CN113166413A - Polyimide resin composition and polyimide film - Google Patents
Polyimide resin composition and polyimide film Download PDFInfo
- Publication number
- CN113166413A CN113166413A CN201980080632.4A CN201980080632A CN113166413A CN 113166413 A CN113166413 A CN 113166413A CN 201980080632 A CN201980080632 A CN 201980080632A CN 113166413 A CN113166413 A CN 113166413A
- Authority
- CN
- China
- Prior art keywords
- structural unit
- polyimide resin
- mol
- polyimide
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 235
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 139
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 150000001875 compounds Chemical class 0.000 claims abstract description 125
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 61
- 150000004985 diamines Chemical class 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 27
- 125000002971 oxazolyl group Chemical group 0.000 claims abstract description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 17
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 15
- 239000002966 varnish Substances 0.000 claims description 60
- 239000000126 substance Substances 0.000 claims description 53
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical group O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 66
- 239000004642 Polyimide Substances 0.000 description 55
- 239000002904 solvent Substances 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 41
- 239000000243 solution Substances 0.000 description 41
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 29
- 239000011521 glass Substances 0.000 description 23
- 238000004140 cleaning Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 17
- -1 3 ' Chemical compound 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 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 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 description 10
- 150000002596 lactones Chemical class 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 239000007810 chemical reaction solvent Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 5
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 4
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 4
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 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
- ZZMBONADFMYLJG-UHFFFAOYSA-N 3-silyloxysilyloxysilylpropan-1-amine Chemical compound NCCC[SiH2]O[SiH2]O[SiH3] ZZMBONADFMYLJG-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical group C1CN=CO1 IMSODMZESSGVBE-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
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- APZQJHBPRHHRBX-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)NC1=CC=C(N)C=C1 APZQJHBPRHHRBX-UHFFFAOYSA-N 0.000 description 2
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003660 carbonate based solvent Substances 0.000 description 2
- 239000000470 constituent Substances 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BEBFJOSPYYGOKL-UHFFFAOYSA-N (3-ethylphenyl)methanamine Chemical compound CCC1=CC=CC(CN)=C1 BEBFJOSPYYGOKL-UHFFFAOYSA-N 0.000 description 1
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 description 1
- 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
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
-
- 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
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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
- 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
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- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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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Abstract
The present invention provides a polyimide resin composition comprising a polyimide resin and a crosslinking agent having at least 2 oxazole groups, the polyimide resin having: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A comprising: a structural unit (A-1) derived from a compound represented by the following formula (a-1), structural unit B comprising: a structural unit (B-1) derived from a compound represented by the following formula (B-1), a structural unit (B-2) derived from a compound represented by the following formula (B-2), and a structural unit derived from a compound represented by the following formula(B-3) wherein the polyimide resin in the polyimide resin composition is crosslinked with the crosslinking agent. (in the formula (b-1), X is a single bond or a specific group, p is an integer of 0 to 2, m1 is an integer of 0 to 4, m2 is an integer of 0 to 4; in the formula (b-2), R is an integer of 0 to 41～R4Each independently a monovalent aliphatic group or a monovalent aromatic group, Z1And Z2Each independently is a divalent aliphatic group or a divalent aromatic group, and r is a positive integer. )
Description
Technical Field
The present invention relates to a polyimide resin composition and a polyimide film.
Background
Polyimide resins have excellent mechanical properties and heat resistance, and therefore, various applications have been studied in the fields of electric/electronic components and the like. For example, for the purpose of weight reduction and flexibility of devices, it is desired to replace a plastic substrate with a glass substrate used in an image display device such as a liquid crystal display and an OLED display, and research into a polyimide film suitable for the plastic substrate has been advanced. The polyimide film for such applications is required to have colorless transparency.
As a polyimide film suitable for the above-mentioned applications, a polyimide film produced by adding a crosslinking agent to a polyimide resin has been proposed. Patent document 1 discloses a polyimide resin composition containing a polyimide resin having a carboxyl group and a crosslinking agent having at least 2 oxazole groups, and describes that a film having good transparency and high hardness can be formed from the polyimide resin composition.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-222797
Disclosure of Invention
Problems to be solved by the invention
In an image display device, when light emitted from a display element is emitted through a plastic substrate, the plastic substrate is required to have colorless transparency, and when light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, a touch panel, or the like), not only colorless transparency but also high optical isotropy is required. However, patent document 1 does not describe any optical isotropy.
Further, chemical resistance (solvent resistance and acid resistance) is also required for the polyimide film to be suitable as a substrate. For example, when a varnish for forming a resin layer is applied to a polyimide film in order to form another resin layer (for example, a color filter or a resist layer) on the polyimide film, the polyimide film is required to have resistance to a solvent contained in the varnish. If the solvent resistance of the polyimide film is insufficient, the film may be dissolved or swollen, thereby losing its significance as a substrate.
In addition, when a polyimide film is used as a substrate for forming an ITO (Indium Tin Oxide) film, the polyimide film is required to have resistance to an acid used for etching the ITO film. If the acid resistance of the polyimide film is insufficient, the film may be yellowed and the colorless transparency may be impaired.
In patent document 1, the resistance to a solvent (N, N-dimethylacetamide) is evaluated, but the acid resistance is not evaluated.
In addition, a polyimide resin composition containing a polyimide resin and a crosslinking agent is sometimes gelled by crosslinking even when stored at normal temperature by a combination of the polyimide resin and the crosslinking agent, and in such a case, it is not suitable for long-term storage.
Further, the solubility of the polyimide resin composition in a cleaning liquid (for example, "OK 73 thinker" manufactured by tokyo chemical industries co., ltd.) used for pipes and apparatuses used for coating the polyimide resin composition or the like is also required. If the solubility in the cleaning liquid is low, there is a fear that cleaning of piping and equipment using the cleaning liquid becomes insufficient.
Patent document 1 does not describe any storage stability and cleaning property of the polyimide resin composition.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide: a polyimide resin composition which can form a film having excellent colorless transparency, optical isotropy, and chemical resistance (solvent resistance and acid resistance) and has excellent storage stability and cleaning properties; and providing: the polyimide resin in the polyimide resin composition is a polyimide film obtained by crosslinking a polyimide resin with a crosslinking agent.
Means for solving the problems
The inventors of the present invention found that: the present inventors have found that the above problems can be solved by a polyimide resin composition comprising a polyimide resin containing a combination of specific structural units and a specific crosslinking agent, and have completed the present invention.
That is, the present invention relates to the following [1] to [11 ].
[1]
A polyimide resin composition comprising a polyimide resin and a crosslinking agent having at least 2 oxazole groups,
the polyimide resin has: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises: a structural unit (A-1) derived from a compound represented by the following formula (a-1),
the structural unit B includes: a structural unit (B-1) derived from a compound represented by the following formula (B-1), a structural unit (B-2) derived from a compound represented by the following formula (B-2), and a structural unit (B-3) derived from a compound represented by the following formula (B-3).
(in the formula (b-1),
x is a single bond, a substituted or unsubstituted alkylene group, a carbonyl group, an ether group, a group represented by the following formula (b-1-i), or a group represented by the following formula (b-1-ii),
p is an integer of 0 to 2,
m1 is an integer of 0 to 4,
m2 is an integer of 0 to 4,
[ in the formula (b-1-i), m3 is an integer of 0 to 5, and in the formula (b-1-ii), m4 is an integer of 0 to 5. ]
Wherein the content of the first and second substances,
m1+ m2+ m3+ m4 is 1 or more,
when p is 0, m1 is an integer of 1 to 4,
when p is 2, 2X and 2m 2-m 4 are independently selected;
in the formula (b-2),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic group,
Z1and Z2Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
[2]
The polyimide resin composition according to [1], wherein the structural unit (B-1) is a structural unit (B-11) derived from a compound represented by the following formula (B-11).
[3]
The polyimide resin composition according to the above [1] or [2], wherein the crosslinking agent is: a compound comprising an aromatic ring or an aromatic heterocycle to which at least 2 oxazolyl groups are bonded.
[4]
The polyimide resin composition according to the above [3], wherein the crosslinking agent is: a compound comprising a benzene ring to which at least 2 oxazolyl groups are bonded.
[5]
The polyimide resin composition according to the above [4], wherein the crosslinking agent is 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene.
[6]
The polyimide resin composition according to any one of the above [1] to [5], wherein the proportion of the structural unit (A-1) in the structural unit A is 50 mol% or more.
[7]
The polyimide resin composition according to any one of the above [1] to [6],
the proportion of the structural unit (B-1) in the structural unit B is 20 to 75 mol%,
the proportion of the structural unit (B-2) in the structural unit B is 1 to 25 mol%,
the proportion of the structural unit (B-3) in the structural unit B is 20 to 75 mol%.
[8]
The polyimide resin composition according to any one of the above [1] to [7], wherein the structural unit A further comprises: a structural unit (A-2) derived from a compound represented by the following formula (a-2).
[9]
The polyimide resin composition according to the above [8], wherein,
the proportion of the structural unit (A-1) in the structural unit A is 50 to 99 mol%,
the proportion of the structural unit (A-2) in the structural unit A is 1 to 50 mol%.
[10]
A polyamide varnish comprising: the polyimide resin composition according to any one of the above [1] to [9], and an organic solvent.
[11]
A polyimide film obtained by crosslinking the polyimide resin in the polyimide resin composition according to any one of the above [1] to [9] with the crosslinking agent.
ADVANTAGEOUS EFFECTS OF INVENTION
The polyimide resin composition of the present invention is excellent in storage stability and cleaning properties, and can form a film excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance and acid resistance).
Detailed Description
[ polyimide resin composition ]
The polyimide resin composition of the present invention comprises a polyimide resin and a crosslinking agent. The polyimide resin and the crosslinking agent in the present invention will be described below.
< polyimide resin >
In the present invention, the polyimide resin has: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A comprising: a structural unit (A-1) derived from a compound represented by the following formula (a-1), structural unit B comprising: a structural unit (B-1) derived from a compound represented by the following formula (B-1), a structural unit (B-2) derived from a compound represented by the following formula (B-2), and a structural unit (B-3) derived from a compound represented by the following formula (B-3).
In the formula (b-1),
x is a single bond, a substituted or unsubstituted alkylene group, a carbonyl group, an ether group, a group represented by the following formula (b-1-i), or a group represented by the following formula (b-1-ii),
p is an integer of 0 to 2,
m1 is an integer of 0 to 4,
m2 is an integer of 0 to 4.
(in the formula (b-1-i), m3 is an integer of 0 to 5, and in the formula (b-1-ii), m4 is an integer of 0 to 5.)
Wherein the content of the first and second substances,
m1+ m2+ m3+ m4 is 1 or more,
when p is 0, m1 is an integer of 1 to 4,
when p is 2, 2X's and 2m 2 to m4 are independently selected.
In the formula (b-2),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic group,
Z1and Z2Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer.
(structural unit A)
The structural unit A is a structural unit derived from a tetracarboxylic dianhydride in a polyimide resin, and comprises a structural unit (A-1) derived from a compound represented by the following formula (a-1).
The compound represented by the formula (a-1) is 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.
By including the structural unit (A-1), the colorless transparency and optical isotropy of the film can be improved.
The proportion of the structural unit (a-1) in the structural unit a is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 85 mol% or more. The upper limit of the ratio of the structural unit (A-1) is not particularly limited, i.e., 100 mol%. The structural unit A may be composed of only the structural unit (A-1).
The structural unit A may contain a structural unit other than the structural unit (A-1). The tetracarboxylic dianhydride which provides such a structural unit is not particularly limited, and examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 9 '-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride (excluding the compound represented by formula (a-1)); and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride.
In the present specification, an aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing 1 or more aromatic rings, an alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing neither aromatic rings nor alicyclic rings.
The number of the constitutional units optionally contained in the constitutional unit A (i.e., the constitutional units other than the constitutional unit (A-1)) may be 1, or 2 or more.
Among the above-mentioned compounds, 4' - (hexafluoroisopropylidene) diphthalic anhydride is preferable as the tetracarboxylic dianhydride providing the structural unit arbitrarily contained in the structural unit a. That is, in the polyimide resin composition according to one embodiment of the present invention, the structural unit A of the polyimide resin further contains a structural unit (A-2) derived from a compound represented by the following formula (a-2).
The structural unit A contains the structural unit (A-2), whereby the optical isotropy of the film can be further improved.
When the structural unit a includes the structural unit (a-1) and the structural unit (a-2), the ratio of the structural unit (a-1) in the structural unit a is preferably 50 to 99 mol%, more preferably 50 to 95 mol%, further preferably 70 to 95 mol%, and particularly preferably 85 to 95 mol%, and the ratio of the structural unit (a-2) in the structural unit a is preferably 1 to 50 mol%, more preferably 5 to 50 mol%, further preferably 5 to 30 mol%, and particularly preferably 5 to 15 mol%.
The ratio of the total of the structural unit (A-1) and the structural unit (A-2) in the structural unit A 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 total of the structural unit (A-1) and the structural unit (A-2) is not particularly limited, i.e., 100 mol%. The structural unit A may be composed of only the structural unit (A-1) and the structural unit (A-2).
(structural unit B)
The structural unit B is a structural unit derived from diamine in the polyimide resin, and includes: a structural unit (B-1) derived from a compound represented by the following formula (B-1), a structural unit (B-2) derived from a compound represented by the following formula (B-2), and a structural unit (B-3) derived from a compound represented by the following formula (B-3).
In the formula (b-1),
x is a single bond, a substituted or unsubstituted alkylene group, a carbonyl group, an ether group, a group represented by the following formula (b-1-i), or a group represented by the following formula (b-1-ii),
p is an integer of 0 to 2,
m1 is an integer of 0 to 4,
m2 is an integer of 0 to 4.
(in the formula (b-1-i), m3 is an integer of 0 to 5, and in the formula (b-1-ii), m4 is an integer of 0 to 5.)
Wherein the content of the first and second substances,
m1+ m2+ m3+ m4 is 1 or more,
when p is 0, m1 is an integer of 1 to 4,
when p is 2, 2X's and 2m 2 to m4 are independently selected.
In the formula (b-2),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic group,
Z1and Z2Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer.
Specific examples of the compound represented by the formula (b-1) include compounds represented by the following formulae (b-11) to (b-17).
Among the above compounds, the compound represented by the formula (b-11) is preferable, and the compound represented by the following formula (b-111), that is, 3, 5-diaminobenzoic acid is more preferable.
The structural unit (B-1) is a structural unit which provides a carboxyl group to the polyimide resin. The polyimide resins have carboxyl groups, and thus the polyimide resins can be crosslinked with each other by a crosslinking agent described later. The structural unit B contains the structural unit (B-1), and thus the chemical resistance of the film can be improved.
R in the formula (b-2)1、R2、R3And R4Each independently represents a monovalent aliphatic group or a monovalent aromatic group, which is optionally substituted with a fluorine atom. Examples of the monovalent aliphatic group include a monovalent saturated hydrocarbon group and a monovalent unsaturated hydrocarbon group. Examples of the monovalent saturated hydrocarbon group include alkyl groups having 1 to 22 carbon atoms, and examples thereof include methyl, ethyl and propyl groups. The monovalent unsaturated hydrocarbon group includes an alkenyl group having 2 to 22 carbon atoms, and examples thereof include an ethenyl group and an propenyl group. Examples of the monovalent aromatic group include aryl groups having 6 to 24 carbon atoms and aralkyl groups. As R1、R2、R3And R4Particularly preferred is a methyl group or a phenyl group.
In addition, Z1And Z2Each independently represents a divalent aliphatic group or a divalent aromatic group, these groups being optionally substituted by fluorine atoms, optionally includingAn oxygen atom. When an oxygen atom is contained as an ether bond, the carbon number shown below refers to all the carbon numbers contained in the aliphatic group or the aromatic group. Examples of the divalent aliphatic group include a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include an alkylene group having 1 to 22 carbon atoms, an alkyleneoxy group, and a saturated hydrocarbon group having an ether bond, examples of the alkylene group include a methylene group, an ethylene group, and a propylene group, and examples of the alkyleneoxy group include a propyleneoxy group and a trimethyleneoxy group. Examples of the divalent unsaturated hydrocarbon group include unsaturated hydrocarbon groups having 2 to 22 carbon atoms, and examples thereof include an ethenylene group, an propenylene group, and an alkylene group having an unsaturated double bond at a terminal. Examples of the divalent aromatic group include a phenylene group having 6 to 24 carbon atoms, a phenylene group substituted with an alkyl group, and an aralkylene group. As Z1And Z2Propylene, phenylene and aralkylene are particularly preferable.
R is a positive integer, preferably an integer of 10 to 10000.
As described above, among the compounds represented by the formula (b-2), the compounds represented by the following formula (b-21) are preferred.
(in the formula (b-21), m and n independently represent an integer of 1 or more, and the sum of m and n is an integer of 10 to 10000.)
The sum (m + n) of m and n is preferably 10 to 1000, more preferably 10 to 500, still more preferably 10 to 100, and further preferably 10 to 50.
The ratio of m/n is preferably 5/95 to 50/50, more preferably 10/90 to 40/60, and further preferably 20/80 to 30/70.
Examples of the compound represented by the formula (b-2) include: 1, 3-bis (3-aminopropyl) -1,1,2, 2-tetramethyldisiloxane, 1, 3-bis (3-aminobutyl) -1,1,2, 2-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1, 3-bis (4-aminophenoxy) tetramethyldisiloxane, 1,3, 3-tetramethyl-1, 3-bis (4-aminophenyl) disiloxane, 1,3, 3-tetraphenoxy-1, 3-bis (2-aminoethyl) disiloxane, 1,3, 3-tetraphenyl-1, 3-bis (3-aminopropyl) disiloxane, 1,1,3, 3-tetramethyl-1, 3-bis (2-aminoethyl) disiloxane, 1,3, 3-tetramethyl-1, 3-bis (3-aminopropyl) disiloxane, 1,3, 3-tetramethyl-1, 3-bis (4-aminobutyl) disiloxane, 1, 3-dimethyl-1, 3-dimethoxy-1, 3-bis (4-aminobutyl) disiloxane, 1,3,3,5, 5-hexamethyl-1, 5-bis (4-aminophenyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (5-aminopentyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (2-aminoethyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (5-aminopentyl) trisiloxane, 1,3,3,5, 5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,3,3,5, 5-hexaethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,3,3,5, 5-hexapropyl-1, 5-bis (3-aminopropyl) trisiloxane and the like. The above compounds may be used alone or in combination of 2 or more.
As the commercially available products of the compound represented by the formula (B-2), X-22-9409, X-22-1660B, X-22-161A, X-22-161B and the like, all available from shin-Etsu chemical Co.
The structural unit B contains the structural unit (B-2), whereby the colorless transparency and optical isotropy of the film and the cleanability of the polyimide resin composition can be improved.
The compound represented by the formula (b-3) is 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether.
The structural unit B contains the structural unit (B-3), whereby the optical isotropy of the film, and the storage stability and the cleaning property of the polyimide resin composition can be improved.
The proportion of the structural unit (B-1) in the structural unit B is preferably 20 to 75 mol%, more preferably 25 to 70 mol%, and still more preferably 30 to 60 mol%.
The proportion of the structural unit (B-2) in the structural unit B is preferably 1 to 25 mol%, more preferably 2 to 20 mol%, and still more preferably 3 to 15 mol%.
The proportion of the structural unit (B-3) in the structural unit B is preferably 20 to 75 mol%, more preferably 25 to 70 mol%, and still more preferably 30 to 60 mol%.
The total ratio of the constituent units (B-1) to (B-3) in the constituent unit B is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio of the total of the structural units (B-1) to (B-3) is not particularly limited, i.e., 100 mol%. The structural unit B may be composed of only the structural unit (B-1), the structural unit (B-2) and the structural unit (B-3).
The structural unit B may contain structural units other than the structural units (B-1) to (B-3). The diamine providing such a structural unit is not particularly limited, and examples thereof include: 1, 4-phenylenediamine, p-xylylenediamine, 1, 5-diaminonaphthalene, 2 '-dimethylbiphenyl-4, 4' -diamine, 2 '-bis (trifluoromethyl) benzidine, 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, N '-bis (4-aminophenyl) terephthalamide, N' -bis (4-aminophenyl) terephthalamide, and mixtures thereof, Aromatic diamines such as 4, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane and 9, 9-bis (4-aminophenyl) fluorene (excluding compounds represented by the formula (b-1), compounds represented by the formula (b-2) and compounds represented by the formula (b-3)); alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine (excluding the compound represented by the formula (b-2)).
In the present specification, an aromatic diamine refers to a diamine containing 1 or more aromatic rings, an alicyclic diamine refers to a diamine containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic diamine refers to a diamine containing neither aromatic rings nor alicyclic rings.
The number of the structural units (i.e., the structural units other than the structural units (B-1) to (B-3)) optionally contained in the structural unit B may be 1, or 2 or more.
In the present invention, the number average molecular weight of the polyimide resin 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 standard polymethyl methacrylate (PMMA) conversion value measured by gel filtration chromatography.
< method for producing polyimide resin >
In the present invention, the polyimide resin can be produced by reacting a tetracarboxylic acid component containing a compound that provides the structural unit (A-1), a diamine component containing a compound that provides the structural unit (B-1), a compound that provides the structural unit (B-2), and a compound that provides the structural unit (B-3).
Examples of the compound that can provide the structural unit (A-1) include compounds represented by the formula (a-1), but the compound is not limited thereto, and derivatives thereof may be used as long as the same structural unit is provided. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1) (i.e., 1,2,4, 5-cyclohexanetetracarboxylic acid) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A-1), a compound represented by the formula (a-1) (i.e., dianhydride) is preferred.
The tetracarboxylic acid component preferably contains 50 mol% or more of the compound that provides the structural unit (a-1), more preferably 70 mol% or more, and still more preferably 85 mol% or more. The upper limit of the content ratio of the compound providing the structural unit (A-1) is not particularly limited, i.e., 100 mol%. The tetracarboxylic acid component may be composed of only the compound providing the structural unit (A-1).
The tetracarboxylic acid component may contain a compound other than the compound providing the structural unit (a-1), and examples of the compound include the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, and the like).
The amount of the compound (i.e., a compound other than the compound providing the structural unit (A-1)) optionally contained in the tetracarboxylic acid component may be 1 kind or 2 or more kinds.
As the compound optionally contained in the tetracarboxylic acid component, a compound providing the structural unit (A-2) is preferable.
Examples of the compound that can provide the structural unit (A-2) include compounds represented by the formula (a-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 the tetracarboxylic dianhydride represented by the formula (a-2) and an alkyl ester of the tetracarboxylic acid. As the compound providing the structural unit (A-2), a compound represented by the formula (a-2) (i.e., dianhydride) is preferred.
When the tetracarboxylic acid component contains the compound that provides the structural unit (A-1) and the compound that provides the structural unit (A-2), the tetracarboxylic acid component preferably contains 50 to 99 mol% of the compound that provides the structural unit (A-1), more preferably 50 to 95 mol%, further preferably 70 to 95 mol%, particularly preferably 85 to 95 mol%, preferably 1 to 50 mol%, more preferably 5 to 50 mol%, further preferably 5 to 30 mol%, and particularly preferably 5 to 15 mol%.
The tetracarboxylic acid component contains preferably 50 mol% or more of the compound that provides the structural unit (A-1) and the compound that provides the structural unit (A-2) in total, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the total content ratio of the compound that provides the structural unit (A-1) and the compound that provides the structural unit (A-2) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may be composed of only the compound which provides the structural unit (A-1) and the compound which provides the structural unit (A-2).
Examples of the compound that can provide the structural unit (B-1), the compound that can provide the structural unit (B-2), and the compound that can provide the structural unit (B-3) include, but are not limited to, compounds represented by the formula (B-1), compounds represented by the formula (B-2), and compounds represented by the formula (B-3), 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 formulae (b-1) to (b-3).
As the compound that provides the structural unit (B-1), the compound that provides the structural unit (B-2), and the compound that provides the structural unit (B-3), a compound represented by the formula (B-1) (i.e., diamine), a compound represented by the formula (B-2) (i.e., diamine), and a compound represented by the formula (B-3) (i.e., diamine) are preferable, respectively.
The diamine component preferably contains 20 to 75 mol% of the compound that provides the structural unit (B-1), more preferably 25 to 70 mol%, and still more preferably 30 to 60 mol%.
The diamine component preferably contains 1 to 25 mol% of a compound that provides the structural unit (B-2), more preferably 2 to 20 mol%, and still more preferably 3 to 15 mol%.
The diamine component preferably contains 20 to 75 mol% of a compound that provides the structural unit (B-3), more preferably 25 to 70 mol%, and still more preferably 30 to 60 mol%.
The diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 99 mol% or more of the total of the compound that provides the structural unit (B-1), the compound that provides the structural unit (B-2), and the compound that provides the structural unit (B-3). The upper limit of the total content ratio of the compound that provides the structural unit (B-1), the compound that provides the structural unit (B-2), and the compound that provides the structural unit (B-3) is not particularly limited, that is, 100 mol%. The diamine component may be composed of only the compound that provides the structural unit (B-1), the compound that provides the structural unit (B-2), and the compound that provides the structural unit (B-3).
The diamine component may contain compounds other than the compound that provides the structural unit (B-1), the compound that provides the structural unit (B-2), and the compound that provides the structural unit (B-3), and examples of the compounds include the aromatic diamine, the alicyclic diamine, and the aliphatic diamine, and derivatives thereof (e.g., diisocyanate).
The number of compounds (i.e., compounds other than the compound which provides the structural unit (B-1), the compound which provides the structural unit (B-2), and the compound which provides the structural unit (B-3)) optionally contained in the diamine component may be 1, or 2 or more.
In the present invention, the amount of the tetracarboxylic acid component and the diamine component to be added to the polyimide resin is preferably 0.9 to 1.1 mol based on 1 mol of the tetracarboxylic acid component.
In the present invention, in order to produce a polyimide resin, an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. As the blocking agent, monoamines or dicarboxylic acids are preferred. The amount of the end-capping agent to be introduced is preferably 0.0001 to 0.1 mol, 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, cyclohexane-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, and the like are recommended. Among them, phthalic acid and phthalic anhydride can be suitably used.
The method for reacting the tetracarboxylic acid component 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: a method (1) in which a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor, stirred at room temperature (about 20 ℃) to 80 ℃ for 0.5 to 30 hours, and then heated to carry out 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 (about 20 ℃) 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 the temperature is immediately raised 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 hexamethylphosphine triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide 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, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and the like. The imidization catalyst can be used alone or in combination of 2 or more.
Among the above, from the viewpoint of handling properties, a base catalyst is preferably used, an organic base catalyst is more preferably used, triethylamine is further preferably used, and a combination of triethylamine and triethylenediamine is particularly preferably used.
The temperature of the imidization reaction is preferably 120 to 250 ℃ and more preferably 160 to 200 ℃ from the viewpoints of the reaction rate, the suppression of gelation, and the like. The reaction time is preferably 0.5 to 10 hours after the start of distilling off the produced water.
< crosslinking agent >
In the present invention, the crosslinking agent has at least 2 oxazolyl groups. That is, the crosslinking agent in the present invention is a polyfunctional oxazoline compound having 2 or more oxazolyl groups (oxazoline rings) in the molecule.
The oxazolyl group is reactive with a carboxyl group, and if the carboxyl group reacts with the oxazolyl group, an amide ester bond is formed as shown below. This reaction is particularly easy to proceed when the reaction is heated to 80 ℃ or higher.
The polyimide resin contained in the polyimide resin composition of the present invention has a carboxyl group, and therefore, if the polyimide resin composition of the present invention is heated, the polyimide resins are crosslinked with each other by means of a crosslinking agent to form a crosslinked polyimide resin. For this reason, the chemical resistance of the film is improved.
The crosslinking agent is not particularly limited as long as it is a polyfunctional oxazoline compound having 2 or more oxazolyl groups in the molecule, and specific examples thereof include 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene, 1, 4-bis (4, 5-dihydro-2-oxazolyl) benzene, 2 '-bis (2-oxazoline), K-2010E, K-2020E, K-2030E manufactured by japan catalyst co., ltd., 2, 6-bis (4-isopropyl-2-oxazolin-2-yl) pyridine, 2, 6-bis (4-phenyl-2-oxazolin-2-yl) pyridine, 2' -isopropylidenebis (4-phenyl-2-oxazoline), 2, 2' -isopropylidenebis (4-tert-butyl-2-oxazoline) and the like.
The crosslinking agent preferably contains a compound having an aromatic ring or an aromatic heterocyclic ring to which at least 2 oxazolyl groups are bonded, more preferably contains a benzene ring or a pyridine ring to which at least 2 oxazolyl groups are bonded, further preferably contains a benzene ring to which at least 2 oxazolyl groups are bonded, and particularly preferably contains 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene.
The crosslinking agent may be used alone, or 2 or more kinds may be used in combination.
The polyimide resin composition of the present invention preferably contains a polyimide resin and a crosslinking agent in such a ratio that the molar ratio of the oxazolyl group in the crosslinking agent to the carboxyl group in the polyimide resin (oxazolyl group/carboxyl group) is 1/4-1/0.5. The molar ratio is more preferably 1/4 to 1/1, still more preferably 1/2 to 1/1, still more preferably 1/2 to 1/1.5, and still more preferably 1/2 to 1/1.7.
The molar ratio is calculated based on the amount of the crosslinking agent and the amount of the compound providing the structural unit (B-1), and is a molar ratio of the oxazolyl group contained in the crosslinking agent to the carboxyl group contained in the compound providing the structural unit (B-1) used for producing the polyimide resin.
The polyimide resin composition of the present invention may contain, within a range not impairing the required properties of the polyimide film: inorganic fillers, adhesion promoters, mold release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, antifoaming agents, fluorescent whitening agents, crosslinking agents, polymerization initiators, photosensitizers, and the like.
The method for producing the polyimide resin composition of the present invention is not particularly limited, and a known method can be applied.
The polyimide resin composition of the present invention can form a film having excellent colorless transparency, optical isotropy, and chemical resistance. Suitable physical property values of the film formed by using the polyimide resin composition of the present invention are as follows.
When a film having a thickness of 10 μm is formed, the total light transmittance is preferably 88% or more, more preferably 90% or more, and still more preferably 91% or more.
When a film having a thickness of 10 μm is formed, the Yellowness Index (YI) is preferably 2.5 or less, more preferably 2.3 or less, and still more preferably 2.0 or less.
When a film having a thickness of 10 μm is formed, b＊Preferably 1.5 or less, more preferably 1.2 or less, and further preferably 1.0 or less.
When a film having a thickness of 10 μm is formed, the haze is preferably 2.0% or less, more preferably 1.0% or less, and still more preferably 0.6% or less.
When a film having a thickness of 10 μm is formed, the absolute value of the retardation in thickness (Rth) is preferably 100nm or less, more preferably 90nm or less, and still more preferably 60nm or less.
When a film having a thickness of 10 μm is formed, the mixed acid Δ YI is preferably 1.5 or less, more preferably 1.3 or less, and still more preferably 1.2 or less.
The mixed acid Δ YI is a difference in YI before and after the impregnation when the polyimide film is immersed in a mixture of phosphoric acid, nitric acid, and acetic acid, and can be measured specifically by the method described in examples. The smaller Δ YI indicates the more excellent acid resistance. By using the polyimide resin composition of the present invention, a film having excellent chemical resistance can be formed, and excellent resistance to acids can be exhibited. Particularly, the composition exhibits excellent resistance to a mixed acid (for example, a mixed solution of 50 to 97 mass% phosphoric acid, 1 to 20 mass% nitric acid, 1 to 10 mass% acetic acid and 1 to 20 mass% water, preferably a mixed solution of 63 to 87 mass% phosphoric acid, 5 to 15 mass% nitric acid, 3 to 7 mass% acetic acid and 5 to 15 mass% water).
The film formed by using the polyimide resin composition of the present invention has good mechanical properties and heat resistance, and has the following appropriate physical property values.
The tensile modulus is preferably 2.0GPa or more, more preferably 2.5GPa or more, and still more preferably 2.7GPa or more.
The tensile strength is preferably 60MPa or more, more preferably 70MPa or more, and still more preferably 80MPa or more.
The tensile elongation at break is preferably 5.0% or more, more preferably 6.0% or more, and further preferably 7.5% or more.
The glass transition temperature (Tg) is preferably 230 ℃ or higher, more preferably 250 ℃ or higher, and still more preferably 290 ℃ or higher.
The physical property values in the present invention can be measured specifically by the methods described in examples.
[ polyimide varnish ]
A preferable embodiment of the polyimide resin composition of the present invention is a polyimide resin composition (hereinafter, also referred to as "polyimide varnish") containing an organic solvent in addition to the polyimide resin and the crosslinking agent, and in which the polyimide resin is dissolved.
That is, the polyimide varnish of the present invention comprises a polyimide resin composition and an organic solvent.
The organic solvent is not particularly limited as long as the polyimide resin is dissolved therein, and it is preferable to use the above-mentioned compound alone or 2 or more compounds mixed therein as a reaction solvent used for producing the polyimide resin.
Examples of the organic solvent include an aprotic solvent, a phenol solvent, an ether solvent, and a carbonate solvent.
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 hexamethylphosphine triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide 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 organic solvents, amide solvents or lactone solvents are preferred, and lactone solvents are more preferred from the viewpoint of cleaning properties. Of the lactone-based solvents, gamma-butyrolactone and gamma-valerolactone are preferable, and gamma-butyrolactone is more preferable.
When the lactone-based solvent is used as the organic solvent, the ratio of the lactone-based solvent in the organic solvent contained in the polyimide varnish is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, and the lactone-based solvent alone may be used.
The lactone-based solvent has a low moisture absorption rate, and therefore, the varnish does not absorb moisture in the environment when a film is applied, and whitening due to deposition of polyimide and roughness of the film surface are less likely to occur, which is preferable. Further, it is preferable because the process property can be improved without controlling the humidity in the environment or the like.
The organic solvent may be used alone or in combination of 2 or more.
The polyimide varnish may be obtained by adding a crosslinking agent to a solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or may be obtained by adding a diluting solvent and a crosslinking agent to the solution.
The polyimide resin has solvent solubility and does not substantially undergo a crosslinking reaction with a crosslinking agent at room temperature. Thus, a polyimide varnish stable at room temperature can be formed. The polyimide varnish preferably contains 1 to 40 mass% of a polyimide resin, and more preferably 2 to 40 mass%.
Among them, from the viewpoint of stability, preservation at a high concentration, and good film formation, the content is more preferably 5 to 40% by mass, still more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass. The viscosity of the polyimide varnish is preferably 1 to 200 pas, more preferably 2 to 100 pas. The viscosity of the polyimide varnish was measured at 25 ℃ with an E-type viscometer.
In addition, when a film is applied, it is also preferable to further reduce the concentration of the polyimide resin in the polyimide varnish, and it is also preferable to use the polyimide varnish diluted with the organic solvent. The polyimide varnish used for coating the film preferably contains 1 to 10 mass% of a polyimide resin, more preferably 2 to 8 mass%, and still more preferably 4 to 7 mass%, from the viewpoint of improving the cleanability of the apparatus. The viscosity at this time is preferably 0.1 to 15 pas, more preferably 1 to 10 pas, and still more preferably 2 to 5 pas. By forming the polyimide varnish with a polyimide resin concentration or viscosity in such a range, the varnish inside the apparatus used for film coating with the cleaning liquid can be easily replaced, and the cleaning property is improved.
[ polyimide film ]
The polyimide film of the present invention is obtained by crosslinking the polyimide resin contained in the polyimide resin composition of the present invention with the crosslinking agent. That is, the polyimide film of the present invention contains a crosslinked polyimide resin which is a crosslinked product of polyimide resins with each other by means of a crosslinking agent. Therefore, the polyimide film of the present invention is excellent in colorless transparency, optical isotropy, and chemical resistance. The polyimide film of the present invention has suitable physical property values as described above.
The method for producing a polyimide film of the present invention is not particularly limited as long as it includes the following steps: the heating is carried out at a temperature at which the crosslinking reaction of the polyimide resin and the crosslinking agent proceeds (preferably 80 ℃ or higher, more preferably 100 ℃ or higher, and further preferably 150 ℃ or higher). For example, the following methods may be mentioned: the polyimide varnish is applied to a smooth support such as a glass plate, a metal plate, or a plastic, or is formed into a film, and then heated. By this heat treatment, while the crosslinking reaction between the polyimide resin and the crosslinking agent in the polyimide varnish proceeds, the organic solvent such as the reaction solvent and the diluting solvent contained in the polyimide varnish can be removed.
Examples of the coating method include known coating methods such as spin coating, slit coating, and blade coating.
The heat treatment is preferably carried out by evaporating the organic solvent at a temperature of 60 to 150 ℃ to make it tack-free and then drying the resultant product at a temperature not lower than the boiling point of the organic solvent used (not particularly limited, preferably 200 to 500 ℃). Further, it is preferable to perform drying under an air atmosphere or a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure, or increased pressure.
The method for peeling the polyimide film formed on the support from the support is not particularly limited, and examples thereof include a laser peeling method; a method using a sacrificial layer for peeling (a method of coating a release agent on the surface of a support in advance) is used.
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 can be suitably used as a film for various members such as color filters, flexible displays, semiconductor components, and optical members. The polyimide film of the present invention is particularly suitable for use as a substrate for an image display device such as a liquid crystal display or an OLED display.
Examples
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.
In examples and comparative examples, physical properties were measured by the methods shown below.
(1) Concentration of solid component
The solid content concentrations of the polyimide resin solution and the polyimide varnish were measured as follows: in a small electric furnace "MMF-1" manufactured by AS ONE Corporation, a sample was heated at 320 ℃ for 120 minutes, 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) Tensile strength, tensile modulus, tensile elongation at break
Tensile strength, tensile modulus, and tensile elongation at break in accordance with JIS K7127: 1999, it was measured by using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Seisaku-Sho Ltd. The chuck pitch was set to 50mm, the test piece size was set to 10mm × 70mm, and the test speed was set to 20 mm/min.
(4) Glass transition temperature (Tg)
Using a thermomechanical analyzer "TMA/SS 6100" manufactured by Hitachi High-Tech Science Corporation, temperature was raised to a sufficient temperature for removing residual stress under conditions of a specimen size of 2mm × 20mm, a load of 0.1N, and a temperature raising rate of 10 ℃/min in a tensile mode, residual stress was removed, and then cooling to room temperature was performed. Thereafter, the elongation of the test piece was measured under the same conditions as in the treatment for removing the residual stress, and the inflection point of the visible elongation was determined as the glass transition temperature.
(5) Total light transmittance, Yellow Index (YI), b＊Haze, haze
Total light transmittance, YI, b＊And haze in accordance with JIS K7105: 1981, the measurement was carried out using a color/turbidity simultaneous measurement instrument "COH 400" manufactured by Nippon Denshoku industries Co., Ltd.
(6) Thickness retardation (Rth)
The thickness retardation (Rth) was measured using an ellipsometer "M-220" manufactured by Nippon spectral Co., Ltd. The thickness retardation value at a wavelength of 590nm was measured. When nx is the maximum in-plane refractive index of the polyimide film, ny is the minimum in-plane refractive index, 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
(7) Solvent resistance
At room temperature, a solvent was dropped on a polyimide film formed on a glass plate to confirm whether or not the film surface was changed. As the solvent, Propylene Glycol Monomethyl Ether Acetate (PGMEA) was used.
The evaluation criteria for solvent resistance are as follows.
A: the surface of the film is unchanged.
B: cracks were slightly introduced at the surface of the film.
C: cracks are introduced into the surface of the film, or the surface of the film is dissolved.
(8) Acid resistance (Mixed acid. DELTA. YI)
A polyimide film formed on a glass plate was immersed in a mixed acid (H) heated to 40 DEG C3PO4(70% by mass) + HNO3(10% by mass) + CH3COOH (5 mass%) + H2Mixed solution of O (15 mass%)) was added for 4 minutes, and then washed with water. After washing with water, water was wiped off, and the mixture was heated on a hot plate at 240 ℃ for 50 minutes to dry. YI was measured before and after the test to determine the change(Δ YI). Here, YI measurement is performed in a state where a polyimide film is formed on a glass plate (a state of the glass plate + the polyimide film).
(9) Storage stability
The polyimide varnish was stored at room temperature (23 ℃) for 1 week, and the presence or absence of Haze (Haze) in the varnish was visually confirmed. After 1 week of storage, the one with no Haze was evaluated as A, and the one with Haze was evaluated as C. Specifically, those with less than 5% were designated as those with no Haze and designated as a by the same evaluation method as the Haze (5), and those with 5% or more were designated as those with Haze and designated as C by the same evaluation method as the Haze (5).
(10) Cleaning property
Propylene Glycol Monomethyl Ether (PGME) and Propylene Glycol Monomethyl Ether Acetate (PGMEA) were mixed so that the mass ratio of PGME/PGMEA became 7/3, to prepare a PGME/PGMEA mixed solution. The polyimide varnish was mixed with the PGME/PGMEA mixed solution, and whether the mixture was uniformly mixed at room temperature was confirmed. When not homogeneously mixed, precipitates were formed and the liquid mixture was clouded, and therefore Haze of the liquid mixture was measured by the same evaluation method as that of the Haze (5) to evaluate the cleaning property.
The evaluation criteria for the cleanability were as follows.
A: the polyimide varnish was uniformly mixed with the PGME/PGMEA mixture. Haze is 1% or less.
C: the polyimide varnish and the PGME/PGMEA mixed solution were not uniformly mixed, and precipitates were generated. Haze is greater than 1%.
Abbreviations for the tetracarboxylic acid component, diamine component and crosslinking agent used in examples and comparative examples are as follows.
< tetracarboxylic acid component >
HPMDA: 1,2,4, 5-Cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi gas chemical Co., Ltd.; Compound represented by formula (a-1))
6 FDA: 4, 4' - (Hexafluoroisopropylidene) diphthalic anhydride (manufactured by Daikin Industries, Ltd.; Compound represented by the formula (a-2))
< diamine component >
3, 5-DABA: 3, 5-diaminobenzoic acid (available from Nippon gaku Kogyo Co., Ltd.; Compound represented by the formula (b-1))
X-22-9409: both terminal amino-modified silicone oil "X-22-9409" (produced by shin-Etsu chemical Co., Ltd.; Compound represented by the formula (b-2))
6 FODA: 4,4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether (ChinaTech Chemical (Tianjin) Co., Ltd.; Compound represented by the formula (b-3))
HFBAPP: 2, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (Seika Co., Ltd.)
TFMB: 2, 2' -bis (trifluoromethyl) benzidine (Seika Co., Ltd.)
< crosslinking agent >
1, 3-PBO: 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene (manufactured by Sanguo pharmaceutical industry Co., Ltd.)
< example 1 >
A1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap was charged with 3,5-DABA8.518g (0.056 mol), X-22-940913.709 g (0.010 mol), 6FODA 18.833g (0.056 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 66.873g, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution were added 27.333g (0.122 mol) of HPMDA and 16.718g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) at the same time, 0.617g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 172.409g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (1) having a solid content concentration of 20 mass%.
Then, 1,3-PBO3.784g (0.0175 mol) as a crosslinking agent was added to 200g of the polyimide resin solution (1), and the mixture was stirred at room temperature for 1 hour to obtain a polyimide varnish containing the crosslinking agent and the polyimide resin and having a solid content concentration of 19.6 mass%. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< example 2 >
A1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap was charged with 3,5-DABA8.173g (0.054 mol), X-22-940913.155 g (0.010 mol), 6FODA 18.071g (0.054 mol), and γ -butyrolactone (66.699 g, Mitsubishi chemical corporation) and stirred at a system temperature of 70 ℃ under a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 23.605g (0.105 mol) of HPMDA and 8.338g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, and after stirring was continued for 10 minutes, 5.211g (0.012 mol) of 6FDA and 8.338g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, 0.617g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 172.626g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (2) having a solid content concentration of 20.0 mass%.
Then, to 200g of the polyimide resin solution (2), 1,3-PBO3.655g (0.0169 mol) as a crosslinking agent was added, and the mixture was stirred at room temperature for 1 hour to obtain a polyimide varnish having a solid content concentration of 19.6 mass% and containing the crosslinking agent and the polyimide resin. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 1 >
In a 1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap, 3,5-DABA28.625g (0.188 mol) and gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) 84.928g were charged, and the mixture was stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 42.149g (0.188 mol) of HPMDA and 21.232g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, 0.951g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 149.840g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (3) having a solid content concentration of 20 mass%.
Then, 1,3-PBO12.704g (0.059 mol) as a crosslinking agent was added to 200g of the polyimide resin solution (3), and the mixture was stirred at room temperature for 1 hour to obtain a polyimide varnish containing the crosslinking agent and the polyimide resin and having a solid content concentration of 19.6 mass%. Then, the polyimide varnish was allowed to stand at room temperature, resulting in white precipitates in the polyimide varnish and loss of the fluidity of the polyimide varnish. Therefore, it is difficult to make the film thinner. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
< comparative example 2 >
6FODA41.034g (0.122 mol) and 82.073g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) were put into a 1L five-necked round-bottomed flask equipped with a stainless steel semilunar stirring blade, a nitrogen introduction tube, a dean-Stark trap equipped with a condenser, a thermometer, and a glass end cap, and stirred at 70 ℃ in the system and 200rpm in a nitrogen atmosphere to obtain a solution.
To this solution were added 27.361g (0.122 mol) of HPMDA and 20.518g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) at the same time, 0.617g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 153.408g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (4) having a solid content concentration of 20 mass%.
The polyimide resin solution (4) was used as it was as a polyimide varnish without adding a crosslinking agent 1, 3-PBO. That is, the obtained polyimide varnish (polyimide resin solution (4)) was applied onto a glass plate by spin coating, and kept at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 3 >
In a 1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap, 24.160g (0.075 mol) of TFMBB, 11.478g (0.075 mol) of 3,5-DABA, and 83.318g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were charged, and the mixture was stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 33.794g (0.151 mol) of HPMDA and 20.830g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, and 0.763g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 151.852g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (5) having a solid content concentration of 20 mass%.
Then, to 200g of the polyimide resin solution (5), 1,3-PBO5.069g (0.023 mol) as a crosslinking agent was added, and after stirring at room temperature for 1 hour, a polyimide varnish containing the crosslinking agent and the polyimide resin and having a solid content concentration of 19.5 mass% was obtained. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 4 >
6FODA24.894g (0.074 mol), 3,5-DABA 11.266g (0.074 mol) and γ -butyrolactone (83.198 g, manufactured by Mitsubishi chemical corporation) were put into a 1L five-necked round-bottomed flask equipped with a stainless steel semilunar stirring blade, a nitrogen introduction tube, a dean-Stark trap equipped with a condenser, a thermometer and a glass end cap, and stirred at a system temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 33.172g (0.148 mol) of HPMDA and 20.800g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, and 0.749g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 152.002g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (6) having a solid content concentration of 20 mass%.
Then, 1,3-PBO5.000g (0.023 mol) was added as a crosslinking agent to 200g of the polyimide resin solution (6), and after stirring at room temperature for 1 hour, a polyimide varnish containing the crosslinking agent and the polyimide resin and having a solid content concentration of 19.5 mass% was obtained. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 5 >
A1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap was charged with 3,5-DABA6.994g (0.046 mol), X-22-940913.688 g (0.010 mol), HFBAPP 23.951g (0.046 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 65.994g, and stirred at an internal temperature of 70 ℃ under a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 22.861g (0.102 mol) of HPMDA and 16.498g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, and then 0.516g of triethylamine (manufactured by Kanto chemical corporation) and 0.057g of tetraethylene diamine (manufactured by Tokyo chemical Co., Ltd.) as an imidization catalyst were charged, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 173.51g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (7) having a solid content concentration of 20 mass%.
Then, 1,3-PBO3.784g (0.0175 mol) as a crosslinking agent was added to 200g of the polyimide resin solution (7), and the mixture was stirred at room temperature for 1 hour to obtain a polyimide varnish containing the crosslinking agent and the polyimide resin and having a solid content concentration of 19.6 mass%. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 6 >
A1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap was charged with 3,5-DABA8.640g (0.057 mol), X-22-940913.906 g (0.010 mol), TFMB 18.861g (0.056 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 66.934g, and stirred at an internal temperature of 70 ℃ under a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 27.724g (0.124 mol) of HPMDA and 16.734g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, 0.625g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was charged, and the mixture was heated in a mantle heater to raise the temperature in the reaction system to 190 ℃ over about 20 minutes. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 172.332g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (8) having a solid content concentration of 20 mass%.
Then, 1,3-PBO3.853g (0.0178 mol) as a crosslinking agent was added to 200g of the polyimide resin solution (8), and the mixture was stirred at room temperature for 1 hour to obtain a polyimide varnish containing the crosslinking agent and the polyimide resin and having a solid content concentration of 19.6 mass%. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
< comparative example 7 >
A1L five-necked round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet tube, a dean-Stark trap equipped with a condenser tube, a thermometer, and a glass end cap was charged with 3,5-DABA8.183g (0.054 mol), X-22-940913.859 g (0.010 mol), TFMB 17.224g (0.054 mol), and γ -butyrolactone (manufactured by Mitsubishi chemical corporation) 66.721g, and stirred at a system temperature of 70 ℃ under a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 23.733g (0.106 mol) of HPMDA and 8.340g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, and after stirring was continued for 10 minutes, 5.239g (0.012 mol) of 6FDA and 8.340g of γ -butyrolactone (manufactured by Mitsubishi chemical corporation) were added simultaneously, 0.595g of triethylamine (manufactured by Kanto chemical corporation) as an imidization catalyst was added, and the mixture was 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 in accordance with the increase in viscosity, and the reflux was carried out for about 5 hours while keeping the temperature in the reaction system at 190 ℃.
Thereafter, 172.598g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the temperature in the reaction system was cooled to 120 ℃, and the mixture was further stirred for about 3 hours to obtain a uniform polyimide resin solution (9) having a solid content concentration of 20 mass%.
Then, to 200g of the polyimide resin solution (9), 1,3-PBO3.650g (0.0169 mol) as a crosslinking agent was added, and the mixture was stirred at room temperature for 1 hour to obtain a polyimide varnish containing the crosslinking agent and the polyimide resin and having a solid content concentration of 19.6 mass%. The molar ratio of oxazolyl group/carboxyl group calculated based on the amount of 1,3-PBO added and the amount of 3,5-DABA added was 1/2.
Then, the obtained polyimide varnish was applied onto a glass plate by spin coating, and the plate was held at 80 ℃ for 20 minutes on a hot plate, and then heated at 260 ℃ for 30 minutes in a hot air dryer under an air atmosphere to evaporate the solvent, thereby obtaining a film. The results are shown in Table 1.
[ Table 1]
TABLE 1
As shown in table 1, the polyimide films of examples 1 and 2 were excellent in all of colorless transparency, optical isotropy, and chemical resistance (solvent resistance and acid resistance), and the polyimide varnishes of examples 1 and 2 were excellent in storage stability and cleaning property.
On the other hand, in comparative example 1, the crosslinking agent was added to the polyimide resin solution and stirred for 1 hour to obtain a polyimide varnish, and then the polyimide varnish was allowed to stand at room temperature, whereby white precipitates were generated in the polyimide varnish and the fluidity of the polyimide varnish was lost. That is, the polyimide varnish of comparative example 1 was inferior in storage stability and cleaning property.
The polyimide film of comparative example 2 was inferior in solvent resistance. Further, the value of Δ YI of the mixed acid was as large as 1.57, and the acid resistance was also poor.
The polyimide film of comparative example 3 is inferior in optical isotropy. In addition, the polyimide varnish of comparative example 3 was inferior in cleaning property.
The polyimide varnish of comparative example 4 was inferior in cleaning property.
The polyimide film of comparative example 5 was excellent in solvent resistance. In addition, the polyimide varnish of comparative example 5 was inferior in cleaning property.
The polyimide varnish of comparative example 6 was inferior in storage stability and cleaning property.
The polyimide varnish of comparative example 7 was inferior in cleaning property.
Claims (11)
1. A polyimide resin composition comprising a polyimide resin and a crosslinking agent having at least 2 oxazole groups,
the polyimide resin has: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises: a structural unit (A-1) derived from a compound represented by the following formula (a-1),
the structural unit B includes: a structural unit (B-1) derived from a compound represented by the following formula (B-1), a structural unit (B-2) derived from a compound represented by the following formula (B-2), and a structural unit (B-3) derived from a compound represented by the following formula (B-3),
in the formula (b-1),
x is a single bond, a substituted or unsubstituted alkylene group, a carbonyl group, an ether group, a group represented by the following formula (b-1-i), or a group represented by the following formula (b-1-ii),
p is an integer of 0 to 2,
m1 is an integer of 0 to 4,
m2 is an integer of 0 to 4,
in the formula (b-1-i), m3 is an integer of 0 to 5, in the formula (b-1-ii), m4 is an integer of 0 to 5,
wherein the content of the first and second substances,
m1+ m2+ m3+ m4 is 1 or more,
when p is 0, m1 is an integer of 1 to 4,
when p is 2, 2X and 2m 2-m 4 are independently selected;
in the formula (b-2),
R1～R4each independently a monovalent aliphatic group or a monovalent aromatic group,
Z1and Z2Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer.
2. The polyimide resin composition according to claim 1, wherein the structural unit (B-1) is a structural unit (B-11) derived from a compound represented by the following formula (B-11),
3. the polyimide resin composition according to claim 1 or 2, wherein the crosslinking agent is: a compound comprising an aromatic ring or an aromatic heterocycle to which at least 2 oxazolyl groups are bonded.
4. The polyimide resin composition according to claim 3, wherein the crosslinking agent is: a compound comprising a benzene ring to which at least 2 oxazolyl groups are bonded.
5. The polyimide resin composition according to claim 4, wherein the crosslinking agent is 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene.
6. The polyimide resin composition according to any one of claims 1 to 5, wherein the proportion of the structural unit (A-1) in the structural unit A is 50 mol% or more.
7. The polyimide resin composition according to any one of claims 1 to 6,
the proportion of the structural unit (B-1) in the structural unit B is 20 to 75 mol%,
the proportion of the structural unit (B-2) in the structural unit B is 1 to 25 mol%,
the proportion of the structural unit (B-3) in the structural unit B is 20 to 75 mol%.
8. The polyimide resin composition according to any one of claims 1 to 7, wherein the structural unit A further comprises: a structural unit (A-2) derived from a compound represented by the following formula (a-2),
9. the polyimide resin composition according to claim 8,
the proportion of the structural unit (A-1) in the structural unit A is 50 to 99 mol%,
the proportion of the structural unit (A-2) in the structural unit A is 1 to 50 mol%.
10. A polyamide varnish comprising: the polyimide resin composition according to any one of claims 1 to 9, and an organic solvent.
11. A polyimide film obtained by crosslinking the polyimide resin in the polyimide resin composition according to any one of claims 1 to 9 with the crosslinking agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010209309A (en) * | 2008-06-26 | 2010-09-24 | Sanwa Kagaku Kogyo Kk | Photosensitive polyimide, photosensitive polyimide ink composition and insulating film |
| CN103987763A (en) * | 2011-08-19 | 2014-08-13 | 阿克伦聚合物体系有限公司 | Thermally stable, low birefringent copolyimide films |
| JP2016222797A (en) * | 2015-05-29 | 2016-12-28 | 三菱瓦斯化学株式会社 | Polyimide resin composition |
| KR20180106212A (en) * | 2017-03-17 | 2018-10-01 | 코오롱인더스트리 주식회사 | Polyimide Resin, Polyimide Film and Display Device Comprising Thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010209309A (en) * | 2008-06-26 | 2010-09-24 | Sanwa Kagaku Kogyo Kk | Photosensitive polyimide, photosensitive polyimide ink composition and insulating film |
| CN103987763A (en) * | 2011-08-19 | 2014-08-13 | 阿克伦聚合物体系有限公司 | Thermally stable, low birefringent copolyimide films |
| JP2016222797A (en) * | 2015-05-29 | 2016-12-28 | 三菱瓦斯化学株式会社 | Polyimide resin composition |
| KR20180106212A (en) * | 2017-03-17 | 2018-10-01 | 코오롱인더스트리 주식회사 | Polyimide Resin, Polyimide Film and Display Device Comprising Thereof |
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