JP4967635B2 - Polymer film manufacturing method and polymer film manufacturing apparatus - Google Patents
Polymer film manufacturing method and polymer film manufacturing apparatus Download PDFInfo
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- JP4967635B2 JP4967635B2 JP2006335464A JP2006335464A JP4967635B2 JP 4967635 B2 JP4967635 B2 JP 4967635B2 JP 2006335464 A JP2006335464 A JP 2006335464A JP 2006335464 A JP2006335464 A JP 2006335464A JP 4967635 B2 JP4967635 B2 JP 4967635B2
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- 229920006254 polymer film Polymers 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 238000003825 pressing Methods 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 17
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 32
- 229920001721 polyimide Polymers 0.000 description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 29
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 29
- 150000004984 aromatic diamines Chemical class 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 13
- 239000004642 Polyimide Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 7
- 239000012024 dehydrating agents Substances 0.000 description 7
- 238000001802 infusion Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006798 ring closing metathesis reaction Methods 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical group NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical group OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical group OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 3
- 239000004962 Polyamide-imide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BDWOQDZGSYLSCZ-UHFFFAOYSA-N [1,3]oxazolo[4,5-f][1,3]benzoxazole Chemical compound C1=C2OC=NC2=CC2=C1OC=N2 BDWOQDZGSYLSCZ-UHFFFAOYSA-N 0.000 description 3
- PMJNNCUVWHTTMV-UHFFFAOYSA-N [1,3]oxazolo[5,4-f][1,3]benzoxazole Chemical compound C1=C2OC=NC2=CC2=C1N=CO2 PMJNNCUVWHTTMV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 2
- HKNMCRMFQXTDFE-UHFFFAOYSA-N 2-(2-aminophenyl)-1,3-benzoxazol-4-amine Chemical class NC1=CC=CC=C1C1=NC2=C(N)C=CC=C2O1 HKNMCRMFQXTDFE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- STIUJDCDGZSXGO-UHFFFAOYSA-N (3-amino-4-phenoxyphenyl)-(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C(OC=3C=CC=CC=3)=CC=2)=C1 STIUJDCDGZSXGO-UHFFFAOYSA-N 0.000 description 1
- GSHMRKDZYYLPNZ-UHFFFAOYSA-N (3-amino-4-phenoxyphenyl)-(4-amino-3-phenoxyphenyl)methanone Chemical compound NC1=CC=C(C(=O)C=2C=C(N)C(OC=3C=CC=CC=3)=CC=2)C=C1OC1=CC=CC=C1 GSHMRKDZYYLPNZ-UHFFFAOYSA-N 0.000 description 1
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- NILYJZJYFZUPPO-UHFFFAOYSA-N (4-amino-3-phenoxyphenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C(OC=2C=CC=CC=2)=C1 NILYJZJYFZUPPO-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
- YLHUPYSUKYAIBW-UHFFFAOYSA-N 1-acetylpyrrolidin-2-one Chemical compound CC(=O)N1CCCC1=O YLHUPYSUKYAIBW-UHFFFAOYSA-N 0.000 description 1
- UMGYJGHIMRFYSP-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC(N)=CC=C2O1 UMGYJGHIMRFYSP-UHFFFAOYSA-N 0.000 description 1
- DIXHWJYQQGNWTI-UHFFFAOYSA-N 2-[4-(5-amino-1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazol-5-amine Chemical compound NC1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=C(C=C4N=3)N)=NC2=C1 DIXHWJYQQGNWTI-UHFFFAOYSA-N 0.000 description 1
- SFZGLHDSSSDCHH-UHFFFAOYSA-N 2-[4-(6-amino-1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazol-6-amine Chemical compound C1=C(N)C=C2OC(C3=CC=C(C=C3)C3=NC4=CC=C(C=C4O3)N)=NC2=C1 SFZGLHDSSSDCHH-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-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
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-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
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- ZDBWYUOUYNQZBM-UHFFFAOYSA-N 3-(aminomethyl)aniline Chemical compound NCC1=CC=CC(N)=C1 ZDBWYUOUYNQZBM-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-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
- GBUNNYTXPDCASY-UHFFFAOYSA-N 3-[3-[2-[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(C=CC=2)C(C=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 GBUNNYTXPDCASY-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- UQHPRIRSWZEGEK-UHFFFAOYSA-N 3-[4-[1-[4-(3-aminophenoxy)phenyl]ethyl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 UQHPRIRSWZEGEK-UHFFFAOYSA-N 0.000 description 1
- PHVQYQDTIMAIKY-UHFFFAOYSA-N 3-[4-[1-[4-(3-aminophenoxy)phenyl]propyl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(CC)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 PHVQYQDTIMAIKY-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- BDROEGDWWLIVJF-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]ethyl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(CCC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 BDROEGDWWLIVJF-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- TZFAMRKTHYOODK-UHFFFAOYSA-N 3-[4-[3-[4-(3-aminophenoxy)phenyl]propyl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(CCCC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 TZFAMRKTHYOODK-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
- JERFEOKUSPGKGV-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(SC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 JERFEOKUSPGKGV-UHFFFAOYSA-N 0.000 description 1
- VTHWGYHNEDIPTO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfinylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 VTHWGYHNEDIPTO-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- YSMXOEWEUZTWAK-UHFFFAOYSA-N 3-[4-[[4-(3-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(CC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 YSMXOEWEUZTWAK-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- MITHMOYLTXMLRB-UHFFFAOYSA-N 4-(4-aminophenyl)sulfinylaniline Chemical compound C1=CC(N)=CC=C1S(=O)C1=CC=C(N)C=C1 MITHMOYLTXMLRB-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Moulding By Coating Moulds (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Registering, Tensioning, Guiding Webs, And Rollers Therefor (AREA)
Description
本発明は高分子フィルムの製造方法及び製造装置に関するものであり、特に高分子フィルムを製造する際の最終熱処理時に、高分子前駆体フィルムや不完全乾燥フィルムを高温熱処理して高分子フィルムとなす際におけるテンター式（フィルム搬送）処理部に特徴を有する高分子フィルムの製造方法及び高分子フィルム製造装置に関する。 The present invention relates to a method and apparatus for producing a polymer film, and in particular, at the time of final heat treatment in producing a polymer film, a polymer precursor film or an incompletely dried film is subjected to high-temperature heat treatment to form a polymer film. The present invention relates to a polymer film manufacturing method and a polymer film manufacturing apparatus characterized by a tenter type (film transport) processing unit.
ポリイミドフィルムを製造するとき、溶媒の一部が残っているポリイミド前駆体フィルム（グリーンフィルムともいう）を高温でイミド化する。この場合該ポリイミド前駆体フィルムを搬送しながら加熱して乾燥及び熱処理を行うが、これらの溶媒を少なからず保有しているフィルムは一般的に乾燥されるに従って収縮する。このようなフィルムの搬送・乾燥・熱処理において、フィルムの幅方向の両側端部を多数のピンやクリップで保持することによりフィルムの幅方向を張設した状態で搬送しフィルムを製造する装置として、所謂テンターと呼ばれるフィルム（シート）のテンター式搬送装置が知られている（特許文献１参照）。
また、ポリイミドフィルムの製造にテンター式搬送装置を使用することも多数知られている（特許文献２参照）。
In addition, it is also known to use a tenter type conveying device for manufacturing a polyimide film (see Patent Document 2).
フィルム搬送装置は、布を染色した後の乾燥工程で布に皺が発生しないように乾燥する用途への使用も古くから良く知られている。布の乾燥の他にも溶剤製膜法での未乾燥なプラスチックフィルムのフィルムを乾燥工程で搬送しながら乾燥する場合にも使用される。 フィルム搬送装置を使用することにより乾燥・熱処理時の熱でフィルムがその幅方向に収縮するのを抑制し、乾燥・熱処理後のフィルムに収縮による皺が発生しないようにすることができる。
フィルムの収縮はフィルムの幅方向に限らず全方向に生じるが、フィルムの搬送方向は搬送テンションが作用しており収縮に対しての抑制効果がある。このように、未乾燥のフィルムを乾燥・熱処理する際にフィルムのテンター式搬送装置を使用して搬送することにより、乾燥・熱処理されたフィルムに必要な強度及び平面性を確保することができる。
The film conveying apparatus has been well known for a long time to be used for drying so as not to cause wrinkles in the drying process after dyeing the cloth. In addition to drying the cloth, it is also used for drying an undried plastic film by a solvent casting method while transporting it in the drying step. By using the film conveying apparatus, it is possible to suppress shrinkage of the film in the width direction due to heat during drying and heat treatment, and to prevent wrinkles due to shrinkage from occurring in the film after drying and heat treatment.
The shrinkage of the film occurs not only in the width direction of the film but in all directions. However, the transporting tension acts in the transport direction of the film and has an effect of suppressing the shrinkage. Thus, the strength and flatness required for the dried and heat-treated film can be ensured by transporting the undried film using the film tenter type transport device when drying and heat-treating.
フィルムテンター式搬送装置のうち、フィルムの両側端部に沿って多数のピンを喰い込ませることによりフィルムを幅方向に張設した状態で保持するフィルムのテンター式搬送装置は、平行に配置された一対の移動チェンに列設支持されたピンシート上に多数のピンが配設されて構成される。このフィルムのテンター式搬送装置は、前記クリップ等のフィルム搬送装置に比べ構造が簡単であることあるいは乾燥室内での搬送コンベアの経路を反転させる構造にできる等のことから、装置コスト、装置のコンパクト化の点で優れている一方、フィルムにピンを喰い込ませる際にフィルムの微小片が発塵するために、なるべくピン本数を少なくする必要がある。また、フィルムの収縮力が大きくなると、フィルム面にピンを喰い込ませた孔がフィルムの幅方向に長孔状に破断するなどの課題を抱えている。 Among the film tenter type conveying devices, the tenter type conveying device for the film that holds the film stretched in the width direction by biting a large number of pins along both side edges of the film was arranged in parallel A large number of pins are arranged on a pin sheet supported in a row by a pair of moving chains. This film tenter type transport device is simpler in structure than the film transport device such as the clip, or can be structured to reverse the transport conveyor path in the drying chamber. On the other hand, since the fine pieces of the film generate dust when the pins are bitten into the film, it is necessary to reduce the number of pins as much as possible. Moreover, when the shrinkage force of the film becomes large, there are problems such as the holes that have pinned the film surface break into long holes in the width direction of the film.
これらの改良のために、フィルムのピンによる把持部において引き裂き強度大きいフィルムを別途補強用として重ねて使用する方式も提案されている（特許文献３参照）。
さらに、ウェブなどを搬送する際、ウェブの両側端部に置けるピンの配列を最内側のピン密度を大きくし、外側のピンの配列密度をより小さくしたテンター式搬送装置も提案されている（特許文献４参照）。これら改良提案においても、ピンの搬送方向における配列特にピンシート間のピン配列に配慮されたものはなく、フィルムの収縮によるピンを喰い込ませた孔におけるフィルムの幅方向に長孔状に破断が生じ易いフィルムの製造においては課題を有していた。
従来のフィルムのテンター式搬送装置は、ピンを喰い込ませた孔でのフィルムの幅方向に長孔状に破断する問題、皺の発生などの品質不良が発生し易く、生産ロスの原因となると共に生産効率の低下を招き、使用者にとって十分満足できるものではなかった。
In order to improve these, there has also been proposed a method in which a film having a high tear strength is additionally stacked for reinforcement at the gripping portion of the film pin (see Patent Document 3).
Furthermore, a tenter type conveying device has also been proposed in which the innermost pin density is increased and the outer pin arrangement density is further reduced in the arrangement of pins that can be placed on both ends of the web when the web is conveyed (patent). Reference 4). Even in these proposals for improvement, there is nothing to consider the arrangement in the conveying direction of the pins, particularly the arrangement of the pins between the pin sheets. There was a problem in the production of films that are likely to occur.
Conventional tenter type transport devices for films tend to cause production loss due to problems such as breakage in the shape of a long hole in the width direction of the film at the hole where the pin is entrapped, and generation of wrinkles. At the same time, the production efficiency was lowered, and it was not satisfactory for users.
本発明は、電子部品の基材として好適である平面性及び均質性に優れ、しかも高温処理しても反りやカールの少ない耐熱性に優れた高分子フィルムであるポリイミドフィルムを基材フィルムとして使用した接着シート、この接着シートに金属箔を積層した金属積層シート、及びこの金属積層シートを回路加工したプリント配線板を提供するため、高分子フィルム特にポリイミドフィルムの製造に適した、フィルムのピンで突き刺した部分がピンシートに接触し、ピンシートからの熱を直接的に受けるため、テンター内において、フィルムの中央部と端部の温度差が大きくなり、強度バランスが崩れるために破断しやすくなる。また、ピンシートにフィルムが直接接触するため、場合によってはフィルムがピンシートに融着し、熱処理後にフィルムをピンから外す際に把持部が裂けやすくなり、エッジかけや破断に繋がるなどの課題を解消するための高分子フィルムの製造方法と高分子フィルムの製造装置を提供することを目的とする。 The present invention uses, as a base film, a polyimide film that is a polymer film excellent in flatness and homogeneity that is suitable as a base material for electronic components, and has excellent heat resistance with little warping and curling even when processed at high temperatures. In order to provide an adhesive sheet, a metal laminate sheet obtained by laminating a metal foil on the adhesive sheet, and a printed wiring board obtained by circuit processing of the metal laminate sheet, a film pin suitable for manufacturing a polymer film, particularly a polyimide film, is provided. Since the pierced part comes into contact with the pin sheet and directly receives the heat from the pin sheet, the temperature difference between the center and the end of the film becomes large in the tenter, and the strength balance is lost, so it is easy to break. . In addition, since the film is in direct contact with the pin sheet, in some cases, the film is fused to the pin sheet, and when the film is removed from the pin after the heat treatment, the grip portion is easily torn, leading to problems such as edging and breaking. It is an object of the present invention to provide a polymer film manufacturing method and a polymer film manufacturing apparatus for solving the problem.
すなわち本発明は、以下の構成によるものである。
１．高分子又は高分子前駆体からなるフィルムをフィルム端部固定式テンターにて搬送しながら処理をする際に、フィルムの幅方向の両側端部におけるフィルム端部把持が、多数のピンシートと個々のピンシートに配された多数のピンで構成され、該ピンが押さえブラシロールでフィルムを押し込むことでフィルム両側端部を突き刺して、幅方向及び／又は搬送方向に張設した状態でフィルムを搬送するものであるテンター式処理部を使用する高分子フィルム製造方法であって、該ピンシートが幅方向において外側に設置されたピン台座よりも高い部位を有し、前記押さえブラシロールでフィルムを押さえ込みピンに突き刺す際に、ピン台座とフィルムとの間隔が０．５ｍｍ以上５．０ｍｍ以下で、かつフィルムの位置がピン先端より３ｍｍ以上８ｍｍ以下の範囲となるようにフィルムをピンに突き刺すことを特徴とする高分子フィルムの製造方法。
２．ピン台座よりも高い部位と接触する部分の押さえブラシロールの部材が、フィルムを押さえ込みピンに突き刺す部分のブラシロールの部材よりも剛性が高いものである前記１記載の高分子フィルムの製造方法。
３．押さえブラシロールの幅方向に対して外側に設置する部材が、金属素線のブラシ形
状部材である前記１又は２いずれかに記載の高分子フィルムの製造方法。
４．押さえブラシロールの幅方向に対して外側に設置する部材が、金属製の円筒状部材である前記１又は２いずれかに記載の高分子フィルムの製造方法。
５．高分子又は高分子前駆体からなるフィルムをフィルム端部固定式テンターにて搬送しながら処理をする際に、フィルムの幅方向の両側端部におけるフィルム端部把持が、多数のピンシートと個々のピンシートに配された多数のピンで構成され、該ピンが押さえブラシロールでフィルムを押し込むことでフィルム両側端部を突き刺して、幅方向及び又は搬送方向に張設した状態でフィルムを搬送するものであるテンター式処理部を有する高分子フィルム製造装置であって、該ピンシートが幅方向に対し外側に設置したピン台座よりも高い部位を有し、かつ前記押さえブラシロールでフィルムを押さえ込みピンに突き刺す際に、ピンの台座とフィルムとの間隔が０．５ｍｍ以上５．０ｍｍ以下で、かつピン先端とフィルムとの間隔が３ｍｍ以上８ｍｍ以下の範囲となるように、ピン台座よりも高い部位と接触する部分の押さえブラシロールの部材がフィルムを押さえ込みピンに突き刺す部分のブラシロールの部材よりも剛性が高いものを用いた押さえブラシロールが配置されていることを特徴とする高分子フィルムの製造装置。
That is, this invention is based on the following structures.
1. When a film made of a polymer or a polymer precursor is processed while being transported by a film end fixed tenter, the film end gripping at both ends in the width direction of the film is caused by a large number of pin sheets and individual films. Consists of a large number of pins arranged on the pin sheet, and the pins push the film with a pressing brush roll to pierce the both side ends of the film and transport the film in a state of being stretched in the width direction and / or the transport direction. A method for producing a polymer film using a tenter type processing section, wherein the pin sheet has a portion higher than a pin pedestal installed on the outside in the width direction, and the pin presses the film with the pressing brush roll. When piercing the pin, the distance between the pin base and the film is 0.5 mm or more and 5.0 mm or less, and the film position is 3 mm or more from the tip of the pin. The process for producing a polymer film characterized in that pierce the pin a film so that the mm or less.
2. 2. The method for producing a polymer film as described in 1 above, wherein the member of the holding brush roll in contact with the part higher than the pin base is higher in rigidity than the member of the brush roll in the part of pressing the film into the pin.
3. 3. The method for producing a polymer film according to either 1 or 2, wherein the member installed on the outer side in the width direction of the pressing brush roll is a brush-shaped member of a metal strand.
4). 3. The method for producing a polymer film according to either 1 or 2, wherein the member installed outside in the width direction of the pressing brush roll is a metal cylindrical member.
5). When a film made of a polymer or a polymer precursor is processed while being transported by a film end fixed tenter, the film end gripping at both ends in the width direction of the film is caused by a large number of pin sheets and individual films. Consists of a large number of pins arranged on a pin sheet, and the pins push the film with a pressing brush roll to pierce the film on both sides and transport the film in a stretched state in the width and / or transport direction It is a polymer film manufacturing apparatus having a tenter type processing unit, wherein the pin sheet has a portion higher than a pin base installed outside in the width direction, and the film is pressed into a pin by pressing the film with the pressing brush roll. When piercing, the distance between the pin base and the film is 0.5 mm or more and 5.0 mm or less, and the distance between the pin tip and the film is 3 mm or more 8 Pressing brush roll using a member having a higher rigidity than that of a part of the pressing roller roll that contacts the portion higher than the pin pedestal so as to be in the range of m or less, and pressing the film into the pin. An apparatus for producing a polymer film, wherein:
本発明の高分子フィルム製造装置は、ポリイミドフィルムなどの高分子フィルムにおけるテンター式処理部（搬送装置）において、ピンシートの幅方向外側に設けられたピン台座より高い部位（例えば台部）のために、ピン把持部分において突き刺されたフィルムがピンシートのピン台座に密着状態になることが無いため、ピンシートからフィルム把持部への直接的な伝熱が抑制され、その結果フィルム中央部と把持部との温度差が小さくなり、フィルム搬送中の破断強度差を小さくすることができ、結果的にテンター中でのフィルム破断等のトラブルを未然に防ぐことが可能となる。またフィルムがピンの台座から浮き上がった状態で保持されるため、ピンシートのピン台座部での融着が無く、熱処理後のフィルム取り外しが容易となる。またピンシート自体の汚染も生じないため装置の維持管理の面からも有効である。さらにフィルムをピンに差し込むために使用される押さえブラシロールにおける、幅方向に対して外側に設置されるピン台座よりも高い部位と接触する押さえブラシロールの部材が、幅方向に対して内側部分の部材よりも剛性が高いものを使用したことで、前記の効果がさらに高められる。前記理由での高品位なフィルムを得ることができないなどの課題の解消にも効果があり、高品質なポリイミドフィルムなど高分子フィルムが得られ易く、高分子フィルム製造の生産性にも寄与し、高分子フィルムの製造装置としてまた高分子フィルムの製造方法として工業的に極めて有効である。 The polymer film manufacturing apparatus of the present invention is a tenter type processing unit (conveying device) for a polymer film such as a polyimide film, because it is higher than a pin base provided on the outside in the width direction of the pin sheet (for example, a base). In addition, since the film pierced at the pin gripping part does not come into close contact with the pin base of the pin sheet, direct heat transfer from the pin sheet to the film gripping part is suppressed, and as a result, the film is gripped from the center part of the film. The temperature difference with the portion becomes small, and the difference in breaking strength during film conveyance can be reduced. As a result, troubles such as film breakage in the tenter can be prevented in advance. Further, since the film is held in a state of being lifted from the pedestal of the pins, there is no fusion at the pin pedestal portion of the pin sheet, and the film can be easily removed after the heat treatment. Further, since the pin sheet itself is not contaminated, it is effective from the viewpoint of maintenance of the apparatus. Furthermore, in the presser brush roll used to insert the film into the pin, the presser brush roll member that comes in contact with a portion higher than the pin base installed on the outer side in the width direction is the inner part in the width direction. By using a material having higher rigidity than the member, the above effect can be further enhanced. It is also effective in solving problems such as being unable to obtain a high-quality film for the above reasons, and it is easy to obtain a polymer film such as a high-quality polyimide film, contributing to the productivity of polymer film production, It is industrially extremely effective as a polymer film production apparatus and a polymer film production method.
本発明において、高分子フィルムとは、ポリアミドイミド、ポリイミド、酢酸セルロース、ポリカーボネート、ポリ塩化ビニル、アラミドなど高融点や非溶融性高分子からのフィルムが挙げられる。
本発明の高分子フィルムは、これらの高分子を含む溶液を流延し、乾燥、熱処理してフィルムとなす。これらの高分子を含む溶液に用いられる溶剤としては、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、塩化メチレン、テトラヒドロフラン、メタノール、メタクレゾールなどが挙げられる。
本発明において好ましく用いられる高分子溶液としては、ポリアミドイミドのＮ−メチル−２−ピロリドン溶液、Ｎ，Ｎ−ジメチルアセトアミド溶液、ポリイミド前駆体であるポリアミド酸のＮ−メチル−２−ピロリドン溶液、Ｎ，Ｎ−ジメチルアセトアミド溶液、溶剤可溶なポリイミドのＮ−メチル−２−ピロリドン溶液、Ｎ，Ｎ−ジメチルアセトアミド溶液、酢酸セルロースの塩化メチレン溶液、メタノール溶液、ポリカーボネートの塩化メチレン溶液、メタクレゾール溶液、ポリ塩化ビニルのテトラヒドロフラン溶液、アラミドのＮ−メチル−２−ピロリドン溶液などが挙げられる。
In the present invention, the polymer film includes a film made of a high melting point or non-melting polymer such as polyamideimide, polyimide, cellulose acetate, polycarbonate, polyvinyl chloride, and aramid.
The polymer film of the present invention is cast into a film by casting a solution containing these polymers, drying and heat treatment. Examples of the solvent used for the solution containing these polymers include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, methylene chloride, tetrahydrofuran, methanol, and metacresol.
Examples of the polymer solution preferably used in the present invention include N-methyl-2-pyrrolidone solution of polyamideimide, N, N-dimethylacetamide solution, N-methyl-2-pyrrolidone solution of polyamide acid which is a polyimide precursor, N , N-dimethylacetamide solution, N-methyl-2-pyrrolidone solution of solvent-soluble polyimide, N, N-dimethylacetamide solution, methylene chloride solution of cellulose acetate, methanol solution, methylene chloride solution of polycarbonate, metacresol solution, Examples include a tetrahydrofuran solution of polyvinyl chloride and an N-methyl-2-pyrrolidone solution of aramid.
本発明の高分子フィルムの製造装置及び製造方法は、特にポリイミド前駆体であるポリアミド酸のＮ−メチル−２−ピロリドン溶液、Ｎ，Ｎ−ジメチルアセトアミド溶液やポリイミドベンゾオキサゾールの前駆体であるポリアミド酸のＮ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等の溶液を使用する流延製膜方法による場合に最も好ましく適用し得る。
以下ポリイミドフィルムについて詳述するがこれらに限定されるものではない。
本発明に好ましく適用し得る、ポリイミドフィルムを得るための芳香族ジアミン類と、芳香族テトラカルボン酸類との反応は、溶媒中で芳香族ジアミン類と芳香族テトラカルボン酸（無水物）類とを（開環）重付加反応に供してポリイミド前駆体であるポリアミド酸の溶液を得て、次いで、このポリアミド酸の溶液からポリイミド前駆体フィルム（グリーンフィルムともいう）を成形した後に乾燥・熱処理・脱水縮合（イミド化）することにより製造される。
The apparatus and method for producing a polymer film of the present invention include a polyamic acid which is a precursor of an N-methyl-2-pyrrolidone solution of a polyamic acid which is a polyimide precursor, an N, N-dimethylacetamide solution or a polyimide benzoxazole, in particular. The present invention can be most preferably applied by the casting film forming method using a solution of N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, or the like.
Hereinafter, the polyimide film will be described in detail, but is not limited thereto.
The reaction between an aromatic diamine for obtaining a polyimide film, which can be preferably applied to the present invention, and an aromatic tetracarboxylic acid is carried out by reacting an aromatic diamine and an aromatic tetracarboxylic acid (anhydride) in a solvent. (Ring-opening) Polyamide acid solution that is a polyimide precursor is obtained by polyaddition reaction, and then a polyimide precursor film (also called green film) is formed from this polyamic acid solution, followed by drying, heat treatment, and dehydration It is produced by condensation (imidation).
本発明におけるポリイミドフィルムは、特に限定されるものではないが、下記の芳香族ジアミン類と芳香族テトラカルボン酸（無水物）類との組み合わせが好ましい例として挙げられる。
Ａ．ベンゾオキサゾール構造を有する芳香族ジアミン類と芳香族テトラカルボン酸類との組み合わせ。
Ｂ．ジアミノジフェニルエーテル骨格を有する芳香族ジアミン類とピロメリット酸骨格を有する芳香族テトラカルボン酸類との組み合わせ。
Ｃ．フェニレンジアミン骨格を有する芳香族ジアミン類とビフェニルテトラカルボン酸骨格を有する芳香族テトラカルボン酸類との組み合わせ。
Ｄ．上記のＡＢＣの一種以上の組み合わせ。
本発明で特に好ましく使用できるベンゾオキサゾール構造を有する芳香族ジアミン類として、下記の化合物が例示できる。
Although the polyimide film in this invention is not specifically limited, The combination of the following aromatic diamine and aromatic tetracarboxylic acid (anhydride) is mentioned as a preferable example.
A. A combination of an aromatic diamine having a benzoxazole structure and an aromatic tetracarboxylic acid.
B. A combination of an aromatic diamine having a diaminodiphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyromellitic acid skeleton.
C. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
D. A combination of one or more of the above ABCs.
Examples of aromatic diamines having a benzoxazole structure that can be particularly preferably used in the present invention include the following compounds.
２，２’−ｐ−フェニレンビス（５−アミノベンゾオキサゾール）、２，２’−ｐ−フェニレンビス（６−アミノベンゾオキサゾール）、１−（５−アミノベンゾオキサゾロ）−４−（６−アミノベンゾオキサゾロ）ベンゼン、２，６−（４，４’−ジアミノジフェニル）ベンゾ〔１，２−ｄ：５，４−ｄ’〕ビスオキサゾール、２，６−（４，４’−ジアミノジフェニル）ベンゾ〔１，２−ｄ：４，５−ｄ’〕ビスオキサゾール、２，６−（３，４’−ジアミノジフェニル）ベンゾ〔１，２−ｄ：５，４−ｄ’〕ビスオキサゾール、２，６−（３，４’−ジアミノジフェニル）ベンゾ〔１，２−ｄ：４，５−ｄ’〕ビスオキサゾール、２，６−（３，３’−ジアミノジフェニル）ベンゾ〔１，２−ｄ：５，４−ｄ’〕ビスオキサゾール、２，６−（３，３’−ジアミノジフェニル）ベンゾ〔１，２−ｄ：４，５−ｄ’〕ビスオキサゾール。 2,2′-p-phenylenebis (5-aminobenzoxazole), 2,2′-p-phenylenebis (6-aminobenzoxazole), 1- (5-aminobenzoxazolo) -4- (6- Aminobenzoxazolo) benzene, 2,6- (4,4′-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (4,4′-diaminodiphenyl) ) Benzo [1,2-d: 4,5-d ′] bisoxazole, 2,6- (3,4′-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2- d: 5,4-d '] bisoxazole, 2 6- (3,3'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bis-oxazole.
これらの中でも、合成のし易さの観点から、アミノ（アミノフェニル）ベンゾオキサゾールの各異性体が好ましい。ここで、「各異性体」とは、アミノ（アミノフェニル）ベンゾオキサゾールが有する２つアミノ基が配位位置に応じて定められる各異性体である（例；上記「化１」〜「化４」に記載の各化合物）。これらのジアミンは、単独で用いてもよいし、二種以上を併用してもよい。
本発明においては、前記ベンゾオキサゾール構造を有する芳香族ジアミンを７０モル％以上使用することが好ましい。
Among these, amino (aminophenyl) benzoxazole isomers are preferable from the viewpoint of ease of synthesis. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.
In the present invention, it is preferable to use 70 mol% or more of the aromatic diamine having the benzoxazole structure.
本発明におけるジアミノジフェニルエーテル骨格を有する芳香族ジアミン類としては、４，４’−ジアミノジフェニルエーテル（ＤＡＤＥ）、３，３’−ジアミノジフェニルエーテル及び３，４’−ジアミノジフェニルエーテル及びそれらの誘導体が挙げられる。
本発明におけるフェニレンジアミン骨格を有する芳香族ジアミン類としては、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン及びそれらの誘導体が挙げられる。
本発明におけるポリイミドフィルムには前記に限定されない下記の芳香族ジアミンを使用してもよい。
例えば、４，４’−ビス（３−アミノフェノキシ）ビフェニル、ビス［４−（３−アミノフェノキシ）フェニル］ケトン、ビス［４−（３−アミノフェノキシ）フェニル］スルフィド、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］−１，１，１，３，３，３−ヘキサフルオロプロパン、ｍ−アミノベンジルアミン、ｐ−アミノベンジルアミン、
Examples of the aromatic diamine having a diaminodiphenyl ether skeleton in the present invention include 4,4′-diaminodiphenyl ether (DADE), 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and derivatives thereof.
Examples of the aromatic diamine having a phenylenediamine skeleton in the present invention include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and derivatives thereof.
You may use the following aromatic diamine which is not limited to the above for the polyimide film in this invention.
For example, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3 , 3,3-hexafluoropropane, m-aminobenzylamine, p-aminobenzylamine,
３，３’−ジアミノジフェニルスルフィド、３，３’−ジアミノジフェニルスルホキシド、３，４’−ジアミノジフェニルスルホキシド、４，４’−ジアミノジフェニルスルホキシド、３，３’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノベンゾフェノン、３，４’−ジアミノベンゾフェノン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］エタン、１，２−ビス［４−（４−アミノフェノキシ）フェニル］エタン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、１，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、１，３−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、 3,3′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-diaminodiphenyl sulfone, 3,4′- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4 -(4-aminophenoxy) phenyl] ethane, 1, -Bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
１，１−ビス［４−（４−アミノフェノキシ）フェニル］ブタン、１，３−ビス［４−（４−アミノフェノキシ）フェニル］ブタン、１，４−ビス［４−（４−アミノフェノキシ）フェニル］ブタン、２，２−ビス［４−（４−アミノフェノシ）フェニル］ブタン、２，３−ビス［４−（４−アミノフェノキシ）フェニル］ブタン、２−［４−（４−アミノフェノキシ）フェニル］−２−［４−（４−アミノフェノキシ）−３−メチルフェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）−３−メチルフェニル］プロパン、２−［４−（４−アミノフェノキシ）フェニル］−２−［４−（４−アミノフェノキシ）−３，５−ジメチルフェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）−３，５−ジメチルフェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］−１，１，１，３，３，３−ヘキサフルオロプロパン、 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) Phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) Phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- ( 4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphen Le] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,
１，４−ビス（３−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、ビス［４−（４−アミノフェノキシ）フェニル］ケトン、ビス［４−（４−アミノフェノキシ）フェニル］スルフィド、ビス［４−（４−アミノフェノキシ）フェニル］スルホキシド、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、ビス［４−（３−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、１，３−ビス［４−（４−アミノフェノキシ）ベンゾイル］ベンゼン、１，３−ビス［４−（３−アミノフェノキシ）ベンゾイル］ベンゼン、１，４−ビス［４−（３−アミノフェノキシ）ベンゾイル］ベンゼン、４，４’−ビス［（３−アミノフェノキシ）ベンゾイル］ベンゼン、１，１−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、１，３−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、３，４’−ジアミノジフェニルスルフィド、 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) ) Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3 Aminophenoxy) benzoyl] benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide,
２，２−ビス［３−（３−アミノフェノキシ）フェニル］−１，１，１，３，３，３−ヘキサフルオロプロパン、ビス［４−（３−アミノフェノキシ）フェニル］メタン、１，１−ビス［４−（３−アミノフェノキシ）フェニル］エタン、１，２−ビス［４−（３−アミノフェノキシ）フェニル］エタン、ビス［４−（３−アミノフェノキシ）フェニル］スルホキシド、４，４’−ビス［３−（４−アミノフェノキシ）ベンゾイル］ジフェニルエーテル、４，４’−ビス［３−（３−アミノフェノキシ）ベンゾイル］ジフェニルエーテル、４，４’−ビス［４−（４−アミノ−α，α−ジメチルベンジル）フェノキシ］ベンゾフェノン、４，４’−ビス［４−（４−アミノ−α，α−ジメチルベンジル）フェノキシ］ジフェニルスルホン、ビス［４−｛４−（４−アミノフェノキシ）フェノキシ｝フェニル］スルホン、１，４−ビス［４−（４−アミノフェノキシ）フェノキシ−α，α−ジメチルベンジル］ベンゼン、１，３−ビス［４−（４−アミノフェノキシ）フェノキシ−α，α−ジメチルベンジル］ベンゼン、１，３−ビス［４−（４−アミノ−６−トリフルオロメチルフェノキシ）−α，α−ジメチルベンジル］ベンゼン、１，３−ビス［４−（４−アミノ−６−フルオロフェノキシ）−α，α−ジメチルベンジル］ベンゼン、１，３−ビス［４−（４−アミノ−６−メチルフェノキシ）−α，α−ジメチルベンジル］ベンゼン、１，３−ビス［４−（４−アミノ−６−シアノフェノキシ）−α，α−ジメチルベンジル］ベンゼン、 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1 -Bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4 '-Bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α) , Α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis 4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl Benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene,
３，３’−ジアミノ−４，４’−ジフェノキシベンゾフェノン、４，４’−ジアミノ５，５’−ジフェノキシベンゾフェノン、３，４’−ジアミノ−４，５’−ジフェノキシベンゾフェノン、３，３’−ジアミノ−４−フェノキシベンゾフェノン、４，４’−ジアミノ−５−フェノキシベンゾフェノン、３，４’−ジアミノ−４−フェノキシベンゾフェノン３，４’−ジアミノ−５’−フェノキシベンゾフェノン、３，３’−ジアミノ−４，４’−ジビフェノキシベンゾフェノン、４，４’−ジアミノ−５，５’−ジビフェノキシベンゾフェノン、３，４’−ジアミノ−４，５’−ジビフェノキシベンゾフェノン、３，３’−ジアミノ−４−ビフェノキシベンゾフェノン、４，４’−ジアミノ−５−ビフェノキシベンゾフェノン、３，４’−ジアミノ−４−ビフェノキシベンゾフェノン、３，４’−ジアミノ−５’−ビフェノキシベンゾフェノン、１，３−ビス（３−アミノ−４−フェノキシベンゾイル）ベンゼン、１，４−ビス（３−アミノ−４−フェノキシベンゾイル）ベンゼン、１，３−ビス（４−アミノ−５−フェノキシベンゾイル）ベンゼン、１，４−ビス（４−アミノ−５−フェノキシベンゾイル）ベンゼン、１，３−ビス（３−アミノ−４−ビフェノキシベンゾイル）ベンゼン、１，４−ビス（３−アミノ−４−ビフェノキシベンゾイル）ベンゼン、１，３−ビス（４−アミノ−５−ビフェノキシベンゾイル）ベンゼン、１，４−ビス（４−アミノ−５−ビフェノキシベンゾイル）ベンゼン、２，６−ビス［４−（４−アミノ−α，α−ジメチルベンジル）フェノキシ］ベンゾニトリル及び上記芳香族ジアミンにおける芳香環上の水素原子の一部もしくは全てがハロゲン原子、炭素数１〜３のアルキル基又はアルコキシル基、シアノ基、又はアルキル基又はアルコキシル基の水素原子の一部もしくは全部がハロゲン原子で置換された炭素数１〜３のハロゲン化アルキル基又はアルコキシル基で置換された芳香族ジアミン等が挙げられる。
本発明におけるポリイミドフィルムに置ける好ましく使用できる芳香族テトラカルボン酸類として、ピロメリット酸骨格を有する芳香族テトラカルボン酸類すなわちピロメリット酸及びその無水物又はハロゲン化物、ビフェニルテトラカルボン酸骨格を有する芳香族テトラカルボン酸類すなわちビフェニルテトラカルボン酸及びその無水物又はハロゲン化物が挙げられる。
前記に限定されないで下記の芳香族テトラカルボン酸を使用してもよい。
3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino 5,5′-diphenoxybenzophenone, 3,4′-diamino-4,5′-diphenoxybenzophenone, 3,3 '-Diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone 3,4'-diamino-5'-phenoxybenzophenone, 3,3'- Diamino-4,4′-dibiphenoxybenzophenone, 4,4′-diamino-5,5′-dibiphenoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino- 4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxy Nzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) Benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5- Biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile and the above aromatics Some or all of the hydrogen atoms on the aromatic ring in the diamine are halogen atoms, some or all of the hydrogen atoms of the alkyl group or alkoxyl group having 1 to 3 carbon atoms, cyano group, or alkyl group or alkoxyl group are halogen atoms. And aromatic diamines substituted with a substituted C1-C3 halogenated alkyl group or alkoxyl group.
As aromatic tetracarboxylic acids that can be preferably used in the polyimide film of the present invention, aromatic tetracarboxylic acids having a pyromellitic acid skeleton, that is, pyromellitic acid and anhydrides or halides thereof, and aromatic tetracarboxylic acids having a biphenyltetracarboxylic acid skeleton are used. Carboxylic acids, that is, biphenyltetracarboxylic acid and anhydrides or halides thereof can be mentioned.
Without being limited thereto, the following aromatic tetracarboxylic acids may be used.
芳香族ジアミン類と、芳香族テトラカルボン酸無水物類とを重合してポリアミド酸を得るときに用いる溶媒は、原料となるモノマー及び生成するポリアミド酸のいずれをも溶解するものであれば特に限定されないが、極性有機溶媒が好ましく、例えば、Ｎ−メチル−２−ピロリドン、Ｎ−アセチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホリックアミド、エチルセロソルブアセテート、ジエチレングリコールジメチルエーテル、スルホラン、ハロゲン化フェノール類等があげられるが、なかでもＮ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミドが好ましく適用される。これらの溶媒は、単独あるいは混合して使用することができる。溶媒の使用量は、原料となるモノマーを溶解するのに十分な量であればよく、具体的な使用量としては、モノマーを溶解した溶液に占めるモノマーの質量が、通常５〜４０質量％、好ましくは１０〜２０質量％となるような量が挙げられる。 The solvent used when polymerizing aromatic diamines and aromatic tetracarboxylic acid anhydrides to obtain polyamic acid is particularly limited as long as it dissolves both the raw material monomer and the polyamic acid to be produced. Although not preferred, polar organic solvents are preferred, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide Hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, halogenated phenols and the like, among which N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferably applied. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the mass of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by mass, The amount is preferably 10 to 20% by mass.
ポリアミド酸を得るための重合反応（以下、単に「重合反応」ともいう）の条件は従来公知の条件を適用すればよく、具体例として、有機溶媒中、０〜８０℃の温度範囲で、１０分〜３０時間連続して撹拌及び／又は混合することが挙げられる。必要により重合反応を分割したり、温度を上下させてもかまわない。この場合に、両モノマーの添加順序には特に制限はないが、芳香族ジアミン類の溶液中に芳香族テトラカルボン酸無水物類を添加するのが好ましい。重合反応によって得られるポリアミド酸溶液に占めるポリアミド酸の質量は、好ましくは５〜４０質量％、より好ましくは１０〜３０質量％であり、前記溶液の粘度はブルックフィールド粘度計による測定（２５℃）で、送液の安定性の点から、好ましくは１０〜２０００Ｐａ・ｓであり、より好ましくは１００〜１０００Ｐａ・ｓである。
本発明におけるポリアミド酸の還元粘度（ηｓｐ／Ｃ）は、特に限定するものではないが３．０ｄｌ／ｇ以上が好ましく、４．０ｄｌ／ｇ以上がさらに好ましく、なおさらに５．０ｄｌ／ｇ以上が好ましい。
Conventionally known conditions may be applied for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”). As a specific example, in a temperature range of 0 to 80 ° C., 10 Stirring and / or mixing continuously for 30 minutes. If necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of adding both monomers is not particularly limited, but it is preferable to add aromatic tetracarboxylic acid anhydrides to the solution of aromatic diamines. The mass of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and the viscosity of the solution is measured with a Brookfield viscometer (25 ° C.). From the viewpoint of the stability of liquid feeding, it is preferably 10 to 2000 Pa · s, and more preferably 100 to 1000 Pa · s.
The reduced viscosity (ηsp / C) of the polyamic acid in the present invention is not particularly limited, but is preferably 3.0 dl / g or more, more preferably 4.0 dl / g or more, and still more preferably 5.0 dl / g or more. preferable.
また、重合反応の前に芳香族ジアミン類に少量の末端封止剤を添加して重合を制御することを行ってもよい。末端封止剤としては、無水マレイン酸等といった炭素−炭素二重結合を有する化合物が挙げられる。無水マレイン酸を使用する場合の使用量は、芳香族ジアミン類１モル当たり好ましくは０．００１〜１．０モルである。
重合反応中に真空脱泡することは、良質なポリアミド酸の溶液を製造するのに有効である。
さらに、以下述べるポリアミド酸の溶液を支持体上に流延・塗布するに際して予め減圧などの処理によって該溶液中の気泡や溶存気体を除去しておくことも、本発明のポリイミドフィルムを得るために有効な処理である。
Moreover, you may perform superposition | polymerization by adding a small amount of terminal blockers to aromatic diamines before a polymerization reaction. Examples of the end capping agent include compounds having a carbon-carbon double bond such as maleic anhydride. The amount of maleic anhydride used is preferably 0.001 to 1.0 mol per mol of aromatic diamine.
Vacuum degassing during the polymerization reaction is effective in producing a good quality polyamic acid solution.
Furthermore, in order to obtain the polyimide film of the present invention, it is possible to remove bubbles and dissolved gas in the solution in advance by treatment such as decompression when casting and applying a polyamic acid solution described below onto the support. This is an effective process.
ポリアミド酸溶液を塗布する支持体は、ポリアミド酸溶液をフィルム状に成形するに足る程度の平滑性、剛性を有していればよく、表面が金属、プラスチック、ガラス、磁器などであるドラム又はベルト状回転体などが挙げられる。また、適度な剛性と高い平滑性を有する高分子フィルムを利用する方法も好ましい態様である。中でも、支持体の表面は好ましくは金属であり、より好ましくは錆びなくて耐腐食に優れるステンレスである。支持体の表面にはＣｒ、Ｎｉ、Ｓｎなどの金属メッキを施してもよい。支持体表面は必要に応じて鏡面にしたり、あるいは梨地状に加工することができる。また支持体の差によって乾燥における風量や温度は適宜選択採用すればよく、支持体へのポリアミド酸溶液の塗布は、スリット付き口金からの流延、押出機による押出し、スキージコーティング、リバースコーティング、ダイコーティング、アプリケータコーティング、ワイヤーバーコーティング等を含むが、これらに限られず、従来公知の溶液の塗布手段を適宜用いることができる。 The support on which the polyamic acid solution is applied is only required to have smoothness and rigidity sufficient to form the polyamic acid solution into a film, and a drum or belt whose surface is made of metal, plastic, glass, porcelain, etc. And the like. A method using a polymer film having moderate rigidity and high smoothness is also a preferred embodiment. Among them, the surface of the support is preferably a metal, more preferably stainless steel that does not rust and has excellent corrosion resistance. The surface of the support may be plated with metal such as Cr, Ni, or Sn. The surface of the support can be mirror-finished or processed into a satin finish as required. The air volume and temperature in drying may be appropriately selected and adopted depending on the difference in the support, and the polyamic acid solution can be applied to the support by casting from a nozzle with a slit, extrusion by an extruder, squeegee coating, reverse coating, die Including, but not limited to, coating, applicator coating, wire bar coating and the like, conventionally known solution application means can be used as appropriate.
イミド化・熱処理として、閉環（イミド化）触媒や脱水剤を含まないポリアミド酸溶液を用いて、熱処理に供することでイミド化反応を進行させる方法（所謂、熱閉環法）やポリアミド酸溶液に閉環触媒及び脱水剤を含有させておいて、上記閉環触媒及び脱水剤の作用によってイミド化反応を行わせる、化学閉環法を挙げることができる。
熱閉環法の熱処理温度は、１５０〜５００℃が好ましく、熱処理温度がこの範囲より低いと充分に閉環されづらくなり、またこの範囲より高いと劣化が進行し、フィルムが脆くなりやすくなる。より好ましい態様としては、１５０〜２５０℃で３〜２０分間処理した後に３５０〜５００℃で３〜２０分間熱処理するところの初期段階熱処理と後段階熱処理とを有する２段階熱処理工程が挙げられる。
As imidization / heat treatment, a polyamic acid solution that does not contain a ring-closure (imidization) catalyst or a dehydrating agent is used, and the imidization reaction is advanced by subjecting to a heat treatment (so-called thermal ring closure method) or ring closure in the polyamic acid solution. Examples thereof include a chemical ring closure method in which a catalyst and a dehydrating agent are contained and an imidization reaction is performed by the action of the ring closing catalyst and the dehydrating agent.
The heat treatment temperature of the thermal ring closure method is preferably 150 to 500 ° C. If the heat treatment temperature is lower than this range, it is difficult to sufficiently close the ring, and if it is higher than this range, the deterioration proceeds and the film tends to become brittle. A more preferable embodiment includes a two-stage heat treatment step having an initial stage heat treatment and a subsequent stage heat treatment in which a heat treatment is performed at 150 to 250 ° C. for 3 to 20 minutes and then heat treatment at 350 to 500 ° C. for 3 to 20 minutes.
閉環触媒をポリアミド酸溶液に加えるタイミングは特に限定はなく、ポリアミド酸を得るための重合反応を行う前に予め加えておいてもよい。閉環触媒の具体例としては、トリメチルアミン、トリエチルアミンなどといった脂肪族第３級アミンや、イソキノリン、ピリジン、ベータピコリンなどといった複素環式第３級アミンなどが挙げられ、中でも、複素環式第３級アミンから選ばれる少なくとも一種のアミンが好ましい。ポリアミド酸１モルに対する閉環触媒の使用量は特に限定はないが、好ましくは０．５〜８モルである。
脱水剤をポリアミド酸溶液に加えるタイミングも特に限定はなく、ポリアミド酸を得るための重合反応を行う前に予め加えておいてもよい。脱水剤の具体例としては、無水酢酸、無水プロピオン酸、無水酪酸などといった脂肪族カルボン酸無水物や、無水安息香酸などといった芳香族カルボン酸無水物などが挙げられ、中でも、無水酢酸、無水安息香酸あるいはそれらの混合物が好ましい。また、ポリアミド酸１モルに対する脱水剤の使用量は特に限定はないが、好ましくは０．１〜４モルである。脱水剤を用いる場合には、アセチルアセトンなどといったゲル化遅延剤を併用してもよい。
The timing for adding the ring-closing catalyst to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylamine, and heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. Among them, heterocyclic tertiary amines are mentioned. At least one amine selected from is preferred. Although the usage-amount of a ring-closing catalyst with respect to 1 mol of polyamic acids does not have limitation in particular, Preferably it is 0.5-8 mol.
The timing of adding the dehydrating agent to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Among them, acetic anhydride, benzoic anhydride, etc. Acids or mixtures thereof are preferred. Moreover, the usage-amount of the dehydrating agent with respect to 1 mol of polyamic acids is not particularly limited, but is preferably 0.1 to 4 mol. When a dehydrating agent is used, a gelation retarder such as acetylacetone may be used in combination.
熱閉環反応であっても、化学閉環法であっても、支持体に形成されたポリイミドフィルムの前駆体（グリーンフィルムともいう）を完全にイミド化する前に支持体から剥離してもよいし、イミド化後に剥離してもよい。
ポリイミドフィルムの厚さは特に限定されないが、後述するプリント配線基板用ベース基板に用いることを考慮すると、５〜１５０μｍ、好ましくは１０〜１００μｍである。この厚さはポリアミド酸溶液を支持体に塗布する際の塗布量や、ポリアミド酸溶液の濃度によって容易に制御し得る。
本発明のポリイミドフィルムには、滑剤をポリイミド中に添加含有せしめるなどしてフィルム表面に微細な凹凸を付与しフィルムの滑り性を改善することが好ましい。
滑剤としては、無機や有機の０．０３μｍ〜３μｍ程度の平均粒子径を有する微粒子が使用でき、具体例として、酸化チタン、アルミナ、シリカ、炭酸カルシウム、燐酸カルシウム、燐酸水素カルシウム、ピロ燐酸カルシウム、酸化マグネシウム、酸化カルシウム、粘土鉱物などが挙げられる。
Whether it is a thermal ring closure reaction or a chemical ring closure method, the polyimide film precursor (also referred to as a green film) formed on the support may be peeled off from the support before it is completely imidized. The film may be peeled after imidization.
Although the thickness of a polyimide film is not specifically limited, Considering using it for the base substrate for printed wiring boards mentioned later, it is 5-150 micrometers, Preferably it is 10-100 micrometers. This thickness can be easily controlled by the amount of the polyamic acid solution applied to the support and the concentration of the polyamic acid solution.
The polyimide film of the present invention is preferably provided with a lubricant in the polyimide to give fine irregularities on the film surface to improve the slipping property of the film.
As the lubricant, inorganic or organic fine particles having an average particle diameter of about 0.03 μm to 3 μm can be used. Specific examples include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, Examples include magnesium oxide, calcium oxide, and clay minerals.
本発明の、高分子フィルム又は高分子前駆体からなるフィルムをフィルム端部固定式テンターにて熱処理などの処理をする際に、フィルムの幅方向の両側端部におけるフィルム端部把持が、多数のピンシートと個々のピンシートに配された多数のピンで構成され、該ピンが押さえブラシロールによりフィルム両側端部を突き刺すことでなされ、幅方向及び又は搬送方向に張設した状態でフィルムを搬送するテンター式処理部を有する高分子フィルム製造方法において、ピンシートの幅方向に対し外側に設置したピン台座より高い部位の形状は特に限定されず、ピンの植え込まれている面であるピン台座より位置的に高くそのことによってフィルムがピン台座に接触しない機能を有すればよく、例えばピンシートの幅方向の外側（ピンの植え込まれていない幅方向での外側位置）のみが高くその位置でのみフィルムに接触するようにした台であるものでもよく、またピン台座が幅方向に外側に向かって傾斜したピンシートであってもよく、例えば台の場合、台の形状や大きさは、好ましくは、（１）該台の高さがピン先端より３ｍｍ以上８ｍｍ以下の範囲で低く、より好ましくは、４ｍｍ以上６ｍｍ以下の範囲で低く設置されており、該台の高さがピン先端より３ｍｍ未満の低さであると、フィルム両端部を突き刺したピンの深さが浅く、その後の熱処理工程中でフィルムがピンから外れる頻度が高くなり好ましくなく、また、該台の高さがピン先端より８ｍｍより低いと、熱処理後にフィルムをピンシートから外すときに大きな抵抗となり、最悪フィルム両端部を引き裂くことにつながり好ましくない。また、（２）該台の高さがピンの設置されている台座より０．５ｍｍ以上５ｍｍ以下の範囲で高く、より好ましくは、２ｍｍ以上３ｍｍ以下の範囲で高く設置されており、ピンシートへのフィルム把持時に、押さえブラシロールによるフィルムのピン挿入深さが安定的に決定され、ピンシートからフィルム把持部への直接的な伝熱抑制効果が発現し、その結果フィルム中央部と把持部との温度差が小さくなり、フィルム搬送中の破断強度差が小さくなり、結果的にテンター中、及びテンターでの熱処理後ピンシートからフィルムを剥離する際のフィルム破断等のトラブルを低減することが出来る。一方、該台の高さがピンの設置されている台座より０．５ｍｍ未満の高さであると、ピンシートからフィルム把持部への直接的な伝熱抑制効果が低減され、その結果フィルム中央部と把持部との温度差が大きくなり、フィルム搬送中の破断強度差が大きくなり、結果的にテンター中でのフィルム破断等のトラブルにつながり好ましくなく、また、該台の高さがピンの設置されている台座より５ｍｍより高いと、熱処理工程におけるピンシート自体の汚染を促進するために好ましくない。また、（３）該台の周囲を面取りしていることが好ましく、面取り加工をしないと、該台周囲に接触したフィルムに裂けが生じ好ましくない。また、（４）ピンが設置されている台座に空洞を設けることは、ピンシートからフィルム把持部への直接的な伝熱抑制効果が発生し、その結果フィルム中央部と把持部との温度差が小さくなり、フィルム搬送中の破断強度差が小さくなり、結果的にテンター中でのフィルム破断等のトラブル防止につながり好ましい。 When a film made of a polymer film or a polymer precursor of the present invention is subjected to a treatment such as a heat treatment with a film end fixed type tenter, the film end gripping at both side ends in the width direction of the film is a large number. Consists of a pin sheet and a large number of pins arranged on each pin sheet. The pins are pierced on both sides of the film with a pressing brush roll, and the film is transported in a stretched state in the width direction and / or the transport direction. In the polymer film manufacturing method having a tenter type processing section, the shape of the portion higher than the pin pedestal installed outside in the width direction of the pin sheet is not particularly limited, and the pin pedestal is a surface in which the pin is implanted It only needs to have a function that the film is higher in position and the film does not contact the pin base. For example, the outside of the pin sheet in the width direction (pin implantation) It may be a base that is only high in contact with the film only at that position, and the pin base is a pin sheet that is inclined outward in the width direction. Well, for example, in the case of a table, the shape and size of the table are preferably (1) the height of the table is lower in the range of 3 mm to 8 mm than the tip of the pin, more preferably in the range of 4 mm to 6 mm. If the height of the platform is less than 3 mm below the tip of the pin, the depth of the pin that pierced both ends of the film is shallow, and the frequency of the film coming off the pin during the subsequent heat treatment process is low. If the height of the base is lower than 8 mm from the tip of the pin, it will be a great resistance when the film is removed from the pin sheet after heat treatment, and it will cause tearing at both ends of the worst film. Rising undesirable. (2) The height of the base is higher than the pedestal on which the pin is installed in the range of 0.5 mm to 5 mm, more preferably higher in the range of 2 mm to 3 mm. When the film is gripped, the pin insertion depth of the film by the pressing brush roll is stably determined, and the direct heat transfer suppression effect from the pin sheet to the film gripping portion is expressed. As a result, the film center portion and the gripping portion The difference in temperature of the film becomes smaller, and the difference in breaking strength during film conveyance becomes smaller. As a result, troubles such as film breakage in the tenter and when the film is peeled off from the pin sheet after heat treatment in the tenter can be reduced. . On the other hand, if the height of the base is less than 0.5 mm from the pedestal on which the pins are installed, the direct heat transfer suppression effect from the pin sheet to the film gripping portion is reduced, and as a result, the center of the film The difference in temperature between the gripping part and the grip part becomes large, and the difference in breaking strength during film transportation increases, resulting in troubles such as film breakage in the tenter, which is not preferable. If it is higher than 5 mm from the installed pedestal, it is not preferable in order to promote contamination of the pin sheet itself in the heat treatment step. Further, (3) it is preferable that the periphery of the table is chamfered, and if the chamfering is not performed, the film in contact with the periphery of the table is not preferable. Also, (4) providing a cavity in the pedestal on which the pins are installed has a direct heat transfer suppression effect from the pin sheet to the film gripping part, resulting in a temperature difference between the film center part and the gripping part. Is reduced, and the difference in breaking strength during film conveyance is reduced, resulting in prevention of troubles such as film breakage in the tenter.
本発明の、高分子フィルム又は高分子前駆体からなるフィルムをフィルム端部固定式テンターにて熱処理などの処理をする際に、フィルムの幅方向の両側端部におけるフィルム端部把持が、多数のピンシートと個々のピンシートに配された多数のピンで構成され、該ピンが押さえブラシロールによりフィルム両側端部を突き刺すことでなされ、幅方向及び又は搬送方向に張設した状態でフィルムを搬送するテンター式処理部を有する高分子フィルム製造方法と、ピンシートの幅方向に対し外側に台が設置されたことを特徴とする高分子フィルムの製造装置において、該ピンがフィルム両側端部を突き刺す時点で、融点又は軟化点が１５０℃以上で弾性率４ＧＰａ以上の素材からなる毛材からなるブラシを備えた部材でフィルム端部をピンに突き刺す手段を使用することも好ましい実施態様である。
また、この押さえブラシロールにおける、幅方向に対して外側に設置されるピン台座よりも高い部位と接触する押さえブラシロールの部材が、幅方向に対して内側部分の部材よりも剛性が高いもの、具体的には押さえブラシロールの幅方向に対して外側に設置する部材が、金属素線のブラシ形状部材であるものや金属製の円筒状部材であるものがより好ましい態様である。
融点又は軟化点が１５０℃以上で弾性率４ＧＰａ以上の素材からなる毛材からなるブラシを備えた部材としては特に限定されないが、ブラシが円筒平面周上に設けられたブラシロールが好ましく使用できる。
融点又は軟化点が１５０℃以上で弾性率４ＧＰａ以上の素材からなる毛材からなるブラシは、この物性を有することでフィルムの突き刺しが均一に行われかつ長時間の使用によってもその機能の劣化が極めて少ないものであり、この物性を有さないものを使用した場合には前記の２点を同時に満足することができないものである。
融点又は軟化点が１５０℃以上で弾性率４ＧＰａ以上の素材からなる毛材からなるブラシとしてはこの物性を備えたものであれば特に限定されるものではなく、例えば高弾性率の高分子繊維、カーボンファイバー、ガラスファイバー、などが挙げられるが、より好ましくは高分子繊維などの高分子素材であり、芳香族ポリアミド、例えばコーネックス（帝人製）などが挙げられる。
When a film made of a polymer film or a polymer precursor of the present invention is subjected to a treatment such as a heat treatment with a film end fixed type tenter, the film end gripping at both side ends in the width direction of the film is a large number. Consists of a pin sheet and a large number of pins arranged on each pin sheet. The pins are pierced on both sides of the film with a pressing brush roll, and the film is transported in a stretched state in the width direction and / or the transport direction. A polymer film manufacturing method having a tenter-type processing section and a polymer film manufacturing apparatus characterized in that a base is installed outside in the width direction of the pin sheet. At the time, the end of the film hits the pin with a member having a brush made of a bristle made of a material having a melting point or softening point of 150 ° C. or higher and an elastic modulus of 4 GPa or higher. It is also a preferred embodiment to use a means of stabbing.
Further, in this presser brush roll, the member of the presser brush roll that comes into contact with a portion higher than the pin base installed outside in the width direction is higher in rigidity than the member in the inner part in the width direction, Specifically, it is more preferable that the member installed on the outer side in the width direction of the pressing brush roll is a metal wire brush-shaped member or a metal cylindrical member.
Although it does not specifically limit as a member provided with the brush which consists of a bristle material which has melting | fusing point or a softening point 150 degreeC or more and whose elasticity modulus is 4 GPa or more, The brush roll provided with the brush on the cylindrical plane periphery can use it preferably.
A brush made of a bristle material having a melting point or softening point of 150 ° C. or more and an elastic modulus of 4 GPa or more has the properties so that the film can be pierced uniformly and its function is deteriorated even after long-term use. The amount is extremely small, and when the material having no physical properties is used, the above two points cannot be satisfied at the same time.
A brush made of a hair material made of a material having a melting point or softening point of 150 ° C. or higher and an elastic modulus of 4 GPa or higher is not particularly limited as long as it has this physical property. For example, a high elastic modulus polymer fiber, Carbon fibers, glass fibers, and the like can be mentioned, and more preferred are polymer materials such as polymer fibers, and aromatic polyamides such as Cornex (manufactured by Teijin) are preferred.
先に述べたように本発明におけるピンテンターの把持部は、例えば図１に一例を示すように個々のピンシートに配された多数のピンで構成され、この個々のピンシートが多数配されてフィルムを搬送するものである。
本発明においては、好ましい態様として、フィルム熱処理が終了して、ピン又はピンシートがターンしてフィルム把持を開始する位置に戻る直前の部位において冷却手段を設けて、ピンがフィルム把持開始時点においては充分に冷却され、ピンによるフィルム両端の突き刺しにおいて、フィルム把持の均一性が保たれ、ピンを喰い込ませた孔でのフィルムの幅方向又は搬送方向にも孔が拡大することや破断が生じることが抑制され、フィルム全体での歪の減少、フィルム厚さ斑の低減が達成できるようにした冷却手段を備えた製造装置であり、この装置を使用する製造方法である。冷却手段としては、空冷、水冷いずれでもよく、また空気、水以外の冷媒を用いても良い。冷却効率の点からは液体の冷媒を用いることが好ましく、さらに、テンター自身が一般の有機溶剤の発火点以上に加熱されることを考えると、水冷仕様による冷却手段にすることが最も好ましい。
この冷却手段を設けることで、ピン及びピンシートがフィルム両端を把持して搬送を開始する時点で、一端熱処理温度例えば４５０℃などの高温に加熱され冷却手段がないときにピンなどが高温に維持されており、この高温のピンによるフィルム両端の突き刺しにおいて、フィルム把持の均一性が保たれ難く、ピンを喰い込ませた孔でのフィルムの幅方向又は搬送方向にも孔が拡大することや破断が生じることが容易くなり、フィルム全体での歪の増加、フィルム厚さ斑の拡大が生じるなどの問題をある程度解消することができる。
さらに本発明において、好ましい態様としては、ピンテンターのピン配置において、フィルム搬送時のフィルム幅方向における最内側に配列された個々のピンが互いに、フィルム搬送方向で個々のピンシート内においても、他のピンシート間においても、全て等間隔で配されていることが好ましい。
As described above, the gripping portion of the pin tenter according to the present invention is composed of a large number of pins arranged on each pin sheet, for example, as shown in FIG. 1, and a film is formed by arranging a large number of these individual pin sheets. Are to be transported.
In the present invention, as a preferred embodiment, a cooling means is provided at a position immediately before the film heat treatment is finished and the pin or pin sheet turns and returns to the position where film gripping is started. When the film is sufficiently cooled and the both ends of the film are pierced by the pins, the film holding uniformity is maintained, and the holes expand and break in the width direction or the conveying direction of the film at the holes where the pins are entrapped. Is a manufacturing apparatus equipped with cooling means that can suppress the distortion of the entire film and reduce film thickness unevenness, and uses this apparatus. As the cooling means, either air cooling or water cooling may be used, and a refrigerant other than air or water may be used. From the viewpoint of cooling efficiency, it is preferable to use a liquid refrigerant. Further, considering that the tenter itself is heated above the ignition point of a general organic solvent, it is most preferable to use a cooling means based on water cooling specifications.
By providing this cooling means, when the pins and the pin sheet start gripping both ends of the film and start conveyance, the pins etc. are kept at a high temperature when they are heated to a high temperature such as one end heat treatment temperature such as 450 ° C. and there is no cooling means. In the piercing of both ends of the film with this high-temperature pin, it is difficult to maintain the uniformity of film gripping, and the hole expands or breaks in the film width direction or the conveyance direction at the hole where the pin is bitten. Can easily occur, and problems such as an increase in distortion in the entire film and an increase in film thickness unevenness can be solved to some extent.
Furthermore, in the present invention, as a preferred embodiment, in the pin arrangement of the pin tenter, the individual pins arranged on the innermost side in the film width direction during film conveyance are mutually different from each other in the individual pin sheet in the film conveyance direction. It is preferable that the pin sheets are all arranged at equal intervals.
以下、実施例及び比較例を示して本発明をより具体的に説明するが、本発明は以下の実施例によって限定されるものではない。なお、以下の実施例における物性の評価方法は以下の通りである。
１．ポリアミド酸の還元粘度（ηｓｐ／Ｃ）
ポリマー濃度が０．２ｇ／ｄｌとなるようにＮ−メチル−２−ピロリドン（又は、Ｎ，Ｎ−ジメチルアセトアミド）に溶解した溶液をウベローデ型の粘度管により３０℃で測定した。（ポリアミド酸溶液の調製に使用した溶媒がＮ，Ｎ−ジメチルアセトアミドの場合は、Ｎ，Ｎ−ジメチルアセトアミドを使用してポリマーを溶解し、測定した。）
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in the following examples is as follows.
1. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube. (When the solvent used for preparing the polyamic acid solution was N, N-dimethylacetamide, the polymer was dissolved using N, N-dimethylacetamide and measured.)
２．ポリイミドフィルムの厚さ
マイクロメーター（ファインリューフ社製、ミリトロン１２５４Ｄ）を用いて測定した。
2. The thickness of the polyimide film The thickness was measured using a micrometer (Millitron 1254D manufactured by Fine Reef).
３．ポリイミドフィルムの引張弾性率、引張破断強度及び引張破断伸度
測定対象のポリイミドフィルムを、流れ方向（ＭＤ方向）及び幅方向（ＴＤ方向）にそれぞれ１００ｍｍ×１０ｍｍの短冊状に切り出したものを試験片とした。引張試験機（島津製作所製、オートグラフ（商品名）、機種名ＡＧ−５０００Ａ）を用い、引張速度５０ｍｍ／分、チャック間距離４０ｍｍの条件で、ＭＤ方向、ＴＤ方向それぞれについて、引張弾性率、引張破断強度及び引張破断伸度を測定した。
４．フィルムの線膨張係数（ＣＴＥ）
下記条件で伸縮率を測定し、３０〜３００℃までを１５℃間隔で分割し、各分割範囲の伸縮率／温度の平均値より求めた。ＭＤ方向、ＴＤ方向の意味は上記と同様である。
装置名 ； ＭＡＣサイエンス社製ＴＭＡ４０００Ｓ
試料長さ ； ２０ｍｍ
試料幅 ； ２ｍｍ
昇温開始温度 ； ２５℃
昇温終了温度 ； ４００℃
昇温速度 ； ５℃／ｍｉｎ
雰囲気 ； アルゴン
3. Test specimens obtained by cutting a polyimide film to be measured into strips of 100 mm × 10 mm in the flow direction (MD direction) and the width direction (TD direction), respectively. It was. Using a tensile tester (manufactured by Shimadzu Corporation, Autograph (trade name), model name AG-5000A) under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 40 mm, the tensile modulus of elasticity in each of the MD direction and TD direction, Tensile rupture strength and tensile rupture elongation were measured.
4). Film linear expansion coefficient (CTE)
The expansion / contraction rate was measured under the following conditions, and the range from 30 to 300 ° C. was divided at 15 ° C. intervals and obtained from the average value of the expansion / contraction rate / temperature of each divided range. The meanings of the MD direction and the TD direction are the same as described above.
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon
〔参考例１〕
（無機粒子の予備分散）
アモルファスシリカの球状粒子シーホスターＫＥ−Ｐ１０（日本触媒株式会社製）を１．２２質量部、Ｎ−メチル−２−ピロリドン４２０質量部を、容器の接液部、及び輸液用配管はオーステナイト系ステンレス鋼ＳＵＳ３１６Ｌである容器に入れホモジナイザーＴ−２５ベイシック（ＩＫＡ Ｌａｂｏｒ ｔｅｃｈｎｉｋ社製）にて、回転数１０００回転／分で１分間攪拌し予備分散液を得た。予備分散液中の平均粒子径は０．１１μｍであった。
（ポリアミド酸溶液の調製）
窒素導入管、温度計、攪拌棒を備えた容器の接液部、及び輸液用配管はオーステナイト系ステンレス鋼ＳＵＳ３１６Ｌである反応容器内を窒素置換した後、２２３質量部の５−アミノ−２−（ｐ−アミノフェニル）ベンゾオキサゾールを入れた。次いで、４０００質量部のＮ−メチル−２−ピロリドンを加えて完全に溶解させてから、先に得た予備分散液を４２０質量部と２１７質量部のピロメリット酸二無水物を加えて、２５℃にて２４時間攪拌すると、褐色の粘調なポリアミド酸溶液Ａが得られた。この還元粘度（ηｓｐ／Ｃ）は３．８ｄｌ／ｇであった。
[Reference Example 1]
(Preliminary dispersion of inorganic particles)
1.22 parts by mass of spherical particles of amorphous silica Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 420 parts by mass of N-methyl-2-pyrrolidone, the wetted part of the container, and the piping for infusion are austenitic stainless steel The mixture was placed in a container of SUS316L and stirred with a homogenizer T-25 basic (manufactured by IKA Labortechnik) at a rotation speed of 1000 rpm for 1 minute to obtain a preliminary dispersion. The average particle size in the preliminary dispersion was 0.11 μm.
(Preparation of polyamic acid solution)
A nitrogen inlet tube, a thermometer, a liquid contact part of a container equipped with a stirring rod, and an infusion pipe were replaced with nitrogen in the reaction container made of austenitic stainless steel SUS316L, and then 223 parts by mass of 5-amino-2- ( p-Aminophenyl) benzoxazole was added. Next, 4000 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, and then the preliminary dispersion obtained above was added with 420 parts by mass and 217 parts by mass of pyromellitic dianhydride. When the mixture was stirred at ° C. for 24 hours, a brown viscous polyamic acid solution A was obtained. The reduced viscosity (ηsp / C) was 3.8 dl / g.
〔参考例２〕
窒素導入管，温度計，攪拌棒を備えた容器の接液部、及び輸液用配管はオーステナイト系ステンレス鋼ＳＵＳ３１６Ｌである反応容器内を窒素置換した後，５−アミノ−２−（ｐ−アミノフェニル）ベンゾオキサゾール２２３質量部、Ｎ，Ｎ−ジメチルアセトアミド４４１６質量部を加えて完全に溶解させた後，コロイダルシリカをジメチルアセトアミドに分散してなるスノーテックスＤＭＡＣ−ＳＴ３０（日産化学工業株式会社製）４０．５質量部（シリカを８．１質量部含む）、ピロメリット酸二無水物２１７質量部を加え，２５℃の反応温度で２４時間攪拌すると，褐色で粘調なポリアミド酸溶液Ｂが得られた。このもののηｓｐ／Ｃは４．０ｄｌ／ｇであった。
[Reference Example 2]
The nitrogen inlet tube, the thermometer, the wetted part of the vessel equipped with the stirring rod, and the infusion pipe were replaced with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 5-amino-2- (p-aminophenyl) ) After adding 223 parts by mass of benzoxazole and 4416 parts by mass of N, N-dimethylacetamide and completely dissolving them, Snowtex DMAC-ST30 (manufactured by Nissan Chemical Industries, Ltd.) 40 in which colloidal silica is dispersed in dimethylacetamide .5 parts by mass (including 8.1 parts by mass of silica) and 217 parts by mass of pyromellitic dianhydride are added and stirred at a reaction temperature of 25 ° C. for 24 hours to obtain a brown and viscous polyamide acid solution B. It was. Ηsp / C of this product was 4.0 dl / g.
〔参考例３〕
（無機粒子の予備分散）
アモルファスシリカの球状粒子シーホスターＫＥ−Ｐ１０（日本触媒株式会社製）を７．６質量部、Ｎ−メチル−２−ピロリドン３９０質量部を容器の接液部、及び輸液用配管はオーステナイト系ステンレス鋼ＳＵＳ３１６Ｌである容器に入れホモジナイザーＴ−２５ベイシック（ＩＫＡ Ｌａｂｏｒ ｔｅｃｈｎｉｋ社製）にて、回転数１０００回転／分で１分間攪拌し予備分散液を得た。
（ポリアミド酸溶液の調製）
窒素導入管、温度計、攪拌棒を備えた容器の接液部、及び輸液用配管はオーステナイト系ステンレス鋼ＳＵＳ３１６Ｌである反応容器内を窒素置換した後、２００質量部のジアミノジフェニルエーテルを入れた。次いで、３８００質量部のＮ−メチル−２−ピロリドンを加えて完全に溶解させてから、先に得た予備分散液を３９０質量部と２１７質量部のピロメリット酸二無水物を加えて、２５℃にて５時間攪拌すると、褐色の粘調なポリアミド酸溶液Ｃが得られた。この還元粘度（ηｓｐ／Ｃ）は３．７ｄｌ／ｇであった。
[Reference Example 3]
(Preliminary dispersion of inorganic particles)
7.6 parts by weight of amorphous silica spherical particles Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 390 parts by weight of N-methyl-2-pyrrolidone, the liquid contact part of the container, and the infusion pipe are austenitic stainless steel SUS316L And stirred for 1 minute at a rotation speed of 1000 rpm with a homogenizer T-25 basic (manufactured by IKA Labortechnik) to obtain a preliminary dispersion.
(Preparation of polyamic acid solution)
The liquid contact part of the vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, and the infusion pipe were purged with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 200 parts by mass of diaminodiphenyl ether was added. Next, after 3800 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, 390 parts by mass and 217 parts by mass of pyromellitic dianhydride were added to the preliminary dispersion obtained above. When the mixture was stirred at 0 ° C. for 5 hours, a brown viscous polyamic acid solution C was obtained. The reduced viscosity (ηsp / C) was 3.7 dl / g.
〔参考例４〕
（無機粒子の予備分散）
アモルファスシリカの球状粒子シーホスターＫＥ−Ｐ１０（日本触媒株式会社製）を３．７質量部、Ｎ−メチル−２−ピロリドン４２０質量部を容器の接液部、及び輸液用配管はオーステナイト系ステンレス鋼ＳＵＳ３１６Ｌである容器に入れホモジナイザーＴ−２５ベイシック（ＩＫＡ Ｌａｂｏｒ ｔｅｃｈｎｉｋ社製）にて、回転数１０００回転／分で１分間攪拌し予備分散液を得た。
（ポリアミド酸溶液の調製）
窒素導入管、温度計、攪拌棒を備えた容器の接液部、及び輸液用配管はオーステナイト系ステンレス鋼ＳＵＳ３１６Ｌである反応容器内を窒素置換した後、１０８質量部のフェニレンジアミンを入れた。次いで、３６００質量部のＮ−メチル−２−ピロリドンを加えて完全に溶解させてから、先に得た予備分散液を４２０質量部と２９２．５質量部のジフェニルテトラカルボン酸二無水物を加えて、２５℃にて１２時間攪拌すると、褐色の粘調なポリアミド酸溶液Ｄが得られた。この還元粘度（ηｓｐ／Ｃ）は４．５ｄｌ／ｇであった。
[Reference Example 4]
(Preliminary dispersion of inorganic particles)
Amorphous silica spherical particle Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 3.7 parts by mass, N-methyl-2-pyrrolidone, 420 parts by mass, the container wetted part, and the infusion pipe are austenitic stainless steel SUS316L And stirred for 1 minute at a rotation speed of 1000 rpm with a homogenizer T-25 basic (manufactured by IKA Labortechnik) to obtain a preliminary dispersion.
(Preparation of polyamic acid solution)
The wetted part of the vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, and the infusion pipe were replaced with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 108 parts by mass of phenylenediamine was added. Next, after 3600 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, 420 parts by mass and 292.5 parts by mass of diphenyltetracarboxylic dianhydride were added to the preliminary dispersion obtained above. When the mixture was stirred at 25 ° C. for 12 hours, a brown viscous polyamic acid solution D was obtained. The reduced viscosity (ηsp / C) was 4.5 dl / g.
〔実施例１〜４〕
参考例１〜４で得たポリアミド酸溶液を、ポリエチレンテレフタレート製フィルムＡ−４１００（東洋紡績株式会社製）の無滑剤面上に、コンマコーターを用いてコーティングし（ギャップは、１２０μｍ、塗工幅１２４０ｍｍ）、９０℃にて６０分間乾燥した。乾燥後に自己支持性となったポリアミド酸フィルムを支持体から剥離して両端をカットし、厚さ１７μｍ、幅１２００ｍｍのそれぞれのグリーンフィルムを得た。
[Examples 1 to 4]
The polyamic acid solution obtained in Reference Examples 1 to 4 was coated on the non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater (gap: 120 μm, coating width). 1240 mm), and dried at 90 ° C. for 60 minutes. The polyamic acid film which became self-supporting after drying was peeled from the support and cut at both ends to obtain respective green films having a thickness of 17 μm and a width of 1200 mm.
得られたこれらのグリーンフィルムを、図１に示す幅方向外側に台が設置されたピンシートにピンを植え込んだ構成のピンテンターに通し熱処理を行った。ピンは、ピンシートが並んだ際にピン間隔が一定となるように配置されており、ピン台座からのピン高さは８ｍｍ、ピンシート間隔は１１４０ｍｍであり、ピンシートの長手方向の長さは９５ｍｍ、幅方向の長さは３５ｍｍで、ピンシートの幅方向外側に設定した該台の長手方向の長さは９５ｍｍ、幅方向の長さは１５ｍｍであり、該台の周囲は面取り加工を施した。また、ブラシロールは幅方向に２種類の素材を用いた２層構造を用い、ピンシートの幅方向外側に設置した台の高さと共に、表１に記載する。
テンターの熱処理設定は以下の通りである。第１段が２００℃で５分、昇温速度４℃／秒で昇温して第２段として４５０℃で５分の条件で２段階の加熱を施して、イミド化反応を進行させた。その後、５分間で室温にまで冷却し、フィルムの両端部の平面性が悪い部分をスリッターにて切り落とし、ロール状に巻き上げ、褐色を呈する実施例１〜４のそれぞれのポリイミドフィルムを得た。熱処理中の搬送状態、得られたポリイミドフィルムの特性などの測定結果を表１に記載する。
なお、フィルムの平面性、有効幅は、以下のように定義した。
まず得られたフィルムを清浄な表面を有する定盤に広げ、フィルム端部にてウネリにより定盤との間に空間が空いてしまう部分を平面性不良な部分として捉えた。フィルムの端部が定盤表面から持ち上がらずに、フィルム全体が定盤に密着するようになるまで、フィルム両端をカットし、その時のフィルム幅を有効幅と定義した。
また、ピン裂けは、フィルムの先頭から１０ｍ程度の部分にて、ピン部での幅方向のフィルム裂け幅を物差しにて測定した。
また、フィルムの搬送状態は、熱処理過程でのピンシートによるフィルムの把持状態を目視評価し、ピンよりフィルムが外れることがあるのかどうかを評価した。
また、ピンシートからの剥離性は、熱処理が終了してフィルムが引き離しロールによりピンシートより剥離するときの状態を目視評価し，スムースな引き離しは良好とし，ピンにフィルムが引っ掛る場合をやや不良とし、引っ掛りによりフィルムに流れ方向の裂けが生じる場合は不良とした。
These obtained green films were subjected to a heat treatment through a pin tenter having a structure in which pins are implanted in a pin sheet having a table installed outside in the width direction shown in FIG. The pins are arranged so that the pin interval is constant when the pin sheets are arranged, the pin height from the pin base is 8 mm, the pin sheet interval is 1140 mm, and the length of the pin sheet in the longitudinal direction is The length in the width direction is 95 mm, the length in the longitudinal direction of the table set outside the pin sheet in the width direction is 95 mm, the length in the width direction is 15 mm, and the periphery of the table is chamfered. did. In addition, the brush roll uses a two-layer structure using two kinds of materials in the width direction, and is described in Table 1 together with the height of the table installed on the outer side in the width direction of the pin sheet.
The heat treatment settings for the tenter are as follows. The first stage was heated at 200 ° C. for 5 minutes and the heating rate was 4 ° C./second, and the second stage was heated at 450 ° C. for 5 minutes under two conditions to proceed the imidization reaction. Then, it cooled to room temperature in 5 minutes, cut off the part with the poor planarity of the both ends of a film with a slitter, wound up in roll shape, and obtained each polyimide film of Examples 1-4 which exhibits brown. Table 1 shows the measurement results such as the conveyance state during the heat treatment and the characteristics of the obtained polyimide film.
The flatness and effective width of the film were defined as follows.
First, the obtained film was spread on a surface plate having a clean surface, and a portion where a space was left between the surface plate due to undulation at the end of the film was regarded as a portion having poor flatness. The ends of the film were not lifted from the surface of the platen, and both ends of the film were cut until the entire film was in close contact with the platen, and the film width at that time was defined as the effective width.
Moreover, the pin tear measured the film tear width of the width direction in a pin part in a part about 10m from the head of a film with a ruler.
Moreover, the conveyance state of the film evaluated the visual observation of the holding | grip state of the film by the pin sheet in the heat processing process, and evaluated whether the film might remove | deviate from a pin.
Also, the peelability from the pin sheet is evaluated by visual evaluation of the state when the film is separated from the pin sheet by the roll after the heat treatment is finished, and the smooth pull is good, and the film is caught slightly on the pin. In the case where the film tears in the flow direction due to catching, it was regarded as defective.
〔比較例１〜４〕
参考例１〜４のポリアミド酸溶液を、実施例と同様に支持体上に塗布乾燥し、乾燥後に自己支持性となったポリアミド酸フィルムを支持体から剥離して、厚さ１７μｍのそれぞれのグリーンフィルムを得た。
得られたこれらのグリーンフィルムを、表１に示す様にピンシートやブラシロールの条件でピンテンターにて両端を把持し、他は実施例と同様の条件にて熱処理し、フィルムの両端部の平面性が悪い部分をスリッターにて切り落とし、ロール状に巻き上げ、褐色を呈する比較例１〜４のそれぞれのポリイミドフィルムを得た。熱処理中の搬送状態、得られたポリイミドフィルムの特性など結果を表１に記載する。なお、ピンシートの長手方向の長さは９５ｍｍ、幅方向の長さは４０ｍｍで、ピン台座からのピン高さは８ｍｍである。
結果のとおり、比較例においてはフィルム端の平面性が悪い部分の幅が広く、結果的に有効幅が狭くなっている。またピン裂けが大きく、生産安定性に欠けることが示唆される。
[Comparative Examples 1-4]
The polyamic acid solutions of Reference Examples 1 to 4 were applied and dried on a support in the same manner as in the Examples, and the polyamic acid film that became self-supporting after drying was peeled off from the support, and each green having a thickness of 17 μm. A film was obtained.
As shown in Table 1, the obtained green films were gripped at both ends with a pin tenter under the conditions of a pin sheet and a brush roll, and the others were heat-treated under the same conditions as in the examples. A portion having poor properties was cut off with a slitter, rolled up into a roll, and each polyimide film of Comparative Examples 1 to 4 exhibiting a brown color was obtained. Table 1 shows the results such as the conveyance state during the heat treatment and the characteristics of the obtained polyimide film. The length of the pin sheet in the longitudinal direction is 95 mm, the length in the width direction is 40 mm, and the pin height from the pin base is 8 mm.
As a result, in the comparative example, the width of the portion having poor flatness at the film edge is wide, and as a result, the effective width is narrow. Moreover, pin tearing is large, suggesting that production stability is lacking.
以上述べてきたように、本発明においては、ピンシートにフィルムが焦げ付くことがなく、安定した搬送性が得られ、またフィルムをピンシートから剥がす際にもスムースな剥離状態が得られ、さらにフィルムの安定なる搬送が可能であるが故にフィルムの裂けや破断が生じにくく、有効幅が広く無駄の少ないフィルム製膜が可能であり、さらに得られたフィルムは幅方向の品位、フィルム厚の均一性にも優れたものとなり、当該製造方法、製造装置は、ポリイミドフィルム、ポリベンザゾールフィルム、セルロース系フィルム、ポリアミドフィルム、ポリアミドイミドフィルムなどの流延製膜方法として産業上有意義なものである。 As described above, in the present invention, the film does not burn on the pin sheet, stable transportability is obtained, and a smooth peeling state is obtained even when the film is peeled off from the pin sheet. Therefore, it is possible to produce a film with a wide effective width and less waste, and the obtained film has a uniform quality in the width direction and film thickness. The manufacturing method and the manufacturing apparatus are industrially significant as casting film forming methods for polyimide films, polybenzazole films, cellulose-based films, polyamide films, polyamideimide films, and the like.
１：ブラシロール
２：ピン
３：ピン台座
４：台
1: Brush roll 2: Pin 3: Pin base 4: Stand
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