CN114867766B - Polyimide resin, varnish and polyimide film - Google Patents
Polyimide resin, varnish and polyimide film Download PDFInfo
- Publication number
- CN114867766B CN114867766B CN202080089527.XA CN202080089527A CN114867766B CN 114867766 B CN114867766 B CN 114867766B CN 202080089527 A CN202080089527 A CN 202080089527A CN 114867766 B CN114867766 B CN 114867766B
- Authority
- CN
- China
- Prior art keywords
- structural unit
- varnish
- mol
- derived
- compound represented
- 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.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 102
- 239000002966 varnish Substances 0.000 title claims abstract description 68
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 103
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 59
- 150000004985 diamines Chemical class 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 42
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 38
- -1 imidazole compound Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 7
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract description 21
- 125000006158 tetracarboxylic acid group Chemical group 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 description 32
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 23
- 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
- 239000000243 solution Substances 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
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 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
- 239000004952 Polyamide Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000013585 weight reducing agent Substances 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 238000005259 measurement Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000011369 resultant mixture Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 241001272720 Medialuna californiensis Species 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
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 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
- 238000001723 curing 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
- 238000004090 dissolution Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 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
- 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
- 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
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- 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
- 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 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 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
- 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
- 238000004458 analytical method Methods 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
- 238000005282 brightening Methods 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
- 238000004040 coloring Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 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
- 239000013530 defoamer Substances 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane 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
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000013007 heat curing Methods 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
- 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
- 229920000435 poly(dimethylsiloxane) 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
- 239000000126 substance 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
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 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
- 230000000930 thermomechanical effect Effects 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention is a polyimide resin comprising: structural units a derived from tetracarboxylic dianhydride and structural units B derived from diamine, the structural units 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: polyimide resins which can be molded into films having low residual stress, excellent heat resistance and low linear thermal expansion coefficient; a varnish containing a polyamic acid as a precursor of the polyimide resin; and polyimide films.
Description
Technical Field
The present invention relates to polyimide resins, varnishes and polyimide films.
Background
Various uses of polyimide resins in the fields of electric/electronic components and the like have been studied. For example, for the purpose of weight reduction and flexibility of a device, it is desired to replace a glass substrate used in an image display device such as a liquid crystal display or an OLED display with a plastic substrate, and research on a polyimide film suitable as the plastic substrate has been advanced. Polyimide films for such applications are required to have high transparency, small retardation due to birefringence, i.e., low retardation, and the like.
In addition, when a polyimide film is formed by heating and curing a varnish applied to a glass support or a silicon wafer, residual stress is generated in the polyimide film. If the residual stress of the polyimide film is large, warpage of the glass support and the silicon wafer occurs, and therefore, reduction of the residual stress is also required for the polyimide film.
Patent document 1 discloses, as a polyimide resin providing a film with low residual stress, a polyimide resin synthesized using α, ω -aminopropyl polydimethylsiloxane and 4,4' -diaminodiphenyl ether as diamine components.
Patent document 2 discloses, as a polyimide film having low residual stress, a polyimide film formed by imidizing a polyimide resin precursor synthesized using bis (trifluoromethyl) benzidine and a silicon-containing diamine as diamine components.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2005-232383
Patent document 2: international publication No. 2014/098235
Disclosure of Invention
Problems to be solved by the invention
As described above, polyimide films require various characteristics, but it is not easy to satisfy these characteristics at the same time.
In particular, miniaturization and precision of substrates have recently advanced, and integration of electronic circuits has also advanced, so that thermal stability has been increasingly demanded in order to cope with the foregoing low residual stress. For example, heat resistance and low thermal expansion coefficient 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 molded into a film having low residual stress, excellent heat resistance and low linear thermal expansion coefficient, a varnish containing a polyamic acid as a precursor of the polyimide resin, and a polyimide film.
Solution for solving the problem
The inventors found that: the polyimide resin containing a combination of specific structural units can solve the above-mentioned 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, comprising: structural units A derived from tetracarboxylic dianhydrides and structural units B derived from diamines,
The structural unit B comprises: 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: structural unit (A1) derived from a compound represented by the following formula (A1).
[3]
The polyimide resin according to the aforementioned [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 polyamic acid as a precursor of the polyimide resin according to any one of the above [1] to [3] dissolved in an organic solvent.
[5]
The varnish according to the above [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 described in any one of [4] to [7] to a support and heating the same.
[9]
A method for producing a polyimide film, wherein the varnish described in any one of [4] to [7] is applied to a support and heated.
[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 may be provided: a polyimide resin which can be molded into a film having low residual stress, excellent heat resistance and low linear thermal expansion coefficient, a varnish containing a polyamic acid as a precursor of the polyimide resin, and a polyimide film.
Detailed Description
[ Polyimide resin ]
The polyimide resin of the present invention comprises: structural units A derived from tetracarboxylic dianhydrides and structural units B derived from diamines,
The structural unit B comprises: 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 be any structural unit as long as it can react with the structural unit B to form an imide bond, and preferably comprises: structural unit (A1) derived from a compound represented by the following formula (A1).
The compound shown in the formula (a 1) is norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5', 6' -tetracarboxylic dianhydride.
The structural unit a can make the film of the present invention low in residual stress and linear thermal expansion coefficient, and can also improve heat resistance and optical isotropy by containing the structural unit derived from the compound represented by the formula (a 1).
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, particularly preferably 99 mol% or more, from the viewpoint of improving heat resistance and optical isotropy. The upper limit of the ratio is not particularly limited, and is 100 mol%.
The structural unit a may contain structural units other than the structural unit (A1) within a range that does not impair the effects of the present invention. The tetracarboxylic dianhydride providing such a structural unit is not particularly limited, and examples thereof include pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 9 '-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, 3', aromatic tetracarboxylic dianhydrides such as 4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, and 2,2', 3' -benzophenone tetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, and dicyclohexyl tetracarboxylic dianhydride; aliphatic tetracarboxylic dianhydrides such as1, 2,3, 4-butanetetracarboxylic dianhydride.
Among these, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride are preferable from the viewpoints of improving heat resistance, optical isotropy, and transparency.
The number of structural units other than the structural unit (A1) optionally included in the structural unit a may be 1 or 2 or more.
The structural unit a preferably contains no 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 not containing an aromatic ring, and an aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing neither an aromatic ring nor an alicyclic ring.
< Structural Unit B >)
The structural unit B is a structural unit derived from diamine in a 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).
The structural unit B is considered to have low residual stress, excellent heat resistance, low linear thermal expansion coefficient, and excellent thermal properties by including any one of the structural unit (B1) and the structural unit (B2).
The compound represented by the formula (b 1) is 2,2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (6 FODA).
By including 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 (b 2) is 4,4' -Diaminobenzanilide (DABA).
By including the structural unit (B2) derived from the compound represented by the formula (B2), residual stress can be reduced.
The ratio 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 ratio 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, that is, 100 mol%. The structural unit B may be constituted only by 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, still more preferably 5/95 to 40/60, 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 5/95 to 60/40, more preferably 10/90 to 60/40, still more preferably 30/70 to 60/40, and still more preferably 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 contains, in addition to the structural units (B1) and (B2), a structural unit (B3), the structural unit (B3) being 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 (b 31) is 4,4 '-diaminodiphenyl ether (ODA), the compound represented by the formula (b 32) is 9, 9-bis (4-aminophenyl) fluorene, and the compound represented by the formula (b 33) is 2,2' -bis (trifluoromethyl) benzidine.
The structural unit (B3) may be only the structural unit (B31), may be only the structural unit (B32), may be only the structural unit (B33), or may be 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, still more 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%, still more 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 value of the total ratio of the structural unit (B1), the structural unit (B2) and the structural unit (B3) is not particularly limited, that is, 100 mol%. The structural unit B may be constituted only by 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 providing 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-trimethyl-1H-inden-5-amine, and alpha, aromatic diamines such as α' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, N '-bis (4-aminophenyl) terephthalamide, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 1, 4-bis (4-aminophenoxy) benzene; alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; aliphatic diamines such as ethylenediamine and hexamethylenediamine.
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 containing 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 included in the structural unit B may be 1 kind or 2 kinds or more.
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 bonded through an 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 of the present invention preferably contains a polyimide chain (structure in which structural unit a and structural unit B are bonded via an imide) as a main structure. Therefore, the ratio of the polyimide chain of the present invention to the polyimide resin is preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 90 mass% or more, particularly preferably 99 mass% or more, and may be 100 mass% or more.
By using the polyimide resin of the present invention, a film having low residual stress, excellent heat resistance and low linear thermal expansion coefficient can be formed, and the film has suitable physical properties as described below.
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, 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, still more preferably 400℃or higher.
The physical property values in the present invention can be specifically measured by the methods described in examples.
[ Method for producing Polyamic acid and polyimide resin ]
The polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component comprising a compound providing the above-mentioned structural unit a with a diamine component comprising a compound providing the above-mentioned structural unit (B1) and a compound providing the above-mentioned structural unit (B2).
The polyimide resin of the present invention is preferably produced by a method of imidizing (dehydrating and ring-closing) a polyamic acid which is a precursor of the polyimide resin. Specifically, it is preferable to apply the polyamic acid contained in the varnish to be described later to a support or to form the varnish, then to remove the organic solvent by heating and to imidize (dehydrate and ring-close) the varnish by heating, thereby obtaining a polyimide resin. The polyimide film, which is a film-like polyimide resin, is produced as follows. The polyamic acid is a product of addition polymerization reaction of the tetracarboxylic acid component and the diamine component.
Among the compounds for providing the structural unit a, the compound for providing the structural unit (A1), that is, the compound represented by the formula (A1), may be exemplified as a preferable compound, but the compound is not limited thereto, and may be a derivative thereof within a range where the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a 1) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A1), a compound represented by the formula (A1) (i.e., dianhydride) is preferable.
The tetracarboxylic acid component may contain compounds other than the compound providing the structural unit (A1), and examples of the compound include the aromatic tetracarboxylic dianhydride, the alicyclic tetracarboxylic dianhydride, the aliphatic tetracarboxylic dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl esters 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.
The compound providing the structural unit (B1) may be a compound represented by the general formula (B1), but is not limited thereto, and may be a derivative thereof within a range in which the same structural unit is provided. The derivative may be a diisocyanate corresponding to the compound 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 preferable.
Similarly, the compound providing the structural unit (B2) may be a compound represented by the general formula (B2), but is not limited thereto, and may be a derivative thereof within a range in which the same structural unit is provided. The derivative may be a diisocyanate corresponding to the compound 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%, still more preferably 20 to 30 mol% of the compound providing the structural unit (B1).
Similarly, the diamine component preferably contains 40 to 95 mol%, more preferably 60 to 90 mol%, still more preferably 70 to 80 mol% of the compound providing the structural unit (B2).
The total content ratio of the compound providing the structural unit (B1) and the compound providing 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 providing the structural unit (B1) and the compound providing the structural unit (B2).
The molar ratio [ (B1)/(B2) ] of the compound providing the structural unit (B1) to the compound providing 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, 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 5/95 to 60/40, more preferably 10/90 to 60/40, still more preferably 30/70 to 60/40, and still more preferably 40/60 to 60/40.
The diamine component may contain a compound providing the aforementioned structural unit (B3) in addition to the compound providing the structural unit (B1) and the compound providing the structural unit (B2).
The compound providing the structural unit (B3) includes a compound represented by the general formula (B31), a compound represented by the general formula (B32), and a compound represented by the general formula (B33), but is not limited thereto, and may be a derivative thereof within a range in which the same structural unit is provided. The derivative includes diisocyanates corresponding to the compound represented by the general formula (b 31), the compound represented by the general formula (b 32) and the compound represented by the general formula (b 33). As the compound providing the structural unit (B3), preferred are a compound represented by the general formula (B31), a compound represented by the general formula (B32), and a compound represented by the general formula (B33) (i.e., diamine).
In the case where the diamine component contains the compound providing the structural unit (B3), the diamine component preferably contains 1 to 50 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 30 mol% of the compound providing the structural unit (B3).
The total content ratio of the compound for providing the structural unit (B1), the compound for providing the structural unit (B2) and the compound for providing 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 entire diamine component. The upper limit 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, 100 mol%. The diamine component may be composed of only the compound providing the structural unit (B1), the compound providing the structural unit (B2), and the compound providing the structural unit (B3).
The diamine component may contain a compound other than the compound providing the structural unit (B1), the compound providing the structural unit (B2) and the compound providing the structural unit (B3), and examples of the compound include the above aromatic diamine, alicyclic diamine, aliphatic diamine, and derivatives thereof (diisocyanate, etc.).
The number of compounds other than the compound providing the structural unit (B1) and the compound providing the structural unit (B2) to be optionally contained in the diamine component may be 1 or 2 or more.
In the present invention, the ratio of the amount of the diamine component to be added to the tetracarboxylic acid component used in the production of the polyimide resin is preferably 0.9 to 1.1 mol based on 1 mol of the tetracarboxylic acid component.
In the present invention, a blocking agent may be used in addition to the tetracarboxylic acid component and the diamine component in the production of the polyimide resin. As the blocking agent, monoamines or dicarboxylic acids are preferable. The amount of the blocking agent to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, based on 1mol of the tetracarboxylic acid component. As monoamine-type blocking agents, for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Among them, benzylamine and aniline can be suitably used. The dicarboxylic acid-based capping agent is preferably a dicarboxylic acid, and a part of the dicarboxylic acid may be closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2, 3-benzophenone dicarboxylic acid, 3, 4-benzophenone dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, and the like are recommended. Among them, phthalic acid and phthalic anhydride can be suitably used.
The method for reacting the tetracarboxylic acid component and 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 can be exemplified: the tetracarboxylic acid component, diamine component and solvent are put into a reactor and stirred for 1 to 72 hours at a temperature of 0to 120 ℃, preferably 5 to 80 ℃.
When the reaction is carried out at 80℃or lower, the molecular weight of the obtained polyamic acid does not change depending on the temperature history during polymerization, and the progress of thermal imidization can be suppressed, so that polyamic acid can be stably produced.
The solvent used in the production of the polyamic acid may be any solvent that can dissolve the polyamic acid produced. Examples thereof include aprotic solvents, phenolic solvents, ether solvents, and carbonate solvents.
Specific examples of the aprotic solvent include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1, 3-dimethylimidazolidinone, tetramethylurea, lactone solvents such as γ -butyrolactone and γ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoramide and hexamethylphosphoric triamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone, and ester solvents such as (2-methoxy-1-methylethyl) acetate.
Specific examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol.
Specific examples of the ether solvent include 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [ 2- (2-methoxyethoxy) ethyl ] ether, tetrahydrofuran, and 1, 4-dioxane.
Specific examples of the carbonate-based solvent include diethyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
Among the above reaction solvents, an amide-based solvent or a lactone-based solvent is preferable, an amide-based solvent is more preferable, and N-methyl-2-pyrrolidone is still more preferable. The above reaction solvents may be used alone or in combination of 2 or more.
By the above method, a polyamic acid solution containing polyamic acid dissolved in a solvent can be obtained.
The concentration of the polyamide acid in the obtained polyamide acid solution is usually in the range of 1 to 50% by mass, preferably 3 to 35% by mass, more preferably 10 to 30% by mass in the polyamide acid solution.
From the viewpoint of mechanical strength of the obtained polyimide film, the number average molecular weight of the polyamic acid is preferably 5000 to 300000. The number average molecular weight of the polyamic acid can be obtained, for example, from a standard polymethyl methacrylate (PMMA) equivalent measured by gel permeation chromatography.
[ Varnish ]
The varnish of the present invention is obtained by dissolving a polyamic 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, and the polyamic acid is dissolved in the organic solvent.
The organic solvent is not particularly limited as long as it dissolves the polyamic acid, and as the solvent used in the production of the polyamic acid, it is preferable to use the above-mentioned compounds alone or in combination of 2 or more.
The varnish of the present invention may be the polyamic acid solution itself, or may be a solution obtained by adding a diluting solvent to the polyamic acid solution.
The varnish of the present invention preferably further contains an imidization catalyst and may further contain a dehydration catalyst from the viewpoint of efficiently imidizing.
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, still more preferably 200℃or higher, still more preferably 250℃or higher. The upper limit of the boiling point is not 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, more preferably contains imidazole compounds.
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 polyimide increases, and thus the tensile strength, elongation can be improved. In addition, the linear thermal expansion coefficient and residual stress can be further reduced, and the colorless transparency when polyimide is formed into a film is also improved.
The imidization catalyst may 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 still more preferably 5000ppm or more, with respect to the polyamic acid contained in the varnish. In addition, it is preferably 50000ppm or less.
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. They may 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 thus can form a varnish of high concentration 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 100pa·s, more preferably 0.1 to 20pa·s. The viscosity of the varnish is the value measured with an E-type viscometer at 25 ℃.
The varnish of the present invention may contain, within a range that does not impair the desired properties of the polyimide film: inorganic filler, adhesion promoter, stripping agent, flame retardant, ultraviolet stabilizer, surfactant, leveling agent, defoamer, fluorescent brightening agent, cross-linking 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 contains the polyimide resin of the present invention. Therefore, the polyimide film of the present invention has low residual stress, excellent heat resistance and low linear thermal expansion coefficient. The polyimide film of the present invention has suitable physical properties as described above.
The polyimide film of the present invention is preferably produced using a varnish obtained by dissolving the polyamic acid 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, the varnish of the present invention is applied to a smooth support such as a glass plate, a metal plate, or a plastic, or is formed into a film, and then an organic solvent such as a reaction solvent or a dilution solvent contained in the varnish is removed by heating to obtain a polyamic acid film, and the polyamic acid in the polyamic acid film is imidized (dehydrated and closed-loop) by heating, followed by peeling from the support, whereby a polyimide film can be produced.
The heating temperature for drying the polyamic acid varnish to obtain a polyamic acid film is preferably 50 to 150 ℃. The heating temperature at the time of imidizing the polyamic acid by heating is preferably 350 to 450 ℃, 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 the temperature and time to those mentioned above, the physical properties of the obtained polyimide film are improved.
The heating atmosphere may be, for example, an air gas, nitrogen gas, oxygen gas, hydrogen gas, or a nitrogen/hydrogen mixed gas, and in order to suppress coloring of the polyimide resin obtained, it is preferable to include a nitrogen gas having an oxygen concentration of 100ppm or less and a nitrogen/hydrogen mixed gas having a hydrogen concentration of 0.5% or less.
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 may be appropriately selected depending on the application, etc., and is preferably in the range of 1 to 250. Mu.m, more preferably 5 to 100. Mu.m, still more preferably 7 to 50. Mu.m. The thickness in the above range makes practical use as a self-standing film possible.
The thickness of the polyimide film can be easily controlled by adjusting the solid concentration and viscosity of the varnish
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these examples.
< Film Properties and evaluation >
The physical properties of the films obtained in examples and comparative examples were measured by the methods shown below.
(1) Film thickness
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 color/turbidity was measured by using a color/turbidity simultaneous measuring instrument "COH400" manufactured by Nippon Denshoku industries Co.
(3) Haze (Haze)
The measurement was carried out in accordance with JIS K7361-1 using a color/turbidity simultaneous measuring instrument "COH7700" manufactured by Nippon Denshoku Kogyo Co.
(4) Glass transition temperature (Tg)
The thermal mechanical analyzer "TMA/SS6100" manufactured by HITACHI HIGH-TECH SCIENCE Corporation was used, and in the tensile mode, the residual stress was removed by heating to a sufficient temperature required for removing the residual stress under conditions of a sample size of 3mm×20mm, a load of 0.1N, a nitrogen gas flow (flow rate of 200 mL/min), and a heating rate of 10℃per minute, and then cooled to room temperature. Thereafter, the elongation of the test piece was measured under the same conditions as in the treatment for removing the residual stress, and the glass transition temperature was obtained as the inflection point of the visible elongation.
(5) Coefficient of linear thermal expansion (CTE)
The CTE was determined by TMA measurement under conditions of a sample size of 2 mm. Times.20 mm, a load of 0.1N and a heating rate of 10 ℃/min in a tensile mode using a thermo-mechanical analysis apparatus "TMA/SS6100" manufactured by HITACHI HIGH-TECH SCIENCE Corporation, and the CTE was 100 to 350 ℃.
(6) 1% Weight reduction temperature (Td 1%)
The apparatus "TG/DTA6200" was also measured using a differential thermogravimetry made by HITACHI HIGH-TECH SCIENCE Corporation. The sample was heated from 40℃to 550℃at a heating rate of 10℃per minute, and the temperature at which the weight was reduced by 1% was set as a 1% weight reduction temperature, 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 the strength were measured according to JIS K7127, and the tensile elastic modulus and the tensile strength were measured by using a tensile tester "Stroggraph VG-1E" manufactured by Toyo Seisakusho Co., ltd.
(8) Elongation percentage
Elongation was measured according to the tensile test (measurement of elongation) in accordance with JIS K7127. A test piece having a width of 10mm and a thickness of 10 to 60 μm was used.
(9) Residual stress
Using a residual stress measuring device "FLX-2320" manufactured by KLA-Tencor, the polyamic acid varnish was applied on a 4-inch silicon wafer of 525 μm.+ -. 25 μm in thickness, which was previously measured for "warpage", by a spin coater and prebaked. Then, a heat curing treatment was performed at 350℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere to prepare a silicon wafer having a polyimide film with a thickness of 6 to 20 μm after curing. The warpage amount of the wafer was measured by the residual stress measuring device, and residual stress generated between the silicon wafer and the polyimide film was evaluated.
The tetracarboxylic acid component and the diamine component used in examples and comparative examples, abbreviations thereof and the like are as follows.
< Tetracarboxylic acid component >
CpODA: norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5', 6' -tetracarboxylic dianhydride (JXTG Nippon Oil & Energy Corporation; compound represented by formula (a 1))
< Diamine component >
6FODA:2,2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (CHINATECH (TIANJIN) Chemical Co., ltd., compound represented by formula (b 1))
DABA:4,4' -diaminobenzanilide (Compound represented by the formula (b 2))
Abbreviations for solvents and the like used in examples and comparative examples are as follows.
NMP: n-methyl-2-pyrrolidone (Mitsubishi chemical Co., ltd.)
Example 1
A500 mL five-necked round-bottomed flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet pipe, a dean-Stark trap equipped with a condenser, a thermometer, and a glass end cap was charged with DABA 17.405g (0.075 mol), 6FODA 8.406g (0.025 mol), and NMP 94.921g, and the mixture was stirred at a temperature of 70℃in the system under a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, cpODA 38.438g (0.100 mol) and 23.730g of NMP were charged simultaneously, and the temperature was raised to 100℃in a covered heater and kept for 30 minutes. After confirming dissolution, the mixture was cooled to 25℃and stirred at 25℃for 7 hours.
Thereafter, 243.388g of NMP was added to homogenize the resultant mixture, thereby obtaining 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 was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 1.
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 DABA was changed from 17.405g (0.075 mol) to 14.773g (0.065 mol) and the amount of 6FODA was changed from 8.406g (0.025 mol) to 11.768g (0.035 mol).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 1.
Example 3
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 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 was kept at 80℃for 20 minutes on a heating plate, and then heated at 420℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, 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 was kept at 80℃for 20 minutes on a heating plate, and then heated at 420℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The resulting film is brittle and difficult to maintain in shape when peeled from glass, and therefore, glass transition temperature (Tg), coefficient of linear thermal expansion (CTE), elastic modulus, strength, elongation and residual stress cannot 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 was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 1.
TABLE 1
TABLE 1
* The numbers indicate the molar ratio
Example 4
To a 500mL five-necked round-bottomed flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet pipe, a dean-Stark trap equipped with a condenser, a thermometer, and a glass end cap were charged 18.182g (0.080 mol) of DABA, 6.725g (0.020 mol) of FODA, and 94.112g of NMP, and the mixture was stirred at a temperature of 70℃in the system under a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, cpODA 38.438g (0.100 mol) and 23.528g of NMP were charged simultaneously, and the temperature was raised to 100℃in a covered heater and kept for 30 minutes. After confirming dissolution, the mixture was cooled to 25℃and stirred at 25℃for 7 hours.
Thereafter, 241.312g of NMP was added to homogenize the resultant mixture, and 0.633g of imidazole (0.00930 mol: 1% by mass based on the total amount of the tetracarboxylic acid component and the diamine component) was added to the resultant mixture 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 was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 2.
Example 5
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 15.909g (0.070 mol) and the amount of 6FODA was changed from 6.725g (0.020 mol) to 10.087g (0.030 mol).
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and was kept at 80℃for 20 minutes on a heating plate, and then heated at 420℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 2.
Example 6
A polyamic acid varnish having a solid content of 15 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 was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 2.
Example 7
A polyamic acid varnish having a solid content of 15% by mass was obtained in the same manner as in example 5, except that 0.633g (0.00930 mol: 1% by mass based on the total amount of the tetracarboxylic acid component and the diamine component) of imidazole was changed to 0.633g (0.00659 mol: 1% by mass based on the total amount of the tetracarboxylic acid component and the diamine component) of 1, 2-imidazole.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 2.
Example 8
A polyamic acid varnish having a solid content of 15% by mass was obtained in the same manner as in example 6, except that 0.655g (0.00962 mol: 1% by mass based on the total amount of the tetracarboxylic acid component and the diamine component) of imidazole was changed to 0.655g (0.00682 mol: 1% by mass based on the total amount of the tetracarboxylic acid component and the diamine component) of 1, 2-imidazole.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 2.
Example 9
A polyamic acid varnish having a solid content of 15% by mass was obtained in the same manner as in example 6, except that 0.655g (0.00962 mol: 1% by mass based on the total amount of the tetracarboxylic acid component and the diamine component) of imidazole was changed to 0.655g (0.00380 mol: 1% by mass based on the total amount of the tetracarboxylic acid component and the diamine component) of 1-benzyl-2-methylimidazole.
Then, the obtained polyamic acid varnish was applied to a glass plate by a spin coater, and was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 2.
Example 10
A polyamide 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 was kept at 80℃for 20 minutes on a heating plate, and then heated at 400℃for 30 minutes (a heating rate of 5℃per minute) in a hot air dryer under a nitrogen atmosphere, whereby the solvent was evaporated, and further thermally imidized, to obtain a polyimide film. The results are shown in Table 2.
TABLE 2
TABLE 2
* The numbers indicate the molar ratio
As shown in tables 1 and 2, it is understood that the polyimide films of the examples have high glass transition temperature, excellent heat resistance, low residual stress and low linear thermal expansion coefficient.
Industrial applicability
The polyimide film of the present invention is suitable for use 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 image display devices such as liquid crystal displays and OLED displays.
Claims (9)
1. A polyimide resin, comprising: structural units A derived from tetracarboxylic dianhydrides and structural units B derived from diamines,
The structural unit B comprises: 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 structural unit A comprises: a structural unit (A1) derived from a compound represented by the following formula (A1),
The ratio of the structural unit (B1) in the structural unit B is 5 to 60 mol%, the ratio of the structural unit (B2) is 40 to 95 mol%,
2. The polyimide resin according to claim 1, wherein the 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),
3. A varnish comprising a polyamic acid as a precursor of the polyimide resin according to claim 1 or 2 dissolved in an organic solvent.
4. The varnish of claim 3 further comprising: at least one selected from the group consisting of imidazole compounds and tertiary amines.
5. The varnish of claim 4 wherein the imidazole compound is at least one selected from the group consisting of imidazole and 1-benzyl-2-methylimidazole.
6. The varnish of claim 4 or 5 wherein the tertiary amine is triethylenediamine.
7. A polyimide film obtained by applying the varnish according to any one of claims 3 to 6 to a support and heating the same.
8. A process for producing a polyimide film, comprising applying the varnish according to any one of claims 3 to 6 to a support and heating the applied varnish.
9. A polyimide film comprising the polyimide resin according to claim 1 or 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-239648 | 2019-12-27 | ||
| JP2019239648 | 2019-12-27 | ||
| PCT/JP2020/047791 WO2021132197A1 (en) | 2019-12-27 | 2020-12-22 | Polyimide resin, varnish, and polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114867766A CN114867766A (en) | 2022-08-05 |
| CN114867766B true CN114867766B (en) | 2024-07-19 |
Family
ID=76572988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080089527.XA Active CN114867766B (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) | CN114867766B (en) |
| TW (1) | TW202134318A (en) |
| WO (1) | WO2021132197A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20240095412A (en) * | 2021-11-11 | 2024-06-25 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyimide resin, varnish and polyimide film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11282157A (en) * | 1997-10-31 | 1999-10-15 | Nippon Zeon Co Ltd | Polymide type photosensitive composition |
| JP2005232383A (en) | 2004-02-20 | 2005-09-02 | Asahi Kasei Electronics Co Ltd | Polyamic acid derivative |
| TWI523913B (en) | 2012-12-21 | 2016-03-01 | Asahi Kasei E Materials Corp | A polyimide precursor and a resin composition containing the same |
| JP7011231B2 (en) * | 2016-11-24 | 2022-01-26 | 日産化学株式会社 | Composition for forming a flexible device substrate |
| CN113227206B (en) * | 2018-12-28 | 2024-03-08 | 三菱瓦斯化学株式会社 | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film |
-
2020
- 2020-12-22 KR KR1020227021125A patent/KR20220123394A/en active Search and Examination
- 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 CN CN202080089527.XA patent/CN114867766B/en active Active
- 2020-12-23 TW TW109145612A patent/TW202134318A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202134318A (en) | 2021-09-16 |
| KR20220123394A (en) | 2022-09-06 |
| WO2021132197A1 (en) | 2021-07-01 |
| JPWO2021132197A1 (en) | 2021-07-01 |
| CN114867766A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6996609B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| JP7205491B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| CN111902457A (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN111683992A (en) | Polyimide resin composition and polyimide film | |
| WO2020110947A1 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| CN114867767B (en) | Polyimide resin, polyimide varnish and polyimide film | |
| CN114867766B (en) | Polyimide resin, varnish and polyimide film | |
| CN117043229A (en) | Polyimide precursor composition | |
| CN114729122B (en) | Polyimide resin, polyimide varnish and polyimide film | |
| CN115380059B (en) | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film | |
| CN111133034B (en) | Polyimide resin, polyimide 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 | |
| CN115210292B (en) | Polyimide resin, polyimide varnish and polyimide film | |
| CN115038737B (en) | Polyimide resin, polyimide varnish and polyimide film | |
| CN116157463A (en) | Polyimide resin, polyamic acid, varnish and polyimide film | |
| WO2021153379A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| WO2021177145A1 (en) | Polyimide resin, 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |