JP4534117B2 - Polyimide resin, polyimide resin composition, film-forming material using the same, and electronic component - Google Patents
Polyimide resin, polyimide resin composition, film-forming material using the same, and electronic component Download PDFInfo
- Publication number
- JP4534117B2 JP4534117B2 JP2003197090A JP2003197090A JP4534117B2 JP 4534117 B2 JP4534117 B2 JP 4534117B2 JP 2003197090 A JP2003197090 A JP 2003197090A JP 2003197090 A JP2003197090 A JP 2003197090A JP 4534117 B2 JP4534117 B2 JP 4534117B2
- Authority
- JP
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- Prior art keywords
- polyimide resin
- component
- resin composition
- polyimide
- film
- 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.)
- Expired - Fee Related
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- 229920001721 polyimide Polymers 0.000 title claims description 67
- 239000009719 polyimide resin Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 26
- 239000000463 material Substances 0.000 title claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 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 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000005056 polyisocyanate Substances 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 10
- 125000004018 acid anhydride group Chemical group 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 25
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 22
- 239000002966 varnish Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- -1 siloxanes Chemical class 0.000 description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 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 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 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 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- DGQOZCNCJKEVOA-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1CC(=O)OC1=O DGQOZCNCJKEVOA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002783 friction material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- AORTZIIKTZPIQU-UHFFFAOYSA-N 3-butyl-4-methyloxolane-2,5-dione Chemical compound CCCCC1C(C)C(=O)OC1=O AORTZIIKTZPIQU-UHFFFAOYSA-N 0.000 description 1
- JASHGAIOBWYPBI-UHFFFAOYSA-N 3a,4a,7a,7b-tetrahydrodifuro[5,4-a:5',4'-d]furan-1,3,5,7-tetrone Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C1O2 JASHGAIOBWYPBI-UHFFFAOYSA-N 0.000 description 1
- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 125000006840 diphenylmethane group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002737 metalloid compounds Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 1
- YKWDNEXDHDSTCU-UHFFFAOYSA-N pyrrolidine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1NC(C(O)=O)C(C(O)=O)C1C(O)=O YKWDNEXDHDSTCU-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ポリイミド樹脂、ポリイミド樹脂組成物及びこれを用いて得られる被膜形成材料、電子部品に関する。
【０００２】
【従来の技術】
近年、電子部品の分野においては、小型化、薄型化、高速化への対応から、耐熱性、電気特性及び耐湿性（耐ＰＣＴ性）に優れる樹脂としてエポキシ樹脂に代わり、ポリイミド樹脂、ポリアミドイミド樹脂、ポリアミド樹脂が使用されている。これらの樹脂は、樹脂構造が剛直であり、薄膜基材に用いた場合、硬化後の基材が大きく反り、硬化膜は柔軟性に欠け、屈曲性に劣る問題があった。
そこで、樹脂を可とう化及び低弾性率化したポリイミド樹脂が種々提案されている。
従来、ワニス化のための溶媒としてＮ−メチル−２−ピロリドン等の高沸点含窒素系極性溶媒が用いられている。
一方、非含窒素系極性溶媒に可溶であり、低反り性及び柔軟性を有する樹脂として例えば、特許文献１、特許文献２にポリイミドシロキサンが開示されている。
【０００３】
【特許文献１】
特開平７−３０４９５０号
【特許文献２】
特開平８−３３３４５５号
【０００４】
【発明が解決しようとする課題】
高沸点含窒素系極性溶媒を用いた場合、硬化時には２００℃以上の高温硬化が必要となり、電子部材の熱劣化が生じる問題がある。また、基材へワニスを塗工した後、放置が長くなった場合、吸湿による塗膜の白化及びボイドが生じ、作業条件が煩雑になる問題がある。
一方、ポリイミドシロキサンを使用した場合、これらのポリイミドシロキサンは、低弾性率化のため、高価なジメチルシロキサン結合を有するジアミンを出発原料として用いており、経済性に劣っている。また、シロキサンの変性量の増加に伴い、封止材との密着性、耐溶剤性、耐薬品性（耐ハンダフラックス性）に加えてさらに耐ＰＣＴ性が低下する問題がある。
本発明は、上記の従来技術の問題点を解消し、耐ＰＣＴ性に優れ、しかも非含窒素系極性溶媒に可溶で低温硬化性を有し、耐熱性、電気特性、低反り性、柔軟性、封止材との密着性、耐溶剤性、耐薬品性、作業性及び経済性に優れるポリイミド樹脂組成物及びそれを用いた優れた前記特性を有する被膜形成材と電子部品を提供するものである。
【０００５】
【課題を解決するための手段】
本発明は、（Ａ）一般式（Ｉ）
【化４】
【化５】
【化６】
また本発明は、前記（Ａ）成分が、さらに（ｃ）ポリイソシアネート化合物を反応成分として得られるものであるポリイミド樹脂に関する。
また本発明は、前記（Ａ）成分のポリイミド樹脂を製造する際の（ｂ）成分及び（ｃ）成分の配合割合が（ｂ）成分及び（ｃ）成分の当量比で０．１／０．９〜０．９／０．１であり、（ｂ）及び（ｃ）成分中のイソシアネート基の総数に対する（ａ）成分の酸無水物基の総数の比が０．６〜１．４であるポリイミド樹脂に関する。
また本発明は、前記（Ａ）ポリイミド樹脂１００重量部並びに（Ｂ）エポキシ樹脂１〜５０重量部を含有してなるポリイミド樹脂組成物に関する。
また本発明は、前記エポキシ樹脂（Ｂ）がエポキシ基を３個以上有するアミン型エポキシ樹脂であるポリイミド樹脂組成物に関する。
また、本発明は、前記の何れかに記載のポリイミド樹脂またはポリイミド樹脂組成物を用いて形成される被膜を有する被膜形成材に関する。
また、本発明は、前記の何れかに記載のポリイミド樹脂またはポリイミド樹脂組成物を用いて形成された電子部品に関する。
【０００６】
【発明の実施の形態】
本発明のポリイミド樹脂またはポリイミド樹脂組成物は、前記の様な（Ａ）ポリイミド樹脂を必須成分として含有する。
【０００７】
本発明に用いる（Ａ）成分のポリイミド樹脂は、酸無水物基を有する４価のポリカルボン酸とジイソシアネート成分とを反応させて得られる。酸無水物基を有する４価のポリカルボン酸としては、一般式（ＩＩ）
【化７】
【０００８】
上記の一般式（ＩＩ）で表される酸無水物基を有する４価のポリカルボン酸としては、例えば、大日本インキ化学工業（株）製の商品名、ＥＰＩＣＬＯＮ Ｂ−４４００として市販されているものが挙げられる。
【０００９】
また、上記のテトラカルボン酸二無水物の他に必要に応じて、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、ピラジン−２，３，５，６−テトラカルボン酸二無水物、チオフェン−２，３，４，５−テトラカルボン酸二無水物、デカヒドロナフタレン−１，４，５，８−テトラカルボン酸二無水物、４，８−ジメチル−１，２，３，５，６，７−ヘキサヒドロナフタレン−１，２，５，６−テトラカルボン酸二無水物、シクロペンタン−１，２，３，４−テトラカルボン酸二無水物、ピロリジン−２，３，４，５−テトラカルボン酸二無水物、１，２，３，４−シクロブタンテトラカルボン酸二無水物、ビス（エキソービシクロ［２，２，１］ヘプタン−２，３−ジカルボン酸無水物）スルホン、ビシクロ−（２，２，２）−オクト（７）−エン−２，３，５，６−テトラカルボン酸二無水物、テトラヒドロフラン−２，３，４，５−テトラカルボン酸二無水物等のテトラカルボン酸二無水物、酸無水物基を有する３価のトリカルボン酸（トリメリット酸無水物等）、脂肪族又は芳香族二塩基酸などに置き換えてもよい。
【００１０】
本発明において（ｂ）成分として用いる前記一般式（ＩＩＩ）で表されるジイソシアネートは、例えば、一般式（ＩＶ）
【化８】
【化９】
【００１１】
上記の一般式（ＩＶ）で表されるカーボネートジオール類としては、例えば、ダイセル化学（株）製の商品名、ＰＬＡＣＣＥＬ、ＣＤ−２０５、２０５ＰＬ、２０５ＨＬ、２１０、２１０ＰＬ、２１０ＨＬ、２２０、２２０ＰＬ、２２０ＨＬとして市販されているものが挙げられ、これらを単独で又は２種類以上を組み合わせて使用できる。
【００１２】
また、上記一般式（Ｖ）で表されるジイソシアネート類としては例えば、ジフェニルメタン−２，４’−ジイソシアネート、３，２’−又は３，３’−又は４，２’−又は４，３’−又は５，２’−又は５，３’−又は６，２’−又は６，３’−ジメチルジフェニルメタン−２，４’−ジイソシアネート、３，２’−又は３，３’−又は４，２’−又は４，３’−又は５，２’−又は５，３’−又は６，２’−又は６，３’−ジエチルジフェニルメタン−２，４’−ジイソシアネート、３，２’−又は３，３’−又は４，２’−又は４，３’−又は５，２’−又は５，３’−又は６，２’−又は６，３’−ジメトキシジフェニルメタン−２，４’−ジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、ジフェニルメタン−３，３’−ジイソシアネート、ジフェニルメタン−３，４’−ジイソシアネート、ジフェニルエーテル−４、４’−ジイソシアネート、ベンゾフェノン−４，４’−ジイソシアネート、ジフェニルスルホン−４，４’−ジイソシアネート、トリレン−２，４−ジイソシアネート、トリレン−２，６−ジイソシアネート、ｍ−キシリレンジイソシアネート、ｐ−キシリレンジイソシアネート、ナフタレン−２，６−ジイソシアネート、４，４’−［２，２ビス（４−フェノキシフェニル）プロパン］ジイソシアネートなどの芳香族ポリイソシアネートを使用することが好ましい。これらは、単独で又は２種類以上を組み合わせて使用することができる。
【００１３】
また、ヘキサメチレンジイソシアネート、２，２，４−トリメチルへキサメチレンジイソシアネート、イソホロンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、トランスシクロヘキサン−１，４−ジイソシアネート、水添ｍ−キシリレンジイソシアネート、リジンジイソシアネート等の脂肪族又は脂環式イソシアネート及び３官能以上のポリイソシアネートを用いてもよく、経日変化を避けるために必要なブロック剤で安定化したものを使用してもよい。ブロック剤としては、アルコール、フェノール、オキシム等があるが、特に制限はない。
上記の一般式（ＩＶ）で表されるカーボネートジオール類と一般式（Ｖ）で表されるジイソシアネートの配合量は、水酸基数とイソシアネート基数の比率がイソシアネート基／水酸基＝１．０１以上なるようにすることが好ましい。
【００１４】
反応は、無溶媒あるいは有機溶媒の存在下で行うことができる。反応温度は、６０〜２００℃とすることが好ましく、反応時間は、バッチの規模、採用される反応条件などにより適宜選択することができる。
【００１５】
このようにして得られる（ｂ）成分のジイソシアネートの数平均分子量は、５００〜１０，０００であることが好ましく、１，０００〜９，５００であることがより好ましく、１，５００〜９，０００であることが特に好ましい。数平均分子量がこの範囲を外れるとイソシアネートの反応性が低下し、ポリイミド樹脂化することが困難となる傾向がある。なお、本明細書において、数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定し、標準ポリスチレンの検量線を用いて換算した値である。
【００１６】
本発明においては、さらに（ｃ）成分として上記（ｂ）成分以外のポリイソシアネート化合物を用いることが、耐熱性の点で好ましい。このようなポリイソシアネート成分としては、特に制限はなく、例えば、（ｂ）成分で用いられる一般式（Ｖ）で表されるジイソシアネート類又は３価以上のポリイソシアネート類を単独で又は２種類以上を組み合わせて使用することができる。（ｃ）成分のポリイソシアネート化合物としては、その総量の５０〜１００重量％が芳香族ポリイソシアネートであることが好ましく、耐熱性、溶解性、機械特性、コスト面などのバランスを考慮すれば、４，４’−ジフェニルメタンジイソシアネートが特に好ましい。
【００１７】
本発明における（ｂ）成分の一般式（ＩＩＩ）で表されるジイソシアネートと（ｃ）成分のポリイソシアネートの配合割合は、（ｂ）成分／（ｃ）成分の当量比で０．１／０．９〜０．９／０．１とすることが好ましく、０．２／０．８〜０．８／０．２とすることがより好ましく、０．３／０．７〜０．７／０．３とすることが特に好ましい。この当量比が０．１／０．９未満では、低弾性率化できず、反り性及び密着性が低下する傾向があり、０．９／０．１を超えると、耐熱性等の膜特性が低下する傾向がある。
【００１８】
また、（ａ）成分の酸無水物基を有する４価のポリカルボン酸の配合割合は、（ｂ）成分と（ｃ）成分中のイソシアネート基の総数に対する（ａ）成分の酸無水物基の総数の比が０．６〜１．４となるようにすることが好ましく、０．７〜１．３となるようにすることがより好ましく、０．８〜１．２となるようにすることが特に好ましい。この比が０．６未満又は１．４を超えると、ポリイミド樹脂の分子量を高くすることが困難となる傾向がある。
【００１９】
本発明のポリイミド樹脂の製造法における反応は、有機溶媒、好ましくは非含窒素系極性溶媒の存在下に、遊離発生してくる炭酸ガスを反応系より除去しながら加熱縮合させることにより行うことができる。
【００２０】
上記非含窒素系極性溶媒としてはエーテル系溶媒、例えば、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、含硫黄系溶媒、例えば、ジメチルスルホキシド、ジエチルスルホキシド、ジメチルスルホン、スルホラン、エステル系溶媒、例えば、γ−ブチロラクトン、酢酸セロソルブ、ケトン系溶媒、例えば、シクロヘキサノン、メチルエチルケトン、芳香族炭化水素系溶媒、例えば、トルエン、キシレン等が挙げられ、これらは単独で又は２種類以上組み合わせて使用することができる。生成する樹脂を溶解する溶剤を選択して使用するのが好ましい。合成後、そのままワニスの溶媒として好適なものを使用することが好ましい。高揮発性であって、低温硬化性を付与でき、かつ効率良く均一系で反応を行うためには、γ−ブチロラクトンが最も好ましい。
【００２１】
溶媒の使用量は、生成するポリイミド樹脂の０．８〜５．０倍（重量比）とすることが好ましい。０．８倍未満では、合成時の粘度が高すぎて、攪拌不能により合成が困難となる傾向があり、５．０倍を超えると、反応速度が低下する傾向がある。
反応温度は、８０〜２１０℃とすることが好ましく、１００〜１９０℃とすることがより好ましく、１２０〜１８０℃とすることが特に好ましい。８０℃未満では反応時間が長くなり過ぎ、２１０℃を超えると反応中に三次元化反応が生じてゲル化が生じることがある。また、必要に応じて、三級アミン類、アルカリ金属、アルカリ土類金属、錫、亜鉛、チタニウム、コバルト等の金属又は半金属化合物等の触媒存在下に反応を行っても良い。
【００２２】
このようにして得られたポリイミド樹脂の数平均分子量は、４，０００〜４０，０００であることが好ましく、５，０００〜３８，０００であることがより好ましく、６，０００〜３６，０００であることが特に好ましい。数平均分子量が４，０００未満であると、耐熱性等の膜特性が低下する傾向があり、４０，０００を超えると、非含窒素系極性溶媒に溶解しにくくなり、合成中に不溶化しやすい。また、作業性に劣る傾向がある。
また、合成終了後に樹脂末端のイソシアネート基をアルコール類、ラクタム類、オキシム類等のブロック剤でブロックすることもできる。
【００２３】
本発明に用いられる（Ｂ）成分のエポキシ樹脂としては、例えば、油化シェルエポキシ（株）製の商品名、エピコート８２８等のビスフェノールＡ型エポキシ樹脂、東都化成（株）製の商品名、ＹＤＦ−１７０等のビスフェノールＦ型エポキシ樹脂、油化シェルエポキシ（株）製の商品名、エピコート１５２、１５４、日本化薬（株）製の商品名、ＥＰＰＮ−２０１、ダウケミカル社製の商品名、ＤＥＮ−４３８等のフェノールノボラック型エポキシ樹脂、日本化薬（株）製の商品名、ＥＯＣＮ−１２５Ｓ、１０３Ｓ、１０４Ｓ等のｏ−クレゾールノボラック型エポキシ樹脂、油化シェルエポキシ（株）製の商品名、Ｅｐｏｎ１０３１Ｓ、チバ・スペシャルティ・ケミカルズ（株）製の商品名、アラルダイト０１６３、ナガセ化成（株）製の商品名、デナコールＥＸ−６１１、ＥＸ−６１４、ＥＸ−６１４Ｂ、ＥＸ−６２２、ＥＸ−５１２、ＥＸ−５２１、ＥＸ−４２１、ＥＸ−４１１、ＥＸ−３２１等の多官能エポキシ樹脂、油化シェルエポキシ（株）製の商品名、エピコート６０４、東都化成（株）製の商品名、ＹＨ４３４、三菱ガス化学（株）製の商品名、ＴＥＴＲＡＤ−Ｘ、ＴＥＲＲＡＤ−Ｃ、日本化薬（株）製の商品名、ＧＡＮ、住友化学（株）製の商品名、ＥＬＭ−１２０等のアミン型エポキシ樹脂、チバ・スペシャルティ・ケミカルズ（株）製の商品名、アラルダイトＰＴ８１０等の複素環含有エポキシ樹脂、ＵＣＣ社製、商品名、ＥＲＬ４２３４，４２９９、４２２１、４２０６等の脂環式エポキシ樹脂などが挙げられ、これらを単独で又は２種類以上組合せて使用することができる。
【００２４】
本発明における（Ｂ）成分のエポキシ樹脂の使用量は、（Ａ）成分のポリイミド樹脂１００重量部に対して好ましくは１〜５０重量部、より好ましくは２〜４５重量部、さらに好ましくは３〜４０重量部とされる。エポキシ樹脂の配合量が１重量部未満では、耐溶剤性、耐薬品性、耐湿性が低下する傾向にあり、５０重量部を超えると、耐熱性及び粘度安定性が低下する傾向にある。
【００２５】
エポキシ樹脂の添加方法としては、添加するエポキシ樹脂を予めポリイミド樹脂に含まれる溶媒と同一の溶媒に溶解してから添加してもよく、また、直接ポリイミド樹脂に添加してもよい。
【００２６】
本発明のポリイミド樹脂またはポリイミド樹脂組成物には、塗工時の作業性及び被膜形成前後の膜特性を向上させるため、必要に応じて、有機又は無機のフィラー類、消泡剤、レベリング剤等の界面活性剤類、染料又は顔料等の着色剤類、硬化促進剤、熱安定剤、酸化防止剤、難燃剤、滑剤を添加することができる。
【００２７】
本発明のポリイミド樹脂またはポリイミド樹脂組成物には、被膜形成材料として、例えば、半導体素子や各種電子部品用オーバーコート材、リジット又はフレキ基板分野などにおける層間絶縁膜、表面保護膜、ソルダレジスト層、接着層などや、液状封止材、エナメル線用ワニス、電気絶縁用含浸ワニス、注型ワニス、マイカ、ガラスクロス等の基材と組み合わせたシート用ワニス、ＭＣＬ積層板用ワニス、摩擦材料用ワニスにも使用できる。
発明における被膜形成材は、上記ポリイミド樹脂またはその組成物を用いて形成される被膜を有する、半導体素子、フレキシブル回路基板、積層板、エナメル線等を指す。
本発明におけるポリイミド樹脂またはポリイミド樹脂組成物は、前記した（ｂ）成分のジイソシアネートを用いて得られるポリイミド樹脂を用いること又はさらにエポキシ樹脂を用いることにより所期の目的の効果を得ることができる。
【００２８】
【実施例】
以下、本発明を実施例により詳細に説明するが、本発明はこれらに限定されるものではない。
【００２９】
実施例１
攪拌機、油水分離器付き冷却管、窒素導入管及び温度計を備えた５リットルの四つ口フラスコに、（ｂ）成分としてＰＬＡＣＣＥＬ ＣＤ−２２０（ダイセル化学（株）製１，６−ヘキサンジオール系ポリカーボネートジオールの商品名）１０００．０ｇ（０．５０モル）及び４、４’−ジフェニルメタンジイソシアネート２５０．２７ｇ（１．００モル）と、γ−ブチロラクトン８３３．５１ｇを仕込み、１４０℃まで昇温した。１４０℃で５時間反応させ、ジイソシアネート［一般式（Ｉ）において、Ｒがすべてヘキサメチレン基を示し、Ｘがジフェニルメタン基を示し、ｍ＝１３、ｎ＝１であるジイソシアネート］を得た。
更に、この反応液に（ａ）成分として５−（２，５−ジオキソテトラヒドロ−３−フラニル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸無水物２６４．２５ｇ（１．００モル、（ｃ）成分として４、４’−ジフェニルメタンジイソシアネート１２５．１４ｇ（０．５０モル）及びγ−ブチロラクトン５８４．９７ｇを仕込み、１６０℃まで昇温した後、５時間反応させて、数平均分子量が１６，０００の樹脂を得た。得られた樹脂をγ−ブチロラクトンで希釈し、粘度９０Ｐａ・ｓ、不揮発分５２重量％のポリイミド樹脂溶液を得た。なお、（ｂ）成分／（ｃ）成分のモル比は、０．５／０．５である。
【００３０】
実施例２
実施例１で得られたポリイミド樹脂溶液の樹脂分１００重量部に対してＹＨ−４３４（東都化成（株）製アミン型エポキシ樹脂の商品名、エポキシ当量約１２０、エポキシ基４個／分子）１０重量部を加え、γ−ブチロラクトンで希釈して、粘度５２Ｐａ・ｓ、不揮発分５２重量％のポリイミド樹脂組成物を得た。
【００３１】
実施例３
実施例２において、ＹＨ−４３４、１０重量部の代わりに、エピコート８２８（油化シェルエポキシ（株）製ビスフェノールＡ型エポキシ樹脂の商品名、エポキシ当量約１８９、エポキシ基２個／分子）１０重量部を用いた以外は、実施例１と全く同様の操作を行い、粘度４６Ｐａ・ｓ、不揮発分５２重量％の樹脂組成物を得た。
【００３２】
比較例１
フラスコを３Ｌとした以外は実施例１と同様のフラスコに（ａ）成分として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５３７．４４ｇ（１．５０モル）、（ｃ）成分として４、４’−ジフェニルメタンジイソシアネート３８２．９ｇ（１．５３モル）及びγ−ブチロラクトン１３８０．５１ｇを仕込み、１６０℃まで昇温した。反応中、ワニスに濁りが生じ均一なポリイミド溶液を得ることはできなかった。
【００３３】
比較例２
実施例１と同様のフラスコに（ｂ）成分としてシリコーンジオールＢＸ１６−００１（東レ・ダウコーニング・シリコーン（株）製ジメチルポリシロキサン系ジオールの商品名）７００ｇ（０．５０モル）及び４、４’−ジフェニルメタンジイソシアネート２５０．２７ｇ（１．００モル）と、γ−ブチロラクトン３１６．７６ｇ及びＮ−メチル−２−ピロリドン３１６．７６ｇを仕込み、１４０℃まで昇温した。１４０℃で３時間反応させ、更に、この反応液に（ａ）成分として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３５８．２９ｇ（１．００モル）、（ｃ）成分として４、４’−ジフェニルメタンジイソシアネート１２５．１４ｇ（０．５０モル）及びγ−ブチロラクトン２６９．７５ｇ及びＮ−メチル−２−ピロリドン２６９．７５ｇを仕込み、１６０℃まで昇温した後、４時間反応させて、数平均分子量が１５，０００の樹脂を得た。得られた樹脂をγ−ブチロラクトンで希釈し、粘度３０Ｐａ・ｓ、不揮発分５２重量％のポリイミド樹脂溶液を得た。
【００３４】
比較例３
比較例２で得られたポリイミド樹脂溶液の樹脂分１００重量部に対してＹＨ−４３４を１０重量部を加え、γ−ブチロラクトンで希釈して、粘度１２Ｐａ・ｓ、不揮発分５２重量％のポリイミド樹脂組成物を得た。
【００３５】
上記の実施例及び比較例で得られたポリイミド樹脂溶液及びポリイミド樹脂組成物の物性を下記の方法で測定し、結果を表１に示した。
【００３６】
（１）反り性
厚さ５０μｍ、縦３５ｍｍ、横２０ｍｍのポリイミドフィルム上に、得られたポリイミド樹脂組成物を塗布し、９０℃で１５分乾燥した後、空気雰囲気下、１２０℃で１２０分又は１６０℃で６０分加熱し、得られた塗膜（厚さ：２０μｍ）について、塗布面を下にして定盤上に置き、反り高さを評価した。
【００３７】
（２）耐溶剤性
厚さ３５μｍの電解銅箔の粗面上に、得られたポリイミド樹脂組成物を塗布し、９０℃で１５分乾燥した後、空気雰囲気下、１２０℃で１２０分又は１６０℃で６０分加熱し、得られた塗膜（厚さ：２０〜３０μｍ）について、室温でアセトン中に１時間塗膜を浸漬させ、塗膜外観の変化について下記基準で評価した。
○：外観変化なし
△：一部外観に変化あり
×：全面外観に変化あり
【００３８】
（３）封止材に対する密着性
厚さ３５μｍの電解銅箔の粗面又は厚さ５０μｍのポリイミドフィルム上に、得られたポリイミド樹脂組成物を塗布し、９０℃で１５分乾燥した後、空気雰囲気下、１２０℃で１２０分又は１６０℃で６０分加熱し、得られた塗膜（厚さ：２０〜３０μｍ）上に、エポキシ系封止材〔日立化成工業（株）製、商品名：ＣＥＬ−Ｃ−５０２０〕を０．０６ｇポッティングし、１２０℃で１２０分、さらに１５０℃で１２０分加熱する。得られた塗膜は、封止材側が外側になるように折り曲げ、剥離のモードを下記の基準で評価した。
○：基材／塗膜の界面剥離
△：塗膜／封止材の界面剥離
×：全く接着せず
【００３９】
（４）耐ＰＣＴ性
厚さ３５μｍの電解銅箔の粗面又は厚さ５０μｍのポリイミドフィルム上に、得られたポリイミド樹脂組成物を塗布し、９０℃で１５分乾燥した後、空気雰囲気下、１２０℃で１２０分又は１６０℃で６０分加熱し、得られた塗膜（厚さ：２０〜３０μｍ）についてプレッシャークッカーテスト（ＰＣＴと略す、条件１２１℃、２．０２６５×１０ ５ Ｐａ、１００時間）を行った後の塗膜外観変化について下記の基準で評価した。
○：外観変化なし
△：一部外観に変化あり
×：全面外観に変化あり
【表１】
【発明の効果】
本発明のポリイミド樹脂またはポリイミド樹脂組成物は、耐ＰＣＴ性に優れ、しかも非含窒素系極性溶媒に可溶で低温硬化性を有し、耐熱性、電気特性、低反り性、柔軟性、封止材との密着性、耐溶剤性、耐薬品性、作業性及び経済性に優れるものである。
また、本発明のポリイミド樹脂組成物は被膜形成材料として、上記の優れた特性を有するものであり、半導体素子や各種電子部品用オーバーコート材、リジット又はフレキ基板分野などにおける層間絶縁膜、表面保護膜、ソルダレジスト層、接着層などや、液状封止材、エナメル線用ワニス、電気絶縁用含浸ワニス、注型ワニス、マイカ、ガラスクロス等の基材と組み合わせたシート用ワニス、ＭＣＬ積層板用ワニス、摩擦材料用ワニスに好適に用いられる。被膜を形成して得られる各種電気部品、電子部品等の被膜形成材は、信頼性に優れる物となる。本発明のポリイミド樹脂またはポリイミド樹脂組成物を用いた電子部品は信頼性に優れるものとなる。[0001]
BACKGROUND OF THE INVENTION
The present inventionPolyimide resin,The present invention relates to a polyimide resin composition, a film-forming material obtained using the same, and an electronic component.
[0002]
[Prior art]
In recent years, in the field of electronic components, in response to miniaturization, thinning, and high speed, instead of epoxy resin as a resin excellent in heat resistance, electrical characteristics and moisture resistance (PCT resistance), polyimide resin and polyamideimide resin Polyamide resin is used. These resins have a rigid resin structure, and when used for a thin film substrate, the cured substrate is greatly warped, and the cured film lacks flexibility and has poor flexibility.
Therefore, various polyimide resins in which the resin is made flexible and have a low elastic modulus have been proposed.
Conventionally, a high-boiling nitrogen-containing polar solvent such as N-methyl-2-pyrrolidone has been used as a solvent for varnishing.
On the other hand, as a resin that is soluble in a non-nitrogen-containing polar solvent and has low warpage and flexibility, for example, Patent Document 1 and Patent Document 2 disclose polyimide siloxane.
[0003]
[Patent Document 1]
JP-A-7-304950
[Patent Document 2]
JP-A-8-333455
[0004]
[Problems to be solved by the invention]
When a high-boiling nitrogen-containing polar solvent is used, there is a problem that high temperature curing of 200 ° C. or more is required at the time of curing, and thermal deterioration of the electronic member occurs. In addition, when the varnish is applied to the substrate and then left to stand for a long time, there is a problem that the coating conditions are whitened and voids due to moisture absorption, resulting in complicated working conditions.
On the other hand, when polyimide siloxane is used, these polyimide siloxanes use expensive diamine having a dimethylsiloxane bond as a starting material in order to lower the elastic modulus, and are inferior in economic efficiency. In addition to the increase in the amount of siloxane modification, there is a problem that the PCT resistance is further lowered in addition to the adhesion to the sealing material, solvent resistance, and chemical resistance (solder flux resistance).
The present invention eliminates the above-mentioned problems of the prior art, has excellent PCT resistance, is soluble in non-nitrogen-containing polar solvents, has low-temperature curability, and has heat resistance, electrical characteristics, low warpage, and flexibility. Providing a polyimide resin composition having excellent properties, adhesion to a sealing material, solvent resistance, chemical resistance, workability, and economic efficiency, and a film-forming material having the above characteristics and an electronic component using the same It is.
[0005]
[Means for Solving the Problems]
The present invention relates to (A) the general formula (I)
[Formula 4]
[Chemical formula 5]
[Chemical 6]
The present invention also relates to a polyimide resin in which the component (A) is obtained by further using (c) a polyisocyanate compound as a reaction component..
MaIn the present invention, the blending ratio of the component (b) and the component (c) in the production of the polyimide resin of the component (A) is 0.1 / 0.00 by the equivalent ratio of the component (b) and the component (c). 9 to 0.9 / 0.1, and the ratio of the total number of acid anhydride groups in component (a) to the total number of isocyanate groups in components (b) and (c) is 0.6 to 1.4 It relates to a polyimide resin.
The present invention also relates to a polyimide resin composition comprising (A) 100 parts by weight of the polyimide resin and (B) 1 to 50 parts by weight of the epoxy resin.
The present invention also relates to a polyimide resin composition in which the epoxy resin (B) is an amine type epoxy resin having three or more epoxy groups.
Moreover, this invention relates to the film forming material which has a film formed using the polyimide resin or polyimide resin composition in any one of the above.
Moreover, this invention relates to the electronic component formed using the polyimide resin or polyimide resin composition in any one of the above.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Of the present inventionPolyimide resin orThe polyimide resin composition contains (A) polyimide resin as described above as an essential component.
[0007]
The polyimide resin of component (A) used in the present invention is obtained by reacting a tetravalent polycarboxylic acid having an acid anhydride group with a diisocyanate component. Examples of the tetravalent polycarboxylic acid having an acid anhydride group include those represented by the general formula (II)
[Chemical 7]
[0008]
The tetravalent polycarboxylic acid having an acid anhydride group represented by the above general formula (II) is commercially available, for example, as a trade name, EPICLON B-4400, manufactured by Dainippon Ink & Chemicals, Inc. Things.
[0009]
In addition to the above tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, pyrazine-2, 3, 5, 6 -Tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl- 1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine -2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis(Exobicyclo [2,2,1]Heptane-2,3-dicarboxylic anhydride)Sulfone, bicyclo- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride These may be replaced with tetracarboxylic dianhydrides such as trivalent tricarboxylic acids (trimellitic anhydride etc.) having an acid anhydride group, aliphatic or aromatic dibasic acids and the like.
[0010]
In the present invention, the diisocyanate represented by the general formula (III) used as the component (b) is, for example, the general formula (IV).
[Chemical 8]
[Chemical 9]
[0011]
As carbonate diols represented by the above general formula (IV), for example, trade name, PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL, manufactured by Daicel Chemical Industries, Ltd. Is commercially available asRumoThese can be used alone or in combination of two or more.
[0012]
Moreover, it represents with the said general formula (V).TheExamples of isocyanates include diphenylmethane-2,4.'Diisocyanates, 3,2'- or 3,3'-Or 4,2'- or 4,3'-Or 5,2'- or 5,3'-Or 6,2'- or 6,3'-Dimethyldiphenylmethane-2,4'Diisocyanates, 3,2'- or 3,3'-Or 4,2'-Or 4,3'- or 5,2'-Or 5,3'- or 6,2'-Or 6,3'-diethyldiphenylmethane-2,4'Diisocyanates, 3,2'- or 3,3'-Or 4,2'-Or 4,3'- or 5,2'-Or 5,3'- or 6,2'-Or 6,3'-dimethoxydiphenylmethane-2,4'-Diisocyanate, diphenylmethane-4,4'-Diisocyanate, diphenylmethane-3,3'-Diisocyanate, diphenylmethane-3,4'-Diisocyanate, diphenyl ether-4, 4'-Diisocyanate, benzophenone-4,4'-Diisocyanate, diphenylsulfone-4,4'-Diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4'It is preferred to use an aromatic polyisocyanate such as-[2,2bis (4-phenoxyphenyl) propane] diisocyanate. These can be used alone or in combination of two or more.
[0013]
Hexamethylene diisocyanate, 2,2,4-trimethylWhatXamethylene diisocyanate, isophorone diisocyanate, 4,4'-Aliphatic or cycloaliphatic isocyanates such as dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate, and trifunctional or higher polyisocyanates may be used. You may use what was stabilized with the blocking agent required in order to avoid. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.
The blending amount of the carbonate diols represented by the general formula (IV) and the diisocyanate represented by the general formula (V) is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group / hydroxyl group = 1.01 or more. It is preferable to do.
[0014]
The reaction can be carried out without solvent or in the presence of an organic solvent. The reaction temperature is preferably 60 to 200 ° C., and the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like.
[0015]
The number average molecular weight of the diisocyanate as the component (b) thus obtained is preferably 500 to 10,000, more preferably 1,000 to 9,500, and 1,500 to 9,000. It is particularly preferred that Number averageIf the molecular weight is outside this range,There is a tendency that the reactivity of the socyanate is lowered and it is difficult to obtain a polyimide resin. In the present specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
[0016]
In the present invention, it is preferable from the viewpoint of heat resistance to use a polyisocyanate compound other than the component (b) as the component (c). Such a polyisocyanate component is not particularly limited. For example, the diisocyanate represented by the general formula (V) used in the component (b) or a polyisocyanate having a valence of 3 or more may be used alone or in combination of two or more. Can be used in combination. As the polyisocyanate compound of component (c), 50 to 100% by weight of the total amount is preferably aromatic polyisocyanate, and considering the balance of heat resistance, solubility, mechanical properties, cost, etc., 4 , 4'-Diphenylmethane diisocyanate is particularly preferred.
[0017]
In the present invention, the blending ratio of the diisocyanate represented by the general formula (III) of the component (b) and the polyisocyanate of the component (c) is 0.1 / 0.0. It is preferably 9 to 0.9 / 0.1, more preferably 0.2 / 0.8 to 0.8 / 0.2, and 0.3 / 0.7 to 0.7 / 0. .3 is particularly preferable. If the equivalent ratio is less than 0.1 / 0.9, the elastic modulus cannot be lowered, and the warpage and adhesion tend to decrease. If the equivalent ratio exceeds 0.9 / 0.1, film properties such as heat resistance can be obtained. Tends to decrease.
[0018]
The blending ratio of the tetravalent polycarboxylic acid having an acid anhydride group of the component (a) is such that the acid anhydride group of the component (a) with respect to the total number of isocyanate groups in the component (b) and the component (c). The ratio of the total number is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, and 0.8 to 1.2. Is particularly preferred. When this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the polyimide resin.
[0019]
The reaction in the method for producing the polyimide resin of the present invention can be carried out by heat condensation in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent, while removing the liberated carbon dioxide gas from the reaction system. it can.
[0020]
Examples of the non-nitrogen-containing polar solvent include ether solvents such as diethylene glycol dimethyl ether and diethylene glycol.RujiEthyl ether, triethylene glycolRujiMethyl ether, triethylene glycolRujiEthyl ether, sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, ester solvents such as γ-butyrolactone, cellosolve acetate, ketone solvents such as cyclohexanone, methyl ethyl ketone, aromatic hydrocarbon solvents For example, toluene, xylene, etc. are mentioned, These can be used individually or in combination of 2 or more types. It is preferable to select and use a solvent that dissolves the resin to be formed. After the synthesis, it is preferable to use a suitable varnish solvent as it is. Γ-Butyrolactone is the most preferable because it is highly volatile, can impart low-temperature curability, and reacts efficiently in a homogeneous system.
[0021]
It is preferable that the usage-amount of a solvent shall be 0.8 to 5.0 times (weight ratio) of the polyimide resin to produce | generate. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir. If it exceeds 5.0 times, the reaction rate tends to decrease.
The reaction temperature is preferably 80 to 210 ° C, more preferably 100 to 190 ° C, and particularly preferably 120 to 180 ° C. If it is less than 80 ° C, the reaction time becomes too long, and if it exceeds 210 ° C, a three-dimensional reaction occurs during the reaction and gelation occurs.May occur. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
[0022]
The number average molecular weight of the polyimide resin thus obtained is preferably 4,000 to 40,000, more preferably 5,000 to 38,000, and 6,000 to 36,000. It is particularly preferred. When the number average molecular weight is less than 4,000, film properties such as heat resistance tend to be lowered. . In addition, workability tends to be inferior.
In addition, the isocyanate group at the end of the resin can be blocked with a blocking agent such as alcohols, lactams, or oximes after completion of the synthesis.
[0023]
Examples of the epoxy resin of component (B) used in the present invention include, for example, product names manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resins such as Epicoat 828, product names manufactured by Toto Kasei Co., Ltd., YDF -170 and other bisphenol F type epoxy resins, Yuka Shell Epoxy Co., Ltd. trade name, Epicoat 152, 154, Nippon Kayaku Co., Ltd. trade name, EPPN-201, Dow Chemical Company trade name, Phenol novolac type epoxy resins such as DEN-438, trade names made by Nippon Kayaku Co., Ltd., o-cresol novolac type epoxy resins such as EOCN-125S, 103S, 104S, etc., trade names made by Yuka Shell Epoxy Co., Ltd. , Epon1031S, trade name of Ciba Specialty Chemicals Co., Ltd., Araldite 0163, manufactured by Nagase Kasei Co., Ltd. Product name, polyfunctional epoxy resin such as Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, oil-based shell epoxy ( Co., Ltd. trade name, Epicote 604, Toto Kasei Co., Ltd. trade name, YH434, Mitsubishi Gas Chemical Co., Ltd. trade name, TETRAD-X, TERRAD-C, Nippon Kayaku Co., Ltd. Name, GAN, trade name manufactured by Sumitomo Chemical Co., Ltd., amine type epoxy resin such as ELM-120, product name manufactured by Ciba Specialty Chemicals Co., Ltd., heterocyclic-containing epoxy resin such as Araldite PT810, manufactured by UCC , Product names, alicyclic epoxy resins such as ERL4234, 4299, 4221, 4206, etc., which can be used alone or in combination of two or more. It can be.
[0024]
The amount of the (B) component epoxy resin used in the present invention is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, and even more preferably 3 to 100 parts by weight of the (A) component polyimide resin. 40 parts by weight. When the compounding amount of the epoxy resin is less than 1 part by weight, the solvent resistance, chemical resistance and moisture resistance tend to decrease, and when it exceeds 50 parts by weight, the heat resistance and viscosity stability tend to decrease.
[0025]
As a method for adding the epoxy resin, the epoxy resin to be added may be added after dissolving in advance in the same solvent as that contained in the polyimide resin, or may be added directly to the polyimide resin.
[0026]
Of the present inventionPolyimide resin orIn order to improve the workability at the time of coating and the film properties before and after the film formation, the polyimide resin composition, if necessary, surfactants such as organic or inorganic fillers, antifoaming agents, leveling agents, Colorants such as dyes or pigments, curing accelerators, heat stabilizers, antioxidants, flame retardants, and lubricants can be added.
[0027]
Of the present inventionPolyimide resin orIn the polyimide resin composition, as a film forming material, for example, an overcoat material for semiconductor elements and various electronic components, an interlayer insulating film, a surface protective film, a solder resist layer, an adhesive layer, etc. in the field of rigid or flexible substrates, etc. It can also be used for sealing materials, enameled wire varnishes, electrical insulation impregnating varnishes, cast varnishes, mica, glass cloth varnishes, MCL laminate varnishes, and friction material varnishes.
The film forming material in the invention is the abovePolyimide resin or itsIt refers to a semiconductor element, a flexible circuit board, a laminate, an enameled wire, etc. having a film formed using the composition.
In the present inventionPolyimide resin orThe intended effect of the polyimide resin composition can be obtained by using a polyimide resin obtained by using the diisocyanate of the component (b) described above or by using an epoxy resin.
[0028]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
[0029]
Example 1
In a 5-liter four-necked flask equipped with a stirrer, a cooling pipe with an oil / water separator, a nitrogen introduction pipe and a thermometer, PLACEL CD-220 (produced by Daicel Chemical Co., Ltd., 1,6-hexanediol system as a component (b) (Product name of polycarbonate diol) 1000.0 g (0.50 mol), 4,4′-diphenylmethane diisocyanate 250.27 g (1.00 mol) and γ-butyrolactone 833.51 g were charged, and the temperature was raised to 140 ° C. Reaction was carried out at 140 ° C. for 5 hours to obtain a diisocyanate [in the general formula (I), R represents all hexamethylene groups, X represents a diphenylmethane group, and m = 13 and n = 1].
Furthermore, 264.25 g (1.00 of 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride as component (a) was added to this reaction solution. Mole, as component (c), 4,4′-diphenylmethane diisocyanate 125.14 g (0.50 mol) and γ-butyrolactone 584.97 g were charged, heated to 160 ° C., reacted for 5 hours, and number average molecular weight The resulting resin was diluted with γ-butyrolactone to obtain a polyimide resin solution having a viscosity of 90 Pa · s and a non-volatile content of 52% by weight (component (b) / component (c)). The molar ratio of the components is 0.5 / 0.5.
[0030]
Example 2
YH-434 (trade name of amine type epoxy resin manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 120, 4 epoxy groups / molecule) with respect to 100 parts by weight of the resin content of the polyimide resin solution obtained in Example 1 10 Part by weight was added and diluted with γ-butyrolactone to obtain a polyimide resin composition having a viscosity of 52 Pa · s and a nonvolatile content of 52% by weight.
[0031]
Example 3
In Example 2, instead of 10 parts by weight of YH-434, Epicoat 828 (trade name of bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent of about 189, 2 epoxy groups / molecule) 10 weights Except for using parts, the same operation as in Example 1 was performed to obtain a resin composition having a viscosity of 46 Pa · s and a nonvolatile content of 52% by weight.
[0032]
Comparative Example 1
A flask similar to that of Example 1 except that the flask was made 3 L.', 4,4′-diphenylsulfonetetracarboxylic dianhydride 537.44 g (1.50 mol), (4) 4,4′-diphenylmethane diisocyanate (1.53 mol) as component (c) and γ-butyrolactone 1380 .51 g was charged and the temperature was raised to 160 ° C. During the reaction, the varnish became cloudy and a uniform polyimide solution could not be obtained.
[0033]
Comparative Example 2
In the same flask as in Example 1, as a component (b), silicone diol BX16-001 (trade name of dimethylpolysiloxane diol manufactured by Toray Dow Corning Silicone Co., Ltd.) 700 g (0.50 mol) and 4, 4 ′ -Diphenylmethane diisocyanate 250.27 g (1.00 mol), γ-butyrolactone 316.76 g and N-methyl-2-pyrrolidone 316.76 g were charged, and the temperature was raised to 140 ° C. The reaction was carried out at 140 ° C. for 3 hours, and this reaction solution was further mixed with 3, 3 as component (a).', 4,4′-diphenylsulfonetetracarboxylic dianhydride 358.29 g (1.00 mol), 4,4′-diphenylmethane diisocyanate 125.14 g (0.50 mol) as component (c) and γ-butyrolactone 269 .75 g and N-methyl-2-pyrrolidone 269.75 g were charged, and the temperature was raised to 160 ° C., followed by reaction for 4 hours to obtain a resin having a number average molecular weight of 15,000. The obtained resin was diluted with γ-butyrolactone to obtain a polyimide resin solution having a viscosity of 30 Pa · s and a nonvolatile content of 52% by weight.
[0034]
Comparative Example 3
Comparative Example 2so10 parts by weight of YH-434 is added to 100 parts by weight of the resin content of the obtained polyimide resin solution and diluted with γ-butyrolactone to obtain a polyimide resin composition having a viscosity of 12 Pa · s and a nonvolatile content of 52% by weight. It was.
[0035]
The physical properties of the polyimide resin solutions and polyimide resin compositions obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.
[0036]
(1) Warpage
The obtained polyimide resin composition is applied onto a polyimide film having a thickness of 50 μm, a length of 35 mm, and a width of 20 mm, dried at 90 ° C. for 15 minutes, and then 120 minutes at 120 ° C. or 60 minutes at 160 ° C. in an air atmosphere. The coating film (thickness: 20 μm) obtained by heating was placed on a surface plate with the coating surface down, and the warp height was evaluated.
[0037]
(2) Solvent resistance
The obtained polyimide resin composition is applied onto a rough surface of an electrolytic copper foil having a thickness of 35 μm, dried at 90 ° C. for 15 minutes, and then heated at 120 ° C. for 120 minutes or 160 ° C. for 60 minutes in an air atmosphere. The obtained coating film (thickness: 20 to 30 μm) was immersed in acetone for 1 hour at room temperature, and the change in coating film appearance was evaluated according to the following criteria.
○: No change in appearance
Δ: Some changes in appearance
×: Change in overall appearance
[0038]
(3) Adhesion to sealing material
The obtained polyimide resin composition is applied onto a rough surface of an electrolytic copper foil having a thickness of 35 μm or a polyimide film having a thickness of 50 μm, dried at 90 ° C. for 15 minutes, and then 120 minutes at 120 ° C. in an air atmosphere. Heated at 160 ° C. for 60 minutes, an epoxy-based encapsulant [manufactured by Hitachi Chemical Co., Ltd., trade name: CEL-C-5020] was added to the obtained coating film (thickness: 20 to 30 μm) by 0. Potted with 06 g, heated at 120 ° C. for 120 minutes and further at 150 ° C. for 120 minutes. The obtained coating film was bent so that the sealing material side was on the outside, and the mode of peeling was evaluated according to the following criteria.
○: Interfacial peeling of substrate / coating film
Δ: Interfacial peeling of coating film / sealing material
×: No adhesion
[0039]
(4) PCT resistance
The obtained polyimide resin composition is applied onto a rough surface of an electrolytic copper foil having a thickness of 35 μm or a polyimide film having a thickness of 50 μm, dried at 90 ° C. for 15 minutes, and then 120 minutes at 120 ° C. in an air atmosphere. A pressure cooker test (abbreviated as PCT, conditions 121 ° C., 2.0265 × 10 6) was performed at 160 ° C. for 60 minutes and the resulting coating film (thickness: 20 to 30 μm) was obtained. 5 (Pa, 100 hours) The appearance change after coating was evaluated according to the following criteria.
○: No change in appearance
Δ: Some changes in appearance
×: Change in overall appearance
[Table 1]
【The invention's effect】
Of the present inventionPolyimide resin orThe polyimide resin composition has excellent PCT resistance, is soluble in non-nitrogen-containing polar solvents, has low-temperature curability, heat resistance, electrical properties, low warpage, flexibility, and adhesion to sealing materials It is excellent in solvent resistance, chemical resistance, workability and economy.
In addition, the polyimide resin composition of the present invention has the above-mentioned excellent characteristics as a film forming material, and is used as an interlayer insulating film and surface protection in the field of semiconductor device and overcoat materials for various electronic parts, rigid or flexible substrates. For film, solder resist layer, adhesive layer, liquid encapsulant, varnish for enamel wire, impregnating varnish for electrical insulation, cast varnish, mica, glass cloth, sheet varnish, for MCL laminates It is suitably used for varnishes and varnishes for friction materials. Film forming materials such as various electric parts and electronic parts obtained by forming a film are excellent in reliability. Of the present inventionPolyimide resin orAn electronic component using the polyimide resin composition has excellent reliability.
Claims (8)
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| JP2003197090A JP4534117B2 (en) | 2003-07-15 | 2003-07-15 | Polyimide resin, polyimide resin composition, film-forming material using the same, and electronic component |
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| JP5135698B2 (en) * | 2005-03-28 | 2013-02-06 | 宇部興産株式会社 | Modified polyimide resin containing polycarbonate, composition thereof and cured insulating film |
| JP5208399B2 (en) | 2006-10-24 | 2013-06-12 | ニッタ株式会社 | Polyimide resin |
| JP5755401B2 (en) | 2009-04-30 | 2015-07-29 | 株式会社ピーアイ技術研究所 | Method for producing modified polyimide and modified polyimide |
| WO2016129541A1 (en) * | 2015-02-09 | 2016-08-18 | 味の素株式会社 | Heat-curable resin composition |
| JP6062090B1 (en) * | 2016-04-14 | 2017-01-18 | 第一工業製薬株式会社 | Method for producing polyimide aqueous dispersion |
| WO2017179268A1 (en) * | 2016-04-14 | 2017-10-19 | 第一工業製薬株式会社 | Aqueous polyimide dispersion, binder for electrodes, electrode, secondary battery and method for producing aqueous polyimide dispersion |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57177050A (en) * | 1981-04-24 | 1982-10-30 | Dainippon Ink & Chem Inc | Preparation of heat-resistant thermosetting resin |
| JPH11199669A (en) * | 1998-01-14 | 1999-07-27 | Ajinomoto Co Inc | Modified polyimide resin and thermoset resin composition containing the same |
| JP2002145981A (en) * | 2000-11-07 | 2002-05-22 | Hitachi Chem Co Ltd | Polyimide resin composition and file-forming material |
| JP2003198105A (en) * | 2001-12-28 | 2003-07-11 | Hitachi Chem Co Ltd | Resin paste and flexible wiring board using the same |
| JP2003335944A (en) * | 2002-05-21 | 2003-11-28 | Hitachi Chem Co Ltd | Polyimide resin paste and coating film-forming material containing the same |
| JP2005002192A (en) * | 2003-06-11 | 2005-01-06 | Hitachi Chem Co Ltd | Polyimide resin paste and film forming material containing the same |
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2003
- 2003-07-15 JP JP2003197090A patent/JP4534117B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57177050A (en) * | 1981-04-24 | 1982-10-30 | Dainippon Ink & Chem Inc | Preparation of heat-resistant thermosetting resin |
| JPH11199669A (en) * | 1998-01-14 | 1999-07-27 | Ajinomoto Co Inc | Modified polyimide resin and thermoset resin composition containing the same |
| JP2002145981A (en) * | 2000-11-07 | 2002-05-22 | Hitachi Chem Co Ltd | Polyimide resin composition and file-forming material |
| JP2003198105A (en) * | 2001-12-28 | 2003-07-11 | Hitachi Chem Co Ltd | Resin paste and flexible wiring board using the same |
| JP2003335944A (en) * | 2002-05-21 | 2003-11-28 | Hitachi Chem Co Ltd | Polyimide resin paste and coating film-forming material containing the same |
| JP2005002192A (en) * | 2003-06-11 | 2005-01-06 | Hitachi Chem Co Ltd | Polyimide resin paste and film forming material containing the same |
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