CN114867766A - Polyimide resin, varnish, and polyimide film - Google Patents
Polyimide resin, varnish, and polyimide film Download PDFInfo
- Publication number
- CN114867766A CN114867766A CN202080089527.XA CN202080089527A CN114867766A CN 114867766 A CN114867766 A CN 114867766A CN 202080089527 A CN202080089527 A CN 202080089527A CN 114867766 A CN114867766 A CN 114867766A
- Authority
- CN
- China
- Prior art keywords
- structural unit
- varnish
- mol
- derived
- polyamic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 104
- 239000002966 varnish Substances 0.000 title claims abstract description 70
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 105
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 69
- 150000004985 diamines Chemical class 0.000 claims abstract description 42
- 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 27
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 16
- -1 imidazole compound Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 7
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 description 32
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 26
- 239000010408 film Substances 0.000 description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 239000011521 glass Substances 0.000 description 19
- 239000012299 nitrogen atmosphere Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NKYXYJFTTIPZDE-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F NKYXYJFTTIPZDE-UHFFFAOYSA-N 0.000 description 2
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 238000009835 boiling Methods 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006210 cyclodehydration reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000004090 dissolution Methods 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
- 238000000265 homogenisation Methods 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-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
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-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
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-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
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 description 1
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 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
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 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
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- APZQJHBPRHHRBX-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)NC1=CC=C(N)C=C1 APZQJHBPRHHRBX-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- DLEPYXFUDLQGDW-UHFFFAOYSA-N FC(F)(F)NC1=CC=C(C2=CC=C(NC(F)(F)F)C=C2)C=C1 Chemical compound FC(F)(F)NC1=CC=C(C2=CC=C(NC(F)(F)F)C=C2)C=C1 DLEPYXFUDLQGDW-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
- 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
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BKDVBBSUAGJUBA-UHFFFAOYSA-N bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Chemical compound C1=CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O BKDVBBSUAGJUBA-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000013007 heat curing 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
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 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
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The present invention is 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 B comprising: a structural unit (B1) derived from a compound represented by the following formula (B1) and a structural unit (B2) derived from a compound represented by the following formula (B2). The present invention provides: a polyimide resin which can be molded into a film having low residual stress, excellent heat resistance, and a low linear thermal expansion coefficient; a varnish containing a polyamic acid as a precursor of the polyimide resin; and a polyimide film.
Description
Technical Field
The present invention relates to a polyimide resin, a varnish and a polyimide film.
Background
Polyimide resins have been variously used in the fields of electric/electronic components 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. Polyimide films for such applications are required to have high transparency and a small retardation due to birefringence, that is, a low retardation.
When a varnish applied to a glass support or a silicon wafer is cured by heating to form a polyimide film, residual stress is generated in the polyimide film. If the residual stress of the polyimide film is large, the glass support or the silicon wafer is warped, and therefore, reduction of the residual stress is also required for the polyimide film.
Patent document 1 discloses a polyimide resin synthesized using α, ω -aminopropylpolydimethylsiloxane and 4, 4' -diaminodiphenyl ether as diamine components, as a polyimide resin providing a thin film with low residual stress.
Patent document 2 discloses a polyimide film having a low residual stress, which is obtained by imidizing a polyimide resin precursor synthesized using bis (trifluoromethyl) benzidine and a silicon-containing diamine as a diamine component.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2005-232383
Patent document 2: international publication No. 2014/098235
Disclosure of Invention
Problems to be solved by the invention
As described above, the polyimide film requires various properties, but it is not easy to satisfy these properties at the same time.
In particular, recently, miniaturization and precision of substrates have been advanced, and integration of electronic circuits has been advanced, and therefore, in order to cope with this, not only the above-described low residual stress but also thermal stability has been required. For example, heat resistance and low thermal expansion are required.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide: a polyimide resin which can be formed into a film having a low residual stress, excellent heat resistance and a low linear thermal expansion coefficient, a varnish containing a polyamic acid which is a precursor of the polyimide resin, and a polyimide film.
Means for solving the problems
The inventors of the present invention found that: the polyimide resin containing a combination of specific structural units can solve the above problems, and thus the present invention has been completed.
That is, the present invention relates to the following [1] to [10 ].
[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 B includes: a structural unit (B1) derived from a compound represented by the following formula (B1) and a structural unit (B2) derived from a compound represented by the following formula (B2).
[2]
The polyimide resin according to the above [1], wherein the structural unit A comprises: a structural unit (A1) derived from a compound represented by the following formula (a 1).
[3]
The polyimide resin according to the above [1] or [2], wherein the structural unit B further comprises a structural unit (B3), and the structural unit (B3) is at least one selected from the group consisting of a structural unit (B31) derived from a compound represented by the following formula (B31), a structural unit (B32) derived from a compound represented by the following formula (B32), and a structural unit (B33) derived from a compound represented by the following formula (B33).
[4]
A varnish comprising a polyimide resin precursor of any one of the above-mentioned [1] to [3] and a polyamic acid dissolved in an organic solvent.
[5]
The varnish according to the foregoing [4], further comprising: at least one selected from the group consisting of imidazole compounds and tertiary amines.
[6]
The varnish according to the above [5], wherein the imidazole compound is at least one selected from the group consisting of imidazole, 1, 2-imidazole and 1-benzyl-2-methylimidazole.
[7]
The varnish according to the above [5] or [6], wherein the tertiary amine is triethylenediamine.
[8]
A polyimide film obtained by applying the varnish according to any one of the above [4] to [7] to a support and heating the applied varnish.
[9]
A method for producing a polyimide film, which comprises applying the varnish according to any one of the above [4] to [7] to a support and heating the applied varnish.
[10]
A polyimide film comprising the polyimide resin according to any one of the above [1] to [3 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a polyimide resin which can be formed into a film having a low residual stress, excellent heat resistance and a low coefficient of linear thermal expansion, a varnish containing a polyamic acid which is a precursor of the polyimide resin, and a polyimide film.
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 B includes: a structural unit (B1) derived from a compound represented by the following formula (B1) and a structural unit (B2) derived from a compound represented by the following formula (B2).
< structural unit A >)
The structural unit a is a structural unit derived from tetracarboxylic dianhydride in the polyimide resin.
The structural unit a may react with the structural unit B to form an imide bond, and preferably includes: a structural unit (A1) derived from a compound represented by the following formula (a 1).
The compound represented by the formula (a1) is norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride.
The structural unit a contains a structural unit derived from the compound represented by the formula (a1), whereby the film of the present invention can have a low residual stress and a low linear thermal expansion coefficient, and can also have improved heat resistance and optical isotropy.
From the viewpoint of improving heat resistance and optical isotropy, the ratio of the structural unit (a1) in the structural unit a is preferably 45 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited, i.e., 100 mol%.
The structural unit a may include structural units other than the structural unit (a1) within a range not impairing the effects of the present invention. The tetracarboxylic acid dianhydride which provides such a structural unit is not particularly limited, and examples thereof include aromatic tetracarboxylic acid dianhydrides such as pyromellitic acid dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic acid dianhydride, 9 '-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride, 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid dianhydride, and 2,2 ', 3, 3' -benzophenonetetracarboxylic acid dianhydride; alicyclic tetracarboxylic acid dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, and dicyclohexyltetracarboxylic acid dianhydride; and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride.
Among these, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride are preferable from the viewpoint of improving heat resistance, optical isotropy, and transparency.
The structural unit a may optionally include 1 or 2 or more structural units other than the structural unit (a 1).
The structural unit A preferably does not contain a structural unit other than the aforementioned structural unit (A1).
In the present specification, an aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing 1 or more aromatic rings, an alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing neither aromatic rings nor alicyclic rings.
< structural unit B >
The structural unit B is a structural unit derived from diamine in the polyimide resin, and includes: a structural unit (B1) derived from a compound represented by the following formula (B1) and a structural unit (B2) derived from a compound represented by the following general formula (B2).
It is considered that the structural unit B has low residual stress, excellent heat resistance, low linear thermal expansion coefficient, and excellent thermal properties by including any of the structural unit (B1) and the structural unit (B2).
The compound represented by the formula (b1) is 2,2 '-bis (trifluoromethyl) -4, 4' -diaminodiphenyl ether (6 FODA).
By containing the structural unit (B1) derived from the compound represented by the formula (B1), elongation, strength, and transparency can be imparted in addition to the effects of the present invention.
The compound represented by the formula (b2) is 4, 4' -Diaminobenzanilide (DABA).
By containing the structural unit (B2) derived from the compound represented by the formula (B2), the residual stress can be reduced.
The proportion of the structural unit (B1) in the structural unit B is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and still more preferably 10 to 30 mol%.
The proportion of the structural unit (B2) in the structural unit B is preferably 40 to 95 mol%, more preferably 60 to 90 mol%, and still more preferably 70 to 90 mol%.
The total ratio of the structural units (B1) and (B2) 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 (B1) and (B2) is not particularly limited, i.e., 100 mol%. The structural unit B may be composed of only the structural unit (B1) and the structural unit (B2).
The molar ratio [ (B1)/(B2) ] of the structural unit (B1) to the structural unit (B2) in the structural unit B is preferably 5/95 to 60/40, more preferably 5/95 to 50/50, further preferably 5/95 to 40/60, and further preferably 10/90 to 30/70. On the other hand, from the viewpoint of mechanical properties such as elongation and toughness, it is preferably from 5/95 to 60/40, more preferably from 10/90 to 60/40, even more preferably from 30/70 to 60/40, and even more preferably from 40/60 to 60/40.
The structural unit B may contain structural units other than the structural units (B1) and (B2).
The structural unit B preferably further includes a structural unit (B3) in addition to the structural units (B1) and (B2), and the structural unit (B3) is at least 1 selected from the group consisting of a structural unit (B31) derived from a compound represented by the following formula (B31), a structural unit (B32) derived from a compound represented by the following formula (B32), and a structural unit (B33) derived from a compound represented by the following formula (B33).
The compound represented by the formula (b31) is 4,4 '-diaminodiphenyl ether (ODA), the compound represented by the formula (b32) is 9, 9-bis (4-aminophenyl) fluorene, and the compound represented by the formula (b33) is 2, 2' -bis (trifluoromethyl) benzidine.
The structural unit (B3) may be only the structural unit (B31), only the structural unit (B32), only the structural unit (B33), or any combination thereof.
When the structural unit B includes the structural unit (B1), the structural unit (B2), and the structural unit (B3), the total ratio of the structural unit (B1) to the structural unit (B2) in the structural unit B is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 70 mol% or more, and the ratio of the structural unit (B3) in the structural unit B is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 30 mol%.
The total ratio of the structural unit (B1), the structural unit (B2), and the structural unit (B3) 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 (B1), the structural unit (B2), and the structural unit (B3) is not particularly limited, that is, is 100 mol%. The structural unit B may be composed of only the structural unit (B1), the structural unit (B2), and the structural unit (B3).
The structural unit B may contain structural units other than the structural units (B1) to (B3). The diamine that provides such a structural unit is not particularly limited, and examples thereof include 1, 4-phenylenediamine, p-xylylenediamine, 3, 5-diaminobenzoic acid, 1, 5-diaminonaphthalene, 2 '-dimethylbiphenyl-4, 4' -diamine, 4 '-diaminodiphenylmethane, 1, 4-bis [2- (4-aminophenyl) -2-propyl ] benzene, 2-bis (4-aminophenyl) hexafluoropropane, 4' -diaminodiphenylsulfone, 3,4 '-diaminodiphenylether, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, α' -bis (4-aminophenyl) -1, aromatic diamines such as 4-diisopropylbenzene, N '-bis (4-aminophenyl) terephthalamide, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1, 4-bis (4-aminophenoxy) benzene; alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine.
In the present specification, an aromatic diamine means a diamine containing 1 or more aromatic rings, an alicyclic diamine means a diamine containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic diamine means a diamine containing neither aromatic rings nor alicyclic rings.
The structural units other than the structural units (B1) and (B2) optionally contained in the structural unit B may be 1 type, or 2 or more types.
The polyimide resin of the present invention may contain a structure other than a polyimide chain (a structure in which a structural unit a and a structural unit B are imide-bonded). Examples of the structure other than the polyimide chain that can be contained in the polyimide resin include a structure containing an amide bond.
The polyimide resin of the present invention preferably contains a polyimide chain (a structure in which a structural unit a and a structural unit B are imide-bonded) as a main structure. Therefore, the content of the polyimide chain in the polyimide resin of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 99% by mass or more, and may be 100% by mass.
By using the polyimide resin of the present invention, a film having low residual stress, excellent heat resistance, and a low coefficient of linear thermal expansion can be formed, and suitable physical properties of the film are as follows.
When a film having a thickness of 10 μm is formed, the total light transmittance is preferably 85% or more, more preferably 87% 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 10 or less, more preferably 9 or less, and still more preferably 8 or less.
The residual stress is preferably 30MPa or less, more preferably 25MPa or less, still more preferably 20MPa or less, and still more preferably 15MPa or less.
The glass transition temperature (Tg) is preferably 370 ℃ or higher, more preferably 380 ℃ or higher, still more preferably 390 ℃ or higher, and still more preferably 400 ℃ or higher.
The physical property values in the present invention can be measured specifically by the methods described in examples.
[ production methods of Polyamic acid and polyimide resin ]
The polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component containing a compound that provides the structural unit a with a diamine component containing a compound that provides the structural unit (B1) and a compound that provides the structural unit (B2).
The polyimide resin of the present invention is preferably produced by a method of imidizing (cyclodehydration) a polyamic acid which is a precursor of the polyimide resin. Specifically, it is preferable that the polyamic acid contained in the varnish described later is applied to a support or molded, and then the organic solvent is removed by heating, and imidization (cyclodehydration) is performed by heating to obtain a polyimide resin. The production of a polyimide film as a film-like polyimide resin is described below. The polyamic acid is a product of addition polymerization of the tetracarboxylic acid component and the diamine component.
Among the compounds that provide the structural unit a, preferred compounds include compounds that provide the structural unit (a1), i.e., compounds represented by formula (a1), but the compounds are not limited thereto, and derivatives thereof may be included within the scope of providing the same structural unit. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a1) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (a1), a compound represented by formula (a1) (i.e., dianhydride) is preferable.
The tetracarboxylic acid component may contain a compound other than the compound providing the structural unit (a1), and examples of the compound include the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, and the like).
The number of compounds other than the compound providing the structural unit (a1) optionally contained in the tetracarboxylic acid component may be 1, or 2 or more.
Examples of the compound providing the structural unit (B1) include compounds represented by the general formula (B1), 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 compounds represented by the general formula (b 1). As the compound providing the structural unit (B1), a compound represented by the formula (B1) (i.e., diamine) is generally preferred.
Similarly, examples of the compound providing the structural unit (B2) include compounds represented by the general formula (B2), 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 compounds represented by the general formula (b 2). As the compound providing the structural unit (B2), a compound represented by the general formula (B2) (i.e., diamine) is preferable.
The diamine component preferably contains 5 to 60 mol%, more preferably 10 to 40 mol%, and still more preferably 20 to 30 mol% of a compound that provides the structural unit (B1).
Similarly, the diamine component preferably contains 40 to 95 mol%, more preferably 60 to 90 mol%, and still more preferably 70 to 80 mol% of a compound that provides the structural unit (B2).
The total content ratio of the compound that provides the structural unit (B1) and the compound that provides the structural unit (B2) is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more of the total diamine component. The upper limit of the total content ratio of the compound providing the structural unit (B-1) and the compound providing the structural unit (B2) is not particularly limited, that is, 100 mol%. The diamine component may be composed of only the compound that provides the structural unit (B1) and the compound that provides the structural unit (B2).
The molar ratio [ (B1)/(B2) ] of the compound that provides the structural unit (B1) and the compound that provides the structural unit (B2) in the diamine component is preferably 5/95 to 60/40, more preferably 5/95 to 50/50, still more preferably 5/95 to 40/60, and still more preferably 10/90 to 30/70. On the other hand, from the viewpoint of mechanical properties such as elongation and toughness, it is preferably from 5/95 to 60/40, more preferably from 10/90 to 60/40, even more preferably from 30/70 to 60/40, and even more preferably from 40/60 to 60/40.
The diamine component may contain a compound that provides the aforementioned structural unit (B3) in addition to the compound that provides the structural unit (B1) and the compound that provides the structural unit (B2).
Examples of the compound that provides the structural unit (B3) include a compound represented by general formula (B31), a compound represented by general formula (B32), and a compound represented by general formula (B33), but the present invention 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 the compound represented by the general formula (b31), the compound represented by the general formula (b32), and the compound represented by the general formula (b 33). As the compound providing the structural unit (B3), a compound represented by general formula (B31), a compound represented by general formula (B32), and a compound represented by general formula (B33) (i.e., diamine) are preferable.
When the diamine component contains the compound that provides the structural unit (B3), the compound that provides the structural unit (B3) is preferably contained in an amount of 1 to 50 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 30 mol%.
The total content ratio of the compound that provides the structural unit (B1), the compound that provides the structural unit (B2), and the compound that provides the structural unit (B3) is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 99 mol% or more of the total diamine component. The upper limit value of the total content ratio of the compound providing the structural unit (B1), the compound providing the structural unit (B2), and the compound providing the structural unit (B3) is not particularly limited, that is, is 100 mol%. The diamine component may be composed of only the compound that provides the structural unit (B1), the compound that provides the structural unit (B2), and the compound that provides the structural unit (B3).
The diamine component may contain compounds other than the compound that provides the structural unit (B1), the compound that provides the structural unit (B2), and the compound that provides the structural unit (B3), and examples of the compounds include the aromatic diamine, the alicyclic diamine, and the 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 (B1) and the compound that provides the structural unit (B2).
In the present invention, the amount ratio of the tetracarboxylic acid component to the diamine component used for producing the polyimide resin is preferably 0.9 to 1.1 mol of the diamine component 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 end-capping 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, and particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. As the monoamine-type blocking agent, for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Among them, benzylamine and aniline can be suitably used. As the dicarboxylic acid-based end capping agent, dicarboxylic acids are preferred, and a part thereof may be ring-closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2, 3-benzophenonedicarboxylic acid, 3, 4-benzophenonedicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, and the like are recommended. Among them, phthalic acid and phthalic anhydride can be suitably used.
The method for reacting the tetracarboxylic acid component with the diamine component to obtain the polyamic acid is not particularly limited, and a known method can be used.
As a specific reaction method, the following method may be exemplified: a tetracarboxylic acid component, a diamine component and a solvent are charged into a reactor, and the mixture is stirred at 0 to 120 ℃, preferably 5 to 80 ℃ for 1 to 72 hours.
When the reaction is carried out at 80 ℃ or lower, the molecular weight of the obtained polyamic acid does not vary depending on the temperature history at the time of polymerization, and the progress of thermal imidization can be suppressed, whereby the polyamic acid can be stably produced.
The solvent used for producing the polyamic acid may be any solvent that can dissolve the produced polyamic acid. 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, N-methylcaprolactam, 1, 3-dimethylimidazolidinone, and tetramethylurea, lactone solvents such as γ -butyrolactone 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, methylethylketone, cyclohexanone, and methylcyclohexanone, and ester solvents such as acetic acid (2-methoxy-1-methylethyl) ester.
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, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate.
Among the above reaction solvents, an amide solvent or a lactone solvent is preferable, an amide solvent is more preferable, and N-methyl-2-pyrrolidone is further preferable. The reaction solvent can be used alone or in combination of 2 or more.
By the above method, a polyamic acid solution containing a polyamic acid dissolved in a solvent can be obtained.
The concentration of the polyamic acid in the polyamic acid solution obtained is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 10 to 30% by mass of the polyamic acid solution.
The number average molecular weight of the polyamic acid is preferably 5000 to 300000 from the viewpoint of the mechanical strength of the polyimide film to be obtained. The number average molecular weight of the polyamic acid can be determined, for example, from a standard polymethyl methacrylate (PMMA) value measured by gel permeation chromatography.
[ varnish ]
The varnish of the present invention is obtained by dissolving polyamide acid, which is a precursor of the polyimide resin of the present invention, in an organic solvent. That is, the varnish of the present invention contains a polyamic acid as a precursor of the polyimide resin of the present invention and an organic solvent in which the polyamic acid is dissolved.
The organic solvent is not particularly limited as long as it dissolves the polyamic acid, and the solvent used for producing the polyamic acid is preferably used alone or in a mixture of 2 or more compounds.
The varnish of the present invention may be the polyamic acid solution itself, or may be one obtained by further adding a diluting solvent to the polyamic acid solution.
From the viewpoint of efficient imidization, the varnish of the present invention preferably further contains an imidization catalyst, and may further contain a dehydration catalyst.
The imidization catalyst is preferably liquid at room temperature (25 ℃), and the boiling point of the imidization catalyst is preferably 120 ℃ or higher, more preferably 170 ℃ or higher, further preferably 200 ℃ or higher, and further preferably 250 ℃ or higher. The upper limit of the boiling point is not particularly limited, and is usually about 400 ℃.
Preferred imidization catalysts include imidazole compounds and tertiary amines. That is, the varnish of the present invention preferably contains at least 1 selected from the group consisting of imidazole compounds and tertiary amines, and more preferably contains an imidazole compound.
The imidazole compound is preferably at least 1 selected from the group consisting of imidazole, 1, 2-imidazole and 1-benzyl-2-methylimidazole, more preferably at least 1 selected from the group consisting of imidazole and 1, 2-imidazole, and further preferably 1, 2-imidazole from the viewpoint of improving colorless transparency.
The tertiary amine is preferably triethylenediamine (1, 4-diazabicyclo [2.2.2] octane).
By using the imidazole compound and the tertiary amine shown here, the molecular weight of the polyimide increases, and therefore, the tensile strength and elongation can be improved. Further, the linear thermal expansion coefficient and the residual stress can be further reduced, and the colorless transparency when the polyimide is formed into a film can be improved.
The imidization catalyst can be used alone or in combination of 2 or more.
The content of the imidization catalyst is preferably 100ppm or more, more preferably 1000ppm or more, and further preferably 5000ppm or more, based on the polyamic acid contained in the varnish. Further, 50000ppm or less is preferable.
Examples of the dehydration catalyst include anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. These can be used alone or in combination of 2 or more.
The polyamic acid contained in the varnish of the present invention has solvent solubility, and therefore can form a varnish of high concentration which is stable at room temperature. The varnish of the present invention preferably contains 3 to 40 mass%, more preferably 5 to 30 mass% of polyamic acid. The viscosity of the varnish is preferably 0.1 to 100 pas, more preferably 0.1 to 20 pas. The viscosity of the varnish is a value measured at 25 ℃ with an E-type viscometer.
The varnish of the present invention may contain, within a range not impairing the required properties of the polyimide film: inorganic filler, adhesion promoter, stripping agent, flame retardant, ultraviolet stabilizer, surfactant, leveling agent, defoaming agent, fluorescent whitening agent, crosslinking agent, polymerization initiator, photosensitizer and other additives.
The method for producing the 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 has low residual stress, excellent heat resistance, and a low linear thermal expansion coefficient. The polyimide film of the present invention has suitable physical property values as described above.
The polyimide film of the present invention is preferably produced using a varnish in which the polyamic acid is dissolved in an organic solvent.
The method for producing a polyimide film using the varnish of the present invention is not particularly limited, and a known method can be used. For example, a polyimide film can be produced by applying the varnish of the present invention to a smooth support such as a glass plate, a metal plate, or a plastic, or molding the varnish into a film, then removing an organic solvent such as a reaction solvent or a dilution solvent contained in the varnish by heating to obtain a polyamic acid film, heating the polyamic acid in the polyamic acid film to imidize (dehydrate and ring-close), and then peeling the polyamic acid from the support.
The heating temperature for drying the polyamic acid varnish to obtain a polyamic acid film is preferably 50 to 150 ℃. The heating temperature for imidizing the polyamic acid by heating is preferably 350 to 450 ℃, and more preferably 380 to 420 ℃. The heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, and more preferably 15 minutes to 1 hour. By setting such a temperature/time, the physical properties of the polyimide film obtained become good.
The heating atmosphere may be air gas, nitrogen gas, oxygen gas, hydrogen gas, nitrogen/hydrogen mixed gas, or the like, and preferably contains nitrogen gas having an oxygen concentration of 100ppm or less and nitrogen/hydrogen mixed gas having a hydrogen concentration of 0.5% or less in order to suppress coloration of the polyimide resin to be obtained.
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, and further preferably 7 to 50 μm. When the thickness is within the above range, 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 varnish
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) Total light transmittance, Yellow Index (YI)
Total light transmittance and YI according to JIS K7105: 1981. the measurement was carried out by using a color/turbidity simultaneous measuring instrument "COH 400" manufactured by Nippon Denshoku industries Co., Ltd.
(3) Haze (Haze)
The measurement was carried out according to JIS K7361-1 using a color/turbidity simultaneous measuring instrument "COH 7700" manufactured by Nippon Denshoku industries Co., Ltd.
(4) Glass transition temperature (Tg)
Using a thermomechanical analyzer "TMA/SS 6100" manufactured by Hitachi High-Tech Science Corporation, in a tensile mode, the residual stress was removed by heating to a temperature sufficient for removing the residual stress under conditions of a specimen size of 3mm × 20mm, a load of 0.1N, a nitrogen gas flow (flow rate 200 mL/min), and a heating rate of 10 ℃/min, and then cooled 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 of the visible elongation was determined as the glass transition temperature.
(5) Coefficient of linear thermal expansion (CTE)
The CTE of 100 to 350 ℃ was determined by TMA measurement under the conditions of a specimen size of 2 mm. times.20 mm, a load of 0.1N, and a temperature rise rate of 10 ℃/min in a tensile mode using a thermomechanical analyzer "TMA/SS 6100" manufactured by Hitachi High-Tech Science Corporation.
(6) 1% weight loss temperature (Td 1%)
The apparatus "TG/DTA 6200" was simultaneously measured using a differential thermogravimetry made by Hitachi High-Tech Science Corporation. The temperature of the sample was raised from 40 ℃ to 550 ℃ at a temperature raising rate of 10 ℃/min, and the temperature at which the weight was reduced by 1% was set as the 1% weight reduction temperature as compared with the weight at 300 ℃. The larger the value of the weight reduction temperature, the more excellent.
(7) Modulus of elasticity and strength
The elastic modulus and strength were measured according to JIS K7127 using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Seisaku-Sho K.K.
(8) Elongation percentage
The elongation was performed according to the tensile test (measurement of elongation) according to JIS K7127. A test piece having a width of 10mm and a thickness of 10 to 60 μm was used.
(9) Residual stress
The polyamic acid varnish was applied to a 4-inch silicon wafer having a thickness of 525 μm. + -. 25 μm, on which the "warpage amount" was measured in advance, by a spin coater using a residual stress measuring apparatus "FLX-2320" manufactured by KLA-Tencor and prebaked. Then, a hot air dryer was used to perform a heat curing treatment at 350 ℃ for 30 minutes (rate of temperature rise 5 ℃/minute) in a nitrogen atmosphere, thereby producing a silicon wafer having a polyimide film with a thickness of 6 to 20 μm after curing. The amount of warpage of the wafer was measured by the residual stress measuring apparatus, and the residual stress generated between the silicon wafer and the polyimide film was evaluated.
The tetracarboxylic acid component and the diamine component used in the examples and comparative examples, and abbreviations thereof are as follows.
< tetracarboxylic acid component >
CpODA: norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (JXTG Nippon Oil & Energy Corporation; compound of formula (a 1))
< diamine component >
6 FODA: 2,2 '-bis (trifluoromethyl) -4, 4' -diaminodiphenyl ether (ChinaTech (Tianjin) Chemical Co., Ltd., product of Ltd., compound represented by the formula (b 1))
DABA: 4, 4' -Diaminobenzanilide (Compound represented by the formula (b 2))
Abbreviations of solvents and the like used in examples and comparative examples are as follows.
NMP: n-methyl-2-pyrrolidone (manufactured by Mitsubishi chemical corporation)
Example 1
A500 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 17.405g (0.075 mol) of DABA, 8.406g (0.025 mol) of 6FODA, and 94.921g of NMP, and stirred at a temperature of 70 ℃ in the system and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, CpODA 38.438g (0.100 mol) and NMP 23.730g were charged simultaneously, and the temperature was raised to 100 ℃ in a mantle heater and held for 30 minutes. After confirming the dissolution, the mixture was cooled to 25 ℃ and stirred at 25 ℃ for 7 hours.
Then, NMP 243.388g was added thereto to conduct homogenization, thereby obtaining a polyamic acid varnish having a solid content of 15 mass%.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes (temperature increase rate 5 ℃/minute) in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 1.
Example 2
A polyamic acid varnish having a solid content of 15% by mass was obtained in the same manner as in example 1 except that the amounts of DABA (0.075 mol) and 6FODA (8.406 g, 0.025 mol) were changed from 17.405g to 14.773g (0.065 mol) and 11.768g (0.035 mol), respectively.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes (temperature increase rate 5 ℃/minute) in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 1.
Example 3
A polyamic acid varnish having a solid content of 15% by mass was obtained in the same manner as in example 1, except that the amount of DABA was changed from 17.405g (0.075 mol) to 11.364g (0.050 mol), and the amount of 6FODA was changed from 8.406g (0.025 mol) to 16.812g (0.050 mol).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 420 ℃ for 30 minutes (temperature increase rate 5 ℃/minute) in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 1.
Comparative example 1
A polyamic acid varnish having a solid content of 15 mass% was obtained in the same manner as in example 1, except that the amount of DABA was changed from 17.405g (0.075 mol) to 22.727g (0.100 mol) and 6FODA was not used.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 420 ℃ for 30 minutes (temperature increase rate 5 ℃/minute) in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The resulting film was brittle and it was difficult to maintain the shape of the film when peeled from the glass, so the glass transition temperature (Tg), the linear Coefficient of Thermal Expansion (CTE), the elastic modulus, the strength, the elongation and the residual stress could not be measured. The results are shown in Table 1.
Comparative example 2
A polyamic acid varnish having a solid content of 15 mass% was obtained in the same manner as in example 1 except that the amount of 6FODA was changed from 8.406g (0.025 mol) to 33.624g (0.100 mol), and DABA was not used.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes (temperature increase rate 5 ℃/minute) in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 1.
[ Table 1]
TABLE 1
Number indicates molar ratio
Example 4
A500 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 18.182g (0.080 mol) of DABA, 6FODA 6.725g (0.020 mol), and NMP 94.112g, and stirred at a temperature of 70 ℃ in the system and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, CpODA 38.438g (0.100 mol) and NMP 23.528g were charged simultaneously, and the temperature was raised to 100 ℃ in a mantle heater and held for 30 minutes. After confirming the dissolution, the mixture was cooled to 25 ℃ and stirred at 25 ℃ for 7 hours.
Thereafter, NMP 241.312g was added thereto for homogenization, and thereafter 0.633g of imidazole (0.00930 mol: 1% by mass relative to the polyamic acid (total amount of tetracarboxylic acid component and diamine component)) was added to obtain a polyamic acid varnish having a solid content of 15% by mass.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes (temperature increase rate 5 ℃/minute) in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 2.
Example 5
A polyamic acid varnish having a solid content of 15 mass% was obtained in the same manner as in example 4, except that the amounts of DABA (0.080 mol) and 6FODA (6.725 g, 0.020 mol) were changed from 18.182g to 15.909g (0.070 mol) and from 10.087g (0.030 mol).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 420 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere (temperature rise rate 5 ℃/minute) to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 2.
Example 6
A polyamic acid varnish having a solid content of 15% by mass was obtained in the same manner as in example 4 except that the amount of DABA was changed from 18.182g (0.080 mol) to 13.636g (0.060 mol) and the amount of 6FODA was changed from 6.725g (0.020 mol) to 13.450g (0.040 mol).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere (temperature rise rate 5 ℃/minute) to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 2.
Example 7
A polyamic acid varnish having a solid content of 15 mass% was obtained in the same manner as in example 5 except that 0.633g of imidazole (0.00930 mol: 1 mass% based on the polyamic acid (total amount of tetracarboxylic acid component and diamine component)) was changed to 0.633g of 1, 2-imidazole (0.00659 mol: 1 mass% based on the polyamic acid (total amount of tetracarboxylic acid component and diamine component)).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere (temperature rise rate 5 ℃/minute) to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 2.
Example 8
A polyamic acid varnish having a solid content of 15 mass% was obtained in the same manner as in example 6 except that 0.655g of imidazole (0.00962 mol: 1 mass% based on the polyamic acid (total amount of tetracarboxylic acid component and diamine component)) was changed to 0.655g of 1, 2-imidazole (0.00682 mol: 1 mass% based on the polyamic acid (total amount of tetracarboxylic acid component and diamine component)).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere (temperature rise rate 5 ℃/minute) to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 2.
Example 9
A polyamic acid varnish having a solid content of 15 mass% was obtained in the same manner as in example 6 except that 0.655g of imidazole (0.00962 mol: 1 mass% based on the polyamic acid (total amount of tetracarboxylic acid component and diamine component)) was changed to 0.655g of 1-benzyl-2-methylimidazole (0.00380 mol: 1 mass% based on the polyamic acid (total amount of tetracarboxylic acid component and diamine component)).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere (temperature rise rate 5 ℃/minute) to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 2.
Example 10
A polyimide varnish having a solid content of 15 mass% was obtained in the same manner as in example 9, except that the amount of DABA was changed from 13.636g (0.060 mol) to 11.364g (0.050 mol) and the amount of 6FODA was changed from 13.450g (0.040 mol) to 16.812g (0.050 mol).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and held at 80 ℃ for 20 minutes on a hot plate, and then heated at 400 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere (temperature rise rate 5 ℃/minute) to evaporate the solvent and perform thermal imidization to obtain a polyimide film. The results are shown in Table 2.
[ Table 2]
TABLE 2
Number indicates molar ratio
As shown in tables 1 and 2, the polyimide films of the examples have high glass transition temperatures, excellent heat resistance, low residual stress, and low linear thermal expansion coefficients.
Industrial applicability
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.
Claims (10)
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 B includes: a structural unit (B1) derived from a compound represented by the following formula (B1) and a structural unit (B2) derived from a compound represented by the following formula (B2),
2. the polyimide resin according to claim 1, wherein the structural unit a comprises: a structural unit (A1) derived from a compound represented by the following formula (a1),
3. the polyimide resin according to claim 1 or 2, wherein a structural unit B further comprises a structural unit (B3), the structural unit (B3) being at least one selected from the group consisting of a structural unit (B31) derived from a compound represented by the following formula (B31), a structural unit (B32) derived from a compound represented by the following formula (B32), and a structural unit (B33) derived from a compound represented by the following formula (B33),
4. a varnish comprising a polyimide resin as defined in any one of claims 1 to 3, and a polyamic acid which is a precursor of the polyimide resin, dissolved in an organic solvent.
5. The varnish of claim 4 further comprising: at least one selected from the group consisting of imidazole compounds and tertiary amines.
6. The varnish of claim 5 wherein the imidazole compound is at least one selected from the group consisting of imidazole, 1, 2-imidazole, and 1-benzyl-2-methylimidazole.
7. The varnish of claim 5 or 6 wherein the tertiary amine is triethylenediamine.
8. A polyimide film obtained by applying the varnish according to any one of claims 4 to 7 to a support and heating the applied varnish.
9. A method for producing a polyimide film, which comprises applying the varnish according to any one of claims 4 to 7 to a support and heating the applied varnish.
10. A polyimide film comprising the polyimide resin according to any one of claims 1 to 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019239648 | 2019-12-27 | ||
| JP2019-239648 | 2019-12-27 | ||
| PCT/JP2020/047791 WO2021132197A1 (en) | 2019-12-27 | 2020-12-22 | Polyimide resin, varnish, and polyimide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114867766A true CN114867766A (en) | 2022-08-05 |
Family
ID=76572988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080089527.XA Pending CN114867766A (en) | 2019-12-27 | 2020-12-22 | Polyimide resin, varnish, and polyimide film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2021132197A1 (en) |
| KR (1) | KR20220123394A (en) |
| CN (1) | CN114867766A (en) |
| TW (1) | TW202134318A (en) |
| WO (1) | WO2021132197A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023085041A1 (en) * | 2021-11-11 | 2023-05-19 | 三菱瓦斯化学株式会社 | Polyimide resin, varnish, and polyimide film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11282157A (en) * | 1997-10-31 | 1999-10-15 | Nippon Zeon Co Ltd | Polymide type photosensitive composition |
| WO2018097143A1 (en) * | 2016-11-24 | 2018-05-31 | 日産化学工業株式会社 | Composition for forming flexible device substrate |
| CN109071811A (en) * | 2016-05-02 | 2018-12-21 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide resin composition and Kapton |
| CN109957109A (en) * | 2017-12-22 | 2019-07-02 | 株式会社斗山 | Polyamic acid solution, clear polyimides resin film and transparent substrate using it |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232383A (en) | 2004-02-20 | 2005-09-02 | Asahi Kasei Electronics Co Ltd | Polyamic acid derivative |
| WO2014098235A1 (en) | 2012-12-21 | 2014-06-26 | 旭化成イーマテリアルズ株式会社 | Polyimide precursor and resin composition containing same |
| WO2020138360A1 (en) * | 2018-12-28 | 2020-07-02 | 三菱瓦斯化学株式会社 | Imide-(amic acid) copolymer and method for producing same, varnish, and polyimide film |
-
2020
- 2020-12-22 JP JP2021567461A patent/JPWO2021132197A1/ja active Pending
- 2020-12-22 WO PCT/JP2020/047791 patent/WO2021132197A1/en active Application Filing
- 2020-12-22 KR KR1020227021125A patent/KR20220123394A/en active Search and Examination
- 2020-12-22 CN CN202080089527.XA patent/CN114867766A/en active Pending
- 2020-12-23 TW TW109145612A patent/TW202134318A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11282157A (en) * | 1997-10-31 | 1999-10-15 | Nippon Zeon Co Ltd | Polymide type photosensitive composition |
| CN109071811A (en) * | 2016-05-02 | 2018-12-21 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide resin composition and Kapton |
| WO2018097143A1 (en) * | 2016-11-24 | 2018-05-31 | 日産化学工業株式会社 | Composition for forming flexible device substrate |
| CN109957109A (en) * | 2017-12-22 | 2019-07-02 | 株式会社斗山 | Polyamic acid solution, clear polyimides resin film and transparent substrate using it |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021132197A1 (en) | 2021-07-01 |
| TW202134318A (en) | 2021-09-16 |
| KR20220123394A (en) | 2022-09-06 |
| JPWO2021132197A1 (en) | 2021-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6996609B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| CN111902457B (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN111936553A (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN111683992A (en) | Polyimide resin composition and polyimide film | |
| JPWO2019116940A1 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| WO2020110947A1 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| WO2021132196A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN111133032B (en) | Polyimide, polyimide varnish, and polyimide film | |
| CN114867766A (en) | Polyimide resin, varnish, and polyimide film | |
| WO2022196664A1 (en) | Polyimide precursor composition | |
| CN114729122A (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN111133034B (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN115380059A (en) | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film | |
| CN115380058A (en) | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film | |
| WO2020203264A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN111936554B (en) | Polyimide resin, polyimide varnish and polyimide film | |
| WO2021153379A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| WO2021177145A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN114096589A (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| WO2022091813A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| KR20230044202A (en) | Polyimide resins, polyamic acids, varnishes and polyimide films | |
| CN114245809A (en) | Polyimide resin composition, polyimide varnish, and polyimide film | |
| CN114466902A (en) | Polyimide resin composition, polyimide varnish, and polyimide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |