗佈於剝離PET基底片材上,於80℃乾燥5分鐘,繼而,以成為表1之累積光量之方式照射紫外線而使其進行光自由基聚合,藉此形成含導電
粒子層。使用FT-IR(FT/IR-4100,日本分光股份有限公司)測定該含導電粒子層中之丙烯酸酯系自由基聚合性化合物之反應率,將所獲得之結果示於表1。
(各向異性導電膜之製成)
於第1絕緣性熱硬化型樹脂組成物層重疊含導電粒子層,並進行層壓後,將含導電粒子層側之剝離PET基底片材剝離,使含導電粒子層露出。於該露出之含導電粒子層上重疊第2絕緣性熱硬化型樹脂組成物層,自剝離PET基底片材上於40℃、0.1Pa之條件下進行層壓,藉此獲得各向異性導電膜。
<連接體之評價>
(連接體之製成)
使用各實施例及比較例中製成之各向異性導電膜,將IC晶片之凸塊與玻璃基板之ITO圖案電極之間藉由熱壓接而各向異性導電連接。再者,於各向異性連接時,將第一絕緣性樹脂組成物層配置於IC晶片側。
熱壓接條件:180℃、80MPa、5秒
IC晶片之尺寸:1.5mm×20mm、0.5mmt
IC晶片之凸塊:鍍金凸塊、30μm×85μm、凸塊高度15μm、凸塊間距50μm
設置有200nm厚度之ITO圖案電極之玻璃基板之尺寸:50mm×30mm、0.3mmt(1737F,CORNING公司)
(性能評價)
針對所獲得之連接體,如以下說明般對「初期導通電阻」、「高溫高濕
負載試驗後之導通電阻(導通可靠性)」、「連接體之翹曲」進行測定。將所獲得之結果示於表1。
「初期導通電阻」
使用市售之電阻測定器對剛製成後之連接體之初期導通電阻進行測定。實用上,期望為10 Ω以下。
「高溫高濕負載試驗後之導通電阻(導通可靠性)」
使用市售之電阻測定器對將連接體放置於維持為85℃、85%Rh之腔室中1000小時後之連接體之導通電阻進行測定。實用上,期望為15 Ω以下。
「連接體之翹曲」
關於連接體之翹曲,使用市售之三維形狀測定系統(KEYENCE股份有限公司)對未安裝IC晶片之側之玻璃基板表面中相當於IC晶片之背面側之寬度20mm進行測定。期望翹曲為10μm以內。
<探討>
實施例1~7之各向異性導電膜為導通可靠性優異,翹曲較少者。再者,根據因丙烯酸酯之摻合量相對較少而剛性相對較低之實施例4之各向異性導電膜與因反應率相對較低而剛性相對較低之實施例6之各向異性導電膜之結果,可知各向異性導電膜之剛性相對較低者不易翹曲。又可知,反之,於剛性相對較高之實施例5或實施例7之各向異性導電膜之情形時,容易翹曲。
相對於此,於比較例1、2、4之情形時,由於未對含導電粒子層進行光照射,故而於導通可靠性方面存在問題。於比較例3之情形時,亦未對含導電粒子層進行光照射,但由於不含光自由基聚合起始劑,故而於導通可靠性方面存在問題。又,由於含有熱自由基聚合起始劑,故而各向異性導電連接時立即硬化,產生較大翹曲。
[產業上之可利用性]
根據本發明之各向異性導電膜等電連接材料,抑制於各向異性導電連接部等電連接部產生翹曲,而且不會使藉由各向異性導電連接等電連接而獲得之連接體之導通可靠性降低。因此,本發明之各向異性導電膜於將IC晶片等電氣零件倒裝晶片安裝於配線基板等其他電機零件時有用。
Claims (8)
- 一種電連接材料,其含導電粒子層被第1絕緣性熱硬化型樹脂組成物層與和該第1絕緣性熱硬化型樹脂組成物層相互獨立的第2絕緣性熱硬化型樹脂組成物層夾持,其特徵在於:含導電粒子層係藉由光照射使含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子,但不含有使環氧系非自由基聚合性化合物聚合之聚合起始劑的含導電粒子樹脂組成物層進行光自由基聚合而B階段化而成者,第1絕緣性熱硬化型樹脂組成物層及第2絕緣性熱硬化型樹脂組成物層分別含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑。
- 如申請專利範圍第1項之電連接材料,其中,於含導電粒子層中,丙烯酸酯系自由基聚合性化合物之反應率為70%以上。
- 如申請專利範圍第1或2項之電連接材料,其中,丙烯酸酯系自由基聚合性化合物為雙酚A型環氧丙烯酸酯,光自由基聚合起始劑為α-烷基胺基苯酮(α-alkylamino phenone)系光聚合起始劑。
- 如申請專利範圍第1或2項之電連接材料,其中,環氧系非自由基聚合性化合物為雙酚A型環氧化合物,熱陽離子聚合起始劑為芳香族鋶鹽。
- 如申請專利範圍第1或2項之電連接材料,其中,第1絕緣性熱硬化型樹脂組成物層與第2絕緣性熱硬化型樹脂組成物層之間的硬化收縮率差為10%以下。
- 一種製造方法,用以製造申請專利範圍第1項之電連接材料,且具有如下步驟:將含有丙烯酸酯系自由基聚合性化合物、光自由基聚合起始劑、環氧系非自由基聚合性化合物、及導電粒子,但不含有使環氧系非自由基聚合性化合物聚合之聚合起始劑的含導電粒子樹脂組成物成膜,並對所獲得之膜照射光使其進行光自由基聚合而B階段化,藉此形成含導電粒子層;及以含有環氧系非自由基聚合性化合物與熱陽離子聚合起始劑或熱陰離子聚合起始劑之第1絕緣性熱硬化型樹脂組成物層,與和該第1絕緣性熱硬化型樹脂組成物層相互獨立的第2絕緣性熱硬化型樹脂組成物層來夾持含導電粒子層。
- 如申請專利範圍第6項之製造方法,其係對含導電粒子樹脂組成物之膜照射光,以使丙烯酸酯系自由基聚合性化合物之反應率成為70%以上。
- 一種連接體,其係將第1電氣零件之端子與第2電氣零件之端子經由申請專利範圍第1至5項中任一項之電連接材料藉由熱壓接而電連接而成。
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