CN114096589B - Polyimide resin, polyimide varnish and polyimide film - Google Patents
Polyimide resin, polyimide varnish and polyimide film Download PDFInfo
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- CN114096589B CN114096589B CN202080049420.2A CN202080049420A CN114096589B CN 114096589 B CN114096589 B CN 114096589B CN 202080049420 A CN202080049420 A CN 202080049420A CN 114096589 B CN114096589 B CN 114096589B
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- polyimide
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- acid
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 141
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 56
- 239000002966 varnish Substances 0.000 title claims description 44
- 239000004642 Polyimide Substances 0.000 title claims description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 126
- 150000004985 diamines Chemical class 0.000 claims abstract description 55
- 239000003960 organic solvent Substances 0.000 claims description 13
- 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 abstract description 21
- 125000006158 tetracarboxylic acid group Chemical group 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 description 29
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 22
- 239000002253 acid Substances 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 20
- 239000011521 glass Substances 0.000 description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 229920005575 poly(amic acid) Polymers 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- 239000007810 chemical reaction solvent Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000003513 alkali Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- -1 hexafluoroisopropylidene Chemical group 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 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- YOVXRIACERVBAG-UHFFFAOYSA-N 6-hydroxy-2-oxo-6-phenylhexa-3,5-dienoic acid Chemical compound OC(=O)C(=O)C=CC=C(O)C1=CC=CC=C1 YOVXRIACERVBAG-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 241001272720 Medialuna californiensis Species 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 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
- 238000010992 reflux Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-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
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 3
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 150000001408 amides Chemical class 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000005406 washing Methods 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
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000000010 aprotic solvent 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
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 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
- 230000035484 reaction time Effects 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-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
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 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
- 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
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-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
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 description 1
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 description 1
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- HVSOOROWXIVZSH-UHFFFAOYSA-N 4-(9H-fluoren-1-yl)-2-fluoroaniline Chemical compound NC1=C(C=C(C=C1)C1=CC=CC=2C3=CC=CC=C3CC1=2)F HVSOOROWXIVZSH-UHFFFAOYSA-N 0.000 description 1
- LCCYEGJIEFWDSA-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C=2C3=C(C4=CC=CC=C4C3)C=CC=2)=C1 LCCYEGJIEFWDSA-UHFFFAOYSA-N 0.000 description 1
- RGVHBPPWCQVMDR-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 RGVHBPPWCQVMDR-UHFFFAOYSA-N 0.000 description 1
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 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
- 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
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- APZQJHBPRHHRBX-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)NC1=CC=C(N)C=C1 APZQJHBPRHHRBX-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 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
- 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 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 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
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-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
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent 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
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000003505 polymerization initiator 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
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 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
- 238000004544 sputter deposition Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 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
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
A polyimide resin having a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A comprises a structural unit (A-1) derived from a compound represented by the following formula (a-1) and does not comprise a structural unit (A-2) derived from a compound represented by the following formula (a-2), the structural unit B comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2) derived from a compound represented by the following formula (B-2), the ratio of the structural unit (B-1) in the structural unit B is 30 to 70 mol%, and the ratio of the structural unit (B-2) in the structural unit B is 70 to 30 mol%.
Description
Technical Field
The present invention relates to a polyimide resin, a polyimide varnish and a polyimide film.
Background
Polyimide resins are being studied for various uses in the fields of electric/electronic components and the like. For example, for the purpose of reducing the weight and flexibility of a device, a plastic substrate is desired to be used in place of a glass substrate used in an image display device such as a liquid crystal display or an OLED display, and a polyimide film suitable as the plastic substrate is being studied.
In an image display device, when light emitted from a display element is emitted through a plastic substrate, colorless transparency is required for the plastic substrate, and when light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, a touch panel, or the like), optical isotropy is required to be high (that is, rth is low) in addition to colorless transparency.
In order to satisfy the above-described required performances, various polyimide resins have been developed. For example, patent document 1 describes a polyimide resin produced by using a combination of a specific diamine (second diamine) such as 3,3 '-diaminodiphenyl sulfone (first diamine) and 4,4' -diaminodiphenyl sulfone as a diamine component as a polyimide resin for providing a colorless and transparent polyimide film having low Rth and excellent toughness.
Further, as a polyimide resin having a high refractive index, the applicant has disclosed a polyimide in which 1,2,4, 5-cyclohexane tetracarboxylic dianhydride and 3,3', 4' -biphenyl tetracarboxylic dianhydride are used in combination as dicarboxylic acid components, and 4,4' -diaminodiphenyl sulfone and bis [4- (4-aminophenoxy) phenyl ] sulfone are used in combination as diamine, in patent document 2.
Prior art literature
Patent literature
Patent document 1: international publication No. 2016/158825
Patent document 2: international publication No. 2017/195574
Disclosure of Invention
Problems to be solved by the invention
However, in order to make a polyimide film suitable for a substrate, not only colorless transparency and optical isotropy are important, but also chemical resistance (for example, acid resistance and alkali resistance) is an important physical property.
For example, when a polyimide film is used as a substrate for forming a ITO (Indium Tin Oxide) film, the polyimide film is required to have resistance to an acid used for etching an ITO film. If the acid resistance of the polyimide film is insufficient, the film may be yellowing and the colorless transparency may be impaired.
In addition, for cleaning a support such as a glass plate (support coated with polyimide varnish) used for producing a polyimide film, an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is mainly used. The washing with the aqueous alkali solution may be performed in a state where a polyimide film is formed on a support such as a glass plate. Therefore, polyimide films also require resistance to alkali.
However, in patent document 1, chemical resistance is not evaluated.
When a polyimide film is used as a substrate, a target electronic circuit is formed on the polyimide film through various steps such as a sputtering step and an etching step for forming a metal film, depending on the application, and if the polyimide film is not adhered to a support such as a glass plate during the process, a problem occurs in the process. In addition, a step of peeling the polyimide film from the support is required after these processes. In this case, in order to facilitate the process and prevent breakage during peeling, the polyimide film is required to have a certain toughness, that is, to have high strength and to have good elongation.
Further, when a polyimide is produced, various monomers are combined, but the reactivity is poor due to the kind of monomer, and when the molecular weight of polyimide is to be increased, it takes too much time to polymerize, and therefore, from the viewpoint of production cost, it is required to shorten the polymerization time.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide: a polyimide resin which has excellent colorless transparency, optical isotropy, chemical resistance (for example, acid resistance and alkali resistance) and toughness and which has a short polymerization time, and a polyimide varnish and a polyimide film containing the polyimide resin can be formed.
Solution for solving the problem
The inventors found that: the polyimide resin containing a combination of specific structural units can solve the above-described problems, and thus has completed the present invention.
That is, the present invention relates to [1] to [3] described below.
[1] A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine,
the structural unit A contains a structural unit (A-1) derived from a compound represented by the following formula (a-1) and does not contain a structural unit (A-2) derived from a compound represented by the following formula (a-2),
The structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2) derived from a compound represented by the following formula (B-2),
the ratio of the structural unit (B-1) in the structural unit B is 30 to 70 mol% and the ratio of the structural unit (B-2) in the structural unit B is 70 to 30 mol%.
[2] A polyimide varnish prepared by dissolving the polyimide resin according to the above [1] in an organic solvent.
[3] A polyimide film comprising the polyimide resin according to the above [1 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a film excellent in colorless transparency, optical isotropy, chemical resistance (for example, acid resistance and alkali resistance) and toughness can be formed, and the polymerization time of the polyimide resin is short.
Detailed Description
[ polyimide resin ]
The polyimide resin of the present invention has a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A contains a structural unit (A-1) derived from a compound represented by the following formula (a-1), and does not contain a structural unit (A-2) derived from a compound represented by the following formula (a-2), and the structural unit B contains a structural unit (B-1) derived from a compound represented by the following formula (B-1), and a structural unit (B-2) derived from a compound represented by the following formula (B-2). The ratio of the structural unit (B-1) in the structural unit B is 30 to 70 mol%, and the ratio of the structural unit (B-2) in the structural unit B is 70 to 30 mol%.
< structural Unit A >
The structural unit A is a structural unit derived from tetracarboxylic dianhydride in a polyimide resin, contains a structural unit (A-1) derived from a compound represented by the following formula (a-1), and does not contain a structural unit (A-2) derived from a compound represented by the following formula (a-2).
The compound represented by the formula (a-1) is 1,2,4, 5-cyclohexane tetracarboxylic dianhydride.
By including the structural unit (A-1), the colorless transparency, optical isotropy and chemical resistance of the film can be improved.
The compound represented by the formula (a-2) is 4,4' -oxydiphthalic anhydride. By not including the structural unit (A-2), the polymerization time of the polyimide resin can be shortened.
The ratio of the structural unit (a-1) in the structural unit a is preferably 90 mol% or more, more preferably more than 95 mol%, further preferably 97 mol% or more, and particularly preferably 100 mol%. That is, the structural unit A is particularly preferably formed of only the structural unit (A-1).
The structural unit A may also contain structural units other than the structural unit (A-1). The tetracarboxylic dianhydride providing such a structural unit is not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 9 '-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, and 4,4' - (hexafluoroisopropylidene) dianhydride (excluding the compound represented by formula (a-2)); alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutane tetracarboxylic dianhydride and norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride (excluding the compound represented by the formula (a-1)); aliphatic tetracarboxylic dianhydrides such as 1,2,3, 4-butanetetracarboxylic dianhydride.
In the present specification, the aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing 1 or more aromatic rings, the alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing 1 or more alicyclic rings and not containing an aromatic ring, and the aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride not containing an aromatic ring or an alicyclic ring.
The structural unit optionally contained in the structural unit a is optionally 1 or 2 or more.
< structural Unit B >
The structural unit B is a structural unit derived from diamine in the polyimide resin, and comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2) derived from a compound represented by the following formula (B-2).
The compound represented by the formula (b-1) is 3,3' -diaminodiphenyl sulfone.
The structural unit B includes the structural unit (B-1) to improve the optical isotropy and chemical resistance of the film.
The compound represented by the formula (b-2) is bis [4- (4-aminophenoxy) phenyl ] sulfone.
The structural unit B includes the structural unit (B-2), and thus the film has excellent toughness, and thus the tensile elongation can be improved.
The proportion of the structural unit (B-1) in the structural unit B is 30 to 70 mol%, preferably 40 to 65 mol%, more preferably 50 to 60 mol%. When the ratio of the structural unit (B-1) in the structural unit B is within this range, the polymerization time of the polyimide resin is short, and thus it is preferable.
The ratio of the structural unit (B-2) in the structural unit B is 70 to 30 mol%, preferably 60 to 35 mol%, more preferably 50 to 40 mol%. When the ratio of the structural unit (B-2) in the structural unit B is within this range, the polymerization time of the polyimide resin is short, and thus it is preferable.
The molar ratio [ (B-1)/(B-2) ] of the structural unit (B-1) to the structural unit (B-2) in the structural unit B is preferably 30/70 to 70/30, more preferably 40/60 to 65/35, still more preferably 50/50 to 60/40.
When the ratio or the molar ratio of the structural unit (B-1) to the structural unit (B-2) is in the above range, the polymerization time can be shortened, and the transparency and toughness (elastic modulus, strength and elongation) of the obtained polyimide resin can be improved.
In particular, from the viewpoint of polymerization time, the molar ratio [ (B-1)/(B-2) ] of the structural unit (B-1) to the structural unit (B-2) in the structural unit B is preferably 50/50 to 70/30, more preferably 55/45 to 70/30, still more preferably 60/40 to 70/30.
In particular, from the viewpoints of toughness (strength and elongation) and transparency, the molar ratio [ (B-1)/(B-2) ] of the structural unit (B-1) to the structural unit (B-2) is preferably 30/70 to 60/40, more preferably 30/70 to 55/45, and still more preferably 30/70 to 50/50.
The total ratio of the structural units (B-1) and (B-2) in the structural unit B is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the total ratio of the structural units (B-1) and (B-2) is not particularly limited, and is 100 mol%. The structural unit B may also comprise only the structural unit (B-1) and the structural unit (B-2).
The structural unit B may also comprise structural units other than the structural units (B-1) and (B-2). The diamine providing such a structural unit is not particularly limited, examples thereof include 1, 4-phenylenediamine, p-xylylenediamine, 3, 5-diaminobenzoic acid, 1, 5-diaminonaphthalene, 2 '-dimethylbiphenyl-4, 4' -diamine, 2 '-bis (trifluoromethyl) benzidine, 4' -diaminodiphenyl ether 4,4 '-diaminodiphenylmethane, 2-bis (4-aminophenyl) hexafluoropropane, 4' -diaminodiphenylsulfone, 4 '-diaminobenzanilide, 1- (4-aminophenyl) -2, 3-dihydro-1, 3-trimethyl-1H-inden-5-amine, alpha, aromatic diamines such as α' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, N '-bis (4-aminophenyl) terephthalamide, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 9-bis (4-aminophenyl) fluorene, and 4,4 '-diamino-2, 2' -bistrifluoromethyl diphenyl ether (excluding the compound represented by formula (b-1)); alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; aliphatic diamines such as ethylenediamine and hexamethylenediamine.
In the present specification, an aromatic diamine means a diamine containing 1 or more aromatic rings, an alicyclic diamine means a diamine containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic diamine means a diamine containing no aromatic rings or alicyclic rings.
The structural unit optionally contained in the structural unit B is optionally 1 or 2 or more.
As the diamine providing the structural unit optionally contained in the structural unit B, preferred are a compound represented by the following formula (B-3-1), a compound represented by the following formula (B-3-2), a compound represented by the following formula (B-3-3), and a compound represented by the following formula (B-3-4). That is, in the polyimide resin according to one embodiment of the present invention, the structural unit B may further include at least 1 structural unit (B-3) selected from the group consisting of structural units (B-3-1) derived from the compound represented by the following formula (B-3-1), structural units (B-3-2) derived from the compound represented by the following formula (B-3-2), structural units (B-3-3) derived from the compound represented by the following formula (B-3-3), and structural units (B-3-4) derived from the compound represented by the following formula (B-3-4).
(in the formula (b-3-2), R is each independently a hydrogen atom, a fluorine atom or a methyl group.)
The compound represented by the formula (b-3-1) is 4,4 '-diamino-2, 2' -bistrifluoromethyl diphenyl ether.
The inclusion of the structural unit (B-3-1) can improve the colorless transparency of the film.
In the formula (b-3-2), R is each independently a hydrogen atom, a fluorine atom or a methyl group, preferably a hydrogen atom. Examples of the compound represented by the formula (b-3-2) include 9, 9-bis (4-aminophenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene, 9-bis (3-methyl-4-aminophenyl) fluorene, and the like, and 9, 9-bis (4-aminophenyl) fluorene is preferable.
The inclusion of the structural unit (B-3-2) can improve the optical isotropy and heat resistance of the film.
The compound represented by the formula (b-3-3) is 2, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane.
The inclusion of the structural unit (B-3-3) can improve the colorless transparency of the film.
The compound represented by the formula (b-3-4) is 2,2' -bis (trifluoromethyl) benzidine.
The structural unit B can improve the colorless transparency, chemical resistance and mechanical properties of the film by containing the structural unit (B-3-4).
When the structural unit B includes the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3), the total ratio of the structural unit (B-1) and the structural unit (B-2) in the structural unit B is preferably 70 to 95 mol%, more preferably 75 to 95 mol%, still more preferably 75 to 90 mol%, and the ratio of the structural unit (B-3) in the structural unit B is preferably 5 to 30 mol%, more preferably 5 to 25 mol%, still more preferably 10 to 25 mol%.
The total ratio of the structural units (B-1), the structural units (B-2) and the structural units (B-3) in the structural unit B is preferably 75 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the ratio of the total of the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3) is not particularly limited, that is, 100 mol%. The structural unit B may include only the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3).
The structural unit (B-3) may be only the structural unit (B-3-1), may be only the structural unit (B-3-2), may be only the structural unit (B-3-3), or may be only the structural unit (B-3-4).
The structural unit (B-3) may be a combination of 2 or more structural units selected from the group consisting of the structural units (B-3-1) to (B-3-4).
The number average molecular weight of the polyimide resin of the present invention is preferably 5000 to 200000 from the viewpoint of mechanical strength of the obtained polyimide film. The number average molecular weight of the polyimide resin can be determined, for example, from a standard polymethyl methacrylate (PMMA) conversion value measured by gel filtration chromatography.
The polyimide resin of the present invention may contain a structure other than a polyimide chain (a structure in which a structural unit a and a structural unit B are imide-bonded). Examples of the structure other than the polyimide chain that can be contained in the polyimide resin include a structure containing an amide bond.
The polyimide resin of the present invention preferably contains a polyimide chain (structure in which structural unit a and structural unit B are imide-bonded) as a main structure. Therefore, the polyimide chain content in the polyimide resin of the present invention is preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 90 mass% or more, and particularly preferably 99 mass% or more.
By using the polyimide resin of the present invention, a film excellent in colorless transparency, optical isotropy, chemical resistance (for example, acid resistance and alkali resistance) and toughness can be formed, and the film has the following preferable physical properties.
When a film having a thickness of 10 μm is formed, the total light transmittance is preferably 88% or more, more preferably 88.5% or more, and still more preferably 89% or more.
When a film having a thickness of 10 μm is formed, the Yellowness Index (YI) is preferably 4.0 or less, more preferably 2.5 or less, and further preferably 2.0 or less.
B when a film having a thickness of 10 μm is formed * Preferably 2.0 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.
When a film having a thickness of 10 μm is formed, the absolute value of the thickness retardation (Rth) is preferably 70nm or less, more preferably 60nm or less, and still more preferably 35nm or less. When the ratio is within this range, the optical isotropy is excellent.
The tensile strength is preferably 105MPa or more, more preferably 110MPa or more, and still more preferably 115MPa or more. The tensile elongation is preferably 5 to 20%, more preferably 5 to 15%. When the tensile strength and the tensile elongation are both in these ranges, the film has excellent toughness, and the polyimide film can be easily peeled from the support in the step of peeling, whereby breakage during peeling can be prevented.
When a film having a thickness of 10 μm is formed, the mixed acid ΔYI is preferably 1.5 or less, more preferably 1.3 or less, and still more preferably 1.0 or less.
When a film having a thickness of 10 μm is formed, the acid mixture Δb is mixed * Preferably 0.8 or less, more preferably 0.6 or less, and still more preferably 0.5 or less.
The mixed acid Δyi and the mixed acid Δb are used as the mixed acid * The difference between YI before and after dipping and b when the polyimide film is immersed in a mixture of phosphoric acid, nitric acid and acetic acid * Specifically, the difference (c) can be measured by the method described in the examples. ΔYI and Δb * The smaller the acid resistance, the more excellent. By using the polyimide resin of the present invention, a film having excellent chemical resistance can be formed, and excellent resistance to acid can be exhibited. In particular, the acid mixture exhibits excellent resistance to the above-mentioned acid mixture.
The film formed from the polyimide resin of the present invention is excellent in mechanical properties and heat resistance, and has the following preferable physical properties.
The tensile elastic modulus is preferably 2.0GPa or more, more preferably 2.5GPa or more, and still more preferably 3.0GPa or more.
The glass transition temperature (Tg) is preferably 250℃or higher, more preferably 270℃or higher, and still more preferably 300℃or higher. When the content is within this range, the polyimide substrate is suitably heat-resistant when an image display device such as a liquid crystal display or an OLED display is produced.
The physical property values described above in the present invention can be specifically measured by the methods described in examples.
[ method for producing polyimide resin ]
The polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component comprising a compound providing the above-mentioned structural unit (A-1) (wherein the compound providing the above-mentioned structural unit (A-2) is not contained) with a diamine component comprising a compound providing the above-mentioned structural unit (B-1) and a compound providing the above-mentioned structural unit (B-2).
The compound providing the structural unit (A-1) is exemplified by the compound represented by the formula (a-1), but is not limited thereto, and may be a derivative thereof within the range of providing the same structural unit. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1) (i.e., 1,2,4, 5-cyclohexane tetracarboxylic acid) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A-1), a compound represented by the formula (a-1) (i.e., dianhydride) is preferable.
The tetracarboxylic acid component preferably contains 90 mol% or more, more preferably contains more than 95 mol%, still more preferably contains 97 mol% or more, still more preferably contains 100 mol% of the compound providing the structural unit (a-1).
The tetracarboxylic acid component may contain a compound other than the compound providing the structural unit (A-1), and examples of the compound include the above-mentioned aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl esters of tetracarboxylic acid, and the like).
The compounds optionally contained in the tetracarboxylic acid component are optionally 1 or 2 or more.
The compound providing the structural unit (B-1) is exemplified by the compound represented by the formula (B-1), but is not limited thereto, and may be a derivative thereof within the range where the same structural unit is provided. The derivative may be a diisocyanate corresponding to the diamine represented by the formula (b-1). As the compound providing the structural unit (B-1), a compound represented by the formula (B-1) (i.e., diamine) is preferable.
The compound providing the structural unit (B-2) is exemplified by the compound represented by the formula (B-2), but is not limited thereto, and may be a derivative thereof within the range where the same structural unit is provided. The derivative may be a diisocyanate corresponding to the diamine represented by the formula (b-2). As the compound providing the structural unit (B-2), a compound represented by the formula (B-2) (i.e., diamine) is preferable.
The diamine component preferably contains 30 to 70 mol%, more preferably 40 to 65 mol%, still more preferably 50 to 60 mol% of the compound providing the structural unit (B-1). When the ratio of the compound providing the structural unit (B-1) in the diamine component is within this range, the polymerization time of the polyimide resin is short, and thus it is preferable.
The diamine component preferably contains 70 to 30 mol%, more preferably 60 to 35 mol%, still more preferably 50 to 40 mol% of the compound providing the structural unit (B-2). When the ratio of the compound providing the structural unit (B-2) in the diamine component is within this range, the polymerization time of the polyimide resin is short, and thus it is preferable.
The molar ratio [ (B-1)/(B-2) ] of the compound providing the structural unit (B-1) to the compound providing the structural unit (B-2) in the diamine component is preferably 30/70 to 70/30, more preferably 40/60 to 65/35, still more preferably 50/50 to 60/40.
In particular, from the viewpoint of polymerization time, the molar ratio [ (B-1)/(B-2) ] of the compound providing the structural unit (B-1) to the compound providing the structural unit (B-2) in the diamine component is preferably 50/50 to 70/30, more preferably 55/45 to 70/30, still more preferably 60/40 to 70/30.
In particular, from the viewpoints of toughness (strength and elongation) and transparency, the molar ratio [ (B-1)/(B-2) ] of the compound providing the structural unit (B-1) to the compound providing the structural unit (B-2) in the diamine component is preferably 30/70 to 60/40, more preferably 30/70 to 55/45, still more preferably 30/70 to 50/50.
The diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, particularly preferably 99 mol% or more of the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2) in total. The upper limit of the total content ratio of the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2) is not particularly limited, that is, 100 mol%. The diamine component may also contain only the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2).
The diamine component may contain a compound other than the compound providing the structural unit (B-1) or (B-2), and examples of the compound include the above-mentioned aromatic diamine, alicyclic diamine, aliphatic diamine, and derivatives thereof (diisocyanate, etc.).
The compound optionally contained in the diamine component (i.e., a compound other than the compound providing the structural unit (B-1) or (B-2)) is optionally 1 or 2 or more.
As the compound optionally contained in the diamine component, a compound providing the structural unit (B-3) (i.e., at least 1 selected from the group consisting of a compound providing the structural unit (B-3-1), a compound providing the structural unit (B-3-2), a compound providing the structural unit (B-3-3), and a compound providing the structural unit (B-3-4)) is preferable.
The compound providing the structural unit (B-3) may be a compound represented by the formula (B-3-1), a compound represented by the formula (B-3-2), a compound represented by the formula (B-3-3) or a compound represented by the formula (B-3-4), but the present invention is not limited thereto, and may be a derivative thereof insofar as the same structural unit can be formed. The derivative includes diisocyanates corresponding to the diamines of the formulae (b-3-1) to (b-3-4). As the compound providing the structural unit (B-3), at least 1 selected from the group consisting of compounds represented by the formulae (B-3-1) to (B-3-4) (i.e., diamine) is preferable.
When the diamine component contains the compound providing the structural unit (B-1), the compound providing the structural unit (B-2) and the compound providing the structural unit (B-3), the diamine component preferably contains 70 to 95 mol%, more preferably 75 to 95 mol%, still more preferably 75 to 90 mol% of the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2), preferably 5 to 30 mol%, more preferably 5 to 25 mol%, still more preferably 10 to 25 mol% of the compound providing the structural unit (B-3) in total.
The diamine component preferably contains 75 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 99 mol% or more of the compound providing the structural unit (B-1), the compound providing the structural unit (B-2), and the compound providing the structural unit (B-3) in total. The upper limit of the total content ratio of the compound providing the structural unit (B-1), the compound providing the structural unit (B-2) and the compound providing the structural unit (B-3) is not particularly limited, that is, 100 mol%. The diamine component may contain only the compound providing the structural unit (B-1), the compound providing the structural unit (B-2), and the compound providing the structural unit (B-3).
The compound providing the structural unit (B-3) may be only the compound providing the structural unit (B-3-1), may be only the compound providing the structural unit (B-3-2), may be only the compound providing the structural unit (B-3-3), or may be only the compound providing the structural unit (B-3-4).
The compound providing the structural unit (B-3) may be a combination of 2 or more compounds selected from the group consisting of compounds providing the structural units (B-3-1) to (B-3-4).
In the present invention, the ratio of the amount of the tetracarboxylic acid component to the amount of the diamine component to be added used for producing the polyimide resin is preferably 0.9 to 1.1 mol based on 1 mol of the tetracarboxylic acid component.
In the present invention, in addition to the tetracarboxylic acid component and the diamine component, a capping agent may be used in the production of the polyimide resin. As the blocking agent, monoamines or dicarboxylic acids are preferable. The amount of the blocking agent to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. As monoamine-type blocking agents, for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Among these, benzylamine and aniline can be suitably used. The dicarboxylic acid-based capping agent is preferably a dicarboxylic acid, and a part of the dicarboxylic acid-based capping agent may be closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2, 3-benzophenone dicarboxylic acid, 3, 4-benzophenone dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, and the like are recommended. Among these, phthalic acid and phthalic anhydride can be suitably used.
The method for reacting the tetracarboxylic acid component and the diamine component is not particularly limited, and a known method can be used.
Specific examples of the reaction method include (1) a method in which the tetracarboxylic acid component, the diamine component and the reaction solvent are fed into a reactor, stirred at a temperature of from room temperature to 80 ℃ for 0.5 to 30 hours, and then heated to perform imidization, (2) a method in which the diamine component and the reaction solvent are fed into a reactor to dissolve the components, then the tetracarboxylic acid component is fed into the reactor, stirred at a temperature of from room temperature to 80 ℃ for 0.5 to 30 hours, and then heated to perform imidization, if necessary, and (3) a method in which the tetracarboxylic acid component, the diamine component and the reaction solvent are fed into a reactor, and then directly heated to perform imidization.
The reaction solvent used for producing the polyimide resin may be one which does not inhibit imidization and which can dissolve the polyimide to be produced. Examples thereof include aprotic solvents, phenolic solvents, ether solvents, and carbonate solvents.
Specific examples of the aprotic solvent include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1, 3-dimethylimidazolidinone, tetramethylurea, lactone solvents such as γ -butyrolactone and γ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoramide and hexamethylphosphoric triamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfolane, ketone solvents such as acetone, cyclohexanone and methylcyclohexanone, amine solvents such as picoline and pyridine, and ester solvents such as acetic acid (2-methoxy-1-methylethyl ester).
Specific examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol.
Specific examples of the ether solvent include 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [ 2- (2-methoxyethoxy) ethyl ] ether, tetrahydrofuran, and 1, 4-dioxane.
Specific examples of the carbonate-based solvent include diethyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
Among the above reaction solvents, an amide-based solvent or a lactone-based solvent is preferable. The above reaction solvents may be used alone or in combination of two or more.
In the imidization reaction, the reaction is preferably performed while removing water generated during the production using a dean-stark apparatus or the like. By performing such an operation, the polymerization degree and the imidization rate can be further increased.
In the imidization reaction, a known imidization catalyst can be used. Examples of the imidization catalyst include a base catalyst and an acid catalyst.
Examples of the base catalyst include organic base catalysts such as pyridine, quinoline, isoquinoline, α -picoline, β -picoline, 2, 4-lutidine, 2, 6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N-dimethylaniline, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and the like. The imidization catalyst may be used singly or in combination of two or more.
Among the above, from the viewpoint of handleability, a base catalyst is preferably used, an organic base catalyst is more preferably used, triethylamine is more preferably used, and triethylamine and triethylenediamine are particularly preferably used in combination.
The temperature of the imidization reaction is preferably 120 to 250 ℃, more preferably 160 to 200 ℃, from the viewpoints of the reaction rate, gelation, and the like. The reaction time is preferably 0.5 to 6 hours, more preferably 0.5 to 5.5 hours after the start of distillation of the produced water. The polyimide resin has shorter reaction time.
The solid content concentration in the imidization reaction is preferably 30 to 60 mass%, more preferably 35 to 58 mass%, and particularly preferably 40 to 56 mass%. When the solid content concentration in the imidization reaction is within this range, the imidization reaction proceeds well and water generated in the reaction is easily removed, so that the polymerization degree and imidization rate can be increased.
However, the solid content concentration in the imidization reaction is calculated by the following formula based on the mass of the tetracarboxylic acid component added to the reaction system, the diamine component in the reaction system, and the reaction solvent.
Solid content concentration (mass%) at imidization reaction = (total mass of tetracarboxylic acid component and diamine component)/(total mass of tetracarboxylic acid component, diamine component and reaction solvent) ×100
[ polyimide varnish ]
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 in which the polyimide resin is dissolved.
The organic solvent is not particularly limited as long as it dissolves the polyimide resin, and the above-mentioned compounds are preferably used alone or in combination of 2 or more as the reaction solvent used in the production of the polyimide resin.
The polyimide varnish of the present invention may be a polyimide solution in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or may be a solution in which a diluting solvent is further added to the polyimide solution.
The polyimide resin of the present invention has solvent solubility, and thus can be prepared into a varnish of high concentration which is stable at room temperature. The polyimide varnish of the present invention preferably contains 5 to 40 mass%, more preferably 10 to 30 mass% of the polyimide resin of the present invention. The viscosity of the polyimide varnish is preferably 1 to 200pa·s, more preferably 1.5 to 100pa·s. The viscosity of the polyimide varnish was determined at 25℃using an E-type viscometer.
The polyimide varnish of the present invention may contain various additives such as an inorganic filler, an adhesion promoter, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, a defoaming agent, a fluorescent whitening agent, a crosslinking agent, a polymerization initiator, and a photosensitizer, as far as the required properties of the polyimide film are not impaired.
The method for producing the polyimide varnish of the present invention is not particularly limited, and a known method can be applied.
[ polyimide film ]
The polyimide film of the present invention contains the polyimide resin of the present invention. Therefore, the polyimide film of the present invention is excellent in colorless transparency, optical isotropy, and chemical resistance (for example, acid resistance and alkali resistance). The polyimide film of the present invention has preferable physical properties as described above.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. Examples of the method include a method of applying the polyimide varnish of the present invention to a smooth support such as a glass plate, a metal plate, or a plastic, forming the polyimide varnish into a film, and then removing an organic solvent such as a reaction solvent or a dilution solvent contained in the varnish by heating the film.
The coating method includes known coating methods such as spin coating, slot coating, and blade coating. Among them, slit coating is preferable from the viewpoints of controlling intermolecular orientation and improving chemical resistance and handleability.
As a method for removing the organic solvent contained in the varnish by heating, it is preferable to evaporate the organic solvent at a temperature of 150 ℃ or lower so as not to stick to the hand, and then dry the varnish at a temperature of the boiling point of the organic solvent used or higher (not particularly limited, preferably 200 to 500 ℃). In addition, drying under an air atmosphere or a nitrogen atmosphere is preferable. The pressure of the drying atmosphere may be reduced, normal pressure or increased.
The method for peeling the polyimide film formed by film formation on the support from the support is not particularly limited, and examples thereof include a laser peeling method and a method using a sacrificial layer for peeling (a method of applying a release agent to the surface of the support in advance).
The polyimide film of the present invention can also be produced using a polyamic acid varnish in which a polyamic acid is dissolved in an organic solvent.
The polyamic acid contained in the polyamic acid varnish is a precursor of the polyimide resin of the present invention, and is a product of an addition polymerization reaction of a tetracarboxylic acid component including a compound providing the above-mentioned structural unit (A-1) and a compound providing the above-mentioned structural unit (A-2), and a diamine component including a compound providing the above-mentioned structural unit (B-1) and a compound providing the above-mentioned structural unit (B-2). The polyimide resin of the present invention can be obtained as a final product by imidizing (dehydrating ring-closing) the polyamic acid.
As the organic solvent contained in the polyamic acid varnish, the organic solvent contained in the polyimide varnish of the present invention can be used.
In the present invention, the polyamic acid varnish may be a polyamic acid solution obtained by polyaddition reaction of a tetracarboxylic acid component and a diamine component in a reaction solvent, or may be a solution obtained by adding a diluting solvent to the polyamic acid solution.
The method for producing a polyimide film using the polyamic acid varnish is not particularly limited, and a known method can be used. For example, a polyamic acid varnish may be coated on a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, and an organic solvent such as a reaction solvent or a dilution solvent contained in the varnish is removed by heating to obtain a polyamic acid film, and the polyamic acid in the polyamic acid film is imidized by heating to produce a polyimide film.
The heating temperature for drying the polyamic acid varnish to obtain a polyamic acid film is preferably 50 to 120 ℃. The heating temperature at the time of imidizing the polyamic acid by heating is preferably 200 to 400 ℃.
The imidization method is not limited to thermal imidization, and chemical imidization may be applied.
The thickness of the polyimide film of the present invention may be appropriately selected depending on the application, etc., and is preferably in the range of 1 to 250. Mu.m, more preferably 5 to 100. Mu.m, and still more preferably 10 to 80. Mu.m. The thickness of 1 to 250 μm can be practically used as a self-supporting film.
The thickness of the polyimide film can be easily controlled by adjusting the solid concentration and viscosity of the polyimide varnish.
The polyimide film of the present invention can be suitably used as a film for various members such as color filters, flexible displays, semiconductor components, and optical members. The polyimide film of the present invention can be used particularly suitably as a substrate for an image display device such as a liquid crystal display or an OLED display.
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these examples.
In examples and comparative examples, the physical properties were measured by the methods shown below.
(1) Film thickness
Film thickness was measured using a micrometer manufactured by Sanfeng, inc.
(2) Tensile strength (tensile strength), tensile elastic modulus, and tensile elongation (tensile failure strain)
Tensile strength (tensile strength), tensile elastic modulus and tensile elongation (tensile failure strain) according to JIS K7161:2014 and JIS K7127:1999, using the tensile tester "StrongGraph VG-1E" manufactured by Toyo Seisakusho Co. The distance between chucks was 50mm, the test piece size was 10mm×70mm, and the test speed was 20 mm/min.
(3) Glass transition temperature (Tg)
The sample was heated to a temperature sufficient to remove residual stress under conditions of a sample size of 2mm×20mm, a load of 0.1N, and a heating rate of 10 ℃/min in a stretching mode using a thermo-mechanical analysis apparatus "TMA/SS6100" manufactured by Hitachi High-Tech Science Corporation, and then cooled to room temperature. Thereafter, the elongation of the test piece was measured under the same conditions as in the treatment for removing the residual stress, and the glass transition temperature was obtained at the inflection point where the elongation was observed.
(4) Total light transmittance, yellow Index (YI), b *
According to JIS K7105:1981, measurement of total transmittance, YI and b using a color/turbidity simultaneous measuring instrument "COH400" manufactured by Nippon Denshoku industries Co., ltd * 。
(5) Thickness retardation (Rth)
The thickness retardation (Rth) was measured by using ellipsometer "M-220" manufactured by Nippon spectroscopic Co. The value of the thickness phase difference at a wavelength of 590nm was measured. Note that Rth is represented by the following formula, where nx is the maximum value, ny is the minimum value, nz is the refractive index in the thickness direction, and d is the thickness of the film in the in-plane refractive index of the polyimide film.
Rth＝[{(nx+ny)/2}-nz]×d
(6) Polymerization time
The polymerization time required for the viscosity to be 12pa·s or more when the solid content concentration is set to 20 mass% is the polymerization time. Wherein, the polymerization time refers to the time that the temperature in the reaction system is maintained at 190 ℃ after reaching 190 ℃.
(7) Acid resistance (Mixed acid ΔYI and mixed acid Δb) * )
A polyimide film formed on a glass plate was immersed in a mixed acid (HNO) heated to 40 ℃ 3 (10 mass%) +H 3 PO 4 (70 mass%) +CH 3 COOH (5 mass%) +H 2 O (15 mass%) for 4 minutes, and then washed with water. After washing with water, the water was removed, heated with a hot plate at 240℃for 50 minutes, and dried. YI and b measurement before and after the test * The changes (ΔYI and Δb) were obtained * ). Here, YI measurement and b * The measurement was performed in a state where a polyimide film was formed on a glass plate (glass plate+polyimide film state).
(8) Alkali resistance
The polyimide film formed on the glass plate was immersed in a 3 mass% aqueous potassium hydroxide solution at room temperature for 5 minutes, and then washed with water. After washing with water, the presence or absence of change in the surface of the film was confirmed.
The alkali resistance was evaluated as follows.
A: the film surface is unchanged.
B: the film had slight cracks on its surface.
C: the film surface has cracks or the film surface dissolves.
The tetracarboxylic acid component, the diamine component, the other components, and their abbreviations used in the examples and comparative examples are as follows.
< tetracarboxylic acid component >
HPMDA:1,2,4, 5-cyclohexane tetracarboxylic dianhydride (Mitsubishi gas chemical Co., ltd.; compound represented by formula (a-1))
< diamine component >
3,3' -DDS:3,3' -diaminodiphenyl sulfone (Seika Co., ltd.; compound represented by formula (b-1))
BAPS: bis [4- (4-aminophenoxy) phenyl ] sulfone (Seika Co., ltd.; compound represented by formula (b-2))
< others >
GBL: gamma-butyrolactone (Mitsubishi chemical Co., ltd.)
TEA: triethylamine (manufactured by Kanto chemical Co., ltd.)
Example 1 ]
A300 mL five-necked round-bottomed flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3,3' -DDS 14.135g (0.057 mol), BAPS 24.527g (0.057 mol), and GBL 41.945g, and the mixture was stirred at 200rpm under a nitrogen atmosphere at 70℃in the system to obtain a solution.
To this solution were added together 25.421g (0.113 mol) of HPDA and 10.486g of GBL, and then 0.573g of TEA as an imidization catalyst was added thereto, and the mixture was heated by a covered heater to raise the temperature in the reaction system to 190℃over about 20 minutes. The distilled components were collected, the rotation speed was adjusted according to the viscosity increase, and the temperature in the reaction system was kept at 190℃for reflux for 5 hours.
Thereafter, 187.569g of GBL was added so that the solid content became 20% by mass, the temperature in the reaction system was cooled to 100℃and then stirred for about 1 hour to homogenize the mixture, thereby obtaining a polyimide varnish. The viscosity of the varnish solution was 12 Pa.s at 25 ℃.
Then, the obtained polyimide varnish was applied to a glass plate by spin coating, kept at 80℃for 20 minutes with a heating plate, and then heated at 260℃for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
Example 2 ]
A300 mL five-necked round-bottomed flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3,3' -DDS 17.571g (0.071 mol), BAPS 20.326g (0.047 mol), and GBL 42.041g, and the mixture was stirred at 200rpm under a nitrogen atmosphere at 70℃in the system to obtain a solution.
To this solution were added together 26.333g (0.117 mol) of HPDA and 10.510g of GBL, and then 0.594g of TEA as an imidization catalyst was charged, and the mixture was heated by a covered heater to raise the temperature in the reaction system to 190℃over about 20 minutes. The distilled components were collected, the rotation speed was adjusted according to the viscosity increase, and the temperature in the reaction system was kept at 190℃for 4.7 hours under reflux.
Thereafter, 187.449g of GBL was added so that the solid content became 20% by mass, the temperature in the reaction system was cooled to 100℃and then stirred for about 1 hour to homogenize the mixture, thereby obtaining a polyimide varnish. The viscosity of the varnish solution was 12 Pa.s at 25 ℃.
Then, the obtained polyimide varnish was applied to a glass plate by spin coating, kept at 80℃for 20 minutes with a heating plate, and then heated at 260℃for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
Comparative example 1 ]
A300 mL five-necked round-bottomed flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3,3' -DDS 5.122g (0.021 mol), BAPS 35.549g (0.082 mol), and GBL 41.694g, and the mixture was stirred at 200rpm under a nitrogen atmosphere at 70℃in the system to obtain a solution.
To this solution, 23.028g (0.103 mol) of HPDA and 10.388g of GBL were added together, and then 0.519g of TEA as an imidization catalyst was charged, and the mixture was heated by a covered heater, and the temperature in the reaction system was kept at 190℃for about 20 minutes, followed by refluxing for about 7 hours. The viscosity of the varnish solution was 12 Pa.s at 25 ℃.
Thereafter, 187.883g of GBL was added so that the solid content became 20% by mass, the temperature in the reaction system was cooled to 100℃and then stirred for about 1 hour to homogenize the mixture, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied to a glass plate by spin coating, kept at 80℃for 20 minutes with a heating plate, and then heated at 260℃for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
Comparative example 2 ]
A300 mL five-necked round-bottomed flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet tube, a condenser tube, a thermometer, and a glass end cap was charged with 3,3' -DDS 25.239g (0.101 mol), BAPS 10.949g (0.025 mol), and GBL 42.255g, and the mixture was stirred at 200rpm under a nitrogen atmosphere at 70℃in the system to obtain a solution.
To this solution were added together 28.369g (0.126 mol) of HPDA and 10.564g of GBL, and then 0.640g of TEA as an imidization catalyst was charged, and the mixture was heated by a covered heater to raise the temperature in the reaction system to 190℃over about 20 minutes. The distilled off components were collected, the rotation speed was adjusted according to the viscosity increase, and the temperature in the reaction system was kept at 190℃for about 7.5 hours for reflux.
Thereafter, 187.181g of GBL was added so that the solid content became 20% by mass, the temperature in the reaction system was cooled to 100℃and then stirred for about 1 hour to homogenize the mixture, thereby obtaining a polyimide varnish. The viscosity of the varnish solution was 12 Pa.s at 25 ℃.
Then, the obtained polyimide varnish was applied to a glass plate by spin coating, kept at 80℃for 20 minutes with a heating plate, and then heated at 260℃for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
TABLE 1
TABLE 1
As shown in Table 1, the polyimide films of examples 1 to 2 were produced by using HPMDA as the tetracarboxylic acid component and 50 to 60 mol% of 3,3' -DDS and 50 to 40 mol% of BAPS as the diamine component in combination. As a result, the composition exhibits colorless transparency, optical isotropy, acid resistance, alkali resistance, and excellent toughness. Furthermore, the polymerization time was also shorter than that of the comparative example.
On the other hand, the polyimide film of comparative example 1 was produced using HPMDA as the tetracarboxylic acid component and 20 mol% of 3,3' -DDS and 80 mol% of BAPS as the diamine component in combination. As a result, the thickness retardation (retardation, rth) is high, and the optical isotropy is poor. In addition, the polymerization time is long.
The polyimide film of comparative example 2 was produced by using HPMDA as the tetracarboxylic acid component and using 80 mol% of 3,3' -DDS and 20 mol% of BAPS as the diamine component in combination. As a result, the thickness retardation (retardation, rth) is low, and the optical properties are excellent, but the tensile elongation and tensile strength are low, and thus poor. In addition, the polymerization time is long.
Therefore, a polyimide film produced by using HPMDA as the tetracarboxylic acid component and using 3,3' -DDS and BAPS in combination at a specific ratio as the diamine component can be suitably used as a film excellent in colorless transparency, optical isotropy, chemical resistance (for example, acid resistance and alkali resistance) and toughness, and can be suitably used as a plastic substrate for liquid crystal displays, touch panels, and the like. Further, the polymerization time is also short, and the energy at the time of production can be reduced, and the production cost is excellent.
Claims (3)
1. A polyimide resin, comprising: structural units A derived from tetracarboxylic dianhydrides and structural units B derived from diamines,
the structural unit A contains a structural unit (A-1) derived from a compound represented by the following formula (a-1) and does not contain a structural unit (A-2) derived from a compound represented by the following formula (a-2),
the structural unit B comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1) and a structural unit (B-2) derived from a compound represented by the following formula (B-2),
the ratio of the structural unit (B-1) in the structural unit B is 50 to 70 mol%, the ratio of the structural unit (B-2) in the structural unit B is 50 to 30 mol%,
2. a polyimide varnish prepared by dissolving the polyimide resin according to claim 1 in an organic solvent.
3. A polyimide film comprising the polyimide resin of claim 1.
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| TWI609897B (en) * | 2017-02-15 | 2018-01-01 | 律勝科技股份有限公司 | Polyimide resin, thin film and method for manufacturing thereof |
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