KR20230041689A - Polyimide resin, polyimide varnish and polyimide film - Google Patents
Polyimide resin, polyimide varnish and polyimide film Download PDFInfo
- Publication number
- KR20230041689A KR20230041689A KR1020237001498A KR20237001498A KR20230041689A KR 20230041689 A KR20230041689 A KR 20230041689A KR 1020237001498 A KR1020237001498 A KR 1020237001498A KR 20237001498 A KR20237001498 A KR 20237001498A KR 20230041689 A KR20230041689 A KR 20230041689A
- Authority
- KR
- South Korea
- Prior art keywords
- structural unit
- polyimide
- polyimide resin
- mol
- derived
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 142
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 81
- 239000004642 Polyimide Substances 0.000 title claims description 35
- 239000002966 varnish Substances 0.000 title claims description 31
- 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 abstract description 47
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 33
- 150000004985 diamines Chemical class 0.000 claims abstract description 27
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 70
- 125000002723 alicyclic group Chemical group 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000000470 constituent Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 abstract 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 24
- 238000011084 recovery Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 18
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 17
- 238000006358 imidation reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 9
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical compound OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 9
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 7
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-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
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 2
- NKYXYJFTTIPZDE-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F NKYXYJFTTIPZDE-UHFFFAOYSA-N 0.000 description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 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
- 150000002596 lactones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BEBFJOSPYYGOKL-UHFFFAOYSA-N (3-ethylphenyl)methanamine Chemical compound CCC1=CC=CC(CN)=C1 BEBFJOSPYYGOKL-UHFFFAOYSA-N 0.000 description 1
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- RCNBXBQGBCGTPB-UHFFFAOYSA-N (4-dodecylphenyl)methanamine Chemical compound CCCCCCCCCCCCC1=CC=C(CN)C=C1 RCNBXBQGBCGTPB-UHFFFAOYSA-N 0.000 description 1
- DGAGEFUEKIORSQ-UHFFFAOYSA-N (4-ethylphenyl)methanamine Chemical compound CCC1=CC=C(CN)C=C1 DGAGEFUEKIORSQ-UHFFFAOYSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTMABCAIKABEFK-UHFFFAOYSA-N 2-[4-[9-[4-(2-aminophenoxy)phenyl]fluoren-9-yl]phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)C=C1 QTMABCAIKABEFK-UHFFFAOYSA-N 0.000 description 1
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-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
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 1
- UKVQTDPWSWISPM-UHFFFAOYSA-N 3-methylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound CC1=C(C(O)=O)C(C(O)=O)=CC(C(O)=O)=C1C(O)=O UKVQTDPWSWISPM-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-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
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-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
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- OSFGNTLIOUHOKN-UHFFFAOYSA-N 4-[benzyl(methyl)sulfamoyl]benzoic acid Chemical compound C=1C=C(C(O)=O)C=CC=1S(=O)(=O)N(C)CC1=CC=CC=C1 OSFGNTLIOUHOKN-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- DVIPPHSQIBKWSA-UHFFFAOYSA-N 4-chlorophthalic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1C(O)=O DVIPPHSQIBKWSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-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
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- ASJCSAKCMTWGAH-UHFFFAOYSA-N cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCC1C(O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
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- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005825 oxyethoxy group Chemical group [H]C([H])(O[*:1])C([H])([H])O[*:2] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
테트라카르본산 이무수물에서 유래하는 구성단위A, 및 디아민에서 유래하는 구성단위B를 갖는 폴리이미드 수지로서, 구성단위A가, 9,9-비스(3,4-디카르복시페닐)플루오렌산 이무수물에서 유래하는 구성단위(A1)와 지방족 테트라카르본산 이무수물에서 유래하는 구성단위(A2)를 포함하고, 구성단위B가, 2,2’-비스(트리플루오로메틸)-4,4’-디아미노디페닐에테르에서 유래하는 구성단위(B1)를 포함하는, 폴리이미드 수지.A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, wherein the structural unit A is 9,9-bis(3,4-dicarboxyphenyl)fluorenic dianhydride It contains a structural unit (A1) derived from water and a structural unit (A2) derived from aliphatic tetracarboxylic dianhydride, and structural unit B is 2,2'-bis(trifluoromethyl)-4,4' - A polyimide resin containing a constituent unit (B1) derived from diaminodiphenyl ether.
Description
본 발명은, 폴리이미드 수지, 폴리이미드 바니시 및 폴리이미드 필름에 관한 것이다.The present invention relates to a polyimide resin, a polyimide varnish and a polyimide film.
폴리이미드 수지는 방향족 테트라카르본산 무수물과 방향족 디아민으로부터 얻어지고, 일반적으로, 분자의 강직성, 공명안정화, 강한 화학결합에 의해 우수한 내열성, 내약품성, 기계물성, 전기특성을 갖기 때문에, 성형재료, 복합재료, 전기·전자부품, 광학재료, 디스플레이, 항공우주 등의 분야에 있어서 폭넓게 이용되고 있다.Polyimide resin is obtained from aromatic tetracarboxylic acid anhydride and aromatic diamine, and generally has excellent heat resistance, chemical resistance, mechanical properties and electrical properties due to molecular rigidity, resonance stabilization, and strong chemical bonding. It is widely used in fields such as materials, electrical/electronic components, optical materials, displays, and aerospace.
특히, 종래부터 전기·전자부품, 광학재료, 디스플레이 등의 용도로 이용되어 온 유리재료에 대하여, 유연한 점을 살려서, 플렉서블 디바이스에의 응용도 검토되고 있다.In particular, glass materials that have been conventionally used for electrical/electronic components, optical materials, displays, and the like are being considered for application to flexible devices, taking advantage of their flexibility.
예를 들어, 특허문헌 1에는, 내열성, 리타데이션, 유연성, 투명성을 향상시키는 것을 목적으로 하여, 지환식 테트라카르본산 이무수물을 포함하는 테트라카르본산 이무수물 성분과, 함불소 방향족 디아민을 포함하는 디아민 성분의 반응물인 폴리이미드, 및 유기용매를 포함하는, 플렉서블 디바이스기판 형성용 조성물이 개시되어 있다.For example, in Patent Document 1, for the purpose of improving heat resistance, retardation, flexibility, and transparency, a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a fluorinated aromatic diamine containing Disclosed is a composition for forming a flexible device substrate comprising polyimide, which is a reactant of a diamine component, and an organic solvent.
최근에는, 특히 디스플레이나 그것을 보호하는 전면(前面)판의 용도에의 폴리이미드 수지의 응용이 진행되고 있으며, 종래 이용되어 온 유리재료의 대체라는 면에서, 기계강도가 높은 폴리이미드 수지가 필요해지고 있다. 그러나, 고강도 폴리이미드 수지는, 플렉서블성이 충분하지는 않았다.In recent years, the application of polyimide resin to the use of displays and front plates protecting them has been progressing, and polyimide resins with high mechanical strength are required in terms of replacing conventionally used glass materials. there is. However, high-strength polyimide resins do not have sufficient flexibility.
최근에는, 폴더블구조를 갖는 스마트폰의 디스플레이나 보호판으로도 이용되기 때문에, 고강도이면서, 보다 높은 플렉서블성도 요구되며, 폴리이미드 필름이 변형된 후에 형상을 회복시키는 성질이나 필름의 연신과 같은 성질도 필요해지고 있다.In recent years, since it is also used as a display or protective plate of a smartphone having a foldable structure, high strength and higher flexibility are required, and properties such as the property of recovering the shape after the polyimide film is deformed or the stretching of the film are also required. it is becoming necessary
그 때문에, 이들 성질을 겸비한 폴리이미드 수지가 요망되고 있었다.Therefore, a polyimide resin having these properties has been desired.
즉, 본 발명이 해결하고자 하는 과제는, 고강도이면서, 변형회복성과 연신도 우수한 필름을 형성할 수 있는 폴리이미드 수지, 및 고강도이면서, 변형회복성과 연신도 우수한 폴리이미드 필름을 제공하는 것에 있다.That is, an object to be solved by the present invention is to provide a polyimide resin capable of forming a film having high strength and excellent strain recovery and elongation, and a polyimide film having high strength and excellent strain recovery and elongation.
발명자들은 예의 검토한 결과, 특정한 구성단위의 조합을 포함하는 폴리이미드 수지가, 상기 과제를 해결할 수 있는 것을 발견하여, 본 발명에 이르렀다.As a result of intensive studies, the inventors have discovered that a polyimide resin containing a combination of specific structural units can solve the above problems, and have reached the present invention.
즉 본 발명은, 하기 [1]~[12]에 관한 것이다.That is, the present invention relates to the following [1] to [12].
[1] 테트라카르본산 이무수물에서 유래하는 구성단위A, 및 디아민에서 유래하는 구성단위B를 갖는 폴리이미드 수지로서, 구성단위A가, 하기 식(a1)로 표시되는 화합물에서 유래하는 구성단위(A1)와 지방족 테트라카르본산 이무수물에서 유래하는 구성단위(A2)를 포함하고, 구성단위B가 하기 식(b1)로 표시되는 화합물에서 유래하는 구성단위(B1)를 포함하는, 폴리이미드 수지.[1] A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, wherein the structural unit A is a structural unit derived from a compound represented by the following formula (a1) ( A polyimide resin comprising A1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride, wherein structural unit B contains a structural unit (B1) derived from a compound represented by the following formula (b1).
[화학식 1][Formula 1]
[2] 상기 구성단위(A2)가, 지환식 테트라카르본산 이무수물에서 유래하는 구성단위인, 상기 [1]에 기재된 폴리이미드 수지.[2] The polyimide resin according to [1], wherein the structural unit (A2) is a structural unit derived from an alicyclic tetracarboxylic dianhydride.
[3] 상기 구성단위(A2)가, 하기 식(a2-1)로 표시되는 화합물에서 유래하는 구성단위(A2-1) 및 하기 식(a2-2)로 표시되는 화합물에서 유래하는 구성단위(A2-2)로부터 선택되는 적어도 하나를 포함하는, 상기 [1] 또는 [2]에 기재된 폴리이미드 수지.[3] The structural unit (A2) is a structural unit (A2-1) derived from a compound represented by the following formula (a2-1) and a structural unit derived from a compound represented by the following formula (a2-2) ( The polyimide resin as described in [1] or [2] above, containing at least one selected from A2-2).
[화학식 2][Formula 2]
[4] 상기 구성단위(A2)가 상기 구성단위(A2-1)를 포함하는, 상기 [3]에 기재된 폴리이미드 수지.[4] The polyimide resin according to [3], wherein the structural unit (A2) includes the structural unit (A2-1).
[5] 상기 구성단위(A2)가 상기 구성단위(A2-2)를 포함하는, 상기 [3]에 기재된 폴리이미드 수지.[5] The polyimide resin according to [3], wherein the structural unit (A2) includes the structural unit (A2-2).
[6] 상기 구성단위A에 대한 상기 구성단위(A1)와 상기 구성단위(A2)의 합계의 비율이, 50몰% 이상인, 상기 [1]~[5] 중 어느 하나에 기재된 폴리이미드 수지.[6] The polyimide resin according to any one of [1] to [5] above, wherein the ratio of the sum of the structural unit (A1) and the structural unit (A2) to the structural unit A is 50 mol% or more.
[7] 상기 구성단위A에 있어서의 상기 구성단위(A1)와 상기 구성단위(A2)의 몰비[(A1)/(A2)]가, 20/80~99/1인, 상기 [1]~[6] 중 어느 하나에 기재된 폴리이미드 수지.[7] The molar ratio [(A1)/(A2)] of the structural unit (A1) and the structural unit (A2) in the structural unit A is 20/80 to 99/1, the above [1] to The polyimide resin described in any one of [6].
[8] 상기 구성단위A에 있어서의 상기 구성단위(A1)와 상기 구성단위(A2-1)의 몰비[(A1)/(A2-1)]가, 50/50~95/5인, 상기 [4]에 기재된 폴리이미드 수지.[8] The molar ratio [(A1)/(A2-1)] of the structural unit (A1) and the structural unit (A2-1) in the structural unit A is 50/50 to 95/5, The polyimide resin described in [4].
[9] 상기 구성단위A에 있어서의 상기 구성단위(A1)와 상기 구성단위(A2-2)의 몰비[(A1)/(A2-2)]가, 20/80~50/50인, 상기 [5]에 기재된 폴리이미드 수지.[9] The molar ratio [(A1)/(A2-2)] of the structural unit (A1) and the structural unit (A2-2) in the structural unit A is 20/80 to 50/50, the above The polyimide resin described in [5].
[10] 상기 구성단위B에 대한 상기 구성단위(B1)의 비율이, 60몰% 이상인, 상기 [1]~[9] 중 어느 하나에 기재된 폴리이미드 수지.[10] The polyimide resin according to any one of [1] to [9] above, wherein a ratio of the structural unit (B1) to the structural unit B is 60 mol% or more.
[11] 상기 [1]~[10] 중 어느 하나에 기재된 폴리이미드 수지가, 유기용제에 용해되어 이루어지는 폴리이미드 바니시.[11] A polyimide varnish obtained by dissolving the polyimide resin according to any one of [1] to [10] above in an organic solvent.
[12] 상기 [1]~[10] 중 어느 하나에 기재된 폴리이미드 수지를 포함하는, 폴리이미드 필름.[12] A polyimide film containing the polyimide resin according to any one of [1] to [10] above.
본 발명에 따르면, 고강도이면서, 변형회복성과 연신도 우수한 필름을 형성할 수 있는 폴리이미드 수지, 이 폴리이미드 수지를 포함하는 폴리이미드 바니시, 및 고강도이면서, 변형회복성과 연신도 우수한 폴리이미드 필름을 제공할 수 있다.According to the present invention, a polyimide resin capable of forming a film having high strength and excellent strain recovery and elongation, a polyimide varnish containing the polyimide resin, and a polyimide film having high strength and excellent strain recovery and elongation are provided. can do.
[도 1] 폴리이미드 필름의 변형회복성을 측정하는 방법을 나타내는 개념도이다.[Figure 1] is a conceptual diagram showing a method for measuring the deformation recovery of a polyimide film.
[폴리이미드 수지][Polyimide resin]
본 발명의 폴리이미드 수지는, 테트라카르본산 이무수물에서 유래하는 구성단위A, 및 디아민에서 유래하는 구성단위B를 갖는 폴리이미드 수지로서,The polyimide resin of the present invention is a polyimide resin having structural unit A derived from tetracarboxylic dianhydride and structural unit B derived from diamine,
구성단위A가, 하기 식(a1)로 표시되는 화합물에서 유래하는 구성단위(A1)와 지방족 테트라카르본산 이무수물에서 유래하는 구성단위(A2)를 포함하고, 구성단위B가, 하기 식(b1)로 표시되는 화합물에서 유래하는 구성단위(B1)를 포함한다.Structural unit A contains a structural unit (A1) derived from a compound represented by the following formula (a1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride, and structural unit B is represented by the following formula (b1) ) and a structural unit (B1) derived from the compound represented by
[화학식 3][Formula 3]
이하, 본 발명의 폴리이미드 수지에 대하여 설명한다.Hereinafter, the polyimide resin of the present invention will be described.
〔구성단위A〕[Constituent Unit A]
본 발명의 폴리이미드에 포함되는 구성단위A는, 폴리이미드 수지에 차지하는 테트라카르본산 이무수물에서 유래하는 구성단위이다.Structural unit A contained in the polyimide of the present invention is a structural unit derived from tetracarboxylic dianhydride occupying the polyimide resin.
구성단위A는, 상기 식(a1)로 표시되는 화합물에서 유래하는 구성단위(A1)와, 지방족 테트라카르본산 이무수물에서 유래하는 구성단위(A2)를 포함한다.The structural unit A includes a structural unit (A1) derived from the compound represented by the formula (a1) and a structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride.
상기 식(a1)로 표시되는 화합물은, 9,9-비스(3,4-디카르복시페닐)플루오렌산 이무수물(BPAF)이다.The compound represented by the formula (a1) is 9,9-bis(3,4-dicarboxyphenyl)fluorenic dianhydride (BPAF).
구성단위A가 구성단위(A1)를 포함함으로써, 얻어지는 폴리이미드 수지의 기계강도가 향상된다.When structural unit A contains structural unit (A1), mechanical strength of the polyimide resin obtained improves.
구성단위(A2)는, 지방족 테트라카르본산 이무수물에서 유래하는 구성단위이며, 구성단위(A2)는, 바람직하게는 지환식 테트라카르본산 이무수물에서 유래하는 구성단위를 포함하고, 보다 바람직하게는 탄소수 4~15의 지환을 갖는 테트라카르본산 이무수물에서 유래하는 구성단위를 포함한다. 지환을 갖는 테트라카르본산 이무수물에서 유래하는 구성단위를 포함함으로써, 연신이 향상되고, 변형회복성, 투명성이 양호해진다.The structural unit (A2) is a structural unit derived from an aliphatic tetracarboxylic dianhydride, and the structural unit (A2) preferably contains a structural unit derived from an alicyclic tetracarboxylic dianhydride, more preferably It contains structural units derived from tetracarboxylic dianhydride having an alicyclic ring of 4 to 15 carbon atoms. By including a structural unit derived from tetracarboxylic dianhydride having an alicyclic ring, stretching is improved, and strain recovery and transparency are improved.
한편, 본 명세서에 있어서, 지방족 테트라카르본산 이무수물이란 방향환을 포함하지 않는 테트라카르본산 이무수물을 의미하고, 지환식 테트라카르본산 이무수물이란 지방족 테트라카르본산 이무수물 중, 지환을 1개 이상 포함하는 테트라카르본산 이무수물을 의미한다.Meanwhile, in the present specification, aliphatic tetracarboxylic dianhydride means tetracarboxylic dianhydride that does not contain an aromatic ring, and alicyclic tetracarboxylic dianhydride means one or more alicyclics among aliphatic tetracarboxylic dianhydrides. It means a tetracarboxylic acid dianhydride containing
여기서 "지환"이란, 탄소원자가 환상으로 결합한 구조 중, 방향환을 제외한 환상 지방족 탄화수소구조인 것을 말하고, 지환의 탄소수는 환을 구성하는 탄소의 수를 말한다.Here, "alicyclic" refers to a cyclic aliphatic hydrocarbon structure excluding aromatic rings among structures in which carbon atoms are cyclically bonded, and the number of carbon atoms in an alicyclic refers to the number of carbon atoms constituting the ring.
지환식 테트라카르본산 이무수물의 구체예로는, 1,2,4,5-시클로헥산테트라카르본산 이무수물, 1,2,3,4-시클로부탄테트라카르본산 이무수물, 노보난-2-스피로-α-시클로펜탄온-α’-스피로-2’’-노보난-5,5’’,6,6’’-테트라카르본산 이무수물, 비시클로[2.2.2]옥타-7-엔-2,3,5,6-테트라카르본산 이무수물, 디시클로헥실테트라카르본산 이무수물, 또는 이들의 위치이성체 등을 들 수 있다.Specific examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, norbonane-2-spiro -α-cyclopentanone-α'-spiro-2''-norbonane-5,5'',6,6''-tetracarboxylic dianhydride, bicyclo[2.2.2]octa-7-ene- 2,3,5,6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, or positional isomers thereof.
지환식 테트라카르본산 이무수물 이외의 지방족 테트라카르본산 이무수물의 구체예로는, 1,2,3,4-부탄테트라카르본산 이무수물 등을 들 수 있다.Specific examples of aliphatic tetracarboxylic dianhydrides other than alicyclic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride.
이들 중에서도, 지방족 테트라카르본산 이무수물에서 유래하는 구성단위(A2)로는, 하기 식(a2-1)로 표시되는 화합물에서 유래하는 구성단위(A2-1) 및 하기 식(a2-2)로 표시되는 화합물에서 유래하는 구성단위(A2-2)로부터 선택되는 적어도 하나를 포함하는 것이 바람직하고, 하기 식(a2-1)로 표시되는 화합물에서 유래하는 구성단위(A2-1) 및 하기 식(a2-2)로 표시되는 화합물에서 유래하는 구성단위(A2-2)로부터 선택되는 적어도 하나인 것이 보다 바람직하다.Among these, the structural unit (A2) derived from an aliphatic tetracarboxylic dianhydride is represented by the structural unit (A2-1) derived from a compound represented by the following formula (a2-1) and the following formula (a2-2) It is preferable to include at least one selected from the structural unit (A2-2) derived from the compound, and the structural unit (A2-1) derived from the compound represented by the following formula (a2-1) and the following formula (a2) It is more preferable that it is at least one selected from structural units (A2-2) derived from the compound represented by -2).
[화학식 4][Formula 4]
상기 식(a2-1)로 표시되는 화합물은, 1,2,3,4-시클로부탄테트라카르본산 이무수물(CBDA)이다.The compound represented by the formula (a2-1) is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA).
상기 식(a2-2)로 표시되는 화합물은, 1,2,4,5-시클로헥산테트라카르본산 이무수물(HPMDA)이다.The compound represented by the formula (a2-2) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA).
구성단위A가 구성단위(A2)를 포함함으로써, 연신이 향상되고, 변형회복성, 투명성이 양호해진다.When the structural unit A includes the structural unit (A2), stretching is improved, and the deformation recovery property and transparency are improved.
이와 같이, 테트라카르본산 이무수물에서 유래하는 구성단위인 구성단위A가 구성단위(A1)와 (A2)를 가짐으로써, 본 발명의 폴리이미드 수지 및 폴리이미드 필름이, 고강도이면서, 변형회복성과 연신도 우수한 이유는 확실하지는 않으나, 플루오렌기의 강직함과 지방족 화합물의 자유도에서 유래하는 것으로 생각된다.In this way, structural unit A, which is a structural unit derived from tetracarboxylic dianhydride, has structural units (A1) and (A2), so that the polyimide resin and polyimide film of the present invention have high strength, strain recovery and elongation The reason why it is superior is not clear, but it is thought to be derived from the rigidity of the fluorene group and the degree of freedom of the aliphatic compound.
구성단위A에 대한 구성단위(A1)의 비율은, 바람직하게는 20~99몰%이고, 보다 바람직하게는 30~97몰%이고, 더욱 바람직하게는 40~96몰%이고, 보다 더 바람직하게는 50~95몰%이다.The ratio of structural unit (A1) to structural unit A is preferably 20 to 99 mol%, more preferably 30 to 97 mol%, even more preferably 40 to 96 mol%, still more preferably is 50 to 95 mol%.
구성단위A에 대한 구성단위(A2)의 비율은, 바람직하게는 1~80몰%이고, 보다 바람직하게는 3~70몰%이고, 더욱 바람직하게는 4~60몰%이고, 보다 더 바람직하게는 5~50몰%이다.The ratio of the structural unit (A2) to the structural unit A is preferably 1 to 80 mol%, more preferably 3 to 70 mol%, still more preferably 4 to 60 mol%, still more preferably is 5 to 50 mol%.
구성단위A에 있어서의 구성단위(A1)와 구성단위(A2)의 합계의 비율은, 바람직하게는 50몰% 이상이고, 보다 바람직하게는 70몰% 이상이고, 더욱 바람직하게는 90몰% 이상이다. 구성단위(A1) 및 구성단위(A2)의 합계의 비율의 상한값은 특별히 한정되지 않고, 100몰% 이하이다. 구성단위A는, 구성단위(A1)와 구성단위(A2)만으로 이루어져 있을 수도 있다.The ratio of the total of structural units (A1) and (A2) in structural unit A is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more. am. The upper limit of the ratio of the total of the constituent units (A1) and (A2) is not particularly limited, and is 100 mol% or less. The structural unit A may consist only of the structural unit (A1) and the structural unit (A2).
구성단위A에 있어서의 구성단위(A1)와 구성단위(A2)의 몰비[(A1)/(A2)]는, 기계물성 및 변형회복성을 향상시키는 관점에서, 바람직하게는 20/80~99/1이고, 보다 바람직하게는 30/70~97/3이고, 더욱 바람직하게는 40/60~96/4이고, 보다 더 바람직하게는 50/50~95/5이다.The molar ratio [(A1)/(A2)] of the structural units (A1) and (A2) in the structural unit A is preferably 20/80 to 99 from the viewpoint of improving mechanical properties and deformation recovery. /1, more preferably 30/70 to 97/3, still more preferably 40/60 to 96/4, still more preferably 50/50 to 95/5.
그 중에서도 특히 변형회복성을 향상시키는 관점에서는, 바람직하게는 60/40~99/1이고, 보다 바람직하게는 80/20~99/1이고, 더욱 바람직하게는 80/20~97/3이다.Among them, from the viewpoint of improving the deformation recovery property, it is preferably 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 80/20 to 97/3.
특히 강도를 향상시키는 관점에서는, 바람직하게는 60/40~99/1이고, 보다 바람직하게는 80/20~99/1이고, 더욱 바람직하게는 92/8~99/1이다.Especially from the viewpoint of improving the strength, preferably it is 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 92/8 to 99/1.
나아가 연신을 향상시키는 관점에서는, 바람직하게는 20/80~92/8이고, 보다 바람직하게는 30/70~80/20이고, 더욱 바람직하게는 40/60~60/40이다.Furthermore, from the viewpoint of improving stretching, preferably it is 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
구성단위A에 있어서의 구성단위(A1)와 구성단위(A2-1)의 몰비[(A1)/(A2-1)]는, 기계물성 및 변형회복성을 향상시키는 관점에서, 바람직하게는 40/60~99/1이고, 보다 바람직하게는 45/55~96/4이고, 더욱 바람직하게는 50/50~95/5이다.The molar ratio [(A1)/(A2-1)] of the structural unit (A1) to the structural unit (A2-1) in the structural unit A is preferably 40 from the viewpoint of improving mechanical properties and deformation recovery. /60 to 99/1, more preferably 45/55 to 96/4, still more preferably 50/50 to 95/5.
그 중에서도 특히 변형회복성을 향상시키는 관점에서는, 바람직하게는 60/40~99/1이고, 보다 바람직하게는 80/20~99/1이고, 더욱 바람직하게는 80/20~97/3이다.Among them, from the viewpoint of improving the deformation recovery property, it is preferably 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 80/20 to 97/3.
특히 강도를 향상시키는 관점에서는, 바람직하게는 60/40~99/1이고, 보다 바람직하게는 80/20~99/1이고, 더욱 바람직하게는 92/8~99/1이다.Especially from the viewpoint of improving the strength, preferably it is 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 92/8 to 99/1.
나아가 연신을 향상시키는 관점에서는, 바람직하게는 20/80~92/8이고, 보다 바람직하게는 30/70~80/20이고, 더욱 바람직하게는 40/60~60/40이다.Furthermore, from the viewpoint of improving stretching, preferably it is 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
구성단위A에 있어서의 구성단위(A1)와 구성단위(A2-2)의 몰비[(A1)/(A2-2)]는, 기계물성 및 변형회복성을 향상시키는 관점에서, 바람직하게는 20/80~99/1이고, 보다 바람직하게는 20/80~60/40이고, 더욱 바람직하게는 20/80~50/50이다.The molar ratio [(A1)/(A2-2)] of the structural unit (A1) to the structural unit (A2-2) in the structural unit A is preferably 20 from the viewpoint of improving mechanical properties and deformation recovery. /80 to 99/1, more preferably 20/80 to 60/40, still more preferably 20/80 to 50/50.
그 중에서도 특히 변형회복성을 향상시키는 관점에서는, 바람직하게는 20/80~60/40이고, 보다 바람직하게는 20/80~50/50이고, 더욱 바람직하게는 20/80~40/60이다.Among them, from the viewpoint of improving the deformation recovery property, it is preferably 20/80 to 60/40, more preferably 20/80 to 50/50, still more preferably 20/80 to 40/60.
특히 강도를 향상시키는 관점에서는, 바람직하게는 20/80~92/8이고, 보다 바람직하게는 30/70~80/20이고, 더욱 바람직하게는 40/60~60/40이다.In particular, from the viewpoint of improving the strength, preferably it is 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
나아가 연신을 향상시키는 관점에서는, 바람직하게는 20/80~92/8이고, 보다 바람직하게는 30/70~80/20이고, 더욱 바람직하게는 40/60~60/40이다.Furthermore, from the viewpoint of improving stretching, preferably it is 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
본 발명의 폴리이미드 수지는, 본 발명의 효과를 손상시키지 않는 범위에서, 구성단위A 중에, 구성단위(A1) 및 구성단위(A2) 이외의 테트라카르본산 이무수물에서 유래하는 구성단위를 포함하고 있을 수도 있다.The polyimide resin of the present invention contains, in structural unit A, structural units derived from tetracarboxylic dianhydride other than structural units (A1) and (A2) within the scope of not impairing the effects of the present invention; There may be.
구성단위(A1) 및 구성단위(A2) 이외의 구성단위를 부여하는 테트라카르본산 이무수물로는, 특별히 한정되지 않는데, 무수피로멜리트산, 2,3,5,6-톨루엔테트라카르본산 이무수물, 1,4,5,8-나프탈렌테트라카르본산 이무수물 등의 방향족 테트라카르본산 이무수물을 들 수 있다. 이들은 단독으로 또는 2종 이상을 조합하여 이용할 수 있다.The tetracarboxylic dianhydride giving structural units other than the structural unit (A1) and the structural unit (A2) is not particularly limited, but pyromellitic anhydride, 2,3,5,6-toluene tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydrides such as 1,4,5,8-naphthalene tetracarboxylic dianhydride. These can be used individually or in combination of 2 or more types.
한편, 본 명세서에 있어서, 방향족 테트라카르본산 이무수물이란 방향환을 1개 이상 포함하는 테트라카르본산 이무수물을 의미한다.Meanwhile, in the present specification, aromatic tetracarboxylic dianhydride means tetracarboxylic dianhydride containing one or more aromatic rings.
〔구성단위B〕[Constituent unit B]
본 발명의 폴리이미드에 포함되는 구성단위B는, 디아민에서 유래하는 구성단위이다.The structural unit B contained in the polyimide of the present invention is a structural unit derived from diamine.
구성단위B는, 하기 식(b1)로 표시되는 화합물에서 유래하는 구성단위(B1)를 포함한다.The structural unit B includes a structural unit (B1) derived from a compound represented by the following formula (b1).
[화학식 5][Formula 5]
상기 식(b1)로 표시되는 화합물은, 2,2’-비스(트리플루오로메틸)-4,4’-디아미노디페닐에테르(6FODA)이다.The compound represented by the formula (b1) is 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA).
구성단위B가 구성단위(B1)를 포함함으로써, 얻어지는 폴리이미드 수지의 투명성 등의 모든 물성에 더하여, 연신이나 변형회복성을 유지한 채로, 기계강도를 향상시킬 수 있다.By including structural unit (B1) in structural unit B, mechanical strength can be improved while maintaining elongation and deformation recovery properties in addition to all physical properties such as transparency of the obtained polyimide resin.
구성단위B에 대한 구성단위(B1)의 비율은, 바람직하게는 30몰% 이상이고, 보다 바람직하게는 40몰% 이상이고, 더욱 바람직하게는 50몰% 이상이고, 보다 더 바람직하게는 60몰% 이상이고, 보다 더 바람직하게는 70몰% 이상이고, 더욱 바람직하게는 90몰% 이상이다. 또한, 구성단위(B1)의 비율의 상한값은 특별히 한정되지 않고, 100몰% 이하이다. 구성단위B는, 구성단위(B1)만으로 이루어져 있을 수도 있다.The ratio of structural unit (B1) to structural unit B is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, still more preferably 60 mol% % or more, more preferably 70 mol% or more, still more preferably 90 mol% or more. In addition, the upper limit of the ratio of structural unit (B1) is not particularly limited and is 100 mol% or less. The structural unit B may consist only of the structural unit (B1).
본 발명의 폴리이미드 수지는, 본 발명의 효과를 손상시키지 않는 범위에서, 구성단위B 중에, 상기 구성단위(B1) 이외의 구성단위로서, 상기 일반식(b1)로 표시되는 화합물 이외의 디아민에서 유래하는 구성단위를 포함하고 있을 수도 있다.The polyimide resin of the present invention is a diamine other than the compound represented by the general formula (b1) as a structural unit other than the structural unit (B1) in the structural unit B within a range that does not impair the effect of the present invention. It may contain constituent units derived from
상기 일반식(b1)로 표시되는 화합물 이외의 디아민으로는, 특별히 한정되지 않는데, 1,4-페닐렌디아민, p-자일릴렌디아민, 1,5-디아미노나프탈렌, 2,2’-디메틸비페닐-4,4’-디아민, 2,2’-디메틸비페닐-4,4’-디아민, 4,4’-디아미노디페닐메탄, 1,4-비스[2-(4-아미노페닐)-2-프로필]벤젠, 2,2-비스(4-아미노페닐)헥사플루오로프로판, 4,4’-디아미노벤즈아닐리드, 1-(4-아미노페닐)-2,3-디하이드로-1,3,3-트리메틸-1H-인덴-5-아민, α,α’-비스(4-아미노페닐)-1,4-디이소프로필벤젠, N,N’-비스(4-아미노페닐)테레프탈아미드, 2,2-비스(3-아미노-4-하이드록시페닐)헥사플루오로프로판, 및 1,4-비스(4-아미노페녹시)벤젠 등의 방향족 디아민; 1,3-비스(아미노메틸)시클로헥산, 및 1,4-비스(아미노메틸)시클로헥산 등의 지환식 디아민; 에틸렌디아민 및 헥사메틸렌디아민 등의 지방족 디아민; 그리고 변성 실리콘디아민을 들 수 있다. 이들은 단독으로 또는 2종 이상을 조합하여 이용할 수 있다.Diamines other than the compounds represented by the general formula (b1) are not particularly limited, but 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, and 2,2'-dimethyl ratio Phenyl-4,4'-diamine, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis[2-(4-aminophenyl) -2-propyl] benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diaminobenzanilide, 1- (4-aminophenyl) -2,3-dihydro-1 ,3,3-trimethyl-1H-inden-5-amine, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, N,N'-bis(4-aminophenyl)terephthal aromatic diamines such as amide, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 1,4-bis(4-aminophenoxy)benzene; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; aliphatic diamines such as ethylenediamine and hexamethylenediamine; And modified silicon diamine is mentioned. These can be used individually or in combination of 2 or more types.
한편, 본 명세서에 있어서, 방향족 디아민이란 방향환을 1개 이상 포함하는 디아민을 의미하고, 지방족 디아민이란 방향환을 포함하지 않는 디아민을 의미하고, 지환식 디아민이란 지방족 디아민 중, 지환을 1개 이상 포함하는 디아민을 의미한다.On the other hand, in the present specification, aromatic diamine means diamine containing one or more aromatic rings, aliphatic diamine means diamine that does not contain an aromatic ring, and alicyclic diamine means one or more alicyclic diamines among aliphatic diamines. Diamine containing
〔폴리이미드 수지의 특성 등〕[Characteristics of polyimide resin, etc.]
본 발명의 폴리이미드 수지의 수평균분자량은, 얻어지는 폴리이미드 필름의 기계적 강도의 관점에서, 바람직하게는 5,000~100,000이다. 한편, 폴리이미드 수지의 수평균분자량은, 겔 여과 크로마토그래피 등에 의해 측정할 수 있다.The number average molecular weight of the polyimide resin of the present invention is preferably 5,000 to 100,000 from the viewpoint of mechanical strength of the polyimide film obtained. On the other hand, the number average molecular weight of the polyimide resin can be measured by gel filtration chromatography or the like.
본 발명의 폴리이미드 수지는, 본 발명의 효과를 손상시키지 않는 범위에서, 추가로 여러 가지 첨가제를 혼합할 수도 있다. 첨가제로는, 예를 들어, 산화방지제, 광안정제, 계면활성제, 난연제, 가소제, 상기 폴리이미드 수지 이외의 고분자 화합물 등을 들 수 있다.The polyimide resin of the present invention may further contain various additives within a range not impairing the effects of the present invention. Examples of additives include antioxidants, light stabilizers, surfactants, flame retardants, plasticizers, and polymer compounds other than the above polyimide resins.
고분자 화합물로는, 본 발명의 폴리이미드 수지 이외의 폴리이미드, 폴리카보네이트, 폴리스티렌, 폴리아미드, 폴리아미드이미드, 폴리에틸렌테레프탈레이트 등의 폴리에스테르, 폴리에테르설폰, 폴리카르본산, 폴리아세탈, 폴리페닐렌에테르, 폴리설폰, 폴리부틸렌, 폴리프로필렌, 폴리아크릴아미드, 폴리염화비닐 등을 들 수 있다.Examples of the polymer compound include polyimide other than the polyimide resin of the present invention, polycarbonate, polystyrene, polyamide, polyamideimide, polyester such as polyethylene terephthalate, polyethersulfone, polycarboxylic acid, polyacetal, and polyphenylene. ether, polysulfone, polybutylene, polypropylene, polyacrylamide, polyvinyl chloride and the like.
〔폴리이미드 수지의 제조방법〕[Method for producing polyimide resin]
본 발명의 폴리이미드 수지는, 상기 서술한 구성단위(A1)를 부여하는 화합물 및 (A2)를 부여하는 화합물을 포함하는 테트라카르본산 성분과, 구성단위(B1)를 부여하는 화합물을 포함하는 디아민 성분을 반응시킴으로써 제조할 수 있다.The polyimide resin of the present invention is a diamine containing a tetracarboxylic acid component containing the above-described compound providing the structural unit (A1) and a compound providing the structural unit (A2), and a compound providing the structural unit (B1). It can be manufactured by reacting components.
구성단위(A1)를 부여하는 화합물로는, 식(a1)로 표시되는 화합물을 들 수 있는데, 그것으로 한정되지 않고, 동일한 구성단위를 부여하는 범위에서 그의 유도체일 수도 있다. 해당 유도체로는, 식(a1)로 표시되는 테트라카르본산 이무수물에 대응하는 테트라카르본산 및 해당 테트라카르본산의 알킬에스테르를 들 수 있다. 구성단위(A1)를 부여하는 화합물로는, 식(a1)로 표시되는 화합물(즉, 이무수물)이 바람직하다.Examples of the compound imparting the structural unit (A1) include compounds represented by formula (a1), but are not limited thereto, and may be derivatives thereof within the scope of imparting the same structural unit. Examples of the derivative include tetracarboxylic acid corresponding to tetracarboxylic dianhydride represented by formula (a1) and alkyl esters of the tetracarboxylic acid. As a compound which gives structural unit (A1), the compound represented by formula (a1) (ie, dianhydride) is preferable.
마찬가지로, 구성단위(A2)를 부여하는 화합물로는, 지방족 테트라카르본산 이무수물, 바람직하게는 지환식 테트라카르본산 이무수물을 들 수 있고, 보다 바람직하게는 식(a2-1) 또는 식(a2-2)로 표시되는 화합물을 들 수 있는데, 그것으로 한정되지 않고, 동일한 구성단위를 부여하는 범위에서 그의 유도체일 수도 있다. 식(a2-1) 또는 식(a2-2)로 표시되는 화합물의 유도체로는, 식(a2-1) 또는 식(a2-2)로 표시되는 테트라카르본산 이무수물에 대응하는 테트라카르본산 및 해당 테트라카르본산의 알킬에스테르를 들 수 있다. 구성단위(A2)를 부여하는 화합물로는, 식(a2-1) 또는 식(a2-2)로 표시되는 화합물(즉, 이무수물)이 바람직하다.Similarly, examples of the compound giving structural unit (A2) include aliphatic tetracarboxylic dianhydride, preferably alicyclic tetracarboxylic dianhydride, more preferably formula (a2-1) or formula (a2) The compound represented by -2) may be mentioned, but is not limited thereto, and may be a derivative thereof within the scope of giving the same structural unit. As the derivative of the compound represented by formula (a2-1) or formula (a2-2), tetracarboxylic acid corresponding to tetracarboxylic dianhydride represented by formula (a2-1) or formula (a2-2); and Alkyl ester of the said tetracarboxylic acid is mentioned. As the compound giving the structural unit (A2), a compound represented by formula (a2-1) or formula (a2-2) (ie, dianhydride) is preferable.
테트라카르본산 성분은, 구성단위(A1)를 부여하는 화합물을, 바람직하게는 20~99몰% 포함하고, 보다 바람직하게는 30~97몰% 포함하고, 더욱 바람직하게는 40~96몰% 포함하고, 보다 더 바람직하게는 50~95몰% 포함한다.The tetracarboxylic acid component contains preferably 20 to 99 mol%, more preferably 30 to 97 mol%, still more preferably 40 to 96 mol% of the compound that provides the structural unit (A1). and more preferably 50 to 95 mol%.
테트라카르본산 성분은, 구성단위(A2)를 부여하는 화합물을, 바람직하게는 1~80몰% 포함하고, 보다 바람직하게는 3~70몰% 포함하고, 더욱 바람직하게는 4~60몰% 포함하고, 보다 더 바람직하게는 5~50몰% 포함한다.The tetracarboxylic acid component contains preferably 1 to 80 mol%, more preferably 3 to 70 mol%, still more preferably 4 to 60 mol% of the compound that provides the structural unit (A2). And, more preferably 5 to 50 mol%.
구성단위(A1)를 부여하는 화합물과 구성단위(A2)를 부여하는 화합물의 합계의 함유비율은, 전체 테트라카르본산 성분 중, 바람직하게는 50몰% 이상이고, 보다 바람직하게는 70몰% 이상이고, 더욱 바람직하게는 90몰% 이상이다. 구성단위(A1)를 부여하는 화합물과 구성단위(A2)를 부여하는 화합물의 합계의 함유비율의 상한값은 특별히 한정되지 않고, 100몰% 이하이다. 테트라카르본산 성분은, 구성단위(A1)를 부여하는 화합물과 구성단위(A2)를 부여하는 화합물만으로 이루어져 있을 수도 있다.The content ratio of the sum of the compound providing the structural unit (A1) and the compound providing the structural unit (A2) is preferably 50 mol% or more, and more preferably 70 mol% or more, of all the tetracarboxylic acid components. , and more preferably 90 mol% or more. The upper limit of the total content of the compound providing the structural unit (A1) and the compound providing the structural unit (A2) is not particularly limited, and is 100 mol% or less. The tetracarboxylic acid component may consist only of the compound providing the structural unit (A1) and the compound providing the structural unit (A2).
테트라카르본산 성분 중에 있어서의 구성단위(A1)를 부여하는 화합물과 구성단위(A2)를 부여하는 화합물의 몰비[(A1)/(A2)]는, 기계물성 및 변형회복성을 향상시키는 관점에서, 바람직하게는 20/80~99/1이고, 보다 바람직하게는 30/70~97/3이고, 더욱 바람직하게는 40/60~96/4이고, 보다 더 바람직하게는 50/50~95/5이다.The molar ratio [(A1)/(A2)] of the compound constituting the structural unit (A1) and the compound constituting the structural unit (A2) in the tetracarboxylic acid component is determined from the viewpoint of improving mechanical properties and deformation recovery. , preferably 20/80 to 99/1, more preferably 30/70 to 97/3, still more preferably 40/60 to 96/4, still more preferably 50/50 to 95/ It is 5.
그 중에서도 특히 변형회복성을 향상시키는 관점에서는, 바람직하게는 60/40~99/1이고, 보다 바람직하게는 80/20~99/1이고, 더욱 바람직하게는 80/20~97/3이다.Among them, from the viewpoint of improving the deformation recovery property, it is preferably 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 80/20 to 97/3.
특히 강도를 향상시키는 관점에서는, 바람직하게는 60/40~99/1이고, 보다 바람직하게는 80/20~99/1이고, 더욱 바람직하게는 92/8~99/1이다.Especially from the viewpoint of improving the strength, preferably it is 60/40 to 99/1, more preferably 80/20 to 99/1, still more preferably 92/8 to 99/1.
나아가 연신을 향상시키는 관점에서는, 바람직하게는 20/80~92/8이고, 보다 바람직하게는 30/70~80/20이고, 더욱 바람직하게는 40/60~60/40이다.Furthermore, from the viewpoint of improving stretching, preferably it is 20/80 to 92/8, more preferably 30/70 to 80/20, still more preferably 40/60 to 60/40.
테트라카르본산 성분은, 구성단위(A1)를 부여하는 화합물 및 구성단위(A2)를 부여하는 화합물 이외의 화합물을 포함할 수도 있고, 해당 화합물로는, 상기 서술한 방향족 테트라카르본산 이무수물 그리고 그들의 유도체(테트라카르본산, 테트라카르본산의 알킬에스테르 등)를 들 수 있다.The tetracarboxylic acid component may contain compounds other than the compound providing the structural unit (A1) and the compound providing the structural unit (A2), and examples of the compound include the above-mentioned aromatic tetracarboxylic dianhydrides and their and derivatives (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.).
테트라카르본산 성분에 임의로 포함되는 화합물(즉, 구성단위(A1) 및 구성단위(A2)를 부여하는 화합물 이외의 화합물)은, 1종일 수도 있고, 2종 이상일 수도 있다.The compound (that is, the compound other than the compound providing the structural unit (A1) and the structural unit (A2)) optionally included in the tetracarboxylic acid component may be one type or two or more types.
구성단위(B1)를 부여하는 화합물로는, 식(b1)로 표시되는 화합물을 들 수 있는데, 그것으로 한정되지 않고, 동일한 구성단위를 부여하는 범위에서 그의 유도체일 수도 있다. 해당 유도체로는, 식(b1)로 표시되는 디아민에 대응하는 디이소시아네이트를 들 수 있다. 구성단위(B1)를 부여하는 화합물로는, 식(b1)로 표시되는 화합물(즉, 디아민)이 바람직하다.Examples of the compound imparting the structural unit (B1) include compounds represented by formula (b1), but are not limited thereto, and may be derivatives thereof within the scope of imparting the same structural unit. Examples of the derivative include diisocyanate corresponding to the diamine represented by formula (b1). As a compound which gives structural unit (B1), the compound represented by formula (b1) (namely, diamine) is preferable.
디아민 성분은, 구성단위(B1)를 부여하는 화합물을, 바람직하게는 30몰% 이상 포함하고, 보다 바람직하게는 40몰% 이상 포함하고, 더욱 바람직하게는 50몰% 포함하고, 보다 더 바람직하게는 60몰% 이상 포함하고, 보다 더 바람직하게는 70몰% 이상 포함하고, 보다 더 바람직하게는 90몰% 이상 포함한다. 또한, 구성단위(B1)를 부여하는 화합물의 비율의 상한값은 특별히 한정되지 않고, 100몰% 이하이다. 디아민 성분은, 구성단위(B1)를 부여하는 화합물만으로 이루어져 있을 수도 있다.The diamine component contains preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol%, and even more preferably 50 mol% of the compound providing the structural unit (B1). contains 60 mol% or more, more preferably contains 70 mol% or more, and even more preferably includes 90 mol% or more. In addition, the upper limit of the ratio of the compound giving the structural unit (B1) is not particularly limited, and is 100 mol% or less. The diamine component may consist only of the compound which gives structural unit (B1).
디아민 성분은 구성단위(B1)를 부여하는 화합물 이외의 화합물을 포함할 수도 있고, 해당 화합물로는, 상기 서술한 방향족 디아민, 지환식 디아민, 및 지방족 디아민, 변성 실리콘디아민, 그리고 그들의 유도체(디이소시아네이트 등)를 들 수 있다.The diamine component may contain compounds other than the compound giving the structural unit (B1), and the compounds include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, modified silicone diamine, and derivatives thereof (diisocyanate etc.) can be mentioned.
디아민 성분에 임의로 포함되는 화합물(즉, 구성단위(B1)를 부여하는 화합물 이외의 화합물)은, 1종일 수도 있고, 2종 이상일 수도 있다.The compound (that is, the compound other than the compound which provides structural unit (B1)) arbitrarily contained in the diamine component may be one kind or two or more kinds.
본 발명에 따른 폴리이미드 수지를 제조할 때, 테트라카르본산 성분과 디아민 성분의 투입량비는, 테트라카르본산 성분 1몰에 대하여 디아민 성분이 0.9~1.1몰인 것이 바람직하다.When producing the polyimide resin according to the present invention, the amount ratio of the tetracarboxylic acid component and the diamine component added is preferably 0.9 to 1.1 mol of the diamine component per 1 mol of the tetracarboxylic acid component.
본 발명의 폴리이미드 수지를 제조할 때, 상기 테트라카르본산 성분, 상기 디아민 성분 외에, 말단봉지제를 이용할 수도 있다. 말단봉지제로는 모노아민류 혹은 디카르본산류가 바람직하다. 도입되는 말단봉지제의 투입량으로는, 테트라카르본산 성분 1몰에 대하여 0.0001~0.1몰이 바람직하고, 0.001~0.06몰이 보다 바람직하다. 바람직한 모노아민류 말단봉지제로는, 메틸아민, 에틸아민, 프로필아민, 부틸아민, 벤질아민, 4-메틸벤질아민, 4-에틸벤질아민, 4-도데실벤질아민, 3-메틸벤질아민, 3-에틸벤질아민, 아닐린, 3-메틸아닐린, 4-메틸아닐린 등을 들 수 있다. 이들 중, 벤질아민, 아닐린이 보다 바람직하다. 디카르본산류 말단봉지제로는, 디카르본산류가 바람직하고, 그 일부가 폐환되어 있을 수도 있다. 바람직한 디카르본산으로는, 프탈산, 무수프탈산, 4-클로로프탈산, 테트라플루오로프탈산, 2,3-벤조페논디카르본산, 3,4-벤조페논디카르본산, 시클로헥산-1,2-디카르본산, 시클로펜탄-1,2-디카르본산, 4-시클로헥센-1,2-디카르본산 등을 들 수 있다. 이들 중, 프탈산, 무수프탈산이 보다 바람직하다.When producing the polyimide resin of the present invention, an end capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. As the end capping agent, monoamines or dicarboxylic acids are preferable. The amount of the endcapping agent to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component. Preferred monoamine endcaps include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. are mentioned. Among these, benzylamine and aniline are more preferable. As the dicarboxylic acid endcapping agent, dicarboxylic acids are preferable, and some of them may be ring-closed. Preferred dicarboxylic acids include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, and cyclohexane-1,2-dicarboxylic acid. levonic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, and the like. Among these, phthalic acid and phthalic anhydride are more preferable.
전술한 테트라카르본산 성분과 디아민 성분을 반응시키는 방법에는 특별히 제한은 없고, 공지의 방법을 이용할 수 있다.The method for reacting the tetracarboxylic acid component and the diamine component described above is not particularly limited, and a known method can be used.
구체적인 반응방법으로는, (1) 테트라카르본산 성분, 디아민 성분, 및 반응용제를 반응기에 투입하고, 10~110℃에서 0.5~30시간 교반하고, 그 후에 승온하여 이미드화반응을 행하는 방법, (2) 디아민 성분 및 반응용제를 반응기에 투입하여 용해시킨 후, 테트라카르본산 성분을 투입하고, 필요에 따라 10~110℃에서 0.5~30시간 교반하고, 그 후에 승온하여 이미드화반응을 행하는 방법, (3) 테트라카르본산 성분, 디아민 성분, 및 반응용제를 반응기에 투입하고, 즉시 승온하여 이미드화반응을 행하는 방법 등을 들 수 있다.As a specific reaction method, (1) a method of introducing a tetracarboxylic acid component, a diamine component, and a reaction solvent into a reactor, stirring at 10 to 110 ° C. for 0.5 to 30 hours, and then raising the temperature to perform an imidation reaction, ( 2) After dissolving the diamine component and the reaction solvent in a reactor, the tetracarboxylic acid component is added, stirred at 10 to 110 ° C. for 0.5 to 30 hours as necessary, and then the temperature is raised to perform an imidation reaction; (3) A method in which a tetracarboxylic acid component, a diamine component, and a reaction solvent are introduced into a reactor, and the temperature is immediately raised to perform an imidation reaction.
폴리이미드 수지의 제조에 이용되는 반응용제는, 이미드화반응을 저해하지 않고, 생성되는 폴리이미드 수지를 용해할 수 있는 것이면 된다. 예를 들어, 비프로톤성 용제, 페놀계 용제, 에테르계 용제, 카보네이트계 용제 등을 들 수 있다.The reaction solvent used for production of the polyimide resin may be one capable of dissolving the resulting polyimide resin without inhibiting the imidation reaction. Examples thereof include aprotic solvents, phenolic solvents, ether solvents, and carbonate solvents.
비프로톤성 용제의 구체예로는, N,N-디메틸이소부틸아미드, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N-메틸-2-피롤리돈, N-메틸카프로락탐, 1,3-디메틸이미다졸리디논, 테트라메틸요소 등의 아미드계 용제, γ-부티로락톤, γ-발레로락톤 등의 락톤계 용제, 헥사메틸포스포릭아미드, 헥사메틸포스핀트리아미드 등의 함인계 아미드계 용제, 디메틸설폰, 디메틸설폭사이드, 설포란 등의 함황계 용제, 아세톤, 시클로헥사논, 메틸시클로헥산 등의 케톤계 용제, 피콜린, 피리딘 등의 아민계 용제, 아세트산(2-메톡시-1-메틸에틸) 등의 에스테르계 용제 등을 들 수 있다.Specific examples of the aprotic solvent include N,N-dimethylisobutylamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam. , Amide-based solvents such as 1,3-dimethylimidazolidinone and tetramethylurea, lactone-based solvents such as γ-butyrolactone and γ-valerolactone, hexamethylphosphoricamide, hexamethylphosphinetriamide, etc. phosphorus-containing amide-based solvents, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane, ketone-based solvents such as acetone, cyclohexanone, and methylcyclohexane, amine-based solvents such as picoline and pyridine, and acetic acid (2 -Methoxy-1-methylethyl), etc. are mentioned.
페놀계 용제의 구체예로는, 페놀, o-크레졸, m-크레졸, p-크레졸, 2,3-자일레놀, 2,4-자일레놀, 2,5-자일레놀, 2,6-자일레놀, 3,4-자일레놀, 3,5-자일레놀 등을 들 수 있다.Specific examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenol, 3,4-xylenol, 3,5-xylenol, etc. are mentioned.
에테르계 용제의 구체예로는, 1,2-디메톡시에탄, 비스(2-메톡시에틸)에테르, 1,2-비스(2-메톡시에톡시)에탄, 비스〔2-(2-메톡시에톡시)에틸〕에테르, 테트라하이드로푸란, 1,4-디옥산 등을 들 수 있다.Specific examples of the ether solvent include 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethyl) ether, oxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane, and the like.
또한, 카보네이트계 용제의 구체적인 예로는, 디에틸카보네이트, 메틸에틸카보네이트, 에틸렌카보네이트, 프로필렌카보네이트 등을 들 수 있다.In addition, specific examples of the carbonate-based solvent include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
상기 반응용제 중에서도, 아미드계 용제 또는 락톤계 용제가 바람직하다. 또한, 상기 반응용제는 단독으로 또는 2종 이상 혼합하여 이용할 수도 있다.Among the above reaction solvents, amide-based solvents or lactone-based solvents are preferable. In addition, the above reaction solvents may be used alone or in combination of two or more.
이미드화반응에서는, 딘스타크장치 등을 이용하여, 제조시에 생성되는 물을 제거하면서 반응을 행하는 것이 바람직하다. 이러한 조작을 행함으로써, 중합도 및 이미드화율을 보다 상승시킬 수 있다.In the imidation reaction, it is preferable to carry out the reaction while removing water generated during production using a Dean Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidation rate can be further increased.
상기 이미드화반응에 있어서는, 공지의 이미드화촉매를 이용할 수 있다. 이미드화촉매로는, 염기촉매 또는 산촉매를 들 수 있다.In the imidation reaction, a known imidation catalyst can be used. Examples of the imidation catalyst include base catalysts and acid catalysts.
염기촉매로는, 피리딘, 퀴놀린, 이소퀴놀린, α-피콜린, β-피콜린, 2,4-루티딘, 2,6-루티딘, 트리메틸아민, 트리에틸아민, 트리프로필아민, 트리부틸아민, 이미다졸, N,N-디메틸아닐린, N,N-디에틸아닐린 등의 유기염기촉매, 수산화칼륨, 수산화나트륨, 탄산칼륨, 탄산나트륨, 탄산수소칼륨, 탄산수소나트륨 등의 무기염기촉매를 들 수 있다.As the base catalyst, pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine , organic base catalysts such as imidazole, N,N-dimethylaniline, and N,N-diethylaniline; and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate. there is.
또한, 산촉매로는, 크로톤산, 아크릴산, 트랜스-3-헥세노익산, 계피산, 안식향산, 메틸안식향산, 옥시안식향산, 테레프탈산, 벤젠설폰산, 파라톨루엔설폰산, 나프탈렌설폰산 등을 들 수 있다. 상기 이미드화촉매는 단독으로 또는 2종 이상을 조합하여 이용할 수도 있다.Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methyl benzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid. The imidation catalyst may be used alone or in combination of two or more.
상기 중, 취급성의 관점에서, 염기촉매를 이용하는 것이 바람직하고, 유기염기촉매를 이용하는 것이 보다 바람직하고, 트리에틸아민을 이용하는 것이 더욱 바람직하다.Among the above, from the viewpoint of handleability, it is preferable to use a base catalyst, more preferably an organic base catalyst, and even more preferable to use triethylamine.
상기 촉매를 이용하는 경우, 이미드화반응의 온도는, 반응률 및 겔화 등의 억제의 관점에서, 바람직하게는 120~250℃, 보다 바람직하게는 160~190℃이고, 더욱 바람직하게는 180~190℃이다. 또한, 반응시간은, 생성수의 유출 개시 후, 바람직하게는 0.5~10시간이다.In the case of using the above catalyst, the temperature of the imidation reaction is preferably 120 to 250 ° C, more preferably 160 to 190 ° C, still more preferably 180 to 190 ° C, from the viewpoint of reaction rate and suppression of gelation, etc. . In addition, the reaction time is preferably 0.5 to 10 hours after the start of distillation of generated water.
한편, 촉매를 이용하지 않는 경우의 이미드화반응의 온도는, 바람직하게는 200~350℃이다.On the other hand, the temperature of the imidation reaction in the case of not using a catalyst is preferably 200 to 350°C.
[폴리이미드 바니시][Polyimide varnish]
본 발명의 폴리이미드 바니시는, 본 발명의 폴리이미드 수지가 유기용매에 용해되어 이루어지는 것이다. 즉, 본 발명의 폴리이미드 바니시는, 본 발명의 폴리이미드 수지 및 유기용매를 포함하고, 해당 폴리이미드 수지는 해당 유기용매에 용해되어 있다.The polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
유기용매는 폴리이미드 수지가 용해되는 것이면 되고, 특별히 한정되지 않는데, 폴리이미드 수지의 제조에 이용되는 반응용제로서 상기 서술한 화합물을, 단독 또는 2종 이상을 혼합하여 이용하는 것이 바람직하다.The organic solvent may be any organic solvent capable of dissolving the polyimide resin, and is not particularly limited, but it is preferable to use the above compounds alone or in a mixture of two or more as the reaction solvent used for producing the polyimide resin.
본 발명의 폴리이미드 바니시는, 본 발명의 폴리이미드 수지를 5~60질량% 포함하는 것이 바람직하고, 5~45질량% 포함하는 것이 보다 바람직하다. 폴리이미드 바니시의 점도는 0.1~200Pa·s가 바람직하고, 0.5~150Pa·s가 보다 바람직하다.It is preferable that the polyimide varnish of this invention contains 5-60 mass % of the polyimide resin of this invention, and it is more preferable that it contains 5-45 mass %. The viscosity of the polyimide varnish is preferably 0.1 to 200 Pa·s, and more preferably 0.5 to 150 Pa·s.
[폴리이미드 필름][Polyimide film]
본 발명의 폴리이미드 필름은, 상기 폴리이미드 수지를 포함한다. 또한, 본 발명의 폴리이미드 필름은, 바람직하게는 상기 폴리이미드 수지로 이루어진다.The polyimide film of the present invention contains the polyimide resin. In addition, the polyimide film of the present invention preferably consists of the above polyimide resin.
즉, 테트라카르본산 이무수물에서 유래하는 구성단위A, 및 디아민에서 유래하는 구성단위B를 갖고, 구성단위A가, 식(a1)로 표시되는 화합물에서 유래하는 구성단위(A1)와 지방족 테트라카르본산 이무수물에서 유래하는 구성단위(A2)를 포함하고, 구성단위B가, 식(b1)로 표시되는 화합물에서 유래하는 구성단위(B1)를 포함하는, 폴리이미드 수지를 포함한다.That is, it has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, and structural unit A is derived from the compound represented by formula (a1) and a structural unit (A1) derived from an aliphatic tetracarb A polyimide resin containing a structural unit (A2) derived from a basal acid dianhydride, wherein structural unit B contains a structural unit (B1) derived from a compound represented by formula (b1).
이러한 폴리이미드 수지를 포함함으로써, 본 발명의 폴리이미드 필름은, 고강도이면서, 연신과 변형회복성도 우수하다.By including such a polyimide resin, the polyimide film of the present invention has high strength and excellent elongation and deformation recovery properties.
본 발명의 폴리이미드 필름의 제작방법에는 특별히 제한은 없고, 공지의 방법을 이용할 수 있다. 예를 들어, 본 발명의 폴리이미드 수지를 포함하는 용액, 또는 본 발명의 폴리이미드 수지를 포함하는 용액과 기술한 여러 가지 첨가제를 포함하는 용액을, 유리판, 금속판, 플라스틱 등의 평활한 지지체 상에 도포, 또는 필름상으로 성형한 후, 이 용액 중에 포함되는 유기용제 등의 용매 성분을 제거하는 방법 등을 들 수 있다.The method for producing the polyimide film of the present invention is not particularly limited, and known methods can be used. For example, a solution containing the polyimide resin of the present invention, or a solution containing the polyimide resin of the present invention and the various additives described above is put on a smooth support such as a glass plate, a metal plate, or plastic. After coating or forming into a film, a method of removing solvent components such as an organic solvent contained in the solution is exemplified.
상기 폴리이미드 수지를 포함하는 용액은, 중합법에 의해 얻어지는 폴리이미드 수지용액 그 자체일 수도 있다. 또한, 상기 폴리이미드 수지용액에 대하여 폴리이미드 수지가 용해되는 용매로서 상기에서 예시된 화합물로부터 선택되는 적어도 1종을 혼합한 것이어도 된다. 상기와 같이 폴리이미드 수지를 포함하는 용액의 고형분농도나 점도를 조정함으로써, 본 발명의 폴리이미드 필름의 두께를 용이하게 제어할 수 있다.The solution containing the polyimide resin may be a polyimide resin solution itself obtained by a polymerization method. In addition, a mixture of at least one selected from the compounds exemplified above as a solvent in which the polyimide resin is dissolved may be mixed with the polyimide resin solution. As described above, the thickness of the polyimide film of the present invention can be easily controlled by adjusting the solid content concentration and viscosity of the solution containing the polyimide resin.
상기 지지체의 표면에, 필요에 따라 이형제를 도포할 수도 있다. 상기 지지체에 상기 폴리이미드 수지 또는 상기 폴리이미드 수지 조성물을 포함하는 용액을 도포한 후, 가열하여 용매 성분을 증발시키는 방법으로는, 이하의 방법이 바람직하다. 즉, 120℃ 이하의 온도에서 용제를 증발시켜 자기지지성 필름으로 한 후, 이 자기지지성 필름을 지지체로부터 박리하고, 이 자기지지성 필름의 단부를 고정하고, 이용한 용매 성분의 비점 이상 350℃ 이하의 온도에서 건조하여 폴리이미드 필름을 제조하는 것이 바람직하다. 또한, 질소분위기하에서 건조하는 것이 바람직하다. 건조분위기의 압력은, 감압, 상압, 가압 중 어느 것이어도 된다.A release agent may be applied to the surface of the support, if necessary. As a method of applying the solution containing the polyimide resin or the polyimide resin composition to the support and then heating to evaporate the solvent component, the following method is preferable. That is, after evaporating the solvent at a temperature of 120° C. or less to obtain a self-supporting film, the self-supporting film is peeled off from the support, the ends of the self-supporting film are fixed, and the boiling point of the solvent component used is 350° C. or higher. It is preferable to manufacture a polyimide film by drying at the following temperature. Further, drying in a nitrogen atmosphere is preferred. Any of reduced pressure, normal pressure, and pressurization may be sufficient as the pressure of dry atmosphere.
본 발명의 폴리이미드 필름의 두께는 용도 등에 따라 적당히 선택할 수 있는데, 바람직하게는 1~250μm, 보다 바람직하게는 5~100μm, 더욱 바람직하게는 10~80μm의 범위이다. 두께가 1~250μm임으로써, 자립막으로서의 실용적인 사용이 가능해진다.The thickness of the polyimide film of the present invention can be appropriately selected depending on the application and the like, and is preferably in the range of 1 to 250 μm, more preferably 5 to 100 μm, and still more preferably 10 to 80 μm. When the thickness is 1 to 250 μm, practical use as a self-supporting film becomes possible.
본 발명의 폴리이미드 수지를 포함하는 폴리이미드 필름은, 컬러필터, 플렉서블 디스플레이, 반도체부품, 광학부재 등의 각종 부재용의 필름으로서 호적하게 이용된다.A polyimide film containing the polyimide resin of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor components, and optical members.
실시예Example
이하 실시예에 의해 본 발명을 구체적으로 설명한다. 단 본 발명은 이들 실시예에 의해 전혀 제한되는 것은 아니다.The present invention is specifically described by the following examples. However, the present invention is not limited at all by these examples.
하기 실시예 및 비교예에서 얻은 폴리이미드 필름의 물성은 이하에 나타내는 방법에 의해 측정하였다.The physical properties of the polyimide films obtained in the following examples and comparative examples were measured by the methods shown below.
(1) 필름두께(1) Film thickness
필름두께의 측정은, 주식회사미쯔토요제, 마이크로미터를 이용하여 측정하였다.The film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
(2) 인장탄성률, 인장강도(2) Tensile modulus of elasticity, tensile strength
측정은 JIS K7127에 준거하고, 토요정기주식회사제 인장시험기 「스트로그래프 VG1E」를 이용하여 행하였다.The measurement was performed using a tensile tester "Strograph VG1E" manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7127.
(3) 인장파단연신율(연신의 평가)(3) Tensile elongation at break (elongation evaluation)
인장파단연신율은, JIS K7127에 준거한 인장시험(연신율의 측정)에 의해 행하였다. 시험편은 폭 10mm, 두께 10~70μm인 것을 이용하였다.The tensile elongation at break was determined by a tensile test (measurement of elongation) in accordance with JIS K7127. As the test piece, one having a width of 10 mm and a thickness of 10 to 70 μm was used.
(4) 변형회복성(4) Deformation recovery
도 1(a)에 나타내는 바와 같이, 10mm폭×100mm길이로 컷한 폴리이미드 필름1을 지그로 R=3mm로 고정하고, 65℃, 상대습도 90%의 조건하, 또는, 70℃, 건조조건하에 24시간 또는 100시간 정치하였다. 그 후, 23℃, 상대습도 50%에서 지그를 분리하고, 170시간 정치한 후에, 필름의 되돌아옴을 도 1(b)에 나타내는 각도θ를 측정함으로써 변형회복성을 평가하였다. 한편, 측정된 각도가 작을수록 변형회복성이 우수한 것을 나타내고, 수치가 작은 편이 바람직하다.As shown in Fig. 1 (a), a polyimide film 1 cut into a 10 mm width x 100 mm length was fixed with a jig at R = 3 mm, under conditions of 65 ° C. and 90% relative humidity, or 70 ° C. under dry conditions. It was allowed to stand for 24 hours or 100 hours. Thereafter, the jig was removed at 23 ° C. and a relative humidity of 50%, and after standing still for 170 hours, the deformation recovery property was evaluated by measuring the angle θ showing the return of the film in FIG. 1 (b). On the other hand, the smaller the measured angle, the better the deformation recovery property, and the smaller the value, the better.
[실시예 1][Example 1]
스테인리스제 반월형 교반날개, 질소도입관, 냉각관을 장착한 딘스타크장치, 온도계, 유리제 엔드캡을 구비한 300mL의 5구 둥근바닥 플라스크에, 디아민 성분으로서 2,2’-비스(트리플루오로메틸)-4,4’-디아미노디페닐에테르(ChinaTech Chemical(Taijin) Co., Ltd.제, 이하 6FODA) 20.22g(0.060몰), 유기용매로서 γ-부티로락톤(미쯔비시케미컬주식회사제, 이하 GBL) 56.7g, 이미드화촉매로서 트리에틸아민(칸토화학주식회사제, 이하 TEA) 0.309g을 투입하고, 계 내 온도 70℃, 질소분위기하, 회전수 150rpm으로 교반하여 용액을 얻었다. 이것에 테트라카르본산 성분으로서 9,9-비스(3,4-디카르복시페닐)플루오렌산 이무수물(JFE케미컬주식회사제, 이하 BPAF) 26.18g(0.057몰) 및 1,2,3,4-시클로부탄테트라카르본산 이무수물(와코순약공업주식회사제, 이하 CBDA) 0.59g(0.003몰), GBL 30.5g을 일괄로 첨가한 후, 맨틀히터로 가열하고, 약 20분에 걸쳐서 반응계 내 온도를 190℃까지 올렸다. 유거(留去)되는 성분을 포집하고, 회전수를 점도상승에 맞추어 조정하면서, 반응계 내 온도를 190℃로 유지하여 2시간 환류함으로써 폴리이미드용액을 얻었다. 그 후, 반응계 내 온도가 120℃까지 냉각되면 N,N-디메틸아세트아미드(미쯔비시가스화학주식회사제, 이하 DMAc)를 소정의 고형분농도가 되도록 첨가하고, 추가로 약 3시간 교반하여 균일화해서, 고형분농도 15.0질량%의 폴리이미드 바니시(A)를 얻었다.2,2'-bis(trifluoromethyl ) -4,4'-diaminodiphenyl ether (manufactured by ChinaTech Chemical (Taijin) Co., Ltd., hereinafter 6FODA) 20.22 g (0.060 mol), as an organic solvent γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd., hereinafter 56.7 g of GBL) and 0.309 g of triethylamine (manufactured by Kanto Chemical Co., Ltd., hereinafter TEA) were added as an imidation catalyst, and stirred at a rotation speed of 150 rpm under a nitrogen atmosphere at a system temperature of 70 ° C to obtain a solution. To this, 26.18 g (0.057 mol) of 9,9-bis(3,4-dicarboxyphenyl)fluorenic dianhydride (manufactured by JFE Chemical Co., Ltd., hereinafter referred to as BPAF) as a tetracarboxylic acid component and 1,2,3,4- After adding 0.59 g (0.003 mol) of cyclobutanetetracarboxylic dianhydride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter CBDA) and 30.5 g of GBL at once, it was heated with a mantle heater, and the temperature inside the reaction system was raised to 190° C. over about 20 minutes. raised to °C. A polyimide solution was obtained by collecting distilled-off components and refluxing for 2 hours while maintaining the temperature inside the reaction system at 190°C while adjusting the number of rotations according to the increase in viscosity. Then, when the temperature in the reaction system is cooled to 120°C, N,N-dimethylacetamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as DMAc) is added to a predetermined solid content concentration, and further stirred for about 3 hours to homogenize the solid content. A polyimide varnish (A) having a concentration of 15.0% by mass was obtained.
계속해서, 폴리이미드 바니시(A)를 PET기판 상에 도포하고, 60℃에서 20분, 80℃에서 20분, 100℃에서 30분 유지하여, 용매를 휘발시킴으로써 자기지지성을 갖는 투명한 1차 건조 필름을 얻고, 나아가 이 필름을 스테인리스 프레임에 고정하고, 220℃에서 공기분위기하, 20분 건조함으로써 용매를 제거하여, 폴리이미드 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.Subsequently, the polyimide varnish (A) is applied on the PET substrate, maintained at 60°C for 20 minutes, 80°C for 20 minutes, and 100°C for 30 minutes to evaporate the solvent, thereby allowing transparent primary drying having self-supporting properties. A film was obtained, and furthermore, this film was fixed to a stainless frame, and the solvent was removed by drying at 220°C in an air atmosphere for 20 minutes to obtain a polyimide film. Table 1 shows the measurement results and evaluation results of physical properties.
[실시예 2][Example 2]
6FODA의 양을 20.54g(0.061몰), BPAF의 양을 25.21g(0.055몰), CBDA의 양을 1.20g(0.006몰)으로 변경한 것 이외는 실시예 1과 동일한 방법에 의해, 고형분농도 15.0질량%의 폴리이미드 바니시(B)를 얻었다. 얻어진 폴리이미드 바니시(B)를 이용하여, 실시예 1과 동일한 방법에 의해, 폴리이미드 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.Solid content concentration was 15.0 in the same manner as in Example 1 except that the amount of 6FODA was changed to 20.54 g (0.061 mole), the amount of BPAF was changed to 25.21 g (0.055 mole), and the amount of CBDA was changed to 1.20 g (0.006 mole). A polyimide varnish (B) in mass % was obtained. A polyimide film was obtained by the same method as in Example 1 using the obtained polyimide varnish (B). Table 1 shows the measurement results and evaluation results of physical properties.
[실시예 3][Example 3]
6FODA의 양을 21.88g(0.065몰), BPAF의 양을 20.88g(0.046몰), CBDA의 양을 3.83g(0.020몰)으로 변경한 것 이외는 실시예 1과 동일한 방법에 의해, 고형분농도 15.0질량%의 폴리이미드 바니시(C)를 얻었다. 얻어진 폴리이미드 바니시(C)를 이용하여, 실시예 1과 동일한 방법에 의해, 폴리이미드 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.Solid content concentration was 15.0 in the same manner as in Example 1 except that the amount of 6FODA was changed to 21.88 g (0.065 mole), the amount of BPAF was changed to 20.88 g (0.046 mole), and the amount of CBDA was changed to 3.83 g (0.020 mole). A polyimide varnish (C) in mass % was obtained. A polyimide film was obtained by the same method as in Example 1 using the obtained polyimide varnish (C). Table 1 shows the measurement results and evaluation results of physical properties.
[실시예 4][Example 4]
6FODA의 양을 23.41g(0.070몰), BPAF의 양을 15.96g(0.035몰), CBDA의 양을 6.83g(0.035몰)으로 변경한 것 이외는, 실시예 1과 동일한 방법에 의해, 고형분농도 15.0질량%의 폴리이미드 바니시(D)를 얻었다. 얻어진 폴리이미드 바니시(D)를 이용하여, 실시예 1과 동일한 방법에 의해 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.Solid content concentration was obtained in the same manner as in Example 1, except that the amount of 6FODA was changed to 23.41 g (0.070 mol), the amount of BPAF was changed to 15.96 g (0.035 mol), and the amount of CBDA was changed to 6.83 g (0.035 mol). A 15.0% by mass polyimide varnish (D) was obtained. A film was obtained by the same method as in Example 1 using the obtained polyimide varnish (D). Table 1 shows the measurement results and evaluation results of physical properties.
[실시예 5][Example 5]
6FODA의 양을 22.93g(0.068몰), BPAF의 양을 15.63g(0.034몰)으로 변경하고, CBDA를 이용하지 않고, 1,2,4,5-시클로헥산테트라카르본산 이무수물(미쯔비시가스화학주식회사제, 이하 HPMDA)을 7.64g(0.034몰) 첨가한 것 이외는, 실시예 1과 동일한 방법에 의해, 고형분농도 15.0질량%의 폴리이미드 바니시(E)를 얻었다. 얻어진 폴리이미드 바니시(E)를 이용하여, 실시예 1과 동일한 방법에 의해 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.The amount of 6FODA was changed to 22.93 g (0.068 mol) and the amount of BPAF was changed to 15.63 g (0.034 mol), CBDA was not used, and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (Mitsubishi Gas Chemical A polyimide varnish (E) having a solid content concentration of 15.0% by mass was obtained in the same manner as in Example 1 except that 7.64 g (0.034 mol) of HPMDA manufactured by Co., Ltd. (hereinafter referred to as HPMDA) was added. A film was obtained by the same method as in Example 1 using the obtained polyimide varnish (E). Table 1 shows the measurement results and evaluation results of physical properties.
[실시예 6][Example 6]
6FODA의 양을 32.52g(0.097몰), BPAF의 양을 13.30g(0.029몰)으로 변경하고, CBDA를 이용하지 않고, HPMDA를 15.17g(0.068몰) 첨가한 것 이외는, 실시예 1과 동일한 방법에 의해, 고형분농도 20.0질량%의 폴리이미드 바니시(F)를 얻었다. 얻어진 폴리이미드 바니시(F)를 이용하여, 실시예 1과 동일한 방법에 의해 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.Same as Example 1 except that the amount of 6FODA was changed to 32.52 g (0.097 mol) and the amount of BPAF was changed to 13.30 g (0.029 mol), and CBDA was not used and 15.17 g (0.068 mol) of HPMDA was added. According to the method, a polyimide varnish (F) having a solid content concentration of 20.0% by mass was obtained. A film was obtained by the same method as in Example 1 using the obtained polyimide varnish (F). Table 1 shows the measurement results and evaluation results of physical properties.
[실시예 7][Example 7]
6FODA의 양을 11.75g(0.035몰)으로 변경하고, 추가로 9,9-비스[4-(아미노페녹시)페닐]플루오렌(JFE케미컬주식회사제, 이하 BPF-AN)(0.035몰)을 첨가하고, BPAF의 양을 22.43g(0.049몰), CBDA의 양을 4.11g(0.021몰)으로 변경한 것 이외는 실시예 1과 동일한 방법에 의해, 고형분농도 18.5질량%의 폴리이미드 바니시(G)를 얻었다. 얻어진 폴리이미드 바니시(G)를 이용하여, 실시예 1과 동일한 방법에 의해, 폴리이미드 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.The amount of 6FODA was changed to 11.75 g (0.035 mol), and 9,9-bis[4-(aminophenoxy)phenyl]fluorene (manufactured by JFE Chemical Co., Ltd., hereinafter referred to as BPF-AN) (0.035 mol) was added. Polyimide varnish (G) having a solid content concentration of 18.5 mass% in the same manner as in Example 1 except that the amount of BPAF was changed to 22.43 g (0.049 mol) and the amount of CBDA was changed to 4.11 g (0.021 mol). got A polyimide film was obtained by the same method as in Example 1 using the obtained polyimide varnish (G). Table 1 shows the measurement results and evaluation results of physical properties.
[비교예 1][Comparative Example 1]
6FODA의 양을 19.93g(0.059몰), BPAF의 양을 27.18g(0.059몰)으로 변경하고, CBDA를 사용하지 않은 것 이외는, 실시예 1과 동일한 방법에 의해, 고형분농도 15.0질량%의 폴리이미드 바니시(H)를 얻었다. 얻어진 폴리이미드 바니시(H)를 이용하여, 실시예 1과 동일한 방법에 의해 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.6FODA was changed to 19.93 g (0.059 mol) and the amount of BPAF was changed to 27.18 g (0.059 mol), and polyi having a solid content concentration of 15.0 mass% was obtained in the same manner as in Example 1 except that CBDA was not used. Mid varnish (H) was obtained. A film was obtained by the same method as in Example 1 using the obtained polyimide varnish (H). Table 1 shows the measurement results and evaluation results of physical properties.
[비교예 2][Comparative Example 2]
6FODA의 양을 38.45g(0.11몰), HPMDA의 양을 25.63g(0.11몰)으로 변경하고, BPAF를 사용하지 않은 것 이외는, 실시예 5와 동일한 방법에 의해 폴리이미드 바니시를 제작하여, 고형분농도 20질량%의 폴리이미드 바니시(I)를 얻었다. 얻어진 폴리이미드 바니시(I)를 이용하여, 실시예 1과 동일한 방법에 의해 필름을 얻었다.A polyimide varnish was produced in the same manner as in Example 5, except that the amount of 6FODA was changed to 38.45 g (0.11 mol) and the amount of HPMDA was changed to 25.63 g (0.11 mol), and BPAF was not used. A polyimide varnish (I) having a concentration of 20% by mass was obtained. A film was obtained by the same method as in Example 1 using the obtained polyimide varnish (I).
[비교예 3][Comparative Example 3]
6FODA의 양을 19.44g(0.058몰), HPMDA의 양을 5.18g(0.023몰)으로 변경하고, BPAF를 대신하여 2,2’,3,3’,5,5’-헥사메틸[1,1’-비페닐]-4,4’-디일=비스(1,3-디옥소-1,3-디하이드로-2-벤조푸란-5-카르복실레이트)(혼슈화학공업주식회사제, 이하 TMPBP-TME) 21.46g(0.035몰)을 사용한 것 이외는, 실시예 5와 동일한 방법에 의해, 고형분농도 15.0질량%의 폴리이미드 바니시(J)를 얻었다. 얻어진 폴리이미드 바니시(J)를 이용하여, 실시예 1과 동일한 방법에 의해 필름을 얻었다. 물성의 측정결과와 평가결과를 표 1에 나타낸다.The amount of 6FODA was changed to 19.44 g (0.058 mol) and the amount of HPMDA was changed to 5.18 g (0.023 mol), and 2,2',3,3',5,5'-hexamethyl[1,1 '-biphenyl] -4,4'-diyl = bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter TMPBP- A polyimide varnish (J) having a solid content concentration of 15.0% by mass was obtained in the same manner as in Example 5 except that 21.46 g (0.035 mol) of TME) was used. A film was obtained in the same manner as in Example 1 using the obtained polyimide varnish (J). Table 1 shows the measurement results and evaluation results of physical properties.
[표 1][Table 1]
표 1로부터, 실시예 1~7의 폴리이미드 필름은, 고강도이면서, 변형회복성과 연신도 우수한 것을 알 수 있다.From Table 1, it can be seen that the polyimide films of Examples 1 to 7 have high strength and excellent deformation recovery and elongation.
Claims (12)
[화학식 1]
[Formula 1]
상기 구성단위(A2)가, 지환식 테트라카르본산 이무수물에서 유래하는 구성단위인, 폴리이미드 수지.According to claim 1,
The polyimide resin, wherein the structural unit (A2) is a structural unit derived from an alicyclic tetracarboxylic dianhydride.
상기 구성단위(A2)가, 하기 식(a2-1)로 표시되는 화합물에서 유래하는 구성단위(A2-1) 및 하기 식(a2-2)로 표시되는 화합물에서 유래하는 구성단위(A2-2)로부터 선택되는 적어도 하나를 포함하는, 폴리이미드 수지.
[화학식 2]
The structural unit (A2) is a structural unit (A2-1) derived from a compound represented by the following formula (a2-1) and a structural unit (A2-2) derived from a compound represented by the following formula (a2-2) ) Polyimide resin containing at least one selected from.
[Formula 2]
상기 구성단위(A2)가 상기 구성단위(A2-1)를 포함하는, 폴리이미드 수지.According to claim 3,
A polyimide resin in which the structural unit (A2) includes the structural unit (A2-1).
상기 구성단위(A2)가 상기 구성단위(A2-2)를 포함하는, 폴리이미드 수지.According to claim 3,
The polyimide resin, wherein the structural unit (A2) includes the structural unit (A2-2).
상기 구성단위A에 대한 상기 구성단위(A1)와 상기 구성단위(A2)의 합계의 비율이, 50몰% 이상인, 폴리이미드 수지.According to any one of claims 1 to 5,
The polyimide resin, wherein the ratio of the sum of the structural unit (A1) and the structural unit (A2) to the structural unit A is 50 mol% or more.
상기 구성단위A에 있어서의 상기 구성단위(A1)와 상기 구성단위(A2)의 몰비[(A1)/(A2)]가, 20/80~99/1인, 폴리이미드 수지.According to any one of claims 1 to 6,
The polyimide resin in which the molar ratio [(A1)/(A2)] of the structural unit (A1) and the structural unit (A2) in the structural unit A is 20/80 to 99/1.
상기 구성단위A에 있어서의 상기 구성단위(A1)와 상기 구성단위(A2-1)의 몰비[(A1)/(A2-1)]가, 50/50~95/5인, 폴리이미드 수지.According to claim 4,
The polyimide resin in which the molar ratio [(A1)/(A2-1)] of the structural unit (A1) and the structural unit (A2-1) in the structural unit A is 50/50 to 95/5.
상기 구성단위A에 있어서의 상기 구성단위(A1)와 상기 구성단위(A2-2)의 몰비[(A1)/(A2-2)]가, 20/80~50/50인, 폴리이미드 수지.According to claim 5,
The polyimide resin in which the molar ratio [(A1)/(A2-2)] of the structural unit (A1) and the structural unit (A2-2) in the structural unit A is 20/80 to 50/50.
상기 구성단위B에 대한 상기 구성단위(B1)의 비율이, 60몰% 이상인, 폴리이미드 수지.According to any one of claims 1 to 9,
The polyimide resin, wherein the ratio of the structural unit (B1) to the structural unit B is 60 mol% or more.
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| TWI503610B (en) * | 2013-05-03 | 2015-10-11 | Chi Mei Corp | Liquid crystal alignment composition, liquid crystal alignment film and liquid crystal display device having thereof |
| CN105593269B (en) * | 2013-09-27 | 2017-11-21 | 东丽株式会社 | Polyimide precursor, polyimide resin film therefrom and the display element containing it, optical element, photo detector, touch panel, circuit substrate, organic el display and organic EL element and the manufacture method of colour filter |
| WO2019069723A1 (en) * | 2017-10-04 | 2019-04-11 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
| CN111205457B (en) * | 2018-11-22 | 2022-09-23 | 达迈科技股份有限公司 | Method for producing polyimide film |
| JP7367699B2 (en) * | 2018-11-28 | 2023-10-24 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish and polyimide film |
| CN110951078A (en) * | 2019-11-27 | 2020-04-03 | 安徽国风塑业股份有限公司 | Polyimide precursor, polyimide, transparent polyimide film and preparation method thereof |
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| JPWO2022019225A1 (en) | 2022-01-27 |
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