JP6966726B2 - Acid dianhydride and its use - Google Patents
Acid dianhydride and its use Download PDFInfo
- Publication number
- JP6966726B2 JP6966726B2 JP2018542882A JP2018542882A JP6966726B2 JP 6966726 B2 JP6966726 B2 JP 6966726B2 JP 2018542882 A JP2018542882 A JP 2018542882A JP 2018542882 A JP2018542882 A JP 2018542882A JP 6966726 B2 JP6966726 B2 JP 6966726B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acid
- represented
- polyimide
- carbon atoms
- 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
- 239000002253 acid Substances 0.000 title claims description 83
- 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 title claims description 71
- 229920001721 polyimide Polymers 0.000 claims description 110
- 239000004642 Polyimide Substances 0.000 claims description 74
- 229920005575 poly(amic acid) Polymers 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 61
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 22
- 150000004985 diamines Chemical class 0.000 claims description 20
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 45
- 239000010408 film Substances 0.000 description 40
- 239000002904 solvent Substances 0.000 description 35
- -1 dianhydride compound Chemical class 0.000 description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 239000012024 dehydrating agents Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 125000006159 dianhydride group Chemical group 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- WVOLTBSCXRRQFR-DLBZAZTESA-N cannabidiolic acid Chemical compound OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- MDEIZAFOJJIXIS-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-1-ol Chemical compound C(C)OC(COC(CC)O)C MDEIZAFOJJIXIS-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 2
- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- MNUSMUGFHGAOIW-UHFFFAOYSA-N cyclohexane-1,1,2-tricarboxylic acid Chemical compound OC(=O)C1CCCCC1(C(O)=O)C(O)=O MNUSMUGFHGAOIW-UHFFFAOYSA-N 0.000 description 2
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920000642 polymer Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229940116423 propylene glycol diacetate Drugs 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-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
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 0 *=C(C1C2CCIC1)OC2=O Chemical compound *=C(C1C2CCIC1)OC2=O 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
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical compound CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- BNGPVKSKKYIJCR-UHFFFAOYSA-N 2-chloro-1,3-dimethylimidazolidine;hydrochloride Chemical compound [Cl-].CN1CC[NH+](C)C1Cl BNGPVKSKKYIJCR-UHFFFAOYSA-N 0.000 description 1
- FGSUUFDRDVJCLT-UHFFFAOYSA-N 3-methylazepan-2-one Chemical compound CC1CCCCNC1=O FGSUUFDRDVJCLT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YZIIFXXQXRRNED-UHFFFAOYSA-N O=C(C(CCC1C(O2)=O)CC1C2=O)Oc(cc1)c(C2c3ccccc3C3c4ccccc24)c3c1OC(C(CCC1C(O2)=O)CC1C2=O)=O Chemical compound O=C(C(CCC1C(O2)=O)CC1C2=O)Oc(cc1)c(C2c3ccccc3C3c4ccccc24)c3c1OC(C(CCC1C(O2)=O)CC1C2=O)=O YZIIFXXQXRRNED-UHFFFAOYSA-N 0.000 description 1
- DSFWTHYIHNKYDA-UHFFFAOYSA-N O=C(C1C2C[IH]CC1)OC2=O Chemical compound O=C(C1C2C[IH]CC1)OC2=O DSFWTHYIHNKYDA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical class ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LXCHSZSNUOVMSM-UHFFFAOYSA-N stk367285 Chemical compound C12=CC=CC=C2C2C(C(O)=CC=C3O)=C3C1C1=CC=CC=C12 LXCHSZSNUOVMSM-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005922 tert-pentoxy group Chemical group 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
Description
本発明は、新規な酸二無水物およびそのポリアミック酸及びポリイミドへの利用に関する。 The present invention relates to novel acid dianhydrides and their use in polyamic acids and polyimides.
近年、液晶ディスプレイや有機エレクトロルミネッセンスディスプレイ等のエレクトロニクスの急速な進歩に伴い、デバイスの薄型化や軽量化、更には、フレキシブル化が要求されるようになってきた。
これらのデバイスにおいては、ガラス基板上に様々な電子素子、例えば、薄膜トランジスタや透明電極等が形成されているが、このガラス材料を柔軟かつ軽量な樹脂材料に替えることで、デバイス自体の薄型化や軽量化、フレキシブル化が期待される。
そして、そのような樹脂材料の候補としてはポリイミドが注目を集めており、ポリイミドフィルムに関する種々の報告が従来よりなされている（例えば特許文献１，２参照）。In recent years, with the rapid progress of electronics such as liquid crystal displays and organic electroluminescence displays, there has been a demand for devices to be thinner, lighter, and more flexible.
In these devices, various electronic elements such as thin film transistors and transparent electrodes are formed on a glass substrate. By replacing this glass material with a flexible and lightweight resin material, the device itself can be made thinner. It is expected to be lighter and more flexible.
Polyimide has been attracting attention as a candidate for such a resin material, and various reports on polyimide films have been made conventionally (see, for example, Patent Documents 1 and 2).
ところで、ポリイミド樹脂材料をディスプレイの基板として用いるとき、その樹脂材料が透明性に優れるだけでなく、要求性能の一つとしてリタデーション（Ｒｅｔａｒｄａｔｉｏｎ）が低い材料であることが望ましい。
すなわち、リタデーション（位相差）とは、複屈折（直交する２つの屈折率の差）と膜厚との積をいうが、この数値、特に厚さ方向のリタデーションは視野角特性に影響する重要な数値である。大きなリタデーション値は、ディスプレイの表示品質の低下を招く原因となり得る（例えば特許文献３参照）。フレキシブルディスプレイ基板にあっても、高い柔軟性（可撓性）以外に、これらの特性も求められている。By the way, when a polyimide resin material is used as a substrate for a display, it is desirable that the resin material not only has excellent transparency but also has low retardation as one of the required performances.
That is, the retardation (phase difference) is the product of birefringence (difference between two orthogonal refractive indexes) and the film thickness, and this numerical value, especially the retardation in the thickness direction, is important to affect the viewing angle characteristics. It is a numerical value. A large retardation value can cause deterioration of the display quality of the display (see, for example, Patent Document 3). Even in a flexible display substrate, these characteristics are required in addition to high flexibility (flexibility).
本発明は、このような事情に鑑みてなされたものであって、耐熱性、柔軟性及び透明性に優れるだけでなく、リタデーションが低いという特徴をも有するポリイミド膜を与えるポリアミック酸及びポリイミド、並びにポリアミック酸及びポリイミドの製造に用いる新規な酸二無水物を提供することを目的とする。 The present invention has been made in view of such circumstances, and is a polyamic acid and a polyimide that gives a polyimide film having not only excellent heat resistance, flexibility and transparency but also low retardation. It is an object of the present invention to provide a novel acid dianhydride used for the production of polyamic acid and polyimide.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、下記式（１−１）で表される酸二無水物化合物を、テトラシクロブタン酸二無水物等の脂環式テトラカルボン酸二無水物と共に、２，２’−ジ（トリフルオロメチル）ベンジジン等の芳香族ジアミンと共重合させることで、有機溶媒に良好な溶解性を示すポリアミック酸及びポリイミドが得られること、及び当該ポリアミック酸及びポリイミドを有機溶媒に溶解させて得られる組成物（溶液）から、耐熱性、柔軟性及び透明性に優れるだけでなく、リタデーションが低いという特徴をも有するポリイミド膜が得られることを見出し、本発明を完成させた。 As a result of diligent studies to solve the above problems, the present inventors have introduced an acid dianhydride compound represented by the following formula (1-1) into an alicyclic tetra such as tetracyclobutanoic acid dianhydride. By copolymerizing with aromatic diamine such as 2,2'-di (trifluoromethyl) benzidine together with carboxylic acid dianhydride, polyamic acid and polyimide showing good solubility in organic solvents can be obtained, and From the composition (solution) obtained by dissolving the polyamic acid and polyimide in an organic solvent, a polyimide film having not only excellent heat resistance, flexibility and transparency but also low retardation can be obtained. Find out and complete the present invention.
すなわち、本発明は、第１観点として、酸二無水物成分と、ジアミン成分とを反応させて得られるポリアミック酸であって、
前記酸二無水物成分が下記式（１−１）で表される酸二無水物を含むことを特徴とする、ポリアミック酸に関する。
Ｒ6及びＲ7は、互いに独立して、水素原子、ハロゲン原子、炭素原子数１乃至５のアルキル基又は炭素原子数１乃至５のアルコキシ基を表し、
ａおよびｂは、互いに独立して、０〜４の整数を表し、
ｃおよびｄは、互いに独立して、０〜９の整数を表し、
ｅは、０〜２の整数を表す。）
第２観点として、前記ジアミン成分が式（Ａ１）で表されるジアミンを含むことを特徴とする、第１観点に記載のポリアミック酸に関する。
第３観点として、前記酸二無水物成分が、更に式（Ｃ１）で表されるテトラカルボン酸二無水物を含むことを特徴とする、第１観点又は第２観点に記載のポリアミック酸に関する。
第４観点として、第１観点乃至第３観点のうちいずれか一項に記載のポリアミック酸と、有機溶媒とを含むポリイミド膜形成用組成物に関する。
第５観点として、第４観点に記載のポリイミド膜形成用組成物を用いて形成されるポリイミド膜に関する。
第６観点として、第５観点に記載のポリイミド膜からなるフレキシブルデバイス用基板に関する。
第７観点として、第１観点乃至第３観点のうちいずれか一項に記載のポリアミック酸をイミド化して得られるポリイミドに関する。
第８観点として、第７観点に記載のポリイミドと、有機溶媒とを含む膜形成用組成物に関する。
第９観点として、第８観点に記載の膜形成用組成物を用いて形成されるポリイミド膜に関する。
第１０観点として、第９観点に記載のポリイミド膜からなるフレキシブルデバイス用基板に関する。
第１１観点として、式（１−１）で表されることを特徴とする酸二無水物に関する。
Ｒ6及びＲ7は、互いに独立して、水素原子、ハロゲン原子、炭素原子数１乃至５のアルキル基又は炭素原子数１乃至５のアルコキシ基を表し、
ａおよびｂは、互いに独立して、０〜４の整数を表し、
ｃおよびｄは、互いに独立して、０〜９の整数を表し、
ｅは、０〜２の整数を表す。）
第１２観点として、式（１−２）で表されることを特徴とする、第１１観点に記載の酸二無水物に関する。
第１３観点として、式（１−３）で表されることを特徴とする、第１２観点に記載の酸二無水物に関する。
Ｒ6及びＲ7は、互いに独立して、水素原子、ハロゲン原子、炭素原子数１乃至５のアルキル基又は炭素原子数１乃至５のアルコキシ基を表し、
ａおよびｂは、互いに独立して、０〜４の整数を表し、
ｃおよびｄは、互いに独立して、０〜９の整数を表し、
ｅは、０〜２の整数を表す。）
第１５観点として、式（２−２）で表されることを特徴とする、第１４観点に記載のテトラカルボン酸に関する。
第１６観点として、式（２−３）で表されることを特徴とする、第１５観点に記載のテトラカルボン酸に関する。
The present invention relates to a polyamic acid, wherein the acid dianhydride component contains an acid dianhydride represented by the following formula (1-1).
R 6 and R 7 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
a and b represent integers from 0 to 4 independently of each other.
c and d represent integers 0-9 independently of each other.
e represents an integer of 0 to 2. )
The second aspect relates to the polyamic acid according to the first aspect, wherein the diamine component contains a diamine represented by the formula (A1).
As a third aspect, the polyamic acid according to the first aspect or the second aspect, wherein the acid dianhydride component further contains a tetracarboxylic dianhydride represented by the formula (C1).
As a fourth aspect, the present invention relates to a polyimide film forming composition containing the polyamic acid according to any one of the first aspect to the third aspect and an organic solvent.
As a fifth aspect, the present invention relates to a polyimide film formed by using the polyimide film forming composition according to the fourth aspect.
As a sixth aspect, the present invention relates to a substrate for a flexible device made of the polyimide film according to the fifth aspect.
As a seventh aspect, the present invention relates to a polyimide obtained by imidizing the polyamic acid according to any one of the first aspect to the third aspect.
As an eighth aspect, the present invention relates to a film-forming composition containing the polyimide according to the seventh aspect and an organic solvent.
A ninth aspect relates to a polyimide film formed by using the film forming composition as described in the eighth aspect.
As a tenth aspect, the present invention relates to a substrate for a flexible device made of the polyimide film according to the ninth aspect.
As an eleventh aspect, the present invention relates to an acid dianhydride, which is represented by the formula (1-1).
R 6 and R 7 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
a and b represent integers from 0 to 4 independently of each other.
c and d represent integers 0-9 independently of each other.
e represents an integer of 0 to 2. )
As a twelfth aspect, it relates to the acid dianhydride according to the eleventh aspect, which is represented by the formula (1-2).
As a thirteenth aspect, it relates to the acid dianhydride according to the twelfth aspect, which is represented by the formula (1-3).
R 6 and R 7 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
a and b represent integers from 0 to 4 independently of each other.
c and d represent integers 0-9 independently of each other.
e represents an integer of 0 to 2. )
As a fifteenth aspect, it relates to the tetracarboxylic dian according to the fourteenth aspect, which is represented by the formula (2-2).
As the 16th aspect, it relates to the tetracarboxylic dian according to the 15th aspect, which is represented by the formula (2-3).
本発明のポリアミック酸及びポリイミドは有機溶媒に良好な溶解性を示し、また該ポリアミック酸及びポリイミドは、耐熱性、柔軟性及び透明性に優れ、さらに低いリタデーションを実現できるポリイミド膜（樹脂薄膜）を形成できる。
また、本発明のポリイミド膜は、高い透明性（高い光線透過率、低い黄色度）、耐熱性及び低いリタデーションを示すことから、フレキシブルデバイス、特にフレキシブルディスプレイの基板として好適に用いることができる。The polyamic acid and polyimide of the present invention show good solubility in organic solvents, and the polyamic acid and polyimide have excellent heat resistance, flexibility and transparency, and a polyimide film (resin thin film) capable of realizing lower retardation can be obtained. Can be formed.
Further, since the polyimide film of the present invention exhibits high transparency (high light transmittance, low yellowness), heat resistance and low retardation, it can be suitably used as a substrate for a flexible device, particularly a flexible display.
以下、本発明についてさらに詳しく説明する。
本発明に係るポリアミック酸は、下記式（１−１）で表される酸二無水物を含む酸二無水物成分と、ジアミン成分とを重縮合反応させて得られる。そして得られたポリアミック酸を、熱または触媒を用いた脱水閉環反応により、対応するポリイミドとすることができる。該ポリアミック酸のみならず該ポリイミドともに本発明の対象である。なお本発明のポリアミック酸は、下記式（１−１）で表される酸二無水物を含む酸二無水物成分とジアミン成分との反応生成物であり、また、本発明のポリイミドは前記ポリアミック酸のイミド化物である。Hereinafter, the present invention will be described in more detail.
The polyamic acid according to the present invention is obtained by polycondensing a diamine component with an acid dianhydride component containing an acid dianhydride represented by the following formula (1-1). Then, the obtained polyamic acid can be obtained as a corresponding polyimide by a dehydration ring closure reaction using heat or a catalyst. Not only the polyamic acid but also the polyimide is the subject of the present invention. The polyamic acid of the present invention is a reaction product of an acid dianhydride component containing an acid dianhydride represented by the following formula (1-1) and a diamine component, and the polyimide of the present invention is the polyamic acid. It is an acid imidized product.
該式（１−１）で表される酸二無水物として、特に式（１−２）で表される酸二無水物が好ましく、中でも、耐熱性、柔軟性及び透明性に優れ、低リタデーションのポリイミド膜を再現性よく与えるポリアミック酸及び対応するポリイミドを得ることを考慮すると、好ましくは式（１−３）で表される酸二無水物である。
Ｒ6及びＲ7は、互いに独立して、水素原子、ハロゲン原子、炭素原子数１乃至５のアルキル基又は炭素原子数１乃至５のアルコキシ基を表し、
ａおよびｂは、互いに独立して、０〜４の整数を表し、
ｃおよびｄは、互いに独立して、０〜９の整数を表し、
ｅは、０〜２の整数を表す。）As the acid dianhydride represented by the formula (1-1), the acid dianhydride represented by the formula (1-2) is particularly preferable, and among them, excellent heat resistance, flexibility and transparency, and low polyimide. In consideration of obtaining a polyamic acid and a corresponding polyimide that give the polyimide film of the above with good reproducibility, the acid dianhydride represented by the formula (1-3) is preferable.
R 6 and R 7 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
a and b represent integers from 0 to 4 independently of each other.
c and d represent integers 0-9 independently of each other.
e represents an integer of 0 to 2. )
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられる。
上記炭素原子数１乃至５のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソアミル基、ネオペンチル基、ｔｅｒｔ−アミル基、ｓｅｃ−イソアミル基及びシクロペンチル基等が挙げられる。
また炭素原子数１乃至５のアルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペントキシ基、イソペントキシ基、ネオペントキシ基及びｔｅｒｔ−ペントキシ基等が挙げられる。Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.
Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , Isoamyl group, neopentyl group, tert-amyl group, sec-isoamyl group, cyclopentyl group and the like.
Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and an n-pentoxy group. , Isopentoxy group, neopentoxy group, tert-pentoxy group and the like.
本発明の上記式（１−１）〜（１−３）で表される酸二無水物は、それぞれ下記式（２−１）〜（２−３）で表されるテトラカルボン酸を脱水剤にて分子内で脱水させて得ることができる。
具体的には、上記式（１−１）で表される酸二無水物は、一例として下記スキームで示されるように、有機溶媒中、９，１０−［１，２］ベンゼノアントラセン−１，４−ジオール化合物（以下、ベンゼノアントラセンジオール化合物ともいう。）と、シクロヘキサントリカルボン酸ハロゲン化無水物を塩基または酸吸収剤の存在下で反応させて得ることができる［反応式１］。また反応後は溶媒を除去後、反応混合物を再結晶、蒸留、シリカゲルカラムクロマトグラフィ等の公知の手法を用いて精製し、目的物の酸二無水物を得ることができる。
また［反応式１］の反応物を加水分解し、中間体（９，１０−［１，２］ベンゼノアントラセン−１，４−ジイル ビス（シクロヘキサントリカルボン酸エステル）化合物）（式（２−１）で表される化合物）を得［反応式２］、この中間体を脱水剤にて分子内で脱水させる［反応式３］ことでも得ることができる。
なお上記式（１−１）〜（１−３）で表される酸二無水物及びその中間体である上記式（２−１）〜（２−３）で表されるシクロヘキサントリカルボン酸エステル（テトラカルボン酸化合物）も本発明の対象である。
Further, the reaction product of [Reaction formula 1] was hydrolyzed to form an intermediate (9,10- [1,2] benzenoanthracene-1,4-diylbis (cyclohexanetricarboxylic acid ester) compound) (formula (2-1). ) Is obtained [reaction formula 2], and this intermediate is dehydrated in the molecule with a dehydrating agent [reaction formula 3].
The acid dianhydride represented by the above formulas (1-1) to (1-3) and the cyclohexanetricarboxylic acid ester represented by the above formulas (2-1) to (2-3) which is an intermediate thereof ( (Tetracarboxylic acid compound) is also the subject of the present invention.
上記［反応式１］の反応において、ベンゼノアントラセンジオール化合物とシクロヘキサントリカルボン酸ハロゲン化無水物との仕込み比は、ベンゼノアントラセンジオール化合物１モルに対し、シクロヘキサントリカルボン酸ハロゲン化無水物２〜４モルが好ましい。
塩基としては、トリメチルアミン、トリエチルアミン、ジイソプロピルアミン、ジイソプロピルエチルアミン、Ｎ−メチルピペリジン、２，２，６，６−テトラメチル−Ｎ−メチルピペリジン、ピリジン、４−ジメチルアミノピリジン及びＮ−メチルモルホリン等の有機アミン類等の有機塩基が好適に用いられる。また、塩基の使用量は、シクロヘキサントリカルボン酸ハロゲン化無水物１モルに対して１モル以上であれば特に限定されるものではないが、通常１〜５モル程度であり、好ましくは１〜３モル程度である。
また、反応で副生する塩酸等の酸を中和するために、酸吸収剤を用いてもよい。酸吸収剤としては、プロピレンオキシド等のエポキシド類が挙げられる。酸吸収剤の使用量は、ベンゼノアントラセンジオール化合物１モルに対して２モル以上であれば特に限定されるものではないが、通常２〜１０モル程度であり、好ましくは２〜４モル程度である。
有機溶媒としては、反応に影響を及ぼさない溶媒であれば特に限定されるものではないが、ベンゼン、トルエン及びキシレン等の芳香族炭化水素類；Ｎ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦという）、Ｎ，Ｎ−ジメチルアセトアミド（以下、ＤＭＡｃという）及びＮ−メチル−２−ピロリドン（以下、ＮＭＰという）等のアミド類；ジエチルエーテル、テトラヒドロフラン（以下、ＴＨＦという）、１，４−ジオキサン、１，２−ジメトキシエタン、シクロペンチルメチルエーテル及びジエチルエーテル等のエーテル類；２−ブタノン及び４−メチル−２−ペンタノンなどのケトン類；アセトニトリル等のニトリル類並びにジメチルスルホキシド（以下、ＤＭＳＯという）などを用いることができる。これらの溶媒は、単独で用いても、２種以上を組み合わせて用いてもよい。なお、［反応式１］で直接目的物である酸二無水物（１−１）を精製し、取り出す場合は、溶媒中に水分が多く含まれると、エステルの加水分解が起こることから、溶媒は脱水溶媒を使用するか、もしくは、脱水してから使用することが好ましい。また、［反応式２］、［反応式３］を経由して目的物である酸二無水物（１−１）を取り出す場合は、脱水溶媒を使用してもしなくてもよい。
反応温度は、０〜２００℃程度とすることができるが、２０〜１５０℃が好ましい。
反応後は、溶媒を留去し、反応物を精製することで目的物である酸二無水物を得られる。この精製法は任意であり、再結晶、蒸留及びシリカゲルカラムクロマトグラフィ等公知の手法から適宜選択すればよい。また、精製時に使用する有機溶媒は、精製時に生成物と反応しない溶媒であれば特に限定されるものではなく、上記反応に使用する有機溶媒と同様である。
また、反応後の精製が難しい場合は、粗生成物のまま、加水分解し［反応式２］、テトラカルボン酸を得た後に脱水剤にて脱水環化させる［反応式３］ことで目的である酸二無水物を得ることもできる。In the reaction of the above [Reaction Formula 1], the charging ratio of the benzenoanthracenediol compound and the cyclohexanetricarboxylic acid halide anhydride was 2 to 4 mol of the cyclohexanetricarboxylic acid halide anhydride with respect to 1 mol of the benzenoanthracenediol compound. Is preferable.
Examples of the base include organics such as trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine and N-methylmorpholine. Organic bases such as amines are preferably used. The amount of the base used is not particularly limited as long as it is 1 mol or more with respect to 1 mol of the cyclohexanetricarboxylic acid halogenated anhydride, but is usually about 1 to 5 mol, preferably 1 to 3 mol. Degree.
Further, an acid absorber may be used to neutralize an acid such as hydrochloric acid produced as a by-product in the reaction. Examples of the acid absorber include epoxides such as propylene oxide. The amount of the acid absorber used is not particularly limited as long as it is 2 mol or more with respect to 1 mol of the benzenoanthracenediol compound, but is usually about 2 to 10 mol, preferably about 2 to 4 mol. be.
The organic solvent is not particularly limited as long as it does not affect the reaction, but aromatic hydrocarbons such as benzene, toluene and xylene; N, N-dimethylformamide (hereinafter referred to as DMF), Amids such as N, N-dimethylacetamide (hereinafter referred to as DMAc) and N-methyl-2-pyrrolidone (hereinafter referred to as NMP); diethyl ether, tetrahydrofuran (hereinafter referred to as THF), 1,4-dioxane, 1, Use of ethers such as 2-dimethoxyethane, cyclopentylmethyl ether and diethyl ether; ketones such as 2-butanone and 4-methyl-2-pentanone; nitriles such as acetonitrile and dimethylsulfoxide (hereinafter referred to as DMSO). Can be done. These solvents may be used alone or in combination of two or more. When the acid dianhydride (1-1), which is the target product, is directly purified and taken out by [Reaction Formula 1], if the solvent contains a large amount of water, the ester is hydrolyzed, so that the solvent is used. It is preferable to use a dehydrating solvent or to use after dehydrating. Further, when the target acid dianhydride (1-1) is taken out via [Reaction formula 2] and [Reaction formula 3], a dehydration solvent may or may not be used.
The reaction temperature can be about 0 to 200 ° C, but is preferably 20 to 150 ° C.
After the reaction, the solvent is distilled off and the reaction product is purified to obtain the desired acid dianhydride. This purification method is arbitrary and may be appropriately selected from known methods such as recrystallization, distillation and silica gel column chromatography. Further, the organic solvent used at the time of purification is not particularly limited as long as it is a solvent that does not react with the product at the time of purification, and is the same as the organic solvent used for the above reaction.
If purification after the reaction is difficult, the crude product is hydrolyzed as it is [reaction formula 2], and after obtaining tetracarboxylic acid, it is dehydrated and cyclized with a dehydrating agent [reaction formula 3]. Certain acid dianhydrides can also be obtained.
一方、上記［反応式２］の反応は、式（１−１）で表される酸二無水物と水を混合すれば特に限定はないが、例えば［反応式１］で生成した式（１−１）を、水、場合によっては有機溶媒、酸あるいはアルカリを添加し、加熱還流して加水分解することにより、式（２−１）で表されるシクロヘキサントリカルボン酸エステル（テトラカルボン酸化合物）を得ることもできる。
水は、式（１−１）で表される酸二無水物に対して、通常２〜１００質量倍、好ましくは２〜４０質量倍、より好ましくは２〜６質量倍使用される。
また、上記の反応は有機溶媒を添加しても良い。有機溶媒としては、反応に影響を及ぼさない溶媒であれば特に限定されるものではないが、ベンゼン、トルエン及びキシレン等の芳香族炭化水素類；Ｎ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦという）、Ｎ，Ｎ−ジメチルアセトアミド（以下、ＤＭＡｃという）及びＮ−メチル−２−ピロリドン（以下、ＮＭＰという）等のアミド類；ジエチルエーテル、テトラヒドロフラン（以下、ＴＨＦという）、１，４−ジオキサン、１，２−ジメトキシエタン、シクロペンチルメチルエーテル及びジエチルエーテル等のエーテル類；アセトン、酢酸エチル、２−ブタノン及び４−メチル−２−ペンタノンなどのケトン類；アセトニトリル等のニトリル類；並びにジメチルスルホキシド（以下、ＤＭＳＯという）などを用いることができる。これらの溶媒は、単独で用いても、２種以上を組み合わせて用いてもよい。なお、加水分解を効率よく進行させるためには、極性の高い溶媒が好ましく、例えばＤＭＦ、ＤＭＡｃ、ＮＭＰ、ＴＨＦ、１，４−ジオキサン、ジエチルエーテル、アセトニトリル、アセトン及び酢酸エチル等が好ましい。
また、上記の反応は酸を添加してもよい。酸は特に限定されるものではないが、酸としては、リンモリブデン酸及びリンタングステン酸などのヘテロポリ酸；トリメチルボレート及びトリフェニルホスフィンなどの有機酸；塩酸、硫酸及びリン酸などの無機酸；蟻酸、酢酸、プロピオン酸及びｐ−トルエンスルホン酸などの炭化水素酸；並びにトリフルオロ酢酸などのハロゲン系炭化水素酸が挙げられる。好ましくは、塩酸、硫酸、酢酸及びｐ−トルエンスルホン酸が挙げられる。
酸は式（１−１）で表される酸二無水物に対して通常０〜１００倍モル、好ましくは０．０１〜１０倍モル使用される。
また、本反応はアルカリ性水溶液を使用して加水分解をしてもよい。アルカリは特に限定されるものではないが、アルカリとしては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム及び炭酸リチウムなどのアルカリ金属類、水酸化マグネシウム及び水酸化カルシウム等のアルカリ土類金属類が挙げられる。なかでも好ましくは、水酸化ナトリウム、水酸化カリウム、水酸化リチウムが挙げられる。
アルカリの使用量は式（１−１）で表される酸二無水物に対して通常０〜１００倍モル、好ましくは０．０１〜１０倍モル使用される。
反応温度は特に限定されないが、例えば−９０〜２００℃、好ましくは５０〜１３０℃である。
反応時間は、通常、０．１ないし２００時間、好ましくは０．５ないし１００時間である。On the other hand, the reaction of the above [reaction formula 2] is not particularly limited as long as the acid dianhydride represented by the formula (1-1) and water are mixed, but the reaction is, for example, the formula (1) produced by the [reaction formula 1]. A cyclohexanetricarboxylic acid ester (tetracarboxylic acid compound) represented by the formula (2-1) is hydrolyzed by adding water, and in some cases an organic solvent, an acid or an alkali to -1) and heating and refluxing. You can also get.
Water is usually used 2 to 100 times by mass, preferably 2 to 40 times by mass, and more preferably 2 to 6 times by mass with respect to the acid dianhydride represented by the formula (1-1).
In addition, an organic solvent may be added to the above reaction. The organic solvent is not particularly limited as long as it does not affect the reaction, but aromatic hydrocarbons such as benzene, toluene and xylene; N, N-dimethylformamide (hereinafter referred to as DMF), Amids such as N, N-dimethylacetamide (hereinafter referred to as DMAc) and N-methyl-2-pyrrolidone (hereinafter referred to as NMP); diethyl ether, tetrahydrofuran (hereinafter referred to as THF), 1,4-dioxane, 1, Ethers such as 2-dimethoxyethane, cyclopentylmethyl ether and diethyl ether; ketones such as acetone, ethyl acetate, 2-butanone and 4-methyl-2-pentanone; nitriles such as acetonitrile; and dimethylsulfoxide (hereinafter DMSO). ) Etc. can be used. These solvents may be used alone or in combination of two or more. In order to promote the hydrolysis efficiently, a highly polar solvent is preferable, and for example, DMF, DMAc, NMP, THF, 1,4-dioxane, diethyl ether, acetonitrile, acetone, ethyl acetate and the like are preferable.
In addition, an acid may be added to the above reaction. The acid is not particularly limited, but examples of the acid include heteropolyacids such as phosphomolybdic acid and phosphotungstate; organic acids such as trimethylborate and triphenylphosphine; inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; and formic acid. , Hydrocarbic acids such as acetic acid, propionic acid and p-toluenesulfonic acid; and halogenated hydrocarbon acids such as trifluoroacetic acid. Preferred are hydrochloric acid, sulfuric acid, acetic acid and p-toluenesulfonic acid.
The acid is usually used in an amount of 0 to 100 times by mole, preferably 0.01 to 10 times by mole, based on the acid dianhydride represented by the formula (1-1).
Further, this reaction may be hydrolyzed using an alkaline aqueous solution. The alkali is not particularly limited, but examples of the alkali include alkali metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate, magnesium hydroxide and calcium hydroxide. Alkaline earth metals can be mentioned. Of these, sodium hydroxide, potassium hydroxide and lithium hydroxide are preferable.
The amount of alkali used is usually 0 to 100 times mol, preferably 0.01 to 10 times mol, with respect to the acid dianhydride represented by the formula (1-1).
The reaction temperature is not particularly limited, but is, for example, −90 to 200 ° C., preferably 50 to 130 ° C.
The reaction time is usually 0.1 to 200 hours, preferably 0.5 to 100 hours.
また、上記［反応式３］の反応は、公知の方法を採用すればよく、特に制限はないが、例えば、［反応式２］で得た式（２−１）で表されるシクロヘキサントリカルボン酸エステル（テトラカルボン酸化合物）と脱水剤を溶剤中で混合することにより式（１−１）で表される酸二無水物を得ることができる。 Further, the reaction of the above [reaction formula 3] may adopt a known method and is not particularly limited, but for example, the cyclohexanetricarboxylic acid represented by the formula (2-1) obtained in [reaction formula 2]. An acid dianhydride represented by the formula (1-1) can be obtained by mixing an ester (tetracarboxylic acid compound) and a dehydrating agent in a solvent.
脱水剤としては、式（２−１）で表されるシクロヘキサントリカルボン酸エステル（テトラカルボン酸化合物）に脱水剤が接触することができるものであれば特に限定はないが、例えば、脱水は、無水酢酸、無水プロピオン酸、無水トリフルオロ酢酸等の脂肪族カルボン酸無水物、１，３−ジシクロヘキシルカルボジイミド、２−クロロ−１，３−ジメチルイミダゾリニウムクロリド等の脱水剤の存在下で実施することができる。また、炭素数が１〜３の低級カルボン酸無水物が好ましく、より好ましくは炭素数が１〜２の低級カルボン酸無水物が好ましく、中でも無水化後の除去がしやすく経済的に有利な点で無水酢酸が特に好ましい。 The dehydrating agent is not particularly limited as long as the dehydrating agent can come into contact with the cyclohexanetricarboxylic acid ester (tetracarboxylic acid compound) represented by the formula (2-1). For example, dehydration is anhydrous. Perform in the presence of an aliphatic carboxylic acid anhydride such as acetic acid, propionic anhydride or trifluoroacetic anhydride, and a dehydrating agent such as 1,3-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolinium chloride. Can be done. Further, a lower carboxylic acid anhydride having 1 to 3 carbon atoms is preferable, and a lower carboxylic acid anhydride having 1 to 2 carbon atoms is more preferable, and above all, it is easy to remove after anhydrousation, which is economically advantageous. Acetic anhydride is particularly preferred.
脱水剤の使用量は特に限定されないが、式（２−１）で表されるシクロヘキサントリカルボン酸エステル（テトラカルボン酸化合物）に対して、２〜５０当量が好ましく、特に好ましくは４〜２０当量である。２〜５０当量であれば、十分に無水物化が行われ、かつ得られる式（１−１）で表される酸二無水物の溶解量が増加しすぎることなく、高い収率で式（１−１）で表される酸二無水物を析出させることができる。 The amount of the dehydrating agent used is not particularly limited, but is preferably 2 to 50 equivalents, particularly preferably 4 to 20 equivalents, relative to the cyclohexanetricarboxylic acid ester (tetracarboxylic acid compound) represented by the formula (2-1). be. If it is 2 to 50 equivalents, it is sufficiently anhydrated, and the dissolved amount of the acid dianhydride represented by the obtained formula (1-1) does not increase too much, and the formula (1) is obtained in high yield. The acid dianhydride represented by -1) can be precipitated.
上記反応は、反応に直接関与しない有機溶媒を用いることもできる。例えば、トルエン、キシレン等の炭化水素類、１，２−ジクロロエタン、１，２−ジクロロプロパン等のハロゲン化炭化水素類、更に１，４−ジオキサン等が挙げられる。 For the above reaction, an organic solvent that is not directly involved in the reaction can also be used. For example, hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and 1,2-dichloropropane, and further 1,4-dioxane and the like can be mentioned.
なお、式（２−１）で表されるシクロヘキサントリカルボン酸エステル（テトラカルボン酸化合物）を完全に溶解させて均一系で必ずしも無水物化反応させる必要はなく、不均一系で無水物化反応を実施してもよい。 It is not always necessary to completely dissolve the cyclohexanetricarboxylic acid ester (tetracarboxylic acid compound) represented by the formula (2-1) and carry out the anhydrous reaction in a homogeneous system, and carry out the anhydrous reaction in a heterogeneous system. You may.
反応における加熱の温度は、好ましくは３０〜２００℃、より好ましくは４０〜１８０℃の範囲で行うとよく、反応温度が高いほど反応速度が向上する。このため使用溶媒の還流温度で実施するのが好ましい。 The heating temperature in the reaction is preferably in the range of 30 to 200 ° C., more preferably 40 to 180 ° C., and the higher the reaction temperature, the higher the reaction rate. Therefore, it is preferable to carry out at the reflux temperature of the solvent used.
また、反応時間は、使用する脱水剤の種類、温度等の条件に応じて適宜設定すればよいが、０．５〜２０時間であることが好ましい。 The reaction time may be appropriately set according to conditions such as the type of dehydrating agent to be used and the temperature, but is preferably 0.5 to 20 hours.
上記の無水物化反応によって、使用した脱水剤に式（１−１）で表される酸二無水物が懸濁した懸濁液を得ることができる。無水物化反応の後は、得られた懸濁液をろ過することで式（１−１）で表される酸二無水物の粉末を回収できる。また、必要に応じて上記懸濁液を濃縮してもよい。
また、必要に応じて上記ろ取物を有機溶媒で洗浄してもよい。この洗浄溶媒は無水物と反応せず、目的の無水物の溶解度が低い溶媒であれば特に限定されないが、例えば、トルエン、ヘキサン、ヘプタン、アセトニトリル、アセトン、クロロホルム、酢酸エチル、炭酸ジメチル等やこれらの混合溶媒などが挙げられる。中でも酢酸エチル、炭酸ジメチルが好ましい。
さらに、減圧乾燥等により脱水剤や溶媒を除去することで、高純度の式（１−１）で表される酸二無水物を得ることができる。また、必要により再結晶、蒸留、シリカゲルカラムクロマトグラフィ等公知の手法を用いて精製することでも、目的物である酸二無水物を得られる。By the above dehydration reaction, a suspension in which the acid dianhydride represented by the formula (1-1) is suspended in the dehydrating agent used can be obtained. After the anhydrous reaction, the powder of the acid dianhydride represented by the formula (1-1) can be recovered by filtering the obtained suspension. In addition, the suspension may be concentrated if necessary.
Further, the filter may be washed with an organic solvent, if necessary. This washing solvent does not react with the anhydride and is not particularly limited as long as it is a solvent having a low solubility of the target anhydride, but for example, toluene, hexane, heptane, acetonitrile, acetone, chloroform, ethyl acetate, dimethyl carbonate and the like, and the like. Examples include the mixed solvent of. Of these, ethyl acetate and dimethyl carbonate are preferable.
Further, by removing the dehydrating agent and the solvent by drying under reduced pressure or the like, a high-purity acid dianhydride represented by the formula (1-1) can be obtained. Further, if necessary, purification using known methods such as recrystallization, distillation, silica gel column chromatography and the like can also obtain the desired acid dianhydride.
なお、本発明で得られる式（２−１）で表される酸二無水物は、文献未記載の新規化合物であり、上記のように、これから容易に式（１−１）で表される酸二無水物が製造できるなど種々の用途に使用できる。 The acid dianhydride obtained by the present invention and represented by the formula (2-1) is a novel compound not described in the literature, and as described above, it is easily represented by the formula (1-1). It can be used for various purposes such as the production of acid dianhydride.
また、本発明で用いるベンゼノアントラセンジオール化合物は、例えば、一例として下記スキームで示されるように、公知の方法に従い、有機溶媒中、アントラセン化合物と１，４−ベンゾキノン化合物とをＤｉｅｌｓ―Ａｌｄｅｒ反応させて得られる９，１０−［１，２］ベンゼノアントラセン−１３，１６（９Ｈ，１０Ｈ）−ジオン化合物を酢酸溶媒中、４７％臭化水素存在下、加熱条件で処理することで得ることができる。
耐熱性、柔軟性及び透明性に優れるだけでなく、リタデーションが低いという特徴をも有するポリイミド膜を与えるポリアミック酸（及び対応するポリイミド）を再現性よく得る観点から、本発明のポリアミック酸（及び対応するポリイミド）の製造に用いる酸二無水物成分は、上記式（１−１）で表される酸二無水物に加え、好ましくは脂環式テトラカルボン酸二無水物を、より好ましくは下記式（Ｃ１）で表される酸二無水物を含む。
上記式（Ｃ１）で表される酸二無水物の中でも、式中のＢ1が前記式（Ｘ−１）、（Ｘ−２）、（Ｘ−４）、（Ｘ−５）、（Ｘ−６）、（Ｘ−７）、（Ｘ−８）、（Ｘ−９）、（Ｘ−１１）および（Ｘ−１２）で表される酸二無水物が好ましく、前記Ｂ1が前記式（Ｘ−１）、（Ｘ−２）、（Ｘ−６）、（Ｘ−１１）および（Ｘ−１２）で表される酸二無水物が特に好ましい。
また、本発明の効果を損なわない範囲において、前記酸二無水物成分には、上記式（１−１）で表される酸二無水物、上記式（Ｃ１）で表される酸二無水物以外の、その他の酸二無水物を用いてもよい。Among the acid dianhydrides represented by the above formula (C1), B 1 in the formula is the above formulas (X-1), (X-2), (X-4), (X-5), (X). -6), (X-7), (X-8), (X-9), (X-11) and (X-12) are preferably acid dianhydrides, with B 1 being the formula. Acid dianhydrides represented by (X-1), (X-2), (X-6), (X-11) and (X-12) are particularly preferred.
Further, as long as the effect of the present invention is not impaired, the acid dianhydride component includes an acid dianhydride represented by the above formula (1-1) and an acid dianhydride represented by the above formula (C1). Other acid dianhydrides other than the above may be used.
上記酸二無水物成分において、本発明の上記式（１−１）で表される酸二無水物とともに脂環式テトラカルボン酸二無水物を用いる場合における、上記式（１−１）で表される酸二無水物と脂環式テトラカルボン酸二無水物との比率は、通常、上記式（１−１）で表される酸二無水物：脂環式テトラカルボン酸二無水物＝１：０．５〜１：４である。このような範囲とすることで、高耐熱性、高柔軟性、高透明性、低リタデーションのポリイミドを与えるポリアミック酸を再現性よく得ることができる。 In the above acid dianhydride component, when the alicyclic tetracarboxylic acid dianhydride is used together with the acid dianhydride represented by the above formula (1-1) of the present invention, it is represented by the above formula (1-1). The ratio of the acid dianhydride to be alicyclic tetracarboxylic acid dianhydride is usually the acid dianhydride represented by the above formula (1-1): alicyclic tetracarboxylic acid dianhydride = 1. : 0.5 to 1: 4. Within such a range, a polyamic acid that gives polyimide with high heat resistance, high flexibility, high transparency, and low retardation can be obtained with good reproducibility.
耐熱性、柔軟性及び透明性に優れるだけでなく、リタデーションが低いという特徴をも有するポリイミド膜を与えるポリアミック酸（及び対応するポリイミド）を再現性よく得る観点から、本発明のポリアミック酸（及び対応するポリイミド）の製造に用いるジアミン成分は、好ましくは芳香族ジアミンを、より好ましくは下記式（Ａ１）で表されるジアミンを含む。
上記式（Ａ１）で表されるジアミンの中でも、式中のＢ2が前記式（Ｙ−１２）、（Ｙ−１３）、（Ｙ−１４）、（Ｙ−１５）、（Ｙ−１８）、（Ｙ−２７）、（Ｙ−２８）、（Ｙ−３０）および（Ｙ−３３）で表されるジアミンが好ましく、前記Ｂ2が前記式（Ｙ−１２）、（Ｙ−１３）、（Ｙ−１４）、（Ｙ−１５）および（Ｙ−３３）で表されるジアミンが特に好ましい。
また、本発明の効果を損なわない範囲において、前記ジアミン成分には、上記式（Ａ１）で表されるジアミン以外の、その他のジアミン化合物を用いてもよい。Among the diamines represented by the above formula (A1), B 2 in the formula is the above formula (Y-12), (Y-13), (Y-14), (Y-15), (Y-18). , (Y-27), (Y-28), (Y-30) and (Y-33) are preferable, and the B 2 is the above formula (Y-12), (Y-13),. Diamines represented by (Y-14), (Y-15) and (Y-33) are particularly preferred.
Further, as long as the effect of the present invention is not impaired, other diamine compounds other than the diamine represented by the above formula (A1) may be used as the diamine component.
高耐熱性、高柔軟性、高透明性、低リタデーションのポリイミド膜を与えるポリアミック酸（及び対応するポリイミド）を再現性よく得る観点から、本発明のポリアミック酸（及び対応するポリイミド）の製造に用いるジアミン成分中芳香族ジアミンの含有量は、好ましくは５０ｍｏｌ％以上、より好ましくは６０ｍｏｌ％以上、より一層好ましくは７０モル％、さらに好ましくは８０モル％、さらに一層好ましくは９０モル％、最も好ましくは１００モル％である。 Used in the production of the polyamic acid (and the corresponding polyimide) of the present invention from the viewpoint of obtaining a polyamic acid (and the corresponding polyimide) that gives a polyimide film having high heat resistance, high flexibility, high transparency, and low retardation with good reproducibility. The content of the aromatic diamine in the diamine component is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol%, still more preferably 80 mol%, still more preferably 90 mol%, and most preferably. It is 100 mol%.
なお、上記酸二無水物成分として上記式（１−１）で表される酸二無水物と上記（Ｃ１）で表される酸二無水物とを用い、上記ジアミン成分として上記式（Ａ１）で表されるジアミンを用いた場合、ポリアミック酸は下記式（４−１）で表されるモノマー単位と、下記式（４−２）で表されるモノマー単位とを有するものとなる。
本発明のポリアミック酸を得る方法は特に限定されるものではなく、前述の酸二無水物成分とジアミン成分とを公知の手法によって反応、重合させればよい。
ポリアミック酸を合成する際の酸二無水物成分のモル数とジアミン成分のモル数との比は、酸二無水物成分／ジアミン成分＝０．８〜１．２である。The method for obtaining the polyamic acid of the present invention is not particularly limited, and the above-mentioned acid dianhydride component and diamine component may be reacted and polymerized by a known method.
The ratio of the number of moles of the acid dianhydride component to the number of moles of the diamine component in synthesizing the polyamic acid is acid dianhydride component / diamine component = 0.8 to 1.2.
ポリアミック酸の合成に用いられる溶媒としては、例えば、ｍ−クレゾール、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチルカプロラクタム、ジメチルスルホキシド（ＤＭＳＯ）、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルホスホルアミド及びγ−ブチロラクトンなどが挙げられる。これらは、単独で使用しても、混合して使用してもよい。さらに、ポリアミック酸を溶解しない溶媒であっても、均一な溶液が得られる範囲内で上記溶媒に加えて使用してもよい。
重縮合反応の温度は、−２０〜１５０℃、好ましくは−５〜１００℃の任意の温度を選択することができる。Solvents used for the synthesis of polyamic acid include, for example, m-cresol, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N- Examples thereof include methylcaprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide and γ-butyrolactone. These may be used alone or in combination. Further, even if the solvent does not dissolve the polyamic acid, it may be used in addition to the above solvent as long as a uniform solution can be obtained.
The temperature of the polycondensation reaction can be selected from any temperature of -20 to 150 ° C, preferably −5 to 100 ° C.
上述したポリアミック酸の重合反応により得られたポリアミック酸含有溶液は、そのまま、あるいは希釈もしくは濃縮した後、後述するポリイミド膜形成用組成物として使用することができる。また該ポリアミック酸含有溶液に、メタノール、エタノールなどの貧溶媒を加えてポリアミック酸を沈殿させて単離し、その単離したポリアミック酸を適当な溶媒に再溶解させてポリアミック酸含有溶液とし、これをポリイミド膜形成用組成物として使用することもできる。
ポリアミック酸含有溶液の希釈用溶媒並びに単離したポリアミック酸の再溶解用溶媒は、得られたポリアミック酸を溶解させるものであれば特に限定されるものではなく、例えば、ｍ−クレゾール、２−ピロリドン、ＮＭＰ、Ｎ−エチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドン、ＤＭＡｃ、ＤＭＦ及びγ−ブチロラクトンなどが挙げられる。The polyamic acid-containing solution obtained by the above-mentioned polymerization reaction of polyamic acid can be used as it is, or after being diluted or concentrated, as a composition for forming a polyimide film described later. Further, a poor solvent such as methanol or ethanol is added to the polyamic acid-containing solution to precipitate the polyamic acid, and the isolated polyamic acid is redissolved in an appropriate solvent to prepare a polyamic acid-containing solution. It can also be used as a composition for forming a polyimide film.
The solvent for diluting the polyamic acid-containing solution and the solvent for redissolving the isolated polyamic acid are not particularly limited as long as they dissolve the obtained polyamic acid, and are, for example, m-cresol and 2-pyrrolidone. , NMP, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, DMAc, DMF, γ-butyrolactone and the like.
また、単独ではポリアミック酸を溶解しない溶媒であっても、ポリアミック酸が析出しない範囲であれば上記溶媒に加えて使用することができる。その具体例としては、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、エチレングリコール、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、１−ブトキシ−２−プロパノール、１−フェノキシ−２−プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール−１−モノメチルエーテル−２−アセテート、プロピレングリコール−１−モノエチルエーテル−２−アセテート、ジプロピレングリコール、２−（２−エトキシプロポキシ）プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸ｎ−プロピルエステル、乳酸ｎ−ブチルエステル及び乳酸イソアミルエステルなどが挙げられる。 Further, even if the solvent does not dissolve the polyamic acid by itself, it can be used in addition to the above solvent as long as the polyamic acid does not precipitate. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-butoxy-2-propanol. , 1-Phenoxy-2-propanol, Propylene Glycol Monoacetate, Propylene Glycol Diacetate, Propylene Glycol-1-monomethyl Ether-2-acetate, Propylene Glycol-1-monoethyl Ether-2-acetate, Dipropylene Glycol, 2- Examples thereof include (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester and lactic acid isoamyl ester.
本発明のポリイミドは、上記説明したポリアミック酸を、加熱により脱水閉環（熱イミド化）するか、または公知の脱水閉環触媒を使用して化学的に閉環して得ることができる。
加熱による方法は、１００〜３００℃、好ましくは１２０〜２５０℃の任意の温度で行うことができる。
化学的に閉環する方法は、例えば、ピリジン、トリエチルアミン又は１−エチルピペリジンなどと、無水酢酸などとの存在下で行うことができ、この際の温度は、−２０〜２００℃の任意の温度を選択することができる。The polyimide of the present invention can be obtained by dehydrating and ring-closing (thermal imidizing) the polyamic acid described above by heating, or by chemically closing the ring using a known dehydration and ring-closing catalyst.
The heating method can be carried out at any temperature of 100 to 300 ° C, preferably 120 to 250 ° C.
The method of chemically closing the ring can be carried out in the presence of, for example, pyridine, triethylamine or 1-ethylpiperidine and acetic anhydride, and the temperature at this time can be any temperature of -20 to 200 ° C. You can choose.
こうして得られる上記式（４−１）で表されるモノマー単位と上記記式（４−２）で表されるモノマー単位とを有するポリアミック酸から得られるポリイミドは、下記式（５−１）で表されるモノマー単位と下記式（５−２）で表されるモノマー単位とを有するものである。
上述したポリアミック酸の閉環反応により得られたポリイミド含有溶液（以下、ポリイミド溶液ともいう）は、そのまま、あるいは希釈もしくは濃縮した後、後述する膜形成用組成物として使用することができる。また該ポリイミド含有溶液に、メタノール、エタノールなどの貧溶媒を加えてポリイミドを沈殿させてポリイミドを単離し、その単離したポリイミドを適当な溶媒に再溶解させ、これを後述する膜形成用組成物として使用することができる。
再溶解用溶媒は、得られたポリイミドを溶解させるものであれば特に限定されるものではなく、例えば、ｍ−クレゾール、２−ピロリドン、ＮＭＰ、Ｎ−エチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドン、ＤＭＡｃ、ＤＭＦ及びγ−ブチロラクトンなどが挙げられる。The polyimide-containing solution (hereinafter, also referred to as a polyimide solution) obtained by the ring closure reaction of the polyamic acid described above can be used as it is, or after being diluted or concentrated, as a film-forming composition described later. Further, a poor solvent such as methanol or ethanol is added to the polyimide-containing solution to precipitate the polyimide to isolate the polyimide, and the isolated polyimide is redissolved in an appropriate solvent, which is described later in a film-forming composition. Can be used as.
The solvent for redissolution is not particularly limited as long as it dissolves the obtained polyimide, and is, for example, m-cresol, 2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, N-vinyl-2. -Pyrrolidone, DMAc, DMF and γ-butyrolactone and the like can be mentioned.
また、単独ではポリイミドを溶解しない溶媒であっても、ポリイミドが析出しない範囲であれば上記溶媒に加えて使用することができる。その具体例としては、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、エチレングリコール、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、１−ブトキシ−２−プロパノール、１−フェノキシ−２−プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール−１−モノメチルエーテル−２−アセテート、プロピレングリコール−１−モノエチルエーテル−２−アセテート、ジプロピレングリコール、２−（２−エトキシプロポキシ）プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸ｎ−プロピルエステル、乳酸ｎ−ブチルエステル及び乳酸イソアミルエステルなどが挙げられる。 Further, even if the solvent does not dissolve the polyimide by itself, it can be used in addition to the above solvent as long as the polyimide does not precipitate. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-butoxy-2-propanol. , 1-Phenoxy-2-propanol, Propylene Glycol Monoacetate, Propylene Glycol Diacetate, Propylene Glycol-1-monomethyl Ether-2-acetate, Propylene Glycol-1-monoethyl Ether-2-acetate, Dipropylene Glycol, 2- Examples thereof include (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester and lactic acid isoamyl ester.
なお本発明において、ポリアミック酸及び対応するポリイミドの数平均分子量は、得られる薄膜の柔軟性、強度等を向上させるという観点から、好ましくは５，０００以上、より好ましくは７，０００以上、より一層好ましくは１０，０００以上であり、また得られるポリアミック酸及び対応するポリイミドの溶解性を確保するという観点から、好ましくは２００，０００以下、より好ましくは１００，０００以下、より一層好ましくは５０，０００以下である。なお本明細書において、数平均分子量は、ＧＰＣ（ゲル浸透クロマトグラフィー）装置によって測定し、ポリスチレン換算値として算出される値である。 In the present invention, the number average molecular weight of the polyamic acid and the corresponding polyimide is preferably 5,000 or more, more preferably 7,000 or more, and further, from the viewpoint of improving the flexibility, strength, etc. of the obtained thin film. It is preferably 10,000 or more, and is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000, from the viewpoint of ensuring the solubility of the obtained polyamic acid and the corresponding polyimide. It is as follows. In the present specification, the number average molecular weight is a value measured by a GPC (gel permeation chromatography) apparatus and calculated as a polystyrene-equivalent value.
［膜形成用組成物・ポリイミド膜形成用組成物］
上述の本発明のポリイミドと、有機溶媒とを含む膜形成用組成物、並びに、本発明のポリアミック酸と、有機溶媒とを含むポリイミド膜形成用組成物も本発明の対象である。ここで本発明の膜形成用組成物及びポリイミド膜形成用組成物は、均一なものであって、相分離は認められないものである。[Membrane-forming composition / polyimide film-forming composition]
The above-mentioned composition for forming a film containing the polyimide of the present invention and an organic solvent, and the composition for forming a polyimide film containing the polyamic acid of the present invention and an organic solvent are also objects of the present invention. Here, the film-forming composition and the polyimide film-forming composition of the present invention are uniform and no phase separation is observed.
＜有機溶媒＞
本発明の膜形成用組成物又はポリイミド膜形成用組成物は、前記ポリイミド又はポリアミック酸に加えて、有機溶媒を含む。該有機溶媒は、特に限定されるものではなく、例えば、上記ポリアミック酸及びポリイミドの調製時に用いた反応溶媒の具体例と同様のものが挙げられる。より具体的には、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、１，３−ジメチル−２−イミダゾリジノン、Ｎ−エチル−２−ピロリドン、γ−ブチロラクトンなどが挙げられる。なお、有機溶媒は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。
これらの中でも、平坦性の高い膜を再現性よく得ることを考慮すると、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトンが好ましい。<Organic solvent>
The film-forming composition or the polyimide film-forming composition of the present invention contains an organic solvent in addition to the polyimide or the polyamic acid. The organic solvent is not particularly limited, and examples thereof include the same as the specific examples of the reaction solvent used in the preparation of the polyamic acid and the polyimide. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ- Butyrolactone and the like can be mentioned. As the organic solvent, one type may be used alone, or two or more types may be used in combination.
Among these, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone are preferable in consideration of obtaining a highly flat film with good reproducibility.
本発明の膜形成用組成物又はポリイミド膜形成用組成物における固形分量の配合量は、通常０．５〜３０質量％程度、好ましくは５〜２５質量％程度である。固形分濃度が０．５質量％未満であると膜を作製する上において製膜効率が低くなり、また膜形成用組成物又はポリイミド膜形成用組成物の粘度が低くなるため、表面が均一な塗膜を得られにくい。また固形分濃度が３０質量％を超えると、膜形成用組成物又はポリイミド膜形成用組成物の粘度が高くなりすぎて、やはり成膜効率の悪化や塗膜の表面均一性に欠ける虞がある。なおここでいう固形分量とは、有機溶媒以外の成分の総質量を意味し、液状のモノマー等であっても固形分として重量に含めるものとする。
なお膜形成用組成物又はポリイミド膜形成用組成物の粘度は、作製する膜の厚み等を勘案し適宜設定するものではあるが、特に５〜５０μｍ程度の厚さの膜を再現性よく得ること目的とする場合、通常、２５℃で５００〜５０，０００ｍＰａ・ｓ程度、好ましくは１，０００〜２０，０００ｍＰａ・ｓ程度である。The blending amount of the solid content in the film-forming composition or the polyimide film-forming composition of the present invention is usually about 0.5 to 30% by mass, preferably about 5 to 25% by mass. When the solid content concentration is less than 0.5% by mass, the film forming efficiency is low in forming the film, and the viscosity of the film forming composition or the polyimide film forming composition is low, so that the surface is uniform. It is difficult to obtain a coating film. Further, if the solid content concentration exceeds 30% by mass, the viscosity of the film-forming composition or the polyimide film-forming composition becomes too high, and there is a possibility that the film-forming efficiency deteriorates and the surface uniformity of the coating film is lacking. .. The solid content amount referred to here means the total mass of the components other than the organic solvent, and even a liquid monomer or the like is included in the weight as a solid content.
The viscosity of the film-forming composition or the polyimide film-forming composition is appropriately set in consideration of the thickness of the film to be produced, etc., but in particular, a film having a thickness of about 5 to 50 μm can be obtained with good reproducibility. For the purpose, it is usually about 500 to 50,000 mPa · s at 25 ° C., preferably about 1,000 to 20,000 mPa · s.
本発明の膜形成用組成物又はポリイミド膜形成用組成物には、加工特性や各種機能性を付与するために、その他に様々な有機又は無機の低分子又は高分子化合物を配合してもよい。例えば、触媒、消泡剤、レベリング剤、界面活性剤、染料、可塑剤、微粒子、カップリング剤、増感剤等を用いることができる。
なおその他成分を含む場合も含め、本発明の膜形成用組成物又はポリイミド膜形成用組成物の固形分量において、上記ポリイミド又はポリアミック酸の割合は７０〜１００質量％とすることができる。
本発明の膜形成用組成物又はポリイミド膜形成用組成物は、上述の方法で得られたポリイミド又はポリアミック酸を上述の有機溶媒に溶解して得ることができるし、ポリイミド又はポリアミック酸の調製後の反応溶液に、所望により前記有機溶媒を更に加えたものとしてもよい。In addition, various organic or inorganic small molecule or polymer compounds may be blended in the film-forming composition or the polyimide film-forming composition of the present invention in order to impart processing characteristics and various functionalities. .. For example, catalysts, defoamers, leveling agents, surfactants, dyes, plasticizers, fine particles, coupling agents, sensitizers and the like can be used.
The proportion of the polyimide or the polyamic acid can be 70 to 100% by mass in the solid content of the film-forming composition or the polyimide film-forming composition of the present invention, including the case where other components are contained.
The film-forming composition or the polyimide film-forming composition of the present invention can be obtained by dissolving the polyimide or polyamic acid obtained by the above-mentioned method in the above-mentioned organic solvent, and after preparation of the polyimide or polyamic acid. If desired, the organic solvent may be further added to the reaction solution of.
［膜］
以上説明した本発明の膜形成用組成物又はポリイミド膜形成用組成物を基材に塗布して乾燥・加熱することで有機溶媒を除去し、高い耐熱性と、高い透明性と、適度な柔軟性と、適度な線膨張係数とを有し、しかもリタデーションの小さい膜（ポリイミド膜）を得ることができる。
すなわち、基材上に塗布した上記膜形成用組成物（ポリイミド含有溶液）を加熱し、溶媒を蒸発させることで、ポリイミドを含む本発明の膜を得ることができ、該膜は、上記膜形成用組成物の固形分からなるものである。
あるいは、基材上に塗布した上記ポリイミド膜形成用組成物（ポリアミック酸含有溶液）を加熱し、溶媒を蒸発させつつイミド化反応をさせることで、ポリイミドを含む本発明の膜を得ることができ、該膜は上記ポリイミド膜形成用組成物の固形分からなり、該固形分中のポリアミック酸のイミド化物を含むものである
そして上記膜、すなわち上記ポリイミドを含有する膜（薄膜）も本発明の対象である。[film]
The organic solvent is removed by applying the film-forming composition of the present invention or the polyimide film-forming composition described above to a substrate, drying and heating to remove organic solvents, resulting in high heat resistance, high transparency, and appropriate flexibility. It is possible to obtain a film (polyimide film) having properties and an appropriate coefficient of linear expansion and having a small retardation.
That is, the film of the present invention containing polyimide can be obtained by heating the film-forming composition (polyimide-containing solution) applied on the substrate and evaporating the solvent, and the film can be formed. It consists of the solid content of the composition for use.
Alternatively, the film of the present invention containing polyimide can be obtained by heating the above-mentioned polyimide film-forming composition (polyamic acid-containing solution) applied on a substrate and allowing an imidization reaction while evaporating the solvent. The film is composed of the solid content of the polyimide film-forming composition and contains an imidized polyamic acid in the solid content, and the film, that is, the film (thin film) containing the polyimide film is also an object of the present invention. ..
膜の製造に用いる基材としては、例えば、プラスチック（ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ、メラミン、トリアセチルセルロース、ＡＢＳ、ＡＳ、ノルボルネン系樹脂等）、金属、ステンレス鋼（ＳＵＳ）、木材、紙、ガラス、シリコンウェハ及びスレート等が挙げられる。
特に、電子デバイスの基板材料として適用する場合においては、既存設備を利用することができるという観点から、適用する基材がガラス又はシリコンウェハであることが好ましく、また得られる膜が良好な剥離性を示すことからガラスであることがさらに好ましい。なお、適用する基材の線膨張係数としては塗工後の基材の反りの観点から、好ましくは３５ｐｐｍ／℃以下、より好ましくは３０ｐｐｍ／℃以下、より一層好ましくは２５ｐｐｍ／℃以下、さらに好ましくは、２０ｐｐｍ／℃以下である。Examples of the base material used for producing the film include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, etc.), metals, and stainless steel (SUS). , Wood, paper, glass, silicon wafers, slate and the like.
In particular, when it is applied as a substrate material for an electronic device, it is preferable that the base material to be applied is a glass or silicon wafer from the viewpoint that existing equipment can be used, and the obtained film has good peelability. Therefore, it is more preferable to use glass. The coefficient of linear expansion of the applied base material is preferably 35 ppm / ° C. or less, more preferably 30 ppm / ° C. or less, still more preferably 25 ppm / ° C. or less, still more preferably, from the viewpoint of warping of the base material after coating. Is 20 ppm / ° C. or less.
基材への膜形成用組成物又はポリイミド膜形成用組成物の塗布法は、特に限定されるものではないが、例えば、キャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法（凸版、凹版、平版、スクリーン印刷等）等が挙げられ、目的に応じてこれらを適宜用いることができる。 The method for applying the film-forming composition or the polyimide film-forming composition to the substrate is not particularly limited, but for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, or a roll coating method is used. A method, a bar coating method, a die coating method, an inkjet method, a printing method (relate plate, concave plate, lithographic plate, screen printing, etc.) and the like can be mentioned, and these can be appropriately used depending on the purpose.
加熱温度は、通常４０〜５００℃程度であるが、３００℃以下が好ましい。３００℃を超えると、得られる膜が脆くなり、特にディスプレイ基板用途に適した膜を得ることができない場合がある。
また、得られる膜の耐熱性と線膨張係数特性を考慮すると、塗布した膜形成用組成物又はポリイミド膜形成用組成物を４０℃〜１００℃で５分間〜２時間加熱した後に、そのまま段階的に加熱温度を上昇させ、最終的に１７５℃超〜２８０℃で３０分〜２時間加熱することが望ましい。このように、溶媒を乾燥させる段階と分子配向を促進する段階の２段階以上の温度で加熱することにより、低熱膨張特性を発現させることができる。
特に、塗布した膜形成用組成物は、４０℃〜１００℃で５分間〜２時間加熱した後に、１００℃超〜１７５℃で５分間〜２時間、次いで、１７５℃超〜２８０℃で５分〜２時間加熱することが好ましい。
また、ポリアミック酸を含有するポリイミド膜形成用組成物の場合には、塗膜を加熱し、溶媒を蒸発させつつイミド化反応をさせるべく、例えば、４０〜１００℃の範囲、１００〜１５０℃の範囲、１８０〜３００℃の範囲などにて段階的に加熱することができる。
加熱に用いる器具は、例えばホットプレート、オーブン等が挙げられる。加熱雰囲気は、空気下であっても窒素等の不活性ガス下であってもよく、また、常圧下であっても減圧下であってもよく、また加熱の各段階において異なる圧力を適用してもよい。The heating temperature is usually about 40 to 500 ° C., but is preferably 300 ° C. or lower. If the temperature exceeds 300 ° C., the obtained film becomes brittle, and it may not be possible to obtain a film particularly suitable for display substrate applications.
Further, considering the heat resistance and the coefficient of linear expansion characteristics of the obtained film, the applied film-forming composition or polyimide film-forming composition is heated at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, and then stepwise as it is. It is desirable to raise the heating temperature to 30 ° C to 280 ° C for 30 minutes to 2 hours. As described above, the low thermal expansion characteristic can be exhibited by heating at a temperature of two or more steps, that is, a step of drying the solvent and a step of promoting molecular orientation.
In particular, the applied film-forming composition is heated at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, then heated at over 100 ° C. to 175 ° C. for 5 minutes to 2 hours, and then at 175 ° C. to 280 ° C. for 5 minutes. It is preferable to heat for ~ 2 hours.
Further, in the case of a composition for forming a polyimide film containing a polyamic acid, for example, in the range of 40 to 100 ° C. and 100 to 150 ° C., in order to heat the coating film and cause an imidization reaction while evaporating the solvent. It can be heated stepwise in a range, such as in the range of 180 to 300 ° C.
Examples of the appliance used for heating include a hot plate and an oven. The heating atmosphere may be under air or under an inert gas such as nitrogen, under normal pressure or under reduced pressure, and different pressures may be applied at each stage of heating. You may.
膜の厚さは、特にフレキシブルディスプレイ用の基板として用いる場合、通常１〜６０μｍ程度、好ましくは５〜５０μｍ程度であり、加熱前の塗膜の厚さを調整して所望の厚さの膜を形成する。
なおこのようにして形成された膜を基材から剥離する方法としては特に限定はなく、該膜を基材ごと冷却し、膜に切れ目を入れ剥離する方法やロールを介して張力を与えて剥離する方法等が挙げられる。The thickness of the film is usually about 1 to 60 μm, preferably about 5 to 50 μm, particularly when used as a substrate for a flexible display, and the thickness of the coating film before heating is adjusted to obtain a film of a desired thickness. Form.
The method of peeling the film thus formed from the substrate is not particularly limited, and the film is cooled together with the substrate, a cut is made in the film and the film is peeled off, or tension is applied via a roll to peel the film. How to do it, etc.
そして、前記膜形成用組成物又はポリイミド膜形成用組成物から形成された膜からなるフレキシブルデバイス用基板、すなわち、前記膜形成用組成物又はポリイミド膜形成用組成物の硬化物（膜形成用組成物の固形分の硬化物）又はポリイミド膜形成用組成物の硬化物（ポリイミド膜形成用組成物の固形分中のポリアミック酸のイミド化物）からなる、フレキシブルデバイス用基板も、本発明の対象である。 Then, a substrate for a flexible device made of a film formed of the film-forming composition or the polyimide film-forming composition, that is, a cured product of the film-forming composition or the polyimide film-forming composition (film-forming composition). A substrate for a flexible device made of a cured product of a solid content of a product) or a cured product of a composition for forming a polyimide film (imimided product of a polyamic acid in the solid content of the composition for forming a polyimide film) is also an object of the present invention. be.
以下に実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれらに限定されるものではない。
なお、使用した試薬の略語は以下のとおりである
ＴＨ：トリプチセンヒドロキノン（９，１０−ジヒドロ−９，１０−［１，２］ベンゼノアントラセン−１，４−ジオール）
ＨＴＡＣ：無水核水添トリメリット酸クロリド（Ｈｙｄｒｏｇｅｎａｔｅｄ ｔｒｉｍｅｌｌｉｔｉｃ ａｎｈｙｄｒｉｄｅ ｃｈｌｏｒｉｄｅ）
ＴＨ−ＨＴＡＣ−ＣＡ：トリプチセンヒドロキノン ＨＴＡＣカルボン酸
ＴＨ−ＨＴＡＣ：トリプチセンヒドロキノン ＨＴＡＣ
ＴＨＦ：テトラヒドロフラン
ＣＢＤＡ：１，２，３，４−シクロブタンテトラカルボン酸二無水物
ＴＦＭＢ：２，２’−ジ（トリフルオロメチル）ベンジジン
ＢＯＤＡｘｘ：ビシクロ［２，２，２］オクタン−２，３，５，６−テトラカルボン酸二無水物Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
The abbreviations for the reagents used are as follows: TH: trypticene hydroquinone (9,10-dihydro-9,10- [1,2] benzenoanthracene-1,4-diol).
HTAC: Anhydrous Hydrogenated Trimellitic Acid Chloride
TH-HTAC-CA: Trypticene Hydroquinone HTAC Carboxylic Acid TH-HTAC: Trypticene Hydroquinone HTAC
THF: Tetrahydrofuran CBDA: 1,2,3,4-Cyclobutanetetracarboxylic dianhydride TFMB: 2,2'-di (trifluoromethyl) benzidine BODAxx: Bicyclo [2,2,2] octane-2,3 5,6-tetracarboxylic dianhydride
また試料の調製及び物性の分析及び評価に用いた装置及びその条件は、以下の通りである。
１）ＨＰＬＣ分析
カラム：Ｉｎｅｒｔｓｉｌ ＯＤＳ−３、５μｍ、４．６ｍｍ×２５０ｍｍ
オーブン：４０℃
検出波長：２５４ｎｍ
流速：１．０ｍＬ／分
溶離液：
ＴＨ−ＨＴＡＣ−ＣＡ：アセトニトリル／０．５％リン酸水溶液＝５０／５０ サンプル注入量：５μＬ
ＴＨ−ＨＴＡＣ：アセトニトリル／０．５％リン酸水溶液＝５０／５０ サンプル注入量：５μＬ※
※ＴＨ−ＨＴＡＣを溶離液で１００倍に希釈し、７０℃で１時間撹拌後、ＴＨ−ＨＴＡＣ−ＣＡとして測定
２）1ＨＮＭＲ分析
装置：フーリエ変換型超伝導核磁気共鳴装置（ＦＴ−ＮＭＲ）（ＩＮＯＶＡ−４００（Ｖａｒｉａｎ社）４００ＭＨｚ
溶媒：ＤＭＳＯ−ｄ６
内標準物質：テトラメチルシラン（ＴＭＳ）The equipment and conditions used for sample preparation and analysis and evaluation of physical properties are as follows.
1) HPLC analysis column: Inertsil ODS-3, 5 μm, 4.6 mm × 250 mm
Oven: 40 ° C
Detection wavelength: 254 nm
Flow rate: 1.0 mL / min Eluent:
TH-HTAC-CA: Acetonitrile / 0.5% aqueous phosphoric acid solution = 50/50 Sample injection amount: 5 μL
TH-HTAC: acetonitrile / 0.5% aqueous phosphoric acid solution = 50/50 Sample injection amount: 5 μL *
* TH-HTAC is diluted 100-fold with an eluent, stirred at 70 ° C. for 1 hour, and then measured as TH-HTAC-CA. 2) 1 HNMR analyzer: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) (INOVA-400 (Varian) 400MHz
Solvent: DMSO-d6
Internal standard substance: Tetramethylsilane (TMS)
［１］化合物の合成
＜実施例１−１＞（ＴＨ−ＨＴＡＣ−ＣＡの合成）
窒素雰囲気下、ＴＨ（３０ｇ）、ＨＴＡＣ（６８．１ｇ）をテトラヒドロフラン（ＴＨＦ、３００ｇ）に溶解し、５℃に冷却した。この溶液に、ピリジン（２４．９ｇ）とテトラヒドロフラン（９０ｇ）の混合溶液を３０分間かけて滴下し、テトラヒドロフラン（３０ｇ）で溶液を洗いこんだ。１９時間撹拌後、反応溶液を５℃に冷却し、水（１２６０ｇ）を加え、２５℃に昇温後、３０分撹拌した。析出物をろ過後、水（９０ｇ）で３回洗浄し、得られたろ取物（１２１．４ｇ）を７０℃にて減圧乾燥し、ＴＨ−ＨＴＡＣ粗物を８２．５ｇ得た。
次にこのＴＨ−ＨＴＡＣ粗物（８２．５ｇ）を、酢酸エチル（７８７ｇ）及び０．５％リン酸水溶液（７８７ｇ）の混合溶液に加え、この懸濁溶液を還流条件下（７８℃）で６時間撹拌し、該粗物を完全溶解させた。この溶液を２５℃まで冷却後、水層を除去した後、有機層に水（７００ｇ）を加え、３０分間撹拌後、水層を除去した。得られた有機層を濃縮後、７０℃にて減圧乾燥し、ＴＨ−ＨＴＡＣ−ＣＡ粗物を８２．５ｇ得た。このＴＨ−ＨＴＡＣ−ＣＡ粗物（８２．５ｇ）をアセトニトリル（３３９ｇ）に加え、７０℃に昇温し１時間撹拌した後、５℃まで冷却した。析出物をろ過後、アセトニトリル（３３９ｇ）で２回洗浄し、得られたろ取物を７０℃にて減圧乾燥することでＴＨ−ＨＴＡＣ−ＣＡ異性体混合物を３７．９ｇ得た（収率；５３．０％（２Ｓｔｅｐｓ）、ＨＰＬＣ面百（保持時間；４．９ｍｉｎ，５．１ｍｉｎ，５．６ｍｉｎ，６．２ｍｉｎ，６．４ｍｉｎ）；９６．５％）。Under a nitrogen atmosphere, TH (30 g) and HTAC (68.1 g) were dissolved in tetrahydrofuran (THF, 300 g) and cooled to 5 ° C. A mixed solution of pyridine (24.9 g) and tetrahydrofuran (90 g) was added dropwise to this solution over 30 minutes, and the solution was washed with tetrahydrofuran (30 g). After stirring for 19 hours, the reaction solution was cooled to 5 ° C., water (1260 g) was added, the temperature was raised to 25 ° C., and the mixture was stirred for 30 minutes. After filtering the precipitate, the precipitate was washed 3 times with water (90 g), and the obtained filtrate (121.4 g) was dried under reduced pressure at 70 ° C. to obtain 82.5 g of a crude TH-HTAC.
Next, this crude TH-HTAC (82.5 g) is added to a mixed solution of ethyl acetate (787 g) and a 0.5% aqueous phosphoric acid solution (787 g), and this suspended solution is added under reflux conditions (78 ° C.). The crude product was completely dissolved by stirring for 6 hours. After cooling this solution to 25 ° C. and removing the aqueous layer, water (700 g) was added to the organic layer, and the mixture was stirred for 30 minutes and then the aqueous layer was removed. The obtained organic layer was concentrated and then dried under reduced pressure at 70 ° C. to obtain 82.5 g of TH-HTAC-CA crude. The crude TH-HTAC-CA (82.5 g) was added to acetonitrile (339 g), the temperature was raised to 70 ° C., the mixture was stirred for 1 hour, and then cooled to 5 ° C. The precipitate was filtered, washed twice with acetonitrile (339 g), and the obtained filtrate was dried under reduced pressure at 70 ° C. to obtain 37.9 g of a TH-HTAC-CA isomer mixture (yield; 53). 9.0% (2 Steps), HPLC surface 100 (holding time; 4.9 min, 5.1 min, 5.6 min, 6.2 min, 6.4 min); 96.5%).
＜実施例１−２＞（ＴＨ−ＨＴＡＣの合成）
ＴＨ−ＨＴＡＣ−ＣＡ（３７．９ｇ）を無水酢酸（１１４ｇ）に加え、還流条件下（１３０℃）にて３０分間撹拌後、反応液を２５℃に冷却した。析出物を窒素気流化でろ過後、ろ物を無水酢酸（３８ｇ）で洗浄した。得られた未乾燥のろ物にヘキサンを加え、１３０℃にて減圧乾燥しＴＨ−ＨＴＡＣを３１．０ｇ得た。（収率；８６．３％、ＨＰＬＣ面百（保持時間；４．９ｍｉｎ，５．６ｍｉｎ，６．４ｍｉｎ）；９６．８％）。
この結晶は、1ＨＮＭＲ分析およびＨＰＬＣによる分析結果から、ＴＨ−ＨＴＡＣ異性体混合物（３５．１：３５．５：２６．３）であることを確認した。
1ＨＮＭＲ（ＤＭＳＯ−ｄ６、δｐｐｍ）：７．４（ｍ，４Ｈ)、７．０（ｍ，４Ｈ )、６．９（ｍ，２Ｈ）、５．６（ｍ，２Ｈ）、３．７（ｍ，２Ｈ）、３．４（ｍ，２Ｈ）、３．０（ｍ，２Ｈ）、２．５（ｍ，２Ｈ）、２．２−１．７（ｍ，１０Ｈ）．<Example 1-2> (Synthesis of TH-HTAC)
TH-HTAC-CA (37.9 g) was added to acetic anhydride (114 g), and the mixture was stirred under reflux conditions (130 ° C.) for 30 minutes, and then the reaction solution was cooled to 25 ° C. The precipitate was filtered through a nitrogen stream, and the filtrate was washed with acetic anhydride (38 g). Hexane was added to the obtained undried filtrate and dried under reduced pressure at 130 ° C. to obtain 31.0 g of TH-HTAC. (Yield; 86.3%, HPLC surface 100 (holding time; 4.9 min, 5.6 min, 6.4 min); 96.8%).
From the results of 1 HNMR analysis and analysis by HPLC, it was confirmed that this crystal was a TH-HTAC isomer mixture (35.1: 35.5: 26.3).
1 1 HNMR (DMSO-d6, δppm): 7.4 (m, 4H), 7.0 (m, 4H), 6.9 (m, 2H), 5.6 (m, 2H), 3.7 ( m, 2H), 3.4 (m, 2H), 3.0 (m, 2H), 2.5 (m, 2H), 2.2-1.7 (m, 10H).
［２］ポリイミドの製造
＜実施例１−３ ポリイミド（ＩＩＩ）の製造［ＴＨ−ＨＴＡＣ：ＣＢＤＡ：ＢＯＤＡｘｘ：ＴＦＭＢ＝１０：４０：５０：１００（モル比）］
次いで、得られた反応混合物を５００ｇのメタノール中に加えて３０分間撹拌し、ろ過によって析出物であるポリイミドを回収した。この操作を３回繰り返した。
最後に、得られたポリイミド中のメタノール残渣を真空オーブンにより、１２０℃で８時間乾燥し、乾燥したポリイミド（ＩＩＩ）を得た（１０．５ｇ、収率：９５．１％）。[2] Production of Polyimide <Example 1-3 Production of Polyimide (III) [TH-HTAC: CBDA: BODAxx: TFMB = 10: 40: 50: 100 (molar ratio)]
Then, the obtained reaction mixture was added to 500 g of methanol and stirred for 30 minutes, and the polyimide as a precipitate was recovered by filtration. This operation was repeated 3 times.
Finally, the methanol residue in the obtained polyimide was dried in a vacuum oven at 120 ° C. for 8 hours to obtain a dried polyimide (III) (10.5 g, yield: 95.1%).
［３］ポリイミド溶液（ワニス）の調製及びポリイミド膜の作製
室温にて、前記ポリイミド（ＩＩＩ）３ｇを、固形分濃度が１２質量％となるようにＮ−メチル−２−ピロリドン（ＮＭＰ）に溶解し、得られたポリイミド溶液を、５μｍのフィルターを用いて加圧ろ過した。
その後、ろ過したポリイミド溶液をガラス基板上に塗布し、大気下で、５０℃で３０分間、１４０℃で３０分間、２００℃で６０分間、順次加熱し、透明のポリイミドの膜を得た。そして、得られたポリイミドの膜を機械的切断にて剥がし、評価試料とした。[3] Preparation of polyimide solution (wanice) and preparation of polyimide film At room temperature, 3 g of the polyimide (III) is dissolved in N-methyl-2-pyrrolidone (NMP) so that the solid content concentration is 12% by mass. Then, the obtained polyimide solution was pressure-filtered using a 5 μm filter.
Then, the filtered polyimide solution was applied onto a glass substrate and heated in the atmosphere at 50 ° C. for 30 minutes, 140 ° C. for 30 minutes, and 200 ° C. for 60 minutes in sequence to obtain a transparent polyimide film. Then, the obtained polyimide film was peeled off by mechanical cutting and used as an evaluation sample.
上述の手順にて作製した薄膜（評価試料）の耐熱性及び光学特性、すなわち、５０℃乃至２００℃及び２００℃乃至２５０℃における線熱膨張係数（ＣＴＥ）、光線透過率（Ｔ400nm、Ｔ550nm）、５％重量減少温度（Ｔｄ5%）、ＣＩＥ ｂ*値（黄色評価）、リタデーション（Ｒth、Ｒ0）並びに複屈折（Δｎ）に関して、下記手順に従いそれぞれ評価した。また、上記ポリイミドの数平均分子量及び重量平均分子量についても、下記手順に従い測定した。結果を表１に示す。The heat resistance and optical properties of the thin film (evaluation sample) prepared by the above procedure, that is, the coefficient of linear thermal expansion (CTE) at 50 ° C to 200 ° C and 200 ° C to 250 ° C, and the light transmittance (T 400 nm , T 550 nm). ), 5% weight loss temperature (Td 5% ), CIE b * value (yellow evaluation), retardation (R th , R 0 ) and birefringence (Δn) were evaluated according to the following procedure. In addition, the number average molecular weight and the weight average molecular weight of the polyimide were also measured according to the following procedure. The results are shown in Table 1.
１）ＣＩＥ ｂ値（ＣＩＥ ｂ*）
ＣＩＥ ｂ値（ＣＩＥ ｂ*）は、日本電色工業（株）製 ＳＡ４０００スペクトロメーターを用いて、室温にて、リファレンスを空気として、測定を行った。
２）光線透過率（透明性）（Ｔ400nm、Ｔ550nm）
波長４００ｎｍ及び５５０ｎｍの光線透過率（Ｔ400nm、Ｔ550nm［％］）は、（株）島津製作所 紫外可視分光光度計 ＵＶ−Ｖｉｓｉｂｌｅ ３６００を用い、室温にて、リファレンスを空気として、測定を行った。
３）リタデーション（Ｒth、Ｒ0）
厚さ方向リタデーション（Ｒth）及び面内リタデーション（Ｒ0）を、王子計測機器（株）製、ＫＯＢＵＲＡ ２１００ＡＤＨを用いて、室温にて測定した。
なお、厚さ方向リタデーション（Ｒth）及び面内リタデーション（Ｒ0）は以下の式にて算出される。
Ｒ0＝（Ｎｘ−Ｎｙ）×ｄ＝ΔＮｘｙ×ｄ
Ｒth＝［（Ｎｘ＋Ｎｙ）／２−Ｎｚ］×ｄ＝［（ΔＮｘｚ×ｄ）＋（ΔＮｙｚ×ｄ）／２
Ｎｘ、Ｎｙ：面内の直交する２つの屈折率（Ｎｘ＞Ｎｙ、Ｎｘを遅相軸、Ｎｙを進相軸とも称する）
Ｎｚ：面に対して厚さ（垂直）方向の屈折率
ｄ：膜厚
ΔＮｘｙ：面内の２つの屈折率の差（Ｎｘ−Ｎｙ）（複屈折）
ΔＮｘｚ：面内の屈折率Ｎｘと厚さ方向の屈折率Ｎｚの差（複屈折）
ΔＮｙｚ：面内の屈折率Ｎｙと厚さ方向の屈折率Ｎｚの差（複屈折）
４）線膨張係数（ＣＴＥ）
各評価試料を幅５ｍｍ、長さ１６ｍｍのサイズにカットし、これをＴＡインスツルメンツ社製 ＴＭＡ Ｑ４００を用いて、まず１０℃／ｍｉｎで昇温して５０℃乃至３００℃まで加熱（第一加熱）し、次いで１０℃／ｍｉｎで降温して３０℃まで冷却した後に、１０℃／ｍｉｎで昇温して３０℃乃至４１０℃まで加熱（第二加熱）した際の、第二加熱の５０℃乃至２００℃、並びに２００℃乃至２５０℃における線膨張係数（ＣＴＥ［ｐｐｍ／℃］）の値を測定することで求めた。なお、第一加熱、冷却および第二加熱を通じて、荷重０．０５Ｎを加えた。
５）５％重量減少温度（Ｔｄ5%）
５％重量減少温度（Ｔｄ5%［℃］）は、ＴＡインスツルメンツ社製 ＴＧＡ Ｑ５００を用い、窒素中、樹脂薄膜約５乃至１０ｍｇを５０乃至８００℃まで１０℃／ｍｉｎで昇温して測定することで求めた。なお、１５０℃における重量を重量減少０％とした。
６）膜厚
得られた樹脂薄膜の膜厚は、（株）テクロック製 シックネスゲージにて測定した。
７）面内複屈折（Δｎ）
前述の＜３）リタデーション＞により得られた厚さ方向リタデーション（Ｒth）の値を用い、以下の式にて算出した。
ΔＮ＝［Ｒth／ｄ（フィルム膜厚）］／１０００
８）数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）
数平均分子量（以下、Ｍｎと略す）と重量平均分子量（以下、Ｍｗと略す）は、ポリテトラフルオロエチレン（ＰＴＦＥ）製０．４５μｍのフィルタにてろ過したポリマー試料を、装置：昭和電工（株）製、Ｓｈｏｗｄｅｘ ＧＰＣ−１０１、カラム：ＫＤ８０３およびＫＤ８０５、カラム温度：５０℃、溶出溶媒：ＤＭＦ、流量：１．５ｍｌ／分、検量線：標準ポリスチレン、の条件にて測定した。1) CIE b value (CIE b * )
The CIE b value (CIE b * ) was measured using a SA4000 spectrometer manufactured by Nippon Denshoku Kogyo Co., Ltd. at room temperature and using the reference as air.
2) Light transmittance (transparency) (T 400nm , T 550nm )
The light transmittances (T 400 nm , T 550 nm [%]) at wavelengths of 400 nm and 550 nm were measured using an ultraviolet-visible spectrophotometer UV-Visible 3600 manufactured by Shimadzu Corporation at room temperature with the reference as air. ..
3) Ritalization (R th , R 0 )
Thickness direction retardation (R th ) and in-plane retardation (R 0 ) were measured at room temperature using KOBURA 2100ADH manufactured by Oji Measuring Instruments Co., Ltd.
The thickness direction retardation (R th ) and the in-plane retardation (R 0 ) are calculated by the following formulas.
R 0 = (Nx−Ny) × d = ΔNxy × d
R th = [(Nx + Ny) /2-Nz] × d = [(ΔNxz × d) + (ΔNyz × d) / 2
Nx, Ny: Two orthogonal refractive indexes in the plane (Nx> Ny, Nx is also referred to as a slow axis, Ny is also referred to as a phase advance axis).
Nz: Refractive index in the thickness (perpendicular) direction with respect to the plane d: Film thickness ΔNxy: Difference between two refractive indexes in the plane (Nx-Ny) (birefringence)
ΔNxz: Difference between in-plane refractive index Nx and refractive index Nz in the thickness direction (birefringence)
ΔNyz: Difference between the in-plane refractive index Ny and the refractive index Nz in the thickness direction (birefringence)
4) Coefficient of linear expansion (CTE)
Each evaluation sample is cut into a size of 5 mm in width and 16 mm in length, and this is first heated at 10 ° C./min using TMA Q400 manufactured by TA Instruments and heated to 50 ° C. to 300 ° C. (first heating). Then, after lowering the temperature at 10 ° C./min and cooling to 30 ° C., the temperature is raised at 10 ° C./min and heated to 30 ° C. to 410 ° C. (second heating). It was determined by measuring the value of the coefficient of linear expansion (CTE [ppm / ° C.]) at 200 ° C. and 200 ° C. to 250 ° C. A load of 0.05 N was applied through the first heating, cooling and the second heating.
5) 5% weight loss temperature (Td 5% )
The 5% weight loss temperature (Td 5% [° C.]) is measured by raising the temperature of about 5 to 10 mg of the resin thin film in nitrogen to 50 to 800 ° C. at 10 ° C./min using TGA Q500 manufactured by TA Instruments. I asked for it. The weight at 150 ° C. was set to 0% weight loss.
6) Film thickness The film thickness of the obtained resin thin film was measured with a thickness gauge manufactured by Teclock Co., Ltd.
7) In-plane birefringence (Δn)
Using the value of the thickness direction retardation (R th ) obtained by the above-mentioned <3) retardation>, it was calculated by the following formula.
ΔN = [R th / d (film thickness)] / 1000
8) Number average molecular weight (Mn) and weight average molecular weight (Mw)
The number average molecular weight (hereinafter abbreviated as Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) are polymer samples filtered through a 0.45 μm filter made of polytetrafluoroethylene (PTFE). ), Showdex GPC-101, columns: KD803 and KD805, column temperature: 50 ° C., elution solvent: DMF, flow rate: 1.5 ml / min, calibration line: standard polystyrene.
表１に示すように、本発明の新規な酸二無水物を用いて作製したポリイミド膜は、厚さ方向のリタデーションＲthは５００ｎｍ未満の値、面内リタデーションＲ0が５未満といった非常に低い値を有する結果となった。また波長４００ｎｍにおける透過率（Ｔ400nm）と波長５５０ｎｍにおける透過率（Ｔ550nm）、そして５０℃−２００℃におけるＣＴＥ値と２００℃−２５０℃におけるＣＴＥ値が、それぞれ異なる値となった。そしてＴｄ5%値に示すように高い耐熱性を有することが確認された。
本発明の新規な酸二無水物は、共役系を破壊し光伝送のためのより大きな自由体積をもたらす嵩高い構造によって特異な配列方向を有すると考えられ、そしてそのことがポリイミド膜において、透過率とリタデーション（位相差）に優れた性能をもたらすと考えられる。
このように、本発明の新規な酸二無水物を用いて製造したポリイミド膜は、高い透明性（高い光線透過率）及び耐熱性、そして低いリタデーションという特性を有し、すなわちフレキシブルディスプレイ基板のベースフィルムとして必要な要件を満たすものであり、フレキシブルディスプレイ基板のベースフィルムとして特に好適に用いることができることが期待できる。As shown in Table 1, the polyimide film produced by using the novel acid dianhydride of the present invention has a very low retardation R th in the thickness direction of less than 500 nm and an in-plane retardation R 0 of less than 5. The result has a value. Further, the transmittance at a wavelength of 400 nm (T 400 nm ) and the transmittance at a wavelength of 550 nm (T 550 nm ), and the CTE value at 50 ° C.-200 ° C. and the CTE value at 200 ° C.-250 ° C. were different values. And it was confirmed that it had high heat resistance as shown in the Td 5% value.
The novel acid dianhydrides of the present invention are believed to have a unique alignment orientation due to the bulky structure that disrupts the conjugated system and provides a larger free volume for optical transmission, which is transmitted in the polyimide film. It is considered to bring excellent performance to rate and retardation (phase difference).
As described above, the polyimide film produced by using the novel acid dianhydride of the present invention has the characteristics of high transparency (high light transmittance), heat resistance, and low retardation, that is, the base of a flexible display substrate. It satisfies the requirements required as a film, and can be expected to be particularly suitably used as a base film for a flexible display substrate.
Claims (16)
前記酸二無水物成分が下記式（１−１）で表される酸二無水物を含むことを特徴とする、ポリアミック酸。
Ｒ6及びＲ7は、互いに独立して、水素原子、ハロゲン原子、炭素原子数１乃至５のアルキル基又は炭素原子数１乃至５のアルコキシ基を表し、
ａおよびｂは、互いに独立して、０〜４の整数を表し、
ｃおよびｄは、互いに独立して、０〜９の整数を表し、
ｅは、０〜２の整数を表す。）A polyamic acid obtained by reacting an acid dianhydride component with a diamine component.
A polyamic acid, wherein the acid dianhydride component contains an acid dianhydride represented by the following formula (1-1).
R 6 and R 7 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
a and b represent integers from 0 to 4 independently of each other.
c and d represent integers 0-9 independently of each other.
e represents an integer of 0 to 2. )
Ｒ6及びＲ7は、互いに独立して、水素原子、ハロゲン原子、炭素原子数１乃至５のアルキル基又は炭素原子数１乃至５のアルコキシ基を表し、
ａおよびｂは、互いに独立して、０〜４の整数を表し、
ｃおよびｄは、互いに独立して、０〜９の整数を表し、
ｅは、０〜２の整数を表す。）An acid dianhydride characterized by being represented by the formula (1-1).
R 6 and R 7 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
a and b represent integers from 0 to 4 independently of each other.
c and d represent integers 0-9 independently of each other.
e represents an integer of 0 to 2. )
Ｒ6及びＲ7は、互いに独立して、水素原子、ハロゲン原子、炭素原子数１乃至５のアルキル基又は炭素原子数１乃至５のアルコキシ基を表し、
ａおよびｂは、互いに独立して、０〜４の整数を表し、
ｃおよびｄは、互いに独立して、０〜９の整数を表し、
ｅは、０〜２の整数を表す。）A tetracarboxylic acid represented by the formula (2-1).
R 6 and R 7 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
a and b represent integers from 0 to 4 independently of each other.
c and d represent integers 0-9 independently of each other.
e represents an integer of 0 to 2. )
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016190090 | 2016-09-28 | ||
| JP2016190090 | 2016-09-28 | ||
| PCT/JP2017/035328 WO2018062428A1 (en) | 2016-09-28 | 2017-09-28 | Acid dianhydride and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2018062428A1 JPWO2018062428A1 (en) | 2019-08-29 |
| JP6966726B2 true JP6966726B2 (en) | 2021-11-17 |
Family
ID=61760493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018542882A Active JP6966726B2 (en) | 2016-09-28 | 2017-09-28 | Acid dianhydride and its use |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6966726B2 (en) |
| TW (1) | TWI735667B (en) |
| WO (1) | WO2018062428A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182962A (en) * | 2002-10-09 | 2004-07-02 | Hitachi Chem Co Ltd | Polyimide resin having triptycene skeleton and optical component |
| WO2009101885A1 (en) * | 2008-02-14 | 2009-08-20 | Kyowa Hakko Chemical Co., Ltd. | Polyimide |
| WO2014207559A2 (en) * | 2013-06-06 | 2014-12-31 | King Abdullah University Of Science And Technlology | Triptycene-based dianhydrides, polyimides, methods of making each, and methods of use |
-
2017
- 2017-09-28 TW TW106133364A patent/TWI735667B/en active
- 2017-09-28 JP JP2018542882A patent/JP6966726B2/en active Active
- 2017-09-28 WO PCT/JP2017/035328 patent/WO2018062428A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018062428A1 (en) | 2018-04-05 |
| JPWO2018062428A1 (en) | 2019-08-29 |
| TW201829368A (en) | 2018-08-16 |
| TWI735667B (en) | 2021-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102062939B1 (en) | Polyimide and molded body thereof | |
| JP6748378B2 (en) | Diamine and its use | |
| JP6631804B2 (en) | Method for producing resin thin film and composition for forming resin thin film | |
| US7795370B2 (en) | Tetracarboxylic acid compound, polyimide thereof, and production method thereof | |
| JP2021102770A (en) | Polyamic acid composition with improved adhesive strength and polyimide film comprising the same | |
| JP7072140B2 (en) | Polyimide film | |
| JP5320668B2 (en) | Tetracarboxylic acid compound, polyimide thereof, and production method thereof | |
| JP5985977B2 (en) | Polyimide resin solution | |
| JP6806089B2 (en) | Diamine and its use | |
| KR101787807B1 (en) | Polyimide-based film and mehtod for preparing same | |
| JP6966725B2 (en) | Acid dianhydride and its use | |
| JP7037122B2 (en) | Diamine and its use | |
| JP6966726B2 (en) | Acid dianhydride and its use | |
| TWI691491B (en) | Tetracarboxylic acid dianhydride, polyamic acid and polyimide | |
| JP7054064B2 (en) | Composition for forming a flexible device substrate | |
| CN113348200A (en) | Method for producing polyimide resin powder | |
| JP5163898B2 (en) | Polyamic acid and polyimide | |
| JP2013028578A (en) | Method of producing amide group-containing tetracarboxylic dianhydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200825 |
|
| 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: 20210922 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20211005 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6966726 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |