CN114466902A - Polyimide resin composition, polyimide varnish, and polyimide film - Google Patents
Polyimide resin composition, polyimide varnish, and polyimide film Download PDFInfo
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- CN114466902A CN114466902A CN202080067488.3A CN202080067488A CN114466902A CN 114466902 A CN114466902 A CN 114466902A CN 202080067488 A CN202080067488 A CN 202080067488A CN 114466902 A CN114466902 A CN 114466902A
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- structural unit
- polyimide resin
- mol
- resin composition
- polyimide
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 216
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 130
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 239000002966 varnish Substances 0.000 title claims description 57
- 239000004642 Polyimide Substances 0.000 title claims description 55
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims description 182
- 150000004985 diamines Chemical class 0.000 claims description 46
- 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 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 17
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 11
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 10
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 52
- 239000010408 film Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 22
- -1 rare earth hydroxide Chemical class 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 229920005575 poly(amic acid) Polymers 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 11
- 239000007810 chemical reaction solvent Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 102100031503 Barrier-to-autointegration factor-like protein Human genes 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 101000729827 Homo sapiens Barrier-to-autointegration factor-like protein Proteins 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 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 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000001035 drying Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 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
- 230000000704 physical effect Effects 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 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 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-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
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-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
- 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 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 238000010943 off-gassing Methods 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BEBFJOSPYYGOKL-UHFFFAOYSA-N (3-ethylphenyl)methanamine Chemical compound CCC1=CC=CC(CN)=C1 BEBFJOSPYYGOKL-UHFFFAOYSA-N 0.000 description 1
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- RCNBXBQGBCGTPB-UHFFFAOYSA-N (4-dodecylphenyl)methanamine Chemical compound CCCCCCCCCCCCC1=CC=C(CN)C=C1 RCNBXBQGBCGTPB-UHFFFAOYSA-N 0.000 description 1
- DGAGEFUEKIORSQ-UHFFFAOYSA-N (4-ethylphenyl)methanamine Chemical compound CCC1=CC=C(CN)C=C1 DGAGEFUEKIORSQ-UHFFFAOYSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
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- ASJCSAKCMTWGAH-UHFFFAOYSA-N cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCC1C(O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
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- 239000005453 ketone based solvent Substances 0.000 description 1
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
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- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
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- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
Abstract
A polyimide resin composition comprising: polyimide resin, and rare earth element oxide or rare earth element hydroxide.
Description
Technical Field
The present invention relates to a polyimide resin composition, a polyimide varnish, and a polyimide film.
Background
Polyimide resins have been studied for various uses in the fields of electric/electronic components and the like. For example, for the purpose of weight reduction and flexibility of displays, it is desired to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays with plastic substrates, and studies on polyimide films suitable for the plastic substrates have been advanced. The polyimide film for such applications is required to have colorless transparency.
In an image display device such as a liquid crystal display or an OLED display, a Thin Film Transistor (TFT) is used as a pixel switching element. Polycrystalline silicon (Polysilicon) having excellent crystallinity has a high electron mobility as compared with amorphous silicon, and thus, TFT characteristics are greatly improved. One of methods for forming a polysilicon film is an excimer laser/annealing (ELA) method. The dehydrogenation process of the amorphous silicon in the method is a high-temperature process, and the higher the treatment temperature is, the more the TFT characteristics are improved. Although a high-temperature treatment has been performed on a glass substrate, studies have been made to replace the glass substrate with a plastic substrate, and a high glass transition temperature is required for the plastic substrate in order to form a good-quality polycrystalline silicon film on the plastic substrate. Further, in the dehydrogenation process of amorphous silicon, a high temperature state may be maintained for, for example, about 30 minutes to 60 minutes, and during this time, there is a concern that an organic compound (outgassing) derived from the material of the plastic substrate itself may exert a profound adverse effect on the device. Therefore, it is necessary to suppress the occurrence of outgassing as much as possible even when the plastic substrate is held for a long time in a high temperature region, and extremely high thermal stability (i.e., heat resistance when it is held for a long time at a high temperature) exceeding the conventional level is also required. Further, when light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, an OLED display, a touch panel, or the like), the plastic substrate is required to have high optical isotropy in addition to colorless transparency.
Further, in the manufacturing process of the image display device, there is a case where a high temperature process and a temperature cycle of cooling to room temperature are repeated. Therefore, excellent dimensional stability (i.e., a low linear thermal expansion coefficient) against temperature cycling is also required for the plastic substrate.
The applicant disclosed in patent document 1 a polyimide resin which is excellent in mechanical properties, heat resistance and transparency, and is excellent in dimensional stability against heat and laser peelability.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2019/065523
Disclosure of Invention
Problems to be solved by the invention
As described above, various properties are required for the plastic substrate, but it is not easy to satisfy these properties simultaneously with the polyimide film. In addition, further improvement in high thermal stability (i.e., high thermal decomposition temperature) is required for the polyimide resin.
Accordingly, an object to be solved by the present invention is to provide: a polyimide resin composition capable of forming a film having extremely high heat resistance and thermal stability and having both excellent colorless transparency and optical isotropy, and a polyimide varnish and a polyimide film comprising the polyimide resin composition.
Means for solving the problems
The inventors of the present invention found that: the present inventors have completed the present invention by solving the above problems with a polyimide resin composition containing a specific rare earth oxide or rare earth hydroxide.
That is, the present invention relates to the following <1> to <18 >.
<1> a polyimide resin composition comprising: polyimide resin, and rare earth element oxide or rare earth element hydroxide.
<2> the polyimide resin composition according to <1> above, wherein the rare earth oxide or rare earth hydroxide is at least one selected from the group consisting of cerium oxide, lanthanum oxide, cerium hydroxide and lanthanum hydroxide.
<3> the polyimide resin composition according to <1> or <2>, wherein a total content of the rare earth oxide and the rare earth hydroxide in the polyimide resin composition is 10 to 20000 mass ppm with respect to the polyimide resin.
<4> the polyimide resin composition according to any one of <1> to <3>, wherein the polyimide resin is the following polyimide resin 1: having a structural unit A1 derived from a tetracarboxylic dianhydride and a structural unit B1 derived from a diamine,
the structural unit A1 contains a structural unit (A1-1) derived from a compound represented by the following formula (a1-1),
the structural unit B1 includes a structural unit (B1-1), and the structural unit (B1-1) is at least 1 selected from the group consisting of a structural unit (B1-1-1) derived from a compound represented by the following formula (B1-1-1), a structural unit (B1-1-2) derived from a compound represented by the following formula (B1-1-2), and a structural unit (B1-1-3) derived from a compound represented by the following formula (B1-1-3),
cyclohexane rings are not present in the resin.
(in the formula (b1-1-1), each R is independently a hydrogen atom, a fluorine atom or a methyl group.)
<5> the polyimide resin composition according to <4> above, wherein the ratio of the structural unit (A1-1) in the structural unit A1 is 40 mol% or more.
<6> the polyimide resin composition according to <4> or <5> above, wherein the ratio of the structural unit (B1-1) in the structural unit B1 is 50 mol% or more.
<7> the polyimide resin composition according to any one of <4> to <6>, wherein the structural unit (B1-1) is a structural unit (B1-1-1).
<8> the polyimide resin composition according to any one of <4> to <6>, wherein the structural unit (B1-1) is a structural unit (B1-1-2).
<9> the polyimide resin composition according to any one of <4> to <6>, wherein the structural unit (B1-1) is a structural unit (B1-1-3).
<10> the polyimide resin composition according to any one of <4> to <6> and <9>, wherein the structural unit (B1-1-3) is at least 1 selected from the group consisting of a structural unit (B1-1-31) derived from a compound represented by the following formula (B1-1-31) and a structural unit (B1-1-32) derived from a compound represented by the following formula (B1-1-32).
<11> the polyimide resin composition according to <10> above, wherein the structural unit (B1-1-3) is a structural unit (B1-1-31).
<12> the polyimide resin composition according to any one of <4> to <11>, wherein the structural unit A1 further comprises: a structural unit (A1-2) derived from a compound represented by the following formula (a 1-2).
<13> the polyimide resin composition according to any one of <1> to <3>, wherein the polyimide resin is the following polyimide resin 2: having a structural unit A2 derived from a tetracarboxylic dianhydride and a structural unit B2 derived from a diamine,
the structural unit A2 contains a structural unit (A2-1) derived from a compound represented by the following formula (a2-1) and a structural unit (A2-2) derived from a compound represented by the following formula (a2-2),
the structural unit B2 includes a structural unit (B2-1) derived from a compound represented by the following formula (B2-1).
<14> the polyimide resin composition according to <13> above, wherein the ratio of the structural unit (A2-1) in the structural unit A2 is 40 mol% or more and 95 mol% or less,
the proportion of the structural unit (A2-2) in the structural unit A2 is 5 mol% or more and 60 mol% or less.
<15> the polyimide resin composition according to <13> or <14> above, wherein the ratio of the structural unit (B2-1) in the structural unit B2 is 50 mol% or more.
<16> a polyimide varnish obtained by dissolving the polyimide resin composition according to any one of <1> to <15> in an organic solvent.
<17> a polyimide film comprising the polyimide resin composition according to any one of <1> to <15 >.
<18> the polyimide film according to <17> above, wherein the time for mass reduction of 1% when the film is held at 450 ℃ under nitrogen is 10 minutes or more.
ADVANTAGEOUS EFFECTS OF INVENTION
The polyimide resin composition of the present invention can form a film having extremely high heat resistance and thermal stability and having both excellent colorless transparency and optical isotropy.
Detailed Description
The present invention will be described in detail below. In the present specification, the term "a to B" in the description of numerical values means "a to B inclusive" (in the case of a < B) or "a to B inclusive" (in the case of a > B). In the present invention, a combination of preferred embodiments is a more preferred embodiment.
The aromatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride containing 1 or more aromatic rings, the alicyclic tetracarboxylic dianhydride is a tetracarboxylic dianhydride containing 1 or more alicyclic rings and no aromatic rings, and the aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride containing neither aromatic rings nor alicyclic rings.
The aromatic diamine refers to a diamine containing 1 or more aromatic rings, the alicyclic diamine refers to a diamine containing 1 or more alicyclic rings and no aromatic rings, and the aliphatic diamine refers to a diamine containing neither aromatic rings nor alicyclic rings.
The polyimide resin composition of the present invention comprises: polyimide resin, and rare earth element oxide or rare earth element hydroxide.
< rare earth element oxide or rare earth element hydroxide >
The polyimide resin composition of the present invention contains a rare earth element oxide or a rare earth element hydroxide. The polyimide resin composition of the present invention has extremely high heat resistance and thermal stability by containing a rare earth element oxide or a rare earth element hydroxide. In addition, surprisingly, it has also been found that: by containing a rare earth element oxide or a rare earth element hydroxide, the optical isotropy (Rth) is improved.
As a preferable rare earth oxide, cerium oxide and lanthanum oxide can be exemplified, and cerium oxide, CeO can be exemplified2、Ce2O3. As lanthanum oxide, La can be exemplified2O3. As preferable rare earth element hydroxides, cerium hydroxide and lanthanum hydroxide can be exemplified. As cerium hydroxide, Ce (OH) may be exemplified3、Ce(OH)4. As lanthanum hydroxide, La (OH) can be exemplified3. These substances may be hydrates or anhydrous. The rare earth element oxide or rare earth element hydroxide is preferably: at least one selected from the group consisting of cerium oxide, lanthanum oxide, cerium hydroxide and lanthanum hydroxide.
The total content of the rare earth oxide and the rare earth hydroxide in the polyimide resin composition of the present invention is preferably 10 to 20000 mass ppm, more preferably 100 to 10000 mass ppm, and further preferably 1000 to 7000 mass ppm, based on the polyimide resin. When the amount is within this range, the film can have improved heat resistance and thermal stability, and is also excellent in transparency.
The method of adding the rare earth oxide or the rare earth hydroxide to the polyimide resin is not limited, and for example, the rare earth oxide or the rare earth hydroxide is preferably added to a polyimide resin solution (varnish) after being dispersed in an organic solvent. By this addition method, the dispersibility of the rare earth element oxide or rare earth element hydroxide to the polyimide varnish becomes good. Specifically, it is preferable to prepare a liquid in which a rare earth element oxide or a rare earth element hydroxide is dispersed in an organic solvent so as to have a concentration of 1 to 10% by mass, and to mix the liquid and the polyimide resin dissolved in the organic solvent so as to have a desired composition ratio. The mixing method is preferably as follows: a method of stirring for 0.1 to 3 hours at 10 to 1000rpm using a mixing tank having a stirring blade; a method of stirring for 3 to 10 minutes at 500 to 5000rpm by using a rotation revolution mixer; and the like.
According to the polyimide resin composition of the present invention, a film having extremely high heat resistance and thermal stability and having both excellent colorless transparency and optical isotropy can be formed. Suitable physical property values of the film are as follows. By setting the content in the following range, the film can be suitably used as a film excellent in colorless transparency, heat resistance, thermal stability and optical isotropy.
When a film having a thickness of 10 μm is formed, the total light transmittance is preferably 85% or more, more preferably 86% or more, and still more preferably 87% or more.
When a film having a thickness of 10 μm is formed, the Yellowness Index (YI) is preferably 11 or less, more preferably 9 or less, and still more preferably 8 or less.
The glass transition temperature (Tg) is preferably 420 ℃ or higher, more preferably 430 ℃ or higher, and still more preferably 440 ℃ or higher.
The time for which the mass of the film is reduced by 1% when the film is held at 450 ℃ under nitrogen is preferably 10 minutes or longer, more preferably 15 minutes or longer.
The resin composition of the present invention contains a rare earth element oxide or a rare earth element hydroxide, so that the time for which the film is kept at 450 ℃ under nitrogen to decrease in mass by 1% can be prolonged, and therefore, decomposition of the polyimide resin by heat can be suppressed, and occurrence of degassing can be suppressed even in a high temperature region, thereby providing extremely high thermal stability. Thus, in the process of manufacturing a TFT on a polyimide film, the occurrence of defects due to decomposition of the polyimide resin can be prevented, and the product yield can be improved. Further, surprisingly, the resin composition of the present invention has improved glass transition temperature (Tg) by containing a rare earth element oxide or a rare earth element hydroxide.
When a film having a thickness of 10 μm is formed, the absolute value of the retardation in thickness (Rth) is preferably 200nm or less, more preferably 100nm or less, and still more preferably 50nm or less.
The physical property values in the present invention can be measured specifically by the methods described in examples.
< polyimide resin >
The polyimide resin that can be used in the polyimide resin composition of the present invention may have the following preferred composition, but is not limited thereto.
[ polyimide resin 1]
The polyimide resin 1 which can be used in the polyimide resin composition of the present invention has a structural unit A1 derived from a tetracarboxylic dianhydride and a structural unit B1 derived from a diamine, the structural unit A1 includes a structural unit (A1-1) derived from a compound represented by the following formula (a1-1), the structural unit B1 includes a structural unit (B1-1), and the structural unit (B1-1) is at least 1 selected from the group consisting of a structural unit (B1-1-1) derived from a compound represented by the following formula (B1-1-1), a structural unit (B1-1-2) derived from a compound represented by the following formula (B1-1-2), and a structural unit (B1-1-3) derived from a compound represented by the following formula (B1-1-3), cyclohexane rings were not present in the resin.
(in the formula (b1-1-1), each R is independently a hydrogen atom, a fluorine atom or a methyl group.)
The polyimide resin 1 does not contain a cyclohexane ring, and thus the thermal stability of the film is improved. In addition, while polyimide resin containing a cyclohexane ring generally tends to be excellent in colorless transparency, polyimide resin 1 is excellent in colorless transparency even if it does not contain a cyclohexane ring.
(structural unit A1)
The structural unit a1 contains a structural unit derived from a tetracarboxylic dianhydride in the polyimide resin 1, that is, a structural unit (a1-1) derived from a compound represented by the following formula (a 1-1).
The compound represented by the formula (a1-1) is 9, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride.
The structural unit a1 contains the structural unit (a1-1), and thus the heat resistance, thermal stability, optical isotropy, and dimensional stability against temperature cycling of the film are improved.
The proportion of the structural unit (A1-1) in the structural unit A1 is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio of the structural unit (A1-1) is not particularly limited, i.e., 100 mol%. The structural unit A1 may be composed of only the structural unit (A1-1).
The structural unit A1 may contain a structural unit other than the structural unit (A1-1). However, since the polyimide resin 1 does not have a cyclohexane ring, a structural unit containing a cyclohexane ring is excluded as a structural unit other than the structural unit (a1-1) arbitrarily contained in the structural unit a 1.
The structural unit A1 preferably contains, in addition to the structural unit (A1-1), a structural unit (A1-2) derived from a compound represented by the following formula (a 1-2).
The compound represented by the formula (a1-2) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a1-2s), 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a1-2a), and 2,2 ', 3, 3' -biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a1-2 i).
When a1 includes a structural unit (a1-1) and a structural unit (a1-2), the ratio of the structural unit (a1-1) in the structural unit a1 is preferably 40 to 95 mol%, more preferably 45 to 90 mol%, and still more preferably 45 to 85 mol%, and the ratio of the structural unit (a1-2) in the structural unit a1 is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, and still more preferably 15 to 55 mol%.
The total ratio of the structural units (A1-1) and (A1-2) in the structural unit A1 is preferably 50 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 of the total of the structural units (A1-1) and (A1-2) is not particularly limited, i.e., 100 mol%. The structural unit A1 may be composed of only the structural unit (A1-1) and the structural unit (A1-2).
The structural unit A1 further contains the structural unit (A1-2), whereby the dimensional stability of the film against temperature cycles is improved.
The structural unit other than the structural unit (A1-1) optionally contained in the structural unit A1 is not limited to the structural unit (A1-2). The tetracarboxylic dianhydride providing an arbitrary structural unit is not particularly limited, and aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride and 4, 4' - (hexafluoroisopropylidene) phthalic anhydride (excluding the compound represented by the formula (a 1-1)); alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutane tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride.
The structural unit other than the structural unit (A1-1) optionally contained in the structural unit A1 may be 1 type or 2 or more types.
(structural unit B1)
The structural unit B1 includes a diamine-derived structural unit (B1-1) which is a structural unit (B3556-1) in the polyimide resin 1, and the structural unit (B1-1) is at least 1 selected from the group consisting of a structural unit (B1-1-1) derived from a compound represented by the following formula (B1-1-1), a structural unit (B1-1-2) derived from a compound represented by the following formula (B1-1-2), and a structural unit (B1-1-3) derived from a compound represented by the following formula (B1-1-3).
(in the formula (b1-1-1), each R is independently a hydrogen atom, a fluorine atom or a methyl group.)
In the formula (b1-1-1), R is each independently a hydrogen atom, a fluorine atom, or a methyl group, preferably a hydrogen atom. Examples of the compound represented by the formula (b1-1) include 9, 9-bis (4-aminophenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene and 9, 9-bis (3-methyl-4-aminophenyl) fluorene, and 9, 9-bis (4-aminophenyl) fluorene is preferable.
The compound represented by the formula (b1-1-2) is 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether.
Examples of the compound represented by the formula (b1-1-3) include a compound represented by the following formula (b1-1-31) (i.e., 4,4 '-diaminodiphenyl sulfone) and a compound represented by the following formula (b1-1-32) (i.e., 3, 3' -diaminodiphenyl sulfone).
The structural unit (B1-1-3) is preferably at least 1 selected from the group consisting of a structural unit (B1-1-31) derived from a compound represented by the formula (B1-1-31) and a structural unit (B1-1-32) derived from a compound represented by the formula (B1-1-32).
The structural unit (B1-1-3) may be only the structural unit (B1-1-31), may be only the structural unit (B1-1-32), or may be a combination of the structural unit (B1-1-31) and the structural unit (B1-1-32).
Further, as an embodiment of the polyimide resin 1, there can be mentioned a polyimide resin in which the structural unit B1 does not contain the structural units (B-1 to 32).
The structural unit B1 contains the structural unit (B1-1), and thus the colorless transparency, heat resistance, and thermal stability of the film are improved. Further, when the structural unit (B1-1) is contained as the structural unit (B1-1-1), the heat resistance and the thermal stability are particularly excellent, and the optical isotropy is further excellent.
The structural unit (B1-1) may be only the structural unit (B1-1-1), only the structural unit (B1-1-2) or only the structural unit (B1-1-3).
Further, the structural unit (B1-1) may be a combination of the structural unit (B1-1-1) and the structural unit (B1-1-2), a combination of the structural unit (B1-1-2) and the structural unit (B1-1-3), or a combination of the structural unit (B1-1-1) and the structural unit (B1-1-3).
Further, the structural unit (B1-1) may be a combination of the structural unit (B1-1-1) with the structural unit (B1-1-2) with the structural unit (B1-1-3).
The proportion of the structural unit (B1-1) in the structural unit B1 is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio of the structural unit (B1-1) is not particularly limited, i.e., 100 mol%. The structural unit B1 may be composed of only the structural unit (B1-1).
The structural unit B1 may contain a structural unit other than the structural unit (B1-1). However, since the polyimide resin 1 does not have a cyclohexane ring, a structural unit containing a cyclohexane ring is excluded as a structural unit other than the structural unit (B1-1) arbitrarily contained in the structural unit B1.
The diamine that provides a structural unit other than the structural unit (B1-1) optionally contained in the structural unit B1 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, 2 '-bis (trifluoromethyl) benzidine, 4' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane, 2-bis (4-aminophenyl) hexafluoropropane, 4' -diaminobenzanilide, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, and mixtures thereof, Aromatic diamines such as α, α ' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, N ' -bis (4-aminophenyl) terephthalamide, 4 ' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, and 2, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (excluding compounds represented by the formula (b1-1-1), compounds represented by the formula (b1-1-2), and compounds represented by the formula (b 1-1-3)); an alicyclic diamine; and aliphatic diamines such as ethylenediamine and hexamethylenediamine. Among them, 2' -bis (trifluoromethyl) benzidine is preferable.
The structural unit other than the structural unit (B1-1) optionally contained in the structural unit B1 may be 1 type or 2 or more types.
The number average molecular weight of the polyimide resin 1 is preferably 5000 to 100000 from the viewpoint of the mechanical strength of the polyimide film to be obtained. The number average molecular weight of the polyimide resin can be determined, for example, from a value obtained by conversion to standard polymethyl methacrylate (PMMA) measured by gel permeation chromatography.
The polyimide resin 1 may contain a structure other than a polyimide chain (a structure in which the structural unit a1 and the structural unit B1 are bonded via imide). Examples of the structure other than the polyimide chain that can be contained in the polyimide resin 1 include a structure containing an amide bond.
The polyimide resin 1 preferably contains a polyimide chain (a structure in which the structural unit a1 and the structural unit B1 are bonded via imide) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin 1 is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 99% by mass or more.
[ method for producing polyimide resin 1]
The polyimide resin 1 can be produced by reacting a tetracarboxylic acid component containing a compound that provides the structural unit (A1-1) with a diamine component containing a compound that provides the structural unit (B1-1).
Examples of the compound that can provide the structural unit (A1-1) include compounds represented by the formula (a1-1), but the compound is not limited thereto, and derivatives thereof may be used as long as the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to a tetracarboxylic dianhydride represented by the formula (a1-1) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A1-1), a compound represented by the formula (a1-1) (i.e., dianhydride) is preferable.
The tetracarboxylic acid component preferably contains 40 mol% or more, more preferably 60 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the compound that provides the structural unit (a 1-1). The upper limit of the content of the compound providing the structural unit (A1-1) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may be composed of only the compound providing the structural unit (A1-1).
The tetracarboxylic acid component may contain a compound other than the compound providing the structural unit (A1-1). The tetracarboxylic acid component preferably contains a compound that provides the structural unit (A1-2) in addition to the compound that provides the structural unit (A1-1).
Examples of the compound that can provide the structural unit (A1-2) include compounds represented by the formula (a1-2), but the compound is not limited thereto, and derivatives thereof may be used as long as the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to a tetracarboxylic dianhydride represented by the formula (a1-2) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A1-2), a compound represented by the formula (a1-2) (i.e., dianhydride) is preferable.
When the tetracarboxylic acid component contains a compound that can provide the structural unit (a1-1) and a compound that can provide the structural unit (a1-2), the tetracarboxylic acid component preferably contains 40 to 95 mol%, more preferably 45 to 90 mol%, and still more preferably 45 to 85 mol% of the compound that can provide the structural unit (a1-1), and further preferably contains 5 to 60 mol%, more preferably 10 to 55 mol%, and still more preferably 15 to 55 mol% of the compound that can provide the structural unit (a 1-2).
The tetracarboxylic acid component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the compound that provides the structural unit (A1-1) and the compound that provides the structural unit (A1-2) in total. The upper limit value of the total content of the compound providing the structural unit (A1-1) and the compound providing the structural unit (A1-2) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may be composed of only the compound providing the structural unit (A1-1) and the compound providing the structural unit (A1-2).
The compound other than the compound providing the structural unit (A1-1) optionally contained in the tetracarboxylic acid component is not limited to the compound providing the structural unit (A1-2). Examples of such optional compounds include the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (e.g., tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.).
The tetracarboxylic acid component may contain 1 or 2 or more compounds other than the compound providing the structural unit (A1-1).
As the compound providing the structural unit (B1-1), at least 1 selected from the group consisting of a compound providing the structural unit (B1-1-1), a compound providing the structural unit (B1-1-2), and a compound providing the structural unit (B1-1-3) is used.
Examples of the compound that can provide the structural unit (B1-1-1), the compound that can provide the structural unit (B1-1-2), and the compound that can provide the structural unit (B1-1-3) include, but are not limited to, a compound represented by formula (B1-1-1), a compound represented by formula (B1-1-2), and a compound represented by formula (B1-1-3), and derivatives thereof may be included within a range in which the same structural unit is provided. Examples of the derivative include a diisocyanate corresponding to a diamine represented by the compound represented by the formula (b1-1-1), a diisocyanate corresponding to a diamine represented by the compound represented by the formula (b1-1-2), and a diisocyanate corresponding to a diamine represented by the compound represented by the formula (b 1-1-3). As the compound that provides the structural unit (B1-1-1), the compound that provides the structural unit (B1-1-2), and the compound that provides the structural unit (B1-1-3), a compound represented by the formula (B1-1-1) (i.e., a diamine), a compound represented by the formula (B1-1-2) (i.e., a diamine), and a compound represented by the formula (B1-1-3) (i.e., a diamine) are preferable, respectively.
As the compound that provides the structural unit (B1-1), only the compound that provides the structural unit (B1-1-1), only the compound that provides the structural unit (B1-1-2), or only the compound that provides the structural unit (B1-1-3) may be used.
Further, as the compound which can provide the structural unit (B1-1), a combination of a compound which can provide the structural unit (B1-1-1) and a compound which can provide the structural unit (B1-1-2), a combination of a compound which can provide the structural unit (B1-1-2) and a compound which can provide the structural unit (B1-1-3), or a combination of a compound which can provide the structural unit (B1-1-1) and a compound which can provide the structural unit (B1-1-3) can be used.
Further, as the compound providing the structural unit (B1-1), a combination of a compound providing the structural unit (B1-1-1) and a compound providing the structural unit (B1-1-2) and a compound providing the structural unit (B1-1-3) can be used.
The diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the compound that provides the structural unit (B1-1). The upper limit of the content of the compound providing the structural unit (B1-1) is not particularly limited, i.e., 100 mol%. The diamine component may be composed of only the compound providing the structural unit (B1-1).
The diamine component may contain compounds other than the compound providing the structural unit (B1-1), and examples of the compounds include the above aromatic diamine, alicyclic diamine, and aliphatic diamine, and derivatives thereof (e.g., diisocyanate).
The diamine component may optionally contain 1 or 2 or more compounds other than the compound providing the structural unit (B1-1).
The amount ratio of the tetracarboxylic acid component to the diamine component to be used for producing the polyimide resin 1 is preferably 0.9 to 1.1 mol of the diamine component relative to 1 mol of the tetracarboxylic acid component.
In addition, in the production of the polyimide resin 1, an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. As the blocking agent, monoamines or dicarboxylic acids are preferred. The amount of the end-capping agent to be introduced is preferably 0.0001 to 0.1 mol, and particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. As the blocking agent of the monoamine type, 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 is not particularly limited, and a known method can be used.
Specific examples of the reaction method include the following methods: the method (1) comprises the steps of adding a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor, stirring at room temperature to 80 ℃ for 0.5 to 30 hours, and then heating to perform imidization; a method (2) in which a diamine component and a reaction solvent are charged into a reactor to dissolve them, a tetracarboxylic acid component is charged, and the mixture is stirred at room temperature to 80 ℃ for 0.5 to 30 hours, if necessary, and then heated to carry out an imidization reaction; a method (3) in which a tetracarboxylic acid component, a diamine component and a reaction solvent are charged into a reactor, and immediately heated to effect imidization; and the like.
The reaction solvent used in the production of the polyimide resin may be any solvent which can dissolve the polyimide produced without inhibiting the imidization reaction. Examples thereof include aprotic solvents, phenol solvents, ether solvents, carbonate solvents, and the like.
Specific examples of the aprotic solvent include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1, 3-dimethylimidazolidinone, and tetramethylurea, lactone solvents such as γ -butyrolactone and γ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoramide and hexamethylphosphorous triamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane, ketone solvents such as acetone, cyclohexanone, and methylcyclohexanone, amine solvents such as picoline and pyridine, and ester solvents such as 2-methoxy-1-methylethyl) acetate.
Specific examples of the phenol solvent include phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, 5-xylenol, and the like.
Specific examples of the ether solvent include 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [ 2- (2-methoxyethoxy) ethyl ] ether, tetrahydrofuran, and 1, 4-dioxane.
Specific examples of the carbonate-based solvent include diethyl carbonate, methylethyl carbonate, ethylene carbonate, and propylene carbonate.
Among the above reaction solvents, an amide solvent or a lactone solvent is preferable. The reaction solvent may be used alone or in combination of 2 or more.
In the imidization reaction, it is preferable to carry out the reaction while removing water produced during the production, using a dean-Stark trap apparatus or the like. By performing such an operation, the degree of polymerization and the imidization ratio can be further increased.
In the imidization reaction, a known imidization catalyst can be used. Examples of the imidization catalyst include a base catalyst and an acid catalyst.
Examples of the base catalyst include organic base catalysts such as pyridine, quinoline, isoquinoline, α -picoline, β -picoline, 2, 4-lutidine, 2, 6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N-dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and the like. The imidization catalyst can be used alone or in combination of 2 or more.
Among the above, from the viewpoint of handling properties, it is preferable to use a basic catalyst, more preferable to use an organic basic catalyst, still more preferable to use triethylamine, and particularly preferable to use triethylamine and triethylenediamine in combination.
The temperature of the imidization reaction is preferably 120 to 250 ℃ and more preferably 160 to 200 ℃ from the viewpoints of the reaction rate, the suppression of gelation, and the like. The reaction time is preferably 0.5 to 10 hours after the start of distillation of the product water.
[ polyimide resin 2]
The polyimide resin 2 that can be used in the polyimide resin composition of the present invention has a tetracarboxylic dianhydride-derived structural unit a2 and a diamine-derived structural unit B2, the structural unit a2 includes a structural unit (a2-1) derived from a compound represented by the following formula (a2-1) and a structural unit (a2-2) derived from a compound represented by the following formula (a2-2), and the structural unit B2 includes a structural unit (B2-1) derived from a compound represented by the following formula (B2-1).
(structural unit A2)
The structural unit A2 contains a structural unit derived from a tetracarboxylic dianhydride in the polyimide resin 2, namely, a structural unit (A2-1) derived from a compound represented by the following formula (a2-1) and a structural unit (A2-2) derived from a compound represented by the following formula (a 2-2).
The compound represented by the formula (a2-1) is 9, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride.
The structural unit A2 contains the structural unit (A2-1), and thus the colorless transparency, heat resistance, and thermal stability of the film are improved.
The compound represented by the formula (a2-2) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a2-2s), 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a2-2a), and 2,2 ', 3, 3' -biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a2-2 i).
The structural unit A2 contains the structural unit (A2-2), and thus the heat resistance and thermal stability of the film are improved and the residual stress is reduced.
The proportion of the structural unit (a2-1) in the structural unit a2 is preferably 25 mol% or more, more preferably 30 mol% or more, further preferably 35 mol% or more, particularly preferably 40 mol% or more, and further preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, particularly preferably 80 mol% or less.
The proportion of the structural unit (a2-2) in the structural unit a2 is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and further preferably 75 mol% or less, more preferably 70 mol% or less, further preferably 65 mol% or less, particularly preferably 60 mol% or less.
The total ratio of the structural units (A2-1) and (A2-2) in the structural unit A2 is preferably 50 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 of the total of the structural units (A2-1) and (A2-2) is not particularly limited, i.e., 100 mol%. The structural unit A2 may be composed of only the structural unit (A2-1) and the structural unit (A2-2).
The structural unit A2 may contain structural units other than the structural units (A2-1) and (A2-2). The tetracarboxylic dianhydride providing such a structural unit is not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride and 4, 4' - (hexafluoroisopropylidene) phthalic anhydride (excluding compounds represented by the formula (a2-1) and compounds represented by the formula (a 2-2)); alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, and norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride; and aliphatic tetracarboxylic dianhydrides such as 1,2,3, 4-butanetetracarboxylic dianhydride.
The structural unit contained in any of the structural units A2 other than the structural units (A2-1) and (A2-2) may be 1 type or 2 or more types.
(structural unit B2)
The structural unit B2 contains a diamine-derived structural unit in the polyimide resin 2, that is, a structural unit (B2-1) derived from a compound represented by the following formula (B2-1).
The compound represented by the formula (b2-1) is 2, 2' -bis (trifluoromethyl) benzidine.
By including the structural unit (B2-1) in the structural unit B2, the colorless transparency, heat resistance, and thermal stability of the film are improved, and the residual stress is reduced.
The proportion of the structural unit (B2-1) in the structural unit B2 is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio of the structural unit (B2-1) is not particularly limited, i.e., 100 mol%. The structural unit B2 may be composed of only the structural unit (B2-1).
The structural unit B2 may contain a structural unit other than the structural unit (B2-1). 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 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane, 2-bis (4-aminophenyl) hexafluoropropane, 4 ' -diaminodiphenylsulfone, 4 ' -diaminobenzanilide, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, α ' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, and, Aromatic diamines such as N, N '-bis (4-aminophenyl) terephthalamide, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane and 9, 9-bis (4-aminophenyl) fluorene (excluding the compounds represented by the formula (b 2-1)); alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine. Among them, 9-bis (4-aminophenyl) fluorene is preferable.
The structural unit other than the structural unit (B2-1) optionally contained in the structural unit B2 may be 1 type or 2 or more types.
The number average molecular weight of the polyimide resin 2 is preferably 5000 to 100000 from the viewpoint of the mechanical strength of the polyimide film to be obtained. The number average molecular weight of the polyimide resin can be determined, for example, from a value obtained by conversion to standard polymethyl methacrylate (PMMA) measured by gel permeation chromatography.
The polyimide resin 2 may contain a structure other than a polyimide chain (a structure in which the structural unit a2 and the structural unit B2 are bonded via imide). Examples of the structure other than the polyimide chain that can be contained in the polyimide resin include a structure containing an amide bond.
The polyimide resin 2 preferably contains a polyimide chain (a structure in which the structural unit a2 and the structural unit B2 are bonded via imide) as a main structure. Therefore, the ratio of the polyimide chain in the polyimide resin 2 is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 99% by mass or more.
[ method for producing polyimide resin 2]
The polyimide resin 2 can be produced by reacting a tetracarboxylic acid component containing a compound that provides the structural unit (a2-1) and a compound that provides the structural unit (a2-2) with a diamine component containing a compound that provides the structural unit (B2-1).
Examples of the compound that can provide the structural unit (A2-1) include compounds represented by the formula (a2-1), but the compound is not limited thereto, and derivatives thereof may be used as long as the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to a tetracarboxylic dianhydride represented by the formula (a2-1) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A2-1), a compound represented by the formula (a2-1) (i.e., dianhydride) is preferable.
Similarly, examples of the compound that can provide the structural unit (A2-2) include, but are not limited to, compounds represented by formula (a2-2), and derivatives thereof may be included within the scope that provides the same structural unit. Examples of the derivative include a tetracarboxylic acid corresponding to a tetracarboxylic dianhydride represented by the formula (a2-2) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A2-2), a compound represented by the formula (a2-2) (i.e., dianhydride) is preferable.
The tetracarboxylic acid component preferably contains a compound that provides the structural unit (a2-1) in an amount of 25 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, and particularly preferably 40 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, and particularly preferably 80 mol% or less.
The tetracarboxylic acid component preferably contains a compound that provides the structural unit (a2-2) in an amount of 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and particularly preferably 20 mol% or more, and also preferably 75 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, and particularly preferably 60 mol% or less.
The tetracarboxylic acid component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the compound that provides the structural unit (A2-1) and the compound that provides the structural unit (A2-2) in total. The upper limit value of the total content of the compound providing the structural unit (A2-1) and the compound providing the structural unit (A2-2) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may be composed of only the compound providing the structural unit (A2-1) and the compound providing the structural unit (A2-2).
The tetracarboxylic acid component may contain compounds other than the compound providing the structural unit (a2-1) and the compound providing the structural unit (a2-2), and examples of the compounds include the aromatic tetracarboxylic acid dianhydride, the alicyclic tetracarboxylic acid dianhydride, and the aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, and the like).
The tetracarboxylic acid component may contain 1 or 2 or more compounds other than the compound that provides the structural unit (A2-1) and the compound that provides the structural unit (A2-2).
Examples of the compound that can provide the structural unit (B2-1) include compounds represented by the formula (B2-1), but the compound is not limited thereto, and derivatives thereof may be used as long as the same structural unit is provided. Examples of the derivative include diisocyanates corresponding to diamines represented by the formula (b 2-1). As the compound providing the structural unit (B2-1), a compound represented by the formula (B2-1) (i.e., diamine) is preferable.
The diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the compound that provides the structural unit (B2-1). The upper limit of the content of the compound providing the structural unit (B2-1) is not particularly limited, i.e., 100 mol%. The diamine component may be composed of only the compound providing the structural unit (B2-1).
The diamine component may contain compounds other than the compound providing the structural unit (B2-1), and examples of the compounds include the above aromatic diamine, alicyclic diamine, and aliphatic diamine, and derivatives thereof (e.g., diisocyanate).
The diamine component may optionally contain 1 or 2 or more compounds other than the compound providing the structural unit (B2-1).
The amount ratio of the tetracarboxylic acid component to the diamine component to be used for producing the polyimide resin 2 is preferably 0.9 to 1.1 mol of the diamine component relative to 1 mol of the tetracarboxylic acid component.
In addition, in the production of the polyimide resin 2, an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. The blocking agent is the same as the blocking agent that can be used for producing the polyimide resin 1, and the same preferable range is also used.
The method for reacting the tetracarboxylic acid component with the diamine component is not particularly limited, and a known method can be used. As to the specific reaction method, conditions, as described in relation to the production of the polyimide resin 1.
[ polyimide varnish ]
The polyimide varnish of the present invention is obtained by dissolving the polyimide resin composition of the present invention in an organic solvent. That is, the polyimide varnish of the present invention comprises the polyimide resin composition of the present invention and an organic solvent, and the polyimide resin composition is dissolved in the organic solvent.
The organic solvent is not particularly limited as long as it dissolves the polyimide resin composition, and it is preferable to use the above compound alone or in combination of 2 or more as a reaction solvent used for producing the polyimide resin.
The polyimide varnish of the present invention may be one obtained by adding a rare earth oxide or a rare earth hydroxide to a polyimide solution itself obtained by dissolving a polyimide resin obtained by a polymerization method in a reaction solvent, or one obtained by adding a dilution solvent to the polyimide solution and adding a rare earth oxide or a rare earth hydroxide to the polyimide solution.
The polyimide resin composition of the present invention has solvent solubility, and therefore, can form a varnish of a stable high concentration at room temperature. The polyimide varnish of the present invention preferably contains 5 to 40% by mass, more preferably 7 to 30% by mass of the polyimide resin composition of the present invention. The viscosity of the polyimide varnish is preferably 1 to 200 pas, more preferably 2 to 150 pas. The viscosity of the polyimide varnish was measured at 25 ℃ with an E-type viscometer.
The polyimide varnish of the present invention may contain various additives such as inorganic fillers, adhesion promoters, mold release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, antifoaming agents, fluorescent brighteners, crosslinking agents, polymerization initiators, and photosensitizers, as long as the required properties of the polyimide film are not impaired.
The method for producing the polyimide varnish of the present invention is not particularly limited, and a known method can be applied.
[ polyimide film ]
The polyimide film of the present invention comprises the polyimide resin composition of the present invention. Therefore, the polyimide film of the present invention is excellent in colorless transparency, heat resistance, thermal stability, optical isotropy, and dimensional stability against temperature cycle. The polyimide film of the present invention has suitable physical property values as described above.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. Examples thereof include the following: the polyimide varnish of the present invention is coated on a smooth support such as a glass plate, a metal plate, or plastic; or after molding into a film form, the organic solvent such as the reaction solvent and the diluting solvent contained in the varnish is removed by heating. If necessary, a release agent may be applied to the surface of the support in advance.
As a method for removing the organic solvent contained in the varnish by heating, the following method is preferable. That is, it is preferable to form a self-supporting film by evaporating an organic solvent at a temperature of 120 ℃ or lower, and then dry the film at a temperature of the boiling point of the organic solvent to be used or higher, thereby producing a polyimide film. Further, it is preferable to perform drying under a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure, or increased pressure. The heating temperature for drying the self-supporting film to produce the polyimide film is not particularly limited, but is preferably 200 to 480 ℃, more preferably 300 to 470 ℃, and particularly preferably 400 to 450 ℃. When the amount is in this range, the heat resistance of the film is improved. Further, the self-supporting film may be peeled off from the support, and the end of the self-supporting film may be fixed and dried.
The polyimide film of the present invention can also be produced using a polyamic acid varnish in which a polyamic acid is dissolved in an organic solvent.
The polyamic acid contained in the polyamic acid varnish is a precursor of the polyimide resin of the present invention, that is, a product of addition polymerization of a tetracarboxylic acid component containing a compound providing the structural unit (A-1) and a diamine component containing a compound providing the structural unit (B-1). The polyamic acid is imidized (cyclodehydrated) to obtain a polyimide resin of the present invention as a final product.
As the organic solvent contained in the polyamic acid varnish, the organic solvent contained in the polyimide varnish of the present invention can be used.
In the present invention, the polyamic acid varnish may be a polyamic acid solution itself obtained by addition polymerization of a tetracarboxylic acid component containing a compound providing the structural unit (A-1) and a diamine component containing a compound providing the structural unit (B-1) in a reaction solvent, or may be a polyamic acid solution to which a diluting solvent is further added.
The method for producing the polyimide film using the polyamic acid varnish is not particularly limited, and a known method can be used. For example, a polyamic acid varnish is applied to a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, an organic solvent such as a reaction solvent or a diluting solvent contained in the varnish is removed by heating to obtain a polyamic acid film, and the polyamic acid in the polyamic acid film is imidized by heating to produce a polyimide film.
The heating temperature for drying the polyamic acid varnish to obtain a polyamic acid film is preferably 50 to 120 ℃. The heating temperature for imidizing the polyamic acid by heating is preferably 200 to 450 ℃.
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, etc., and is preferably in the range of 1 to 250. mu.m, more preferably 5 to 100. mu.m, and further preferably 10 to 80 μm. The thickness is 1 to 250 μm, and the film can be practically used as a self-supporting film.
The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide varnish.
The polyimide film of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor components, and optical members. The polyimide film of the present invention is particularly suitable for use as a substrate for an image display device such as a liquid crystal display or an OLED display.
Examples
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
The solid content concentration of the polyimide varnish and the physical properties of the polyimide film obtained in the examples and comparative examples were measured by the following methods.
(1) Concentration of solid component
The solid content concentration of the polyimide varnish was measured as follows: the sample was heated at 320 ℃ for 120 minutes in a small electric furnace "MMF-1" manufactured by AS ONE Corporation, and the mass difference between the sample before and after heating was calculated.
(2) Thickness of film
The film thickness was measured using a micrometer manufactured by Mitutoyo co.
(3) Total light transmittance, Yellow Index (YI)
Total light transmittance and YI were measured in accordance with JIS K7361-1: 1997. measured by a color/turbidity simultaneous measuring instrument "COH 400" manufactured by Nippon Denshoku industries Co., Ltd.
(4)L*、a*、b*
L*、a*、b*According to JIS Z8781: 2013. measured by a color/turbidity simultaneous measuring instrument "COH 7700" manufactured by Nippon Denshoku industries Co., Ltd.
(5) Thickness phase difference (Rth)
The thickness retardation (Rth) was measured by an ellipsometer "M-220" manufactured by Nippon spectral Co., Ltd. The determination is as follows: the thickness retardation value was measured at a wavelength of 590 nm. When nx is the maximum in-plane refractive index of the polyimide film, ny is the minimum in-plane refractive index, nz is the refractive index in the thickness direction, and d is the thickness of the film, Rth is expressed by the following formula.
Rth＝[{(nx+ny)/2}-nz]×d
(6) Glass transition temperature (Tg)
The temperature was raised to a temperature sufficient to eliminate the residual stress in a tensile mode under the conditions of a specimen size of 2mm × 20mm, a load of 0.1N, and a temperature raising rate of 10 ℃/minute by using a thermomechanical analysis apparatus "TMA/SS 6100" manufactured by High-Tech Science Corporation, and the residual stress was eliminated, followed by cooling to room temperature. Thereafter, the elongation of the test piece was measured under the same conditions as the treatment for eliminating the residual stress, and the inflection point where the elongation was observed was determined as the glass transition temperature.
(7) The time required for 1% weight loss when held at 450 DEG C
The time required for the weight loss of 1% when the sample was held at 450 ℃ was measured by using a differential thermal-thermogravimetric simultaneous measurement apparatus "DTG-60" manufactured by Shimadzu corporation. First, the sample was heated from 40 ℃ to 450 ℃ at a heating rate of 20 ℃/min under nitrogen and held at that temperature. The mass at the time of 450 ℃ was defined as the reference, and the time until the mass was reduced by 1% was defined as the time required for the mass to be reduced by 1% when the sample was held at 450 ℃.
The tetracarboxylic acid component and the diamine component used in the synthesis examples, and comparative examples, and their abbreviations are as follows. In addition, the rare earth element oxide or rare earth element hydroxide used in the examples is as described below.
< tetracarboxylic acid component >
BPAF: 9, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.; Compound represented by formula (a1-1) or (a 2-1))
BPDA: 3,3 ', 4, 4' -Biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation; a compound represented by the formula (a1-2) or (a 2-2))
HPMDA: 1,2,4, 5-Cyclohexanetetracarboxylic dianhydride (Mitsubishi gas chemical Co., Ltd.)
< diamine component >
BAFL: 9, 9-bis (4-aminophenyl) fluorene (a compound represented by the formula (b1-1-1, manufactured by Taoka chemical Co., Ltd.))
6 FODA: 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether (ChinaTech (Tianjin) Chemical Co., Ltd.; Compound represented by the formula (b 1-1-2))
4, 4-DDS: 4, 4' -diaminodiphenyl sulfone (available from Hill Seiko Kogyo Co., Ltd.; Compound represented by the formula (b 1-1-3))
TFMB: 2, 2' -bis (trifluoromethyl) benzidine (manufactured by Harris Hill Seiki Kogyo Co., Ltd.; Compound represented by the formula (b 2-1))
< rare earth element oxide or rare earth element hydroxide >
Cerium oxide: use of CeO as CAS No. 1306-38-32(cerium (IV) oxide).
Lanthanum oxide: use of La as CAS number 1312-81-82O3(lanthanum (III) oxide).
Cerium hydroxide: use of Ce (OH) as CAS No. 23322-64-74·nH2O (cerium (IV) hydroxide n hydrate).
Lanthanum hydroxide: use La (OH) as CAS number 14507-19-83(lanthanum (III) hydroxide).
< others >
NMP: n-methylpyrrolidone (manufactured by Mitsubishi Chemical Corporation)
GBL: gamma-butyrolactone (manufactured by Mitsubishi Chemical Corporation)
TEA: triethylamine (manufactured by Kanto chemical Co., Ltd.)
Synthesis example 1
34.845g (0.100 mol) of BAFL and 98.826g of NMP were put into a 1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a dean-Stark trap, a thermometer, and a glass end cap, and stirred at a temperature of 70 ℃ in the system and a nitrogen atmosphere at a rotation speed of 150rpm to obtain a solution.
To this solution, 45.843g (0.100 mol) of BPAF and 24.206g of NMP were added simultaneously, and then 0.506g of TEA as an imidization catalyst was charged and heated in a hood heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted with an increase in viscosity, and the reaction system was refluxed for 3 hours while maintaining the temperature at 190 ℃.
Thereafter, 572.724g of NMP was added to cool the temperature in the reaction system to 120 ℃ and then the mixture was stirred for about 3 hours to homogenize the mixture, thereby obtaining a polyimide varnish having a solid content of 10.0 mass%.
Synthesis example 2
A polyimide varnish was prepared in the same manner as in Synthesis example 1 except that 34.845g (0.100 mol) of BAFL was changed to 33.620g (0.100 mol) of 6FODA, and a polyimide varnish having a solid content of 10.0 mass% was obtained.
Synthesis example 3
A polyimide varnish was prepared in the same manner as in Synthesis example 1 except that 34.845g (0.100 mol) of BAFL was changed to 24.830g (0.100 mol) of 4,4-DDS, and a polyimide varnish having a solid content of 10.0 mass% was obtained.
Synthesis example 4
A polyimide varnish was prepared in the same manner as in Synthesis example 1 except that the amount of BPAF was changed from 45.843g (0.100 mol) to 36.674g (0.080 mol), and 4.884g (0.020 mol) of BPDA was added, thereby obtaining a polyimide varnish having a solid content of 10.0 mass%.
Synthesis example 5
34.545g (0.100 mol) of BAFL and 107.861g of NMP were put into a 1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a dean-Stark trap, a thermometer, and a glass end cap, and stirred at a temperature of 70 ℃ in the system and a nitrogen atmosphere at a rotation speed of 150rpm to obtain a solution.
To this solution, 22.922g (0.050 mol) of BPAF, 14.711g (0.050 mol) of BPDA and 26.920g of NMP were added simultaneously, and then 0.506g of TEA as an imidization catalyst was charged and heated in a hood heater to raise the temperature in the reaction system to 180 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted with an increase in viscosity, and the reaction temperature was maintained at 180 ℃ and the reflux was carried out for 3 hours.
Thereafter, 485.260g of NMP was added to cool the temperature in the reaction system to 120 ℃ and then the mixture was stirred for about 3 hours to homogenize the mixture, thereby obtaining a polyimide varnish having a solid content of 10.0 mass%.
Synthesis example 6
A1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a dean-Stark trap, a thermometer, and a glass end cap was charged with 17.423g (0.050 mole) of BAFL, 16.012g (0.050 mole) of TFMB, and 132.854g of GBL, and the mixture was stirred at a system internal temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 150rpm to obtain a solution.
To this solution, 22.922g (0.050 mol) of BPAF, 14.711g (0.050 mol) of BPDA and 33.213g of GBL were added simultaneously, and then 0.506g of TEA as an imidization catalyst was charged and heated in a hood heater to raise the temperature in the reaction system to 180 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted with an increase in viscosity, and the reaction temperature was maintained at 180 ℃ and the reflux was carried out for 3 hours.
Thereafter, 442.042g of GBL was added thereto, the temperature in the reaction system was cooled to 120 ℃, and then the mixture was stirred for about 3 hours to obtain a polyimide varnish having a solid content of 10.0 mass%.
Synthesis example 7
32.024g (0.100 mol) of TFMB and 89.499g of NMP were put into a 1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a condenser tube, a dean-Stark trap, a thermometer, and a glass end cap, and stirred at a temperature of 70 ℃ in the system and a nitrogen atmosphere at a rotation speed of 150rpm to obtain a solution.
To this solution, 36.674g (0.080 mol) of BPAF, 5.884g (0.020 mol) of BPDA and 22.375g of NMP were added simultaneously, and then 0.506g of TEA as an imidization catalyst was charged and heated in a hood heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted with an increase in viscosity, and the reaction system was refluxed for 3 hours while maintaining the temperature at 190 ℃.
Thereafter, 526.935g of GBL was added thereto, the temperature in the reaction system was cooled to 120 ℃, and then the mixture was stirred for about 3 hours to obtain a polyimide varnish having a solid content of 10.0 mass%.
Synthesis example 8
A polyimide varnish was prepared in the same manner as in synthesis example 7 except that the amounts of BPAF and BPDA were changed from 36.674g (0.080 mol) to 27.506g (0.060 mol) and 5.884g (0.020 mol) to 11.769g (0.040 mol), respectively, to obtain a polyimide varnish having a solid content of 10.0 mass%.
Synthesis example 9
A polyimide varnish was prepared in the same manner as in synthesis example 7 except that the amounts of BPAF and BPDA were changed from 36.674g (0.080 mol) to 18.337g (0.040 mol) and 5.884g (0.020 mol) and 17.653g (0.060 mol), respectively, and the diluted solution obtained after the reaction for 3 hours was changed from GBL to NMP, thereby obtaining a polyimide varnish having a solid content of 10.0 mass%.
[ Table 1]
TABLE 1
Example 1
A liquid in which cerium hydroxide was dispersed so as to have a concentration of 1 mass% with respect to NMP was prepared and added to the polyimide varnish obtained in synthesis example 5. At this time, cerium hydroxide was added so that the concentration thereof was 5000 ppm by mass based on the polyimide component in the polyimide varnish. The resultant was stirred and mixed at 2000rpm for 3 minutes using a revolution and rotation mixer to obtain a varnish containing the polyimide resin composition.
The resulting varnish was applied to a glass plate, and the plate was 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 to evaporate the solvent, thereby obtaining a film.
Examples 2 to 5
A thin film was obtained in the same manner as in example 1 except that in example 1, the amount of cerium hydroxide was changed to the amount of the rare earth oxide or the rare earth hydroxide shown in table 2.
Comparative example 1
A thin film was obtained in the same manner as in example 1, except that cerium hydroxide was not added in example 1.
Example 6
A liquid in which lanthanum hydroxide was dispersed so as to have a concentration of 1 mass% relative to GBL was prepared and added to the polyimide varnish obtained in synthesis example 6. At this time, lanthanum hydroxide was added so that the concentration thereof was 3000 ppm by mass based on the polyimide component in the polyimide varnish. The resultant was stirred and mixed at 2000rpm for 3 minutes using a revolution and rotation mixer to obtain a varnish containing the polyimide resin composition.
The resulting varnish was applied to a glass plate, and the plate was 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 to evaporate the solvent, thereby obtaining a film.
Example 7
A thin film was obtained in the same manner as in example 6, except that the amount of lanthanum hydroxide in example 6 was changed to 5000 ppm by mass.
Comparative example 2
A thin film was obtained in the same manner as in example 6, except that lanthanum hydroxide was not added in example 6.
The evaluation results of the films obtained in examples and comparative examples are shown in table 2.
[ Table 2]
As is clear from the results in table 2: by adding rare earth element oxide or rare earth element hydroxide, the time for the mass reduction of 1% when the film is kept at 450 ℃ under nitrogen can be prolonged. This indicates that: decomposition of the polyimide resin due to heat can be suppressed, and occurrence of degassing can be suppressed even in a high-temperature region, thereby providing extremely high thermal stability. In addition, it can be seen that: by adding a rare earth element oxide or a rare earth element hydroxide, Rth is decreased and optical isotropy is improved. It is also found that the addition of the rare earth element oxide or the rare earth element hydroxide does not adversely affect the optical properties of the thin film.
Therefore, the polyimide resin composition of the present invention can form a film having extremely high heat resistance and thermal stability and having both excellent colorless transparency and optical isotropy.
Although only the polyimide varnish obtained in synthesis examples 5 and 6 was tested, other polyimide varnishes also showed the same tendency, and by adding a rare earth element oxide or a rare earth element hydroxide, a film having extremely high heat resistance and thermal stability and having both excellent colorless transparency and optical isotropy can be formed.
Claims (18)
1. A polyimide resin composition comprising: polyimide resin, and rare earth element oxide or rare earth element hydroxide.
2. The polyimide resin composition according to claim 1, wherein the rare earth element oxide or rare earth element hydroxide is at least one selected from the group consisting of cerium oxide, lanthanum oxide, cerium hydroxide, and lanthanum hydroxide.
3. The polyimide resin composition according to claim 1 or 2, wherein a total content of the rare earth element oxide and the rare earth element hydroxide in the polyimide resin composition is 10 to 20000 mass ppm with respect to the polyimide resin.
4. The polyimide resin composition according to any one of claims 1 to 3, wherein the polyimide resin is the following polyimide resin 1: having a structural unit A1 derived from a tetracarboxylic dianhydride and a structural unit B1 derived from a diamine,
the structural unit A1 contains a structural unit (A1-1) derived from a compound represented by the following formula (a1-1),
the structural unit B1 includes a structural unit (B1-1), and the structural unit (B1-1) is at least 1 selected from the group consisting of a structural unit (B1-1-1) derived from a compound represented by the following formula (B1-1-1), a structural unit (B1-1-2) derived from a compound represented by the following formula (B1-1-2), and a structural unit (B1-1-3) derived from a compound represented by the following formula (B1-1-3),
the absence of a cyclohexane ring in the resin,
in the formula (b1-1-1), R is each independently a hydrogen atom, a fluorine atom or a methyl group.
5. The polyimide resin composition according to claim 4, wherein the proportion of the structural unit (A1-1) in the structural unit A1 is 40 mol% or more.
6. The polyimide resin composition according to claim 4 or 5, wherein the proportion of the structural unit (B1-1) in the structural unit B1 is 50 mol% or more.
7. The polyimide resin composition according to any one of claims 4 to 6, wherein the structural unit (B1-1) is a structural unit (B1-1-1).
8. The polyimide resin composition according to any one of claims 4 to 6, wherein the structural unit (B1-1) is a structural unit (B1-1-2).
9. The polyimide resin composition according to any one of claims 4 to 6, wherein the structural unit (B1-1) is a structural unit (B1-1-3).
10. The polyimide resin composition according to any one of claims 4 to 6 and 9, wherein the structural unit (B1-1-3) is at least 1 selected from the group consisting of a structural unit (B1-1-31) derived from a compound represented by the following formula (B1-1-31) and a structural unit (B1-1-32) derived from a compound represented by the following formula (B1-1-32),
11. the polyimide resin composition according to claim 10, wherein the structural unit (B1-1-3) is a structural unit (B1-1-31).
12. The polyimide resin composition according to any one of claims 4 to 11, wherein the structural unit a1 further comprises: a structural unit (A1-2) derived from a compound represented by the following formula (a1-2),
13. the polyimide resin composition according to any one of claims 1 to 3, wherein the polyimide resin is the following polyimide resin 2: having a structural unit A2 derived from a tetracarboxylic dianhydride and a structural unit B2 derived from a diamine,
the structural unit A2 contains a structural unit (A2-1) derived from a compound represented by the following formula (a2-1) and a structural unit (A2-2) derived from a compound represented by the following formula (a2-2),
the structural unit B2 contains a structural unit (B2-1) derived from a compound represented by the following formula (B2-1),
14. the polyimide resin composition according to claim 13, wherein a ratio of the structural unit (A2-1) in the structural unit A2 is 40 mol% or more and 95 mol% or less,
the proportion of the structural unit (A2-2) in the structural unit A2 is 5 mol% or more and 60 mol% or less.
15. The polyimide resin composition according to claim 13 or 14, wherein the proportion of the structural unit (B2-1) in the structural unit B2 is 50 mol% or more.
16. A polyimide varnish prepared by dissolving the polyimide resin composition according to any one of claims 1 to 15 in an organic solvent.
17. A polyimide film comprising the polyimide resin composition according to any one of claims 1 to 15.
18. The polyimide film according to claim 17, wherein the time for which the film is reduced in mass by 1% when held at 450 ℃ under nitrogen is 10 minutes or more.
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| JP2019-179782 | 2019-09-30 | ||
| JP2019179782 | 2019-09-30 | ||
| PCT/JP2020/035061 WO2021065509A1 (en) | 2019-09-30 | 2020-09-16 | Polyimide resin composition, polyimide varnish, polyimide film |
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| KR (1) | KR20220075327A (en) |
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| KR20220075327A (en) | 2022-06-08 |
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