JP5450913B1 - Polyimide resin composition, film, adhesive, and parts - Google Patents
Polyimide resin composition, film, adhesive, and parts Download PDFInfo
- Publication number
- JP5450913B1 JP5450913B1 JP2013548670A JP2013548670A JP5450913B1 JP 5450913 B1 JP5450913 B1 JP 5450913B1 JP 2013548670 A JP2013548670 A JP 2013548670A JP 2013548670 A JP2013548670 A JP 2013548670A JP 5450913 B1 JP5450913 B1 JP 5450913B1
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- Prior art keywords
- polyimide resin
- resin composition
- monomer
- mol
- bis
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 240
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 185
- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 239000010408 film Substances 0.000 title claims description 36
- 239000000853 adhesive Substances 0.000 title claims description 35
- 230000001070 adhesive effect Effects 0.000 title claims description 31
- 239000000178 monomer Substances 0.000 claims abstract description 137
- 125000003118 aryl group Chemical group 0.000 claims abstract description 32
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 19
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 16
- 239000004305 biphenyl Substances 0.000 claims abstract description 16
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 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 42
- 150000004985 diamines Chemical class 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- -1 4-aminophenoxy Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 14
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 13
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000012787 coverlay film Substances 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 230000004580 weight loss Effects 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 claims description 4
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 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 claims description 3
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 claims description 3
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 3
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 claims description 3
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005548 dental material Substances 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 description 29
- 239000004642 Polyimide Substances 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- 239000002966 varnish Substances 0.000 description 18
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 13
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920005575 poly(amic acid) Polymers 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 125000006159 dianhydride group Chemical group 0.000 description 7
- 238000010292 electrical insulation Methods 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 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 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- WZEYZMKZKQPXSX-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1.CC1=CC(C)=CC(C)=C1 WZEYZMKZKQPXSX-UHFFFAOYSA-N 0.000 description 3
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- JVOQNVBQVMOFPV-UHFFFAOYSA-N 3-[3-[3-[3-(3-aminophenoxy)phenoxy]phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(OC=4C=C(OC=5C=C(N)C=CC=5)C=CC=4)C=CC=3)C=CC=2)=C1 JVOQNVBQVMOFPV-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 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 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000012762 magnetic filler Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 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 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- GRPTWLLWXYXFLX-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclodecane Chemical compound BrC1(Br)CCCCCCCC(Br)(Br)C1(Br)Br GRPTWLLWXYXFLX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
本発明のポリイミド樹脂組成物は、極性溶媒とポリイミド樹脂を少なくとも含み、ポリイミド樹脂の粘度平均分子量を0.6〜1.60とする。ポリイミド樹脂の全モノマーの95〜100mol%を主鎖に炭素数3以上の脂肪族鎖を有さない芳香族モノマーとし、該芳香族モノマーは化学式(1)、(2)で表されるベンゾフェノン骨格の少なくともいずれかを有するモノマー(A)を全モノマー中に5〜30mol%含み、ビフェニル骨格を有さずジフェニルエーテル骨格を有するモノマー(B)を全モノマー中に40〜95mol%含み、ビフェニル骨格を有するモノマー(C)を全モノマー中に45mol%未満とし、モノマー(B)はポリイミド樹脂を構成する全モノマー中、20〜95mol%が芳香環を3個以上有するモノマーである。
The polyimide resin composition of the present invention contains at least a polar solvent and a polyimide resin, and has a viscosity average molecular weight of 0.6 to 1.60. 95 to 100 mol% of the total monomer of the polyimide resin is an aromatic monomer having no aliphatic chain having 3 or more carbon atoms in the main chain, and the aromatic monomer is represented by the chemical formulas (1) and (2) The monomer (A) having at least one of the above is contained in 5 to 30 mol% in all monomers, the monomer (B) having no diphenyl ether skeleton and no biphenyl skeleton is contained in 40 to 95 mol% in all monomers, and has a biphenyl skeleton. Monomer (C) is less than 45 mol% in all monomers, and monomer (B) is a monomer having 20 to 95 mol% of three or more aromatic rings in all monomers constituting the polyimide resin.
Description
本発明は、極性溶媒とポリイミド樹脂を少なくとも含むポリイミド樹脂組成物に関する。また、前記ポリイミド樹脂組成物から形成されたフィルムに関する。また、前記ポリイミド樹脂組成物を含む接着剤、及び前記ポリイミド樹脂組成物から形成された成形体を含む部品に関する。 The present invention relates to a polyimide resin composition containing at least a polar solvent and a polyimide resin. Moreover, it is related with the film formed from the said polyimide resin composition. Moreover, it is related with the components containing the molded object formed from the adhesive agent containing the said polyimide resin composition, and the said polyimide resin composition.
近年、車載用を中心に電子回路基板や半導体デバイスなどにおいて、耐熱性に優れた接着剤が強く求められるようになってきている。現在使用されている主たる接着剤は、エポキシ樹脂であるが、エポキシ樹脂の耐熱性は十分でなく、熱硬化反応に長時間を要するという問題があった。 In recent years, an adhesive having excellent heat resistance has been strongly demanded for electronic circuit boards, semiconductor devices, and the like mainly for in-vehicle use. The main adhesive currently used is an epoxy resin, but the heat resistance of the epoxy resin is not sufficient, and there is a problem that a long time is required for the thermosetting reaction.
一方、熱可塑性ポリイミド樹脂は、高い耐熱性を有し、熱硬化反応も比較的短時間であるという利点を有する。しかしながら、通常、ポリイミド樹脂の前駆体であるポリアミック酸ワニスの塗膜を形成し、300℃以上の高温でイミド化するステップを経るため、樹脂の収縮が生じて応力が生じたり、剥離が生じたりする等の問題があった。また、高温処理に適さない部材を用いたものや、高温プロセスが不向きな用途に対して適用できないという問題があった。 On the other hand, a thermoplastic polyimide resin has the advantages of high heat resistance and a relatively short thermosetting reaction. However, since a polyamic acid varnish coating film, which is a precursor of a polyimide resin, is usually formed and subjected to an imidization step at a high temperature of 300 ° C. or higher, the resin contracts, causing stress or peeling. There was a problem such as. Moreover, there existed a problem that it was not applicable to the thing using the member which is not suitable for a high temperature process, or the use which a high temperature process is unsuitable.
上記問題を解決するために、溶媒に可溶なポリイミドワニスを用いる方法が提案されている(特許文献1、2)。溶媒に可溶なポリイミドワニスは、塗膜後にポリイミド前駆体をイミド化するのではなく、ワニスの段階で既にイミド化されているものである。このため、塗膜後に、高温でイミド化するプロセスをカットすることができる。 In order to solve the above problems, methods using a polyimide varnish soluble in a solvent have been proposed (Patent Documents 1 and 2). The polyimide varnish soluble in the solvent is not imidized with the polyimide precursor after the coating, but is already imidized at the varnish stage. For this reason, the process of imidizing at high temperature can be cut after a coating film.
特許文献1には、特定のエステル基を含有するテトラカルボン酸二無水物と脂肪族又は脂環族テトラカルボン酸二無水物とを含有するテトラカルボン酸二無水物混合物(A)と、特定のアルキレンジアミン及び/又はポリオキシアルキレンジアミンを含むジアミン(B)を用い、モル比を(A):(B)=0.80〜1.20:1の範囲としてイミド化反応して得られるポリイミド共重合体が開示されている。 Patent Document 1 discloses a tetracarboxylic dianhydride mixture (A) containing a tetracarboxylic dianhydride containing a specific ester group and an aliphatic or alicyclic tetracarboxylic dianhydride, and a specific Using a diamine (B) containing an alkylene diamine and / or a polyoxyalkylene diamine, a polyimide copolymer obtained by imidization reaction with a molar ratio of (A) :( B) = 0.80-1.20: 1. A polymer is disclosed.
特許文献2には、銅箔を粗化処理することなく、銅箔/ポリイミド樹脂(絶縁樹脂層)間の接着性向上の目的で使用される閉環型ポリイミド(A)及びエポキシ樹脂(B)を含有するプライマー層用樹脂組成物が提案されている。 Patent Document 2 discloses ring-closed polyimide (A) and epoxy resin (B) used for the purpose of improving the adhesion between copper foil / polyimide resin (insulating resin layer) without roughening the copper foil. A primer layer-containing resin composition has been proposed.
溶媒可溶型のポリイミド樹脂組成物は加熱工程が不要であることから、加熱処理ができない用途や熱膨張係数の差が問題となる用途をはじめとする様々な用途への応用展開が期待されている。しかしながら、その一方で、溶媒に可溶させるためにポリイミド樹脂の構造が特定されてしまうため、各種物性を満足させる構造を提供することが難しいという問題を抱えていた。 Since the solvent-soluble polyimide resin composition does not require a heating step, it is expected to be used in various applications including applications where heat treatment is not possible and applications where the difference in thermal expansion coefficient is a problem. Yes. However, on the other hand, since the structure of the polyimide resin is specified in order to be soluble in a solvent, it has been difficult to provide a structure that satisfies various physical properties.
本発明はこのような事情に鑑みてなされたもので、溶媒に可溶でありながら、得られる成形体の機械特性および耐熱性に優れるポリイミド樹脂組成物、並びに、前記ポリイミド樹脂組成物を含有する接着剤、及び前記ポリイミド樹脂組成物から形成された成形体を具備する部品、前記ポリイミド樹脂組成物から形成されたフィルムを提供することを目的とする。 The present invention has been made in view of such circumstances, and contains a polyimide resin composition excellent in mechanical properties and heat resistance of a molded article obtained while being soluble in a solvent, and the polyimide resin composition. It aims at providing the film | membrane formed from the part which comprises the adhesive agent, the molded object formed from the said polyimide resin composition, and the said polyimide resin composition.
本発明者らは、上記課題を解決すべく鋭意検討を重ね、以下の態様において上記課題を解決することを見出し、本発明を完成するに至った。即ち、本発明に係るポリイミド樹脂組成物は、極性溶媒と、ポリイミド樹脂と、を少なくとも含む組成物からなり、前記ポリイミド樹脂の粘度平均分子量ηが、0.6以上、1.60以下のものであり、前記ポリイミド樹脂を構成する全モノマーに対して95mol%以上、100mol%以下を、主鎖に炭素数3以上の脂肪族鎖を有さない芳香族モノマーとする。そして、前記芳香族モノマーは、化学式(1)及び化学式(2)で表されるベンゾフェノン骨格の少なくともいずれかを有するモノマー(A)を、前記ポリイミド樹脂を構成する全モノマー中に5mol%以上、30mol%以下含み、ビフェニル骨格を有さず、ジフェニルエーテル骨格を有するモノマー(B)を、前記ポリイミド樹脂を構成する全モノマー中に40mol%以上、95mol%以下含み、ビフェニル骨格を有するモノマー(C)を、前記ポリイミド樹脂を構成する全モノマー中に0mol%以上、45mol%未満含むものであり、前記モノマー(B)は、前記ポリイミド樹脂を構成する全モノマー中、20mol%以上が芳香環を3個以上有するモノマー(B−1)とするものである。
本発明に係るポリイミド樹脂組成物によれば、ポリイミド樹脂の粘度平均分子量ηを特定範囲とし、かつ、ポリイミド樹脂の構造としてベンゾフェノン骨格を有するモノマー(A)を特定量含み、さらに、ビフェニル骨格を有さず、ジフェニルエーテル骨格を有するモノマー(B)を特定量含み、さらに、ビフェニル骨格を有するモノマー(C)を特定量未満とし、さらに、モノマー(B)は、芳香環を3個以上有する構造を特定量含むものを用いる。その結果、極性溶媒に可溶でありながら、得られる成形物の機械特性および耐熱性に優れるポリイミド樹脂組成物を提供することができる。 According to the polyimide resin composition of the present invention, the viscosity average molecular weight η of the polyimide resin is in a specific range, the monomer resin (A) having a benzophenone skeleton is included as a structure of the polyimide resin, and the biphenyl skeleton is further included. First, the monomer (B) having a diphenyl ether skeleton is included in a specific amount, the monomer (C) having a biphenyl skeleton is less than a specific amount, and the monomer (B) has a structure having three or more aromatic rings. Use the one containing the amount. As a result, it is possible to provide a polyimide resin composition excellent in mechanical properties and heat resistance of the obtained molded product while being soluble in a polar solvent.
本発明に係るポリイミド樹脂組成物は、以下の条件を満足することが好ましい。即ち、前記組成物を塗工し、乾燥して得られるポリイミドフィルムが、(a)ガラス転移温度が130℃以上、260℃未満、(b)25℃での引張弾性率が2.0GPa以上、4.0GPa未満、及び(c)窒素雰囲気下での5%熱重量減少温度が500℃以上、を満たすことが好ましい。
前記ポリイミド樹脂の末端基を構成するモノマーは、ジアミンであることが好ましい。
前記ベンゾフェノン骨格を有するモノマーの好ましい例として、3,3'−ジアミノベンゾフェノン、3,4'−ジアミノベンゾフェノン、4,4'−ジアミノベンゾフェノン、3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物、及び2,3',3,4'−ベンゾフェノンテトラカルボン酸二無水物の少なくともいずれかを挙げることができる。
また、前記モノマー(B−1)の芳香環は、ベンゼン環であることが好ましい。
また、前記ビフェニル骨格を有するモノマー(C)は、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、3,3'−ビス(4−アミノフェノキシ)ビフェニル、2,2'−ビス(トリフルオロメチル)−1,1'−ビフェニル−4,4'−ジアミン、4,4'−ビス(3,4−ジカルボキシフェノキシ)ビフェニル二無水物、2,2',3,3'−ビフェニルテトラカルボン酸二無水物、3,3',4,4'−ビフェニルテトラカルボン酸二無水物の少なくともいずれかとすることが好ましい。
また、前記ビフェニル骨格を有するモノマー(C)を、前記ポリイミド樹脂を構成する全モノマー中に10モル%以上含むことが好ましい。
また、前記ポリイミド樹脂を構成するテトラカルボン酸二無水物の合計モル数が、前記ポリイミド樹脂を構成するジアミンの合計モル数に対して、0.99〜0.999であることが好ましい。
また、前記ポリイミド樹脂の重量平均分子量が、120,000以上、300,000以下であり、Mw/Mn比が10以上、12以下であることが好ましい。
また、前記ポリイミドフィルムの300℃での貯蔵弾性率は、1.0×105Pa以上であることが好ましい。
また、ポリイミド樹脂組成物の好ましい態様として、フィラーを含有するものが挙げられる。
また、ポリイミド樹脂組成物の好ましい態様として、さらに、ビスマレイミド化合物、及びナジイミド化合物より選ばれる1種以上の化合物を含有するものが挙げられる。
また、ポリイミド樹脂組成物の好ましい態様として、他の樹脂を含有するものが挙げられる。The polyimide resin composition according to the present invention preferably satisfies the following conditions. That is, the polyimide film obtained by coating and drying the composition is (a) a glass transition temperature of 130 ° C. or higher and lower than 260 ° C., (b) a tensile elastic modulus at 25 ° C. of 2.0 GPa or higher, It is preferable that less than 4.0 GPa and (c) 5% thermogravimetric reduction temperature in a nitrogen atmosphere satisfy 500 ° C. or more.
It is preferable that the monomer which comprises the terminal group of the said polyimide resin is diamine.
Preferred examples of the monomer having the benzophenone skeleton include 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dicarboxylate. An anhydride and at least any one of 2,3 ', 3,4'-benzophenone tetracarboxylic dianhydride can be mentioned.
The aromatic ring of the monomer (B-1) is preferably a benzene ring.
The monomer (C) having the biphenyl skeleton includes 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 3,3′-bis (4- Aminophenoxy) biphenyl, 2,2′-bis (trifluoromethyl) -1,1′-biphenyl-4,4′-diamine, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferable.
Moreover, it is preferable that the monomer (C) which has the said biphenyl skeleton is contained 10 mol% or more in all the monomers which comprise the said polyimide resin.
Moreover, it is preferable that the total mole number of the tetracarboxylic dianhydride which comprises the said polyimide resin is 0.99-0.999 with respect to the total mole number of the diamine which comprises the said polyimide resin.
Moreover, it is preferable that the weight average molecular weights of the said polyimide resin are 120,000 or more and 300,000 or less, and Mw / Mn ratio is 10 or more and 12 or less.
Moreover, it is preferable that the storage elastic modulus at 300 degreeC of the said polyimide film is 1.0 * 10 < 5 > Pa or more.
Moreover, what contains a filler is mentioned as a preferable aspect of a polyimide resin composition.
Moreover, what contains 1 or more types of compounds chosen from a bismaleimide compound and a nadiimide compound further as a preferable aspect of a polyimide resin composition is mentioned.
Moreover, what contains another resin as a preferable aspect of a polyimide resin composition is mentioned.
本発明に係るフィルムは、上記態様のポリイミド樹脂組成物から形成されたものである。
上記フィルムの好ましい例として、カバーレイフィルムが挙げられる。
本発明に係る接着剤は、上記態様のポリイミド樹脂組成物を含有するものである。
上記接着剤の好ましい例として、フレキシブルプリント基板用接着剤、カバーレイフィルム用接着剤、又はボンディングシート用接着剤が挙げられる。The film which concerns on this invention is formed from the polyimide resin composition of the said aspect.
A preferred example of the film is a coverlay film.
The adhesive which concerns on this invention contains the polyimide resin composition of the said aspect.
Preferable examples of the adhesive include a flexible printed circuit board adhesive, a coverlay film adhesive, or a bonding sheet adhesive.
本発明に係る部品は、上記態様のポリイミド樹脂組成物から形成された成形体を含むものである。
上記部品の好ましい例として、電子回路基板部材、半導体デバイス、リチウムイオン電池部材、太陽電池部材、燃料電池部材、モーター巻線、エンジン周辺部材、塗料、光学部品、放熱材、電磁波シールド材、サージ部品、歯科材、摺動コート、及び静電チャックが挙げられる。The component according to the present invention includes a molded body formed from the polyimide resin composition of the above aspect.
Preferred examples of the above components include electronic circuit board members, semiconductor devices, lithium ion battery members, solar cell members, fuel cell members, motor windings, engine peripheral members, paints, optical components, heat dissipation materials, electromagnetic shielding materials, and surge components. Dental materials, sliding coats, and electrostatic chucks.
本発明によれば、溶媒に可溶でありながら、得られる成形体の機械特性および耐熱性に優れるポリイミド樹脂組成物、並びに、前記ポリイミド樹脂組成物を含有する接着剤、及び前記ポリイミド樹脂組成物から形成された成形体を具備する部品、前記ポリイミド樹脂組成物から形成されたフィルムを提供できるという優れた効果がある。 According to the present invention, a polyimide resin composition excellent in mechanical properties and heat resistance of a molded article obtained while being soluble in a solvent, an adhesive containing the polyimide resin composition, and the polyimide resin composition There is an excellent effect that it is possible to provide a part including a molded body formed from the above, and a film formed from the polyimide resin composition.
以下、本発明を適用した実施形態の一例について説明する。なお、本発明の趣旨に合致する限り、他の実施形態も本発明の範疇に含まれることは言うまでもない。 Hereinafter, an example of an embodiment to which the present invention is applied will be described. Needless to say, other embodiments are also included in the scope of the present invention as long as they meet the spirit of the present invention.
本発明に係るポリイミド樹脂組成物は、極性溶媒とポリイミド樹脂とを少なくとも含む。極性溶媒は、ポリイミド樹脂を溶解できるものであれば特に限定されないが、好適な例としては、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N,N−ジエチルホルムアミド、N,N−ジエチルアセトアミド、N,N−ジメチルメトキシアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホルアミド、N−メチル−2−ピロリドン、ジメチルスルホン等が挙げられる。極性溶媒は、単独で、若しくは2種以上の混合溶媒として用いることができる。 The polyimide resin composition according to the present invention includes at least a polar solvent and a polyimide resin. The polar solvent is not particularly limited as long as it can dissolve the polyimide resin. Preferred examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, and N, N-diethyl. Examples include acetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, dimethyl sulfone and the like. A polar solvent can be used individually or as a 2 or more types of mixed solvent.
ポリイミド樹脂組成物中には、ポリイミド樹脂が溶解可能な範囲で、非極性溶媒を混合してもよい。非極性溶媒としては、ベンゼン、トルエン、キシレン、ベンゾニトリル、ジオキサン、シクロヘキサン、メシチレン(1,3,5−トリメチルベンゼン)、1,2,4−トリメチルベンゼン等が挙げられる。非極性溶媒の添加量は、本発明の趣旨を逸脱しない範囲において特に限定されないが、例えば、30質量%以下程度である。 In a polyimide resin composition, you may mix a nonpolar solvent in the range which can melt | dissolve a polyimide resin. Examples of the nonpolar solvent include benzene, toluene, xylene, benzonitrile, dioxane, cyclohexane, mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, and the like. Although the addition amount of a nonpolar solvent is not specifically limited in the range which does not deviate from the meaning of this invention, For example, it is about 30 mass% or less.
ポリイミド樹脂組成物における樹脂固形分の濃度は、特に限定されず、成形体の形状や厚み等に応じて適宜、選択することができる。塗工性を高める観点などからは、5〜50質量%であることが好ましく、10〜30質量%であることがより好ましい。 The density | concentration of the resin solid content in a polyimide resin composition is not specifically limited, According to the shape, thickness, etc. of a molded object, it can select suitably. From the viewpoint of improving coatability, the content is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass.
ポリイミド樹脂は、化学式(3)の構造を有するものである。
化学式(3)中のA1は4価の有機基であり、A2は2価の有機基である。ポリイミド樹脂は、ジアミンとテトラカルボン酸二無水物成分とを反応させてポリイミド前駆体であるポリアミド酸を得、その後、脱水・環化反応によりポリイミド化したものである。ポリイミド樹脂は、ポリイミド前駆体であるポリアミド酸に対してイミド化率を80%以上とすることが好ましい。より好ましくは85%以上である。ポリイミド樹脂は、化学式(3)の構造のみからなることが好ましいが、本発明の趣旨を逸脱しない範囲において別の構造が含まれていてもよい。The polyimide resin has a structure represented by chemical formula (3).
In the chemical formula (3), A 1 is a tetravalent organic group, and A 2 is a divalent organic group. A polyimide resin is obtained by reacting a diamine and a tetracarboxylic dianhydride component to obtain a polyamic acid that is a polyimide precursor, and then polyimidizing it by a dehydration / cyclization reaction. The polyimide resin preferably has an imidization ratio of 80% or more with respect to the polyamic acid which is a polyimide precursor. More preferably, it is 85% or more. The polyimide resin preferably has only the structure represented by the chemical formula (3), but may include another structure without departing from the gist of the present invention.
本発明に係るポリイミド樹脂は、粘度平均分子量ηが、0.6以上、1.60以下のものとする。なお、本明細書でいう粘度平均分子量ηは、以下の方法により算出した値を言うものとする。即ち、測定するポリイミドワニスを三角フラスコに少量採取し、N−メチルピロリドン(NMP)を用いて0.5(g/dL)に希釈する。そして、調製した希釈ワニスを、35℃恒温槽に入れたウベローデ管(柴田科学社製)で落下時間を測定する。そして、η=ln[希釈ワニス落下時間/NMP落下時間]より求めた値を粘度平均分子量ηとする。粘度平均分子量ηを0.6以上とすることにより、即ち、高分子量化することにより、ポリイミド樹脂から得られる成形体の機械強度を効果的に高めることができる。ポリイミド樹脂の粘度平均分子量ηは、0.7以上であることがより好ましく、0.8以上であることがさらに好ましい。溶解性の観点からは、粘度平均分子量ηは1.4以下であることが好ましい。 The polyimide resin according to the present invention has a viscosity average molecular weight η of 0.6 or more and 1.60 or less. The viscosity average molecular weight η referred to in this specification is a value calculated by the following method. That is, a small amount of the polyimide varnish to be measured is collected in an Erlenmeyer flask and diluted to 0.5 (g / dL) using N-methylpyrrolidone (NMP). And the fall time is measured with the Ubbelohde pipe | tube (made by Shibata Kagaku company) which put the prepared dilution varnish in the 35 degreeC thermostat. And let the value calculated | required from (eta) = ln [dilution varnish fall time / NMP fall time] be a viscosity average molecular weight (eta). By setting the viscosity average molecular weight η to 0.6 or more, that is, by increasing the molecular weight, the mechanical strength of the molded product obtained from the polyimide resin can be effectively increased. The viscosity average molecular weight η of the polyimide resin is more preferably 0.7 or more, and further preferably 0.8 or more. From the viewpoint of solubility, the viscosity average molecular weight η is preferably 1.4 or less.
また、本発明のポリイミド樹脂は、ポリイミド樹脂を構成する全モノマーにおいて、95mol%以上、100mol%以下を主鎖に炭素数3以上の脂肪族鎖を有さない芳香族モノマー[以下、「芳香族モノマー(M)」とも表記する]とする。なお、主鎖とは、ポリイミドの鎖の伸長方向であり、ポリイミドを構成するモノマーの2つの末端反応基を連結する構造のうち側鎖を構成する原子を除いたものをいう。また、側鎖には、炭素数3以上の脂肪族鎖を有するものが含まれていてもよい。耐熱性の観点からは、芳香族モノマー(M)の側鎖においても炭素数3以上の脂肪族鎖を有さないことが好ましい。 In addition, the polyimide resin of the present invention is an aromatic monomer having 95 to 100 mol% of the main chain and having no aliphatic chain having 3 or more carbon atoms in the entire monomer constituting the polyimide resin [hereinafter referred to as “aromatics”. Also referred to as “monomer (M)”. The main chain is the direction in which the polyimide chain extends, and refers to the structure in which the two terminal reactive groups of the monomer constituting the polyimide are linked, excluding the atoms constituting the side chain. Further, the side chain may include one having an aliphatic chain having 3 or more carbon atoms. From the viewpoint of heat resistance, it is preferable that the side chain of the aromatic monomer (M) does not have an aliphatic chain having 3 or more carbon atoms.
本発明のポリイミド樹脂は、ポリイミド樹脂を構成する全モノマーが主鎖に炭素数3以上の脂肪族鎖を有さない芳香族モノマー(M)である場合を含む。芳香族モノマー(M)を95mol%以上含むことにより、耐熱性が高くなるという効果が得られる。芳香族モノマー(M)に分類されないモノマーは、5mol%未満の範囲において用いることができる。例えば、主鎖に炭素数3以上の脂肪族鎖を有する芳香族モノマーや、脂環式モノマー、脂肪族モノマーを5mol%未満の範囲において用いてもよい。耐熱性の観点からは、ポリイミド樹脂を構成するモノマーは、全てのモノマーが芳香族モノマー(ここでいう芳香族モノマーは、芳香族モノマー(M)に限定されない)であることが好ましい。 The polyimide resin of the present invention includes the case where all monomers constituting the polyimide resin are aromatic monomers (M) having no aliphatic chain having 3 or more carbon atoms in the main chain. By including 95 mol% or more of the aromatic monomer (M), an effect of increasing heat resistance can be obtained. Monomers that are not classified as aromatic monomers (M) can be used in a range of less than 5 mol%. For example, an aromatic monomer having an aliphatic chain having 3 or more carbon atoms in the main chain, an alicyclic monomer, or an aliphatic monomer may be used in a range of less than 5 mol%. From the viewpoint of heat resistance, it is preferable that all monomers constituting the polyimide resin are aromatic monomers (the aromatic monomer here is not limited to the aromatic monomer (M)).
本発明の芳香族モノマー(M)は、以下の(構造I)〜(構造III)の条件を満足するものとする。 The aromatic monomer (M) of the present invention satisfies the following conditions (Structure I) to (Structure III).
(構造I)下記化学式(1)及び下記化学式(2)で表されるベンゾフェノン骨格の少なくともいずれかを有するモノマー(A)[以下、「モノマーA」とも表記する]を、前記ポリイミド樹脂を構成する全モノマー中に5mol%以上、30mol%以下含むものとする。なお、化学式(1)、(2)は、本発明の趣旨を逸脱しない範囲において、例えば、メチル基、エチル基、ハロゲン等の置換基を含んでいてもよい。
モノマー(A)を5mol%未満とすると、ポリイミド樹脂の極性溶媒への溶解性が低下する傾向にある。また、モノマー(A)を30mol%越えとすると、ゲル化する傾向にある。モノマー(A)は、9mol%以上であることが好ましく、10mol%以上であることが特に好ましい。また、モノマー(A)は、25mol%以下であることが好ましく、15mol%以下であることが特に好ましい。 If the monomer (A) is less than 5 mol%, the solubility of the polyimide resin in a polar solvent tends to be reduced. Further, when the monomer (A) exceeds 30 mol%, gelation tends to occur. The monomer (A) is preferably 9 mol% or more, particularly preferably 10 mol% or more. Moreover, it is preferable that a monomer (A) is 25 mol% or less, and it is especially preferable that it is 15 mol% or less.
モノマー(A)は、特に限定されないが、ジアミンの好適な例は、3,3'−ジアミノベンゾフェノン、3,4'−ジアミノベンゾフェノン、4,4'−ジアミノベンゾフェノン、化学式(4)の化合物、4,4'−ビス[4−(4−アミノ−α,α−ジメチルベンジル)フェノキシ]ベンゾフェノン等が挙げられる。
モノマー(A)として酸二無水物を適用する場合の好適な例は、3,3',4,4'−ベンゾフェノン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、2,2',3,3'−ベンゾフェノンテトラカルボン酸二無水物等が挙げられる。モノマー(A)は、単独で若しくは組み合わせて用いることができる。 Preferred examples in the case of applying an acid dianhydride as the monomer (A) include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic Acid dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, etc. are mentioned. Monomers (A) can be used alone or in combination.
(構造II)ビフェニル骨格を有さず、ジフェニルエーテル骨格を有するモノマー(B)[以下、「モノマー(B)」とも表記する]を、ポリイミド樹脂を構成する全モノマー中に40mol%以上、95mol%以下含むものとする。さらに、モノマー(B)は、前記ポリイミド樹脂を構成する全モノマー中、20mol%以上、95mol%以下は、芳香環を3個以上有するモノマー(B−1)[以下、「モノマー(B−1)」とも表記する]とする。モノマー(B−1)の芳香環は、ベンゼン環とすることが好ましい。なお、モノマー(B)とモノマー(A)は、重複してカウントしてもよい。即ち、ベンゾフェノン骨格を有し、かつ、ビフェニル骨格を有さず、ジフェニルエーテル骨格を有するモノマーは、モノマー(A)でもありモノマー(B)でもある。 (Structure II) A monomer (B) having no diphenyl ether skeleton and having a diphenyl ether skeleton [hereinafter also referred to as “monomer (B)”] is 40 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin. Shall be included. Further, the monomer (B) is a monomer (B-1) [hereinafter referred to as “monomer (B-1)” having 3 or more aromatic rings in the total monomer constituting the polyimide resin, in an amount of 20 mol% or more and 95 mol% or less. Is also expressed as]. The aromatic ring of the monomer (B-1) is preferably a benzene ring. The monomer (B) and the monomer (A) may be counted redundantly. That is, a monomer having a benzophenone skeleton and not having a biphenyl skeleton and having a diphenyl ether skeleton is both a monomer (A) and a monomer (B).
ポリイミド樹脂を構成する全モノマー中にモノマー(B)を40mol%以上、95mol%以下とし、かつ、ポリイミド樹脂を構成する全モノマー中にモノマー(B−1)を20mol%以上、95mol%以下とすることにより、ポリイミド樹脂の極性溶媒に対する溶解性を高めることができる。モノマー(B)が40mol%未満であると、溶解性が低下する傾向にある。モノマー(B−1)は30mol%以上であることが好ましく、40mol%以上であることがさらに好ましい。 The monomer (B) is 40 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin, and the monomer (B-1) is 20 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin. Thereby, the solubility with respect to the polar solvent of a polyimide resin can be improved. If the monomer (B) is less than 40 mol%, the solubility tends to decrease. The monomer (B-1) is preferably 30 mol% or more, and more preferably 40 mol% or more.
モノマー(B−1)は、特に限定されないが、上記化学式(4)のジアミンや下記化学式(5)のジアミンが挙げられる。
化学式(5)中、Xは酸素原子、硫黄原子、スルホン基、メチレン基、イソプロピリデン基またはヘキサフルオロイソプロピリデン基の2価の基を示す。Although a monomer (B-1) is not specifically limited, The diamine of the said Chemical formula (4) and the diamine of following Chemical formula (5) are mentioned.
In the chemical formula (5), X represents a divalent group of an oxygen atom, a sulfur atom, a sulfone group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.
モノマー(B−1)のジアミンの好適な例は、ビス[4−(3−アミノフェノキシ)フェニル]スルフィド、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、1,3−ビス(3−(3−アミノフェノキシ)フェノキシ)ベンゼン、1,3−ビス(3−(4−アミノフェノキシ)フェノキシ)ベンゼン、1,3−ビス(4−(3−アミノフェノキシ)フェノキシ)ベンゼン、1,3−ビス(3−(3−アミノフェノキシ)フェノキシ)−2−メチルベンゼン、1,3−ビス(3−(4−アミノフェノキシ)フェノキシ)−4−メチルベンゼン、1,3−ビス(4−(3−アミノフェノキシ)フェノキシ)−2−エチルベンゼン、1,3−ビス(3−(2−アミノフェノキシ)フェノキシ)−5−sec−ブチルベンゼン、1,3−ビス(4−(3−アミノフェノキシ)フェノキシ)−2,5−ジメチルベンゼン、1,3−ビス(4−(2−アミノ−6−メチルフェノキシ)フェノキシ)ベンゼン、1,3−ビス(2−(2−アミノ−6−エチルフェノキシ)フェノキシ)ベンゼン、1,3−ビス(2−(3−アミノフェノキシ)−4−メチルフェノキシ)ベンゼン、1,3−ビス(2−(4−アミノフェノキシ)−4−tert−ブチルフェノキシ)ベンゼン、1,4−ビス(3−(3−アミノフェノキシ)フェノキシ)−2,5−ジ−tert−ブチルベンゼン、1,4−ビス(3−(4−アミノフェノキシ)フェノキシ)−2,3−ジメチルベンゼン、1,4−ビス(3−(2−アミノ−3−プロピルフェノキシ)フェノキシ)ベンゼン、1,2−ビス(3−(3−アミノフェノキシ)フェノキシ)−4−メチルベンゼン、1,2−ビス(3−(4−アミノフェノキシ)フェノキシ)−3−n−ブチルベンゼン、1,2−ビス(3−(2−アミノ−3−プロピルフェノキシ)フェノキシ)ベンゼン、4,4'−ビス(4−アミノフェニル)−1,4−ジイソプロピルベンゼン、ビス[4−(3−アミノフェノキシ)フェニル]メタン、ビス[4−(4−アミノフェノキシ)フェニル]メタン、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、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、ビス[4−(4−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]スルフィド、ビス[4−(3−アミノフェノキシ)フェニル]スルホキシド、ビス[4−(アミノフェノキシ)フェニル]スルホキシド、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、1,4−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−(3−アミノフェノキシ)ベンゾイル]ベンゼン、4,4'−ビス[3−(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[3−(3−アミノフェノキシ)ベンゾイル]ジフェニルエーテルなどが挙げられる。中でも、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、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンが好ましい。 Suitable examples of the diamine of the monomer (B-1) include bis [4- (3-aminophenoxy) phenyl] sulfide, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino). Phenoxy) benzene, 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,3-bis (4- (3 -Aminophenoxy) phenoxy) benzene, 1,3-bis (3- (3-aminophenoxy) phenoxy) -2-methylbenzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) -4-methyl Benzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2-ethylbenzene, 1,3-bis (3- (2-aminophenoxy) phenoxy)- -Sec-butylbenzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2,5-dimethylbenzene, 1,3-bis (4- (2-amino-6-methylphenoxy) phenoxy) Benzene, 1,3-bis (2- (2-amino-6-ethylphenoxy) phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) -4-methylphenoxy) benzene, 1,3- Bis (2- (4-aminophenoxy) -4-tert-butylphenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) -2,5-di-tert-butylbenzene, 1, 4-bis (3- (4-aminophenoxy) phenoxy) -2,3-dimethylbenzene, 1,4-bis (3- (2-amino-3-propylphenoxy) phenoxy Benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) -4-methylbenzene, 1,2-bis (3- (4-aminophenoxy) phenoxy) -3-n-butylbenzene, 1, 2-bis (3- (2-amino-3-propylphenoxy) phenoxy) benzene, 4,4′-bis (4-aminophenyl) -1,4-diisopropylbenzene, bis [4- (3-aminophenoxy) Phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-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-hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, Bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) Phenyl] sulfone, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- ( 4-Aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] di Phenyl ether and the like. Among these, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are preferable.
モノマー(B−1)として酸二無水物を適用する場合の好適な例は、4,4'−(4,4'−イソプロピリデンジフェノキシ)ビス無水フタル酸、1,3−ビス(3,4−ジカルボキシフェノキシ)ベンゼン二無水物、1,4−ビス(3,4−ジカルボキシフェノキシ)ベンゼン二無水物等がある。モノマー(B−1)は、単独で若しくは組み合わせて用いることができる。 A suitable example in the case of applying acid dianhydride as the monomer (B-1) is 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride, 1,3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, and the like. Monomers (B-1) can be used alone or in combination.
モノマー(B−1)に分類されないモノマー(B)は、特に限定されないが、好ましいジアミンの例として、4,4'−ジアミノジフェニルエーテル、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等が挙げられる。モノマー(B−1)に分類されないモノマー(B)として酸二無水物を適用する場合の好適な例は、4,4'−オキシジフタル酸無水物が挙げられる。モノマー(B)は、単独で若しくは組み合わせて用いることができる。 The monomer (B) not classified into the monomer (B-1) is not particularly limited, but examples of preferred diamines include 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and the like. Is mentioned. A suitable example in the case of applying an acid dianhydride as the monomer (B) not classified into the monomer (B-1) includes 4,4′-oxydiphthalic anhydride. Monomers (B) can be used alone or in combination.
(構造III)ビフェニル骨格を有するモノマー(C)[以下、「モノマー(C)」とも表記する]を、前記ポリイミド樹脂を構成する全モノマー中に0mol%以上、45mol%未満含むようにする。なお、モノマー(C)とモノマー(A)は、重複してカウントしてもよい。即ち、ベンゾフェノン骨格を有し、かつ、ビフェニル骨格を有するモノマーは、モノマー(A)でもありモノマー(C)でもある。 (Structure III) A monomer (C) having a biphenyl skeleton [hereinafter also referred to as “monomer (C)”] is contained in an amount of 0 mol% or more and less than 45 mol% in all monomers constituting the polyimide resin. The monomer (C) and the monomer (A) may be counted redundantly. That is, a monomer having a benzophenone skeleton and a biphenyl skeleton is both a monomer (A) and a monomer (C).
モノマー(C)は、特に限定されないが、ジアミンの好適な例は、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、3,3'−ビス(4−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、2,2'−ビス(トリフルオロメチル)−1,1'−ビフェニル−4,4'−ジアミン、3,3'−ジメチルベンジジン、3,4'−ジメチルベンジジン、4,4'−ジメチルベンジジンが挙げられる。 Although the monomer (C) is not particularly limited, suitable examples of the diamine include 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 3,3 ′. -Bis (4-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2'-bis (trifluoromethyl) -1,1'-biphenyl-4,4'-diamine, 3,3′-dimethylbenzidine, 3,4′-dimethylbenzidine, 4,4′-dimethylbenzidine can be mentioned.
モノマー(C)として酸二無水物を適用する場合の好適な例は、3,3',4,4'−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、4,4'−ビス(3,4−ジカルボキシフェノキシ)ビフェニル二無水物、2,2',3,3'−ビフェニルテトラカルボン酸二無水物等である。モノマー(C)は、単独で若しくは組み合わせて用いることができる。 Preferred examples in the case of applying an acid dianhydride as the monomer (C) include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic Acid dianhydrides, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, and the like. Monomers (C) can be used alone or in combination.
また、芳香族モノマー(M)のうち、上記モノマー(A)、モノマー(B)、モノマー(C)以外の好ましいモノマー[以下、「その他のモノマー(D)」とも表記する]として、下記化学式(6)が例示できる。
化学式(6)中、Yは硫黄原子、スルホン基、メチレン基、イソプロピリデン基またはヘキサフルオロイソプロピリデン基の2価の基を示す。Further, among the aromatic monomers (M), preferable monomers other than the monomers (A), monomers (B), and monomers (C) [hereinafter also referred to as “other monomers (D)”] have the following chemical formula ( 6) can be exemplified.
In chemical formula (6), Y represents a divalent group of a sulfur atom, a sulfone group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.
その他の芳香族モノマー(D)は、特に限定されないが、好適なテトラカルボン酸二無水物の具体例としては、ピロメリット酸二無水物、ビス(3,4−ジカルボキシフェニル)スルフィド二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、ビス(3,4−ジカルボキシフェニル)メタン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン二無水物、2,3,6,7−ナフタレンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、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(2,3−ジカルボキシフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン二無水物、ビス(2,3−ジカルボキシフェニル)スルフィド二無水物、ビス(2,3−ジカルボキシフェニル)スルホン二無水物、1,2,5,6−ナフタレンテトラカルボン酸二無水物、4,4'−イソフタロイルジフタリックアンハイドライド、ジアゾジフェニルメタン−3,3',4,4'−テトラカルボン酸二無水物、ジアゾジフェニルメタン−2,2',3,3'−テトラカルボン酸二無水物、2,3,6,7−チオキサントンテトラカルボン酸二無水物、2,3,6,7−アントラキノンテトラカルボン酸二無水物、2,3,6,7−キサントンテトラカルボン酸二無水物、エチレンテトラカルボン酸二無水物などが挙げられる。 Other aromatic monomers (D) are not particularly limited, but specific examples of suitable tetracarboxylic dianhydrides include pyromellitic dianhydride and bis (3,4-dicarboxyphenyl) sulfide dianhydride. Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)- 1, , 1,3,3,3-hexafluoropropane dianhydride, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride, 4,4′-isophthaloyl diphthalic anhydride, diazodiphenylmethane-3,3 ′, 4,4′-tetracarboxylic dianhydride, diazodiphenylmethane-2, 2 ', 3,3'-tetracarboxylic dianhydride, 2,3,6,7-thioxanthone tetracarboxylic dianhydride, 2,3,6,7-anthraquinone tetracarboxylic dianhydride, 2,3 , 6,7-xanthonetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride and the like.
その他の芳香族モノマー(D)の好適なジアミンとしては、m−フェニレンジアミン、o−フェニレンジアミン、p−フェニレンジアミン、m−アミノベンジルアミン、p−アミノベンジルアミン、ビス(3−アミノフェニル)スルフィド、ビス(4−アミノフェニル)スルフィド、ビス(3−アミノフェニル)スルホキシド、(3−アミノフェニル)(4−アミノフェニル)スルホキシド、ビス(3−アミノフェニル)スルホン、(3−アミノフェニル)(4−アミノフェニル)スルホン、ビス(4−アミノフェニル)スルホン、3,3'−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、4,4'−ジアミノジフェニルメタン等が挙げられる。 Suitable diamines for other aromatic monomers (D) include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide. Bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4 - aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl methane and the like.
また、芳香族モノマー(M)以外のモノマーの好適な例としては、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、ポリ(テトラメチレンオキシド)−ジ−p−アミノベンゾエート(14EL;イハラケミカル社製)、ポリエーテルアミン(XTJ-542、D−2000;HUNTSMAN社製)などが挙げられる。 Moreover, as a suitable example of monomers other than the aromatic monomer (M), 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-diaminoundecane, 1,12-diaminododecane, poly (tetramethylene oxide) -di-p- Examples thereof include aminobenzoate (14EL; manufactured by Ihara Chemical Co., Ltd.), polyetheramine (XTJ-542, D-2000; manufactured by HUNTSMAN), and the like.
芳香環上の水素原子の一部もしくは全ては、フルオロ基、メチル基、メトキシ基、トリフルオロメチル基、及びトリフルオロメトキシ基などから選ばれる基で置換されていてもよい。また、芳香環上には、目的に応じて、エチニル基、ベンゾシクロブテン−4'−イル基、ビニル基、アリル基、シアノ基、イソシアネート基、ニトリロ基、及びイソプロペニル基などから選ばれる架橋点となる基を有していてもよい。これらは、1種又は2種以上を組み合わせてもよい。 Some or all of the hydrogen atoms on the aromatic ring may be substituted with a group selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, a trifluoromethoxy group, and the like. In addition, on the aromatic ring, a bridge selected from an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, an isopropenyl group, and the like depending on the purpose. You may have the group used as a point. These may be used alone or in combination of two or more.
前述の通り、ポリイミド樹脂は、芳香族テトラカルボン酸二無水物または芳香族ジアミン由来のベンゾフェノン骨格を含む。ポリイミド樹脂の末端基は、特に限定されないが、耐熱性の観点からアミン末端とすることが好ましい。アミン末端とすることにより、一のポリイミド分子に含まれるベンゾフェノン骨格由来のカルボニル基と、他のポリイミド分子の末端アミノ基とが水素結合するため、高い耐熱性が得られる。末端アミンにする場合には、テトラカルボン酸二無水物の合計モル数が、ジアミンの合計モル数に対して0.9〜0.999とすることにより容易に得ることができる。テトラカルボン酸二無水物の合計モル数が、ジアミンの合計モル数に対して0.99〜0.999とすることがより好ましい。ポリイミド樹脂は、ランダム重合体であっても、ブロック重合体であってもよいが、ジアミン成分の特性が得られやすいことから、ランダム重合体が好ましい。 As described above, the polyimide resin includes a benzophenone skeleton derived from aromatic tetracarboxylic dianhydride or aromatic diamine. The terminal group of the polyimide resin is not particularly limited, but is preferably an amine terminal from the viewpoint of heat resistance. By using an amine terminal, a carbonyl group derived from a benzophenone skeleton contained in one polyimide molecule and a terminal amino group of another polyimide molecule are hydrogen-bonded, so that high heat resistance is obtained. When making it a terminal amine, it can obtain easily by making the total mole number of tetracarboxylic dianhydride into 0.9-0.999 with respect to the total mole number of diamine. The total number of moles of tetracarboxylic dianhydride is more preferably 0.99 to 0.999 with respect to the total number of moles of diamine. The polyimide resin may be a random polymer or a block polymer, but a random polymer is preferable because the characteristics of the diamine component are easily obtained.
ポリイミド樹脂の好ましい重量平均分子量は、50,000以上、1000,000以下である。重量平均分子量を50,000以上、1000,000以下とすることにより、機械強度を効果的に高めることができる。重量平均分子量は、100,000以上であることがより好ましく、120,000以上であることが特に好ましい。また、重量平均分子量は、500,000以下であることがより好ましく、300,000以下であることが特に好ましい。重量平均分子量を120,000以上、300,000以下の範囲とすることにより、より効果的に機械強度を高めることができる。また、Mw/Mn比の好ましい範囲は、5以上、100以下である。Mw/Mn比を5以上、100以下とすることにより、ポリイミド樹脂組成物におけるポリイミド樹脂の溶解性と、ポリイミド樹脂組成物から得られるフィルム・シート等の成形体の機械特性の両者のバランスを良好に保つことができる。Mw/Mn比は、10以上であることがより好ましく、12以上であることが特に好ましい。また、Mw/Mn比は、50以下であることがより好ましく、30以下であることが特に好ましい。Mw/Mn比を12〜30の範囲とすることにより、より効果的にポリイミド樹脂組成物におけるポリイミド樹脂の溶解性と、ポリイミド樹脂組成物から得られるフィルム・シート等の成形体の機械特性の両者のバランスを良好に保つことができる。なお、ポリイミド樹脂の重量平均分子量、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)により測定できる。 A preferred weight average molecular weight of the polyimide resin is 50,000 or more and 1,000,000 or less. By setting the weight average molecular weight to 50,000 or more and 1,000,000 or less, the mechanical strength can be effectively increased. The weight average molecular weight is more preferably 100,000 or more, and particularly preferably 120,000 or more. The weight average molecular weight is more preferably 500,000 or less, and particularly preferably 300,000 or less. By setting the weight average molecular weight in the range of 120,000 or more and 300,000 or less, the mechanical strength can be increased more effectively. Moreover, the preferable range of Mw / Mn ratio is 5 or more and 100 or less. By setting the Mw / Mn ratio to 5 or more and 100 or less, the balance between the solubility of the polyimide resin in the polyimide resin composition and the mechanical properties of the molded article such as a film / sheet obtained from the polyimide resin composition is good. Can be kept in. The Mw / Mn ratio is more preferably 10 or more, and particularly preferably 12 or more. The Mw / Mn ratio is more preferably 50 or less, and particularly preferably 30 or less. By setting the Mw / Mn ratio in the range of 12 to 30, both the solubility of the polyimide resin in the polyimide resin composition and the mechanical properties of the molded article such as a film / sheet obtained from the polyimide resin composition are more effective. Can maintain a good balance. In addition, the weight average molecular weight and number average molecular weight of a polyimide resin can be measured by gel permeation chromatography (GPC).
数平均分子量の好ましい範囲は、上記重量平均分子量及びMw/Mnから算出すると、500〜200,000であり、特に好ましくは、4,000〜25,000である。ポリイミド樹脂のアミン当量は、数平均分子量を1分子中に含まれるアミノ基の数で除することによって求められる。末端アミンにする場合には、テトラカルボン酸二無水物の合計モル数が、ジアミンの合計モル数に対して0.9〜0.999とすることにより容易に得ることができる。従って、上記数平均分子量から、アミン当量の好ましい範囲は250〜10,000であり、より好ましい範囲は、2,000〜125,00である。 A preferable range of the number average molecular weight is 500 to 200,000, particularly preferably 4,000 to 25,000, when calculated from the weight average molecular weight and Mw / Mn. The amine equivalent of the polyimide resin is determined by dividing the number average molecular weight by the number of amino groups contained in one molecule. When making it a terminal amine, it can obtain easily by making the total mole number of tetracarboxylic dianhydride into 0.9-0.999 with respect to the total mole number of diamine. Therefore, from the number average molecular weight, a preferable range of the amine equivalent is 250 to 10,000, and a more preferable range is 2,000 to 125,000.
ポリイミド樹脂組成物は、本発明の趣旨を逸脱しない範囲において種々の添加剤を含有させることができる。例えば、紫外線吸収剤、保存安定剤、接着助剤、及び表面改質剤、分散剤等を適宜加えることができる。また、耐熱性・柔軟性に影響を与えず、本発明の趣旨を逸脱しない範囲においてポリイミド樹脂以外の他の樹脂を含有していてもよい。好適な例としては、ウレタン樹脂、エポキシ樹脂、アクリル樹脂、PET(ポリエチレンテレフタレート)樹脂、ポリアミド樹脂、ポリアミドイミド樹脂等が挙げられる。 The polyimide resin composition can contain various additives without departing from the gist of the present invention. For example, an ultraviolet absorber, a storage stabilizer, an adhesion aid, a surface modifier, a dispersant, and the like can be added as appropriate. Further, other resins than the polyimide resin may be contained within a range that does not affect the heat resistance and flexibility and does not depart from the gist of the present invention. Preferable examples include urethane resin, epoxy resin, acrylic resin, PET (polyethylene terephthalate) resin, polyamide resin, polyamideimide resin and the like.
また、ポリイミド樹脂組成物には、以下の化合物を含んでいてもよい。ビスフェノールA型エポキシ化合物、ビスフェノールF型エポキシ化合物等のエポキシ化合物;カルボキシエチルアクリレート、プロピレングリコールアクリレート、エトキシ化フェニルアクリレート及び脂肪族エポキシアクリレート等のアクリレート化合物;メチレンビスフェニルジイソシアネート(MDI)、トルエンジイソシアネート(TDI)、ヘキサメチレンジイソシアネート(HDI)及びキシレンジイソシアネート(XDI)等のイソシアネート化合物;4,4'−ジフェニルメタンビスマレイミド、4,4'−ジフェニルオキシビスマレイミド、4,4'−ジフェニルスルホンビスマレイミド、p−フェニレンビスマレイミド、m−フェニレンビスマレイミド、2,4−トリレンビスマレイミド、2,6−トリレンビスマレイミド、エチレンビスマレイミド、ヘキサメチレンビスマレイミド、4,4'-(2,2'−ビス(4'',4'''−フェノキシフェニル)イソプロピリデン)ビスマレイミド、4,4'−(2,2'−ビス(4'',4'''−フェノキシフェニル)ヘキサフルオロイソプロピリデン)マレイミド、4,4'−ビス(3,5−ジメチルフェニル)メタンマレイミド、4,4'−ビス(3,5−ジエチルフェニル)メタンビスマレイミド、4,4'−(3−メチル−5−エチルフェニル)メタンビスマレイミド、4,4'−ビス(3,5−ジイソプロピルフェニル)メタンマレイミド、4,4'−ジシクロヘキシルメタン)ビスマレイミド、p−キシリレンビスマレイミド、m−キシリレンビスマレイミド、1,3−ジメチレンシクロヘキサンビスマレイミド、1,4−ジメチレンシクロヘキサンマレイミド及びアミノフェノキシベンゼン−ビスマレイミド(APB−BMI)等のビスマレイミド化合物およびマレイミド化合物;及びアルケニル置換ナジイミドが挙げられる。アルケニル置換ナジイミドとは例えば、4,4'−(ジフェニルメタン)ビスナジイミド、フェニレンビスナジイミド、4,4'−ビフェニレンビスナジイミド、4,4'−ジフェニルプロパンビスナジイミド、4,4'−ジフェニルエーテルビスナジイミドなどのナジイミド化合物が挙げられる。他の樹脂の添加量は、用途に応じて適宜選択することができる。 Moreover, the following compounds may be included in the polyimide resin composition. Epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds; acrylate compounds such as carboxyethyl acrylate, propylene glycol acrylate, ethoxylated phenyl acrylate and aliphatic epoxy acrylate; methylene bisphenyl diisocyanate (MDI), toluene diisocyanate (TDI) ), Isocyanate compounds such as hexamethylene diisocyanate (HDI) and xylene diisocyanate (XDI); 4,4′-diphenylmethane bismaleimide, 4,4′-diphenyloxy bismaleimide, 4,4′-diphenylsulfone bismaleimide, p- Phenylene bismaleimide, m-phenylene bismaleimide, 2,4-tolylene bismaleimide, 2,6-tolylene bismaleimide , Ethylene bismaleimide, hexamethylene bismaleimide, 4,4 ′-(2,2′-bis (4 ″, 4 ′ ″-phenoxyphenyl) isopropylidene) bismaleimide, 4,4 ′-(2,2 '- bis (4'',4''' - phenoxyphenyl) hexafluoroisopropylidene) maleimide, 4,4-bis (3,5-dimethylphenyl) methanone comma Reimido, 4,4'-bis (3, 5-diethyl-phenyl) meth Nbi Sumareimido, 4,4 '- (3-methyl-5-ethylphenyl) methanone Nbi Sumareimido, 4,4'-bis (3,5-diisopropylphenyl) methanone comma Reimido, 4,4' -Dicyclohexylmethane) bismaleimide, p-xylylene bismaleimide, m-xylylene bismaleimide, 1,3-dimethylenecyclohexane bismaleimide, 1,4-dimethyl And bilemaleimide and maleimide compounds such as tylene cyclohexanemaleimide and aminophenoxybenzene-bismaleimide (APB-BMI); and alkenyl-substituted nadiimides. Examples of the alkenyl-substituted nadiimide include 4,4 ′-(diphenylmethane) bisnadiimide, phenylenebisnadiimide, 4,4′-biphenylenebisnadiimide, 4,4′-diphenylpropane bisnadiimide, 4,4′-diphenylether bisnadiimide, and the like. A nadiimide compound is mentioned. The addition amount of other resin can be suitably selected according to a use.
ポリイミド樹脂組成物には、フィラーが含有されていてもよい。好ましい例として、窒化ホウ素、窒化アルミニウム、アルミナ、アルミナ水和物、酸化ケイ素、窒化ケイ素、ダイヤモンド、ハイドロキシアパタイト、チタン酸バリウム、銅、アルミニウム、シリカ、マグネシア、チタニア、炭化ケイ素などの熱伝導性を有する材料が用いられる。これらのうち、特に、熱伝導性、電気絶縁性に優れ、化学的に安定であることから、アルミナ、窒化ホウ素などが好ましい。また、フィラーとして、金属、金属酸化物、無定形カーボン粉、グラファイト、金属めっきしたフィラーを使用することができる。金属としては、銅、アルミニウム、ニッケル、鉄、金、銀、白金、タングステン、クロム、チタン、スズ、鉛、パラジウムなどが挙げられる。これらは、1種類又は2種以上を組み合わせて用いてもよい。また、フィラーとして軟磁性フィラーを用いてもよい。軟磁性フィラーとしては、例えば、磁性ステンレス(Fe−Cr−Al−Si合金)、センダスト(Fe−Si−Al合金)、パーマロイ(Fe−Ni合金)、ケイ素銅(Fe−Cu−Si合金)、Fe−Si合金、Fe−Si−B(−Cu−Nb)合金、Fe−Ni−Cr−Si合金、Fe−Si−Cr合金、Fe−Si−Al−Ni−Cr合金等が挙げられる。また、フェライトや純鉄粒子を用いてもよい。フェライトとしては、例えば、Mn−Znフェライト、Ni−Znフェライト、Mn−Mgフェライト、Mnフェライト、Cu−Znフェライト、Cu−Mg−Znフェライトなどのソフトフェライト、あるいは永久磁石材料であるハードフェライトが挙げられる。フィラーの平均粒径は、特に限定されないが、例えば、0.5〜100μmである。フィラーの添加量は、用途に応じて適宜選択することができる。 The polyimide resin composition may contain a filler. Preferred examples include boron nitride, aluminum nitride, alumina, alumina hydrate, silicon oxide, silicon nitride, diamond, hydroxyapatite, barium titanate, copper, aluminum, silica, magnesia, titania, thermal conductivity, such as carbonization silicon A material having properties is used. Of these, alumina, boron nitride, and the like are particularly preferable because they are excellent in thermal conductivity and electrical insulation and are chemically stable. Further, as the filler, metal, metal oxide, amorphous carbon powder, graphite, or metal-plated filler can be used. Examples of the metal include copper, aluminum, nickel, iron, gold, silver, platinum, tungsten, chromium, titanium, tin, lead, and palladium. These may be used alone or in combination of two or more. A soft magnetic filler may be used as the filler. Examples of the soft magnetic filler include magnetic stainless steel (Fe—Cr—Al—Si alloy), sendust (Fe—Si—Al alloy), permalloy (Fe—Ni alloy), silicon copper (Fe—Cu—Si alloy), Fe-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Ni-Cr-Si alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni-Cr alloy, etc. are mentioned. Further, ferrite or pure iron particles may be used. Examples of the ferrite include soft ferrite such as Mn—Zn ferrite, Ni—Zn ferrite, Mn—Mg ferrite, Mn ferrite, Cu—Zn ferrite, and Cu—Mg—Zn ferrite, or hard ferrite that is a permanent magnet material. It is done. Although the average particle diameter of a filler is not specifically limited, For example, it is 0.5-100 micrometers. The addition amount of a filler can be suitably selected according to a use.
ポリイミド樹脂組成物には、難燃剤が含有されていてもよい。難燃剤は、特に限定されないが、例えば、ハロゲン系難燃剤、無機系難燃剤、リン系難燃剤を使用することができる。難燃剤は、1種類で用いてもよいし、2種以上を混合して使用してもよい。
ハロゲン系難燃剤としては、塩素を含む有機化合物と臭素を含む化合物が挙げられる。具体的には、ペンタブロモジフェニルエーテル、オクタブロモジフェニルエーテル、デカブロモジフェニルエーテル、テトラブロモビスフェノールA、ヘキサブロモシクロデカンテトラブロモビスフェノールAなどが挙げられる。
無機系難燃剤としては、アンチモン化合物と金属水酸化物などが挙げられる。アンチモン化合物としては三酸化アンチモンと五酸化アンチモンが挙げられる。金属水酸化物としては、水酸化アルミニウム、水酸化マグネシウムなどが挙げられる。
リン系難燃剤としては、ホスファゼン、ホスフィン、ホスフィンオキサイド、リン酸エステルなどが挙げられる。
難燃剤の添加量は、特に限定されず、用いる難燃剤の種類に応じて適宜変更できる。一般的には、ポリイミド樹脂100質量部に対して5質量部から50質量部の範囲で用いることが好ましい。The polyimide resin composition may contain a flame retardant. Although a flame retardant is not specifically limited, For example, a halogen flame retardant, an inorganic flame retardant, and a phosphorus flame retardant can be used. A flame retardant may be used by 1 type and may be used in mixture of 2 or more types.
Examples of the halogen-based flame retardant include an organic compound containing chlorine and a compound containing bromine. Specific examples include pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclodecane tetrabromobisphenol A, and the like.
Examples of inorganic flame retardants include antimony compounds and metal hydroxides. Antimony compounds include antimony trioxide and antimony pentoxide. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
Examples of the phosphorus flame retardant include phosphazene, phosphine, phosphine oxide, and phosphate ester.
The addition amount of the flame retardant is not particularly limited, and can be appropriately changed according to the type of the flame retardant used. Generally, it is preferable to use in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the polyimide resin.
本発明のポリイミド樹脂組成物は、溶媒に可溶なポリイミド樹脂を含むため、ポリイミドワニスとして用いることができる。そのため、本発明のポリイミド樹脂組成物を、基材上に塗布した後、乾燥してフィルム・シート・構造体等の成形体を形成することができる。このように、本発明のポリイミド樹脂組成物は、高温でイミド化するステップが不要となるため、耐熱性の低い基材・部材等にポリイミド成形体を形成したい場合や、高温プロセスに不向きな用途にも幅広く適用することができる。無論、ポリイミド樹脂は耐熱性に優れているので、高温処理を行う用途においても好適に適用することができる。また、溶媒に可溶なため、リフトオフ法などを用いてパターン形成したりすることもできる。 Since the polyimide resin composition of the present invention contains a polyimide resin soluble in a solvent, it can be used as a polyimide varnish. Therefore, after apply | coating the polyimide resin composition of this invention on a base material, it can dry and form molded objects, such as a film, a sheet | seat, and a structure. Thus, since the polyimide resin composition of the present invention does not require a step of imidization at a high temperature, it is not suitable for a high temperature process or when a polyimide molded body is to be formed on a low heat resistance substrate or member. It can also be applied widely. Of course, since the polyimide resin is excellent in heat resistance, it can also be suitably applied in applications where high temperature treatment is performed. Further, since it is soluble in a solvent, a pattern can be formed using a lift-off method or the like.
ポリイミド樹脂組成物は、当該組成物を塗工して乾燥した後の厚みが30μm〜70μmとなるポリイミドフィルムにおいて、以下の条件を満足することが好ましい。即ち、(a)ガラス転移温度が130℃以上、260℃未満、(b)25℃での引張弾性率が2.0GPa以上、4.0GPa未満、及び(c)窒素雰囲気下での5%熱重量減少温度が500℃以上を満たすことが好ましい。なお、乾燥後の塗膜厚みが30μm〜70μmとなるようにするためには、例えば、ポリイミド樹脂組成物の塗膜を300μm〜400μmに塗膜すればよい。 The polyimide resin composition preferably satisfies the following conditions in a polyimide film having a thickness of 30 μm to 70 μm after the composition is applied and dried. That is, (a) glass transition temperature of 130 ° C. or higher and lower than 260 ° C., (b) tensile elastic modulus at 25 ° C. of 2.0 GPa or higher and lower than 4.0 GPa, and (c) 5% heat in a nitrogen atmosphere The weight reduction temperature preferably satisfies 500 ° C. or higher. In addition, what is necessary is just to apply | coat the coating film of a polyimide resin composition to 300 micrometers-400 micrometers, for example so that the coating film thickness after drying may be set to 30 micrometers-70 micrometers.
ポリイミドフィルムの作製方法は特に限定されないが、一例として以下の方法が挙げられる。即ち、ポリイミド樹脂組成物を離型処理されたPETフィルム上に10mm/secの速度で塗工する。得られた塗膜を200℃で30分間乾燥させて、溶媒を除去し、乾燥後、PETフィルムからピンセットなどを用いてフィルム部分を剥離し、十分に乾燥させることによって乾燥後の塗膜厚みが30〜70μmとなるように作製する方法が挙げられる。 Although the production method of a polyimide film is not specifically limited, The following method is mentioned as an example. That is, the polyimide resin composition is applied at a speed of 10 mm / sec on the release-treated PET film. The obtained coating film is dried at 200 ° C. for 30 minutes, the solvent is removed, and after drying, the film part is peeled off from the PET film using tweezers and the like, and the coating film thickness after drying is sufficiently dried. The method of producing so that it may become 30-70 micrometers is mentioned.
なお、本明細書においてガラス転移温度は、以下の方法により測定した値をいう。即ち、上記ポリイミドフィルムの固体粘弾性の温度分散測定(引張モード)を、TA instruments社製のRSA−IIIを用いて引張モードで測定周波数1Hzの条件で行い、貯蔵弾性率E'と損失弾性率E"を測定する。そして、得られた損失正接tanδ=E"/E'のピーク値から「ガラス転移温度」を導出した値とする。 In this specification, the glass transition temperature is a value measured by the following method. That is, the temperature dispersion measurement (tensile mode) of the solid viscoelasticity of the polyimide film is performed under the condition of a measurement frequency of 1 Hz in the tensile mode using RSA-III manufactured by TA instruments, and the storage elastic modulus E ′ and the loss elastic modulus. E ″ is measured. Then, the “glass transition temperature” is derived from the peak value of the obtained loss tangent tan δ = E ″ / E ′.
また、本明細書の引張弾性率は、以下の方法により測定した値をいう。即ち、上記ポリイミドフィルムを90mm長さ×10mm幅サイズに切り出し、実際の測定長を50mm長(両端20mm部分を引っ張り領域)とし、AUTOGRAPH AGS-100D(島津製作所社製)にて、25℃において、速度50mm/minで短冊状のサンプルフィルムを引っ張ったときのチャートにおける初期の傾きを求め、この値を「引張弾性率」とする。 Moreover, the tensile elasticity modulus of this specification says the value measured with the following method. That is, the polyimide film was cut into a size of 90 mm length × 10 mm width, the actual measurement length was 50 mm length (both ends 20 mm portion was a tensile region), and AUTOGRAPH AGS-100D (manufactured by Shimadzu Corporation) at 25 ° C. The initial inclination in the chart when the strip-shaped sample film is pulled at a speed of 50 mm / min is obtained, and this value is defined as “tensile modulus”.
また、本明細書の5%熱重量減少温度は、以下の方法により測定した値をいう。即ち、熱重量測定装置(TGA−51、島津製作所社製)を用いて、ポリイミドフィルムを、石英ルツボに約10mg入れて、窒素雰囲気下で常温より10℃/分で800℃まで昇温した時の5%熱重量減少温度をいう。 Further, the 5% thermogravimetric decrease temperature in the present specification refers to a value measured by the following method. That is, when about 10 mg of a polyimide film is put into a quartz crucible using a thermogravimetric measuring apparatus (TGA-51, manufactured by Shimadzu Corporation), and the temperature is raised from room temperature to 800 ° C. at 10 ° C./min in a nitrogen atmosphere. Of 5% thermal weight loss temperature.
ガラス転移温度を130℃以上にすることにより、ポリイミド樹脂の耐熱性をより効果的に発揮させることができる。また、ガラス転移温度を260℃未満とすることにより、ポリイミド樹脂層を例えば多層化したときに他の層との密着性・柔軟性を効果的に向上させることができる。ガラス転移温度は、135℃以上とすることがより好ましく、また、255℃以下とすることがより好ましい。 By setting the glass transition temperature to 130 ° C. or higher, the heat resistance of the polyimide resin can be more effectively exhibited. Further, by setting the glass transition temperature to less than 260 ° C., for example, when the polyimide resin layer is multilayered, adhesion and flexibility with other layers can be effectively improved. The glass transition temperature is more preferably 135 ° C. or higher, and more preferably 255 ° C. or lower.
引張弾性率を2.0GPa以上、4.0GPa未満とすることにより、機械強度の優れたものを提供することができる。乾燥後の厚みが30μm〜70μmとなるポリイミドフィルムの25℃での引張弾性率は、2.1GPa以上であることがより好ましく、2.2GPa以上であることが特に好ましい。また、3.8GPa以下であることがより好ましく、3.7GPa以下であることがさらに好ましい。 By setting the tensile modulus to 2.0 GPa or more and less than 4.0 GPa, it is possible to provide a material having excellent mechanical strength. The tensile elastic modulus at 25 ° C. of the polyimide film having a thickness after drying of 30 μm to 70 μm is more preferably 2.1 GPa or more, and particularly preferably 2.2 GPa or more. Moreover, it is more preferable that it is 3.8 GPa or less, and it is further more preferable that it is 3.7 GPa or less.
また、乾燥後の厚みが30μm〜70μmとなるポリイミドフィルムの窒素雰囲気下での5%熱重量減少温度は、500℃以上であることが好ましく、より好ましくは520℃以上であり、特に好ましくは530℃以上である。500℃以上とすることにより、耐熱性に優れた成形体を提供することができる。 The 5% thermal weight loss temperature in a nitrogen atmosphere of the polyimide film having a thickness after drying of 30 μm to 70 μm is preferably 500 ° C. or higher, more preferably 520 ° C. or higher, particularly preferably 530. It is above ℃. By setting it as 500 degreeC or more, the molded object excellent in heat resistance can be provided.
乾燥後の厚みが30μm〜70μmとなるポリイミドフィルムの貯蔵弾性率E'(300℃)は、1.0×105Pa以上であることが好ましい。貯蔵弾性率E'(300℃)を1.0×105Pa以上とすることにより、耐熱性の高いポリイミドフィルムを得ることができる。The storage elastic modulus E ′ (300 ° C.) of the polyimide film having a thickness after drying of 30 μm to 70 μm is preferably 1.0 × 10 5 Pa or more. By setting the storage elastic modulus E ′ (300 ° C.) to 1.0 × 10 5 Pa or more, a highly heat-resistant polyimide film can be obtained.
上記(a)〜(c)の特性を全て満足するポリイミド樹脂を用いることにより、溶媒に可溶であり、得られる成形体が機械特性に優れ、かつ高い耐熱性を有するポリイミド樹脂が得られる。 By using a polyimide resin that satisfies all of the above characteristics (a) to (c), a polyimide resin that is soluble in a solvent, has an excellent molded characteristic, and has high heat resistance can be obtained.
次に、ポリイミド樹脂組成物の製造方法について説明する。まず、上述した特定のジアミンと特定のテトラカルボン酸二無水物を反応させてポリアミド酸を得る。ポリイミド前駆体の酸二無水物とジアミンの合成時の割合は、特に限定されないが、ジアミンと前記酸無水物の合計に対し、前記ジアミン成分の合計が47.5〜52.5mol%、酸二無水物成分の合計が47.5〜52.5mol%を満たす範囲で共重合することが好ましい。末端アミンにする場合には、テトラカルボン酸二無水物の合計モル数が、ジアミンの合計モル数に対して0.9〜0.999とすることにより容易に得ることができる。なお、ポリイミド樹脂を合成する際に用いる仕込みモノマーの量比と、得られるポリマー中のモノマーの比率は概ね同等になるので、所望の構造を含むポリマーを得るためには、仕込みモノマーの量を調整すればよい。 Next, the manufacturing method of a polyimide resin composition is demonstrated. First, the above-mentioned specific diamine and specific tetracarboxylic dianhydride are reacted to obtain a polyamic acid. The ratio of the polyimide precursor acid dianhydride and diamine during the synthesis is not particularly limited, but the total of the diamine components is 47.5 to 52.5 mol% and the acid dianhydride is based on the total of the diamine and the acid anhydride. It is preferable to perform copolymerization within a range where the total of the anhydride components satisfies 47.5 to 52.5 mol%. When making it a terminal amine, it can obtain easily by making the total mole number of tetracarboxylic dianhydride into 0.9-0.999 with respect to the total mole number of diamine. In addition, the amount ratio of the charged monomer used when synthesizing the polyimide resin and the ratio of the monomer in the obtained polymer are almost the same. Therefore, in order to obtain a polymer having a desired structure, the amount of the charged monomer is adjusted. do it.
重合は、固相系で行うことも可能であるが、好ましくは液相系で行う。液相系では、重合濃度は、例えば、5〜50質量%程度とする。反応溶媒は、特に限定されないが、沸点が100℃以上のものが好ましい。一般に、ポリイミド前駆体の重合に用いられる溶媒を好適に利用できる。例えば、少なくとも一つの反応物質、好ましくは酸無水物類とジアミン類の両方を溶解するものである。具体的には、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、クレゾール、ジメチルスルホキシド、N−メチル−2−ピロリドン、テトラメチル尿素等が挙げられる。これらの溶媒類は、単独、あるいは1,3,5−トリメチルベンゼン、1,2,4−トリメチルベンゼン、ベンゾニトリル、ジオキサン、キシレンあるいはトルエン等の他の溶媒との組み合わせで用いることもできる。 The polymerization can be carried out in a solid phase system, but is preferably carried out in a liquid phase system. In the liquid phase system, the polymerization concentration is, for example, about 5 to 50% by mass. The reaction solvent is not particularly limited, but preferably has a boiling point of 100 ° C. or higher. In general, a solvent used for polymerization of a polyimide precursor can be suitably used. For example, it dissolves at least one reactant, preferably both acid anhydrides and diamines. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, cresol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and tetramethylurea. These solvents can be used alone or in combination with other solvents such as 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, benzonitrile, dioxane, xylene or toluene.
ポリイミド前駆体の製造においては、適宜、触媒を用いてもよい。触媒は、本発明の趣旨を逸脱しない限りにおいて脱水重縮合反応の進行を実質的に促進するか、架橋剤の副反応の進行を阻害するものである限り、特に制限されない。また、触媒の使用量は、触媒の揮散性や酸強度等の触媒自身の性質、反応条件を考慮して、適宜、調整すればよい。実質的に反応を促進させるか、架橋等の副反応の進行を阻害させることができれば特に制限されない。また、この触媒には、触媒自身に上記性質がなくても流通ガスや反応溶媒と反応することにより上記性質を有する化合物に変化するものも含む。 In the production of the polyimide precursor, a catalyst may be used as appropriate. The catalyst is not particularly limited as long as it substantially accelerates the progress of the dehydration polycondensation reaction or inhibits the progress of the side reaction of the crosslinking agent without departing from the spirit of the present invention. The amount of the catalyst used may be appropriately adjusted in consideration of the properties of the catalyst itself such as the volatility of the catalyst and the acid strength, and the reaction conditions. There is no particular limitation as long as the reaction can be substantially promoted or the progress of side reactions such as crosslinking can be inhibited. In addition, the catalyst includes a catalyst that changes to a compound having the above properties by reacting with a flowing gas or a reaction solvent even if the catalyst itself does not have the above properties.
触媒としてはポリイミドの重合に用いられる一般的な公知触媒のほか、例えば、有機スルホン酸等の酸触媒が挙げられ、さらに詳しくは、例えば、メタンスルホン酸、エタンスルホン酸、1−プロパンスルホン酸、1−ブタンスルホン酸、1−ペンタンスルホン酸、1−ヘキサンスルホン酸、1−ヘプタンスルホン酸、1−オクタンスルホン酸等のアルカンスルホン酸、トリフルオロメタンスルホン酸等のハロゲン化置換アルカンスルホン酸、ベンゼンスルホン酸、p−トルエンスルホン酸、p−キシレン−2−スルホン酸、p−クロロベンゼンスルホン酸、p−ニトロベンゼンスルホン酸等のベンゼンスルホン酸誘導体、ナフタレン−1−スルホン酸、ナフタレン−2−スルホン酸、2,5−ナフタレンジスルホン酸等のナフタレンスルホン酸誘導体等が挙げられる。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。 As the catalyst, in addition to general known catalysts used for polymerization of polyimide, for example, acid catalysts such as organic sulfonic acid can be mentioned, and more specifically, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, alkanesulfonic acid such as 1-octanesulfonic acid, halogenated substituted alkanesulfonic acid such as trifluoromethanesulfonic acid, benzenesulfone Benzenesulfonic acid derivatives such as acid, p-toluenesulfonic acid, p-xylene-2-sulfonic acid, p-chlorobenzenesulfonic acid, p-nitrobenzenesulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 2 , 5-Naphthalenesulfonic acid and other naphthalene sulfones Acid derivatives. These can be used alone or in combination of two or more.
液相反応工程において、原料、溶媒、及び必要に応じて加えられるその他の触媒等の仕込み順序・方法は特に限定されない。反応温度は、必要な重量平均分子量(Mw)が得られるのであれば特に制限されるものではないが、ポリイミド前駆体としてポリアミド酸を重合するときには通常、20℃以上、100℃以下とする。反応時間は必要な重合度を得るのに充分である範囲内に限って限定されない。また、反応に際しては窒素等の不活性ガス雰囲気下で行うことが好ましい。反応系内(反応機内)の固形分濃度は特に限定されないが、通常、5質量%以上〜50質量%以下である。ポリアミド酸を得た後、脱水・環化反応によりポリイミド化する。 In the liquid phase reaction step, the order and method of charging the raw materials, the solvent, and other catalysts added as necessary are not particularly limited. The reaction temperature is not particularly limited as long as a necessary weight average molecular weight (Mw) can be obtained, but is usually 20 ° C. or higher and 100 ° C. or lower when polyamic acid is polymerized as a polyimide precursor. The reaction time is not limited to a range that is sufficient to obtain the required degree of polymerization. Further, the reaction is preferably performed in an inert gas atmosphere such as nitrogen. The solid content concentration in the reaction system (in the reactor) is not particularly limited, but is usually 5% by mass to 50% by mass. After obtaining the polyamic acid, it is polyimideized by dehydration and cyclization reaction.
固相反応に使用する反応装置は、特に限定されないが、スーパーブレンド(住友重機械工業社製)、愛工ケミカルミキサー(愛工舎製作所社製)、プラネタリーミキサー(井上製作所社製)、トリミックス(井上製作所社製)等の混練機が挙げられる。 The reaction apparatus used for the solid phase reaction is not particularly limited, but Super Blend (Sumitomo Heavy Industries, Ltd.), Aiko Chemical Mixer (Aikosha Seisakusho), Planetary Mixer (Inoue Seisakusho), Trimix ( And kneading machines such as those manufactured by Inoue Seisakusho.
通常、溶媒に可溶なポリイミドを得るためには多官能モノマーや立体障害の大きな特殊モノマーを使用して、イミド環同士のパッキングを抑制すること、また、分子量を低下させることが有効である。しかしながら、特許文献1に記載のポリイミド樹脂は、耐熱性・熱重量減少温度が十分ではなかった。また、特許文献2に記載のポリイミド樹脂は、重量平均分子量Mwが低く、それから得られるフィルムの耐熱性・機械特性などが十分とはいえなかった。 Usually, in order to obtain a polyimide soluble in a solvent, it is effective to use a polyfunctional monomer or a special monomer having a large steric hindrance to suppress packing between imide rings and to reduce the molecular weight. However, the polyimide resin described in Patent Document 1 has insufficient heat resistance and thermal weight reduction temperature. Further, the polyimide resin described in Patent Document 2 has a low weight average molecular weight Mw, and the heat resistance and mechanical properties of a film obtained therefrom are not sufficient.
本発明によれば、ポリイミド樹脂の粘度平均分子量を特定範囲とし、かつ、ポリイミド樹脂を構成するモノマーの構造(芳香族モノマー(M)、モノマー(A)〜(C))、及びその含有量を特定することにより、溶媒に可溶でありながら、得られる成形体が機械特性に優れ、かつ高い耐熱性を有するポリイミド樹脂組成物が得られる。より具体的には、ポリイミド樹脂として、上述した特定割合のベンゾフェノン骨格、ビフェニル骨格を有しないジフェニルエーテル骨格を用い、さらにビフェニル骨格を用い、かつ、上述した特定の粘度平均分子量ηを用いることによって、溶媒に可溶でありながら、5%熱重量減少温度が500℃以上となる高い耐熱性を実現できる。また、得られる成形体が機械特性に優れたポリイミド樹脂組成物を容易に提供することができる。しかも、上述したポリイミド樹脂を用いたポリイミド樹脂組成物において固形分のバランスを保つことによって、ポリイミド樹脂組成物のワニスとしての保存安定性を高めることができる。 According to the present invention, the viscosity average molecular weight of the polyimide resin is in a specific range, and the structure of the monomer constituting the polyimide resin (aromatic monomer (M), monomers (A) to (C)) and the content thereof are determined. By specifying, it is possible to obtain a polyimide resin composition that is soluble in a solvent and has an excellent molded product and high heat resistance. More specifically, as the polyimide resin, by using the above-mentioned specific proportion of benzophenone skeleton, diphenyl ether skeleton having no biphenyl skeleton, further using a biphenyl skeleton, and using the above-mentioned specific viscosity average molecular weight η, High heat resistance with a 5% thermal weight loss temperature of 500 ° C. or higher can be realized. Moreover, the obtained molded object can provide the polyimide resin composition excellent in the mechanical characteristic easily. And the storage stability as a varnish of a polyimide resin composition can be improved by maintaining the balance of solid content in the polyimide resin composition using the polyimide resin mentioned above.
本発明に係るポリイミド樹脂組成物は、接着剤等として好適に適用できる。 The polyimide resin composition according to the present invention can be suitably applied as an adhesive or the like.
本発明のポリイミド樹脂組成物に含有するポリイミド樹脂は、半導体デバイス、家電、パソコン、モーター、携帯機器などを冷却するための放熱材用のバインダー樹脂として好ましく用いられる。従来の放熱材用バインダー樹脂にはシリコーン、エポキシ、アクリルなどが用いられているが、耐熱性、可撓性、絶縁性、VOC(揮発性有機化合物)などで課題があった。本発明のポリイミド樹脂組成物に対して放熱性フィラーを体積割合で20〜60体積%含ませた樹脂組成物を用いれば、耐熱性、可撓性、高絶縁性、及び低VOCを併せ持つことが可能となる。従って本発明のポリイミド樹脂組成物は、放熱性部材用途に好適である。 The polyimide resin contained in the polyimide resin composition of the present invention is preferably used as a binder resin for a heat dissipation material for cooling semiconductor devices, home appliances, personal computers, motors, portable devices and the like. Silicone, epoxy, acrylic, and the like have been used for conventional binder resins for heat dissipation materials, but there were problems with heat resistance, flexibility, insulation, VOC (volatile organic compounds), and the like. If the resin composition containing 20 to 60% by volume of the heat dissipating filler in the polyimide resin composition of the present invention is used, it has heat resistance, flexibility, high insulation, and low VOC. It becomes possible. Therefore, the polyimide resin composition of this invention is suitable for a heat radiating member use.
本発明のポリイミド樹脂組成物に含有するポリイミド樹脂は、半導体デバイス、家電、パソコン、自動車などの輸送機器、携帯機器などに影響を及ぼす外部電磁波、又はそれらから発生する内部電磁波を遮断する電磁波シールド部材用のバインダー樹脂として好ましく用いられる。従来の電磁波シールド用バインダー樹脂にはシリコーン、エポキシ、アクリルなどが用いられているが、耐熱性、可撓性、VOCなどで課題があった。本発明のポリイミド樹脂組成物に対して導電性フィラーなどを体積割合で20〜90体積%含ませた樹脂組成物を用いれば、耐熱性、可撓性、及び低VOCを併せ持つことが可能となる。従って、本発明のポリイミド樹脂組成物は、電磁波シールド部材用途に好適である。 The polyimide resin contained in the polyimide resin composition of the present invention is an electromagnetic wave shielding member that blocks external electromagnetic waves that affect semiconductor devices, home appliances, personal computers, automobiles and other transport devices, portable devices, or internal electromagnetic waves generated therefrom. It is preferably used as a binder resin. Silicone, epoxy, acrylic, and the like are used for conventional electromagnetic wave shielding binder resins, but there are problems with heat resistance, flexibility, VOC, and the like. If a resin composition containing 20 to 90% by volume of a conductive filler or the like in the polyimide resin composition of the present invention is used, it becomes possible to have both heat resistance, flexibility, and low VOC. . Therefore, the polyimide resin composition of the present invention is suitable for use as an electromagnetic shielding member.
本発明のポリイミド樹脂組成物は、家電、パソコン、自動車などの輸送機器、携帯機器、電源、サーバー、電話などへ影響を及ぼす異常電流・電圧から保護するためのサージ部品(サージアブソーバー)用接着剤または封止材として好ましく用いられる。従来のサージ部品用接着剤または封止材には銀蝋などの溶接剤が用いられているが、高温プロセスが必要で且つ材料コストが高いなどの課題があった。一方で樹脂系接着剤では耐電圧、耐熱性、VOCなどの課題があった。本発明のポリイミド樹脂組成物を用いれば、低温プロセス化、耐電圧、耐熱、低VOC、及び低コストを併せ持つことが可能となり、本用途に好適である。 The polyimide resin composition of the present invention is an adhesive for surge parts (surge absorbers) for protecting from abnormal currents and voltages that affect household appliances, personal computers, automobiles and other transportation equipment, portable equipment, power supplies, servers, telephones, etc. Or it is preferably used as a sealing material. A welding agent such as silver wax is used for conventional adhesives or sealants for surge parts, but there are problems such as requiring a high temperature process and high material costs. On the other hand, the resin adhesive has problems such as withstand voltage, heat resistance, and VOC. If the polyimide resin composition of the present invention is used, it is possible to have low-temperature process, withstand voltage, heat resistance, low VOC, and low cost, which is suitable for this application.
本発明のポリイミド樹脂組成物は、パソコン、自動車などの輸送機器、携帯機器などに使用されるフレキシブルプリント基板の接着剤として好ましく用いられる。従来のフレキシブルプリント基板の接着剤にはポリアミド酸ワニスなどが使用されているが、高温プロセスが必要であった。本発明のポリイミド樹脂組成物を用いれば、低温プロセス化と耐熱性の両立が可能となり、上記接着剤用途に好適である。 The polyimide resin composition of the present invention is preferably used as an adhesive for flexible printed circuit boards used in transportation devices such as personal computers and automobiles, and portable devices. A polyamic acid varnish or the like is used as a conventional flexible printed circuit board adhesive, but a high temperature process is required. Use of the polyimide resin composition of the present invention makes it possible to achieve both low-temperature process and heat resistance, and is suitable for the adhesive application.
本発明のポリイミド樹脂組成物は、パソコン、自動車などの輸送機器、携帯機器などに使用されるフレキシブルプリント基板のカバーレイフィルム用接着剤として好ましく用いられる。従来のカバーレイフィルムの接着剤にはエポキシ樹脂などが使用されているが、加工性、屈曲性、電気絶縁性、耐熱性、接着性が同時に優れるものはなかった。本発明のポリイミド樹脂組成物を用いれば、加工性、屈曲性、電気絶縁性、耐熱性、及び接着性を同時に満足させることが可能となり、上記接着剤用途に好適である。 The polyimide resin composition of the present invention is preferably used as an adhesive for a cover lay film of a flexible printed circuit board used for transportation equipment such as personal computers and automobiles, and portable equipment. Epoxy resins and the like have been used as conventional coverlay film adhesives, but none of them have excellent workability, flexibility, electrical insulation, heat resistance, and adhesiveness. If the polyimide resin composition of this invention is used, it will become possible to satisfy workability, flexibility, electrical insulation, heat resistance, and adhesiveness simultaneously, and it is suitable for the adhesive application.
本発明のポリイミド樹脂組成物から形成されるフィルムは、パソコン、自動車などの輸送機器、携帯機器などに使用されるフレキシブルプリント基板のカバーレイフィルムとして好ましく用いられる。従来のカバーレイフィルムはポリイミドフィルムにエポキシ樹脂などの接着剤を合わせて2層フィルムとして使用されているが、単層のフィルムとして加工性、屈曲性、電気絶縁性、耐熱性、接着性が同時に優れるものはなかった。本発明のポリイミド樹脂組成物を用いれば、単層のフィルムとして加工性、屈曲性、電気絶縁性、耐熱性、及び接着性を同時に満足させることが可能となり、上記フィルム用途に好適である。 The film formed from the polyimide resin composition of the present invention is preferably used as a cover lay film of a flexible printed circuit board used for transportation devices such as personal computers and automobiles, and portable devices. Conventional coverlay film is used as a two-layer film by combining an adhesive such as an epoxy resin with a polyimide film, but as a single-layer film, workability, flexibility, electrical insulation, heat resistance, and adhesiveness are simultaneously There was nothing excellent. If the polyimide resin composition of the present invention is used, it becomes possible to simultaneously satisfy processability, flexibility, electrical insulation, heat resistance, and adhesiveness as a single-layer film, which is suitable for the above film use.
本発明のポリイミド樹脂組成物は、パソコン、自動車などの輸送機器、携帯機器などに使用されるフレキシブルプリント基板のボンディングシート用接着剤として好ましく用いられる。従来のボンディングシート用の接着剤にはエポキシ樹脂などが使用されているが、加工性、屈曲性、電気絶縁性、耐熱性、接着性が同時に優れるものはなかった。本発明のポリイミド樹脂組成物を用いれば、加工性、屈曲性、電気絶縁性、耐熱性、接着性を同時に満足させることが可能となり、上記接着剤用途に好適である。 The polyimide resin composition of the present invention is preferably used as an adhesive for a bonding sheet of a flexible printed circuit board used for transportation equipment such as personal computers and automobiles, and portable equipment. Epoxy resins and the like have been used as conventional adhesives for bonding sheets, but none of them have excellent workability, flexibility, electrical insulation, heat resistance, and adhesiveness at the same time. If the polyimide resin composition of the present invention is used, processability, flexibility, electrical insulation, heat resistance, and adhesiveness can be satisfied at the same time, which is suitable for the adhesive application.
≪実施例≫
以下、本発明を実施例によってより詳細に説明するが、本発明は以下の実施例によって何ら限定されるものではない。<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by the following example.
(実施例1)
(ポリイミド樹脂組成物の調製) NMPとメシチレン(1,3,5−トリメチルベンゼン)を8:2の比率で調整した溶媒中に、1,3−ビス(3−アミノフェノキシ)ベンゼン(以下、「APB−N」と称する)と、3,3',4,4'−ビフェニルテトラカルボン酸二無水物(以下、「s−BPDA」と称する)(JFEケミカル社製)、3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物(以下、「BTDA」と称する)の2種類の酸二無水物とを、APB−N:s−BPDA:BTDA=1.0:0.69:0.3のモル比で配合した。得られた混合物を、乾燥窒素ガスを導入することができるフラスコ内で4時間以上攪拌して、樹脂固形分質量が18〜25質量%であるポリアミック酸溶液を得た。十分に攪拌した後、ディーンスターク管が付属したフラスコ内で攪拌しながら、反応系を180℃程度まで加熱し、脱水反応により発生した水を系外に取り出すことでポリイミド樹脂組成物を得た。Example 1
(Preparation of polyimide resin composition) In a solvent prepared by adjusting NMP and mesitylene (1,3,5-trimethylbenzene) at a ratio of 8: 2, 1,3-bis (3-aminophenoxy) benzene (hereinafter, “ APB-N ”), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as“ s-BPDA ”) (manufactured by JFE Chemical), 3,3 ′, 4 , 4′-benzophenonetetracarboxylic dianhydride (hereinafter referred to as “BTDA”) and APB-N: s-BPDA: BTDA = 1.0: 0.69: 0 .3 molar ratio. The obtained mixture was stirred for 4 hours or more in a flask into which dry nitrogen gas could be introduced to obtain a polyamic acid solution having a resin solid content of 18 to 25% by mass. After sufficiently stirring, the reaction system was heated to about 180 ° C. while stirring in a flask equipped with a Dean-Stark tube, and water generated by the dehydration reaction was taken out of the system to obtain a polyimide resin composition.
(ポリイミドフィルムの作製) 上記ポリイミド樹脂組成物を、離型処理が施されたPETフィルム上に、10mm/secの速度で塗工した。得られた塗膜を200℃で30分間乾燥させて、溶媒を除去した。乾燥後、PETフィルムから、ピンセットなどを用いてフィルム部分を剥離し、ポリイミドフィルム(膜厚:50μm)を作製した。 (Preparation of a polyimide film) The said polyimide resin composition was apply | coated at a speed | rate of 10 mm / sec on the PET film in which the mold release process was performed. The obtained coating film was dried at 200 ° C. for 30 minutes to remove the solvent. After drying, the film part was peeled off from the PET film using tweezers or the like to prepare a polyimide film (film thickness: 50 μm).
(フィルムの粘弾性評価) 作製したポリイミドフィルムのガラス転移温度を評価した。測定は、固体粘弾性の温度分散測定(引張モード)により、貯蔵弾性率E'と損失弾性率E''を評価し、損失正接tanδ=E''/E'のピーク値からガラス転移温度を導出した。測定装置は、TA instruments社製のRSA−IIIを用い、引張モード、測定周波数1Hzで測定した。
ポリイミドフィルムの粘弾性は、300℃での貯蔵弾性率E'の値に基づいて評価した。
○:貯蔵弾性率E'が1.0×105Pa以上
×:貯蔵弾性率E'が1.0×105Pa未満(Viscoelasticity evaluation of a film) The glass transition temperature of the produced polyimide film was evaluated. The measurement is performed by measuring the storage elastic modulus E ′ and the loss elastic modulus E ″ by temperature dispersion measurement (tensile mode) of solid viscoelasticity, and calculating the glass transition temperature from the peak value of loss tangent tan δ = E ″ / E ′. Derived. The measuring device was RSA-III manufactured by TA instruments, and was measured in a tensile mode and a measurement frequency of 1 Hz.
The viscoelasticity of the polyimide film was evaluated based on the value of the storage elastic modulus E ′ at 300 ° C.
○: Storage elastic modulus E ′ is 1.0 × 10 5 Pa or more ×: Storage elastic modulus E ′ is less than 1.0 × 10 5 Pa
(フィルムの引張弾性率評価) 作製したポリイミドフィルムを、幅10mm、長さ90mmにカットして、サンプルフィルムとした。サンプルフィルムを長さ方向にAUTOGRAPH AGS-100D(島津製作所社製)にて、25℃において、速度50mm/分で幅10mm×長さ90mmのうちの両端20mmを掴み領域として引っ張った。そして、チャートにおける初期の傾きを「引張弾性率」とした。 (Evaluation of tensile modulus of film) The produced polyimide film was cut into a width of 10 mm and a length of 90 mm to obtain a sample film. The sample film was pulled in the length direction by AUTOGRAPH AGS-100D (manufactured by Shimadzu Corporation) at 25 ° C. at a speed of 50 mm / min, with both ends 20 mm out of 10 mm width × 90 mm length as the gripping area. The initial slope in the chart was defined as “tensile modulus”.
(ポリイミドフィルムの5%熱重量減少温度評価) 熱重量測定装置(TGA−51、島津製作所社製)を用いて、5%熱重量減少温度を算出した。具体的には、サンプルフィルムを、石英ルツボに約10mg入れて、窒素雰囲気下で常温より10℃/分で800℃まで昇温した時の5%熱重量減少温度を求めた。 (Evaluation of 5% thermogravimetric decrease of polyimide film) A 5% thermogravimetric decrease temperature was calculated using a thermogravimetric apparatus (TGA-51, manufactured by Shimadzu Corporation). Specifically, about 10 mg of the sample film was put in a quartz crucible, and the 5% thermogravimetric reduction temperature when the temperature was raised from room temperature to 800 ° C. at 10 ° C./min in a nitrogen atmosphere was determined.
(ポリイミド樹脂組成物の粘度平均分子量η評価) 測定するポリイミドワニスを三角フラスコに少量採取し、NMPを用いて0.5(g/dL)に希釈した。作製した希釈ワニスを、35℃恒温槽に入れたウベローデ管(柴田科学社製)で落下時間を測定した。
η=ln[希釈ワニス落下時間/NMP落下時間]より、粘度平均分子量ηを算出した。
(Evaluation of viscosity average molecular weight η of polyimide resin composition) A small amount of polyimide varnish to be measured was collected in an Erlenmeyer flask and diluted to 0.5 (g / dL) using NMP. The produced diluted varnish was measured for the drop time with an Ubbelohde tube (manufactured by Shibata Kagaku Co., Ltd.) placed in a 35 ° C. thermostat.
The viscosity average molecular weight η was calculated from η = ln [dilution varnish falling time / NMP falling time].
(GPC評価) 測定するポリイミドワニスをGPC測定用移動相で希釈し、濃度0.1%に調製した。一晩放置後、メンブレンフィルター(MILLEX-LH;日本ミリポア社製)を用いてろ過し、ろ液を測定に使用した。
装置は515ポンプ、717Plus 自動注入装置(日本ウォーターズ社製)を用い、以下の条件で行った。カラム温度:60℃、分離カラム:TSKgel Super AWM-H 6.0mm I.D. ×15cm 2本(東ソー社製)、移動相:10mM LiBrを添加したNMP、流速:0.5mL/min、検出器:示差屈折計(Shodex(登録商標)RI-101 昭和電工社製)、注入量:20μL、分子量構成:単分散ポリスチレン(EasiCal PS-1;ポリマーラボラトリーズ社製)(GPC Evaluation) A polyimide varnish to be measured was diluted with a mobile phase for GPC measurement to prepare a concentration of 0.1%. After leaving overnight, it was filtered using a membrane filter (MILLEX-LH; manufactured by Nihon Millipore), and the filtrate was used for measurement.
The apparatus used was a 515 pump, 717Plus automatic injection device (manufactured by Nippon Waters) under the following conditions. Column temperature: 60 ° C., separation column: TSKgel Super AWM-H 6.0 mm ID × 15 cm 2 (manufactured by Tosoh Corporation), mobile phase: NMP added with 10 mM LiBr, flow rate: 0.5 mL / min, detector: differential refractometer (Shodex (registered trademark) RI-101, manufactured by Showa Denko KK), injection amount: 20 μL, molecular weight composition: monodisperse polystyrene (EasiCal PS-1; manufactured by Polymer Laboratories)
(ポリイミド樹脂組成物の安定性評価) 作製したポリイミド樹脂組成物の保存安定性を評価した。作製したポリイミド樹脂組成物を小瓶にとりわけ、冷蔵庫(3℃)内にて外観の経時変化を確認し、3ヶ月間保管した状態で樹脂の析出やゲル化していないかを確認した。
○:3ヶ月保管後も、樹脂の析出やゲル化の発生無し
×:3ヶ月以内に、樹脂の析出やゲル化の発生あり(Stability Evaluation of Polyimide Resin Composition) The storage stability of the prepared polyimide resin composition was evaluated. The produced polyimide resin composition was observed in a small bottle, especially in a refrigerator (3 ° C.), and the appearance was changed with time, and whether it was stored for 3 months was checked for resin precipitation or gelation.
○: No resin precipitation or gelation after storage for 3 months ×: Residual precipitation or gelation within 3 months
(実施例2)
NMPとメシチレンを8:2の比率で調整した溶媒中に、2,2−ビス〔4−(4−アミノフェノキシ)フェニル〕プロパン(以下、「p−BAPP」と称する)からなるジアミンと、s−BPDA,BTDAの2種類の酸二無水物とを、p−BAPP:s−BPDA:BTDA=1.0:0.79:0.2のモル比で配合した。当該配合比を除く条件は、実施例1と同様にしてポリイミド樹脂組成物を調製した。そして、実施例1と同様の方法でポリイミドフィルムを作製し、評価した。
(Example 2)
A diamine composed of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “p-BAPP”) in a solvent prepared by adjusting NMP and mesitylene in a ratio of 8: 2, and s -Two types of acid dianhydrides of BPDA and BTDA were blended at a molar ratio of p - BAPP: s-BPDA: BTDA = 1.0: 0.79: 0.2. The polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. And the polyimide film was produced by the method similar to Example 1, and was evaluated.
(実施例3)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−Nと、4,4'−ビス(3−アミノフェノキシ)ビフェニル(以下、「mBP」と称する)の2種類のジアミンと、s−BPDA,BTDA,4,4'−オキシジフタル酸無水物(以下、「ODPA」と称する)の3種類の酸二無水物とを、APB−N:mBP:s−BPDA:BTDA:ODPA=0.5:0.5:0.2:0.3:0.49のモル比で配合した。当該配合比を除く条件は、実施例1と同様にしてポリイミド樹脂組成物を調製した。そして、実施例1と同様の方法でポリイミドフィルムを作製し、評価した。(Example 3)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, two types of diamines, APB-N and 4,4′-bis (3-aminophenoxy) biphenyl (hereinafter referred to as “mBP”), Three types of acid dianhydrides, s-BPDA, BTDA, 4,4′-oxydiphthalic anhydride (hereinafter referred to as “ODPA”), APB-N: mBP: s-BPDA: BTDA: ODPA = 0 .5: 0.5: 0.2: 0.3: 0.49 molar ratio. The polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. And the polyimide film was produced by the method similar to Example 1, and was evaluated.
(実施例4)
NMPとメシチレンを8:2の比率で調整した溶媒中に、1,3−ビス(3−(3−アミノフェノキシ)フェノキシ)ベンゼン(以下、「APB5」と称する)からなる1種類のジアミンと、s−BPDA,BTDAの2種類の酸二無水物とを、APB5:s−BPDA:BTDA=1.0:0.69:0.3のモル比で配合した。当該配合比を除く条件は、実施例1と同様にしてポリイミド樹脂組成物を調製した。また、実施例1と同様の方法によりポリイミドフィルムを作製し、評価した。Example 4
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one kind of diamine composed of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene (hereinafter referred to as “APB5”); Two types of acid dianhydrides of s-BPDA and BTDA were blended in a molar ratio of APB5: s-BPDA: BTDA = 1.0: 0.69: 0.3. The polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. Moreover, the polyimide film was produced by the method similar to Example 1, and evaluated.
(実施例5)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−N,4,4'−オキシジアニリン(以下、「ODA」と称する)の2種類のジアミンと、s−BPDA,BTDAの2種類の酸二無水物とを、APB−N:ODA:s−BPDA:BTDA=0.7:0.3:0.69:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。(Example 5)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, two kinds of diamines of APB-N, 4,4′-oxydianiline (hereinafter referred to as “ODA”) and s-BPDA and BTDA Two types of acid dianhydrides were blended at a molar ratio of APB-N: ODA: s-BPDA: BTDA = 0.7: 0.3: 0.69: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
(実施例6)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−Nの1種類のジアミンと、ODPA、BTDAの2種類の酸二無水物とを、APB−N:ODPA:BTDA=1.0:0.69:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。(Example 6)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one kind of diamine of APB-N and two kinds of acid dianhydrides of ODPA and BTDA, APB-N: ODPA: BTDA = 1. The molar ratio was 0: 0.69: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
(比較例1)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−Nからなる1種類のジアミンと、s−BPDAからなる1種類の酸二無水物とを、APB−N:s−BPDA=1.0:0.99のモル比で配合した。そして、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。(Comparative Example 1)
In a solvent prepared by adjusting NMP and mesitylene in a ratio of 8: 2, one kind of diamine composed of APB-N and one kind of acid dianhydride composed of s-BPDA were added to APB-N: s-BPDA = The molar ratio was 1.0: 0.99. And the polyimide resin composition was prepared similarly to Example 1, and the polyimide film was produced and evaluated.
(比較例2)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−Nからなる1種類のジアミンと、BTDAからなる1種類の酸二無水物とを、APB−N:BTDA=1.0:0.99のモル比で配合した。そして、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。(Comparative Example 2)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one kind of diamine composed of APB-N and one kind of acid dianhydride composed of BTDA were added to APB-N: BTDA = 1.0: It was blended at a molar ratio of 0.99. And the polyimide resin composition was prepared similarly to Example 1, and the polyimide film was produced and evaluated.
(比較例3)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−Nからなる1種類のジアミンと、ODPAからなる1種類の酸二無水物とを、APB−N:ODPA=1.0:0.99のモル比で配合したこと以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。(Comparative Example 3)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one kind of diamine composed of APB-N and one kind of acid dianhydride composed of ODPA were added to APB-N: ODPA = 1.0: A polyimide resin composition was prepared in the same manner as in Example 1 except that it was blended at a molar ratio of 0.99, and a polyimide film was prepared and evaluated.
(比較例4)
NMPとメシチレンを8:2の比率で調整した溶媒中に、1種類のジアミン(APB−N)と1種類の酸二無水物(ODPA)とを、APB−N:ODPA=1.0:1.02のモル比で配合したこと以外は、実施例1と同様に化学式(7)のポリイミドワニスを調製し、評価した。ワニスの粘度が低すぎて、ポリイミドフィルムを作製は不可能であった。
One type of diamine (APB-N) and one type of acid dianhydride (ODPA) in a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, APB-N: ODPA = 1.0: 1. A polyimide varnish of the chemical formula (7) was prepared and evaluated in the same manner as in Example 1 except that it was blended at a molar ratio of 0.02. The viscosity of the varnish was too low to produce a polyimide film.
(比較例5)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−Nからなる1種類のジアミンと、s−BPDA,BTDAからなる2種類の酸二無水物とを、APB−N:BPDA:BTDA=0.99:0.7:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。(Comparative Example 5)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one kind of diamine composed of APB-N and two kinds of acid dianhydrides composed of s-BPDA and BTDA were added to APB-N: BPDA: It was blended at a molar ratio of BTDA = 0.99: 0.7: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
(比較例6)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−N,m−BPの2種類のジアミンと、s−BPDA,BTDAからなる2種類の酸二無水物とを、APB−N:m−BP:BPDA:BTDA=0.3:0.7:0.69:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。(Comparative Example 6)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, two kinds of diamines, APB-N and m-BP, and two kinds of acid dianhydrides composed of s-BPDA and BTDA were added to APB-N. : M-BP: BPDA: BTDA = 0.3: 0.7: 0.69: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
(比較例7)
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB−Nの1種類のジアミンと、BTDAの1種類の酸二無水物とを、APB−N:BTDA=1.0:0.9のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、評価した。ワニスの粘度が低すぎて、ポリイミドフィルムを作製することができなかった。(Comparative Example 7)
In a solvent prepared by adjusting NMP and mesitylene in a ratio of 8: 2, one diamine of APB-N and one acid dianhydride of BTDA were added to APB-N: BTDA = 1.0: 0. It was blended at a molar ratio of 9. Except for the mixing ratio, a polyimide resin composition was prepared and evaluated in the same manner as in Example 1. The viscosity of the varnish was too low to produce a polyimide film.
表1にポリイミド前駆体の調製比率を、表2に得られたポリイミド樹脂組成物から得られたサンプルフィルムの物性値の結果を示す。 Table 1 shows the preparation ratio of the polyimide precursor, and Table 2 shows the physical property values of the sample film obtained from the polyimide resin composition obtained.
なお、実施例1において、GPCにより求めた重量平均分子量Mwは204,000、Mw/Mn比は19であった。一方、比較例5においては、Mwは51,900、Mw/Mn比は5.3であった。 In Example 1, the weight average molecular weight Mw determined by GPC was 204,000, and the Mw / Mn ratio was 19. On the other hand, in Comparative Example 5, Mw was 51,900 and Mw / Mn ratio was 5.3.
本実施例によれば、いずれのポリイミドフィルムにおいても5%熱重量減少温度が500℃以上であり、耐熱性が良好であることがわかった。さらに、引張弾性率が、いずれも2.0GPa以上あり、機械特性に優れることがわかった。さらに、貯蔵弾性率はいずれも>105Paであることがわかった。また、ポリイミド樹脂組成物のワニス安定性を検討したところ、いずれも良好であることを確認した。According to this example, it was found that the 5% thermal weight loss temperature was 500 ° C. or higher in any polyimide film, and the heat resistance was good. Furthermore, it was found that the tensile modulus was 2.0 GPa or more, and the mechanical properties were excellent. Furthermore, the storage modulus was found to be> 10 5 Pa in all cases. Moreover, when the varnish stability of the polyimide resin composition was examined, it was confirmed that all were good.
本発明に係るポリイミド樹脂組成物から得られる成形体は、優れた耐熱性、機械強度を有し、かつ、優れた5%熱重量減少温度を兼ね備えるので、これらが求められる材料全般に適用可能である。例えば、金属箔、セラミック基板、樹脂フィルム、樹脂基板、金属成形物、セラミック成形物、樹脂成形物などに塗布・乾燥・接着させた構造部を有する電子回路基板部材、半導体デバイス、リチウムイオン電池部材(例えば、リチウムイオン電池のバインダー等)、太陽電池部材、燃料電池部材等の各種電池部材および各種電池の周辺部材、モーター巻線、自動車をはじめとする各種エンジン周辺部材やモーター部材、航空宇宙用途部材、塗料、光学部品、放熱材、電磁波シールド材、サージ部品、歯科材、摺動コート、静電チャックとして好適に適用できる。また、本発明に係るポリイミド樹脂組成物は、接着剤として好適に適用できる。接着剤の好適な例としては、フレキシブルプリント基板用接着剤、カバーレイフィルム用接着剤、ボンディング用接着剤が挙げられる。さらに、本発明に係るポリイミド樹脂組成物は、フィルム全般に好適である。好適な例としては、カバーレイフィルムが挙げられる。 The molded body obtained from the polyimide resin composition according to the present invention has excellent heat resistance and mechanical strength, and also has an excellent 5% thermal weight loss temperature, so that it can be applied to all materials for which these are required. is there. For example, electronic circuit board members, semiconductor devices, and lithium ion battery members having structures that are applied, dried, and bonded to metal foils, ceramic substrates, resin films, resin substrates, metal moldings, ceramic moldings, resin moldings, etc. (For example, binders for lithium ion batteries), various battery members such as solar cell members and fuel cell members, various battery peripheral members, motor windings, various engine peripheral members and motor members including automobiles, aerospace applications It can be suitably applied as a member, paint, optical component, heat radiation material, electromagnetic shielding material, surge component, dental material, sliding coating, and electrostatic chuck. Moreover, the polyimide resin composition which concerns on this invention can be applied suitably as an adhesive agent. Preferable examples of the adhesive include flexible printed circuit board adhesives, coverlay film adhesives, and bonding adhesives. Furthermore, the polyimide resin composition according to the present invention is suitable for all films. A suitable example is a coverlay film.
この出願は、2012年6月7日に出願された日本出願特願2012−129897、2012年12月28日に出願された日本出願特願2012−289052を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority based on Japanese Patent Application No. 2012-129897 filed on June 7, 2012 and Japanese Application No. 2012-289052 filed on December 28, 2012, The entire disclosure is incorporated herein.
Claims (19)
ポリイミド樹脂と、を少なくとも含む組成物からなり、
前記ポリイミド樹脂の粘度平均分子量ηが、0.6以上、1.60以下であり、
前記ポリイミド樹脂を構成する全モノマーに対して95mol%以上、100mol%以下を、主鎖に炭素数3以上の脂肪族鎖を有さない芳香族モノマーとし、
前記芳香族モノマーは、
化学式(1)及び化学式(2)で表されるベンゾフェノン骨格の少なくともいずれかを有するモノマー(A)を、前記ポリイミド樹脂を構成する全モノマー中に5mol%以上、30mol%以下含み、
ビフェニル骨格を有さず、ジフェニルエーテル骨格を有するモノマー(B)を、前記ポリイミド樹脂を構成する全モノマー中に40mol%以上、95mol%以下含み、
ビフェニル骨格を有するモノマー(C)を、前記ポリイミド樹脂を構成する全モノマー中に0mol%以上、45mol%未満含むものであり、
前記モノマー(B)は、前記ポリイミド樹脂を構成する全モノマー中、20mol%以上が芳香環を3個以上有するモノマー(B−1)であるポリイミド樹脂組成物。
A composition comprising at least a polyimide resin,
The viscosity average molecular weight η of the polyimide resin is 0.6 or more and 1.60 or less,
95 mol% or more and 100 mol% or less with respect to all monomers constituting the polyimide resin as an aromatic monomer having no aliphatic chain having 3 or more carbon atoms in the main chain,
The aromatic monomer is
The monomer (A) having at least one of the benzophenone skeletons represented by the chemical formula (1) and the chemical formula (2) is included in all monomers constituting the polyimide resin in an amount of 5 mol% or more and 30 mol% or less,
A monomer having no diphenyl ether skeleton and a diphenyl ether skeleton (B) is contained in an amount of 40 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin,
The monomer (C) having a biphenyl skeleton is contained in all monomers constituting the polyimide resin in an amount of 0 mol% or more and less than 45 mol%,
The said monomer (B) is a polyimide resin composition whose 20 mol% or more is a monomer (B-1) which has 3 or more aromatic rings in all the monomers which comprise the said polyimide resin.
(a)ガラス転移温度が130℃以上、260℃未満、
(b)25℃での引張弾性率が2.0GPa以上、4.0GPa未満、
(c)窒素雰囲気下での5%熱重量減少温度が500℃以上、
である請求項1に記載のポリイミド樹脂組成物。A polyimide film obtained by applying the composition and drying it,
(A) glass transition temperature is 130 ° C. or higher and lower than 260 ° C.,
(B) Tensile modulus at 25 ° C. is 2.0 GPa or more and less than 4.0 GPa,
(C) 5% thermal weight loss temperature in a nitrogen atmosphere is 500 ° C. or higher,
The polyimide resin composition according to claim 1.
電子回路基板部材、半導体デバイス、リチウムイオン電池部材、太陽電池部材、燃料電池部材、モーター巻線、エンジン周辺部材、塗料、光学部品、放熱材、電磁波シールド材、サージ部品、歯科材、摺動コート、及び静電チャックのいずれかであることを特徴とする部品。The component according to claim 18 comprises:
Electronic circuit board member, semiconductor device, lithium ion battery member, solar cell member, fuel cell member, motor winding, engine peripheral member, paint, optical component, heat radiation material, electromagnetic shielding material, surge component, dental material, sliding coating And an electrostatic chuck.
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