JP6638744B2 - Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate - Google Patents
Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate Download PDFInfo
- Publication number
- JP6638744B2 JP6638744B2 JP2018009116A JP2018009116A JP6638744B2 JP 6638744 B2 JP6638744 B2 JP 6638744B2 JP 2018009116 A JP2018009116 A JP 2018009116A JP 2018009116 A JP2018009116 A JP 2018009116A JP 6638744 B2 JP6638744 B2 JP 6638744B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- polyimide precursor
- substrate
- film
- precursor composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 title claims description 360
- 239000004642 Polyimide Substances 0.000 title claims description 260
- 239000002243 precursor Substances 0.000 title claims description 185
- 239000000758 substrate Substances 0.000 title claims description 87
- 239000000203 mixture Substances 0.000 title claims description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 108
- 239000000126 substance Substances 0.000 claims description 40
- -1 thiol compounds Chemical class 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000002834 transmittance Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000003504 photosensitizing agent Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 37
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 35
- 150000004985 diamines Chemical class 0.000 description 31
- 239000002966 varnish Substances 0.000 description 31
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 30
- 239000002904 solvent Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 25
- 239000011521 glass Substances 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- 239000005340 laminated glass Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 229920005575 poly(amic acid) Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 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 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 238000006358 imidation reaction Methods 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- SIOVKLKJSOKLIF-HJWRWDBZSA-N trimethylsilyl (1z)-n-trimethylsilylethanimidate Chemical compound C[Si](C)(C)OC(/C)=N\[Si](C)(C)C SIOVKLKJSOKLIF-HJWRWDBZSA-N 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- UIZIZIPEEWDBCL-UHFFFAOYSA-N (4-aminophenyl) 4-[4-(4-aminophenoxy)carbonylphenyl]benzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(=O)OC=2C=CC(N)=CC=2)C=C1 UIZIZIPEEWDBCL-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- XCOBLONWWXQEBS-KPKJPENVSA-N N,O-bis(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CZRKJHRIILZWRC-UHFFFAOYSA-N methyl acetate;propane-1,2-diol Chemical compound COC(C)=O.CC(O)CO CZRKJHRIILZWRC-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RPOHXHHHVSGUMN-UHFFFAOYSA-N 1-n,4-n-bis(4-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(C(=O)NC=2C=CC(N)=CC=2)C=C1 RPOHXHHHVSGUMN-UHFFFAOYSA-N 0.000 description 1
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 description 1
- FTYSULAJAVFRBZ-UHFFFAOYSA-N 2-n,4-n-bis(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine Chemical compound C1=CC(N)=CC=C1NC1=NC(N)=NC(NC=2C=CC(N)=CC=2)=N1 FTYSULAJAVFRBZ-UHFFFAOYSA-N 0.000 description 1
- PBSXNMHNUFQDKL-UHFFFAOYSA-N 2-n,4-n-bis(4-aminophenyl)-6-n-ethyl-1,3,5-triazine-2,4,6-triamine Chemical compound N=1C(NC=2C=CC(N)=CC=2)=NC(NCC)=NC=1NC1=CC=C(N)C=C1 PBSXNMHNUFQDKL-UHFFFAOYSA-N 0.000 description 1
- VVFMZHWAQNSESG-UHFFFAOYSA-N 2-n,4-n-bis(4-aminophenyl)-6-n-methyl-1,3,5-triazine-2,4,6-triamine Chemical compound N=1C(NC=2C=CC(N)=CC=2)=NC(NC)=NC=1NC1=CC=C(N)C=C1 VVFMZHWAQNSESG-UHFFFAOYSA-N 0.000 description 1
- NJHOBWAEBBSZLP-UHFFFAOYSA-N 2-n,4-n-bis(4-aminophenyl)-6-n-phenyl-1,3,5-triazine-2,4,6-triamine Chemical compound C1=CC(N)=CC=C1NC1=NC(NC=2C=CC=CC=2)=NC(NC=2C=CC(N)=CC=2)=N1 NJHOBWAEBBSZLP-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical group C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- FMXFZZAJHRLHGP-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)sulfonylphthalic acid Chemical compound OC(=O)C1=CC=CC(S(=O)(=O)C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O FMXFZZAJHRLHGP-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- UDKYPBUWOIPGDY-UHFFFAOYSA-N 3-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=CC(N)=C1 UDKYPBUWOIPGDY-UHFFFAOYSA-N 0.000 description 1
- FFKSVVOWOROQIU-UHFFFAOYSA-N 4-(2,5-dioxooxolan-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid Chemical compound C12=CC=CC=C2C(C(O)=O)C(C(=O)O)CC1C1CC(=O)OC1=O FFKSVVOWOROQIU-UHFFFAOYSA-N 0.000 description 1
- YARZEPAVWOMMHZ-UHFFFAOYSA-N 4-(3,4-dicarboxy-4-phenylcyclohexa-1,5-dien-1-yl)phthalic acid Chemical compound OC(=O)C1C=C(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=CC1(C(O)=O)C1=CC=CC=C1 YARZEPAVWOMMHZ-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- QNLCDRXVEPWSBQ-UHFFFAOYSA-N 4-(4,5-dicarboxy-5-phenylcyclohexa-1,3-dien-1-yl)phthalic acid Chemical compound OC(=O)C1=CC=C(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)CC1(C(O)=O)C1=CC=CC=C1 QNLCDRXVEPWSBQ-UHFFFAOYSA-N 0.000 description 1
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- LVNPGQZSPDFZNC-UHFFFAOYSA-N 4-(4-amino-3-fluorophenyl)-2-fluoroaniline Chemical group C1=C(F)C(N)=CC=C1C1=CC=C(N)C(F)=C1 LVNPGQZSPDFZNC-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- PJWQLRKRVISYPL-UHFFFAOYSA-N 4-[4-amino-3-(trifluoromethyl)phenyl]-2-(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC=C1C1=CC=C(N)C(C(F)(F)F)=C1 PJWQLRKRVISYPL-UHFFFAOYSA-N 0.000 description 1
- XJJBSSOLWISXSR-UHFFFAOYSA-N 4-amino-1-[4-[4-(4-amino-1-carboxycyclohexa-2,4-dien-1-yl)phenyl]phenyl]cyclohexa-2,4-diene-1-carboxylic acid Chemical compound C1(=CC=C(C=C1)C1(C(=O)O)CC=C(C=C1)N)C1=CC=C(C=C1)C1(C(=O)O)CC=C(C=C1)N XJJBSSOLWISXSR-UHFFFAOYSA-N 0.000 description 1
- LWZQBFQQUIOAAK-UHFFFAOYSA-N 4-amino-2-[4-(5-amino-2-carboxyphenyl)phenyl]benzoic acid Chemical compound NC1=CC=C(C(O)=O)C(C=2C=CC(=CC=2)C=2C(=CC=C(N)C=2)C(O)=O)=C1 LWZQBFQQUIOAAK-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- LGTGOCSQAOUUFP-UHFFFAOYSA-N 4-amino-n-[4-[(4-aminobenzoyl)amino]phenyl]benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC(C=C1)=CC=C1NC(=O)C1=CC=C(N)C=C1 LGTGOCSQAOUUFP-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- AKGMGEBXJHRCGH-UHFFFAOYSA-N 4-chlorophenol;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=C(Cl)C=C1 AKGMGEBXJHRCGH-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- CFTXGNJIXHFHTH-UHFFFAOYSA-N bis(4-aminophenyl) benzene-1,4-dicarboxylate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C(=O)OC=2C=CC(N)=CC=2)C=C1 CFTXGNJIXHFHTH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、透明性に優れ、線熱膨張係数が小さく、しかも耐熱性がより高く、機械的特性にも優れたポリイミドが得られるポリイミド前駆体を含む溶液組成物（ポリイミド前駆体組成物）、及びポリイミドの製造方法に関する。また、本発明は、透明性に優れ、線熱膨張係数が小さく、耐熱性も高く、機械的特性にも優れたポリイミド、ポリイミドフィルム、及び基板にも関する。 The present invention is a solution composition (polyimide precursor composition) containing a polyimide precursor that is excellent in transparency, has a small linear thermal expansion coefficient, and has higher heat resistance, and also provides a polyimide excellent in mechanical properties. And a method for producing a polyimide. The present invention also relates to a polyimide, a polyimide film, and a substrate having excellent transparency, a small coefficient of linear thermal expansion, high heat resistance, and excellent mechanical properties.
近年、高度情報化社会の到来に伴い、光通信分野の光ファイバーや光導波路等、表示装置分野の液晶配向膜やカラーフィルター用保護膜等の光学材料の開発が進んでいる。特に表示装置分野で、ガラス基板の代替として軽量でフレキシブル性に優れたプラスチック基板の検討や、曲げたり丸めたりすることが可能なディスプレイの開発が盛んに行われている。このため、その様な用途に用いることができる、より高性能の光学材料が求められている。 In recent years, with the advent of the highly information-oriented society, the development of optical materials such as liquid crystal alignment films and protective films for color filters in the field of display devices, such as optical fibers and optical waveguides in the field of optical communication, has been progressing. In particular, in the field of display devices, a plastic substrate which is lightweight and excellent in flexibility as an alternative to a glass substrate, and a display which can be bent or rounded, are being actively developed. Therefore, there is a need for a higher-performance optical material that can be used for such purposes.
芳香族ポリイミドは、分子内共役や電荷移動錯体の形成により、本質的に黄褐色に着色する。このため着色を抑制する手段として、例えば分子内へのフッ素原子の導入、主鎖への屈曲性の付与、側鎖として嵩高い基の導入などによって、分子内共役や電荷移動錯体の形成を阻害して、透明性を発現させる方法が提案されている。 Aromatic polyimide is colored essentially yellow-brown due to intramolecular conjugation and formation of a charge transfer complex. Therefore, as means for suppressing coloring, for example, introduction of a fluorine atom into the molecule, imparting flexibility to the main chain, introduction of a bulky group as a side chain, etc., inhibit the intramolecular conjugation and the formation of the charge transfer complex. Then, a method of expressing transparency has been proposed.
例えば、特許文献１に、フッ素原子を含有する、透明性が高い芳香族ポリイミドが開示されている。 For example, Patent Document 1 discloses a highly transparent aromatic polyimide containing a fluorine atom.
しかしながら、用途によっては、さらに耐熱性が高いポリイミドが求められている。また、特に表示装置などの分野において、透明性をさらに向上させることが望まれている。用途によっては、線熱膨張係数を低下させることも望まれている。ポリイミドの線熱膨張係数が大きく、金属などの導体との線熱膨張係数の差が大きいと、回路基板を形成する際に反りが増大するなどの不具合が生じることがあり、特にディスプレイ用途などの微細な回路形成プロセスが容易ではないことがある。 However, a polyimide having higher heat resistance is required for some applications. Further, particularly in the field of display devices and the like, it is desired to further improve the transparency. For some applications, it is also desired to reduce the coefficient of linear thermal expansion. If the coefficient of linear thermal expansion of polyimide is large and the difference between the coefficient of linear thermal expansion of a conductor such as metal is large, problems such as increased warpage when forming a circuit board may occur, especially for display applications. A fine circuit formation process may not be easy.
一方、特許文献２には、ポリイミド前駆体（ポリアミド酸）にイミダゾリン系化合物および／またはイミダゾール系化合物を配合してなる塗液を加熱することによって形成されてなるポリイミドが開示されている。より具体的には、実施例１では、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物と４，４’−ジアミノビフェニルエーテルから得られるポリアミド酸の溶液に２，４−ジメチルイミダゾリンを加えた溶液を基板上に塗布し、２００℃、１時間加熱して、膜厚１０００Å（０．１μｍ）の芳香族ポリイミド皮膜を得ている。実施例２では、ピロメリット酸二無水物と４，４’−ジアミノビフェニルエーテルから得られるポリアミド酸の溶液に２−エチルイミダゾリンおよび１，２−ジメチルイミダゾールを加えた溶液を基板上に塗布し、１５０℃、１時間加熱して、膜厚８００Å（０．０８μｍ）の芳香族ポリイミド皮膜を得ている。特許文献２には、イミダゾリン系化合物および／またはイミダゾール系化合物の添加により茶褐色の著しい着色は免れることになり、光線透過率の高い透明性に優れた液晶表示素子を得ることが可能となった、と記載されている。しかしながら、実施例１のポリイミド皮膜（液晶配向膜）を用いた液晶表示素子の波長４００ｎｍの光透過率は８２％（ポリイミド膜厚：０．１μｍ）、実施例２のポリイミド皮膜（液晶配向膜）を用いた液晶表示素子の波長４００ｎｍの光透過率は８３％（ポリイミド膜厚：０．０８μｍ）であり、このポリイミドは十分な透明性を有するものではない。 On the other hand, Patent Document 2 discloses a polyimide formed by heating a coating liquid obtained by mixing an imidazoline-based compound and / or an imidazole-based compound with a polyimide precursor (polyamic acid). More specifically, in Example 1, 2,4-dimethyl was added to a solution of polyamic acid obtained from 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 4,4′-diaminobiphenyl ether. A solution containing imidazoline was applied onto the substrate and heated at 200 ° C. for 1 hour to obtain an aromatic polyimide film having a thickness of 1000 ° (0.1 μm). In Example 2, a solution obtained by adding 2-ethylimidazoline and 1,2-dimethylimidazole to a solution of polyamic acid obtained from pyromellitic dianhydride and 4,4′-diaminobiphenyl ether was applied on a substrate, By heating at 150 ° C. for 1 hour, an aromatic polyimide film having a thickness of 800 ° (0.08 μm) was obtained. Patent Document 2 discloses that addition of an imidazoline-based compound and / or an imidazole-based compound avoids remarkable brownish coloring and makes it possible to obtain a liquid crystal display device having high light transmittance and excellent transparency. It is described. However, the light transmittance at a wavelength of 400 nm of the liquid crystal display device using the polyimide film (liquid crystal alignment film) of Example 1 was 82% (polyimide film thickness: 0.1 μm), and the polyimide film of Example 2 (liquid crystal alignment film). Has a light transmittance of 83% (polyimide film thickness: 0.08 μm) at a wavelength of 400 nm, and this polyimide does not have sufficient transparency.
また、透明性が低い芳香族ポリイミドの製造方法として、特許文献３には、ポリイミド前駆体樹脂、及び、イミダゾール、Ｎ−メチルイミダゾール等のポリイミド前駆体樹脂の硬化促進剤を有機極性溶媒に溶解したポリイミド前駆体樹脂含有溶液を基材上に塗布し、続く熱処理で乾燥及びイミド化によるポリイミド樹脂層の形成を２８０〜３８０℃の範囲内で完結するポリイミド樹脂層の形成方法が開示されており、これらの硬化促進剤を使用することで、熱線膨張係数を低く制御できることが記載されている。特許文献３には、また、硬化促進剤は、その沸点が１２０℃を越えるものを使用することが好ましく、沸点が、熱処理の上限温度を超えないものを選択することが好ましいことが記載されており、沸点が、例えば４００℃以上の硬化促進剤は、イミド化後のポリイミド樹脂層中に残存する割合が高くなり、ポリイミド樹脂層の機能に影響を与える傾向にあることが記載されている。 As a method for producing an aromatic polyimide having low transparency, Patent Document 3 discloses a polyimide precursor resin, and a curing accelerator for the polyimide precursor resin such as imidazole and N-methylimidazole dissolved in an organic polar solvent. A method for forming a polyimide resin layer in which a polyimide precursor resin-containing solution is applied on a substrate, followed by drying and imidization in a subsequent heat treatment to complete the formation of the polyimide resin layer within the range of 280 to 380 ° C, is disclosed. It is described that by using these curing accelerators, the coefficient of linear thermal expansion can be controlled to be low. Patent Document 3 describes that it is preferable to use a curing accelerator whose boiling point exceeds 120 ° C., and it is preferable to select a curing accelerator whose boiling point does not exceed the upper limit temperature of the heat treatment. It is described that a curing accelerator having a boiling point of, for example, 400 ° C. or more tends to remain in the polyimide resin layer after imidation and tends to affect the function of the polyimide resin layer.
本発明は、以上のような状況に鑑みてなされたものであり、透明性に優れ、線熱膨張係数が小さく、しかも耐熱性がより高く、機械的特性にも優れたポリイミドが得られるポリイミド前駆体組成物（ポリイミド前駆体を含む溶液組成物）、及びポリイミドの製造方法を提供することを目的とする。 The present invention has been made in view of the above situation, polyimide precursor having excellent transparency, a small coefficient of linear thermal expansion, higher heat resistance, and a polyimide excellent in mechanical properties can be obtained. It is an object to provide a body composition (a solution composition containing a polyimide precursor) and a method for producing a polyimide.
本発明は、以下の各項に関する。
１． 下記化学式（１）で表される繰り返し単位を含むポリイミド前駆体と、
イミダゾール系化合物を含み、
イミダゾール系化合物の含有量が、ポリイミド前駆体の繰り返し単位１モルに対して４モル未満であることを特徴とするポリイミド前駆体組成物。
The present invention relates to the following items.
1. A polyimide precursor containing a repeating unit represented by the following chemical formula (1),
Including an imidazole compound,
A polyimide precursor composition, wherein the content of the imidazole-based compound is less than 4 mol per 1 mol of the repeating unit of the polyimide precursor.
２． 前記化学式（１）中のＸ１が下記化学式（１−Ｘ）で表される基であり、前記化学式（１）中のＹ１が下記化学式（１−Ｙ）で表される基であることを特徴とする前記項１に記載のポリイミド前駆体組成物。
2. X 1 in the chemical formula (1) is a group represented by the following chemical formula (1-X), and Y 1 in the chemical formula (1) is a group represented by the following chemical formula (1-Y) Item 3. The polyimide precursor composition according to Item 1, wherein
４． 前記イミダゾール系化合物の含有量が、ポリイミド前駆体の繰り返し単位１モルに対して０．０５モル以上２モル以下であることを特徴とする前記項１〜３のいずれかに記載のポリイミド前駆体組成物。
５． 前記イミダゾール系化合物が、１，２−ジメチルイミダゾール、１−メチルイミダゾール、２−メチルイミダゾール、２−フェニルイミダゾール、イミダゾール、またはベンゾイミダゾールのいずれかであることを特徴とする前記項１〜４のいずれかに記載のポリイミド前駆体組成物。
６． 前記項１〜５のいずれかに記載のポリイミド前駆体組成物を、最高加熱温度３５０℃以上で加熱処理して、ポリイミド前駆体をイミド化することを特徴とするポリイミドの製造方法。
７． 前記項１〜５のいずれかに記載のポリイミド前駆体組成物を基材上に塗布する工程と、
基材上のポリイミド前駆体組成物を、最高加熱温度３５０℃以上で加熱処理して、ポリイミド前駆体をイミド化する工程と
を有することを特徴とする前記項６に記載のポリイミドの製造方法。
８． 前記項６又は７に記載の方法により製造されるポリイミド。
９． 厚さ１０μｍのフィルムでの波長４００ｎｍの光透過率が８０％以上であることを特徴とする前記項８に記載のポリイミド。
１０． 前記項６又は７に記載の方法により製造されるポリイミドフィルム。
１１． 前記項８又は９に記載のポリイミド、又は前記項１０に記載のポリイミドフィルムを含むことを特徴とするディスプレイ用、タッチパネル用、または太陽電池用の基板。
4. The polyimide precursor composition according to any one of Items 1 to 3, wherein the content of the imidazole-based compound is 0.05 mol or more and 2 mol or less per 1 mol of the repeating unit of the polyimide precursor. object.
5. The imidazole compound is any of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole, or benzimidazole. A polyimide precursor composition according to any one of the above.
6. 6. A method for producing a polyimide, comprising subjecting the polyimide precursor composition according to any of the above items 1 to 5 to a heat treatment at a maximum heating temperature of 350 ° C. or higher to imidize the polyimide precursor.
7. A step of applying the polyimide precursor composition according to any one of Items 1 to 5 on a substrate,
A process of heating the polyimide precursor composition on the base material at a maximum heating temperature of 350 ° C. or more to imidize the polyimide precursor.
8. Item 7. A polyimide produced by the method according to item 6 or 7.
9. Item 10. The polyimide according to item 8, wherein the film having a thickness of 10 µm has a light transmittance at a wavelength of 400 nm of 80% or more.
10. Item 8. A polyimide film produced by the method according to item 6 or 7.
11. A substrate for a display, a touch panel, or a solar cell, comprising the polyimide according to item 8 or 9, or the polyimide film according to item 10.
本発明によって、透明性に優れ、線熱膨張係数が小さく、しかも耐熱性がより高く、機械的特性にも優れたポリイミドが得られるポリイミド前駆体組成物（ポリイミド前駆体を含む溶液組成物）、及びポリイミドの製造方法を提供することができる。 According to the present invention, a polyimide precursor composition (solution composition containing a polyimide precursor), which is excellent in transparency, has a small linear thermal expansion coefficient, and has higher heat resistance, and can obtain a polyimide excellent in mechanical properties, And a method for producing polyimide.
本発明のポリイミド前駆体組成物から得られるポリイミド（本発明のポリイミド）は、耐熱性が高く、透明性が高く、且つ低線熱膨張係数であって微細な回路の形成が容易であり、ディスプレイ用途などの基板を形成するために好適に用いることができる。また、本発明のポリイミドは、タッチパネル用、太陽電池用の基板を形成するためにも好適に用いることができる。 The polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention has high heat resistance, high transparency, low coefficient of linear thermal expansion, easy formation of fine circuits, and display. It can be suitably used for forming a substrate for use or the like. Further, the polyimide of the present invention can be suitably used for forming substrates for touch panels and solar cells.
本発明のポリイミド前駆体組成物は、前記化学式（１）で表される繰り返し単位の少なくとも１種を含むポリイミド前駆体と、イミダゾール系化合物を含み、イミダゾール系化合物の含有量は、ポリイミド前駆体の繰り返し単位１モルに対して４モル未満である。 The polyimide precursor composition of the present invention includes a polyimide precursor containing at least one kind of the repeating unit represented by the chemical formula (1) and an imidazole-based compound, and the content of the imidazole-based compound is the same as that of the polyimide precursor. Less than 4 mol per 1 mol of the repeating unit.
前記化学式（１）で表される繰り返し単位の少なくとも１種を含むポリイミド前駆体から得られるポリイミド、すなわちフッ素原子を含有する芳香族ポリイミドは、透明性が高い。このような透明性が高いポリイミドの場合、着色の要因となりえる添加物の使用は好まれない。しかしながら、イミダゾール系化合物を、ポリイミド前駆体の繰り返し単位１モルに対して４モル未満、好ましくは０．０５モル以上２モル以下の割合で、ポリイミド前駆体組成物に加えることにより、高い透明性を保ったまま、得られるポリイミドの耐熱性が高くなる。すなわち、本発明によれば、同一組成のポリイミド前駆体から、高い透明性を維持しながら、耐熱性がより高いポリイミドが得られる。また、１気圧における沸点が３６０℃未満、好ましくは３４０℃以下であるイミダゾール系化合物を用いた場合、得られるポリイミドの透明性がさらに向上することがある。 A polyimide obtained from a polyimide precursor containing at least one kind of the repeating unit represented by the chemical formula (1), that is, an aromatic polyimide containing a fluorine atom has high transparency. In the case of such a highly transparent polyimide, the use of additives that can cause coloring is not preferred. However, by adding the imidazole-based compound to the polyimide precursor composition in a proportion of less than 4 mol, preferably 0.05 mol or more and 2 mol or less per 1 mol of the repeating unit of the polyimide precursor, high transparency can be obtained. The heat resistance of the obtained polyimide increases while keeping it. That is, according to the present invention, a polyimide having higher heat resistance can be obtained from a polyimide precursor having the same composition while maintaining high transparency. When an imidazole compound having a boiling point of less than 360 ° C., preferably 340 ° C. or less at 1 atm is used, the transparency of the resulting polyimide may be further improved.
さらに、透明性が高いポリイミドを得るためには、ポリイミド前駆体を比較的低温度で加熱処理してイミド化を完了する方が好ましいと一般に考えられているが、本発明によれば、最高加熱温度が３５０℃以上の加熱処理によってポリイミド前駆体をイミド化しても、透明性が高いポリイミドを製造することができる。その結果、イミド化のための加熱処理の最高加熱温度を３５０℃以上とすることが可能になるので、得られるポリイミドの機械的特性が向上する。すなわち、本発明によれば、透明性が高く、線熱膨張係数が低く、耐熱性も高く、しかも機械的特性にも優れたポリイミドが得られる。 Furthermore, in order to obtain a polyimide having high transparency, it is generally considered that it is preferable to complete the imidization by heat-treating the polyimide precursor at a relatively low temperature. Even when the polyimide precursor is imidized by a heat treatment at a temperature of 350 ° C. or higher, a highly transparent polyimide can be produced. As a result, the maximum heating temperature of the heat treatment for imidization can be 350 ° C. or higher, so that the mechanical properties of the obtained polyimide are improved. That is, according to the present invention, a polyimide having high transparency, low linear thermal expansion coefficient, high heat resistance, and excellent mechanical properties can be obtained.
前記のとおり、本発明のポリイミド前駆体組成物は、前記化学式（１）で表される繰り返し単位の少なくとも１種を含むポリイミド前駆体を含む。 As described above, the polyimide precursor composition of the present invention includes the polyimide precursor containing at least one kind of the repeating unit represented by the chemical formula (1).
前記化学式（１）中のＸ１としては、炭素数が６〜４０の芳香族環を有する４価の基が好ましく、Ｙ１としては、炭素数が６〜４０の芳香族環を有する２価の基が好ましい。また、Ｘ１またはＹ１の一方がフッ素原子を含有するものであってもよく、Ｘ１とＹ１の両方がフッ素原子を含有するものであってもよい。 X 1 in the chemical formula (1) is preferably a tetravalent group having an aromatic ring having 6 to 40 carbon atoms, and Y 1 is a divalent group having an aromatic ring having 6 to 40 carbon atoms. Are preferred. The may be one in which one of X 1 or Y 1 contains a fluorine atom, or may be both of X 1 and Y 1 contains a fluorine atom.
前記化学式（１）の繰り返し単位を与える、フッ素原子を含有するテトラカルボン酸成分としては、例えば、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパンや、これのテトラカルボン酸二無水物、テトラカルボン酸シリルエステル、テトラカルボン酸エステル、テトラカルボン酸クロライド等の誘導体が挙げられる。また、フッ素原子を含有しないテトラカルボン酸成分としては、例えば、４−（２，５−ジオキソテトラヒドロフラン−３−イル）−１，２，３，４−テトラヒドロナフタレン−１，２−ジカルボン酸、ピロメリット酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸、３，３’，４，４’−ビフェニルテトラカルボン酸、２，３，３’，４’−ビフェニルテトラカルボン酸、４，４’−オキシジフタル酸、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、ｍ−ターフェニル−３，４，３’，４’−テトラカルボン酸二無水物、ｐ−ターフェニル−３，４，３’，４’−テトラカルボン酸二無水物、ビスカルボキシフェニルジメチルシラン、ビスジカルボキシフェノキシジフェニルスルフィド、スルホニルジフタル酸や、これらのテトラカルボン酸二無水物、テトラカルボン酸シリルエステル、テトラカルボン酸エステル、テトラカルボン酸クロライド等の誘導体が挙げられる。テトラカルボン酸成分は、単独で使用してもよく、また複数種を組み合わせて使用することもできる。 Examples of the fluorine atom-containing tetracarboxylic acid component that gives the repeating unit of the chemical formula (1) include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane and tetracarboxylic acid Derivatives such as anhydride, silyl ester of tetracarboxylic acid, ester of tetracarboxylic acid, and tetracarboxylic acid chloride are exemplified. Examples of the tetracarboxylic acid component containing no fluorine atom include 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, Pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, , 4'-oxydiphthalic acid, bis (3,4-dicarboxyphenyl) sulfone dianhydride, m-terphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride, p-terphenyl-3 , 4,3 ', 4'-tetracarboxylic dianhydride, biscarboxyphenyldimethylsilane, bisdicarboxyphenoxydiphenyl sulfide, sulfonyl diphthalic acid, These tetracarboxylic acid dianhydrides, tetracarboxylic acid silyl ester, tetracarboxylic acid esters, derivatives of such tetracarboxylic acid chloride. The tetracarboxylic acid component may be used alone or in combination of two or more.
前記化学式（１）の繰り返し単位を与える、フッ素原子を含有するジアミン成分としては、例えば、２，２’−ビス（トリフルオロメチル）ベンジジン、３，３’−ビス（トリフルオロメチル）ベンジジン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、２，２’−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパンが挙げられる。また、フッ素原子を含有しないジアミン成分としては、例えば、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、ベンジジン、３，３'−ジアミノ−ビフェニル、ｏ−トリジン、ｍ−トリジン、４，４’−ジアミノベンズアニリド、３，４’−ジアミノベンズアニリド、Ｎ，Ｎ’−ビス（４−アミノフェニル）テレフタルアミド、Ｎ，Ｎ’−ｐ−フェニレンビス（ｐ−アミノベンズアミド）、４−アミノフェノキシ−４−ジアミノベンゾエート、ビス（４−アミノフェニル）テレフタレート、ビフェニル−４，４’−ジカルボン酸ビス（４−アミノフェニル）エステル、ｐ−フェニレンビス（ｐ−アミノベンゾエート）、ビス（４−アミノフェニル）-[１,１'-ビフェニル]-４,４'-ジカルボキシレート、[１,１'-ビフェニル]-４,４'-ジイル ビス(４-アミノベンゾエート)、４，４’−オキシジアニリン、３，４’−オキシジアニリン、３，３’−オキシジアニリン、ｐ−メチレンビス（フェニレンジアミン）、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ビス（３−アミノフェノキシ）ビフェニル、ビス（４−アミノフェニル）スルホン、３，３’−ビス（（アミノフェノキシ）フェニル）プロパン、ビス（４−（４−アミノフェノキシ）ジフェニル）スルホン、ビス（４−（３−アミノフェノキシ）ジフェニル）スルホン、オクタフルオロベンジジン、３，３'−ジメトキシ−４，４'−ジアミノビフェニル、３，３'−ジクロロ−４，４'−ジアミノビフェニル、３，３'−ジフルオロ−４，４'−ジアミノビフェニル、２，４−ビス（４−アミノアニリノ）−６−アミノ−１，３，５−トリアジン、２，４−ビス（４−アミノアニリノ）−６−メチルアミノ−１，３，５−トリアジン、２，４−ビス（４−アミノアニリノ）−６−エチルアミノ−１，３，５−トリアジン、２，４−ビス（４−アミノアニリノ）−６−アニリノ−１，３，５−トリアジンが挙げられる。ジアミン成分は、単独で使用してもよく、また複数種を組み合わせて使用することもできる。 Examples of the fluorine atom-containing diamine component that gives the repeating unit of the chemical formula (1) include 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, , 2-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-hydroxyphenyl) Hexafluoropropane is mentioned. Examples of the diamine component containing no fluorine atom include, for example, p-phenylenediamine, m-phenylenediamine, benzidine, 3,3′-diamino-biphenyl, o-tolidine, m-tolidine, 4,4′-diaminobenz Anilide, 3,4'-diaminobenzanilide, N, N'-bis (4-aminophenyl) terephthalamide, N, N'-p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diamino Benzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid bis (4-aminophenyl) ester, p-phenylenebis (p-aminobenzoate), bis (4-aminophenyl)-[1 , 1'-biphenyl] -4,4'-dicarboxylate, [1,1'-biphenyl] -4,4'-diylbis ( 4-aminobenzoate), 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, p-methylenebis (phenylenediamine), 1,3-bis (4-amino Phenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis (4-aminophenyl) sulfone, 3,3′-bis ((aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) diphenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfone, octafluorobenzidine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3 , 3'-Dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,4-bis (4-aminoanilino) -6-amino-1,3,5- Triazine, 2,4-bis (4-aminoanilino) -6-methylamino-1,3,5-triazine, 2,4-bis (4-aminoanilino) -6-ethylamino-1,3,5-triazine, 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine. The diamine components may be used alone or in combination of two or more.
このポリイミド前駆体は、前記化学式（１）で表される繰り返し単位以外の、他の繰り返し単位を含むことができる。他の繰り返し単位を与えるテトラカルボン酸成分およびジアミン成分としては、特に限定されず、他の公知の芳香族または脂肪族テトラカルボン酸類、公知の芳香族または脂肪族ジアミン類いずれも使用することができる。他のテトラカルボン酸成分も、単独で使用してもよく、また複数種を組み合わせて使用することもできる。他のジアミン成分も、単独で使用してもよく、また複数種を組み合わせて使用することもできる。 This polyimide precursor can include other repeating units other than the repeating unit represented by the chemical formula (1). The tetracarboxylic acid component and the diamine component providing other repeating units are not particularly limited, and any other known aromatic or aliphatic tetracarboxylic acids, and any known aromatic or aliphatic diamines can be used. . Other tetracarboxylic acid components may be used alone or in combination of two or more. Other diamine components may be used alone or in combination of two or more.
前記化学式（１）で表される繰り返し単位以外の、他の繰り返し単位の含有量は、全繰り返し単位に対して、好ましくは３０モル％以下または３０モル％未満、より好ましくは２０モル％以下、さらに好ましくは１０モル％以下であることが好ましい。 The content of other repeating units other than the repeating unit represented by the chemical formula (1) is preferably 30 mol% or less, or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is preferably at most 10 mol%.
ある実施態様においては、ポリイミド前駆体としては、例えば、Ｘ１が前記化学式（１−Ｘ）で表される基であり、Ｙ１が前記化学式（１−Ｙ）で表される基である前記化学式（１）で表される繰り返し単位を含むポリイミド前駆体が好ましい。 In one embodiment, as the polyimide precursor, for example, X 1 is a group represented by the chemical formula (1-X), and Y 1 is a group represented by the chemical formula (1-Y). A polyimide precursor containing a repeating unit represented by the chemical formula (1) is preferable.
換言すれば、ある実施態様においては、ポリイミド前駆体は、４，４’−（２，２−ヘキサフルオロイソプロピレン）ジフタル酸類等（ジフタル酸を含むテトラカルボン酸類等とは、テトラカルボン酸と、テトラカルボン酸二無水物、テトラカルボン酸シリルエステル、テトラカルボン酸エステル、テトラカルボン酸クロライド等のテトラカルボン酸誘導体を表す）を含むテトラカルボン酸成分と、２，２’−ビス（トリフルオロメチル）ベンジジンを含むジアミン成分から得られるポリイミド前駆体である。テトラカルボン酸成分としては、４，４’−（２，２−ヘキサフルオロイソプロピレン）ジフタル酸類等の、１種を単独で使用してもよく、また複数種を組み合わせて使用することもできる。 In other words, in one embodiment, the polyimide precursor comprises 4,4 ′-(2,2-hexafluoroisopropylene) diphthalic acid or the like (tetracarboxylic acid including diphthalic acid or the like is a tetracarboxylic acid; Tetracarboxylic acid derivatives including tetracarboxylic dianhydrides, tetracarboxylic silyl esters, tetracarboxylic esters, and tetracarboxylic acid chlorides), and 2,2'-bis (trifluoromethyl) It is a polyimide precursor obtained from a diamine component containing benzidine. As the tetracarboxylic acid component, one kind such as 4,4 '-(2,2-hexafluoroisopropylene) diphthalic acid may be used alone, or a plurality of kinds may be used in combination.
このポリイミド前駆体は、前記化学式（１）で表される繰り返し単位１００モル％中、Ｘ１が前記化学式（１−Ｘ）で表される基であり、Ｙ１が前記化学式（１−Ｙ）で表される基である化学式（１）で表される繰り返し単位の割合が、好ましくは５０モル％以上、より好ましくは６０モル％以上、さらに好ましくは７０モル％以上であることが好ましい。また、ある実施態様においては、得られるポリイミドの特性の点から、前記化学式（１）で表される繰り返し単位１００モル％中、Ｘ１が前記化学式（１−Ｘ）で表される基であり、Ｙ１が前記化学式（１−Ｙ）で表される基である化学式（１）で表される繰り返し単位の割合が、好ましくは６０モル％以下、より好ましくは７０モル％以下であることが好ましいことがある。例えば、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物等の、他のテトラカルボン酸類等を、前記化学式（１）の繰り返し単位を与えるテトラカルボン酸成分１００モル％中、例えば４０モル％以下、好ましくは３０モル％以下で使用することが好ましいことがある。 The polyimide precursor recurring units of 100 mol% represented by the chemical formula (1) is a group X 1 is represented by the formula (1-X), Y 1 is the formula (1-Y) The proportion of the repeating unit represented by the chemical formula (1), which is a group represented by the formula, is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 70 mol% or more. In one embodiment, from the viewpoint of the properties of the obtained polyimide, X 1 is a group represented by the chemical formula (1-X) in 100 mol% of the repeating unit represented by the chemical formula (1). , Y 1 is a group represented by the chemical formula (1-Y), and the proportion of the repeating unit represented by the chemical formula (1) is preferably 60 mol% or less, more preferably 70 mol% or less. May be preferred. For example, another tetracarboxylic acid such as 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used in 100 mol% of a tetracarboxylic acid component giving the repeating unit of the above formula (1). It may be preferred to use up to 40 mol%, preferably up to 30 mol%.
なお、Ｘ１が前記化学式（１−Ｘ）で表される基であり、Ｙ１が前記化学式（１−Ｙ）で表される基である前記化学式（１）で表される繰り返し単位を含むポリイミド前駆体は、それ以外の、他の前記化学式（１）で表される繰り返し単位を含むことができ、また、前記化学式（１）で表される繰り返し単位以外の、他の繰り返し単位を含むこともできる。前記化学式（１）で表される繰り返し単位以外の、他の繰り返し単位の含有量は、全繰り返し単位に対して、好ましくは３０モル％以下または３０モル％未満、より好ましくは２０モル％以下、さらに好ましくは１０モル％以下であることが好ましい。 X 1 is a group represented by the chemical formula (1-X), and Y 1 includes a repeating unit represented by the chemical formula (1), which is a group represented by the chemical formula (1-Y). The polyimide precursor may include other repeating units represented by the above-mentioned chemical formula (1), and may include other repeating units other than the repeating unit represented by the above-mentioned chemical formula (1). You can also. The content of other repeating units other than the repeating unit represented by the chemical formula (1) is preferably 30 mol% or less, or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is preferably at most 10 mol%.
本発明のポリイミド前駆体において、前記化学式（１）のＲ１、Ｒ２はそれぞれ独立に水素、炭素数１〜６、好ましくは炭素数１〜３のアルキル基、または炭素数３〜９のアルキルシリル基のいずれかである。Ｒ１及びＲ２は、後述する製造方法によって、その官能基の種類、及び、官能基の導入率を変化させることができる。 In the polyimide precursor of the present invention, R 1 and R 2 in the chemical formula (1) are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 3 to 9 carbon atoms. Any of silyl groups. For R 1 and R 2 , the type of the functional group and the rate of introduction of the functional group can be changed by the production method described below.
Ｒ１及びＲ２が水素である場合、ポリイミドの製造が容易である傾向がある。 When R 1 and R 2 are hydrogen, production of polyimide tends to be easy.
また、Ｒ１及びＲ２が炭素数１〜６、好ましくは炭素数１〜３のアルキル基である場合、ポリイミド前駆体の保存安定性に優れる傾向がある。この場合、Ｒ１及びＲ２はメチル基もしくはエチル基であることがより好ましい。 When R 1 and R 2 are an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms, the storage stability of the polyimide precursor tends to be excellent. In this case, R 1 and R 2 are more preferably a methyl group or an ethyl group.
更に、Ｒ１及びＲ２が炭素数３〜９のアルキルシリル基である場合、ポリイミド前駆体の溶解性が優れる傾向がある。この場合、Ｒ１及びＲ２はトリメチルシリル基もしくはｔ−ブチルジメチルシリル基であることがより好ましい。 Further, when R 1 and R 2 are an alkylsilyl group having 3 to 9 carbon atoms, the solubility of the polyimide precursor tends to be excellent. In this case, R 1 and R 2 are more preferably a trimethylsilyl group or a t-butyldimethylsilyl group.
官能基の導入率は、特に限定されないが、アルキル基もしくはアルキルシリル基を導入する場合、Ｒ１及びＲ２はそれぞれ、２５％以上、好ましくは５０％以上、より好ましくは７５％以上をアルキル基もしくはアルキルシリル基にすることができる。 The rate of introduction of the functional group is not particularly limited. When an alkyl group or an alkylsilyl group is introduced, R 1 and R 2 each represent 25% or more, preferably 50% or more, more preferably 75% or more of the alkyl group. Alternatively, it can be an alkylsilyl group.
本発明のポリイミド前駆体は、Ｒ１及びＲ２が取る化学構造によって、１）ポリアミド酸（Ｒ１及びＲ２が水素）、２）ポリアミド酸エステル（Ｒ１及びＲ２の少なくとも一部がアルキル基）、３）４）ポリアミド酸シリルエステル（Ｒ１及びＲ２の少なくとも一部がアルキルシリル基）に分類することができる。そして、本発明のポリイミド前駆体は、この分類ごとに、以下の製造方法により容易に製造することができる。ただし、本発明のポリイミド前駆体の製造方法は、以下の製造方法に限定されるものではない。 Polyimide precursors of the present invention, the chemical structure wherein R 1 and R 2 are taken, 1) a polyamic acid (R 1 and R 2 are hydrogen), 2) at least partially alkyl polyamic acid ester (R 1 and R 2 Groups), 3) 4) Polyamic acid silyl esters (at least some of R 1 and R 2 are alkylsilyl groups). And the polyimide precursor of this invention can be easily manufactured by the following manufacturing methods for every classification. However, the method for producing the polyimide precursor of the present invention is not limited to the following production method.
１）ポリアミド酸
本発明のポリイミド前駆体は、溶媒中でテトラカルボン酸成分としてのテトラカルボン酸二無水物とジアミン成分とを略等モル、好ましくはテトラカルボン酸成分に対するジアミン成分のモル比［ジアミン成分のモル数／テトラカルボン酸成分のモル数］が好ましくは０．９０〜１．１０、より好ましくは０．９５〜１．０５の割合で、例えば１２０℃以下の比較的低温度でイミド化を抑制しながら反応することによって、ポリイミド前駆体溶液組成物として好適に得ることができる。
1) Polyamic acid In the polyimide precursor of the present invention, a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component are substantially equimolar in a solvent, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [diamine Component / mol number of tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, for example, at a relatively low temperature of 120 ° C. or lower. By reacting while suppressing the above, a polyimide precursor solution composition can be suitably obtained.
限定するものではないが、より具体的には、有機溶剤にジアミンを溶解し、この溶液に攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、０〜１２０℃、好ましくは５〜８０℃の範囲で１〜７２時間攪拌することで、ポリイミド前駆体が得られる。８０℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。上記製造方法でのジアミンとテトラカルボン酸二無水物の添加順序は、ポリイミド前駆体の分子量が上がりやすいため、好ましい。また、上記製造方法のジアミンとテトラカルボン酸二無水物の添加順序を逆にすることも可能であり、析出物が低減することから、好ましい。 Although not limited, more specifically, a diamine is dissolved in an organic solvent, and tetracarboxylic dianhydride is gradually added to the solution while stirring, and the solution is added at 0 to 120 ° C, preferably 5 to 80 ° C. The polyimide precursor is obtained by stirring for 1 to 72 hours in the range of ° C. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidation proceeds due to heat, so that there is a possibility that a polyimide precursor cannot be produced stably. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor tends to increase. In addition, the order of addition of the diamine and the tetracarboxylic dianhydride in the above-mentioned production method can be reversed, which is preferable from the viewpoint of reducing precipitates.
また、テトラカルボン酸成分とジアミン成分のモル比がジアミン成分過剰である場合、必要に応じて、ジアミン成分の過剰モル数に略相当する量のカルボン酸誘導体を添加し、テトラカルボン酸成分とジアミン成分のモル比を略当量に近づけることができる。ここでのカルボン酸誘導体としては、実質的にポリイミド前駆体溶液の粘度を増加させない、つまり実質的に分子鎖延長に関与しないテトラカルボン酸、もしくは末端停止剤として機能するトリカルボン酸とその無水物、ジカルボン酸とその無水物などが好適である。 If the molar ratio between the tetracarboxylic acid component and the diamine component is excessive, the carboxylic acid derivative is added, if necessary, in an amount substantially corresponding to the number of excess moles of the diamine component. The molar ratio of the components can be approximated to an equivalent. As the carboxylic acid derivative here, does not substantially increase the viscosity of the polyimide precursor solution, that is, a tetracarboxylic acid that does not substantially participate in elongation of the molecular chain, or a tricarboxylic acid and an anhydride thereof that functions as a terminal stopper, Dicarboxylic acids and their anhydrides are preferred.
２）ポリアミド酸エステル
テトラカルボン酸二無水物を任意のアルコールと反応させ、ジエステルジカルボン酸を得た後、塩素化試薬（チオニルクロライド、オキサリルクロライドなど）と反応させ、ジエステルジカルボン酸クロライドを得る。このジエステルジカルボン酸クロライドとジアミンを−２０〜１２０℃、好ましくは−５〜８０℃の範囲で１〜７２時間攪拌することで、ポリイミド前駆体が得られる。８０℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。また、ジエステルジカルボン酸とジアミンを、リン系縮合剤や、カルボジイミド縮合剤などを用いて脱水縮合することでも、簡便にポリイミド前駆体が得られる。
2) Polyamic acid ester Tetracarboxylic dianhydride is reacted with an arbitrary alcohol to obtain diester dicarboxylic acid, and then reacted with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain diester dicarboxylic acid chloride. The diester dicarboxylic acid chloride and the diamine are stirred at -20 to 120 ° C, preferably -5 to 80 ° C, for 1 to 72 hours to obtain a polyimide precursor. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidation proceeds due to heat, so that there is a possibility that a polyimide precursor cannot be produced stably. Alternatively, a polyimide precursor can be easily obtained by dehydrating and condensing diester dicarboxylic acid and diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.
この方法で得られるポリイミド前駆体は、安定なため、水やアルコールなどの溶剤を加えて再沈殿などの精製を行うこともできる。 Since the polyimide precursor obtained by this method is stable, it can be purified by reprecipitation by adding a solvent such as water or alcohol.
３）ポリアミド酸シリルエステル（間接法）
あらかじめ、ジアミンとシリル化剤を反応させ、シリル化されたジアミンを得る。必要に応じて、蒸留等により、シリル化されたジアミンの精製を行う。そして、脱水された溶剤中にシリル化されたジアミンを溶解させておき、攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、０〜１２０℃、好ましくは５〜８０℃の範囲で１〜７２時間攪拌することで、ポリイミド前駆体が得られる。８０℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
3) Polyamic acid silyl ester (indirect method)
The diamine is reacted with the silylating agent in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Then, the silylated diamine is dissolved in the dehydrated solvent, and tetracarboxylic dianhydride is gradually added with stirring, and 1 to 120 ° C., preferably 5 to 80 ° C. By stirring for ~ 72 hours, a polyimide precursor is obtained. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidation proceeds due to heat, so that there is a possibility that a polyimide precursor cannot be produced stably.
ここで用いるシリル化剤として、塩素を含有しないシリル化剤を用いることは、シリル化されたジアミンを精製する必要がないため、好適である。塩素原子を含まないシリル化剤としては、Ｎ，Ｏ−ビス（トリメチルシリル）トリフルオロアセトアミド、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミド、ヘキサメチルジシラザンが挙げられる。フッ素原子を含まず低コストであることから、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミド、ヘキサメチルジシラザンが特に好ましい。 It is preferable to use a chlorine-free silylating agent as the silylating agent used here because it is not necessary to purify the silylated diamine. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable because they contain no fluorine atom and are low in cost.
また、ジアミンのシリル化反応には、反応を促進するために、ピリジン、ピペリジン、トリエチルアミンなどのアミン系触媒を用いることができる。この触媒はポリイミド前駆体の重合触媒として、そのまま使用することができる。 Further, in the silylation reaction of the diamine, an amine catalyst such as pyridine, piperidine or triethylamine can be used to promote the reaction. This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
４）ポリアミド酸シリルエステル（直接法）
１）の方法で得られたポリアミド酸溶液とシリル化剤を混合し、０〜１２０℃、好ましくは５〜８０℃の範囲で１〜７２時間攪拌することで、ポリイミド前駆体が得られる。８０℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
4) Polyamic acid silyl ester (direct method)
The polyamic acid solution obtained by the method 1) and the silylating agent are mixed, and the mixture is stirred at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72 hours to obtain a polyimide precursor. When the reaction is carried out at 80 ° C. or higher, the molecular weight fluctuates depending on the temperature history at the time of polymerization, and imidation proceeds due to heat, so that there is a possibility that a polyimide precursor cannot be produced stably.
ここで用いるシリル化剤として、塩素を含有しないシリル化剤を用いることは、シリル化されたポリアミド酸、もしくは、得られたポリイミドを精製する必要がないため、好適である。塩素原子を含まないシリル化剤としては、Ｎ，Ｏ−ビス（トリメチルシリル）トリフルオロアセトアミド、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミド、ヘキサメチルジシラザンが挙げられる。フッ素原子を含まず低コストであることから、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミド、ヘキサメチルジシラザンが特に好ましい。 It is preferable to use a chlorine-free silylating agent as the silylating agent used here, since it is not necessary to purify the silylated polyamic acid or the obtained polyimide. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable because they contain no fluorine atom and are low in cost.
前記製造方法は、いずれも有機溶媒中で好適に行なうことができるので、その結果として、ポリイミド前駆体を含む溶液または溶液組成物を容易に得ることができる。 Since any of the above production methods can be suitably performed in an organic solvent, as a result, a solution or a solution composition containing the polyimide precursor can be easily obtained.
ポリイミド前駆体を調製する際に使用する溶媒は、例えば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、ジメチルスルホキシド等の非プロトン性溶媒が好ましく、特にＮ，Ｎ−ジメチルアセトアミドが好ましいが、原料モノマー成分と生成するポリイミド前駆体が溶解すれば、どんな種類の溶媒であっても問題はなく使用できるので、特にその構造には限定されない。溶媒として、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−メチルピロリドン等のアミド溶媒、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトン、α−メチル−γ−ブチロラクトン等の環状エステル溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート溶媒、トリエチレングリコール等のグリコール系溶媒、ｍ−クレゾール、ｐ−クレゾール、３−クロロフェノール、４−クロロフェノール等のフェノール系溶媒、アセトフェノン、１，３−ジメチル−２−イミダゾリジノン、スルホラン、ジメチルスルホキシドなどが好ましく採用される。さらに、その他の一般的な有機溶剤、即ちフェノール、ｏ−クレゾール、酢酸ブチル、酢酸エチル、酢酸イソブチル、プロピレングリコールメチルアセテート、エチルセロソルブ、ブチルセロソルブ、２−メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、ジブチルエーテル、ジエチレングリコールジメチルエーテル、メチルイソブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロへキサノン、メチルエチルケトン、アセトン、ブタノール、エタノール、キシレン、トルエン、クロルベンゼン、ターペン、ミネラルスピリット、石油ナフサ系溶媒なども使用できる。なお、溶媒は、複数種を組み合わせて使用することもできる。 Solvents used for preparing the polyimide precursor include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide Non-protic solvents are preferred, and N, N-dimethylacetamide is particularly preferred. However, any kind of solvent can be used without any problem as long as the raw material monomer components and the polyimide precursor to be formed can be dissolved. The structure is not limited. As the solvent, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α- Cyclic ester solvents such as methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenols such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol A system solvent, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed. Further, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran , Dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpen, mineral spirit, petroleum Naphtha solvents and the like can also be used. In addition, a solvent can also be used in combination of multiple types.
本発明において、ポリイミド前駆体の対数粘度は、特に限定されないが、３０℃での濃度０．５ｇ／ｄＬのＮ，Ｎ−ジメチルアセトアミド溶液における対数粘度が０．２ｄＬ／ｇ以上、より好ましくは０．３ｄＬ／ｇ以上、特に好ましくは０．４ｄＬ／ｇ以上であることが好ましい。対数粘度が０．２ｄＬ／ｇ以上では、ポリイミド前駆体の分子量が高く、得られるポリイミドの機械強度や耐熱性に優れる。 In the present invention, the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in a 0.5 g / dL N, N-dimethylacetamide solution at 30 ° C. is 0.2 dL / g or more, more preferably 0 dL / g. It is preferably at least 0.3 dL / g, particularly preferably at least 0.4 dL / g. When the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the resulting polyimide has excellent mechanical strength and heat resistance.
本発明のポリイミド前駆体組成物は、ポリイミド前駆体と、イミダゾール系化合物とを含むものであり、前記製造方法により得られるポリイミド前駆体溶液または溶液組成物にイミダゾール系化合物を加えて調製することができる。また、必要に応じて、溶媒を除去または加えてもよく、イミダゾール系化合物以外の所望の成分を添加してもよい。また、溶媒にテトラカルボン酸成分（テトラカルボン酸二無水物等）とジアミン成分とイミダゾール系化合物を加え、イミダゾール系化合物の存在下で、テトラカルボン酸成分とジアミン成分とを反応させて、本発明のポリイミド前駆体組成物（ポリイミド前駆体と、イミダゾール系化合物とを含む溶液組成物）を得ることもできる。 The polyimide precursor composition of the present invention contains a polyimide precursor and an imidazole-based compound, and may be prepared by adding an imidazole-based compound to a polyimide precursor solution or a solution composition obtained by the production method. it can. If necessary, the solvent may be removed or added, or a desired component other than the imidazole compound may be added. Further, a tetracarboxylic acid component (tetracarboxylic dianhydride, etc.), a diamine component and an imidazole compound are added to a solvent, and the tetracarboxylic acid component and the diamine component are reacted in the presence of the imidazole compound to form the present invention. (A solution composition containing a polyimide precursor and an imidazole-based compound) can also be obtained.
本発明において用いるイミダゾール系化合物は、イミダゾール骨格を有する化合物であれば特に限定されない。イミダゾール系化合物を添加することによって、より耐熱性が高いポリイミドが得られる。 The imidazole-based compound used in the present invention is not particularly limited as long as it has an imidazole skeleton. By adding the imidazole-based compound, a polyimide having higher heat resistance can be obtained.
ある実施態様においては、イミダゾール系化合物として、１気圧における沸点が３６０℃未満、好ましくは３５０℃以下、より好ましくは３４０℃以下の化合物を用いることが好ましい。１気圧における沸点が３６０℃未満、好ましくは３５０℃以下、より好ましくは３４０℃以下のイミダゾール系化合物を添加することによって、より透明性が高いポリイミドが得られることがある。 In one embodiment, it is preferable to use a compound having a boiling point at 1 atm of less than 360 ° C., preferably 350 ° C. or less, more preferably 340 ° C. or less, as the imidazole compound. By adding an imidazole compound having a boiling point of less than 360 ° C, preferably 350 ° C or less, more preferably 340 ° C or less at 1 atm, a polyimide having higher transparency may be obtained.
また、ある実施態様においては、イミダゾール系化合物として、１気圧における沸点が３４０℃未満、好ましくは３３０℃以下、より好ましくは３００℃以下、特に好ましくは２７０℃以下の化合物を用いることが好ましい。１気圧における沸点が３４０℃未満のイミダゾール系化合物を添加することによって、より線熱膨張係数が小さいポリイミドが得られることがある。 In one embodiment, a compound having a boiling point of less than 340 ° C., preferably 330 ° C. or lower, more preferably 300 ° C. or lower, particularly preferably 270 ° C. or lower at 1 atm is preferably used as the imidazole compound. By adding an imidazole-based compound having a boiling point of less than 340 ° C. at 1 atm, a polyimide having a smaller linear thermal expansion coefficient may be obtained.
本発明において用いるイミダゾール系化合物としては、特に限定されないが、１，２−ジメチルイミダゾール、１−メチルイミダゾール、２−メチルイミダゾール、２−フェニルイミダゾール、イミダゾール、ベンゾイミダゾールなどが挙げられる。１，２−ジメチルイミダゾール（１気圧における沸点：２０５℃）、１−メチルイミダゾール（１気圧における沸点：１９８℃）、２−メチルイミダゾール（１気圧における沸点：２６８℃）、イミダゾール（１気圧における沸点：２５６℃）、２−フェニルイミダゾール（１気圧における沸点：３４０℃）などが好ましく、１，２−ジメチルイミダゾール、１−メチルイミダゾールが特に好ましい。イミダゾール系化合物は、１種を単独で使用してもよく、複数種を組み合わせて使用することもできる。 The imidazole compound used in the present invention is not particularly limited, but includes 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole, benzimidazole and the like. 1,2-dimethylimidazole (boiling point at 1 atm: 205 ° C), 1-methylimidazole (boiling point at 1 atm: 198 ° C), 2-methylimidazole (boiling point at 1 atm: 268 ° C), imidazole (boiling point at 1 atm) : 256 ° C), 2-phenylimidazole (boiling point at 1 atm: 340 ° C) and the like, and 1,2-dimethylimidazole and 1-methylimidazole are particularly preferable. One imidazole compound may be used alone, or two or more imidazole compounds may be used in combination.
本発明において、ポリイミド前駆体組成物のイミダゾール系化合物の含有量は、ポリイミド前駆体の繰り返し単位１モルに対して４モル未満である。イミダゾール系化合物の含有量がポリイミド前駆体の繰り返し単位１モルに対して４モル以上になると、ポリイミド前駆体組成物の保存安定性が悪くなる。イミダゾール系化合物の含有量は、ポリイミド前駆体の繰り返し単位１モルに対して０．０５モル以上であることが好ましく、また、ポリイミド前駆体の繰り返し単位１モルに対して２モル以下であることが好ましい。なお、ここで、ポリイミド前駆体の繰り返し単位１モルは、テトラカルボン酸成分１モルに対応する。 In the present invention, the content of the imidazole-based compound in the polyimide precursor composition is less than 4 mol per 1 mol of the repeating unit of the polyimide precursor. When the content of the imidazole-based compound is 4 mol or more per 1 mol of the repeating unit of the polyimide precursor, the storage stability of the polyimide precursor composition deteriorates. The content of the imidazole compound is preferably 0.05 mol or more per 1 mol of the repeating unit of the polyimide precursor, and 2 mol or less per 1 mol of the repeating unit of the polyimide precursor. preferable. Here, 1 mol of the repeating unit of the polyimide precursor corresponds to 1 mol of the tetracarboxylic acid component.
本発明のポリイミド前駆体組成物は、通常、溶媒を含む。本発明のポリイミド前駆体組成物に用いる溶媒としては、ポリイミド前駆体が溶解すれば問題はなく、特にその構造は限定されない。溶媒として、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−ピロリドン等のアミド溶媒、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトン、α−メチル−γ−ブチロラクトン等の環状エステル溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート溶媒、トリエチレングリコール等のグリコール系溶媒、ｍ−クレゾール、ｐ−クレゾール、３−クロロフェノール、４−クロロフェノール等のフェノール系溶媒、アセトフェノン、１，３−ジメチル−２−イミダゾリジノン、スルホラン、ジメチルスルホキシドなどが好ましく採用される。さらに、その他の一般的な有機溶剤、即ちフェノール、ｏ−クレゾール、酢酸ブチル、酢酸エチル、酢酸イソブチル、プロピレングリコールメチルアセテート、エチルセロソルブ、ブチルセロソルブ、２−メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、ジブチルエーテル、ジエチレングリコールジメチルエーテル、メチルイソブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロへキサノン、メチルエチルケトン、アセトン、ブタノール、エタノール、キシレン、トルエン、クロルベンゼン、ターペン、ミネラルスピリット、石油ナフサ系溶媒なども使用できる。また、これらを複数種組み合わせて使用することもできる。なお、ポリイミド前駆体組成物の溶媒は、ポリイミド前駆体を調製する際に使用した溶媒をそのまま使用することができる。 The polyimide precursor composition of the present invention usually contains a solvent. The solvent used in the polyimide precursor composition of the present invention is not problematic as long as the polyimide precursor is dissolved, and its structure is not particularly limited. Examples of the solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. , Cyclic ester solvents such as α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol Phenol solvents such as acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed. Further, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran , Dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpen, mineral spirit, petroleum Naphtha solvents and the like can also be used. Moreover, these can also be used in combination of multiple types. In addition, the solvent used at the time of preparing a polyimide precursor can be used for the solvent of a polyimide precursor composition as it is.
本発明において、テトラカルボン酸成分とジアミン成分との合計量は、溶媒とテトラカルボン酸成分とジアミン成分との合計量に対して、５質量％以上、好ましくは１０質量％以上、より好ましくは１５質量％以上の割合であることが好適である。なお、通常は、テトラカルボン酸成分とジアミン成分との合計量は、溶媒とテトラカルボン酸成分とジアミン成分との合計量に対して、６０質量％以下、好ましくは５０質量％以下であることが好適である。この濃度は、ポリイミド前駆体に起因する固形分濃度にほぼ近似される濃度であるが、この濃度が低すぎると、例えばポリイミドフィルムを製造する際に得られるポリイミドフィルムの膜厚の制御が難しくなることがある。 In the present invention, the total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the solvent, the tetracarboxylic acid component and the diamine component. It is preferable that the ratio is not less than mass%. The total amount of the tetracarboxylic acid component and the diamine component is usually 60% by mass or less, preferably 50% by mass or less, based on the total amount of the solvent, the tetracarboxylic acid component and the diamine component. It is suitable. This concentration is a concentration that is approximately similar to the solid content concentration due to the polyimide precursor, but if this concentration is too low, for example, it becomes difficult to control the thickness of the polyimide film obtained when manufacturing a polyimide film. Sometimes.
本発明において、ポリイミド前駆体組成物の粘度（回転粘度）は、特に限定されないが、Ｅ型回転粘度計を用い、温度２５℃、せん断速度２０ｓｅｃ−１で測定した回転粘度が、０．０１〜１０００Ｐａ・ｓｅｃが好ましく、０．１〜１００Ｐａ・ｓｅｃがより好ましい。また、必要に応じて、チキソ性を付与することもできる。上記範囲の粘度では、コーティングや製膜を行う際、ハンドリングしやすく、また、はじきが抑制され、レベリング性に優れるため、良好な被膜が得られる。 In the present invention, the viscosity (rotational viscosity) of the polyimide precursor composition is not particularly limited, but the rotational viscosity measured using an E-type rotational viscometer at a temperature of 25 ° C. and a shear rate of 20 sec −1 is 0.01 to 0.01. 1000 Pa · sec is preferable, and 0.1 to 100 Pa · sec is more preferable. In addition, thixotropy can be imparted as necessary. When the viscosity is in the above range, it is easy to handle when performing coating and film formation, and repelling is suppressed, and excellent leveling property is obtained, so that a good film can be obtained.
本発明のポリイミド前駆体組成物は、必要に応じて、化学イミド化剤（無水酢酸などの酸無水物や、ピリジン、イソキノリンなどのアミン化合物）、酸化防止剤、フィラー（シリカ等の無機粒子など）、染料、顔料、シランカップリング剤などのカップリング剤、プライマー、難燃材、消泡剤、レベリング剤、レオロジーコントロール剤（流動補助剤）、剥離剤などを含有することができる。 The polyimide precursor composition of the present invention may contain, if necessary, a chemical imidizing agent (an acid anhydride such as acetic anhydride, or an amine compound such as pyridine or isoquinoline), an antioxidant, and a filler (inorganic particles such as silica). ), Dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agents (flow aids), release agents, and the like.
本発明のポリイミドは、前記のような本発明のポリイミド前駆体組成物をイミド化する（すなわち、ポリイミド前駆体を脱水閉環反応する）ことで得ることができる。イミド化の方法は特に限定されず、公知の熱イミド化、または化学イミド化の方法を好適に適用することができる。得られるポリイミドの形態は、フィルム、ポリイミドフィルムと他の基材との積層体、コーティング膜、粉末、ビーズ、成型体、発泡体などを好適に挙げることができる。 The polyimide of the present invention can be obtained by imidizing the above-described polyimide precursor composition of the present invention (that is, subjecting the polyimide precursor to a dehydration ring-closing reaction). The imidation method is not particularly limited, and a known thermal imidation method or a chemical imidization method can be suitably applied. Examples of the form of the obtained polyimide include a film, a laminate of a polyimide film and another substrate, a coating film, a powder, beads, a molded body, and a foamed body.
本発明においては、ポリイミド前駆体組成物を、最高加熱温度３５０℃以上で加熱処理して、ポリイミド前駆体をイミド化することが好ましい。イミド化のための加熱処理の最高加熱温度を３５０℃以上の温度とすることにより、得られるポリイミドの機械的特性が向上する。加熱処理の最高加熱温度の上限は特に限定されないが、通常、５００℃以下が好ましい。 In the present invention, the polyimide precursor composition is preferably subjected to a heat treatment at a maximum heating temperature of 350 ° C. or more to imidize the polyimide precursor. By setting the maximum heating temperature of the heat treatment for imidization to 350 ° C. or higher, the mechanical properties of the obtained polyimide are improved. Although the upper limit of the maximum heating temperature of the heat treatment is not particularly limited, it is usually preferably 500 ° C. or lower.
例えば、本発明のポリイミド前駆体組成物を基材上に流延・塗布し、この基材上のポリイミド前駆体組成物を最高加熱温度３５０℃以上の温度で加熱処理して、ポリイミド前駆体をイミド化することにより、ポリイミドを好適に製造することができる。なお、加熱プロファイルは特に限定されず、適宜選択することができるが、生産性の点からは、加熱処理する時間は短い方が好ましい。 For example, the polyimide precursor composition of the present invention is cast and applied on a substrate, and the polyimide precursor composition on the substrate is subjected to a heat treatment at a maximum heating temperature of 350 ° C. or higher to obtain a polyimide precursor. By imidization, polyimide can be suitably produced. Note that the heating profile is not particularly limited and can be appropriately selected, but from the viewpoint of productivity, the shorter the heating time, the better.
また、本発明のポリイミド前駆体組成物を基材上に流延・塗布し、好ましくは１８０℃以下の温度範囲で乾燥して、基材上にポリイミド前駆体組成物の膜を形成し、得られたポリイミド前駆体組成物の膜を基材上から剥離して、その膜の端部を固定した状態で、最高加熱温度３５０℃以上の温度で加熱処理して、ポリイミド前駆体をイミド化することによっても、ポリイミドを好適に製造することができる。 Further, the polyimide precursor composition of the present invention is cast and applied on a substrate, preferably dried at a temperature range of 180 ° C. or less to form a film of the polyimide precursor composition on the substrate. The polyimide precursor composition film is peeled off from the substrate, and the polyimide precursor is imidized by heating at a maximum heating temperature of 350 ° C. or more with the end of the film fixed. This also makes it possible to suitably produce polyimide.
より具体的な本発明のポリイミド（ポリイミドフィルム／基材積層体、もしくはポリイミドフィルム）の製造方法の一例については、後述する。 A more specific example of the method for producing the polyimide (polyimide film / substrate laminate or polyimide film) of the present invention will be described later.
本発明のポリイミド前駆体組成物から得られるポリイミド（本発明のポリイミド）は、特に限定されないが、フィルムにしたときの１５０℃から２５０℃までの線熱膨張係数が、好ましくは４０ｐｐｍ／Ｋ以下、より好ましくは３０ｐｐｍ／Ｋ以下、さらに好ましくは２５ｐｐｍ／Ｋ以下、特に好ましくは２０ｐｐｍ／Ｋ以下であることができ、極めて低い線熱膨張係数を有する。線熱膨張係数が大きいと、金属などの導体との線熱膨張係数の差が大きく、回路基板を形成する際に反りが増大するなどの不具合が生じることがある。 The polyimide obtained from the polyimide precursor composition of the present invention (polyimide of the present invention) is not particularly limited, but has a coefficient of linear thermal expansion from 150 ° C to 250 ° C when formed into a film, preferably 40 ppm / K or less, It is more preferably at most 30 ppm / K, even more preferably at most 25 ppm / K, particularly preferably at most 20 ppm / K, and has a very low coefficient of linear thermal expansion. When the coefficient of linear thermal expansion is large, the difference in the coefficient of linear thermal expansion from a conductor such as a metal is large, and problems such as an increase in warpage when a circuit board is formed may occur.
本発明のポリイミド前駆体組成物から得られるポリイミド（本発明のポリイミド）は、特に限定されないが、厚さ１０μｍのフィルムでの全光透過率（波長３８０ｎｍ〜７８０ｎｍの平均光透過率）が、好ましくは８９％以上、より好ましくは９０％以上であり、優れた光透過性を有する。ディスプレイ用途等で使用する場合、全光透過率が低いと光源を強くする必要があり、エネルギーがかかるといった問題等を生じることがある。 The polyimide obtained from the polyimide precursor composition of the present invention (polyimide of the present invention) is not particularly limited, but the total light transmittance (average light transmittance at a wavelength of 380 nm to 780 nm) in a film having a thickness of 10 μm is preferable. Is 89% or more, more preferably 90% or more, and has excellent light transmittance. When used in display applications and the like, if the total light transmittance is low, it is necessary to increase the intensity of the light source, which may cause problems such as the application of energy.
特にディスプレイ用途などのポリイミドフィルムを光が透過する用途に使用する場合、ポリイミドフィルムは透明性が高い方が望ましい。本発明のポリイミド前駆体組成物から得られるポリイミド（本発明のポリイミド）は、特に限定されないが、厚さ１０μｍのフィルムでの波長４００ｎｍにおける光透過率が、好ましくは７９％以上、より好ましくは８０％以上、さらに好ましくは８０％超であることができる。 In particular, when a polyimide film such as a display is used for transmitting light, it is desirable that the polyimide film has high transparency. The polyimide obtained from the polyimide precursor composition of the present invention (polyimide of the present invention) is not particularly limited, but has a light transmittance at a wavelength of 400 nm of a film having a thickness of 10 μm, preferably 79% or more, more preferably 80% or more. % Or more, more preferably more than 80%.
なお、本発明のポリイミド前駆体組成物から得られるポリイミド（本発明のポリイミド）からなるフィルムは、用途にもよるが、フィルムの厚みとしては、好ましくは０．１μｍ〜２５０μｍ、より好ましくは１μｍ〜１５０μｍ、さらに好ましくは１μｍ〜５０μｍ、特に好ましくは１μｍ〜３０μｍである。ポリイミドフィルムを光が透過する用途に使用する場合、ポリイミドフィルムが厚すぎると光透過率が低くなる恐れがある。 In addition, although the film which consists of the polyimide (polyimide of this invention) obtained from the polyimide precursor composition of this invention depends on an application, as film thickness, Preferably it is 0.1 micrometer-250 micrometers, More preferably, it is 1 micrometer- It is 150 μm, more preferably 1 μm to 50 μm, particularly preferably 1 μm to 30 μm. When the polyimide film is used for transmitting light, if the polyimide film is too thick, the light transmittance may decrease.
本発明のポリイミド前駆体組成物から得られるポリイミド（本発明のポリイミド）は、特に限定されないが、ポリイミドフィルムの耐熱性の指標である１％重量減少温度が、好ましくは４９５℃以上、より好ましくは４９８℃以上、さらに好ましくは５００℃以上であることができる。ポリイミド上にトランジスタを形成する等で、ポリイミド上にガスバリア膜等を形成する場合、耐熱性が低いと、ポリイミドとバリア膜との間で、ポリイミドの分解に伴うアウトガスにより膨れが生じることがある。 The polyimide obtained from the polyimide precursor composition of the present invention (polyimide of the present invention) is not particularly limited, but the 1% weight loss temperature, which is an index of the heat resistance of the polyimide film, is preferably 495 ° C or higher, more preferably It can be at least 498 ° C, more preferably at least 500 ° C. In the case of forming a gas barrier film or the like on a polyimide by forming a transistor on the polyimide or the like, if heat resistance is low, swelling may occur between the polyimide and the barrier film due to outgas accompanying decomposition of the polyimide.
本発明のポリイミド前駆体組成物から得られるポリイミド、すなわち本発明のポリイミドは、高い透明性、折り曲げ耐性、高耐熱性などの優れた特性を有し、さらに極めて低い線熱膨張係数を有することから、ディスプレイ用透明基板、タッチパネル用透明基板、或いは太陽電池用基板の用途において、好適に用いることができる。 The polyimide obtained from the polyimide precursor composition of the present invention, that is, the polyimide of the present invention has excellent properties such as high transparency, bending resistance, and high heat resistance, and further has an extremely low linear thermal expansion coefficient. It can be suitably used for a transparent substrate for a display, a transparent substrate for a touch panel, or a substrate for a solar cell.
以下では、本発明のポリイミド前駆体組成物を用いた、ポリイミドフィルム／基材積層体、もしくはポリイミドフィルムの製造方法の一例について述べる。ただし、以下の方法に限定されるものではない。 Hereinafter, an example of a method for producing a polyimide film / substrate laminate or a polyimide film using the polyimide precursor composition of the present invention will be described. However, it is not limited to the following method.
例えばセラミック（ガラス、シリコン、アルミナなど）、金属（銅、アルミニウム、ステンレスなど）、耐熱プラスチックフィルム（ポリイミドフィルムなど）等の基材に、本発明のポリイミド前駆体組成物（ワニス）を流延し、真空中、窒素等の不活性ガス中、或いは空気中で、熱風もしくは赤外線を用いて、２０〜１８０℃、好ましくは２０〜１５０℃の温度範囲で乾燥する。次いで、得られたポリイミド前駆体フィルムを基材上で、もしくはポリイミド前駆体フィルムを基材上から剥離し、そのフィルムの端部を固定した状態で、真空中、窒素等の不活性ガス中、或いは空気中で、熱風もしくは赤外線を用い、例えば２００〜５００℃、好ましくは最高加熱温度３５０℃以上の温度で加熱イミド化することでポリイミドフィルム／基材積層体、もしくはポリイミドフィルムを製造することができる。なお、得られるポリイミドフィルムが酸化劣化するのを防ぐため、加熱イミド化は、真空中、或いは不活性ガス中で行うことが望ましい。ここでのポリイミドフィルム（ポリイミドフィルム／基材積層体の場合は、ポリイミドフィルム層）の厚さは、以後の工程の搬送性のため、好ましくは１〜２５０μｍ、より好ましくは１〜１５０μｍである。 For example, the polyimide precursor composition (varnish) of the present invention is cast on a substrate such as ceramic (glass, silicon, alumina, etc.), metal (copper, aluminum, stainless steel, etc.), heat-resistant plastic film (polyimide film, etc.). Drying is performed in a vacuum, in an inert gas such as nitrogen, or in the air using hot air or infrared rays at a temperature of 20 to 180 ° C, preferably 20 to 150 ° C. Then, the polyimide precursor film obtained on the substrate, or peeled off the polyimide precursor film from the substrate, with the end of the film fixed, in a vacuum, in an inert gas such as nitrogen, Alternatively, it is possible to produce a polyimide film / substrate laminate or a polyimide film by heating and imidizing in air at a temperature of, for example, 200 to 500 ° C., preferably 350 ° C. or higher, using hot air or infrared rays. it can. Note that, in order to prevent the obtained polyimide film from being oxidized and degraded, it is preferable to perform the heat imidization in a vacuum or in an inert gas. The thickness of the polyimide film (polyimide film layer in the case of a polyimide film / substrate laminate) is preferably from 1 to 250 μm, more preferably from 1 to 150 μm, for the convenience of the subsequent steps.
また、ポリイミド前駆体のイミド化反応は、前記のような加熱処理による加熱イミド化に代えて、ポリイミド前駆体をピリジンやトリエチルアミン等の３級アミン存在下、無水酢酸等の脱水環化試薬を含有する溶液に浸漬するなどの化学的処理によって行うことも可能である。また、これらの脱水環化試薬をあらかじめ、ポリイミド前駆体組成物（ワニス）中に投入・攪拌し、それを基材上に流延・乾燥することで、部分的にイミド化したポリイミド前駆体を作製することもでき、これを更に前記のような加熱処理することで、ポリイミドフィルム／基材積層体、もしくはポリイミドフィルムを得ることができる。 In addition, the imidation reaction of the polyimide precursor includes a dehydration cyclizing reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine, in place of the heat imidization by the heat treatment as described above. It is also possible to carry out by chemical treatment such as immersion in a solution to be treated. In addition, these dehydration cyclization reagents are previously charged and stirred in a polyimide precursor composition (varnish), and then cast and dried on a base material to obtain a partially imidized polyimide precursor. A polyimide film / substrate laminate or a polyimide film can be obtained by subjecting this to a heat treatment as described above.
この様にして得られたポリイミドフィルム／基材積層体、もしくはポリイミドフィルムは、その片面もしくは両面に導電性層を形成することによって、フレキシブルな導電性基板を得ることができる。 A flexible conductive substrate can be obtained by forming a conductive layer on one side or both sides of the polyimide film / substrate laminate or the polyimide film thus obtained.
フレキシブルな導電性基板は、例えば次の方法によって得ることができる。すなわち、第一の方法としては、ポリイミドフィルム／基材積層体を基材からポリイミドフィルムを剥離せずに、そのポリイミドフィルム表面に、スパッタ、蒸着、印刷などによって、導電性物質（金属もしくは金属酸化物、導電性有機物、導電性炭素など）の導電層を形成させ、導電性層／ポリイミドフィルム／基材の導電性積層体を製造する。その後必要に応じて、基材より導電性層／ポリイミドフィルム積層体を剥離することによって、導電性層／ポリイミドフィルム積層体からなる透明でフレキシブルな導電性基板を得ることができる。 A flexible conductive substrate can be obtained, for example, by the following method. That is, as the first method, the polyimide film / substrate laminate is not peeled off from the substrate, but the conductive film (metal or metal oxide) is formed on the surface of the polyimide film by sputtering, vapor deposition, printing, or the like. A conductive layer of a conductive layer / polyimide film / substrate. Thereafter, if necessary, the conductive layer / polyimide film laminate is peeled off from the substrate, whereby a transparent and flexible conductive substrate composed of the conductive layer / polyimide film laminate can be obtained.
第二の方法としては、ポリイミドフィルム／基材積層体の基材からポリイミドフィルムを剥離して、ポリイミドフィルムを得、そのポリイミドフィルム表面に、導電性物質（金属もしくは金属酸化物、導電性有機物、導電性炭素など）の導電層を、第一の方法と同様にして形成させ、導電性層／ポリイミドフィルム積層体、導電性層／ポリイミドフィルム積層体／導電性層からなる透明でフレキシブルな導電性基板を得ることができる。 As a second method, the polyimide film is peeled from the substrate of the polyimide film / substrate laminate to obtain a polyimide film, and a conductive substance (metal or metal oxide, conductive organic substance, A conductive layer of conductive carbon / polyimide film, or a conductive layer / polyimide film laminate / conductive layer / polyimide film laminate / conductive layer. A substrate can be obtained.
なお、第一、第二の方法において、必要に応じて、ポリイミドフィルムの表面に導電層を形成する前に、スパッタ、蒸着やゲル−ゾル法などによって、水蒸気、酸素などのガスバリヤ層、光調整層などの無機層を形成しても構わない。 In the first and second methods, if necessary, before forming a conductive layer on the surface of the polyimide film, a gas barrier layer of water vapor, oxygen, etc., by sputtering, vapor deposition, gel-sol method, etc. An inorganic layer such as a layer may be formed.
また、導電層は、フォトリソグラフィ法や各種印刷法、インクジェット法などの方法によって、回路が好適に形成される。 The conductive layer is preferably formed with a circuit by a photolithography method, various printing methods, an inkjet method, or the like.
このようにして得られる本発明の基板は、本発明のポリイミドによって構成されたポリイミドフィルムの表面に、必要に応じてガスバリヤ層や無機層を介し、導電層の回路を有するものである。この基板は、フレキシブルであり、高い透明性、折り曲げ性、耐熱性が優れ、さらに極めて低い線熱膨張係数や優れた耐溶剤性を併せ有するので微細な回路の形成が容易である。したがって、この基板は、ディスプレイ用、タッチパネル用、または太陽電池用の基板として好適に用いることができる。 The substrate of the present invention thus obtained has a circuit of a conductive layer on the surface of the polyimide film composed of the polyimide of the present invention via a gas barrier layer or an inorganic layer as necessary. This substrate is flexible, has excellent transparency, bendability, and heat resistance, and has an extremely low coefficient of linear thermal expansion and excellent solvent resistance, so that it is easy to form a fine circuit. Therefore, this substrate can be suitably used as a substrate for a display, a touch panel, or a solar cell.
すなわち、この基板に、蒸着、各種印刷法、或いはインクジェット法などによって、さらにトランジスタ（無機トランジスタ、有機トランジスタ）が形成されてフレキシブル薄膜トランジスタが製造され、そして、表示デバイス用の液晶素子、ＥＬ素子、光電素子として好適に用いられる。 That is, a transistor (inorganic transistor, organic transistor) is further formed on the substrate by vapor deposition, various printing methods, an inkjet method, or the like to manufacture a flexible thin film transistor, and a liquid crystal element for a display device, an EL element, It is suitably used as an element.
以下、実施例及び比較例によって本発明を更に説明する。尚、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. The present invention is not limited to the following embodiments.
以下の各例において評価は次の方法で行った。 In each of the following examples, the evaluation was performed by the following method.
＜ポリイミド前駆体のワニスの評価＞
［保存安定性］
２３℃でワニスを保存し、３日後に流動性のある均一な状態であれば○、
３日後に白濁、もしくはゲル化していれば×とする。
<Evaluation of varnish of polyimide precursor>
[Storage stability]
Store the varnish at 23 ° C.
If it became cloudy or gelled after 3 days, it was evaluated as x.
＜ポリイミドフィルムの評価＞
［４００ｎｍ光透過率、全光透過率］
紫外可視分光光度計／Ｖ−６５０ＤＳ（日本分光製）を用いて、膜厚約１０μｍのポリイミド膜の４００ｎｍにおける光透過率と、全光透過率（３８０ｎｍ〜７８０ｎｍにおける平均透過率）を測定した。測定した４００ｎｍにおける光透過率と、全光透過率を反射率を１０％としてランベルト・ベール式を用いて、１０μｍ厚の４００ｎｍにおける光透過率と、全光透過率を算出した。算出式を下記に示す。
<Evaluation of polyimide film>
[400 nm light transmittance, total light transmittance]
Using an ultraviolet-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation), the light transmittance at 400 nm and the total light transmittance (average transmittance at 380 nm to 780 nm) of the polyimide film having a thickness of about 10 μm were measured. The measured light transmittance at 400 nm and the light transmittance at 400 nm with a thickness of 10 μm and the total light transmittance were calculated using the Lambert-Beer equation with the reflectance of the total light transmittance being 10%. The calculation formula is shown below.
Ｌｏｇ１０（（Ｔ１＋１０）／１００）＝１０／Ｌ×（Ｌｏｇ１０（（Ｔ１’＋１０）／１００））
Ｌｏｇ１０（（Ｔ２＋１０）／１００）＝１０／Ｌ×（Ｌｏｇ１０（（Ｔ２’＋１０）／１００））
Ｔ１：反射率を１０％としたときの１０μｍ厚のポリイミドフィルムの４００ｎｍにおける光透過率（％）
Ｔ１’：測定した４００ｎｍにおける光透過率（％）
Ｔ２：反射率を１０％としたときの１０μｍ厚のポリイミドフィルムの全光透過率（％）
Ｔ２’：測定した全光透過率（％）
Ｌ：測定したポリイミドフィルムの膜厚（μｍ）
Log 10 ((T 1 +10) / 100) = 10 / L × (Log 10 ((T 1 ′ +10) / 100))
Log 10 ((T 2 +10) / 100) = 10 / L × (Log 10 ((T 2 ′ +10) / 100))
T 1 : light transmittance (%) at 400 nm of a 10 μm-thick polyimide film when the reflectance is 10%
T 1 ′: measured light transmittance at 400 nm (%)
T 2 : total light transmittance (%) of a polyimide film having a thickness of 10 μm when the reflectance is 10%
T 2 ′: measured total light transmittance (%)
L: Measured thickness of polyimide film (μm)
［弾性率、破断伸度］
膜厚約１０μｍのポリイミドフィルムをＩＥＣ４５０規格のダンベル形状に打ち抜いて試験片とし、ＯＲＩＥＮＴＥＣ社製ＴＥＮＳＩＬＯＮを用いて、チャック間長３０ｍｍ、引張速度２ｍｍ／分で、初期の弾性率、破断伸度を測定した。
[Elastic modulus, elongation at break]
A polyimide film having a film thickness of about 10 μm is punched into a dumbbell shape conforming to IEC450 standard to prepare a test piece, and the initial elastic modulus and elongation at break are measured using TENSIRON manufactured by ORIENTEC at a chuck length of 30 mm and a tensile speed of 2 mm / min. did.
［線熱膨張係数（ＣＴＥ）］
膜厚約１０μｍのポリイミドフィルムを幅４ｍｍの短冊状に切り取って試験片とし、ＴＭＡ／ＳＳ６１００ （エスアイアイ・ナノテクノロジー株式会社製）を用い、チャック間長１５ｍｍ、荷重２ｇ、昇温速度２０℃／分で５００℃まで昇温した。得られたＴＭＡ曲線から、１５０℃から２５０℃までの線熱膨張係数を求めた。
[Linear coefficient of thermal expansion (CTE)]
A polyimide film having a film thickness of about 10 μm is cut into a strip having a width of 4 mm to form a test piece, and using TMA / SS6100 (manufactured by SII Nanotechnology Co., Ltd.), the distance between the chucks is 15 mm, the load is 2 g, and the heating rate is 20 ° C. / The temperature was raised to 500 ° C. in minutes. From the obtained TMA curve, a linear thermal expansion coefficient from 150 ° C. to 250 ° C. was determined.
［１％重量減少温度］
膜厚約１０μｍのポリイミドフィルムを試験片とし、ＴＡインスツルメント社製 熱量計測定装置（Ｑ５０００ＩＲ）を用い、窒素気流中、昇温速度１０℃／分で２５℃から６００℃まで昇温した。得られた重量曲線から、１％重量減少温度を求めた。
[1% weight loss temperature]
Using a polyimide film having a thickness of about 10 μm as a test piece, the temperature was raised from 25 ° C. to 600 ° C. at a rate of 10 ° C./min in a nitrogen stream using a calorimeter (Q5000IR) manufactured by TA Instruments. The 1% weight loss temperature was determined from the obtained weight curve.
以下の各例で使用した原材料の略称、純度等は、次のとおりである。 The abbreviations, purity, etc. of the raw materials used in each of the following examples are as follows.
［ジアミン成分］
ＴＦＭＢ： ２，２’−ビス（トリフルオロメチル）ベンジジン〔純度：９９．８３％（ＧＣ分析）〕
［テトラカルボン酸成分］
ｓ−ＢＰＤＡ：３，３’，４，４’−ビフェニルテトラカルボン酸二無水物〔純度９９．９％（Ｈ−ＮＭＲ分析）〕
６ＦＤＡ：４，４’−（２，２−ヘキサフルオロイソプロピレン）ジフタル酸二無水物〔純度 ９９．７７％（Ｈ−ＮＭＲ分析）〕
[Diamine component]
TFMB: 2,2'-bis (trifluoromethyl) benzidine [purity: 99.83% (GC analysis)]
[Tetracarboxylic acid component]
s-BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride [purity 99.9% (H-NMR analysis)]
6FDA: 4,4 '-(2,2-hexafluoroisopropylene) diphthalic dianhydride [purity 99.77% (H-NMR analysis)]
［溶媒］
ＮＭＰ： Ｎ−メチル−２−ピロリドン
[solvent]
NMP: N-methyl-2-pyrrolidone
表１−１に実施例、比較例で使用したテトラカルボン酸成分、表１−２に実施例、比較例で使用したジアミン成分、表１−３に実施例、比較例で使用したイミダゾール・イミダゾリン化合物の構造式を記す。 Table 1-1 shows the tetracarboxylic acid components used in the examples and comparative examples, Table 1-2 shows the examples and diamine components used in the comparative examples, and Table 1-3 shows the examples and imidazole / imidazoline used in the comparative examples. The structural formula of the compound is described.
〔合成例１〕
窒素ガスで置換した反応容器中にＴＦＭＢ ３２．０２ｇ（０．１００ミリモル）を入れ、Ｎ−メチル−２−ピロリドンを、仕込みモノマー総質量（ジアミン成分とカルボン酸成分の総和）が ２０質量％となる量の２８７．７９ｇを加え、室温で１時間攪拌した。この溶液にｓ−ＢＰＤＡ ８．８３ｇ（０．０３０モル）と６ＦＤＡ ３１．１０（０．０７０モル）を徐々に加えた。室温で１２時間撹拌し、均一で粘稠なポリイミド前駆体溶液を得た。
[Synthesis Example 1]
In a reaction vessel purged with nitrogen gas, 32.02 g (0.100 mmol) of TFMB was added, and N-methyl-2-pyrrolidone was added to the reaction vessel so that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was 20 mass%. An additional amount of 287.79 g was added, and the mixture was stirred at room temperature for 1 hour. To this solution, 8.83 g (0.030 mol) of s-BPDA and 31.10 (0.070 mol) of 6FDA were gradually added. The mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution.
〔実施例１〕
１，２−ジメチルイミダゾール ０．１９ｇ（２．０ミリモル）とＮ−メチル−２−ピロリドン ０．１９ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、１，２−ジメチルイミダゾールのモル数は０．２等量である。
[Example 1]
0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 1,2-dimethylimidazole is 0.2 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例２〕
１，２−ジメチルイミダゾール ０．３８ｇ（４．０ミリモル）とＮ−メチル−２−ピロリドン ０．３８ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、１，２−ジメチルイミダゾールのモル数は０．４等量である。
[Example 2]
0.38 g (4.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 1,2-dimethylimidazole is 0.4 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例３〕
１，２−ジメチルイミダゾール ０．９６ｇ（１０．０ミリモル）とＮ−メチル−２−ピロリドン ０．５０ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、１，２−ジメチルイミダゾールのモル数は１．０等量である。
[Example 3]
0.96 g (10.0 mmol) of 1,2-dimethylimidazole and 0.50 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 1,2-dimethylimidazole is 1.0 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例４〕
１，２−ジメチルイミダゾール １．９２ｇ（２０．０ミリモル）とＮ−メチル−２−ピロリドン ０．５０ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、１，２−ジメチルイミダゾールのモル数は２．０等量である。
[Example 4]
1.92 g (20.0 mmol) of 1,2-dimethylimidazole and 0.50 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 1,2-dimethylimidazole is 2.0 equivalents per 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例５〕
１−メチルイミダゾール ０．１６ｇ（２．０ミリモル）とＮ−メチル−２−ピロリドン ０．１６ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、１−メチルイミダゾールのモル数は０．２等量である。
[Example 5]
0.16 g (2.0 mmol) of 1-methylimidazole and 0.16 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 1-methylimidazole is 0.2 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例６〕
２−メチルイミダゾール ０．１６ｇ（２．０ミリモル）とＮ−メチル−２−ピロリドン ０．１６ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、２−メチルイミダゾールのモル数は０．２等量である。
[Example 6]
0.16 g (2.0 mmol) of 2-methylimidazole and 0.16 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 2-methylimidazole is 0.2 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例７〕
イミダゾール ０．１４ｇ（２．０ミリモル）とＮ−メチル−２−ピロリドン ０．１４ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、イミダゾールのモル数は０．２等量である。
[Example 7]
0.14 g (2.0 mmol) of imidazole and 0.14 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of imidazole is 0.2 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例８〕
２−フェニルイミダゾール ０．２９ｇ（２．０ミリモル）とＮ−メチル−２−ピロリドン ０．２９ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、２−フェニルイミダゾールのモル数は０．２等量である。
Example 8
0.29 g (2.0 mmol) of 2-phenylimidazole and 0.29 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 2-phenylimidazole is 0.2 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔実施例９〕
ベンゾイミダゾール ０．２４ｇ（２．０ミリモル）とＮ−メチル−２−ピロリドン ０．２４ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、ベンゾイミダゾールのモル数は０．２等量である。
[Example 9]
0.24 g (2.0 mmol) of benzimidazole and 0.24 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of benzimidazole is 0.2 equivalent to 1 mole of the repeating unit of the polyimide precursor.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。 A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 350 ° C. on a glass substrate as it is under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to thermally imidize, and colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔比較例１〕
ＰＴＦＥ製メンブレンフィルターでろ過した合成例１で得られたワニスをガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）、そのままガラス基板上で室温から３５０℃まで加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、乾燥して、膜厚が約１０μｍのポリイミドフィルムを得た。
[Comparative Example 1]
The varnish obtained in Synthesis Example 1 obtained by filtration with a PTFE membrane filter was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) from room temperature to 350 ° C. and thermally imidized on the glass substrate. To obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
このポリイミドフィルムの特性を測定した結果を表２に示す。 Table 2 shows the measurement results of the characteristics of the polyimide film.
〔比較例２〕
２−エチル−２−イミダゾリン ０．１０ｇ（１．０ミリモル）とＮ−メチル−２−ピロリドン ０．９０ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加えるとワニスがゲル化した。そのまま室温で３時間攪拌しても、均一なポリイミド前駆体溶液を得られなかった。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、２−エチル−２−イミダゾリンのモル数は０．１等量である。
[Comparative Example 2]
0.10 g (1.0 mmol) of 2-ethyl-2-imidazoline and 0.90 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. When 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, the varnish gelled. Even if the mixture was stirred at room temperature for 3 hours, a uniform polyimide precursor solution could not be obtained. When calculated from the charged amount, the number of moles of 2-ethyl-2-imidazoline is 0.1 equivalent to 1 mole of the repeating unit of the polyimide precursor.
〔比較例３〕
２−エチル−２−イミダゾリン ０．１８ｇ（２．０ミリモル）とＮ−メチル−２−ピロリドン １．８０ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加えるとワニスがゲル化した。そのまま室温で３時間攪拌しても、均一なポリイミド前駆体溶液を得られなかった。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、２−エチル−２−イミダゾリンのモル数は０．２等量である。
[Comparative Example 3]
0.18 g (2.0 mmol) of 2-ethyl-2-imidazoline and 1.80 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. When 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, the varnish gelled. Even if the mixture was stirred at room temperature for 3 hours, a uniform polyimide precursor solution could not be obtained. When calculated from the charged amount, the number of moles of 2-ethyl-2-imidazoline is 0.2 equivalent to 1 mole of the repeating unit of the polyimide precursor.
〔比較例４〕
１，２−ジメチルイミダゾール ３．８５ｇ（４０．０ミリモル）とＮ−メチル−２−ピロリドン ０．５０ｇを反応容器に加え均一な溶液を得た。その溶液に合成例１で得られたワニス ３５．９７ｇ（ワニス中のポリイミド前駆体の繰返しユニットの分子量に対して、１０ミリモル）加え、室温で３時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。仕込み量から計算すると、ポリイミド前駆体の繰り返し単位１モルに対する、１，２−ジメチルイミダゾールのモル数は４．０等量である。得られたポリイミド前駆体溶液を２３℃で保管すると、３日目までにポリイミド前駆体溶液がゲル化した。
[Comparative Example 4]
3.85 g (40.0 mmol) of 1,2-dimethylimidazole and 0.50 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.97 g of the varnish obtained in Synthesis Example 1 (10 mmol based on the molecular weight of the repeating unit of the polyimide precursor in the varnish) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor. A solution was obtained. When calculated from the charged amount, the number of moles of 1,2-dimethylimidazole is 4.0 equivalents per 1 mole of the repeating unit of the polyimide precursor. When the obtained polyimide precursor solution was stored at 23 ° C., the polyimide precursor solution gelled by the third day.
表２に示した結果から、イミダゾール系化合物を含むポリイミド前駆体組成物から得られたポリイミドは、より耐熱性が高いことが分かる（実施例１〜９と比較例１）。また、イミダゾール系化合物の含有量が、ポリイミド前駆体の繰り返し単位１モルに対して４モル未満であると、保存安定性にも優れることが分かる（実施例１〜４と比較例４）。 From the results shown in Table 2, it can be seen that the polyimide obtained from the polyimide precursor composition containing the imidazole-based compound has higher heat resistance (Examples 1 to 9 and Comparative Example 1). In addition, when the content of the imidazole-based compound is less than 4 mol per 1 mol of the repeating unit of the polyimide precursor, it is understood that the storage stability is excellent (Examples 1 to 4 and Comparative Example 4).
前記のとおり、本発明のポリイミド前駆体組成物から得られたポリイミドは、優れた光透過性、耐熱性、機械的特性を有すると共に、低線熱膨張係数を有しており、本発明のポリイミドフィルムは、ディスプレイ用途などの無色透明で微細な回路形成可能な透明基板として好適に用いることができる。 As described above, the polyimide obtained from the polyimide precursor composition of the present invention has excellent light transmittance, heat resistance, and mechanical properties, and has a low linear thermal expansion coefficient. The film can be suitably used as a transparent substrate capable of forming a fine and colorless circuit for use in displays and the like.
本発明によって、透明性に優れ、低い線熱膨張係数を有し、しかも耐熱性がより高く、機械的特性にも優れたポリイミドが得られるポリイミド前駆体組成物（ポリイミド前駆体を含む溶液組成物）、及びポリイミドの製造方法を提供することができる。このポリイミド前駆体組成物から得られるポリイミドは、透明性が高く、且つ低線熱膨張係数であって微細な回路の形成が容易であるので、特にディスプレイ用、タッチパネル用、太陽電池用などの基板を形成するために好適に用いることができる。 Advantageous Effects of Invention According to the present invention, a polyimide precursor composition (solution composition containing a polyimide precursor) from which a polyimide having excellent transparency, a low coefficient of linear thermal expansion, higher heat resistance, and excellent mechanical properties can be obtained ), And a method for producing polyimide. Polyimide obtained from this polyimide precursor composition has high transparency, and has a low linear thermal expansion coefficient and easy formation of a fine circuit. Therefore, especially for a display, a touch panel, a substrate for a solar cell and the like. Can be suitably used to form
Claims (11)
１気圧における沸点が３４０℃以上のイミダゾール系化合物を含み、
イミダゾール系化合物の含有量が、ポリイミド前駆体の繰り返し単位１モルに対して４モル未満であり、
ベンズトリアゾールおよびその誘導体、チオール化合物とその誘導体、および感光剤のいずれも含まない、
ディスプレイの基板製造用、タッチパネルの基板製造用、または太陽電池の基板製造用ポリイミド前駆体組成物。
Including an imidazole-based compound having a boiling point of 340 ° C. or more at 1 atm,
The content of the imidazole-based compound is less than 4 mol per 1 mol of the repeating unit of the polyimide precursor,
Benztriazole and its derivatives, thiol compounds and their derivatives, and does not include any of the photosensitizer,
A polyimide precursor composition for manufacturing a display substrate , a touch panel substrate , or a solar cell substrate.
基材上のポリイミド前駆体組成物を、最高加熱温度３５０℃以上で加熱処理して、ポリイミド前駆体をイミド化する工程と
を有することを特徴とする請求項６に記載のディスプレイの基板用、タッチパネルの基板用、または太陽電池の基板用のポリイミドの製造方法。 A step of applying the polyimide precursor composition according to any one of claims 1 to 5 on a substrate,
Heating the polyimide precursor composition on the substrate at a maximum heating temperature of 350 ° C. or more, and imidizing the polyimide precursor, for a display substrate according to claim 6 , A method for producing a polyimide for a touch panel substrate or a solar cell substrate .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018009116A JP6638744B2 (en) | 2018-01-23 | 2018-01-23 | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018009116A JP6638744B2 (en) | 2018-01-23 | 2018-01-23 | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013245489A Division JP6461470B2 (en) | 2013-11-27 | 2013-11-27 | Polyimide precursor composition, polyimide production method, polyimide, polyimide film, and substrate |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2018080344A JP2018080344A (en) | 2018-05-24 |
| JP2018080344A5 JP2018080344A5 (en) | 2018-12-06 |
| JP6638744B2 true JP6638744B2 (en) | 2020-01-29 |
Family
ID=62197103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018009116A Active JP6638744B2 (en) | 2018-01-23 | 2018-01-23 | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6638744B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW202346422A (en) * | 2022-03-28 | 2023-12-01 | 日商Ｕｂｅ股份有限公司 | Polyimide precursor composition, polyimide film, and polyimide film/substrate layered-product |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2683291B2 (en) * | 1990-02-26 | 1997-11-26 | 日本電信電話株式会社 | Liquid crystal display device |
| JPH05295115A (en) * | 1992-04-24 | 1993-11-09 | Sumitomo Bakelite Co Ltd | Polyimide resin having low thermal expansion and production thereof |
| JPH10265572A (en) * | 1996-02-13 | 1998-10-06 | Nitto Denko Corp | Circuit board, suspension board with circuit and their production |
| JP2004115813A (en) * | 1996-03-14 | 2004-04-15 | Toshiba Corp | Polyimide precursor composition, method of forming polyimide film, electronic part, and liquid crystal element |
| JPH09302225A (en) * | 1996-03-14 | 1997-11-25 | Toshiba Corp | Polyimide precursor composition, method of forming polyimide film, electronic part and liquid crystal element |
| JP4130003B2 (en) * | 1998-03-13 | 2008-08-06 | 宇部興産株式会社 | Method for producing aromatic polyimide film |
| JP4823953B2 (en) * | 2007-03-27 | 2011-11-24 | 新日鐵化学株式会社 | Method for producing flexible laminate |
| JP2009091413A (en) * | 2007-10-05 | 2009-04-30 | Ist Corp | Polyimide precursor composition, photosensitive polyimide precursor composition and electronic part using it, and film forming method |
| WO2009148060A1 (en) * | 2008-06-02 | 2009-12-10 | 宇部興産株式会社 | Method for producing aromatic polyimide film wherein linear expansion coefficient in transverse direction is lower than linear expansion coefficient in machine direction |
| JP5362385B2 (en) * | 2009-02-23 | 2013-12-11 | 旭化成イーマテリアルズ株式会社 | Polyamic acid varnish composition and polyimide metal laminate using the same |
| JP5391905B2 (en) * | 2009-07-31 | 2014-01-15 | 宇部興産株式会社 | Polyimide film and method for producing polyimide film |
| KR101292886B1 (en) * | 2009-09-29 | 2013-08-02 | 코오롱인더스트리 주식회사 | Transparent Polyimide film with improved Solvent Resistance |
| JP2011209578A (en) * | 2010-03-30 | 2011-10-20 | Nitto Denko Corp | Tubular body and method for manufacturing the same |
| JP2012146905A (en) * | 2011-01-14 | 2012-08-02 | Kaneka Corp | Utilization of soluble polyimide resin film |
| JP5845911B2 (en) * | 2012-01-13 | 2016-01-20 | 宇部興産株式会社 | Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition |
-
2018
- 2018-01-23 JP JP2018009116A patent/JP6638744B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018080344A (en) | 2018-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6721070B2 (en) | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate | |
| JP6531812B2 (en) | Polyimide precursor and polyimide | |
| JP6669074B2 (en) | Polyimide film, polyimide precursor, and polyimide | |
| JP6516048B2 (en) | Polyimide precursor and polyimide | |
| JP6627510B2 (en) | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate | |
| JP6607193B2 (en) | Polyimide precursor, polyimide, and polyimide film | |
| JP6283954B2 (en) | Polyimide precursor, polyimide, varnish, polyimide film, and substrate | |
| WO2015053312A1 (en) | Polyimide precursor, polyimide, polyimide film, varnish, and substrate | |
| JP7047852B2 (en) | Polyimide precursors, polyimides, polyimide films, varnishes, and substrates | |
| JP6461470B2 (en) | Polyimide precursor composition, polyimide production method, polyimide, polyimide film, and substrate | |
| WO2014038714A1 (en) | Polyimide precursor, polyimide, varnish, polyimide film, and substrate | |
| JP2016035073A (en) | Polyimide precursor and polyimide | |
| JP7069478B2 (en) | Polyimide, polyimide solution composition, polyimide film, and substrate | |
| JP6638744B2 (en) | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate | |
| WO2015080156A1 (en) | Polyimide precursor composition, polyimide manufacturing process, polyimide, polyimide film, and base material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180220 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180220 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20180409 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181025 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20181120 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181204 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190201 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190521 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190722 |
|
| 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: 20191126 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191209 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6638744 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |