JP5458384B2 - Polyimide sheet - Google Patents
Polyimide sheet Download PDFInfo
- Publication number
- JP5458384B2 JP5458384B2 JP2010033169A JP2010033169A JP5458384B2 JP 5458384 B2 JP5458384 B2 JP 5458384B2 JP 2010033169 A JP2010033169 A JP 2010033169A JP 2010033169 A JP2010033169 A JP 2010033169A JP 5458384 B2 JP5458384 B2 JP 5458384B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- polyimide film
- sheet
- film
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title claims description 81
- 239000004642 Polyimide Substances 0.000 title claims description 27
- 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 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000010954 inorganic particle Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 5
- 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 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 16
- 229920005575 poly(amic acid) Polymers 0.000 description 14
- 238000003475 lamination Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- -1 fatty acid halides Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 2
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YTCGLFCOUJIOQH-UHFFFAOYSA-N 1,3,4-oxadiazole-2,5-diamine Chemical compound NC1=NN=C(N)O1 YTCGLFCOUJIOQH-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- XMXCPDQUXVZBGQ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=C(Cl)C(Cl)=C(C(O)=O)C2=C1C(O)=O XMXCPDQUXVZBGQ-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- ZRJAHFLFCRNNMR-UHFFFAOYSA-N 3-amino-2-(4-aminophenyl)benzoic acid Chemical compound C1=CC(N)=CC=C1C1=C(N)C=CC=C1C(O)=O ZRJAHFLFCRNNMR-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-UHFFFAOYSA-N 0.000 description 1
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- ZWIBGDOHXGXHEV-UHFFFAOYSA-N 4,4-dimethylheptane-1,7-diamine Chemical compound NCCCC(C)(C)CCCN ZWIBGDOHXGXHEV-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- OSGFBINRYVUILV-UHFFFAOYSA-N 4-[(4-aminophenyl)-diethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](CC)(CC)C1=CC=C(N)C=C1 OSGFBINRYVUILV-UHFFFAOYSA-N 0.000 description 1
- BLMSGSGJGUHKFW-UHFFFAOYSA-N 4-[(4-aminophenyl)-diphenylsilyl]aniline Chemical compound C1=CC(N)=CC=C1[Si](C=1C=CC(N)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BLMSGSGJGUHKFW-UHFFFAOYSA-N 0.000 description 1
- NMLVVZNIIWJNTI-UHFFFAOYSA-N 4-[(4-aminophenyl)-ethylphosphoryl]aniline Chemical compound C=1C=C(N)C=CC=1P(=O)(CC)C1=CC=C(N)C=C1 NMLVVZNIIWJNTI-UHFFFAOYSA-N 0.000 description 1
- KTZLSMUPEJXXBO-UHFFFAOYSA-N 4-[(4-aminophenyl)-phenylphosphoryl]aniline Chemical compound C1=CC(N)=CC=C1P(=O)(C=1C=CC(N)=CC=1)C1=CC=CC=C1 KTZLSMUPEJXXBO-UHFFFAOYSA-N 0.000 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- DBOLXXRVIFGDTI-UHFFFAOYSA-N 4-benzylpyridine Chemical compound C=1C=NC=CC=1CC1=CC=CC=C1 DBOLXXRVIFGDTI-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- LBNFPUAJWZYIOQ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-methylbenzene-1,4-diamine Chemical compound C=1C=C(N)C=CC=1N(C)C1=CC=C(N)C=C1 LBNFPUAJWZYIOQ-UHFFFAOYSA-N 0.000 description 1
- FRGXNJWEDDQLFH-UHFFFAOYSA-N 4-propan-2-ylpyridine Chemical compound CC(C)C1=CC=NC=C1 FRGXNJWEDDQLFH-UHFFFAOYSA-N 0.000 description 1
- AQVOMFPTJXMAQE-UHFFFAOYSA-N 4-propylphthalic acid Chemical compound CCCC1=CC=C(C(O)=O)C(C(O)=O)=C1 AQVOMFPTJXMAQE-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- MMDNZKASBVVBBC-UHFFFAOYSA-N 5-(4-amino-3-methylphenyl)-2-methylaniline Chemical group C1=C(N)C(C)=CC=C1C1=CC=C(N)C(C)=C1 MMDNZKASBVVBBC-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- VFKXEFSEPKMOMS-UHFFFAOYSA-N CC1=C(CC2=CC=C(C=C2)CC2=C(C=C(C=C2)N)C)C=CC(=C1)N Chemical compound CC1=C(CC2=CC=C(C=C2)CC2=C(C=C(C=C2)N)C)C=CC(=C1)N VFKXEFSEPKMOMS-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- FOLJMFFBEKONJP-UHFFFAOYSA-N adamantane-1,3-diamine Chemical compound C1C(C2)CC3CC1(N)CC2(N)C3 FOLJMFFBEKONJP-UHFFFAOYSA-N 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- VQXBKCWOCJSIRT-UHFFFAOYSA-N octadecane-1,12-diamine Chemical compound CCCCCCC(N)CCCCCCCCCCCN VQXBKCWOCJSIRT-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- SKFLCXNDKRUHTA-UHFFFAOYSA-N phenyl(pyridin-4-yl)methanone Chemical compound C=1C=NC=CC=1C(=O)C1=CC=CC=C1 SKFLCXNDKRUHTA-UHFFFAOYSA-N 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Description
本発明は、複数枚のポリイミドフィルムを積層一体化してなるポリイミドシートに関する。さらに詳しくは、積層時にポリイミドフィルムにスリキズを発生させることのない高品位のポリイミドシートに関するものである。 The present invention relates to a polyimide sheet formed by laminating and integrating a plurality of polyimide films. More specifically, the present invention relates to a high-quality polyimide sheet that does not generate a scratch on the polyimide film during lamination.
ポリイミド樹脂は、優れた耐熱性と耐摩耗性を持つことから機械・電機部品を始め幅広い用途で使用されている。 Polyimide resins are used in a wide range of applications including mechanical and electrical parts because of their excellent heat resistance and wear resistance.
ポリイミドシートを作成する方法としては、ポリイミド粉体をシート状に成形する方法が一般的であるが、同方法では成形できるシートの厚さに限界があるため、成形したシートを切削加工し、目的とする厚さへ加工する工程が必要であった。 As a method of creating a polyimide sheet, a method of forming a polyimide powder into a sheet shape is general, but since there is a limit to the thickness of the sheet that can be formed by this method, the formed sheet is cut and processed. The process to process to the thickness to be required.
このため、ポリイミドフィルムを積層して目的厚さを調整する方法（例えば、特許文献１参照）が考えられているが、ポリイミドフィルムを積層する場合には、フィルムを重ねる際にフィルム同士が擦れ、フィルム表面にスリキズが発生し、このスリキズが発生した状態での積層を行うと、スリキズによって圧着時の圧力ムラが発生し、積層が不十分となるばかりか、クラックの発生による亀裂などの不具合を生じるという問題があった。 For this reason, although the method (for example, refer patent document 1) of adjusting the target thickness by laminating a polyimide film is considered, when laminating a polyimide film, the films rub against each other when the films are laminated, When scratching occurs on the film surface and laminating with this scratch occurring, pressure scratches occur during pressure bonding due to the scratching, resulting in inadequate lamination, and problems such as cracking due to cracking. There was a problem that occurred.
本発明の課題は、積層時にポリイミドフィルムに対しスリキズを発生させることすることがない高品位なポリイミドシートを提供することにある。 The subject of this invention is providing the high quality polyimide sheet which does not generate | occur | produce a scratch with respect to a polyimide film at the time of lamination | stacking.
上記の課題を解決するため本発明によれば、粒子径が１．５μｍ以下の無機粒子をフィルム樹脂重量あたり０．１〜０．９重量％の割合で含み、厚さが２５０μ以下の１種類のポリイミドフィルムのみを複数枚積層して成ることを特徴とするポリイミドシートが提供される。 In order to solve the above problems, according to the present invention, one kind of inorganic particles having a particle size of 1.5 μm or less is contained in a proportion of 0.1 to 0.9% by weight per film resin weight, and the thickness is 250 μm or less . There is provided a polyimide sheet comprising a plurality of laminated polyimide films alone.
なお、本発明のポリイミドシートにおいては、
前記無機粒子の平均粒子径が０．７μｍ以下で、さらに粒子径０．６μｍ以下の無機粒子が全粒子中８０体積％以上の割合を占める粒度分布を有すること、
前記ポリイミドフィルムが、ジアミン成分としてパラフェニレンジアミンおよび４，４’−ジアミノジフェニルエーテルを主たる構成成分とすること、
前記ポリイミドフィルムが、酸二無水物成分としてピロメリット酸二無水物および３，３’−４，４’−ビフェニルテトラカルボン酸二無水物を主たる構成成分とすること、
シート片面の任意方向の熱膨張係数が３０ｐｐｍ／℃以下であること、および
シート片面の任意方向の２５℃雰囲気下における破断点ひずみが２０％以上であること
が、いずれも好ましい条件として挙げられる。
In the polyimide sheet of the present invention,
The average particle size of the inorganic particles is 0.7 μm or less, and the inorganic particles having a particle size of 0.6 μm or less have a particle size distribution that accounts for 80% by volume or more of the total particles,
The polyimide film is mainly composed of paraphenylenediamine and 4,4′-diaminodiphenyl ether as a diamine component,
The polyimide film is mainly composed of pyromellitic dianhydride and 3,3′-4,4′-biphenyltetracarboxylic dianhydride as an acid dianhydride component,
A preferable condition is that the thermal expansion coefficient in an arbitrary direction on one side of the sheet is 30 ppm / ° C. or lower and the strain at break in an arbitrary direction on the single side of the sheet is 20% or more.
本発明によれば、積層時にポリイミドフィルムに対しスリキズを発生させることすることがない高品位なポリイミドシートを作成することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to produce the high quality polyimide sheet which does not generate a scratch with respect to a polyimide film at the time of lamination | stacking.
以下に本発明のポリイミドシートについて具体的に説明する。 The polyimide sheet of the present invention will be specifically described below.
本発明のポリイミドシートは、粒子径が１．５μｍ以下の無機粒子をフィルム樹脂重量あたり０．１−０．９重量％の割合で含む、厚さが２５０μｍ以下の１種類のポリイミドフィルムを複数枚積層したものである。 The polyimide sheet of the present invention includes a plurality of one type of polyimide film having a thickness of 250 μm or less, containing inorganic particles having a particle diameter of 1.5 μm or less at a ratio of 0.1 to 0.9% by weight per film resin weight. Laminated.
本発明のポリイミドシートにおいて素材として用いるポリイミドフィルムの製造方法には特に限定がなく、一般的に知られている方法で製造されたポリイミドフィルムである。例えば、酸二無水物とジアミンを反応させたポリアミド酸溶液を流延またはフィルム状に押出し、乾燥、熱処理を行って、イミド化を進行させることにより、製膜するのが一般的である。 There is no limitation in particular in the manufacturing method of the polyimide film used as a raw material in the polyimide sheet of this invention, It is a polyimide film manufactured by the method generally known. For example, a polyamic acid solution obtained by reacting an acid dianhydride and a diamine is cast or extruded into a film form, dried, heat-treated, and then imidized to form a film.
この際、乾燥・熱処理は、流延またはフィルム状に押し出されたポリアミド酸溶液を、２００〜６００℃、好ましくは２５０〜５５０℃の高温雰囲気に維持した乾燥熱処理ゾーンを通過させることにより達成することができる。 At this time, the drying / heat treatment is achieved by passing the polyamic acid solution extruded into a cast or film through a drying heat treatment zone maintained in a high temperature atmosphere of 200 to 600 ° C., preferably 250 to 550 ° C. Can do.
一般的に知られているイミド化の方法には、加熱することにより脱水をおこなう熱閉環法と触媒、脱水剤を使用して化学的に脱水をおこなう化学閉環法があるが、本発明に用いられるイミド化の方法は特に限定されない。ただ、線膨張係数を小さくすることから化学閉環法の方が好ましい。イミド化触媒としては、第三級アミン類が好ましく、具体例として、トリメチルアミン、トリエチルアミン、トリエチレンジアミン、ピリジン、イソキノリン、２−エチルピリジン、２−メチルピリジン、Ｎ−エチルモルフォリン、Ｎ−メチルモルフォリン、ジエチルシクロヘキシルアミン、Ｎ−ジメチルシクロヘキシルアミン、４−ベンゾイルピリジン、２，４−ルチジン、２，６−ルチジン、２，４，６−コリジン、３，４−ルチジン、３，５−ルチジン、４−メチルピリジン、３−メチルピリジン、４−イソプロピルピリジン、Ｎ−ジメチルベンジルアミン、４−ベンジルピリジン、およびＮ−ジメチルドデシルアミンなどが挙げられる。また、脱水剤としては、有機カルボン酸無水物、Ｎ，Ｎ−ジアルキルカルボジイミド類、低級脂肪酸ハロゲン化物、ハロゲン化低級脂肪酸ハロゲン化物、ハロゲン化低級脂肪酸無水物、アリールホスホン酸ジハロゲン化物およびチオニルハロゲン化物が挙げられる。 Generally known imidization methods include a thermal ring closure method in which dehydration is performed by heating, and a chemical ring closure method in which dehydration is performed chemically using a catalyst and a dehydrating agent. The imidization method to be performed is not particularly limited. However, the chemical ring closure method is preferred because it reduces the linear expansion coefficient. As the imidation catalyst, tertiary amines are preferable. Specific examples include trimethylamine, triethylamine, triethylenediamine, pyridine, isoquinoline, 2-ethylpyridine, 2-methylpyridine, N-ethylmorpholine, N-methylmorpholine. , Diethylcyclohexylamine, N-dimethylcyclohexylamine, 4-benzoylpyridine, 2,4-lutidine, 2,6-lutidine, 2,4,6-collidine, 3,4-lutidine, 3,5-lutidine, 4- Examples include methylpyridine, 3-methylpyridine, 4-isopropylpyridine, N-dimethylbenzylamine, 4-benzylpyridine, and N-dimethyldodecylamine. Examples of the dehydrating agent include organic carboxylic acid anhydrides, N, N-dialkylcarbodiimides, lower fatty acid halides, halogenated lower fatty acid halides, halogenated lower fatty acid anhydrides, arylphosphonic acid dihalides, and thionyl halides. Can be mentioned.
本発明で用いるポリイミドフィルムを構成する酸二無水物の具体例としては、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３’，３，４’−ビフェニルテトラカルボン酸二無水物、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、２，２’−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、ビス（３，４−カルボキシフェニル）エーテル二無水物、ナフタレン−１，２，４，５−テトラカルボン酸二無水物、ナフタレン−１，４，５，８−テトラカルボン酸二無水物、デカヒドロ−ナフタレン−１，４，５，８−テトラカルボン酸二無水物、４，８−ジメチル−１，２，３，５，７−ヘキサヒドロナフタレン−１，２，５，６−テトラカルボン酸二無水物、２，６，−ジクロロナフタレン−１，４，５８−テトラカルボン酸二無水物、２，７−ジクロロナフタレン−１，４，５，８−テトラカルボン酸二無水物、２，３，６，７−テトラクロロナフタレン−１，４，５，８−テトラカルボン酸二無水物、フェナントレン−１，８，９，１０−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）エタン二無水物、１，１−ビス（３，４−ジカルボキシフェニル）エタン二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、ベンゼン−１，２，３，４−テトラカルボン酸二無水物、３，４，３’，４’−ベンゾフェノンテトラカルボン酸二無水物などが挙げられ、これらを単独で使用しても良いし、２種類以上を併用しても良い。 Specific examples of the acid dianhydride constituting the polyimide film used in the present invention include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3. , 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2 ′ -Bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3 , 4-carboxyphenyl) ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydro-naphthalene 1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6, -dichloronaphthalene-1,4,58-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7 -Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) ) Ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) Methane dianhydride, bis (3,4 Dicarboxyphenyl) sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, and the like. You may use individually and may use 2 or more types together.
これらの酸二無水物の中で好ましいものはピロメリット酸二無水物および３，３’，４，４’−ビフェニルテトラカルボン酸二無水物である。好ましい形態としては、本発明で用いるポリイミドフィルムの全酸成分のうち、ピロメリット酸成分を０〜８５ｍｏｌ％含有することが好ましく、さらに好ましくは１０〜８０ｍｏｌ％、さらに好ましくは２０〜７５ｍｏｌ％である。また、３，３’，４，４’−ビフェニルテトラカルボン酸成分は０〜６０ｍｏｌ％が好ましく、さらに好ましくは５〜５０ｍｏｌ％、さらに好ましくは５〜４０ｍｏｌ％である。 Among these acid dianhydrides, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride are preferred. As a preferable form, it is preferable that the pyromellitic acid component is contained in the total acid component of the polyimide film used in the present invention in an amount of 0 to 85 mol%, more preferably 10 to 80 mol%, and further preferably 20 to 75 mol%. . The 3,3 ′, 4,4′-biphenyltetracarboxylic acid component is preferably 0 to 60 mol%, more preferably 5 to 50 mol%, and further preferably 5 to 40 mol%.
本発明で用いるポリイミドフィルムを構成するジアミン成分としては、４，４’−ジアミノジフェニルエーテル、パラフェニレンジアミン、３，４’−ジアミノジフェニルエーテル、メタフェニレンジアミン、４，４’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルメタン、ベンチジン、４，４’−ジアミノジフェニルサルファイド、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、２，６−ジアミノピリジン、ビス−（４−アミノフェニル）ジエチルシラン、ビス−（４−アミノフェニル）ジフェニルシラン、３，３’−ジクロロベンチジン、ビス−（４−アミノフェニル）エチルホスフィンオキサイド、ビス−（４−アミノフェニル）フェニルホスフィンオキサイド、ビス−（４−アミノフェニル）−Ｎ−フェニルアミン、ビス−（４−アミノフェニル）−Ｎ−メチルアミン、１，５−ジアミノナフタレン、３，３’−ジメチル−４，４’−ジアミノビフェニル、３，４’−ジメチル−３’，４−ジアミノビフェニル、３，３’−ジメトキシベンチジン、２，４−ビス（β−アミノ−ｔ−ブチル）トルエン、ビス（ｐ−β−アミノ−ｔ−ブチル−フェニル）エーテル、ｐ−ビス−（２−メチル−４−アミノ−ベンチル）ベンゼン、ｐ−ビス−（１，１−ジメチル−５−アミノ−ベンチル）ベンゼン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、１，３−ジアミノアダマンタン、３，３７−ジアミノ−１，１７−ジアダマンタン、３，３’−ジアミノ−１，１’−ジアダマンタン、ビス（ｐ−アミノ−シクロヘキシル）メタン、ヘキサメチレンジアミン、ペプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、３−メチルヘプタメチレンジアミン、４，４−ジメチルヘプタメチレンジアミン、２，１１−ジアミノ−ドデカン、１，２−ビス−（３−アミノ−プロポキシ）エタン、２，２−ジメチルプロピレンジアミン、３−メトキシ−ヘキサメチレンジアミン、２，５−ジメチルヘキサメチレンジアミン、５−メチルノナメチレンジアミン、５−メチルノナメチレンジアミン、１，４−ジアミノ−シクロヘキサン、１，１２−ジアミノ−オクタデカン、２，５−ジアミノ−１，３，４−オキサジアゾール、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、Ｎ−（３−アミノフェニル）−４−アミノベンズアミド、４−アミノフェニル−３−アミノベンゾエートなどが挙げられ、これらを単独で使用しても良いし、２種類以上を併用しても良い。 As the diamine component constituting the polyimide film used in the present invention, 4,4′-diaminodiphenyl ether, paraphenylenediamine, 3,4′-diaminodiphenyl ether, metaphenylenediamine, 4,4′-diaminodiphenylpropane, 4,4 '-Diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,6-diaminopyridine, bis- (4-aminophenyl) diethyl Silane, bis- (4-aminophenyl) diphenylsilane, 3,3′-dichlorobenzidine, bis- (4-aminophenyl) ethylphosphine oxide, bis- (4-aminophenyl) phenylphosphine oxide, bis- (4 -A Nophenyl) -N-phenylamine, bis- (4-aminophenyl) -N-methylamine, 1,5-diaminonaphthalene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,4′-dimethyl -3 ′, 4-diaminobiphenyl, 3,3′-dimethoxybenzidine, 2,4-bis (β-amino-t-butyl) toluene, bis (p-β-amino-t-butyl-phenyl) ether, p-bis- (2-methyl-4-amino-benzyl) benzene, p-bis- (1,1-dimethyl-5-amino-benzyl) benzene, m-xylylenediamine, p-xylylenediamine, 1, 3-diaminoadamantane, 3,37-diamino-1,17-diadamantane, 3,3′-diamino-1,1′-diadamantane, bis (p-amino-cyclohexyl) Tan, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diamino-dodecane, 1,2 -Bis- (3-amino-propoxy) ethane, 2,2-dimethylpropylenediamine, 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 5-methylnonamethylenediamine, 5-methylnonamethylenediamine 1,4-diamino-cyclohexane, 1,12-diamino-octadecane, 2,5-diamino-1,3,4-oxadiazole, 2,2-bis (4-aminophenyl) hexafluoropropane, N- (3-Aminophenyl) -4-amino Nzuamido, and 4-aminophenyl-3-aminobenzoate and the like, it may be used them individually or as a combination of two or more.
これらのジアミンの中で好ましいものは４，４’−ジアミノジフェニルエーテルおよびパラフェニレンジアミンである。好ましい形態としては、本発明で用いるポリイミドフィルムの全ジアミン成分のうち、４，４’−ジアミノジフェニルエーテルを０〜９５ｍｏｌ％含有することが好ましく、さらに好ましくは１０〜９０ｍｏｌ％、さらに好ましくは２０〜８５ｍｏｌ％である。また、パラフェニレンジアミン成分は０〜６０ｍｏｌ％が好ましく、さらに好ましくは５〜５０ｍｏｌ％、さらに好ましくは５〜４０ｍｏｌ％である。 Preferred among these diamines are 4,4'-diaminodiphenyl ether and paraphenylene diamine. As a preferable form, it is preferable to contain 0-95 mol% of 4,4'-diaminodiphenyl ether among all the diamine components of the polyimide film used by this invention, More preferably, it is 10-90 mol%, More preferably, it is 20-85 mol%. %. Further, the paraphenylenediamine component is preferably 0 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 5 to 40 mol%.
得られたポリイミドフィルムは別途、熱処理、またはコロナ放電処理やプラズマ放電処理等の表面処理法によって処理されていても良い。 The obtained polyimide film may be separately treated by heat treatment or a surface treatment method such as corona discharge treatment or plasma discharge treatment.
本発明のポリイミドシートは、粒子径が１．５μｍ以下の無機粒子をフィルム樹脂重量あたり０．１−０．９重量％の割合で含む、厚さが２５０μｍ以下のポリイミドフィルムのみを使用して作成したものである。 The polyimide sheet of the present invention is prepared by using only a polyimide film having a thickness of 250 μm or less, containing inorganic particles having a particle diameter of 1.5 μm or less at a ratio of 0.1 to 0.9% by weight per film resin weight. It is a thing.
ポリイミドフィルム中に無機粒子を含ませることにより、フィルム表面に突起を形成させることができる。この突起によりポリイミドフィルムの滑性が向上し、積層時にスリキズが発生しない積層板の作成が可能となる。本発明において、ポリイミドフィルムに添加する無機粒子は、その粒子径が１．５μｍ以下であり、好ましくは０．１〜１．０μｍ、さらにこのましくは０．３〜０．５μｍである。この粒子径よりも大きい場合は、フィルム間に空間ができて接着不良になるため好ましくない。 By including inorganic particles in the polyimide film, protrusions can be formed on the film surface. This protrusion improves the lubricity of the polyimide film, and makes it possible to create a laminate that does not generate scratches during lamination. In the present invention, the inorganic particles added to the polyimide film have a particle size of 1.5 μm or less, preferably 0.1 to 1.0 μm, more preferably 0.3 to 0.5 μm. When the particle diameter is larger than this, it is not preferable because a space is formed between the films, resulting in poor adhesion.
また、本発明に使用される無機粒子は、フィルム樹脂重量あたり０．１〜０．９重量％の割合で含むことが好ましく、より好ましくは０．３〜０．８重量％である。０．１重量％以下であるとフィルム表面の突起数が不足するために滑性が不足し好ましくない。また、逆に０．９重量％以上であると外観不良やフィルムの伸度が低下することで物性不良になるばかりか、突起数の増大によってフィルム間に空間ができ接着不良になるために好ましくない。 Moreover, it is preferable that the inorganic particle used for this invention is included in the ratio of 0.1-0.9 weight% per film resin weight, More preferably, it is 0.3-0.8 weight%. When the content is 0.1% by weight or less, the number of protrusions on the film surface is insufficient, so that the lubricity is insufficient, which is not preferable. On the other hand, if it is 0.9% by weight or more, it is preferable not only because of poor physical properties due to poor appearance and reduced film elongation, but also because of the increase in the number of protrusions and a space between the films, resulting in poor adhesion. Absent.
本発明で使用する無機粒子としては、リン酸水素カルシウム、リン酸カルシウム、炭酸カルシウム、酸化チタン、シリカなどが挙げられ、なかでもリン酸水素カルシウムが好ましく使用できる。 Examples of the inorganic particles used in the present invention include calcium hydrogen phosphate, calcium phosphate, calcium carbonate, titanium oxide, silica and the like, among which calcium hydrogen phosphate can be preferably used.
本発明においては、このような無機粒子をポリイミドフィルムの製造に使用されるものと同じ溶媒に分散させたスラリー状とし、ポリイミドフィルム製造工程中のポリアミック酸溶液中に添加した後、脱環化、脱溶媒させてポリイミドフィルムとすることが好ましいが、ポリアミック酸重合前の溶媒中に無機粒子スラリーまたは無機粒子を添加した後、ポリアミック酸を重合、脱環化、脱溶媒を経てポリイミドフィルムを得る方法など、脱環化、脱溶媒前であればいかなる工程においても無機粒子を添加することが可能である。 In the present invention, such inorganic particles are in the form of a slurry dispersed in the same solvent as used in the production of polyimide film, and added to the polyamic acid solution in the polyimide film production process, then decyclized, It is preferable to remove the solvent to form a polyimide film, but after adding inorganic particle slurry or inorganic particles to the solvent before polyamic acid polymerization, a method of polymerizing, decyclizing, and removing the polyamic acid to obtain a polyimide film It is possible to add inorganic particles in any process before decyclization and solvent removal.
本発明におけるポリイミドシートに使用するポリイミドフィルムの厚みの範囲は２５０μｍ以下である。好ましくは５〜２００μｍであり、より好ましくは１０〜５０μｍである。これは、ポリイミドフィルムが薄い場合は、積層枚数が多くなるために空気泡が発生しシートの収率が悪化する傾向となり、逆にポリイミドフィルムが厚い場合は、ポリイミドフィルム内で相分離がおこり、十分な密着力が得られないという好ましくない傾向が招かれる。 The range of the thickness of the polyimide film used for the polyimide sheet in the present invention is 250 μm or less. Preferably it is 5-200 micrometers, More preferably, it is 10-50 micrometers. This is because when the polyimide film is thin, air bubbles are generated due to an increase in the number of laminated sheets, and the yield of the sheet tends to deteriorate. Conversely, when the polyimide film is thick, phase separation occurs in the polyimide film, This leads to an unfavorable tendency that sufficient adhesion cannot be obtained.
本発明では、上記のポリイミドフィルムを複数枚積層圧着して一体化し、一枚のシートにする。積層圧着手段は特に限定されないが、通常は同種のポリイミドフィルムを所望の枚数積層し、適宜の温度と圧力で圧着する。加圧には通常のプレス機を用いることができるが、積層したポリイミドフィルム間に空気層ができるのを防止できることから、真空プレス機を用いることが好ましい。 In the present invention, a plurality of the polyimide films are laminated and bonded together to form a single sheet. The lamination pressure-bonding means is not particularly limited, but usually, a desired number of polyimide films of the same kind are laminated and pressure-bonded at an appropriate temperature and pressure. A normal press can be used for pressurization, but it is preferable to use a vacuum press because it can prevent an air layer from forming between the laminated polyimide films.
本発明のポリイミドシートは、任意の面の熱膨張係数が３０ｐｐｍ／℃以下であることが好ましく、より好ましくは２０ｐｐｍ／℃以下である。 In the polyimide sheet of the present invention, the thermal expansion coefficient of an arbitrary surface is preferably 30 ppm / ° C. or less, and more preferably 20 ppm / ° C. or less.
また、本発明のポリイミドシートは、任意の面の２５℃雰囲気下での破断点ひずみが２０％以上であることが好ましく、より好ましくは３０％以上である。 The polyimide sheet of the present invention preferably has a strain at break at an arbitrary surface in an atmosphere of 25 ° C. of 20% or more, more preferably 30% or more.
ポリイミド樹脂は、一般的に直方体のポリイミド樹脂を切削加工して得られる。しかし、最近は切削加工技術の向上や最終用途の高密度化、小型化により、従来よりもピッチの狭い加工が求められている。このため、高精細な切削に耐えられるだけの破断点ひずみが必要となる。また、これらの樹脂は高い温度領域で使用されることが多いため、これらの温度領域における精度を保つためには低い熱膨張率が必要となる。 The polyimide resin is generally obtained by cutting a rectangular parallelepiped polyimide resin. Recently, however, machining with narrower pitches has been demanded due to improvements in cutting technology and higher density and miniaturization of end uses. For this reason, strain at the breaking point that can withstand high-definition cutting is required. In addition, since these resins are often used in a high temperature region, a low coefficient of thermal expansion is required to maintain accuracy in these temperature regions.
かくしてなる本発明のポリイミドシートは、積層時にポリイミドフィルムに対しスリキズを発生させることすることがなく高品位であることから、耐熱性、摺動性、寸法安定性が求められる電子部品用途などに有効に利用することができる。 The polyimide sheet of the present invention thus formed is high quality without causing scratches on the polyimide film during lamination, and is therefore effective for applications such as electronic parts that require heat resistance, slidability, and dimensional stability. Can be used.
以下、実施例により本発明を具体的に説明する。但し本発明はこれらの実施例のみによって限定されない。また、シートの各物性は以下の方法に従って測定した。 Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited only to these examples. Each physical property of the sheet was measured according to the following method.
［破断点ひずみ］
ＡＳＴＭ Ｄ１７８０に準じた。この時の引っ張り速度は１ｍｍ／ｍｉｎであり、試験片は試験部が長さ２２．５ｍｍ、幅４．７５ｍｍ、つかみ部の幅が１１５．８８ｍｍ、試験部、つかみ部を合わせた全体の長さが６０ｍｍである。
[Strain at break]
According to ASTM D1780. The pulling speed at this time is 1 mm / min, and the test piece has a length of 22.5 mm and a width of 4.75 mm, a width of the grip portion of 115.88 mm, and a total length of the test portion and the grip portion combined. Is 60 mm.
［熱膨張係数］
長さ５ｍｍ、幅５ｍｍ、高さ３ｍｍの試験片を作成し、１０℃／ｍｉｎの昇温速度で、室温〜５００℃まで測定した。このときの５０〜２５０℃平均膨張の値を熱膨張係数とした。
[Thermal expansion coefficient]
A test piece having a length of 5 mm, a width of 5 mm, and a height of 3 mm was prepared and measured from room temperature to 500 ° C. at a temperature rising rate of 10 ° C./min. The value of 50-250 degreeC average expansion at this time was made into the thermal expansion coefficient.
（ポリアミック酸１の作成）
ケミカルスターラーを備えた３００ｍｌセパラブルフラスコ中に、４，４’−ジアミノジフェニルエーテル１５．０２ｇ（０．０７５ｍｏｌ）、パラフェニレンジアミン２．７０ｇ（０．０２５ｍｏｌ）、Ｎ，Ｎ’−ジメチルアセトアミド１５５．４９ｇを入れ、窒素雰囲気下、室温で撹拌した。６０分撹拌後、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物７．３６ｇ（０．０２５ｍｏｌ）とピロメリット酸二無水物１５．７０ｇ（０．０７２ｍｏｌ）を数回に分けて投入し、更に１８０分撹拌後、ピロメリット酸二無水物のＮ，Ｎ’−ジメチルアセトアミド溶液（溶液濃度６ｗｔ％）適量を３０分かけて滴下し、更に６０分攪拌してポリアミック酸溶液を得た。この時のポリマーをポリアミック酸１とする。
(Preparation of polyamic acid 1)
In a 300 ml separable flask equipped with a chemical stirrer, 15.42 g (0.075 mol) of 4,4′-diaminodiphenyl ether, 2.70 g (0.025 mol) of paraphenylenediamine, 155.49 g of N, N′-dimethylacetamide And stirred at room temperature under a nitrogen atmosphere. After stirring for 60 minutes, 7.36 g (0.025 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 15.70 g (0.072 mol) of pyromellitic dianhydride were divided into several times. After further stirring for 180 minutes, a suitable amount of pyromellitic dianhydride N, N′-dimethylacetamide solution (solution concentration 6 wt%) was added dropwise over 30 minutes, and stirring was continued for 60 minutes to obtain a polyamic acid solution. Obtained. The polymer at this time is designated as polyamic acid 1.
（ポリイミドフィルム１の作成）
全粒子の粒子径が１．５μｍ以下に収まっており、平均粒子径０．３０μｍ、粒子径０．１５〜０．６０μｍの粒子が全粒子中８７．２体積％のシリカのＮ，Ｎ’−ジメチルアセトアミドスラリーを、上記ポリアミック酸１に樹脂重量あたり０．３５重量％添加し、十分攪拌、分散させた後、ポリアミック酸溶液を連続製膜装置に供し、ポリイミドに転化すると同時に乾燥固化し、ポリイミドフィルムを得た。得られたフィルムをポリイミドフィルム１とする。この時のポリイミドフィルム１の平均厚みは３９μｍであった。
(Preparation of polyimide film 1)
The particle diameter of all the particles is within 1.5 μm, and the average particle diameter of 0.30 μm and the particle diameter of 0.15 to 0.60 μm is 87.2% by volume of silica N, N′− The dimethylacetamide slurry was added to the polyamic acid 1 at 0.35% by weight per resin weight, sufficiently stirred and dispersed, then the polyamic acid solution was subjected to a continuous film forming apparatus, converted into polyimide and simultaneously dried and solidified. A film was obtained. The obtained film is referred to as “polyimide film 1”. At this time, the average thickness of the polyimide film 1 was 39 μm.
［実施例１］
上記で得られたポリイミドフィルム１を７５枚積層し、真空プレス機を用いて３５０℃、１０．２ＭＰａで積層圧着し、ポリイミドシートを得た。積層条件と結果を表１に示す。
[Example 1]
75 polyimide films 1 obtained as described above were laminated and laminated and pressure-bonded at 350 ° C. and 10.2 MPa using a vacuum press machine to obtain a polyimide sheet. The lamination conditions and results are shown in Table 1.
（ポリイミドフィルム２の作成）
シリカのＮ，Ｎ’−ジメチルアセトアミドスラリーを添加しない以外は、ポリイミドフィルム１と同様にして、ポリアミック酸１を使用してポリイミドフィルムを得た。得られたフィルムをポリイミドフィルム２とする。この時のポリイミドフィルム１の平均厚みは４０μｍであった。
(Preparation of polyimide film 2)
Polyamic acid 1 was used to obtain a polyimide film in the same manner as polyimide film 1 except that no N, N′-dimethylacetamide slurry of silica was added. The obtained film is referred to as “polyimide film 2”. The average thickness of the polyimide film 1 at this time was 40 μm.
（ポリイミドフィルム３の作成）
粒子径範囲が０．１〜４．５μｍ、平均粒子径１．１μｍ、添加量０．２重量％、粒子径０．１５〜０．６μｍの粒子の全粒子中に占める割合２７．３体積％のリン酸水素カルシウムを、上記ポリアミック酸１に樹脂重量あたり０．３５重量％添加し、十分攪拌、分散させた後、ポリアミック酸溶液を連続製膜装置を用い、ポリイミドに転化すると同時に乾燥固化し、ポリイミドフィルムを得た。得られたフィルムをポリイミドフィルム３とする。この時のポリイミドフィルム３の平均厚みは４０μｍであった。
(Preparation of polyimide film 3)
The particle size range is 0.1 to 4.5 μm, the average particle size is 1.1 μm, the addition amount is 0.2% by weight, and the proportion of the particles having a particle size of 0.15 to 0.6 μm is 27.3% by volume. After adding 0.35% by weight of calcium hydrogen phosphate to the polyamic acid 1 and thoroughly stirring and dispersing the polyamic acid solution, the polyamic acid solution is converted into polyimide using a continuous film-forming apparatus and simultaneously dried and solidified. A polyimide film was obtained. The obtained film is referred to as “polyimide film 3”. At this time, the average thickness of the polyimide film 3 was 40 μm.
［比較例１−２］
上記で得られたポリイミドフィルム２および３を、それぞれ７５枚積層し、真空プレス機を用いて３５０℃、１０．２ＭＰａで積層圧着したが、いずれの場合にも重ねた際にスリキズが発生した。
[Comparative Example 1-2]
75 polyimide films 2 and 3 obtained as described above were each laminated and pressure-bonded at 350 ° C. and 10.2 MPa using a vacuum press machine.
実施例１および比較例１、２における積層条件と結果を表１に示す。 The lamination conditions and results in Example 1 and Comparative Examples 1 and 2 are shown in Table 1.
本発明のポリイミドシートは、積層時にポリイミドフィルムに対しスリキズを発生させることすることがなく高品位であることから、耐熱性、摺動性、寸法安定性が求められる電子部品用途などに有効に利用することができる。 Since the polyimide sheet of the present invention is high quality without causing scratches on the polyimide film during lamination, it is effectively used for electronic component applications that require heat resistance, slidability, and dimensional stability. can do.
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| JP5126734B2 (en) * | 2006-12-11 | 2013-01-23 | 東レ・デュポン株式会社 | Copper plate |
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| JP5069048B2 (en) * | 2007-06-29 | 2012-11-07 | 東レ・デュポン株式会社 | Polyimide film, polyimide laminate and polymer optical waveguide using the same |
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