CN114729122A - Polyimide resin, polyimide varnish, and polyimide film - Google Patents
Polyimide resin, polyimide varnish, and polyimide film Download PDFInfo
- Publication number
- CN114729122A CN114729122A CN202080078721.8A CN202080078721A CN114729122A CN 114729122 A CN114729122 A CN 114729122A CN 202080078721 A CN202080078721 A CN 202080078721A CN 114729122 A CN114729122 A CN 114729122A
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- mol
- polyimide
- film
- compound
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 177
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 60
- 239000002966 varnish Substances 0.000 title claims description 82
- 239000004642 Polyimide Substances 0.000 title claims description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 144
- 150000004985 diamines Chemical class 0.000 claims abstract description 45
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 125000001931 aliphatic group Chemical group 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 30
- 239000002904 solvent Substances 0.000 description 27
- 230000003287 optical effect Effects 0.000 description 25
- 239000000126 substance Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 229920005575 poly(amic acid) Polymers 0.000 description 17
- -1 3 ' Chemical compound 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000011955 best available control technology Methods 0.000 description 11
- 239000007810 chemical reaction solvent Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 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 9
- 125000002723 alicyclic group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 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 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- OVASAEXSPYGGES-UHFFFAOYSA-N C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 Chemical compound C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 OVASAEXSPYGGES-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000005259 measurement Methods 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
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- 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
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 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
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal 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
- 239000002245 particle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 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
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 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
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 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
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-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
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 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
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-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
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-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
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-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
- 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
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- 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 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
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-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
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
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- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000202785 Calyptronoma Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-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
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 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
- 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
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling 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
- 238000006210 cyclodehydration reaction Methods 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
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- ASJCSAKCMTWGAH-UHFFFAOYSA-N cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCC1C(O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 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
- 229910052757 nitrogen 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
- 229920002647 polyamide Polymers 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
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission 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
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
- C08G73/14—Polyamide-imides
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A polyimide resin having: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A comprising: a structural unit (A-1) derived from a compound represented by the following formula (a-1), structural unit B comprising: 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).
Description
Technical Field
The present invention relates to a polyimide resin, a polyimide varnish, and a polyimide film.
Background
Polyimide resins have been studied for various uses in the fields of electric and electronic parts and the like. For example, for the purpose of weight reduction and flexibility of devices, it is desired to replace a glass substrate used in an image display device such as a liquid crystal display and an OLED display with a plastic substrate, and research into a polyimide film suitable for the plastic substrate has been advanced.
In an image display device, when light emitted from a display element passes through a plastic substrate and is emitted, the plastic substrate is required to have colorless transparency, but when light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, a touch panel, or the like), the plastic substrate is required to have high optical isotropy (that is, low Rth) in addition to colorless transparency.
In order to satisfy the above properties, polyimide resins having various compositions have been developed. For example, patent document 1 discloses a polyimide film having a structure formed by combining 3, 3' -diaminodiphenyl sulfone, which is a diamine component, with another specific diamine, for the purpose of obtaining a polyimide film containing a polyamide having good solubility in a solvent and excellent processability, and having colorless transparency and excellent toughness.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2016/158825
Disclosure of Invention
Problems to be solved by the invention
As described above, the polyimide film is required to have good optical properties such as colorless transparency and optical isotropy. In particular, in applications such as liquid crystal displays, optical isotropy is important.
On the other hand, since polyimide has a rigid and strong molecular structure, breakage is a problem when a film is produced or when the polyimide is used for a product having a movable portion. In order to suppress the cleavage, when a component having high flexibility is introduced into a molecule or an additive is added to a resin, the optical properties are generally degraded. Thus, a polyimide film having good optical properties and ductility has been desired.
Further, chemical resistance is also important. For example, when a varnish for forming a resin layer is applied to a polyimide film in order to form another resin layer (for example, a color filter or a protective layer) on the polyimide film, the polyimide film is required to have resistance to a solvent contained in the varnish. If the solvent resistance of the polyimide film is insufficient, the film may be dissolved or swollen, thereby losing its significance as a substrate. However, in order to ensure optical characteristics, it is necessary to form a solution when a polyimide film is formed, and it is difficult to achieve both of these properties.
Thus, it is sought to obtain: a polyimide resin having excellent flexibility and chemical resistance while maintaining the optical properties, particularly optical isotropy, of the polyimide film obtained.
Accordingly, an object of the present invention is to provide: a polyimide resin, a polyimide varnish and a polyimide film which can form a film having excellent optical isotropy and further having excellent flexibility and chemical resistance.
Means for solving the problems
The inventors of the present invention found that: the polyimide resin comprising a combination of a structural unit derived from a specific tetracarboxylic dianhydride and a structural unit derived from a specific 2 kinds of diamines can solve the above problems, and the invention has been completed.
That is, the present invention relates to the following <1> - <8 >.
<1> a polyimide resin having: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises: a structural unit (A-1) derived from a compound represented by the following formula (a-1),
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).
<2> the polyimide resin according to <1>, wherein the ratio of the structural unit (B-1) in the structural unit B is 5 to 80 mol%, and the ratio of the structural unit (B-2) in the structural unit B is 20 to 95 mol%.
<3> the polyimide resin according to <1> or <2> above, wherein 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 5/95 to 80/20.
<4> the polyimide resin according to any one of <1> to <3>, wherein the structural unit A further comprises: at least 1 member selected from the group consisting of a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1) and a structural unit (A-2-2) derived from a compound represented by the following formula (a-2-2).
<5> the polyimide resin according to any one of <1> to <4>, wherein the structural unit B further comprises: at least 1 selected from the group consisting of a structural unit (B-3-1) derived from a compound represented by the following formula (B-3-1) and a structural unit (B-3-2) derived from a compound represented by the following formula (B-3-2).
(in the formula (b-3-1), Z1And Z2Each independently represents a 2-valent aliphatic group optionally containing an oxygen atom, or a 2-valent aromatic group, R1And R2Each independently represents a 1-valent aromatic group or a 1-valent aliphatic groupGroup, R3And R4Each independently represents a 1-valent aliphatic group, R5And R6Each independently represents a 1-valent aliphatic group or a 1-valent aromatic group, m and n each independently represent an integer of 1 or more, and the sum of m and n represents an integer of 2 to 1000. Wherein R is1And R2At least one of them represents a 1-valent aromatic group. )
<6>According to the above<5>The polyimide resin is represented by the formula (b-3-1) wherein R1And R2Is phenyl.
<7> a polyimide varnish obtained by dissolving the polyimide resin according to any one of <1> to <6> in an organic solvent.
<8> a polyimide film comprising the polyimide resin according to any one of <1> to <6 >.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a polyimide resin, a polyimide varnish and a polyimide film which can form a film having excellent optical isotropy and further having excellent flexibility and chemical resistance.
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, the structural unit A comprising: a structural unit (A-1) derived from a compound represented by the following formula (a-1), structural unit B comprising: 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).
And (3) resin.
The reason why the polyimide resin of the present invention maintains optical isotropy and is excellent in flexibility and chemical resistance is not clear, but it is considered that: the polyimide resin of the present invention has an alicyclic structure, an ether skeleton and an aromatic ring at an appropriate ratio, and therefore maintains optical isotropy and is excellent in flexibility and chemical resistance. Among them, it is considered that: since the structure of the polyimide has a structural unit derived from a small diamine having an alicyclic structure, the imide group concentration is high, the optical isotropy is maintained, and the chemical resistance is very excellent.
< structural unit A >)
The structural unit a is a structural unit derived from a tetracarboxylic dianhydride in the polyimide resin.
The structural unit A comprises: a structural unit (A-1) derived from a compound represented by the following formula (a-1).
The compound represented by the formula (a-1) is 4, 4' -oxydiphthalic anhydride.
The structural unit A contains the structural unit (A-1), whereby the chemical resistance and toughness of the film can be improved.
The proportion of the structural unit (a-1) in the structural unit a is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 55 mol% or more, and further preferably 60 mol% or more. From the viewpoint of toughness of the film, more preferably 70 mol% or more. The upper limit of the ratio of the structural unit (A-1) is not particularly limited, i.e., 100 mol%. The structural unit A may be composed of only the structural unit (A-1).
The structural unit A may contain a structural unit other than the structural unit (A-1).
From the viewpoint of heat resistance, the structural unit A preferably further comprises a structural unit (A-2) in addition to the structural unit (A-1), and the structural unit (A-2) is at least 1 selected from the group consisting of a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1) and a structural unit (A-2-2) derived from a compound represented by the following formula (a-2-2). That is, the structural unit (A-2-1) and the structural unit (A-2-2) are collectively referred to as the structural unit (A-2).
The compound represented by the formula (a-2-1) is 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.
The compound shown in the formula (a-2-2) is norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride.
The proportion of the structural unit (a-2) in the structural unit a is preferably 10 to 50 mol%, more preferably 15 to 45 mol%, and still more preferably 20 to 40 mol%, from the viewpoint of improving heat resistance, chemical resistance, and optical isotropy.
When the structural unit A contains the structural unit (A-2), the molar ratio [ (A-1)/(A-2) ] of the structural unit (A-1) to the structural unit (A-2) in the structural unit A is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and further preferably 60/40 to 80/20, from the viewpoint of improving heat resistance, chemical resistance and optical isotropy.
The structural unit A may contain structural units other than the structural unit (A-1) and the structural unit (A-2). The tetracarboxylic dianhydride providing such a structural unit is not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides (including the compound represented by the formula (a-1) and not including the compound represented by the formula (a-1)) such as pyromellitic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 9 '-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (wherein compounds represented by the formulae (a-2-1) and (a-2-2) are not included); and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride.
In the present specification, an aromatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing 1 or more aromatic rings, an alicyclic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing neither aromatic rings nor alicyclic rings.
The number of the structural units optionally contained in the structural unit a may be 1, or 2 or more.
< structural unit B >
The structural unit B is a diamine-derived structural unit that is occupied in the polyimide resin, and 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 compound represented by the formula (b-1) is 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether.
The structural unit B contains the structural unit (B-1), whereby the optical isotropy and the colorless transparency of the film can be improved.
The compound represented by the formula (b-2) is bis (aminomethyl) cyclohexane, and specific examples thereof include 1, 3-bis (aminomethyl) cyclohexane represented by the following formula (b-2a) and 1, 4-bis (aminomethyl) cyclohexane represented by the following formula (b-2 b).
From the viewpoint of organic solvent resistance and heat resistance, the compound represented by the formula (b-2) has a cis form: the trans ratio is preferably 0: 100-80: 20. more preferably 0.1: 99.9-70: 30. further preferably 0.5: 99.5-60: 40. still more preferably 1: 99-20: 80.
the structural unit B contains the structural unit (B-2), whereby the optical isotropy, flexibility and chemical resistance of the film can be improved.
The proportion of the structural unit (B-1) in the structural unit B is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 30 to 60 mol%.
The proportion of the structural unit (B-2) in the structural unit B is preferably 20 to 95 mol%, more preferably 30 to 90 mol%, and still more preferably 40 to 70 mol%.
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, and still more preferably 90 mol% or more. The upper limit of the total ratio of the structural units (B-1) and (B-2) is not particularly limited, i.e., 100 mol%. The structural unit B may be composed of only the structural unit (B-1) and the structural unit (B-2).
From the viewpoint of improving optical isotropy and chemical resistance, 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 5/95 to 80/20, more preferably 10/90 to 70/30, and further preferably 30/70 to 60/40.
The structural unit B may contain structural units other than the structural units (B-1) and (B-2).
The structural unit B preferably further comprises a structural unit (B-3) in addition to the structural units (B-1) and (B-2), and the structural unit (B-3) is at least 1 selected from the group consisting of a structural unit (B-3-1) derived from a compound represented by the following formula (B-3-1) and a structural unit (B-3-2) derived from a compound represented by the following formula (B-3-2). That is, the structural unit (B-3-1) and the structural unit (B-3-2) are collectively referred to as a structural unit (B-3). Among them, the structural unit B preferably further contains a structural unit (B-3-1) derived from a compound represented by the following formula (B-3-1).
In the formula (b-3-1), Z1And Z2Each independently represents a 2-valent aliphatic group optionally containing an oxygen atom, or a 2-valent aromatic group, R1And R2Each independently represents a 1-valent aromatic group or a 1-valent aliphatic group, R3And R4Each independently represents a 1-valent aliphatic group, R5And R6Each independently represents a 1-valent aliphatic group or a 1-valent aromatic group, m and n each independently represent an integer of 1 or more, and the sum of m and n represents an integer of 2 to 1000. Wherein R is1And R2At least one of them represents a 1-valent aromatic group.
In the formula (b-3-1), 2 or more different repeating units described in [ ] may be repeated in random, alternating, or block form, and in any order, regardless of the order of [ ].
In the formula (b-3-1), Z1And Z2The 2-valent aliphatic group or the 2-valent aromatic group in (1) is optionally substituted by a fluorine atom. Examples of the aliphatic group having a valence of 2 include saturated or unsaturated aliphatic groups having a valence of 2 and having 1 to 20 carbon atoms and aliphatic groups containing an oxygen atom. The number of carbon atoms of the 2-valent aliphatic group is preferably 3 to 20.
Examples of the saturated aliphatic group having a valence of 2 include alkylene groups having 1 to 20 carbon atoms, and examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylene.
Examples of the unsaturated aliphatic group having a valence of 2 include an alkenylene group having 2 to 20 carbon atoms, and examples thereof include an ethenylene group, an propenylene group, and an alkenylene group having an unsaturated double bond at a terminal.
Examples of the aliphatic group containing an oxygen atom include an alkyleneoxy group and an aliphatic group having an ether bond.
As the alkyleneoxy group, propyleneoxy group, trimethyleneoxy group and the like can be exemplified.
Examples of the aromatic group having a valence of 2 include an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms. As Z1And Z2Specific examples of the arylene group having 6 to 20 carbon atoms in (A) include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 4, 4' -biphenylene group, and a 2, 6-naphthylene group.
As Z1And Z2Particularly preferred are trimethylene group and p-phenylene group, and more preferred is trimethylene group.
In the formula (b-3-1), as R1～R6Examples of the 1-valent aliphatic group in (1) include 1-valent saturated or unsaturated aliphatic groups. Examples of the saturated aliphatic group having a valence of 1 include alkyl groups having 1 to 22 carbon atoms, and examples thereof include methyl, ethyl, and propyl groups. The 1-valent unsaturated aliphatic group includes alkenyl groups having 2 to 22 carbon atoms, for exampleThere may be exemplified vinyl, propenyl, etc. These groups are optionally substituted with fluorine atoms.
R as formula (b-3-1)1、R2、R5And R6Examples of the aromatic group having a valence of 1 in (1) include aryl groups having 6 to 20 carbon atoms, aryl groups having 7 to 30 carbon atoms and substituted with alkyl groups, and aralkyl groups having 7 to 30 carbon atoms. The aromatic group having a valence of 1 is preferably an aryl group, and more preferably a phenyl group.
For R1And R2At least one of them represents a 1-valent aromatic group, preferably R1And R2All of which are aromatic radicals having a valence of 1, more preferably R1And R2Are all phenyl groups.
As R3And R4The alkyl group having 1 to 6 carbon atoms is preferable, and the methyl group is more preferable.
As R5And R6The aliphatic group having a valence of 1 is preferable, and the methyl group is more preferable.
As described above, among the compounds represented by the formula (b-3-1), the compounds represented by the following formula (b-3-11) are preferred.
(in the formula (b-3-11), m and n have the same meanings as those of m and n in the formula (b-3-1), respectively, and the preferred ranges are the same.)
M in the formula (b-3-1) and the formula (b-3-11) represents the number of repetitions of a siloxane unit to which at least 1 aromatic group having a valence of 1 is bonded, and n in the formula (b-3-1) and the formula (b-3-11) represents the number of repetitions of a siloxane unit to which an aliphatic group having a valence of 1 is bonded.
M and n in the formulas (b-3-1) and (b-3-11) are respectively independent integers more than 1, and the sum of m and n (m + n) is an integer of 2-1000. The sum of m and n is preferably an integer of 3 to 500, more preferably an integer of 3 to 100, and further preferably an integer of 3 to 50.
The ratio of m/n in the formulae (b-3-1) and (b-3-11) is preferably 5/95 to 50/50, more preferably 10/90 to 40/60, and still more preferably 20/80 to 30/70.
The functional group equivalent (amine equivalent) of the compound represented by the formula (b-3-1) is preferably 150 to 5000g/mol, more preferably 400 to 4000g/mol, and further preferably 500 to 3000 g/mol.
The functional group equivalent means the mass of the compound represented by the formula (b-3-1) per 1 mol of the functional group (amino group).
Examples of the compounds represented by the formula (B-3-1) include "X-22-9409", "X-22-1660B", "X-22-161A" and "X-22-161B" manufactured by shin-Etsu chemical Co., Ltd.
The structural unit B contains the structural unit (B-3-1), whereby the colorless transparency, optical isotropy and flexibility of the film can be improved.
The formula (b-3-2) is 4, 4' -diaminodiphenyl sulfone. The structural unit B can improve the colorless transparency, toughness and chemical resistance of the film by including the structural unit (B-3-2).
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) to the structural unit (B-2) in the structural unit B is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, and the ratio of the structural unit (B-3) in the structural unit B is preferably 0.1 to 30 mol%, more preferably 1 to 25 mol%, further preferably 2 to 20 mol%, further preferably 3 to 15 mol%.
The total ratio of the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3) in the structural unit B is preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the total ratio 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 be composed of only the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3).
When the structural unit B includes the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-1), the total ratio of the structural unit (B-1) to the structural unit (B-2) in the structural unit B is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, and the ratio of the structural unit (B-3-1) in the structural unit B is preferably 0.1 to 30 mol%, more preferably 1 to 25 mol%, still more preferably 2 to 20 mol%, still more preferably 3 to 15 mol%, and still more preferably 3 to 10 mol%.
The total ratio of the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-1) in the structural unit B is preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the total ratio of the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-1) is not particularly limited, that is, 100 mol%. The structural unit B may be composed of only the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-1).
When the structural unit B includes the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-2), the total ratio of the structural unit (B-1) and the structural unit (B-2) in the structural unit B is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, and the ratio of the structural unit (B-3-2) in the structural unit B is preferably 2 to 30 mol%, more preferably 3 to 30 mol%, still more preferably 10 to 30 mol%, still more preferably 15 to 30 mol%, and still more preferably 15 to 25 mol%, from the viewpoints of colorless transparency, toughness, and chemical resistance of the film.
The total ratio of the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-2) in the structural unit B is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the total ratio of the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-2) is not particularly limited, that is, 100 mol%. The structural unit B may be composed of only the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3-2).
The structural unit (B-3) may be only the structural unit (B-3-1), only the structural unit (B-3-2) or a combination of the structural unit (B-3-1) and the structural unit (B-3-2).
The structural unit B may contain structural units other than the structural units (B-1), (B-2) and (B-3). The diamine providing such a structural unit is not particularly limited, and examples thereof include 1, 4-phenylenediamine, p-xylylenediamine, 1, 5-diaminonaphthalene, 2 ' -dimethylbiphenyl-4, 4 ' -diamine, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane, 2-bis (4-aminophenyl) hexafluoropropane, 4 ' -diaminobenzanilide, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, α ' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, N ' -bis (4-aminophenyl) terephthalamide, N-bis (4-aminophenyl) terephthalamide, and mixtures thereof, Aromatic diamines such as 4, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane and 9, 9-bis (4-aminophenyl) fluorene (which do not contain the compound represented by the formula (b-1), the compound represented by the formula (b-3-1) and the compound represented by the formula (b-3-2)); an alicyclic diamine (wherein the compound represented by the formula (b-2) is not contained); and aliphatic diamines such as ethylenediamine and hexamethylenediamine.
In the present specification, an aromatic diamine refers to a diamine containing 1 or more aromatic rings, an alicyclic diamine refers to a diamine containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic diamine refers to a diamine containing neither aromatic rings nor alicyclic rings.
The structural unit B may optionally contain 1 or 2 or more structural units other than the structural units (B-1), (B-2) and (B-3).
< Property of polyimide resin >
The number average molecular weight of the polyimide resin is preferably 5000 to 300000 from the viewpoint of mechanical strength of the polyimide film to be obtained. 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 may contain a structure other than a polyimide chain (a structure in which the structural unit a and the structural unit B are bonded via imide). 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 preferably contains a polyimide chain (a structure in which a structural unit a and a structural unit B are bonded via imide) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 99% by mass or more.
The polyimide resin composition of the present invention containing the polyimide resin can form a film having excellent colorless transparency, optical isotropy and chemical resistance, and the film has suitable physical property values as described below.
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 4.5 or less, more preferably 3.0 or less, still more preferably 2.0 or less, and still more preferably 1.5 or less.
When a film having a thickness of 10 μm is formed, the absolute value of the retardation in thickness (Rth) is preferably 70nm or less, more preferably 60nm or less, and still more preferably 50nm or less.
Further, the film formed by using the polyimide resin is also excellent in mechanical properties and heat resistance, and has the following suitable physical property values.
The film formed by using the polyimide resin of the present invention has good mechanical properties and heat resistance, and has the following suitable physical property values.
The tensile strength is preferably 70MPa or more, more preferably 80MPa or more, and still more preferably 90MPa or more.
The tensile modulus is preferably 2.0GPa or more, more preferably 2.5GPa or more, and still more preferably 3.0GPa or more.
The elongation at break is preferably 8% or more, more preferably 10% or more, and further preferably 15% or more.
The glass transition temperature (Tg) is preferably 200 ℃ or higher, more preferably 230 ℃ or higher, and still more preferably 250 ℃ or higher.
The physical property values in the present invention can be measured specifically by the methods described in examples.
< method for producing polyimide resin >
In the present invention, the polyimide resin can be produced by reacting a tetracarboxylic acid component containing a compound that provides the structural unit (A-1) with a diamine component containing a compound that provides the structural unit (B-1) and a compound that provides the structural unit (B-2).
Examples of the compound providing the structural unit (A-1) include compounds represented by the formula (a-1), but the compound is not limited thereto, and derivatives thereof may be included within a range 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., 4, 4' -oxydiphthalic acid) and an alkyl ester of the tetracarboxylic acid. Among them, tetracarboxylic dianhydrides represented by the formula (a-1) are preferable.
The tetracarboxylic acid component contains preferably 40 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% or more of a compound that provides the structural unit (a-1). The upper limit of the content of the compound providing the structural unit (A-1) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may be composed of only 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).
The tetracarboxylic acid component may contain a compound that provides the structural unit (A-2) in addition to the compound that provides the structural unit (A-1).
Examples of the compound that can provide the structural unit (A-2) include a compound represented by the formula (a-2-1) and a compound represented by the formula (a-2-2), but the compound is not limited thereto, and derivatives thereof may be provided as long as the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to the compounds represented by the formulae (a-2-1) and (a-2-2) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A-2), compounds represented by the formulae (a-2-1) and (a-2-2) (i.e., dianhydrides) are preferable.
When the tetracarboxylic acid component contains a compound that provides the structural unit (a-2), the tetracarboxylic acid component preferably contains 10 to 50 mol%, more preferably 15 to 45 mol%, and still more preferably 20 to 40 mol% of the compound that provides the structural unit (a-2).
The compound other than the compound which provides the structural unit (A-1) and which is optionally contained in the tetracarboxylic acid component is not limited to the compound which provides the structural unit (A-2). Examples of such optional compounds include the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (e.g., tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.).
The tetracarboxylic acid component may contain 1 or 2 or more compounds other than the compound that provides the structural unit (A-1) and the compound that provides the structural unit (A-2).
Examples of the compound providing the structural unit (B-1) include compounds represented by the formula (B-1), but the compound is not limited thereto, and derivatives thereof may be included within a range providing the same structural unit. Examples of the derivative include diisocyanates corresponding to the compound (diamine) represented by the formula (b-1). Among them, the compound represented by the formula (b-1) (i.e., diamine) is preferable.
Similarly, examples of the compound that can provide the structural unit (B-2) include, but are not limited to, compounds represented by the formula (B-2), and derivatives thereof may be included within the range that provides the same structural unit. Examples of the derivative include diisocyanates corresponding to the compound (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 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 30 to 60 mol% of a compound that provides the structural unit (B-1).
The diamine component preferably contains 20 to 95 mol%, more preferably 30 to 90 mol%, and still more preferably 40 to 70 mol% of a compound that provides the structural unit (B-2).
The diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more of the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2) in total. The upper limit of the total content of the compound which provides the structural unit (B-1) and the compound which provides the structural unit (B-2) is not particularly limited, that is, 100 mol%. The diamine component may be composed of only the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2).
The diamine component may contain compounds other than the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2).
The diamine component may contain a compound that can provide the structural unit (B-3) in addition to the compound that can provide the structural unit (B-1) and the compound that can provide the structural unit (B-2).
Examples of the compound that can provide the structural unit (B-3) include a compound represented by the formula (B-3-1) and a compound represented by the formula (B-3-2), but the compound is not limited thereto, and derivatives thereof may be provided as long as the same structural unit is provided. Examples of the derivative include diisocyanates corresponding to diamines represented by the formula (b-3-1) and diisocyanates corresponding to diamines represented by the formula (b-3-2). As the compound providing the structural unit (B-3), a compound represented by the formula (B-3-1) and a compound represented by the formula (B-3-2) (i.e., a diamine) are preferable.
The compound that provides the structural unit (B-3) may be only the compound represented by the formula (B-3-1), only the compound represented by the formula (B-3-2), or a combination of the compound represented by the formula (B-3-1) and the compound represented by the formula (B-3-2).
When the diamine component contains a compound that provides the structural unit (B-3), the diamine component preferably contains 0.1 to 30 mol%, more preferably 1 to 25 mol%, and still more preferably 5 to 25 mol% of the compound that provides the structural unit (B-3).
When the diamine component contains the compound that can provide the structural unit (B-3), the diamine component preferably contains 80 mol% or more, more preferably 90 mol% or more, and still more preferably 99 mol% or more of the compound that can provide the structural unit (B-1), the compound that can provide the structural unit (B-2), and the compound that can provide the structural unit (B-3) in total. The upper limit of the total content of the compound which provides the structural unit (B-1), the compound which provides the structural unit (B-2) and the compound which provides the structural unit (B-3) is not particularly limited, that is, 100 mol%. The diamine component may be composed of only the compound that provides the structural unit (B-1), the compound that provides the structural unit (B-2), and the compound that provides the structural unit (B-3).
The compound other than the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2) optionally contained in the diamine component is not limited to the compound providing the structural unit (B-3). Examples of such optional compounds include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and derivatives thereof (e.g., diisocyanate).
The diamine component may contain 1 or 2 or more compounds other than the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2).
In the present invention, the charging amount ratio of the tetracarboxylic acid component and the diamine component used for producing the polyimide resin is preferably: the diamine component is 0.9 to 1.1 mol relative to 1 mol of the tetracarboxylic acid component.
In the present invention, in the production of the polyimide resin, an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. As the blocking agent, monoamines or dicarboxylic acids are preferred. The amount of the end-capping agent to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. Examples of the blocking agent of the monoamine type include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline and 4-methylaniline, with benzylamine and aniline being preferred. As the dicarboxylic acid-based end capping agent, dicarboxylic acids are preferred, and a part thereof may be ring-closed. Examples thereof include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2, 3-benzophenonedicarboxylic acid, 3, 4-benzophenonedicarboxylic acid, cyclohexane-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, and 4-cyclohexene-1, 2-dicarboxylic acid, and phthalic acid and phthalic anhydride are preferable.
The method for reacting the tetracarboxylic acid component with the diamine component is not particularly limited, and a known method can be used.
Specific reaction methods include: a method (1) in which a tetracarboxylic acid component, a diamine component and a reaction solvent are charged into a reactor, stirred at 0 to 80 ℃ for 0.5 to 30 hours, and then heated to effect imidization; a method (2) in which a diamine component and a reaction solvent are charged into a reactor to dissolve them, a tetracarboxylic acid component is charged, and the mixture is stirred at room temperature of 0 to 80 ℃ for 0.5 to 30 hours, if necessary, and then heated to carry out an imidization reaction; (3) a method comprising charging a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor, immediately heating the reactor to effect imidization; and the like.
The reaction solvent used in the production of the polyimide resin may be any solvent which can dissolve the polyimide produced without inhibiting the imidization reaction. Examples thereof include aprotic solvents, phenol solvents, ether solvents, carbonate solvents, and the like.
Specific examples of the aprotic solvent include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1, 3-dimethylimidazolidinone, and tetramethylurea, lactone solvents such as γ -butyrolactone (GBL) and γ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoramide and hexamethylphosphinotriamide, 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 2-methoxy-1-methylethyl) acetate.
Specific examples of the phenol solvent include phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, 5-xylenol, and the like.
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, and propylene carbonate.
Among the above reaction solvents, aprotic solvents are preferable, and amide solvents and lactone solvents are more preferable. The reaction solvent may be used alone or in combination of 2 or more.
In the imidization reaction, it is preferable to carry out the reaction while removing water produced during the production, using a dean-Stark trap apparatus or the like. By performing such an operation, the degree of polymerization and the imidization ratio 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 (TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N-dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
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 can be used alone or in combination of 2 or more.
Among the above, from the viewpoint of handling properties, a base catalyst is preferably used, an organic base catalyst is more preferably used, and triethylamine is further preferably used.
The temperature of the imidization reaction is preferably 120 to 250 ℃ and more preferably 160 to 200 ℃ from the viewpoints of the reaction rate, the suppression of gelation, and the like. The reaction time is preferably 0.5 to 10 hours after the start of distilling off the product water.
[ 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 comprises 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 it is preferable to use the above-mentioned compound alone or in a mixture of 2 or more as a reaction solvent used for producing the polyimide resin.
The polyimide varnish of the present invention may be a polyimide solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or may be a polyimide solution diluted by adding a solvent thereto.
The polyimide resin of the present invention has solvent solubility, and therefore, can form a varnish having a high concentration which is stable at room temperature. The polyimide varnish of the present invention preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass of the polyimide resin of the present invention. The viscosity of the polyimide varnish is preferably 1 to 200 pas, more preferably 1 to 100 pas. The viscosity of the polyimide varnish was measured at 25 ℃ with an E-type viscometer.
The polyimide varnish of the present invention may contain various additives such as inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, antifoaming agents, fluorescent brighteners, crosslinking agents, polymerization initiators, and photosensitizers, as long 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 comprises the polyimide resin of the present invention. Therefore, the polyimide film of the present invention is excellent in optical isotropy, flexibility and chemical resistance. The polyimide film of the present invention has suitable physical property values 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 thereof include the following: the polyimide varnish of the present invention is applied to a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, and then heated to remove an organic solvent such as a reaction solvent or a diluting solvent contained in the varnish.
Examples of the coating method include known coating methods such as spin coating, slit coating, and blade coating. Among them, slit coating is preferable from the viewpoint of controlling intermolecular orientation, improving chemical resistance, and workability.
The organic solvent contained in the varnish is preferably removed by heating, and after evaporating the organic solvent at a temperature of 150 ℃ or lower to form tack-free particles, the particles are dried at a temperature of 200 to 500 ℃ or higher (not particularly limited) than the boiling point of the organic solvent used. Further, it is preferable to perform drying under an air atmosphere or a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure or increased pressure.
The method for peeling the polyimide film formed on the support from the support is not particularly limited, and examples thereof include a laser peeling method, a method using a sacrificial layer for peeling (a method in which a release agent is applied in advance to the surface of the support), and a method in which a peeling agent is added.
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 addition polymerization of a tetracarboxylic acid component containing a compound that provides the structural unit (A-1) and a diamine component containing a compound that provides the structural unit (B-1) and a compound that provides the structural unit (B-2). The polyimide resin of the present invention can be obtained as a final product by imidizing (cyclodehydration) 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 itself obtained by addition polymerization of a tetracarboxylic acid component and a diamine component in a reaction solvent, or may be a polyamic acid solution diluted by adding a solvent thereto.
The method for producing the polyimide film using the polyamic acid varnish is not particularly limited, and a known method can be used. For example, a polyamic acid varnish is applied to a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, an organic solvent such as a reaction solvent or a diluting 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 for imidizing the polyamic acid by heating is preferably 200 to 400 ℃.
The method of imidization is not limited to thermal imidization, and chemical imidization may be applied.
The thickness of the polyimide film of the present invention can be suitably selected depending on the application, and is preferably in the range of 1 to 250. mu.m, more preferably 5 to 100. mu.m, further preferably 8 to 80 μm, and further preferably 10 to 80 μm. The thickness is 1 to 250 μm, and thus the film can be practically used as a self-supporting film.
The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide varnish.
The polyimide film of the present invention is 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 is particularly suitable for use as a substrate for an image display device such as a liquid crystal display or an OLED display.
Examples
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
< film Property and evaluation >
The physical properties of the films obtained in examples and comparative examples were measured by the methods shown below.
(1) Thickness of film
The film thickness was measured using a micrometer manufactured by Mitutoyo co.
(2) Tensile strength, tensile modulus and tensile elongation at break (tensile elongation at break is an evaluation of flexibility)
Tensile strength, tensile modulus and tensile elongation at break in accordance with JIS K7127: 1999. the measurement was carried out using a tensile tester "Strograp VG-1E" manufactured by Toyo Seiki Seisaku-Sho Ltd. The chuck pitch was set to 50mm, the test piece size was set to 10mm × 70mm, and the test speed was set to 20 mm/min.
(3) Glass transition temperature (Tg)
Using a thermomechanical analyzer "TMA/SS 6100" manufactured by Hitachi High-Tech Science Corporation, temperature was raised to a temperature sufficient to remove residual stress under conditions of a specimen size of 2mm × 20mm, a load of 0.1N, and a temperature raising rate of 10 ℃/min in a tensile mode, residual stress was removed, and then cooling was performed to room temperature. Thereafter, the elongation of the test piece was measured under the same conditions as the treatment for removing the residual stress, and the inflection point where the elongation was observed was determined as the glass transition temperature.
(4) Total light transmittance and Yellow Index (YI)
The total light transmittance and YI were measured in accordance with JIS K7136 using a color/turbidity simultaneous measuring instrument "COH 7700" manufactured by Nippon Denshoku industries Co., Ltd.
(5) Haze degree
The measurement was carried out in accordance with JIS K7361-1 using a color/turbidity simultaneous measuring instrument "COH 7700" manufactured by Nippon Denshoku industries Co., Ltd.
(6) Thickness retardation (Rth) (evaluation of optical isotropy)
The thickness retardation (Rth) was measured by an ellipsometer "M-220" manufactured by Nippon spectral Co., Ltd. The value of thickness retardation at a measurement wavelength of 590nm was measured. When nx is the maximum in-plane refractive index of the polyimide film, ny is the minimum in-plane refractive index of the polyimide film, nz is the refractive index in the thickness direction, and d is the thickness of the film, Rth is expressed by the following formula. Rth was also calculated by converting the thickness of the film to 10 μm.
Rth＝[{(nx+ny)/2}-nz]×d
(7) Solvent resistance (evaluation of chemical resistance)
The polyimide film formed on a glass plate was immersed in a solvent at room temperature, and it was confirmed whether or not there was a change in the film surface. Propylene Glycol Monomethyl Ether Acetate (PGMEA) was used as the solvent.
The evaluation criteria for solvent resistance are as follows.
Good component: no change on the surface of the film.
And (delta): slight cracks appeared on the surface of the film.
X: cracks appear on the surface of the film or the film surface is dissolved.
< abbreviations of Components etc. >
The tetracarboxylic acid component and the diamine component used in examples and comparative examples, and abbreviations thereof are as follows.
(tetracarboxylic acid component)
ODPA: 4, 4' -oxydiphthalic anhydride (manufactured by Manac Inc.; Compound represented by formula (a-1))
HPMDA: 1,2,4, 5-Cyclohexanetetracarboxylic dianhydride (Mitsubishi gas chemical Co., Ltd.; Compound represented by formula (a-2-1))
CpODA: norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (JXTG Nippon Oil & Energy Corp., manufactured by Ltd.; Compound represented by formula (a-2-2))
6 FDA: 4, 4' - (Hexafluoroisopropylidene) diphthalic anhydrides
(diamine component)
6 FODA: 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether (ChinaTech Chemical (Tianjin) Co., Ltd.; Compound represented by the formula (b-1))
1, 3-BAC: 1, 3-bis (aminomethyl) cyclohexane (manufactured by Mitsubishi gas chemical Co., Ltd.; Compound represented by formula (b-2 a))
1, 4-BAC: 1, 4-bis (aminomethyl) cyclohexane (compound represented by the formula (b-2 b); trans ratio: 40%)
1, 4-BACT: 1, 4-bis (aminomethyl) cyclohexane (product of Mitsubishi gas chemical Co., Ltd.; Compound represented by formula (b-2 b); Trans ratio: 85%)
X-22-9409: (Compound represented by the formula (b-3-1), manufactured by shin-Etsu chemical Co., Ltd.)
4, 4' -DDS: 4, 4' -diaminodiphenyl sulfone (Seika Co., Ltd.; product of Ltd.; Compound represented by the formula (b-3-2))
3, 3' -DDS: 3, 3' -diaminodiphenyl sulfone (Seika Co., Ltd.)
TFMB: 2, 2' -bis (trifluoromethyl) benzidine (Seika Co., Ltd.)
< production of polyimide resin, varnish and polyimide film >
Example 1
A300 mL five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap was charged with 6FODA 16.812g (0.0500 mol), 1,4-BACT 7.113g (0.0500 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 65.935g, and stirred at an internal system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added ODPA 31.021g (0.100 mol) and gamma-butyrolactone 16.484g (Mitsubishi chemical corporation) at the same time, and then 0.506g of triethylamine (Kanto chemical corporation) as an imidization catalyst was charged and heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, while the temperature in the reaction system was kept at 190 ℃ and the reflux was carried out for about 5 hours.
Thereafter, 208.517g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added so that the solid content concentration became 15 mass%, the temperature in the reaction system was cooled to 100 ℃, and then the mixture was stirred for about 1 hour to be homogenized, thereby obtaining a polyimide varnish.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 300 ℃ for 30 minutes (temperature increase rate 5 ℃/minute) in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film.
Example 2
A polyimide varnish was prepared in the same manner as in example 1 except that the amount of ODPA was changed from 31.021g (0.100 mol) to 24.817g (0.080 mol), and CpODA 7.688g (0.020 mol) was added to obtain a polyimide varnish having a solid content of 15 mass%.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Example 3
A polyimide varnish was prepared in the same manner as in example 2 except that the amount of 6FODA was changed from 16.812g (0.0500 mol) to 16.429g (0.04886 mol), the amount of 1,4-BACT was changed from 7.113g (0.0500 mol) to 6.950g (0.04886 mol), and X-22-94092.941 g (0.00228 mol) was added, thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Example 4
A polyimide varnish having a solid content of 15 mass% was prepared in the same manner as in example 2 except that the amount of 6FODA was changed from 16.812g (0.0500 mol) to 16.012g (0.04762 mol), the amount of 1,4-BACT was changed from 7.113g (0.0500 mol) to 6.774g (0.04762 mol), and X-22-94096.140 g (0.00476 mol) was added.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Example 5
A polyimide varnish was prepared in the same manner as in example 1 except that the amount of ODPA was changed from 31.021g (0.100 mol) to 15.511g (0.050 mol), CpODA 19.219g (0.050 mol) was added, the amount of 6FODA was changed from 16.812g (0.0500 mol) to 15.980g (0.04753 mol), the amount of 1,4-BACT was changed from 7.113g (0.0500 mol) to 6.760g (0.04753 mol), and X-22-94096.386 g (0.00495 mol), thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Example 6
A polyimide varnish was prepared in the same manner as in example 1 except that the amount of ODPA was changed from 31.021g (0.100 mol) to 15.511g (0.050 mol), and HPMDA 11.209g (0.050 mol) was added, thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Example 7
A polyimide varnish was produced in the same manner as in example 2 except that CpODA 7.688g (0.020 mol) was changed to HPMDA 4.483(0.020 mol), and a polyimide varnish having a solid content of 15 mass% was obtained.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Example 8
A polyimide varnish was prepared in the same manner as in example 6 except that the amount of 6FODA was changed from 16.812g (0.0500 mol) to 6.725g (0.020 mol) and the amount of 1,4-BACT was changed from 7.113g (0.0500 mol) to 11.380g (0.080 mol), thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 240 ℃ for 60 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film.
Example 9
1,4-BACT 7.113g (0.0500 mol) was changed to 1,3-BAC 7.113g (0.0500 mol),
in addition, a polyimide varnish was produced in the same manner as in example 1, and a polyimide varnish having a solid content of 15 mass% was obtained.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Example 10
A polyimide varnish was prepared in the same manner as in example 6 except that the amount of 6FODA was changed from 16.812g (0.0500 mol) to 13.450g (0.0400 mol) and the amount of 1,4-BACT was changed from 7.113g (0.0500 mol) to 8.535g (0.0600 mol), thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot 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.
Example 11
A polyimide varnish was prepared in the same manner as in example 6 except that 1,4-BACT 7.113g (0.0500 mol) was changed to 1,4-BAC 7.113g (0.0500 mol), and a polyimide varnish having a solid content of 15 mass% was obtained.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 10.
Example 12
A polyimide varnish was prepared in the same manner as in example 6 except that the amount of 6FODA was changed from 16.812g (0.0500 mol) to 10.087g (0.0300 mol), and 4, 4' -DDS 4.966g (0.0200 mol) was added, thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 10.
Comparative example 1
A polyimide varnish was prepared in the same manner as in example 1 except that 6FODA 16.812g (0.0500 mol) was changed to TFMB 16.012g (0.0500 mol), and a polyimide varnish having a solid content of 15 mass% was obtained.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Comparative example 2
A polyimide varnish was prepared in the same manner as in example 1 except that the amount of 6FODA was changed from 16.812g (0.0500 mol) to 33.624g (0.100 mol) and the amount of 1,4-BACT was changed from 7.113g (0.0500 mol) to 0g (0 mol), thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Comparative example 3
A polyimide varnish was prepared in the same manner as in example 9 except that 16.812g (0.0500 mol) of 6FODA was changed to 12.415g (0.0500 mol) of 3, 3' -DDS, and a polyimide varnish having a solid content of 15 mass% was obtained.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Comparative example 4
A polyimide varnish was prepared in the same manner as in example 1 except that ODPA 31.021g (0.100 mol) was changed to 6FDA 44.424g (0.100 mol), and a polyimide varnish having a solid content of 15 mass% was obtained.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 1.
Comparative example 5
A polyimide varnish was prepared in the same manner as in example 1 except that ODPA 31.021g (0.100 mol) was changed to HPMDA 22.417g (0.100 mol), the amount of 6FODA was changed from 16.812g (0.0500 mol) to 33.624g (0.100 mol), and the amount of 1,4-BACT was changed from 7.113g (0.0500 mol) to 0g (0 mol), thereby obtaining a polyimide varnish having a solid content of 15 mass%.
Using the obtained polyimide varnish, a film was obtained in the same manner as in example 10.
The polyimide films obtained in examples and comparative examples were subjected to the above-described measurement and evaluation of physical properties. The results are shown in Table 1.
[ Table 1]
As shown in table 1, it can be seen that: the polyimide films of the examples have good optical isotropy, and are excellent in flexibility and chemical resistance.
Claims (8)
1. A polyimide resin having: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises: a structural unit (A-1) derived from a compound represented by the following formula (a-1),
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),
2. the polyimide resin according to claim 1, wherein the proportion of the structural unit (B-1) in the structural unit B is 5 to 80 mol%, and the proportion of the structural unit (B-2) in the structural unit B is 20 to 95 mol%.
3. The polyimide resin according to claim 1 or 2, wherein 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 5/95 to 80/20.
4. The polyimide resin according to any one of claims 1 to 3, wherein the structural unit A further comprises: at least 1 selected from the group consisting of a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1) and a structural unit (A-2-2) derived from a compound represented by the following formula (a-2-2),
5. the polyimide resin according to any one of claims 1 to 4, wherein the structural unit B further comprises: at least 1 selected from the group consisting of a structural unit (B-3-1) derived from a compound represented by the following formula (B-3-1) and a structural unit (B-3-2) derived from a compound represented by the following formula (B-3-2),
in the formula (b-3-1), Z1And Z2Each independently represents a 2-valent aliphatic group optionally containing an oxygen atom, or a 2-valent aromatic group, R1And R2Each independently represents a 1-valent aromatic group or a 1-valent aliphatic group, R3And R4Each independently represents a 1-valent aliphatic group, R5And R6Each independently represents a 1-valent aliphatic group or a 1-valent aromatic group, m and n each independently represents an integer of 1 or more, and the sum of m and n represents an integer of 2 to 1000, wherein R1And R2At least one of them represents a 1-valent aromatic group.
6. The polyimide resin according to claim 5, wherein R in the formula (b-3-1)1And R2Is phenyl.
7. A polyimide varnish obtained by dissolving the polyimide resin according to any one of claims 1 to 6 in an organic solvent.
8. A polyimide film comprising the polyimide resin according to any one of claims 1 to 6.
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| JP2019-239645 | 2019-12-27 | ||
| JP2019239645 | 2019-12-27 | ||
| PCT/JP2020/042883 WO2021100727A1 (en) | 2019-11-18 | 2020-11-18 | Polyimide resin, polyimide varnish, and polyimide film |
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| JP (1) | JPWO2021100727A1 (en) |
| KR (1) | KR20220104696A (en) |
| CN (1) | CN114729122B (en) |
| TW (1) | TW202124531A (en) |
| WO (1) | WO2021100727A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115038737A (en) * | 2020-01-31 | 2022-09-09 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023048148A1 (en) * | 2021-09-22 | 2023-03-30 | デクセリアルズ株式会社 | Manufacturing method for connection structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044916A (en) * | 2012-12-24 | 2013-04-17 | 南京依麦德光电材料科技有限公司 | Flexible transparent polyimide thin film and preparation method thereof |
| JP2018203906A (en) * | 2017-06-06 | 2018-12-27 | 旭化成株式会社 | Polyimide film, product using polyimide film, and laminate |
| CN110330644A (en) * | 2019-06-14 | 2019-10-15 | 广州奥松电子有限公司 | A kind of wet sensory material and the preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102052150B1 (en) | 2015-03-31 | 2019-12-05 | 아사히 가세이 가부시키가이샤 | Polyimide film, polyimide varnish, products and laminates using polyimide film |
| JP7047852B2 (en) * | 2017-12-28 | 2022-04-05 | 宇部興産株式会社 | Polyimide precursors, polyimides, polyimide films, varnishes, and substrates |
-
2020
- 2020-11-18 JP JP2021558404A patent/JPWO2021100727A1/ja active Pending
- 2020-11-18 WO PCT/JP2020/042883 patent/WO2021100727A1/en active Application Filing
- 2020-11-18 TW TW109140355A patent/TW202124531A/en unknown
- 2020-11-18 KR KR1020227016090A patent/KR20220104696A/en active Search and Examination
- 2020-11-18 CN CN202080078721.8A patent/CN114729122B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044916A (en) * | 2012-12-24 | 2013-04-17 | 南京依麦德光电材料科技有限公司 | Flexible transparent polyimide thin film and preparation method thereof |
| JP2018203906A (en) * | 2017-06-06 | 2018-12-27 | 旭化成株式会社 | Polyimide film, product using polyimide film, and laminate |
| CN110330644A (en) * | 2019-06-14 | 2019-10-15 | 广州奥松电子有限公司 | A kind of wet sensory material and the preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115038737A (en) * | 2020-01-31 | 2022-09-09 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
| CN115038737B (en) * | 2020-01-31 | 2024-10-25 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish and polyimide film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220104696A (en) | 2022-07-26 |
| TW202124531A (en) | 2021-07-01 |
| WO2021100727A1 (en) | 2021-05-27 |
| CN114729122B (en) | 2024-06-18 |
| JPWO2021100727A1 (en) | 2021-05-27 |
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