JP7548236B2 - Polyimide resin composition, polyimide varnish and polyimide film - Google Patents
Polyimide resin composition, polyimide varnish and polyimide film Download PDFInfo
- Publication number
- JP7548236B2 JP7548236B2 JP2021542748A JP2021542748A JP7548236B2 JP 7548236 B2 JP7548236 B2 JP 7548236B2 JP 2021542748 A JP2021542748 A JP 2021542748A JP 2021542748 A JP2021542748 A JP 2021542748A JP 7548236 B2 JP7548236 B2 JP 7548236B2
- Authority
- JP
- Japan
- Prior art keywords
- structural unit
- group
- polyimide resin
- formula
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 title claims description 170
- 239000009719 polyimide resin Substances 0.000 title claims description 102
- 239000000203 mixture Substances 0.000 title claims description 48
- 239000004642 Polyimide Substances 0.000 title claims description 30
- 239000002966 varnish Substances 0.000 title claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 102
- 125000003118 aryl group Chemical group 0.000 claims description 36
- 150000004985 diamines Chemical class 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 29
- 239000011737 fluorine Substances 0.000 claims description 29
- 125000002723 alicyclic group Chemical group 0.000 claims description 26
- 125000001931 aliphatic group Chemical group 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 22
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 24
- 239000002904 solvent Substances 0.000 description 22
- 239000006096 absorbing agent Substances 0.000 description 15
- -1 phosphate ester Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000007810 chemical reaction solvent Substances 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 5
- 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 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000010 aprotic solvent 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
- 239000000470 constituent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229920001296 polysiloxane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BEBFJOSPYYGOKL-UHFFFAOYSA-N (3-ethylphenyl)methanamine Chemical compound CCC1=CC=CC(CN)=C1 BEBFJOSPYYGOKL-UHFFFAOYSA-N 0.000 description 1
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- RCNBXBQGBCGTPB-UHFFFAOYSA-N (4-dodecylphenyl)methanamine Chemical compound CCCCCCCCCCCCC1=CC=C(CN)C=C1 RCNBXBQGBCGTPB-UHFFFAOYSA-N 0.000 description 1
- DGAGEFUEKIORSQ-UHFFFAOYSA-N (4-ethylphenyl)methanamine Chemical compound CCC1=CC=C(CN)C=C1 DGAGEFUEKIORSQ-UHFFFAOYSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- PXXUHFVEJQHLSK-UHFFFAOYSA-N 2-[[2-aminoethyl(dimethyl)silyl]oxy-dimethylsilyl]ethanamine Chemical compound NCC[Si](C)(C)O[Si](C)(C)CCN PXXUHFVEJQHLSK-UHFFFAOYSA-N 0.000 description 1
- ZTJDHPJOEXLRHO-UHFFFAOYSA-N 2-[[2-aminoethyl(diphenoxy)silyl]oxy-diphenoxysilyl]ethanamine Chemical compound C=1C=CC=CC=1O[Si](O[Si](CCN)(OC=1C=CC=CC=1)OC=1C=CC=CC=1)(CCN)OC1=CC=CC=C1 ZTJDHPJOEXLRHO-UHFFFAOYSA-N 0.000 description 1
- IQMVIUWWZGWTLG-UHFFFAOYSA-N 2-[[2-aminoethyl(diphenyl)silyl]oxy-diphenylsilyl]ethanamine Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(CCN)O[Si](CCN)(C=1C=CC=CC=1)C1=CC=CC=C1 IQMVIUWWZGWTLG-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical compound OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- XRAAFZNZEZFTCV-UHFFFAOYSA-N 3-[[3-aminopropyl(diphenyl)silyl]oxy-diphenylsilyl]propan-1-amine Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(CCCN)O[Si](CCCN)(C=1C=CC=CC=1)C1=CC=CC=C1 XRAAFZNZEZFTCV-UHFFFAOYSA-N 0.000 description 1
- AAOTXAXPBHMDLB-UHFFFAOYSA-N 3-[[[3-aminopropyl(diethyl)silyl]oxy-diethylsilyl]oxy-diethylsilyl]propan-1-amine Chemical compound NCCC[Si](CC)(CC)O[Si](CC)(CC)O[Si](CC)(CC)CCCN AAOTXAXPBHMDLB-UHFFFAOYSA-N 0.000 description 1
- ZWRBLCDTKAWRHT-UHFFFAOYSA-N 3-[[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)O[Si](C)(C)CCCN ZWRBLCDTKAWRHT-UHFFFAOYSA-N 0.000 description 1
- JKWTWAKSRCPWLP-UHFFFAOYSA-N 3-[[[3-aminopropyl(diphenyl)silyl]oxy-dimethylsilyl]oxy-diphenylsilyl]propan-1-amine Chemical compound C=1C=CC=CC=1[Si](CCCN)(C=1C=CC=CC=1)O[Si](C)(C)O[Si](CCCN)(C=1C=CC=CC=1)C1=CC=CC=C1 JKWTWAKSRCPWLP-UHFFFAOYSA-N 0.000 description 1
- DOVNOYLOWBNHKQ-UHFFFAOYSA-N 3-[[[3-aminopropyl(dipropyl)silyl]oxy-dipropylsilyl]oxy-dipropylsilyl]propan-1-amine Chemical compound NCCC[Si](CCC)(CCC)O[Si](CCC)(CCC)O[Si](CCC)(CCC)CCCN DOVNOYLOWBNHKQ-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- IDLYVPNAAUXRPW-UHFFFAOYSA-N 4-[(4-aminobutyl-methoxy-methylsilyl)oxy-methoxy-methylsilyl]butan-1-amine Chemical compound NCCCC[Si](C)(OC)O[Si](C)(CCCCN)OC IDLYVPNAAUXRPW-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- DVJCVFJDBHWFNC-UHFFFAOYSA-N 4-[[(4-aminophenoxy)-dimethylsilyl]oxy-dimethylsilyl]oxyaniline Chemical compound C=1C=C(N)C=CC=1O[Si](C)(C)O[Si](C)(C)OC1=CC=C(N)C=C1 DVJCVFJDBHWFNC-UHFFFAOYSA-N 0.000 description 1
- OJXULZRBAPPHNY-UHFFFAOYSA-N 4-[[(4-aminophenyl)-dimethylsilyl]oxy-dimethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=C(N)C=C1 OJXULZRBAPPHNY-UHFFFAOYSA-N 0.000 description 1
- ILCGTNBULCHWOE-UHFFFAOYSA-N 4-[[4-aminobutyl(dimethyl)silyl]oxy-dimethylsilyl]butan-1-amine Chemical compound NCCCC[Si](C)(C)O[Si](C)(C)CCCCN ILCGTNBULCHWOE-UHFFFAOYSA-N 0.000 description 1
- MHQAJTTYAPWHHM-UHFFFAOYSA-N 4-[[[(4-aminophenyl)-dimethylsilyl]oxy-dimethylsilyl]oxy-dimethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C1=CC=C(N)C=C1 MHQAJTTYAPWHHM-UHFFFAOYSA-N 0.000 description 1
- OSFGNTLIOUHOKN-UHFFFAOYSA-N 4-[benzyl(methyl)sulfamoyl]benzoic acid Chemical compound C=1C=C(C(O)=O)C=CC=1S(=O)(=O)N(C)CC1=CC=CC=C1 OSFGNTLIOUHOKN-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- DVIPPHSQIBKWSA-UHFFFAOYSA-N 4-chlorophthalic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1C(O)=O DVIPPHSQIBKWSA-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001272720 Medialuna californiensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PLGBRGZNHLWMKD-UHFFFAOYSA-N bis[2-aminoethyl(dimethyl)silyl] dimethyl silicate Chemical compound NCC[Si](C)(C)O[Si](OC)(OC)O[Si](C)(C)CCN PLGBRGZNHLWMKD-UHFFFAOYSA-N 0.000 description 1
- AOMMCEXPXYKABF-UHFFFAOYSA-N bis[4-aminobutyl(dimethyl)silyl] dimethyl silicate Chemical compound NCCCC[Si](C)(C)O[Si](OC)(OC)O[Si](C)(C)CCCCN AOMMCEXPXYKABF-UHFFFAOYSA-N 0.000 description 1
- QCKVTJUJXXGBDQ-UHFFFAOYSA-N bis[4-aminobutyl(diphenyl)silyl] dimethyl silicate Chemical compound C=1C=CC=CC=1[Si](CCCCN)(C=1C=CC=CC=1)O[Si](OC)(OC)O[Si](CCCCN)(C=1C=CC=CC=1)C1=CC=CC=C1 QCKVTJUJXXGBDQ-UHFFFAOYSA-N 0.000 description 1
- JQDSSRRIHBKYPJ-UHFFFAOYSA-N bis[5-aminopentyl(dimethyl)silyl] dimethyl silicate Chemical compound NCCCCC[Si](C)(C)O[Si](OC)(OC)O[Si](C)(C)CCCCCN JQDSSRRIHBKYPJ-UHFFFAOYSA-N 0.000 description 1
- OOJITEPTYTVULX-UHFFFAOYSA-N bis[5-aminopentyl(diphenyl)silyl] dimethyl silicate Chemical compound C=1C=CC=CC=1[Si](CCCCCN)(C=1C=CC=CC=1)O[Si](OC)(OC)O[Si](CCCCCN)(C=1C=CC=CC=1)C1=CC=CC=C1 OOJITEPTYTVULX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- ASJCSAKCMTWGAH-UHFFFAOYSA-N cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCC1C(O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明はポリイミド樹脂組成物、ポリイミドワニス及びポリイミドフィルムに関する。 The present invention relates to a polyimide resin composition, a polyimide varnish and a polyimide film.
ポリイミド樹脂は、優れた機械的特性及び耐熱性を有することから、電気・電子部品等の分野において様々な利用が検討されている。例えば、液晶ディスプレイやＯＬＥＤディスプレイ等の画像表示装置に用いられるガラス基板をポリイミドフィルム基板へ代替することが望まれており、光学材料としての性能を満たすポリイミド樹脂の開発が行われている。
たとえば、特許文献１には、光学部品又は光学素子の周辺部材として用いることを目的として、ヘキサヒドロ無水ピロメリット酸と芳香族酸二無水物とからなる酸二無水物と、多環の芳香族基、シロキサン含有基等の有機基を有するジアミンとを反応させて得られるポリイミド共重合体が開示されている。
Polyimide resins have excellent mechanical properties and heat resistance, and therefore various applications are being considered in the fields of electric and electronic components, etc. For example, it is desirable to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays with polyimide film substrates, and polyimide resins that meet the performance requirements as optical materials are being developed.
For example, Patent Document 1 discloses a polyimide copolymer obtained by reacting an acid dianhydride consisting of hexahydropyromellitic anhydride and an aromatic acid dianhydride with a diamine having an organic group such as a polycyclic aromatic group or a siloxane-containing group, for the purpose of using it as a peripheral member of an optical component or an optical element.
このようなポリイミドフィルムは、通常、ポリイミドと溶媒を含むワニスを、平滑な金属製ベルト等の上に塗布し、乾燥して、剥離することで製造される。
ベルトからの剥離性が悪い場合、フィルムの厚さにムラが生じたり、フィルム表面に傷が生じてしまう。そこで、剥離性を改善するための検討がなされている。
たとえば、特許文献２には、自己支持性フィルムの基体からの剥離を容易にすることを目的として、特定のリン酸エステル等を含有する芳香族ポリアミック酸溶液を基体上にフィルム上に流延し、加熱及び後加熱を行う芳香族ポリイミドフィルムの製造法が開示されている。
また、特許文献３には、極薄のポリイミドフィルムを製造する方法として、離型剤を含有するポリイミド樹脂前駆体溶液を基材上に塗布する工程、乾燥する工程、熱硬化する工程、剥離する工程を含む製造方法が開示されている。
Such a polyimide film is usually produced by applying a varnish containing polyimide and a solvent onto a smooth metal belt or the like, drying it, and peeling it off.
If the film is not easily peeled from the belt, the thickness of the film may become uneven and the film surface may become scratched. Therefore, efforts are being made to improve the peelability.
For example, Patent Document 2 discloses a method for producing an aromatic polyimide film, in which an aromatic polyamic acid solution containing a specific phosphate ester or the like is cast onto a substrate and the film is heated and post-heated, for the purpose of facilitating peeling of the self-supporting film from the substrate.
Furthermore, Patent Document 3 discloses a method for producing an extremely thin polyimide film, which includes a step of applying a polyimide resin precursor solution containing a release agent onto a substrate, a step of drying, a step of thermally curing, and a step of peeling.
前記の通り、ポリイミドフィルムは、平滑な金属製ベルト等の支持体から剥離して得るが、高い透明性と平滑性を必要とされる画像表示装置用途では、剥離時のわずかな破損が問題となる。なかでもフレキシブルデバイスに用いられる柔軟性を有する、低弾性率のポリイミド樹脂はフィルム成形時にベルト等の支持体からの剥離性が悪くなる傾向にあり、特に高い剥離性が要求される。
前記特許文献２、３では離型剤を用いることで剥離性は改善されるものの、樹脂と反応性を有するためか、特に高温多湿環境下で樹脂の分子量が低下する等の問題が生じていた。
更に離型剤等の添加剤を用いても、光学材料に必要な高い無色透明性を有するポリイミド樹脂組成物が求められていた。
そこで、本発明は、ベルト等の支持体からの剥離性に優れ、高温多湿環境下での分子量低下も抑制され、無色透明性にも優れるフィルムの形成が可能なポリイミド樹脂組成物を提供することを課題とする。
As described above, polyimide films are obtained by peeling them off from supports such as smooth metal belts, but in image display device applications that require high transparency and smoothness, slight breakage during peeling can be a problem. In particular, flexible polyimide resins with low elastic modulus used in flexible devices tend to have poor peelability from supports such as belts during film formation, and therefore require particularly high peelability.
In Patent Documents 2 and 3, the releasability is improved by using a release agent, but since the release agent has reactivity with the resin, there arises a problem that the molecular weight of the resin decreases, particularly in a high-temperature and high-humidity environment.
Furthermore, there has been a demand for a polyimide resin composition that has high colorless transparency required for optical materials even when additives such as a mold release agent are used.
Therefore, an object of the present invention is to provide a polyimide resin composition which is excellent in releasability from a support such as a belt, suppresses a decrease in molecular weight in a high-temperature and high-humidity environment, and is capable of forming a film which is colorless and has excellent transparency.
本発明者らは、特定の繰り返し単位を含むポリイミド樹脂とフッ素含有ポリマーを含む組成物が上記課題を解決できることを見出し、発明を完成させるに至った。The inventors discovered that a composition containing a polyimide resin having a specific repeating unit and a fluorine-containing polymer can solve the above problems, and thus completed the invention.
すなわち、本発明は、下記の［１］～［１４］に関する。
［１］
下記式（１）で表される繰り返し単位及び下記式（２）で表される繰り返し単位を含むポリイミド樹脂（Ｘ）と、フッ素含有ポリマー（Ｙ）とを含む、ポリイミド樹脂組成物。
（式（１）中、Ｒ1～Ｒ4は、それぞれ独立して、一価の脂肪族基又は一価の芳香族基であり、Ｚ1及びＺ2は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、ｒは、正の整数であり、Ｒ5は炭素数４～３９の４価の脂環基である。
式（２）中、Ｒ6は炭素数４～３９の４価の脂環基であり、Φは合計の炭素数が２～３９の２価の脂肪族基、脂環基、芳香族基又はこれらの組合せからなる基であって、結合基として－Ｏ－、－ＳＯ2－、－ＣＯ－、－ＣＨ2－、－Ｃ（ＣＨ3）2－、－Ｃ2Ｈ4Ｏ－及び－Ｓ－からなる群から選ばれる少なくとも１つを有していてもよい。）
［２］
フッ素含有ポリマー（Ｙ）の含有量が、ポリイミド樹脂（Ｘ）１００質量部に対して、０．０１～１質量部である、［１］に記載のポリイミド樹脂組成物。
［３］
フッ素含有ポリマー（Ｙ）が、フッ素含有アクリルポリマーである、［１］又は［２］に記載のポリイミド樹脂組成物。
［４］
ポリイミド樹脂（Ｘ）中の前記式（１）で表される繰り返し単位の比率が１０～５０モル％である、［１］～［３］のいずれか１つに記載のポリイミド樹脂組成物。
［５］
前記式（１）で表される繰り返し単位が、下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）と下記式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）から構成される、［１］～［４］のいずれか１つに記載のポリイミド樹脂組成物。
（式（ｂ－１）中、Ｒ1～Ｒ4は、それぞれ独立して、一価の脂肪族基又は一価の芳香族基であり、Ｚ1及びＺ2は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、ｒは、正の整数である。）
［６］
前記式（２）で表される繰り返し単位が、下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）と、下記式（ｂ－２－１）で表される化合物に由来する構成単位（Ｂ－２－１）、下記式（ｂ－２－２）で表される化合物に由来する構成単位（Ｂ－２－２）、及び下記式（ｂ－２－３）で表される化合物に由来する構成単位（Ｂ－２－３）からなる群より選ばれる少なくとも１つに由来する構成単位（Ｂ－２）から構成される、［１］～［５］のいずれか１つに記載のポリイミド樹脂組成物。
［７］
ポリイミド樹脂（Ｘ）を構成するテトラカルボン酸二無水物に由来する構成単位中の構成単位（Ａ－１）の比率が５０モル％以上である、［５］又は［６］に記載のポリイミド樹脂組成物。
［８］
ポリイミド樹脂（Ｘ）を構成するジアミンに由来する構成単位中の構成単位（Ｂ－１）の比率が１０～５０モル％である、［５］～［７］のいずれか１つに記載のポリイミド樹脂組成物。
［９］
ポリイミド樹脂（Ｘ）を構成するジアミンに由来する構成単位中の構成単位（Ｂ－２）の比率が５０～９０モル％である、［６］～［８］のいずれか１つに記載のポリイミド樹脂組成物。
［１０］
構成単位（Ｂ－２）が構成単位（Ｂ－２－１）である、［６］～［９］のいずれか１つに記載のポリイミド樹脂組成物。
［１１］
構成単位（Ｂ－２）が構成単位（Ｂ－２－２）である、［６］～［９］のいずれか１つに記載のポリイミド樹脂組成物。
［１２］
構成単位（Ｂ－２）が構成単位（Ｂ－２－３）である、［６］～［９］のいずれか１つに記載のポリイミド樹脂組成物。
［１３］
［１］～［１２］のいずれか１つに記載のポリイミド樹脂組成物が有機溶媒に溶解してなるポリイミドワニス。
［１４］
［１］～［１２］のいずれか１つに記載のポリイミド樹脂組成物を含む、ポリイミドフィルム。
That is, the present invention relates to the following [1] to [14].
[1]
A polyimide resin composition comprising: a polyimide resin (X) containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); and a fluorine-containing polymer (Y).
In formula (1), R 1 to R 4 are each independently a monovalent aliphatic group or a monovalent aromatic group, Z 1 and Z 2 are each independently a divalent aliphatic group or a divalent aromatic group, r is a positive integer, and R 5 is a tetravalent alicyclic group having 4 to 39 carbon atoms.
In formula (2), R 6 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and Φ is a divalent aliphatic group, alicyclic group, aromatic group or a combination thereof having a total of 2 to 39 carbon atoms, which may have at least one bonding group selected from the group consisting of -O-, -SO 2 -, -CO-, -CH 2 -, -C(CH 3 ) 2 -, -C 2 H 4 O-, and -S-.
[2]
The polyimide resin composition according to [1], wherein the content of the fluorine-containing polymer (Y) is 0.01 to 1 part by mass per 100 parts by mass of the polyimide resin (X).
[3]
The polyimide resin composition according to [1] or [2], wherein the fluorine-containing polymer (Y) is a fluorine-containing acrylic polymer.
[4]
The polyimide resin composition according to any one of [1] to [3], wherein the ratio of the repeating unit represented by the formula (1) in the polyimide resin (X) is 10 to 50 mol %.
[5]
The polyimide resin composition according to any one of [1] to [4], wherein the repeating unit represented by formula (1) is composed of a structural unit (A-1) derived from a compound represented by formula (a-1) below and a structural unit (B-1) derived from a compound represented by formula (b-1) below:
(In formula (b-1), R 1 to R 4 each independently represent a monovalent aliphatic group or a monovalent aromatic group, Z 1 and Z 2 each independently represent a divalent aliphatic group or a divalent aromatic group, and r is a positive integer.)
[6]
The polyimide resin composition according to any one of [1] to [5], wherein the repeating unit represented by formula (2) is composed of a structural unit (A-1) derived from a compound represented by formula (a-1) below, a structural unit (B-2-1) derived from a compound represented by formula (b-2-1) below, a structural unit (B-2-2) derived from a compound represented by formula (b-2-2) below, and a structural unit (B-2-3) derived from a compound represented by formula (b-2-3) below.
[7]
The polyimide resin composition according to [5] or [6], wherein the ratio of the structural unit (A-1) in the structural units derived from a tetracarboxylic dianhydride constituting the polyimide resin (X) is 50 mol % or more.
[8]
The polyimide resin composition according to any one of [5] to [7], wherein the ratio of the structural unit (B-1) in the structural units derived from diamine constituting the polyimide resin (X) is 10 to 50 mol %.
[9]
The polyimide resin composition according to any one of [6] to [8], wherein the ratio of the structural unit (B-2) in the structural units derived from diamine constituting the polyimide resin (X) is 50 to 90 mol %.
[10]
The polyimide resin composition according to any one of [6] to [9], wherein the structural unit (B-2) is a structural unit (B-2-1).
[11]
The polyimide resin composition according to any one of [6] to [9], wherein the structural unit (B-2) is a structural unit (B-2-2).
[12]
The polyimide resin composition according to any one of [6] to [9], wherein the structural unit (B-2) is a structural unit (B-2-3).
[13]
A polyimide varnish obtained by dissolving the polyimide resin composition according to any one of [1] to [12] in an organic solvent.
[14]
A polyimide film comprising the polyimide resin composition according to any one of [1] to [12].
本発明によれば、ベルト等の支持体からの剥離性に優れ、高温多湿環境下での分子量低下も抑制され、無色透明性にも優れるフィルムの形成が可能なポリイミド樹脂組成物を提供することができる。According to the present invention, it is possible to provide a polyimide resin composition capable of forming a film that has excellent peelability from a support such as a belt, suppresses molecular weight reduction in a high temperature and humidity environment, and has excellent colorless transparency.
［ポリイミド樹脂組成物］
本発明のポリイミド樹脂組成物は、下記式（１）で表される繰り返し単位及び下記式（２）で表される繰り返し単位を含むポリイミド樹脂（Ｘ）と、フッ素含有ポリマー（Ｙ）とを含む。
（式（１）中、Ｒ1～Ｒ4は、それぞれ独立して、一価の脂肪族基又は一価の芳香族基であり、Ｚ1及びＺ2は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、ｒは、正の整数であり、Ｒ5は炭素数４～３９の４価の脂環基である。
式（２）中、Ｒ6は炭素数４～３９の４価の脂環基であり、Φは合計の炭素数が２～３９の２価の脂肪族基、脂環基、芳香族基又はこれらの組合せからなる基であって、結合基として－Ｏ－、－ＳＯ2－、－ＣＯ－、－ＣＨ2－、－Ｃ（ＣＨ3）2－、－Ｃ2Ｈ4Ｏ－及び－Ｓ－からなる群から選ばれる少なくとも１つを有していてもよい。）
[Polyimide resin composition]
The polyimide resin composition of the present invention contains a polyimide resin (X) containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and a fluorine-containing polymer (Y).
In formula (1), R 1 to R 4 are each independently a monovalent aliphatic group or a monovalent aromatic group, Z 1 and Z 2 are each independently a divalent aliphatic group or a divalent aromatic group, r is a positive integer, and R 5 is a tetravalent alicyclic group having 4 to 39 carbon atoms.
In formula (2), R 6 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and Φ is a divalent aliphatic group, alicyclic group, aromatic group or a group consisting of a combination thereof having a total of 2 to 39 carbon atoms, which may have at least one bonding group selected from the group consisting of -O-, -SO 2 -, -CO-, -CH 2 -, -C(CH 3 ) 2 -, -C 2 H 4 O-, and -S-.
＜ポリイミド樹脂（Ｘ）＞
本発明のポリイミド樹脂組成物に含まれるポリイミド樹脂（Ｘ）は、下記式（１）で表される繰り返し単位及び下記式（２）で表される繰り返し単位を含む。
（式（１）中、Ｒ1～Ｒ4は、それぞれ独立して、一価の脂肪族基又は一価の芳香族基であり、Ｚ1及びＺ2は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、ｒは、正の整数であり、Ｒ5は炭素数４～３９の４価の脂環基である。
式（２）中、Ｒ6は炭素数４～３９の４価の脂環基であり、Φは合計の炭素数が２～３９の２価の脂肪族基、脂環基、芳香族基又はこれらの組合せからなる基であって、結合基として－Ｏ－、－ＳＯ2－、－ＣＯ－、－ＣＨ2－、－Ｃ（ＣＨ3）2－、－Ｃ2Ｈ4Ｏ－及び－Ｓ－からなる群から選ばれる少なくとも１つを有していてもよい。）
<Polyimide resin (X)>
The polyimide resin (X) contained in the polyimide resin composition of the present invention contains a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
In formula (1), R 1 to R 4 are each independently a monovalent aliphatic group or a monovalent aromatic group, Z 1 and Z 2 are each independently a divalent aliphatic group or a divalent aromatic group, r is a positive integer, and R 5 is a tetravalent alicyclic group having 4 to 39 carbon atoms.
In formula (2), R 6 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and Φ is a divalent aliphatic group, alicyclic group, aromatic group or a combination thereof having a total of 2 to 39 carbon atoms, which may have at least one bonding group selected from the group consisting of -O-, -SO 2 -, -CO-, -CH 2 -, -C(CH 3 ) 2 -, -C 2 H 4 O-, and -S-.
（式（１）で表される繰り返し単位）
ポリイミド樹脂（Ｘ）は、無色透明性と柔軟性の観点から、前記式（１）で表される繰り返し単位を含む。
前記式（１）において、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に一価の脂肪族基又は一価の芳香族基であり、これらの基は少なくとも一部の水素原子がフッ素原子で置換されていてもよい。一価の脂肪族基としては、一価の飽和炭化水素基、一価の不飽和炭化水素基、一価の炭化水素オキシ基等が挙げられる。一価の飽和炭化水素基としては炭素数１～２２のアルキル基が挙げられ、例えば、メチル基、エチル基、プロピル基が例示できる。一価の不飽和炭化水素基としては炭素数２～２２のアルケニル基が挙げられ、例えば、ビニル基、プロペニル基が例示できる。一価の炭化水素オキシ基としては炭素数１～２２のアルコキシ基が挙げられ、例えば、前記で例示したアルキル基に酸素原子が結合してなる１価の基が例示できる。一価の芳香族基としては、炭素数６～２４のアリール基、炭素数７～２４のアラルキル基、炭素数６～２４のアリールオキシ基等が挙げられ、例えば、フェニル基、フェノキシ基等が例示できる。Ｒ1、Ｒ2、Ｒ3及びＲ4としては、特に、メチル基又はフェニル基が好ましい。
Ｚ1及びＺ2は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、これらの基は少なくとも一部の水素原子がフッ素原子で置換されていてもよい。二価の脂肪族基としては、二価の飽和炭化水素基又は二価の不飽和炭化水素基が挙げられる。二価の飽和炭化水素基としては炭素数１～２２のアルキレン基が挙げられ、例えば、メチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基、ドデカメチレン基等が例示できる。二価の不飽和炭化水素基としては、炭素数２～２２の不飽和炭素水素基が挙げられ、例えば、ビニレン基、プロペニレン基、末端に不飽和二重結合を有するアルキレン基が例示できる。二価の芳香族基としては炭素数６～２４のアリーレン基、炭素数７～２４のアラルキレン基、炭素数６～２４のアリーレンオキシ基等が例示できる。これらの基は芳香環を構成する水素原子の少なくとも一部がアルキル基で置換されていてもよい。Ｚ1及びＺ2における炭素数６～２４のアリーレン基の具体例としては、ｏ－フェニレン基、ｍ－フェニレン基、ｐ－フェニレン基、４，４’－ビフェニリレン基、２，６－ナフチレン基等が挙げられる。炭素数７～２４のアラルキレン基の具体例としては、ベンジレン基、フェネチレン基等が挙げられる。炭素数６～２４のアリーレンオキシ基の具体例としては、前記で例示したアリーレン基に酸素原子が結合してなる２価の基が挙げられる。Ｚ1及びＺ2としては、プロピレン基、トリメチレン基、テトラメチレン基、ｐ－フェニレン基、ベンジレン基が好ましく、トリメチレン基、テトラメチレン基、p－フェニレン基がより好ましい。
また、ｒは正の整数であり、２～５０の整数であることが好ましい。ｒが２以上のとき、複数のＲ1及びＲ2はそれぞれ、互いに同一でも異なってもよい。
Ｒ5は、炭素数４～３９の４価の脂環基であり、炭素数４～８の４価の脂環基が好ましく、炭素数４～６の４価の脂環基がより好ましく、炭素数６の４価の脂環基が更に好ましい。
(Repeating unit represented by formula (1))
The polyimide resin (X) contains a repeating unit represented by the above formula (1) from the viewpoints of colorless transparency and flexibility.
In the formula (1), R 1 , R 2 , R 3 and R 4 are each independently a monovalent aliphatic group or a monovalent aromatic group, and at least some of the hydrogen atoms of these groups may be substituted with fluorine atoms. Examples of the monovalent aliphatic group include a monovalent saturated hydrocarbon group, a monovalent unsaturated hydrocarbon group, and a monovalent hydrocarbonoxy group. Examples of the monovalent saturated hydrocarbon group include an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, and a propyl group. Examples of the monovalent unsaturated hydrocarbon group include an alkenyl group having 2 to 22 carbon atoms, such as a vinyl group and a propenyl group. Examples of the monovalent hydrocarbonoxy group include an alkoxy group having 1 to 22 carbon atoms, such as a monovalent group formed by bonding an oxygen atom to the alkyl group exemplified above. Examples of the monovalent aromatic group include an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms, such as a phenyl group, a phenoxy group, etc. R 1 , R 2 , R 3 and R 4 are particularly preferably a methyl group or a phenyl group.
Z 1 and Z 2 are each independently a divalent aliphatic group or a divalent aromatic group, and at least a portion of the hydrogen atoms in these groups may be substituted with fluorine atoms. Examples of the divalent aliphatic group include a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include an alkylene group having 1 to 22 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group. Examples of the divalent unsaturated hydrocarbon group include an unsaturated hydrocarbon group having 2 to 22 carbon atoms, such as a vinylene group, a propenylene group, and an alkylene group having an unsaturated double bond at the terminal. Examples of the divalent aromatic group include an arylene group having 6 to 24 carbon atoms, an aralkylene group having 7 to 24 carbon atoms, and an aryleneoxy group having 6 to 24 carbon atoms. In these groups, at least a part of the hydrogen atoms constituting the aromatic ring may be substituted with an alkyl group. Specific examples of the arylene group having 6 to 24 carbon atoms in Z 1 and Z 2 include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 4,4'-biphenylylene group, and a 2,6-naphthylene group. Specific examples of the aralkylene group having 7 to 24 carbon atoms include a benzylene group and a phenethylene group. Specific examples of the aryleneoxy group having 6 to 24 carbon atoms include a divalent group formed by bonding an oxygen atom to the arylene group exemplified above. Z 1 and Z 2 are preferably a propylene group, a trimethylene group, a tetramethylene group, a p-phenylene group, or a benzylene group, and more preferably a trimethylene group, a tetramethylene group, or a p-phenylene group.
Furthermore, r is a positive integer, and is preferably an integer of 2 to 50. When r is 2 or more, the multiple R 1s and R 2s may be the same or different from each other.
R5 is a tetravalent alicyclic group having 4 to 39 carbon atoms, preferably a tetravalent alicyclic group having 4 to 8 carbon atoms, more preferably a tetravalent alicyclic group having 4 to 6 carbon atoms, and even more preferably a tetravalent alicyclic group having 6 carbon atoms.
ポリイミド樹脂（Ｘ）中の前記式（１）で表される繰り返し単位の比率は、好ましくは１０～５０モル％であり、より好ましくは１０～４０モル％であり、更に好ましくは１５～３０モル％であり、特に好ましくは１５～２５モル％である。The ratio of the repeating unit represented by the formula (1) in the polyimide resin (X) is preferably 10 to 50 mol%, more preferably 10 to 40 mol%, even more preferably 15 to 30 mol%, and particularly preferably 15 to 25 mol%.
ポリイミド樹脂（Ｘ）としては、無色透明性と柔軟性の観点から、前記式（１）で表される繰り返し単位が、下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）と下記式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）から構成されることが好ましい。
（式（ｂ－１）中、Ｒ1～Ｒ4は、それぞれ独立して、一価の脂肪族基又は一価の芳香族基であり、Ｚ1及びＺ2は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、ｒは、正の整数である。）
From the viewpoints of colorless transparency and flexibility, it is preferable that the polyimide resin (X) is composed of a repeating unit represented by the formula (1) above, which is composed of a structural unit (A-1) derived from a compound represented by the following formula (a-1) and a structural unit (B-1) derived from a compound represented by the following formula (b-1):
(In formula (b-1), R 1 to R 4 each independently represent a monovalent aliphatic group or a monovalent aromatic group, Z 1 and Z 2 each independently represent a divalent aliphatic group or a divalent aromatic group, and r is a positive integer.)
式（ａ－１）で表される化合物は、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物である。
ポリイミド樹脂（Ｘ）が構成単位（Ａ－１）を含むことによって、フィルムの無色透明性向上に寄与する。
The compound represented by formula (a-1) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
The polyimide resin (X) containing the structural unit (A-1) contributes to improving the colorless transparency of the film.
式（ｂ－１）におけるＲ1～Ｒ4、Ｚ1、Ｚ2、ｒは、それぞれ前記式（１）におけるＲ1～Ｒ4、Ｚ1、Ｚ2、ｒと同義である。 In the formula (b-1), R 1 to R 4 , Z 1 , Z 2 and r respectively have the same meanings as R 1 to R 4 , Z 1 , Z 2 and r in the formula (1).
式（ｂ－１）で表される化合物としては、１，３－ビス（３－アミノプロピル）－１，１，２，２－テトラメチルジシロキサン、１，３－ビス（３－アミノブチル）－１，１，２，２－テトラメチルジシロキサン、１，３－ビス（４－アミノフェノキシ）テトラメチルジシロキサン、１，１，３，３－テトラメチル－１，３－ビス（４－アミノフェニル）ジシロキサン、１，１，３，３－テトラフェノキシ－１，３－ビス（２－アミノエチル）ジシロキサン、１，１，３，３－テトラフェニル－１，３－ビス（２－アミノエチル）ジシロキサン、１，１，３，３－テトラフェニル－１，３－ビス（３－アミノプロピル）ジシロキサン、１，１，３，３－テトラメチル－１，３－ビス（２－アミノエチル）ジシロキサン、１，１，３，３－テトラメチル－１，３－ビス（３－アミノプロピル）ジシロキサン、１，１，３，３－テトラメチル－１，３－ビス（４－アミノブチル）ジシロキサン、１，３－ジメチル－１，３－ジメトキシ－１，３－ビス（４－アミノブチル）ジシロキサン、１，１，３，３，５，５－ヘキサメチル－１，５－ビス（４－アミノフェニル）トリシロキサン、１，１，５，５－テトラフェニル－３，３－ジメチル－１，５－ビス（３－アミノプロピル）トリシロキサン、１，１，５，５－テトラフェニル－３，３－ジメトキシ－１，５－ビス（４－アミノブチル）トリシロキサン、１，１，５，５－テトラフェニル－３，３－ジメトキシ－１，５－ビス（５－アミノペンチル）トリシロキサン、１，１，５，５－テトラメチル－３，３－ジメトキシ－１，５－ビス（２－アミノエチル）トリシロキサン、１，１，５，５－テトラメチル－３，３－ジメトキシ－１，５－ビス（４－アミノブチル）トリシロキサン、１，１，５，５－テトラメチル－３，３－ジメトキシ－１，５－ビス（５－アミノペンチル）トリシロキサン、１，１，３，３，５，５－ヘキサメチル－１，５－ビス（３－アミノプロピル）トリシロキサン、１，１，３，３，５，５－ヘキサエチル－１，５－ビス（３－アミノプロピル）トリシロキサン、１，１，３，３，５，５－ヘキサプロピル－１，５－ビス（３－アミノプロピル）トリシロキサン等が挙げられる。式（ｂ－１）で表される化合物は単独で用いてもよく、又は２種類以上組み合わせて用いてもよい。
式（ｂ－１）で表される化合物の市販品として入手できるものとしては、信越化学工業株式会社製の「Ｘ－２２－９４０９」、「Ｘ－２２－１６６０Ｂ」、「Ｘ－２２－１６１ＡＳ」、「Ｘ－２２－１６１Ａ」、「Ｘ－２２－１６１Ｂ」等が挙げられる。
ポリイミド樹脂（Ｘ）が構成単位（Ｂ－１）を含むことによって、フィルムの低弾性率化に寄与する。
Examples of the compound represented by formula (b-1) include 1,3-bis(3-aminopropyl)-1,1,2,2-tetramethyldisiloxane, 1,3-bis(3-aminobutyl)-1,1,2,2-tetramethyldisiloxane, 1,3-bis(4-aminophenoxy)tetramethyldisiloxane, 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl)disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetraphenyl-1,3-bis(2-aminoethyl)disiloxane, and the like. aminoethyl)disiloxane, 1,1,3,3-tetraphenyl-1,3-bis(3-aminopropyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(4-aminobutyl)disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis(4-aminobutyl)disiloxane, 1,1,3,3,5,5-hexamethyl-1 ,5-bis(4-aminophenyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(5-aminopentyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(2-aminoethyl)trisiloxane, 1,1,5,5 -tetramethyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(5-aminopentyl)trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis(3-aminopropyl)trisiloxane, etc. The compounds represented by formula (b-1) may be used alone or in combination of two or more kinds.
Commercially available examples of the compound represented by formula (b-1) include “X-22-9409”, “X-22-1660B”, “X-22-161AS”, “X-22-161A”, and “X-22-161B” manufactured by Shin-Etsu Chemical Co., Ltd.
The polyimide resin (X) containing the structural unit (B-1) contributes to a lower elastic modulus of the film.
（式（２）で表される繰り返し単位）
ポリイミド樹脂（Ｘ）は、前記式（２）で表される繰り返し単位を含む。
前記式（２）において、Ｒ6は、炭素数４～３９の４価の脂環基であり、炭素数４～８の４価の脂環基が好ましく、炭素数４～６の４価の脂環基がより好ましく、炭素数６の４価の脂環基が更に好ましい。
Φは合計の炭素数が２～３９の２価の脂肪族基、脂環基、芳香族基又はこれらの組合せからなる基であり、芳香族基を有する基であることが好ましい。
また、Φには、結合基として－Ｏ－、－ＳＯ2－、－ＣＯ－、－ＣＨ2－、－Ｃ（ＣＨ3）2－、－Ｃ2Ｈ4Ｏ－及び－Ｓ－からなる群から選ばれる少なくとも１つを有していてもよく、結合基として－Ｏ－を有することが好ましい。
(Repeating unit represented by formula (2))
The polyimide resin (X) contains a repeating unit represented by the formula (2).
In the formula (2), R6 is a tetravalent alicyclic group having 4 to 39 carbon atoms, preferably a tetravalent alicyclic group having 4 to 8 carbon atoms, more preferably a tetravalent alicyclic group having 4 to 6 carbon atoms, and even more preferably a tetravalent alicyclic group having 6 carbon atoms.
Φ is a divalent aliphatic group, alicyclic group, aromatic group or a combination thereof having a total of 2 to 39 carbon atoms, and is preferably a group having an aromatic group.
In addition, Φ may have at least one bonding group selected from the group consisting of --O--, --SO 2 --, --CO--, --CH 2 --, --C(CH 3 ) 2 --, --C 2 H 4 O-- and --S--, and preferably has --O-- as a bonding group.
ポリイミド樹脂（Ｘ）としては、無色透明性の観点から、前記式（２）で表される繰り返し単位が、前記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）と、下記式（ｂ－２－１）で表される化合物に由来する構成単位（Ｂ－２－１）、下記式（ｂ－２－２）で表される化合物に由来する構成単位（Ｂ－２－２）、及び下記式（ｂ－２－３）で表される化合物に由来する構成単位（Ｂ－２－３）からなる群より選ばれる少なくとも１つに由来する構成単位（Ｂ－２）から構成されることが好ましい。
式（ｂ－２－１）で表される化合物は、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕ヘキサフルオロプロパンである。
式（ｂ－２－２）で表される化合物は、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンである。
式（ｂ－２－３）で表される化合物は、１－(４－アミノフェニル)－２，３－ジヒドロ－１，３，３－トリメチル－１Ｈ－インデン－５－アミンである。
本発明において、ポリイミド樹脂（Ｘ）が構成単位（Ｂ－２）を含むことにより、フィルムのガラス転移温度を向上させることができる。特に構成単位（Ｂ－１）は、フィルムの低弾性率化に寄与するが、他方で、ガラス転移温度を下げるという側面もある。そこで、構成単位Ｂが構成単位（Ｂ－２）を含むことにより、構成単位（Ｂ－１）によるガラス転移温度の低下幅を小さくし、フィルムのガラス転移温度を制御することができる。また、優れた無色透明性を有するフィルムを得る観点からも、ポリイミド樹脂（Ｘ）に構成単位（Ｂ－２）が含まれることが好ましい。
The compound represented by the formula (b-2-1) is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.
The compound represented by formula (b-2-2) is 2,2-bis[4-(4-aminophenoxy)phenyl]propane.
The compound represented by formula (b-2-3) is 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine.
In the present invention, the polyimide resin (X) contains the structural unit (B-2), thereby improving the glass transition temperature of the film. In particular, the structural unit (B-1) contributes to lowering the elastic modulus of the film, but on the other hand, it also has the aspect of lowering the glass transition temperature. Therefore, by containing the structural unit (B-2) in the structural unit B, the degree of decrease in the glass transition temperature caused by the structural unit (B-1) can be reduced, and the glass transition temperature of the film can be controlled. In addition, from the viewpoint of obtaining a film having excellent colorless transparency, it is preferable that the polyimide resin (X) contains the structural unit (B-2).
構成単位（Ｂ－２）は、構成単位（Ｂ－２－１）のみであってもよく、構成単位（Ｂ－２－２）のみであってもよく、又は構成単位（Ｂ－２－３）のみであってもよい。
また、構成単位（Ｂ－２）は、構成単位（Ｂ－２－１）と構成単位（Ｂ－２－２）の組み合せであってもよく、構成単位（Ｂ－２－２）と構成単位（Ｂ－２－３）の組み合わせであってもよく、又は構成単位（Ｂ－２－１）と構成単位（Ｂ－２－３）の組み合わせであってもよい。
また、構成単位（Ｂ－２）は、構成単位（Ｂ－２－１）と構成単位（Ｂ－２－２）と構成単位（Ｂ－２－３）の組み合わせであってもよい。
The structural unit (B-2) may consist solely of the structural unit (B-2-1), or it may consist solely of the structural unit (B-2-2), or it may consist solely of the structural unit (B-2-3).
In addition, the structural unit (B-2) may be a combination of the structural unit (B-2-1) and the structural unit (B-2-2), or a combination of the structural unit (B-2-2) and the structural unit (B-2-3), or a combination of the structural unit (B-2-1) and the structural unit (B-2-3).
The structural unit (B-2) may also be a combination of the structural unit (B-2-1), the structural unit (B-2-2) and the structural unit (B-2-3).
（各構成単位の比率及びその他の構成単位）
ポリイミド樹脂（Ｘ）を構成するテトラカルボン酸二無水物に由来する構成単位（以下、「構成単位Ａ」ともいう。）中の構成単位（Ａ－１）の比率は、好ましくは５０モル％以上であり、より好ましくは７０モル％以上であり、更に好ましくは９０モル％以上であり、特に好ましくは９９モル％以上である。構成単位（Ａ－１）の比率の上限値は特に限定されず、即ち、１００モル％である。構成単位Ａは構成単位（Ａ－１）のみからなっていてもよい。
(Proportion of each constituent unit and other constituent units)
The ratio of the structural unit (A-1) in the structural unit derived from the tetracarboxylic dianhydride constituting the polyimide resin (X) (hereinafter also referred to as "structural unit A") is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 99 mol% or more. There is no particular upper limit for the ratio of the structural unit (A-1), that is, it is 100 mol%. The structural unit A may be composed only of the structural unit (A-1).
構成単位Ａには、構成単位（Ａ－１）以外の構成単位を含んでもよい。そのような構成単位を与えるテトラカルボン酸二無水物としては、特に限定されないが、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、９，９’－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物、及び４，４’－(ヘキサフルオロイソプロピリデン)ジフタル酸無水物等の芳香族テトラカルボン酸二無水物；１，２，３，４－シクロブタンテトラカルボン酸二無水物及びノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物等の脂環式テトラカルボン酸二無水物（ただし、式（ａ－１）で表される化合物を除く）；並びに１，２，３，４－ブタンテトラカルボン酸二無水物等の脂肪族テトラカルボン酸二無水物が挙げられる。
なお、本明細書において、芳香族テトラカルボン酸二無水物とは芳香環を１つ以上含むテトラカルボン酸二無水物を意味し、脂環式テトラカルボン酸二無水物とは脂環を１つ以上含み、かつ芳香環を含まないテトラカルボン酸二無水物を意味し、脂肪族テトラカルボン酸二無水物とは芳香環も脂環も含まないテトラカルボン酸二無水物を意味する。
構成単位Ａに任意に含まれる構成単位（Ａ－１）以外の構成単位は、１種でもよいし、２種以上であってもよい。
また、ポリイミド樹脂（Ｘ）の一態様として、構成単位Ａが９，９’－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物に由来する構成単位を含まないポリイミド樹脂が挙げられる。
The structural unit A may contain a structural unit other than the structural unit (A-1). The tetracarboxylic dianhydride that gives such a structural unit is not particularly limited, but examples thereof include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutane tetracarboxylic 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 dianhydrides such as 1,2,3,4-butane tetracarboxylic dianhydride.
In this specification, the term "aromatic tetracarboxylic acid dianhydride" refers to a tetracarboxylic acid dianhydride containing one or more aromatic rings, the term "alicyclic tetracarboxylic acid dianhydride" refers to a tetracarboxylic acid dianhydride containing one or more alicyclic rings but no aromatic rings, and the term "aliphatic tetracarboxylic acid dianhydride" refers to a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
The structural unit other than the structural unit (A-1) optionally contained in the structural unit A may be of one type, or of two or more types.
Furthermore, one embodiment of the polyimide resin (X) is a polyimide resin in which the structural unit A does not contain a structural unit derived from 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride.
ポリイミド樹脂（Ｘ）を構成するジアミンに由来する構成単位（以下、「構成単位Ｂ」ともいう。）中の構成単位（Ｂ－１）の比率は、好ましくは１０～５０モル％であり、より好ましくは１０～４０モル％であり、更に好ましくは１５～３０モル％であり、特に好ましくは１５～２５モル％である。
構成単位Ｂ中における構成単位（Ｂ－２）の比率は、好ましくは５０～９０モル％であり、より好ましくは６０～９０モル％であり、更に好ましくは７０～８５モル％であり、特に好ましくは７５～８５モル％である。
構成単位Ｂ中における構成単位（Ｂ－１）及び構成単位（Ｂ－２）の合計の比率は、好ましくは５０モル％以上であり、より好ましくは７０モル％以上であり、更に好ましくは９０モル％以上であり、特に好ましくは９９モル％以上である。構成単位（Ｂ－１）及び構成単位（Ｂ－２）の合計の比率の上限値は特に限定されず、即ち、１００モル％である。構成単位Ｂは構成単位（Ｂ－１）と構成単位（Ｂ－２）とのみからなっていてもよい。
The proportion of the structural unit (B-1) in the structural unit derived from a diamine constituting the polyimide resin (X) (hereinafter also referred to as "structural unit B") is preferably 10 to 50 mol %, more preferably 10 to 40 mol %, even more preferably 15 to 30 mol %, and particularly preferably 15 to 25 mol %.
The proportion of the structural unit (B-2) in the structural unit B is preferably 50 to 90 mol %, more preferably 60 to 90 mol %, even more preferably 70 to 85 mol %, and particularly preferably 75 to 85 mol %.
The total ratio of the structural unit (B-1) and the structural unit (B-2) in the structural unit B is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 99 mol% or more. There is no particular upper limit to the total ratio of the structural unit (B-1) and the structural unit (B-2), that is, it is 100 mol%. The structural unit B may be composed of only the structural unit (B-1) and the structural unit (B-2).
構成単位Ｂは構成単位（Ｂ－１）及び（Ｂ－２）以外の構成単位を含んでもよい。そのような構成単位を与えるジアミンとしては、特に限定されないが、１，４－フェニレンジアミン、ｐ－キシリレンジアミン、３，５－ジアミノ安息香酸、２，２’－ジメチルビフェニル－４，４’－ジアミン、２，２’－ビス（トリフルオロメチル）ベンジジン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、ビス（４－アミノフェニル）スルホン、４，４’－ジアミノベンズアニリド、α，α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼン、Ｎ，Ｎ’－ビス（４－アミノフェニル）テレフタルアミド、４，４’－ビス（４－アミノフェノキシ）ビフェニル、及び９，９－ビス（４－アミノフェニル）フルオレン等の芳香族ジアミン（ただし、式（ｂ－１）で表される化合物、式（ｂ－２－１）で表される化合物、式（ｂ－２－２）で表される化合物及び式（ｂ－２－３）で表される化合物を除く）；１，３－ビス（アミノメチル）シクロヘキサン及び１，４－ビス（アミノメチル）シクロヘキサン等の脂環式ジアミン；並びにエチレンジアミン及びヘキサメチレンジアミン等の脂肪族ジアミン（ただし、式（ｂ－１）で表される化合物を除く）が挙げられる。
なお、本明細書において、芳香族ジアミンとは芳香環を１つ以上含むジアミンを意味し、脂環式ジアミンとは脂環を１つ以上含み、かつ芳香環を含まないジアミンを意味し、脂肪族ジアミンとは芳香環も脂環も含まないジアミンを意味する。
構成単位Ｂに任意に含まれる構成単位（Ｂ－１）及び（Ｂ－２）以外の構成単位は、１種でもよいし、２種以上であってもよい。
The structural unit B may contain a structural unit other than the structural units (B-1) and (B-2). Diamines that provide such structural units are not particularly limited, but include 1,4-phenylenediamine, p-xylylenediamine, 3,5-diaminobenzoic acid, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, bis(4-aminophenyl)sulfone, 4,4'-diaminobenzanilide, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, N,N'- ... aromatic diamines such as 4,4'-bis(aminophenyl)terephthalamide, 4,4'-bis(4-aminophenoxy)biphenyl, and 9,9-bis(4-aminophenyl)fluorene (excluding the compounds represented by formula (b-1), (b-2-1), (b-2-2), and (b-2-3)); 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 compounds represented by formula (b-1)).
In this specification, an aromatic diamine means a diamine containing one or more aromatic rings, an alicyclic diamine means a diamine containing one or more alicyclic rings but no aromatic rings, and an aliphatic diamine means a diamine containing neither an aromatic ring nor an alicyclic ring.
The structural units other than the structural units (B-1) and (B-2) optionally contained in the structural unit B may be of one type, or of two or more types.
（ポリイミド樹脂（Ｘ）の特性）
ポリイミド樹脂（Ｘ）の数平均分子量は、得られるポリイミドフィルムの機械的強度の観点から、好ましくは５，０００～１００，０００である。なお、ポリイミド樹脂の数平均分子量は、例えば、ゲルろ過クロマトグラフィー測定による標準ポリメチルメタクリレート（ＰＭＭＡ）換算値より求めることができる。
(Characteristics of Polyimide Resin (X))
From the viewpoint of the mechanical strength of the resulting polyimide film, the number average molecular weight of the polyimide resin (X) is preferably 5,000 to 100,000. The number average molecular weight of the polyimide resin can be determined, for example, from a standard polymethyl methacrylate (PMMA) equivalent value measured by gel filtration chromatography.
ポリイミド樹脂（Ｘ）を用いることで、無色透明性に優れるフィルムを形成することができる。ポリイミド樹脂（Ｘ）を用いることで得られるフィルムの好適な物性値は以下の通りである。By using polyimide resin (X), a film with excellent colorless transparency can be formed. The preferable physical properties of the film obtained by using polyimide resin (X) are as follows:
ポリイミド樹脂（Ｘ）の引張弾性率は、好ましくは２．１ＧＰａ以下であり、より好ましくは２．０ＧＰａ以下であり、更に好ましくは１．８ＧＰａ以下である。
引張弾性率がこの範囲であることによって、フレキシビリティーが高く、フレキシブルディスプレイ等に適したポリイミドフィルムを得ることができる。
引張強度は、好ましくは４０ＭＰａ以上であり、より好ましくは５０ＭＰａ以上であり、更に好ましくは６０ＭＰａ以上である。
引張弾性率及び引張強度は、ＪＩＳ Ｋ７１２７に準拠して測定される値であり、たとえば東洋精機株式会社製の引張試験機「ストログラフＶＧ－１Ｅ」等を用いて測定することができる。
全光線透過率は、厚さ３０μｍのフィルムとした際に、好ましくは８５％以上であり、より好ましくは８８％以上であり、更に好ましくは９０％以上である。
ヘイズは、厚さ３０μｍのフィルムとした際に、好ましくは１．０％以下であり、より好ましくは０．５％以下であり、更に好ましくは０．３％以下である。
イエローインデックス（ＹＩ）は、厚さ３０μｍのフィルムとした際に、好ましくは６．０以下であり、より好ましくは３．０以下であり、更に好ましくは１．５以下である。
全光線透過率、ヘイズ、イエローインデックス（ＹＩ）は、具体的には実施例に記載の方法で測定することができる。
厚み位相差（Ｒｔｈ）の絶対値は、厚さ３０μｍのフィルムとした際に、好ましくは１００ｎｍ以下であり、より好ましくは５０ｎｍ以下であり、更に好ましく３０ｎｍ以下である。
ガラス転移温度（Ｔｇ）は、好ましくは１５０～３００℃、より好ましくは１５０～２８０℃、更に好ましくは１５０～２５０℃である。
The tensile modulus of elasticity of the polyimide resin (X) is preferably 2.1 GPa or less, more preferably 2.0 GPa or less, and further preferably 1.8 GPa or less.
When the tensile modulus is within this range, a polyimide film having high flexibility and suitable for flexible displays and the like can be obtained.
The tensile strength is preferably 40 MPa or more, more preferably 50 MPa or more, and further preferably 60 MPa or more.
The tensile modulus and tensile strength are values measured in accordance with JIS K7127, and can be measured, for example, using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd.
The total light transmittance, when made into a film having a thickness of 30 μm, is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more.
The haze, when formed into a film having a thickness of 30 μm, is preferably 1.0% or less, more preferably 0.5% or less, and further preferably 0.3% or less.
The yellow index (YI) when made into a film having a thickness of 30 μm is preferably 6.0 or less, more preferably 3.0 or less, and further preferably 1.5 or less.
The total light transmittance, haze, and yellow index (YI) can be specifically measured by the methods described in the examples.
The absolute value of the thickness retardation (Rth) is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less, when the film has a thickness of 30 μm.
The glass transition temperature (Tg) is preferably from 150 to 300°C, more preferably from 150 to 280°C, and even more preferably from 150 to 250°C.
（ポリイミド樹脂（Ｘ）の製造方法）
ポリイミド樹脂（Ｘ）は、前記式（１）で表される繰り返し単位を与える化合物を含有するテトラカルボン酸成分とジアミン成分及び前記式（２）で表される繰り返し単位を与える化合物を含有するテトラカルボン酸成分とジアミン成分とを反応させることにより製造することができる。なかでも、構成単位（Ａ－１）を与える化合物を含有するテトラカルボン酸成分と、構成単位（Ｂ－１）を与える化合物及び構成単位（Ｂ－２）を与える化合物を含むジアミン成分とを反応させることにより製造することが好ましい。
(Method for producing polyimide resin (X))
Polyimide resin (X) can be produced by reacting a tetracarboxylic acid component containing a compound that provides a repeating unit represented by formula (1) with a diamine component, and a tetracarboxylic acid component containing a compound that provides a repeating unit represented by formula (2) with a diamine component. Of these, it is preferable to produce the polyimide resin (X) by reacting a tetracarboxylic acid component containing a compound that provides structural unit (A-1) with a diamine component that includes a compound that provides structural unit (B-1) and a compound that provides structural unit (B-2).
構成単位（Ａ－１）を与える化合物としては、式（ａ－１）で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式（ａ－１）で表されるテトラカルボン酸二無水物に対応するテトラカルボン酸（即ち、１，２，４，５－シクロヘキサンテトラカルボン酸）、及び当該テトラカルボン酸のアルキルエステルが挙げられる。構成単位（Ａ－１）を与える化合物としては、式（ａ－１）で表される化合物（即ち、二無水物）が好ましい。 Compounds that give the structural unit (A-1) include, but are not limited to, compounds represented by formula (a-1), and may be derivatives thereof as long as they give the same structural unit. Such derivatives include tetracarboxylic acids corresponding to the tetracarboxylic dianhydride represented by formula (a-1) (i.e., 1,2,4,5-cyclohexanetetracarboxylic acid) and alkyl esters of the tetracarboxylic acid. Compounds that give the structural unit (A-1) are preferably compounds represented by formula (a-1) (i.e., dianhydrides).
テトラカルボン酸成分は、構成単位（Ａ－１）を与える化合物を、好ましくは５０モル％以上含み、より好ましくは７０モル％以上含み、更に好ましくは９０モル％以上含み、特に好ましくは９９モル％以上含む。構成単位（Ａ－１）を与える化合物の含有量の上限値は特に限定されず、即ち、１００モル％である。テトラカルボン酸成分は構成単位（Ａ－１）を与える化合物のみからなっていてもよい。The tetracarboxylic acid component preferably contains 50 mol% or more of the compound that gives the structural unit (A-1), more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the content of the compound that gives the structural unit (A-1) is not particularly limited, that is, it is 100 mol%. The tetracarboxylic acid component may consist only of the compound that gives the structural unit (A-1).
テトラカルボン酸成分は、構成単位（Ａ－１）を与える化合物以外の化合物を含んでもよく、当該化合物としては、上述の芳香族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物、及び脂肪族テトラカルボン酸二無水物、並びにそれらの誘導体（テトラカルボン酸、テトラカルボン酸のアルキルエステル等）が挙げられる。
テトラカルボン酸成分に任意に含まれる構成単位（Ａ－１）を与える化合物以外の化合物は、１種でもよいし、２種以上であってもよい。
The tetracarboxylic acid component may contain a compound other than the compound that provides the structural unit (A-1). Examples of such compounds include the above-mentioned aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aliphatic tetracarboxylic acid dianhydrides, as well as derivatives thereof (tetracarboxylic acids, alkyl esters of tetracarboxylic acids, etc.).
The compound other than the compound which gives the structural unit (A-1) optionally contained in the tetracarboxylic acid component may be one type or two or more types.
構成単位（Ｂ－１）を与える化合物としては、式（ｂ－１）で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式（ｂ－１）で表されるジアミンに対応するジイソシアネートが挙げられる。構成単位（Ｂ－１）を与える化合物としては、式（ｂ－１）で表される化合物（即ち、ジアミン）が好ましい。 Compounds that provide the structural unit (B-1) include, but are not limited to, compounds represented by formula (b-1), and may be derivatives thereof as long as they provide the same structural unit. Examples of such derivatives include diisocyanates that correspond to the diamines represented by formula (b-1). Compounds that provide the structural unit (B-1) are preferably compounds represented by formula (b-1) (i.e., diamines).
構成単位（Ｂ－２）を与える化合物としては、構成単位（Ｂ－２－１）を与える化合物、構成単位（Ｂ－２－２）を与える化合物、及び構成単位（Ｂ－２－３）を与える化合物からなる群より選ばれる少なくとも１つを用いる。
構成単位（Ｂ－２－１）を与える化合物、構成単位（Ｂ－２－２）を与える化合物、及び構成単位（Ｂ－２－３）を与える化合物としては、それぞれ、式（ｂ－２－１）で表される化合物、式（ｂ－２－２）で表される化合物、及び式（ｂ－２－３）で表される化合物が挙げられるが、それらに限られず、同じ構成単位を与える範囲でそれらの誘導体であってもよい。当該誘導体としては、式（ｂ－２－１）で表される化合物で表されるジアミンに対応するジイソシアネート、式（ｂ－２－２）で表される化合物で表されるジアミンに対応するジイソシアネート、及び式（ｂ－２－３）で表される化合物で表されるジアミンに対応するジイソシアネートが挙げられる。構成単位（Ｂ－２－１）を与える化合物、構成単位（Ｂ－２－２）を与える化合物、及び構成単位（Ｂ－２－３）を与える化合物としては、それぞれ、式（ｂ－２－１）で表される化合物（即ち、ジアミン）、式（ｂ－２－２）で表される化合物（即ち、ジアミン）、及び式（ｂ－２－３）で表される化合物（即ち、ジアミン）が好ましい。
As the compound that provides the structural unit (B-2), at least one selected from the group consisting of compounds that provide the structural unit (B-2-1), compounds that provide the structural unit (B-2-2), and compounds that provide the structural unit (B-2-3) is used.
Examples of the compound that provides the structural unit (B-2-1), the compound that provides the structural unit (B-2-2), and the compound that provides the structural unit (B-2-3) include, but are not limited to, the compounds represented by formula (b-2-1), (b-2-2), and (b-2-3), respectively, and may be derivatives thereof as long as they provide the same structural unit. Examples of the derivatives include diisocyanates corresponding to the diamines represented by the compound represented by formula (b-2-1), diisocyanates corresponding to the diamines represented by the compound represented by formula (b-2-2), and diisocyanates corresponding to the diamines represented by the compound represented by formula (b-2-3). As the compound which provides the structural unit (B-2-1), the compound which provides the structural unit (B-2-2), and the compound which provides the structural unit (B-2-3), a compound represented by formula (b-2-1) (i.e., a diamine), a compound represented by formula (b-2-2) (i.e., a diamine), and a compound represented by formula (b-2-3) (i.e., a diamine), respectively, are preferred.
構成単位（Ｂ－２）を与える化合物として、構成単位（Ｂ－２－１）を与える化合物のみを用いてもよく、構成単位（Ｂ－２－２）を与える化合物のみを用いてもよく、又は構成単位（Ｂ－２－３）を与える化合物のみを用いてもよい。
また、構成単位（Ｂ－２）を与える化合物として、構成単位（Ｂ－２－１）を与える化合物と構成単位（Ｂ－２－２）を与える化合物の組み合せを用いてもよく、構成単位（Ｂ－２－２）を与える化合物と構成単位（Ｂ－２－３）を与える化合物の組み合わせを用いてもよく、又は構成単位（Ｂ－２－１）を与える化合物と構成単位（Ｂ－２－３）を与える化合物の組み合せを用いてもよい。
また、構成単位（Ｂ－２）を与える化合物として、構成単位（Ｂ－２－１）を与える化合物と構成単位（Ｂ－２－２）を与える化合物と構成単位（Ｂ－２－３）を与える化合物の組み合せを用いてもよい。
As the compound that provides the structural unit (B-2), only a compound that provides the structural unit (B-2-1) may be used, only a compound that provides the structural unit (B-2-2) may be used, or only a compound that provides the structural unit (B-2-3) may be used.
Furthermore, as the compound that provides the structural unit (B-2), a combination of a compound that provides the structural unit (B-2-1) and a compound that provides the structural unit (B-2-2) may be used; a combination of a compound that provides the structural unit (B-2-2) and a compound that provides the structural unit (B-2-3) may be used; or a combination of a compound that provides the structural unit (B-2-1) and a compound that provides the structural unit (B-2-3) may be used.
Furthermore, as the compound that provides the structural unit (B-2), a combination of a compound that provides the structural unit (B-2-1), a compound that provides the structural unit (B-2-2), and a compound that provides the structural unit (B-2-3) may be used.
ジアミン成分は、構成単位（Ｂ－１）を与える化合物を、好ましくは１０～５０モル％含み、より好ましくは１０～４０モル％含み、更に好ましくは１５～３０モル％含み、特に好ましくは１５～２５モル％含む。
ジアミン成分は、構成単位（Ｂ－２）を与える化合物を、好ましくは５０～９０モル％含み、より好ましくは６０～９０モル％含み、更に好ましくは７０～８５モル％含み、特に好ましくは７５～８５モル％含む。
ジアミン成分は、構成単位（Ｂ－１）を与える化合物及び構成単位（Ｂ－２）を与える化合物を合計で、好ましくは５０モル％以上含み、より好ましくは７０モル％以上含み、更に好ましくは９０モル％以上含み、特に好ましくは９９モル％以上含む。構成単位（Ｂ－１）を与える化合物及び構成単位（Ｂ－２）を与える化合物の合計の含有量の上限値は特に限定されず、即ち、１００モル％である。ジアミン成分は構成単位（Ｂ－１）を与える化合物と構成単位（Ｂ－２）を与える化合物とのみからなっていてもよい。
The diamine component contains the compound that provides the structural unit (B-1) in an amount of preferably 10 to 50 mol %, more preferably 10 to 40 mol %, even more preferably 15 to 30 mol %, and particularly preferably 15 to 25 mol %.
The diamine component contains the compound that provides the structural unit (B-2) in an amount of preferably 50 to 90 mol %, more preferably 60 to 90 mol %, even more preferably 70 to 85 mol %, and particularly preferably 75 to 85 mol %.
The diamine component contains, in total, the compound that gives the structural unit (B-1) and the compound that gives the structural unit (B-2), preferably at least 50 mol%, more preferably at least 70 mol%, even more preferably at least 90 mol%, and particularly preferably at least 99 mol%. There is no particular upper limit on the total content of the compound that gives the structural unit (B-1) and the compound that gives the structural unit (B-2), that is, it is 100 mol%. The diamine component may consist only of the compound that gives the structural unit (B-1) and the compound that gives the structural unit (B-2).
ジアミン成分は構成単位（Ｂ－１）を与える化合物及び構成単位（Ｂ－２）を与える化合物以外の化合物を含んでもよく、当該化合物としては、上述の芳香族ジアミン、脂環式ジアミン、及び脂肪族ジアミン、並びにそれらの誘導体（ジイソシアネート等）が挙げられる。
ジアミン成分に任意に含まれる構成単位（Ｂ－１）を与える化合物及び構成単位（Ｂ－２）を与える化合物以外の化合物は、１種でもよいし、２種以上であってもよい。
The diamine component may contain a compound other than the compound that provides the structural unit (B-1) and the compound that provides the structural unit (B-2). Examples of such compounds include the above-mentioned aromatic diamines, alicyclic diamines, and aliphatic diamines, as well as derivatives thereof (diisocyanates, etc.).
The compound optionally contained in the diamine component other than the compound providing the structural unit (B-1) and the compound providing the structural unit (B-2) may be one type or two or more types.
本発明において、ポリイミド樹脂（Ｘ）の製造に用いるテトラカルボン酸成分とジアミン成分の仕込み量比は、テトラカルボン酸成分１モルに対してジアミン成分が０．９～１．１モルであることが好ましい。In the present invention, the ratio of the amounts of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin (X) is preferably 0.9 to 1.1 moles of the diamine component per mole of the tetracarboxylic acid component.
また、本発明において、ポリイミド樹脂（Ｘ）の製造には、前述のテトラカルボン酸成分及びジアミン成分の他に、末端封止剤を用いてもよい。末端封止剤としてはモノアミン類あるいはジカルボン酸類が好ましい。導入される末端封止剤の仕込み量としては、テトラカルボン酸成分１モルに対して０．０００１～０．１モルが好ましく、特に０．００１～０．０６モルが好ましい。モノアミン類末端封止剤としては、例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ベンジルアミン、４－メチルベンジルアミン、４－エチルベンジルアミン、４－ドデシルベンジルアミン、３－メチルベンジルアミン、３－エチルベンジルアミン、アニリン、３－メチルアニリン、４－メチルアニリン等が推奨される。これらのうち、ベンジルアミン、アニリンが好適に使用できる。ジカルボン酸類末端封止剤としては、ジカルボン酸類が好ましく、その一部を閉環していてもよい。例えば、フタル酸、無水フタル酸、４－クロロフタル酸、テトラフルオロフタル酸、２，３－ベンゾフェノンジカルボン酸、３，４－ベンゾフェノンジカルボン酸、シクロヘキサン－１，２－ジカルボン酸、シクロペンタン－１，２－ジカルボン酸、４－シクロヘキセン－１，２－ジカルボン酸等が推奨される。これらのうち、フタル酸、無水フタル酸が好適に使用できる。In addition, in the present invention, in addition to the above-mentioned tetracarboxylic acid component and diamine component, a terminal blocking agent may be used in the production of polyimide resin (X). As the terminal blocking agent, monoamines or dicarboxylic acids are preferred. The amount of the terminal blocking agent to be introduced is preferably 0.0001 to 0.1 moles per mole of the tetracarboxylic acid component, and particularly preferably 0.001 to 0.06 moles. As the monoamine terminal blocking agent, for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. are recommended. Of these, benzylamine and aniline are preferably used. As the dicarboxylic acid terminal blocking agent, dicarboxylic acids are preferred, and a part of them 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, etc. are recommended. Of these, phthalic acid and phthalic anhydride are preferably used.
前述のテトラカルボン酸成分とジアミン成分とを反応させる方法には特に制限はなく、公知の方法を用いることができる。
具体的な反応方法としては、（１）テトラカルボン酸成分、ジアミン成分、及び反応溶剤を反応器に仕込み、室温～８０℃で０．５～３０時間撹拌し、その後に昇温してイミド化反応を行う方法、（２）ジアミン成分及び反応溶剤を反応器に仕込んで溶解させた後、テトラカルボン酸成分を仕込み、必要に応じて室温～８０℃で０．５～３０時間撹拌し、その後に昇温してイミド化反応を行う方法、（３）テトラカルボン酸成分、ジアミン成分、及び反応溶剤を反応器に仕込み、直ちに昇温してイミド化反応を行う方法等が挙げられる。
The method for reacting the tetracarboxylic acid component and the diamine component is not particularly limited, and any known method can be used.
Specific reaction methods include: (1) a method in which a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged into a reactor, and the mixture is stirred at room temperature to 80° C. for 0.5 to 30 hours, and then the temperature is raised to carry out the imidization reaction; (2) a method in which a diamine component and a reaction solvent are charged into a reactor and dissolved, and then a tetracarboxylic acid component is charged, and the mixture is stirred at room temperature to 80° C. for 0.5 to 30 hours as necessary, and then the temperature is raised to carry out the imidization reaction; and (3) a method 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 carry out the imidization reaction.
ポリイミド樹脂（Ｘ）の製造に用いられる反応溶剤は、イミド化反応を阻害せず、生成するポリイミドを溶解できるものであればよい。例えば、非プロトン性溶剤、フェノール系溶剤、エーテル系溶剤、カーボネート系溶剤等が挙げられる。The reaction solvent used in the production of polyimide resin (X) may be any solvent that does not inhibit the imidization reaction and can dissolve the resulting polyimide. Examples of such solvents include aprotic solvents, phenolic solvents, ether solvents, and carbonate solvents.
非プロトン性溶剤の具体例としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、１，３－ジメチルイミダゾリジノン、テトラメチル尿素等のアミド系溶剤、γ－ブチロラクトン、γ－バレロラクトン等のラクトン系溶剤、ヘキサメチルホスホリックアミド、ヘキサメチルホスフィントリアミド等の含リン系アミド系溶剤、ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶剤、アセトン、シクロヘキサノン、メチルシクロヘキサノン等のケトン系溶剤、ピコリン、ピリジン等のアミン系溶剤、酢酸（２－メトキシ－１－メチルエチル）等のエステル系溶剤等が挙げられる。 Specific examples of aprotic solvents include amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, and tetramethylurea; lactone-based solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide-based solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, and sulfolane; ketone-based solvents such as acetone, cyclohexanone, and methylcyclohexanone; amine-based solvents such as picoline and pyridine; and ester-based solvents such as 2-methoxy-1-methylethyl acetate.
フェノール系溶剤の具体例としては、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、２，６－キシレノール、３，４－キシレノール、３，５－キシレノール等が挙げられる。
エーテル系溶剤の具体例としては、１，２－ジメトキシエタン、ビス（２－メトキシエチル）エーテル、１，２－ビス（２－メトキシエトキシ）エタン、ビス〔２－（２－メトキシエトキシ）エチル〕エーテル、テトラヒドロフラン、１，４－ジオキサン等が挙げられる。
また、カーボネート系溶剤の具体的な例としては、ジエチルカーボネート、メチルエチルカーボネート、エチレンカーボネート、プロピレンカーボネート等が挙げられる。
上記反応溶剤の中でも、アミド系溶剤又はラクトン系溶剤が好ましい。また、上記の反応溶剤は単独で又は２種以上混合して用いてもよい。
Specific examples of phenol-based solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol.
Specific examples of ether solvents 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 carbonate solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
Among the above reaction solvents, amide-based solvents and lactone-based solvents are preferred. The above reaction solvents may be used alone or in combination of two or more.
イミド化反応では、ディーンスターク装置などを用いて、製造時に生成する水を除去しながら反応を行うことが好ましい。このような操作を行うことで、重合度及びイミド化率をより上昇させることができる。In the imidization reaction, it is preferable to carry out the reaction while removing the water generated during production using a Dean-Stark apparatus or the like. By carrying out such an operation, it is possible to further increase the degree of polymerization and the imidization rate.
上記のイミド化反応においては、公知のイミド化触媒を用いることができる。イミド化触媒としては、塩基触媒又は酸触媒が挙げられる。
塩基触媒としては、ピリジン、キノリン、イソキノリン、α－ピコリン、β－ピコリン、２，４－ルチジン、２，６－ルチジン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリエチレンジアミン、イミダゾール、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジエチルアニリン等の有機塩基触媒、水酸化カリウムや水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウム等の無機塩基触媒が挙げられる。
また、酸触媒としては、クロトン酸、アクリル酸、トランス－３－ヘキセノイック酸、桂皮酸、安息香酸、メチル安息香酸、オキシ安息香酸、テレフタル酸、ベンゼンスルホン酸、パラトルエンスルホン酸、ナフタレンスルホン酸等が挙げられる。上記のイミド化触媒は単独で又は２種以上を組み合わせて用いてもよい。
上記のうち、取り扱い性の観点から、塩基触媒を用いることが好ましく、有機塩基触媒を用いることがより好ましく、トリエチルアミンを用いることが更に好ましく、トリエチルアミンとトリエチレンジアミンを組み合わせて用いること特に好ましい。
In the above imidization reaction, a known imidization catalyst can be used, such as a base catalyst or 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,N-dimethylaniline, and N,N-diethylaniline; and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate.
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, paratoluenesulfonic acid, naphthalenesulfonic acid, etc. The above imidization catalysts may be used alone or in combination of two or more kinds.
Among the above, from the viewpoint of handleability, it is preferable to use a base catalyst, more preferably an organic base catalyst, further preferably triethylamine, and particularly preferably a combination of triethylamine and triethylenediamine.
イミド化反応の温度は、反応率及びゲル化等の抑制の観点から、好ましくは１２０～２５０℃、より好ましくは１６０～２００℃である。また、反応時間は、生成水の留出開始後、好ましくは０．５～１０時間である。The temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C, from the viewpoint of the reaction rate and suppression of gelation, etc. The reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
＜フッ素含有ポリマー（Ｙ）＞
本発明におけるフッ素含有ポリマー（Ｙ）は、フッ素を含むモノマー由来の構成単位を有するポリマーであることが好ましく、フッ化アルキル基を含むモノマー由来の構成単位を有するポリマーであることがより好ましい。
本発明におけるフッ素含有ポリマー（Ｙ）は、フッ素含有アクリルポリマーであることが好ましい。
<Fluorine-Containing Polymer (Y)>
The fluorine-containing polymer (Y) in the present invention is preferably a polymer having a structural unit derived from a monomer containing fluorine, and more preferably a polymer having a structural unit derived from a monomer containing a fluorinated alkyl group.
The fluorine-containing polymer (Y) in the present invention is preferably a fluorine-containing acrylic polymer.
前記フッ素含有アクリルポリマーは、フッ素を含むアクリルモノマー由来の構成単位を含有することが好ましく、フッ素を含むアクリルモノマー由来の構成単位と親水性基を有するアクリルモノマー由来の構成単位を含有することがより好ましい。The fluorine-containing acrylic polymer preferably contains a structural unit derived from an acrylic monomer containing fluorine, and more preferably contains a structural unit derived from an acrylic monomer containing fluorine and a structural unit derived from an acrylic monomer having a hydrophilic group.
フッ素を含むアクリルモノマーとしては、パーフルオロアルキル基を有するモノマーが好ましい。
親水性基を有するアクリルモノマーとしては、アクリル酸、メタクリル酸、ヒドロキシアルキル（メタ）アクリレート、ポリアルキレングリコール（メタ）アクリレート、アクリルアミド、メタクリルアミド等が挙げられる。
フッ素含有アクリルポリマーは、疎水性基を有するアクリルモノマーを含有していてもよい。疎水性基を有するアクリルモノマーとしては、アルキル（メタ）アクリレート、シリコーン含有（メタ）アクリレート、アリール（メタ）アクリレート等が挙げられる。
ここで「（メタ）アクリレート」とは、「アクリレート又はメタクリレート」を意味する。
フッ素を含むアクリルモノマーには、その他のビニル基を有するモノマーが共重合されていてもよい。
本発明のポリイミド樹脂組成物にフッ素を含むポリマーを用いることで、ポリイミド骨格中に高温多湿環境下で加水分解を受けやすく、柔軟性を有するシリコーン部分を有するポリイミドを用いたとしても、分子量低下もほとんどなく、ベルト等の支持体からの剥離性も良好となる。また、得られるフィルムの透明性にも優れる。
As the fluorine-containing acrylic monomer, a monomer having a perfluoroalkyl group is preferable.
Examples of acrylic monomers having a hydrophilic group include acrylic acid, methacrylic acid, hydroxyalkyl (meth)acrylates, polyalkylene glycol (meth)acrylates, acrylamides, and methacrylamides.
The fluorine-containing acrylic polymer may contain an acrylic monomer having a hydrophobic group. Examples of the acrylic monomer having a hydrophobic group include alkyl (meth)acrylate, silicone-containing (meth)acrylate, and aryl (meth)acrylate.
Here, "(meth)acrylate" means "acrylate or methacrylate".
The fluorine-containing acrylic monomer may be copolymerized with another monomer having a vinyl group.
By using a fluorine-containing polymer in the polyimide resin composition of the present invention, even if a polyimide having a silicone moiety that is susceptible to hydrolysis in a high-temperature and high-humidity environment and has flexibility is used in the polyimide skeleton, there is almost no decrease in molecular weight, and the peelability from a support such as a belt is good. In addition, the transparency of the obtained film is also excellent.
フッ素含有ポリマー（Ｙ）の市販品としては、共栄社化学株式会社製のＬＥ－６０５、ＬＥ－６０７、ＬＥ－６０５ＤＭ、ＬＥ－６０７ＤＭ等が挙げられる。Commercially available fluorine-containing polymers (Y) include LE-605, LE-607, LE-605DM, and LE-607DM manufactured by Kyoeisha Chemical Co., Ltd.
本発明のポリイミド樹脂組成物において、フッ素含有ポリマー（Ｙ）の含有量は、ポリイミド樹脂（Ｘ）１００質量部に対して、０．０１～１質量部であることが好ましく、０．０５～０．９質量部であることがより好ましく、０．１～０．８質量部であることが更に好ましく、０．２～０．７質量部であることがより更に好ましい。In the polyimide resin composition of the present invention, the content of the fluorine-containing polymer (Y) is preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.9 parts by mass, even more preferably 0.1 to 0.8 parts by mass, and even more preferably 0.2 to 0.7 parts by mass, per 100 parts by mass of the polyimide resin (X).
＜ポリイミド樹脂組成物の特性＞
本発明のポリイミド樹脂組成物を用いることで、ベルト等の支持体からの剥離性に優れ、高温多湿環境下での分子量低下も抑制され、無色透明性にも優れるフィルムの形成が可能である。本発明のポリイミド樹脂組成物を用いることで得られるフィルムの好適な物性値は以下の通りである。
<Characteristics of Polyimide Resin Composition>
By using the polyimide resin composition of the present invention, it is possible to form a film that is excellent in peelability from a support such as a belt, suppresses a decrease in molecular weight under a high temperature and high humidity environment, and is colorless and transparent. The preferable physical property values of the film obtained by using the polyimide resin composition of the present invention are as follows.
全光線透過率は、厚さ３０μｍのフィルムとした際に、好ましくは８５％以上であり、より好ましくは８８％以上であり、更に好ましくは９０％以上である。
ヘイズは、厚さ３０μｍのフィルムとした際に、好ましくは１．０％以下であり、より好ましくは０．５％以下であり、更に好ましくは０．３％以下である。
イエローインデックス（ＹＩ）は、厚さ３０μｍのフィルムとした際に、好ましくは６．０以下であり、より好ましくは３．０以下であり、更に好ましくは１．５以下である。
全光線透過率、ヘイズ、イエローインデックス（ＹＩ）は、具体的には実施例に記載の方法で測定することができる。
厚み位相差（Ｒｔｈ）の絶対値は、厚さ３０μｍのフィルムとした際に、好ましくは１００ｎｍ以下であり、より好ましくは５０ｎｍ以下であり、更に好ましく３０ｎｍ以下である。
ガラス転移温度（Ｔｇ）は、好ましくは１５０～３００℃、より好ましくは１５０～２８０℃、更に好ましくは１５０～２５０℃である。
また、引張弾性率は、好ましくは２．１ＧＰａ以下であり、より好ましくは２．０ＧＰａ以下であり、更に好ましくは１．８ＧＰａ以下である。
引張弾性率がこの範囲であることによって、フレキシビリティーが高く、フレキシブルディスプレイ等に適したポリイミドフィルムとすることができる。
引張強度は、好ましくは４０ＭＰａ以上であり、より好ましくは５０ＭＰａ以上であり、更に好ましくは６０ＭＰａ以上である。
引張弾性率及び引張強度は、ＪＩＳ Ｋ７１２７に準拠して測定される値であり、たとえば東洋精機株式会社製の引張試験機「ストログラフＶＧ－１Ｅ」等を用いて測定することができる。
The total light transmittance, when made into a film having a thickness of 30 μm, is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more.
The haze, when formed into a film having a thickness of 30 μm, is preferably 1.0% or less, more preferably 0.5% or less, and further preferably 0.3% or less.
The yellow index (YI) when made into a film having a thickness of 30 μm is preferably 6.0 or less, more preferably 3.0 or less, and further preferably 1.5 or less.
The total light transmittance, haze, and yellow index (YI) can be specifically measured by the methods described in the examples.
The absolute value of the thickness retardation (Rth) is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less, when the film has a thickness of 30 μm.
The glass transition temperature (Tg) is preferably from 150 to 300°C, more preferably from 150 to 280°C, and even more preferably from 150 to 250°C.
The tensile modulus is preferably 2.1 GPa or less, more preferably 2.0 GPa or less, and further preferably 1.8 GPa or less.
When the tensile modulus is within this range, the polyimide film has high flexibility and is suitable for flexible displays and the like.
The tensile strength is preferably 40 MPa or more, more preferably 50 MPa or more, and further preferably 60 MPa or more.
The tensile modulus and tensile strength are values measured in accordance with JIS K7127, and can be measured, for example, using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd.
［ポリイミドワニス］
本発明のポリイミドワニスは、本発明のポリイミド樹脂組成物が有機溶媒に溶解してなるものである。すなわち、本発明のポリイミドワニスは、本発明のポリイミド樹脂組成物及び有機溶媒を含み、当該ポリイミド樹脂組成物は当該有機溶媒に溶解している。
有機溶媒はポリイミド樹脂（Ｘ）及びフッ素含有ポリマー（Ｙ）が溶解するものであればよく、特に限定されないが、ポリイミド樹脂の製造に用いられる反応溶剤として上述した化合物を、単独又は２種以上を混合して用いることが好ましい。
本発明のポリイミドワニスは、重合法により得られるポリイミド樹脂（Ｘ）が反応溶剤に溶解したポリイミド溶液そのものであってもよいし、又は当該ポリイミド溶液に対して更に希釈溶剤を追加したものであってもよい。
[Polyimide varnish]
The polyimide varnish of the present invention is obtained by dissolving the polyimide resin composition of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin composition of the present invention and an organic solvent, and the polyimide resin composition is dissolved in the organic solvent.
The organic solvent is not particularly limited as long as it dissolves the polyimide resin (X) and the fluorine-containing polymer (Y). However, it is preferable to use the above-mentioned compounds as a reaction solvent used in the production of a polyimide resin, either alone or in combination of two or more kinds.
The polyimide varnish of the present invention may be a polyimide solution itself in which the polyimide resin (X) obtained by polymerization is dissolved in a reaction solvent, or may be a polyimide solution to which a dilution solvent is further added.
本発明のポリイミド樹脂組成物は溶媒溶解性を有しているため、室温で安定な高濃度のワニスとすることができる。本発明のポリイミドワニスは、ポリイミド樹脂（Ｘ）を５～４０質量％含むことが好ましく、１０～３０質量％含むことがより好ましい。また、フッ素含有ポリマー（Ｙ）をポリイミド樹脂（Ｘ）１００質量部に対して、０．００３～０．３質量部含むことが好ましく、０．０１５～０．３質量部含むことがより好ましく、０．０３～０．２５質量部含むことが更に好ましく、０．０８～０．２質量部含むことがより更に好ましい。
ポリイミドワニスの粘度は１～２００Ｐａ・ｓが好ましく、５～１５０Ｐａ・ｓがより好ましい。ポリイミドワニスの粘度は、Ｅ型粘度計を用いて２５℃で測定された値である。
The polyimide resin composition of the present invention has solvent solubility, and can be made into a highly concentrated varnish that is stable at room temperature. The polyimide varnish of the present invention preferably contains 5 to 40 mass %, more preferably 10 to 30 mass %, of polyimide resin (X). The polyimide varnish of the present invention preferably contains 0.003 to 0.3 mass parts of fluorine-containing polymer (Y) relative to 100 mass parts of polyimide resin (X), more preferably 0.015 to 0.3 mass parts, even more preferably 0.03 to 0.25 mass parts, and even more preferably 0.08 to 0.2 mass parts.
The viscosity of the polyimide varnish is preferably from 1 to 200 Pa·s, and more preferably from 5 to 150 Pa·s. The viscosity of the polyimide varnish is a value measured at 25° C. using an E-type viscometer.
また、本発明のポリイミドワニスは、ポリイミドフィルムの要求特性を損なわない範囲で、無機フィラー、接着促進剤、難燃剤、紫外線吸収剤、界面活性剤、レベリング剤、消泡剤、蛍光増白剤、架橋剤、重合開始剤、感光剤等各種添加剤を含んでもよい。
本発明のポリイミドワニスの製造方法は特に限定されず、公知の方法を適用することができる。
In addition, the polyimide varnish of the present invention may contain various additives such as inorganic fillers, adhesion promoters, flame retardants, ultraviolet absorbers, surfactants, leveling agents, defoamers, fluorescent brightening agents, crosslinking agents, polymerization initiators, and photosensitizers, as long as the additives do not impair the required properties of the polyimide film.
The method for producing the polyimide varnish of the present invention is not particularly limited, and any known method can be applied.
前記添加剤として例示した紫外線吸収剤は、任意の適切な紫外線吸収剤を採用することができる。その具体例としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ベンゾエート系紫外線吸収剤、トリアジン系紫外線吸収剤、ヒンダードアミン系紫外線吸収剤、無機粒子系紫外線吸収剤、その他、蓚酸アニリド系紫外線吸収剤やマロン酸エステル系紫外線吸収剤等の有機系紫外線吸収剤が挙げられる。紫外線吸収剤は１種のみ用いても良いし、２種以上を併用しても良い。中でも、ベンゾトリアゾール系紫外線吸収剤およびトリアジン系紫外線吸収剤が好ましく、ベンゾトリアゾール系紫外線吸収剤がより好ましい。The ultraviolet absorbers exemplified as the additives may be any suitable ultraviolet absorbers. Specific examples include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, triazine-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, inorganic particle-based ultraviolet absorbers, and organic ultraviolet absorbers such as oxalic acid anilide-based ultraviolet absorbers and malonic acid ester-based ultraviolet absorbers. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination. Among these, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers are preferred, and benzotriazole-based ultraviolet absorbers are more preferred.
樹脂組成物における紫外線吸収剤の添加量は、ポリイミド樹脂（Ｘ）１００質量部に対して好ましくは、０．０１～６質量部、より好ましくは０．１～５質量部、更に好ましくは０．５～４質量部である。紫外線吸収剤の量が多いと、光学特性や耐熱性等のポリイミド樹脂の特性が低下したり、フィルムにヘイズが生じたりすることがある。
本発明において、紫外線吸収剤は、樹脂組成物中において紫外線吸収剤の効果を達成できるものである。従って、紫外線吸収剤として添加した化合物がそのままの構造で樹脂組成物中に存在していてもよく、あるいは当該化合物が、加熱処理によって、紫外線吸収の効果を依然として有する変性物に変性されていてもよい。また、紫外線吸収剤は、樹脂組成物中でポリイミド樹脂（Ｘ）と均一に混合されていることが好ましい。
The amount of the ultraviolet absorber added to the resin composition is preferably 0.01 to 6 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 4 parts by mass, based on 100 parts by mass of the polyimide resin (X). If the amount of the ultraviolet absorber is too large, the properties of the polyimide resin, such as optical properties and heat resistance, may deteriorate, or haze may occur in the film.
In the present invention, the ultraviolet absorbent is capable of achieving the effect of ultraviolet absorbent in the resin composition.Therefore, the compound added as ultraviolet absorbent may be present in the resin composition with its original structure, or the compound may be modified by heat treatment into a modified product that still has the effect of ultraviolet absorption.In addition, it is preferable that the ultraviolet absorbent is uniformly mixed with the polyimide resin (X) in the resin composition.
［ポリイミドフィルム］
本発明のポリイミドフィルムは、本発明のポリイミド樹脂組成物を含む。したがって、本発明のポリイミドフィルムは、無色透明性に優れており、高温多湿環境下に置かれても分子量低下がないため、保存安定性にも優れている。
本発明のポリイミドフィルムが有する好適な物性値は＜ポリイミド樹脂組成物の特性＞に示した通りである。
[Polyimide film]
The polyimide film of the present invention contains the polyimide resin composition of the present invention, and therefore has excellent colorless transparency and is not susceptible to molecular weight reduction even when placed in a high-temperature and high-humidity environment, and therefore has excellent storage stability.
The preferred physical properties of the polyimide film of the present invention are as shown in <Characteristics of Polyimide Resin Composition>.
本発明のポリイミドフィルムの製造方法には特に制限はなく、公知の方法を用いることができる。例えば、本発明のポリイミドワニスを、ガラス板、金属板、プラスチックなどの平滑な支持体上に塗布、又はフィルム状に成形した後、該ワニス中に含まれる反応溶剤や希釈溶剤等の有機溶媒を加熱により除去し、支持体から剥離する方法等が挙げられる。工業的には、金属性のベルトにポリイミドワニスを塗布した後、該ワニス中に含まれる有機溶媒を加熱により除去し、ベルトから剥離する方法が好ましい。
有機溶媒は、好ましくは１２０℃以下の温度で有機溶媒を蒸発させて、自己支持性フィルムとした後、支持体から剥離する。
本発明のポリイミド樹脂組成物は、支持体からの剥離性に優れるため、得られる自己支持性フィルムが柔軟であっても、フィルムに損傷が生じることなく、剥離することができる。
次に支持体から剥離された自己支持性フィルムの端部を固定し、用いた有機溶媒の沸点以上の温度で乾燥してポリイミドフィルムを製造することが好ましい。また、窒素雰囲気下で乾燥することが好ましい。乾燥雰囲気の圧力は、減圧、常圧、加圧のいずれでもよい。自己支持性フィルムを乾燥してポリイミドフィルムを製造する際の加熱温度は、特に限定されないが、２００～４００℃が好ましい。
The method for producing the polyimide film of the present invention is not particularly limited, and known methods can be used.For example, the polyimide varnish of the present invention is applied to a smooth support such as a glass plate, a metal plate, or a plastic, or formed into a film, and then the organic solvent contained in the varnish, such as a reaction solvent or a dilution solvent, is removed by heating, and the film is peeled off from the support.Industrially, the method of applying the polyimide varnish to a metal belt, removing the organic solvent contained in the varnish by heating, and peeling off from the belt is preferred.
The organic solvent is evaporated, preferably at a temperature of 120° C. or less, to form a self-supporting film, which is then peeled off from the support.
The polyimide resin composition of the present invention has excellent releasability from a support, and therefore, even if the obtained self-supporting film is flexible, it can be peeled off without causing damage to the film.
Next, the end of the self-supporting film peeled off from the support is preferably fixed, and the film is dried at a temperature equal to or higher than the boiling point of the organic solvent used to produce a polyimide film. Drying is preferably performed under a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure, or increased pressure. The heating temperature when the self-supporting film is dried to produce a polyimide film is not particularly limited, but is preferably 200 to 400°C.
本発明のポリイミドフィルムの厚さは用途等に応じて適宜選択することができるが、好ましくは１～２５０μｍ、より好ましくは５～１００μｍ、更に好ましくは１０～８０μｍの範囲である。厚さが１～２５０μｍであることで、自立膜としての実用的な使用が可能となる。
ポリイミドフィルムの厚さは、ポリイミドワニスの固形分濃度や粘度を調整することにより、容易に制御することができる。
The thickness of the polyimide film of the present invention can be appropriately selected depending on the application, etc., but is preferably in the range of 1 to 250 μm, more preferably 5 to 100 μm, and further preferably 10 to 80 μm. When the thickness is 1 to 250 μm, practical use as a free-standing film becomes possible.
The thickness of the polyimide film can be easily controlled by adjusting the solids concentration and viscosity of the polyimide varnish.
本発明のポリイミドフィルムは、カラーフィルター、フレキシブルディスプレイ、半導体部品、光学部材等の各種部材用のフィルムとして好適に用いられる。本発明のポリイミドフィルムは、液晶ディスプレイやＯＬＥＤディスプレイ等の画像表示装置の基板として、特に好適に用いられる。The polyimide film of the present invention is suitable for use as a film for various components such as color filters, flexible displays, semiconductor parts, and optical components. The polyimide film of the present invention is particularly suitable for use as a substrate for image display devices such as liquid crystal displays and OLED displays.
以下に、実施例により本発明を具体的に説明する。但し、本発明はこれらの実施例により何ら制限されるものではない。
実施例及び比較例で得たポリイミドワニスの固形分濃度及びポリイミドフィルムの各物性は以下に示す方法によって測定し、ポリイミドフィルムの各評価を行った。
The present invention will be described in detail below with reference to examples, although the present invention is not limited to these examples in any way.
The solids concentration of the polyimide varnishes and the various physical properties of the polyimide films obtained in the Examples and Comparative Examples were measured by the methods described below, and the polyimide films were evaluated.
（１）固形分濃度
固形分濃度は、アズワン株式会社製の小型電気炉「ＭＭＦ－１」で試料を３２０℃×１２０ｍｉｎで加熱して、加熱前後の試料の質量差から算出した。
（２）フィルム厚さ
フィルム厚さは、株式会社ミツトヨ製のマイクロメーターを用いて測定した。
（３）剥離性
各実施例及び比較例に記載した通り、ポリイミドワニスを＃１０００番で仕上げたＳＵＳ基板上に塗布し、１００℃で２０分保持し、溶媒を揮発させて一次乾燥フィルムを得た。ＳＵＳ基板上から一次乾燥フィルムを剥がす際の剥離の可否を評価した。表１において、剥離できたものを〇、剥離できなかったものを×とした。ここで「剥離できなかったもの」とは、ＳＵＳ基材とフィルムの密着性が強く、剥離時に一次乾燥フィルムの一部が破壊したものをいう。
（４）ポリイミドフィルムの対数粘度
ポリイミドフィルムの対数粘度は、ポリイミドフィルムを濃度が０．５ｇ／ｄＬ溶液となるようにＮ－メチル－２－ピロリドンに均一に溶解した溶液を調整し、その溶液と溶媒との溶液粘度をキャノン－フェンスケ粘度計を用い３０℃で測定して次式で算出した。
対数粘度＝｛ｌｎ（ポリイミドフィルム調整液粘度／溶媒粘度）｝／溶液の濃度
（５）湿熱環境試験（分子量変化の評価）
ポリイミドフィルムを、温度６０℃、湿度９０％ＲＨの恒温恒湿機中で１２０時間処理を行った。その後、（４）ポリイミドフィルムの対数粘度と同様の方法で、湿熱環境試験後の対数粘度を測定した。このようにして得られたポリイミドフィルムの湿熱環境試験前後の対数粘度の差を算出し、分子量変化について評価した。湿熱環境試験前後の対数粘度の差が小さいほど、分子量の低下が抑制できている。
（６）全光線透過率、イエローインデックス（ＹＩ）及びヘイズ
全光線透過率、ＹＩ及びヘイズは、日本電色工業株式会社製の色彩・濁度同時測定器「ＣＯＨ４００」を用いて測定した。
全光線透過率及びＹＩの測定はＪＩＳ Ｋ７３６１－１：１９９７に準拠し、ヘイズの測定はＪＩＳ Ｋ７１３６：２０００に準拠して行った。
(1) Solid Content Concentration The solid content concentration was calculated from the mass difference of the sample before and after heating by heating the sample at 320° C. for 120 min in a small electric furnace “MMF-1” manufactured by AS ONE Corporation.
(2) Film Thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
(3) Peelability As described in each Example and Comparative Example, the polyimide varnish was applied to a SUS substrate finished with #1000 grit, and the substrate was held at 100°C for 20 minutes to evaporate the solvent, thereby obtaining a primary dried film. The primary dried film was evaluated for peelability when peeled off from the SUS substrate. In Table 1, films that could be peeled off were marked with ◯, and films that could not be peeled off were marked with ×. Here, "films that could not be peeled off" refers to films that had strong adhesion between the SUS substrate and the film, and a part of the primary dried film was destroyed during peeling.
(4) Logarithmic Viscosity of Polyimide Film The logarithmic viscosity of the polyimide film was calculated by the following formula: a solution was prepared by uniformly dissolving the polyimide film in N-methyl-2-pyrrolidone to a concentration of 0.5 g/dL, and the solution viscosity of the solution and the solvent was measured at 30° C. using a Cannon-Fenske viscometer.
Logarithmic viscosity={ln(polyimide film preparation solution viscosity/solvent viscosity)}/solution concentration (5) Humidity and heat environment test (evaluation of molecular weight change)
The polyimide film was treated in a thermohygrostat at a temperature of 60° C. and a humidity of 90% RH for 120 hours. Thereafter, the logarithmic viscosity after the humid heat environment test was measured in the same manner as in (4) Logarithmic Viscosity of Polyimide Film. The difference in logarithmic viscosity of the polyimide film obtained in this manner before and after the humid heat environment test was calculated, and the change in molecular weight was evaluated. The smaller the difference in logarithmic viscosity before and after the humid heat environment test, the more the molecular weight decrease was suppressed.
(6) Total Light Transmittance, Yellow Index (YI) and Haze Total light transmittance, YI and haze were measured using a color and turbidity simultaneous measuring instrument "COH400" manufactured by Nippon Denshoku Industries Co., Ltd.
The total light transmittance and YI were measured in accordance with JIS K7361-1:1997, and the haze was measured in accordance with JIS K7136:2000.
実施例及び比較例にてポリイミド樹脂の原料として使用したテトラカルボン酸成分及びジアミン成分、並びにその略号は以下の通りである。
＜テトラカルボン酸成分＞
ＨＰＭＤＡ：１，２，４，５－シクロヘキサンテトラカルボン酸二無水物（三菱ガス化学株式会社製；式（ａ－１）で表される化合物）
＜ジアミン成分＞
Ｘ－２２－９４０９：両末端アミノ変性シリコーンオイル「Ｘ－２２－９４０９」（信越化学工業株式会社製；式（ｂ－１）で表される化合物）
ＨＦＢＡＰＰ：２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕ヘキサフルオロプロパン（セイカ株式会社製；式（ｂ－２－１）で表される化合物）
The tetracarboxylic acid components and diamine components used as raw materials for the polyimide resin in the examples and comparative examples, and their abbreviations, are as follows:
<Tetracarboxylic acid component>
HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Company, Inc.; compound represented by formula (a-1))
<Diamine component>
X-22-9409: Amino-modified silicone oil on both ends "X-22-9409" (manufactured by Shin-Etsu Chemical Co., Ltd.; compound represented by formula (b-1))
HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (manufactured by Seika Corporation; compound represented by formula (b-2-1))
＜実施例１＞
ステンレス製半月型撹拌翼、窒素導入管、冷却管を取り付けたディーンスターク、温度計、ガラス製エンドキャップを備えた０．３Ｌの５ツ口ガラス製丸底フラスコ中で、ＨＦＢＡＰＰを２９．０３４ｇ（０．０５６モル）、Ｘ－２２－９４０９を１８．７６ｇ（０．０１４モル）、γ－ブチロラクトン（三菱ケミカル株式会社製）を５０ｇ、及び触媒としてトリエチレンジアミン（東京化成工業株式会社製）を０．０３９ｇ、トリエチルアミン（関東化学株式会社製）を３．５４ｇ、窒素雰囲気下、２００ｒｐｍで撹拌して溶液を得た。この溶液に、ＨＰＭＤＡを１５．６９２ｇ（０．０７０モル）とγ－ブチロラクトン（三菱ケミカル株式会社製）を１３．５ｇ、それぞれ一括で加えた後、マントルヒーターで加熱し、約２０分かけて反応系内温度を２００℃まで上げた。留去される成分を捕集し、反応系内温度を２００℃に３時間維持した。Ｎ，Ｎ－ジメチルアセトアミド（三菱ガス化学株式会社製）を７８．７６ｇ添加後、１００℃付近で約１時間撹拌して、固形分濃度３０質量％の均一なポリイミド溶液を得た。
得られたポリイミド溶液に、フッ素含有ポリマー（ＬＥ－６０７ＤＭ、共栄社化学株式会社製、３０％ジメチルアセトアミド溶液）をポリイミド樹脂１００質量部に対して０．５質量部（有効分換算）添加してポリイミドワニスを得た。
Example 1
In a 0.3 L five-neck glass round-bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean-Stark equipped with a cooling tube, a thermometer, and a glass end cap, 29.034 g (0.056 mol) of HFBAPP, 18.76 g (0.014 mol) of X-22-9409, 50 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation), and 0.039 g of triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.54 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) as catalysts were stirred at 200 rpm under a nitrogen atmosphere to obtain a solution. 15.692 g (0.070 mol) of HPMDA and 13.5 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) were added in one lump, and then heated with a mantle heater, and the temperature in the reaction system was raised to 200 ° C. over about 20 minutes. The components distilled off were collected, and the temperature inside the reaction system was maintained at 200° C. for 3 hours. After adding 78.76 g of N,N-dimethylacetamide (manufactured by Mitsubishi Gas Chemical Company, Inc.), the mixture was stirred at about 100° C. for about 1 hour to obtain a homogeneous polyimide solution with a solid content concentration of 30% by mass.
To the resulting polyimide solution, 0.5 parts by mass (effective component) of a fluorine-containing polymer (LE-607DM, manufactured by Kyoeisha Chemical Co., Ltd., 30% dimethylacetamide solution) was added per 100 parts by mass of the polyimide resin to obtain a polyimide varnish.
続いて、得られたポリイミドワニスを＃１０００番で仕上げたＳＵＳ基板上に塗布し、１００℃で２０分保持し、溶媒を揮発させることで自己支持性を有する無色透明な一次乾燥フィルムを得た。このポリイミドフィルムをＳＵＳ板上から剥離する際に前記剥離性の評価を行った。更に該フィルムをステンレス枠に固定し、２３０℃で窒素雰囲気下、２時間乾燥することにより溶媒を除去し、厚さ６６μｍのフィルムを得た。得られたフィルムのＦＴ－ＩＲ分析により原料ピークの消失及びイミド骨格に由来するピークの出現を確認した。剥離性の評価結果及びこのポリイミドフィルムの評価結果を表１に示す。The resulting polyimide varnish was then applied to a #1000 finished SUS substrate and held at 100°C for 20 minutes to evaporate the solvent, yielding a colorless, transparent, self-supporting primary dried film. The peelability was evaluated when peeling this polyimide film from the SUS plate. The film was then fixed to a stainless steel frame and dried at 230°C for 2 hours in a nitrogen atmosphere to remove the solvent, yielding a film with a thickness of 66 μm. FT-IR analysis of the resulting film confirmed the disappearance of the raw material peak and the appearance of a peak derived from the imide skeleton. The peelability evaluation results and the evaluation results of this polyimide film are shown in Table 1.
＜実施例２＞
実施例１のＬＥ－６０７ＤＭ（フッ素含有ポリマー、共栄社化学株式会社製）をポリイミド樹脂１００質量部に対して０．１質量部（有効分換算）添加した以外は、実施例１と同じ方法で厚さ５４μｍのポリイミドフィルムを得た。評価結果を表１に示す。
Example 2
A polyimide film having a thickness of 54 μm was obtained in the same manner as in Example 1, except that 0.1 parts by mass (effective content equivalent) of LE-607DM (fluorine-containing polymer, manufactured by Kyoeisha Chemical Co., Ltd.) in Example 1 was added per 100 parts by mass of the polyimide resin. The evaluation results are shown in Table 1.
＜比較例１＞
実施例１のＬＥ－６０７ＤＭ（フッ素含有ポリマー、共栄社化学株式会社製）を、ポリイミド樹脂１００質量部に対して０．２質量部のリン酸エステル系離型剤 ＪＰ－５０２（城北化学工業株式会社製、ジエチルホスファネート：モノエチルホスファネート＝１：１（モル比））に変更した以外は、実施例１と同じ方法で厚さ４７μｍのポリイミドフィルムを得た。評価結果を表１に示す。
<Comparative Example 1>
A polyimide film having a thickness of 47 μm was obtained in the same manner as in Example 1, except that LE-607DM (fluorine-containing polymer, manufactured by Kyoeisha Chemical Co., Ltd.) in Example 1 was changed to 0.2 parts by mass of a phosphoric acid ester-based release agent JP-502 (manufactured by Johoku Chemical Industry Co., Ltd., diethyl phosphanate:monoethyl phosphanate=1:1 (molar ratio)) per 100 parts by mass of the polyimide resin. The evaluation results are shown in Table 1.
＜比較例２＞
実施例１において、ＬＥ－６０７ＤＭ（フッ素含有ポリマー、共栄社化学株式会社製）を添加しなかった以外は、実施例１と同じ方法で厚さ６０μｍのポリイミドフィルムを得た。評価結果を表１に示す。
<Comparative Example 2>
A polyimide film having a thickness of 60 μm was obtained in the same manner as in Example 1, except that LE-607DM (fluorine-containing polymer, manufactured by Kyoeisha Chemical Co., Ltd.) was not added. The evaluation results are shown in Table 1.
表１に示したように、本発明のポリイミド樹脂組成物からなる実施例のポリイミドフィルムは、剥離性に優れ、高温多湿環境下での分子量低下も抑制され、無色透明性にも優れることがわかる。As shown in Table 1, the polyimide films of the examples made of the polyimide resin composition of the present invention have excellent peelability, suppressed molecular weight reduction in high temperature and humidity environments, and are colorless and transparent.
Claims (9)
前記式（１）で表される繰り返し単位が、下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）と下記式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）から構成され、
前記式（２）で表される繰り返し単位が、下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）と、下記式（ｂ－２－１）で表される化合物に由来する構成単位（Ｂ－２－１）、下記式（ｂ－２－２）で表される化合物に由来する構成単位（Ｂ－２－２）、及び下記式（ｂ－２－３）で表される化合物に由来する構成単位（Ｂ－２－３）からなる群より選ばれる少なくとも１つに由来する構成単位（Ｂ－２）から構成され、
ポリイミド樹脂（Ｘ）を構成するジアミンに由来する構成単位中の構成単位（Ｂ－１）の比率が１０～５０モル％であり、
ポリイミド樹脂（Ｘ）を構成するジアミンに由来する構成単位中の構成単位（Ｂ－２）の比率が５０～９０モル％であり、
フッ素含有ポリマー（Ｙ）が、パーフルオロアルキル基を有するフッ素含有アクリルポリマーである、ポリイミド樹脂組成物。
（式（１）中、Ｒ1～Ｒ4は、それぞれ独立して、一価の脂肪族基又は一価の芳香族基であり、Ｚ1及びＺ2は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、ｒは、正の整数であり、Ｒ5は炭素数４～３９の４価の脂環基である。
式（２）中、Ｒ6は炭素数４～３９の４価の脂環基であり、Φは合計の炭素数が２～３９の２価の脂肪族基、脂環基、芳香族基又はこれらの組合せからなる基であって、結合基として－Ｏ－、－ＳＯ2－、－ＣＯ－、－ＣＨ2－、－Ｃ（ＣＨ3）2－、－Ｃ2Ｈ4Ｏ－及び－Ｓ－からなる群から選ばれる少なくとも１つを有していてもよい。）
（式（ｂ－１）中、Ｒ 1 ～Ｒ 4 は、それぞれ独立して、一価の脂肪族基又は一価の芳香族基であり、Ｚ 1 及びＺ 2 は、それぞれ独立して、二価の脂肪族基又は二価の芳香族基であり、ｒは、正の整数である。）
The repeating unit represented by the formula (1) is composed of a structural unit (A-1) derived from a compound represented by the following formula (a-1) and a structural unit (B-1) derived from a compound represented by the following formula (b-1),
The repeating unit represented by formula (2) is composed of a structural unit (A-1) derived from a compound represented by formula (a-1) below, and a structural unit (B-2) derived from at least one selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by formula (b-2-1) below, a structural unit (B-2-2) derived from a compound represented by formula (b-2-2) below, and a structural unit (B-2-3) derived from a compound represented by formula (b-2-3) below,
the ratio of the structural unit (B-1) in the structural units derived from diamine constituting the polyimide resin (X) is 10 to 50 mol %,
the ratio of the structural unit (B-2) in the structural units derived from diamine constituting the polyimide resin (X) is 50 to 90 mol %,
A polyimide resin composition , wherein the fluorine-containing polymer (Y) is a fluorine-containing acrylic polymer having a perfluoroalkyl group .
In formula (1), R 1 to R 4 are each independently a monovalent aliphatic group or a monovalent aromatic group, Z 1 and Z 2 are each independently a divalent aliphatic group or a divalent aromatic group, r is a positive integer, and R 5 is a tetravalent alicyclic group having 4 to 39 carbon atoms.
In formula (2), R 6 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and Φ is a divalent aliphatic group, alicyclic group, aromatic group or a combination thereof having a total of 2 to 39 carbon atoms, which may have at least one bonding group selected from the group consisting of -O-, -SO 2 -, -CO-, -CH 2 -, -C(CH 3 ) 2 -, -C 2 H 4 O-, and -S-.
(In formula (b-1), R 1 to R 4 each independently represent a monovalent aliphatic group or a monovalent aromatic group, Z 1 and Z 2 each independently represent a divalent aliphatic group or a divalent aromatic group, and r is a positive integer.)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019155627 | 2019-08-28 | ||
| JP2019155627 | 2019-08-28 | ||
| PCT/JP2020/030894 WO2021039442A1 (en) | 2019-08-28 | 2020-08-14 | Polyimide resin composition, polyimide varnish, and polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2021039442A1 JPWO2021039442A1 (en) | 2021-03-04 |
| JP7548236B2 true JP7548236B2 (en) | 2024-09-10 |
Family
ID=74684841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021542748A Active JP7548236B2 (en) | 2019-08-28 | 2020-08-14 | Polyimide resin composition, polyimide varnish and polyimide film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7548236B2 (en) |
| KR (1) | KR20220054803A (en) |
| CN (1) | CN114364747A (en) |
| WO (1) | WO2021039442A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005061020A1 (en) | 2003-12-22 | 2005-07-07 | I.S.T Corporation | Medical tube and process for producing the same |
| JP2006137796A (en) | 2004-11-10 | 2006-06-01 | Jsr Corp | Liquid crystal-aligning agent and liquid crystal display element |
| WO2014073591A1 (en) | 2012-11-08 | 2014-05-15 | 旭化成イーマテリアルズ株式会社 | Substrate for flexible device, flexible device and method for producing same, laminate and method for producing same, and resin composition |
| JP2019038930A (en) | 2017-08-24 | 2019-03-14 | 味の素株式会社 | Resin composition |
| JP2019077863A (en) | 2017-10-19 | 2019-05-23 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide precursor and polyimide |
| JP2019104843A (en) | 2017-12-13 | 2019-06-27 | Ａｇｃ株式会社 | Resin composition, laminate, metal laminate and printed wiring board |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57195149A (en) * | 1981-05-27 | 1982-11-30 | Nippon Oil & Fats Co Ltd | Coating composition for jig and hanger |
| JPS60244507A (en) | 1984-05-18 | 1985-12-04 | Ube Ind Ltd | Preparation of aromatic polyimide film |
| JPH03181558A (en) * | 1989-12-11 | 1991-08-07 | Mitsubishi Petrochem Co Ltd | Aromatic poly(amide/imide) resin composition |
| JP5283408B2 (en) | 2008-03-19 | 2013-09-04 | ユニチカ株式会社 | Method for producing ultra-thin polyimide film |
| JP2017222745A (en) | 2016-06-14 | 2017-12-21 | 信越化学工業株式会社 | Solventless silicone-modified polyimide resin composition |
| JP2020128521A (en) * | 2019-02-07 | 2020-08-27 | 富士ゼロックス株式会社 | Fluorine resin-containing particle, composition, laminar matter, electrophotographic photoreceptor, process cartridge, and image formation device |
-
2020
- 2020-08-14 JP JP2021542748A patent/JP7548236B2/en active Active
- 2020-08-14 CN CN202080060025.4A patent/CN114364747A/en active Pending
- 2020-08-14 KR KR1020227006182A patent/KR20220054803A/en unknown
- 2020-08-14 WO PCT/JP2020/030894 patent/WO2021039442A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005061020A1 (en) | 2003-12-22 | 2005-07-07 | I.S.T Corporation | Medical tube and process for producing the same |
| JP2006137796A (en) | 2004-11-10 | 2006-06-01 | Jsr Corp | Liquid crystal-aligning agent and liquid crystal display element |
| WO2014073591A1 (en) | 2012-11-08 | 2014-05-15 | 旭化成イーマテリアルズ株式会社 | Substrate for flexible device, flexible device and method for producing same, laminate and method for producing same, and resin composition |
| JP2019038930A (en) | 2017-08-24 | 2019-03-14 | 味の素株式会社 | Resin composition |
| JP2019077863A (en) | 2017-10-19 | 2019-05-23 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide precursor and polyimide |
| JP2019104843A (en) | 2017-12-13 | 2019-06-27 | Ａｇｃ株式会社 | Resin composition, laminate, metal laminate and printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202115156A (en) | 2021-04-16 |
| WO2021039442A1 (en) | 2021-03-04 |
| JPWO2021039442A1 (en) | 2021-03-04 |
| KR20220054803A (en) | 2022-05-03 |
| CN114364747A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6996609B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| JP7367699B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| JPWO2020138360A1 (en) | Imid-amidic acid copolymer and its production method, varnish, and polyimide film | |
| JP7215428B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| JP7180617B2 (en) | Polyimide resin composition and polyimide film | |
| JP7384170B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| WO2019116940A1 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| JP7392657B2 (en) | Polyimide resin composition and polyimide film | |
| WO2020040057A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| JP7306371B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| WO2021132196A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN114729122A (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| TW202120634A (en) | Polyimide resin composition, polyimide varnish, and polyimide film | |
| JP7548236B2 (en) | Polyimide resin composition, polyimide varnish and polyimide film | |
| TW202348399A (en) | Film, method for manufacturing same, and image display device | |
| TWI855132B (en) | Polyimide resin composition, polyimide varnish, and polyimide film | |
| WO2021210641A1 (en) | Imide-amic acid copolymer and method for producing same, varnish, and polyimide film | |
| JPWO2019065522A1 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| KR102730126B1 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| JP7371621B2 (en) | Polyimide resin, polyimide varnish and polyimide film | |
| WO2021177145A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| WO2021132109A1 (en) | Polyimide resin, polyimide resin composition, polyimide varnish, and polyimide film | |
| WO2021153379A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| TW202136393A (en) | Method for producing polyimide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230621 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240319 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240516 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240730 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240812 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7548236 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |