JP2010106207A - Polyimide precursor solution composition - Google Patents
Polyimide precursor solution composition Download PDFInfo
- Publication number
- JP2010106207A JP2010106207A JP2008281978A JP2008281978A JP2010106207A JP 2010106207 A JP2010106207 A JP 2010106207A JP 2008281978 A JP2008281978 A JP 2008281978A JP 2008281978 A JP2008281978 A JP 2008281978A JP 2010106207 A JP2010106207 A JP 2010106207A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- acid
- solution composition
- precursor solution
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 96
- 239000004642 Polyimide Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000002243 precursor Substances 0.000 title claims abstract description 33
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 41
- 239000000126 substance Substances 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 38
- 150000004985 diamines Chemical class 0.000 claims description 21
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 25
- 238000010438 heat treatment Methods 0.000 abstract description 23
- -1 mellitic acid compound Chemical class 0.000 abstract description 22
- 239000009719 polyimide resin Substances 0.000 abstract description 20
- YDSWCNNOKPMOTP-UHFFFAOYSA-N benzenehexacarboxylic acid Natural products OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 abstract 1
- 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 50
- 239000002904 solvent Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 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 5
- 238000006243 chemical reaction Methods 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SNHKMHUMILUWSJ-UHFFFAOYSA-N 5-(1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-yl)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CC2C(=O)OC(=O)C2CC1C1CC2C(=O)OC(=O)C2CC1 SNHKMHUMILUWSJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- RCZJVHXVCSKDKB-UHFFFAOYSA-N tert-butyl 2-[[1-(2-amino-1,3-thiazol-4-yl)-2-(1,3-benzothiazol-2-ylsulfanyl)-2-oxoethylidene]amino]oxy-2-methylpropanoate Chemical compound N=1C2=CC=CC=C2SC=1SC(=O)C(=NOC(C)(C)C(=O)OC(C)(C)C)C1=CSC(N)=N1 RCZJVHXVCSKDKB-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- CFTSORNHIUMCGF-UHFFFAOYSA-N (1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C(F)(F)F)(C(F)(F)F)C1=CC=CC=C1 CFTSORNHIUMCGF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- CYRDONYNCYQNAL-UHFFFAOYSA-N 1-methylheptane-1,2,4,5-tetracarboxylic acid Chemical compound CCC(C(O)=O)C(C(O)=O)CC(C(O)=O)C(C)C(O)=O CYRDONYNCYQNAL-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- IKSUMZCUHPMCQV-UHFFFAOYSA-N 2-(3-aminophenyl)-1,3-benzoxazol-5-amine Chemical compound NC1=CC=CC(C=2OC3=CC=C(N)C=C3N=2)=C1 IKSUMZCUHPMCQV-UHFFFAOYSA-N 0.000 description 1
- VSMRWFMFAFOGGD-UHFFFAOYSA-N 2-(3-aminophenyl)-1,3-benzoxazol-6-amine Chemical compound NC1=CC=CC(C=2OC3=CC(N)=CC=C3N=2)=C1 VSMRWFMFAFOGGD-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
- IBKFNGCWUPNUHY-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-6-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2O1 IBKFNGCWUPNUHY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-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
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- NFSQGQXKVFGKSO-UHFFFAOYSA-N 3-(2-phenylphenoxy)aniline Chemical group NC1=CC=CC(OC=2C(=CC=CC=2)C=2C=CC=CC=2)=C1 NFSQGQXKVFGKSO-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
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-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
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-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
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- XVHOSCGFZMMVNL-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-dimethoxyaniline Chemical group COC1=C(N)C=CC(C=2C=CC(N)=CC=2)=C1OC XVHOSCGFZMMVNL-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
- AMMZSOGDIDWWJV-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenoxy)-dimethylsilyl]oxyphthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1O[Si](C)(C)OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AMMZSOGDIDWWJV-UHFFFAOYSA-N 0.000 description 1
- ASNOFHCTUSIHOM-UHFFFAOYSA-N 4-[10-(4-aminophenyl)anthracen-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(N)C=C1 ASNOFHCTUSIHOM-UHFFFAOYSA-N 0.000 description 1
- ZPUFMXDJOAWORX-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)phenyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 ZPUFMXDJOAWORX-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
- GQUSLIBGUTZKJZ-UHFFFAOYSA-N 4-[3-(3,4-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=CC(OC=2C=C(C(C(O)=O)=CC=2)C(O)=O)=C1 GQUSLIBGUTZKJZ-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
- FOMRNNDDNMWZFO-UHFFFAOYSA-N 4-[4-(3,4-dicarboxybenzoyl)benzoyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=C1 FOMRNNDDNMWZFO-UHFFFAOYSA-N 0.000 description 1
- QCQPSSJUXNVOBU-UHFFFAOYSA-N 4-[4-(3,4-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 QCQPSSJUXNVOBU-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
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- GAUNIEOSKKZOPV-UHFFFAOYSA-N 4-[4-[4-(3,4-dicarboxyphenoxy)benzoyl]phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=C(C(C(O)=O)=CC=3)C(O)=O)=CC=2)C=C1 GAUNIEOSKKZOPV-UHFFFAOYSA-N 0.000 description 1
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-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
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- HJSYPLCSZPEDCQ-UHFFFAOYSA-N 5-[2-(3-amino-4-methylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C)C(N)=C1 HJSYPLCSZPEDCQ-UHFFFAOYSA-N 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- 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
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、主成分としてポリアミド酸を含んでなるポリイミド前駆体溶液組成物に関する。本発明のポリイミド前駆体溶液組成物は、溶液の粘度調節が容易であり、溶液粘度が安定しており、且つ比較的低温或いは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得ることができる。 The present invention relates to a polyimide precursor solution composition comprising polyamic acid as a main component. The polyimide precursor solution composition of the present invention is easy to adjust the viscosity of the solution, has a stable solution viscosity, and is equivalent to or better than linear polyimide by heat treatment at a relatively low temperature or in a short time. A polyimide resin molded body such as a polyimide film having excellent physical properties can be suitably obtained.
ポリイミドはその耐熱性や機械的物性から幅広く開発がなされている。とりわけ全芳香族ポリイミドはその剛直構造から特に高い耐熱性や機械的物性を発揮することができる。しかし、一般に、芳香族ポリイミドは不溶不融であり、その前駆体であるポリアミド酸溶液組成物を用いて成形加工される場合が多い。ポリアミド酸をイミド化する方法は、ａ）加熱イミド化、ｂ）脱水剤による化学イミド化、ｃ）加熱イミド化と化学イミド化の併用、などがある。このうち、ｂ）及びｃ）の化学イミド化を用いる方法は、比較的低温でイミド化できるが、溶液がゲル化し易いので、満足なポリイミド樹脂成形体を得るのが難しいという問題がある。一方、ａ）の加熱イミド化は溶媒除去を伴うので溶液がゲル化する問題は少ないが、優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を得るためには、加熱処理工程で高い物性を付与しながら段階的に最高加熱温度まで昇温するなど、高温で長時間の加熱処理が必要であった。 Polyimide has been widely developed due to its heat resistance and mechanical properties. In particular, wholly aromatic polyimides can exhibit particularly high heat resistance and mechanical properties due to their rigid structure. However, in general, aromatic polyimide is insoluble and infusible, and is often molded using a polyamic acid solution composition that is a precursor thereof. Methods for imidizing polyamic acid include a) heat imidization, b) chemical imidization with a dehydrating agent, and c) combined use of heat imidization and chemical imidization. Among these, the method using chemical imidation of b) and c) can be imidized at a relatively low temperature, but has a problem that it is difficult to obtain a satisfactory polyimide resin molded product because the solution is easily gelled. On the other hand, since the heat imidation of a) involves solvent removal, there is little problem of gelation of the solution. However, in order to obtain a polyimide resin molded body such as a polyimide film having excellent physical properties, high physical properties are required in the heat treatment step. Heat treatment at a high temperature for a long time was necessary, such as stepwise raising the temperature to the maximum heating temperature while applying.
特許文献１には、芳香族テトラカルボン酸二無水物に対して芳香族ジアミンを過剰に用いて調製されたポリアミド酸溶液に、酸成分とジアミン成分とが等モルとなるように、芳香族テトラカルボン酸もしくはその無水物を添加することにより、ポリアミド酸溶液の粘度調整と加熱イミド化後のポリイミド成形物の物性を向上させる方法が開示されている。しかし、この方法で得られるポリイミド成形物の機械的特性などの物性は必ずしも充分とは云えず、比較的低温或いは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得るためには改良の余地があった。 Patent Document 1 discloses that an aromatic tetracarboxylic acid dianhydride is prepared by using an aromatic tetracarboxylic acid dianhydride in an excess amount of an aromatic diamine so that the acid component and the diamine component are equimolar. A method for improving the physical properties of a polyimide molded product after adjusting the viscosity of the polyamic acid solution and heating imidization by adding carboxylic acid or its anhydride is disclosed. However, the physical properties such as the mechanical properties of the polyimide molded product obtained by this method are not necessarily sufficient, and have physical properties equivalent to or better than linear polyimide by heat treatment at a relatively low temperature or in a short time. There was room for improvement in order to suitably obtain a polyimide resin molded body such as a polyimide film.
特許文献２には、分子末端がアミノ基であるポリアミド酸と、アミノ基と反応して３または４個のイミド環を形成し得る下記化学式で示される多官能カルボン酸化合物を架橋成分として含んでなるワニスが開示されている。 Patent Document 2 contains a polyfunctional carboxylic acid compound represented by the following chemical formula, which can form a 3 or 4 imide ring by reacting with an amino group and a polyamic acid having an amino group at the molecular end as a crosslinking component. A varnish is disclosed.
しかし、特許文献２の前記化学式で示される多官能カルボン酸化合物は、芳香族環を４個以上含む特殊な化合物である。このため、ガラス転移温度が２５０℃以下のいわゆる熱可塑性ポリイミドにおいて、その弱点である耐溶剤性の改良には有効かも知れないが、ポリイミド中の前記多官能カルボン酸化合物に由来したセグメントの体積分率が大きくなるために、ポリイミドの結晶性を乱すなど物性に多大な影響を与えることになり、特にガラス転移温度が２５０℃以上の高耐熱性ポリイミド成形体においてポリイミド本来の物性を発現させことが難しいという問題があった。このため、特に高耐熱性ポリイミド樹脂成形体において、比較的低温或いは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得ることは困難であった。
また、前記多官能カルボン酸化合物は、市販されておらずまた容易に合成できないので入手が困難であり非常に高価なものであった。
However, the polyfunctional carboxylic acid compound represented by the chemical formula in Patent Document 2 is a special compound containing four or more aromatic rings. For this reason, in so-called thermoplastic polyimide having a glass transition temperature of 250 ° C. or lower, it may be effective in improving the solvent resistance, which is a weak point, but the volume of the segment derived from the polyfunctional carboxylic acid compound in the polyimide As the rate increases, it will greatly affect the physical properties such as disturbing the crystallinity of the polyimide, and in particular, in the highly heat-resistant polyimide molded body having a glass transition temperature of 250 ° C. or higher, the original physical properties of the polyimide may be expressed. There was a problem that it was difficult. For this reason, particularly in a high heat-resistant polyimide resin molded body, a polyimide resin molded body such as a polyimide film having physical properties equivalent to or better than linear polyimide is suitably obtained by heat treatment at a relatively low temperature or in a short time. It was difficult.
Further, the polyfunctional carboxylic acid compound is not commercially available and cannot be easily synthesized, so that it is difficult to obtain and very expensive.
本発明の目的は、溶液の粘度調節が容易であり、溶液粘度が安定しており、且つ比較的低温或いは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得ることができるポリイミド前駆体溶液組成物を提供することである。 An object of the present invention is to easily adjust the viscosity of a solution, have a stable solution viscosity, and have a physical property equivalent to or better than that of a linear polyimide by heat treatment at a relatively low temperature or in a short time. It is providing the polyimide precursor solution composition which can obtain suitably polyimide resin moldings, such as a film | membrane.
本発明者らは、種々検討の結果、ポリアミド酸溶液に分子量の小さなメリット酸化合物を添加したポリイミド前駆体溶液組成物が、溶液の粘度調節が容易であり、溶液粘度が安定しており、且つ比較的低温或いは短時間の加熱処理段階で高い物性のポリイミド樹脂成形体になり、しかもポリイミドのガラス転移温度などの物性に悪影響を与えることがなく、直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得ることができることを見出して本発明に到達した。 As a result of various studies, the present inventors have found that a polyimide precursor solution composition in which a merit acid compound having a low molecular weight is added to a polyamic acid solution, the viscosity of the solution can be easily adjusted, the solution viscosity is stable, and It becomes a polyimide resin molded article with high physical properties at a relatively low temperature or short heat treatment stage, and it does not adversely affect physical properties such as the glass transition temperature of polyimide, and is equivalent to or better than linear polyimide. It has been found that a polyimide resin molded body such as a polyimide film having physical properties can be suitably obtained, and the present invention has been achieved.
すなわち、本発明は以下の項に関する。
１． （Ａ）ポリアミド酸と、（Ｂ）下記化学式（１）で示されるメリット酸化合物とを含んでなることを特徴とするポリイミド前駆体溶液組成物。
That is, the present invention relates to the following items.
1. A polyimide precursor solution composition comprising (A) a polyamic acid and (B) a merit acid compound represented by the following chemical formula (1).
２． ポリアミド酸（Ａ）を構成するジアミン成分とテトラカルボン酸成分とのモル比［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０．９８〜１．０５の範囲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溶液組成物。 2. The molar ratio of the diamine component and the tetracarboxylic acid component constituting the polyamic acid (A) [number of moles of diamine component / number of moles of tetracarboxylic acid component] is in the range of 0.98 to 1.05. Item 2. The polyimide precursor solution composition according to Item 1.
３． メリット酸化合物（Ｂ）のモル数が、ポリアミド酸（Ａ）を構成するジアミン成分のモル数に対して０．００１〜０．０５倍モルの範囲であることを特徴とする前記項１〜２のいずれかに記載のポリイミド前駆体溶液組成物。 3. Item 1-2 above, wherein the number of moles of merit acid compound (B) is in the range of 0.001 to 0.05 times the number of moles of the diamine component constituting polyamic acid (A). The polyimide precursor solution composition according to any one of the above.
４． ポリアミド酸（Ａ）が、下記化学式（２）からなる繰り返し単位を有す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溶液組成物。 4). The polyimide precursor solution composition according to any one of Items 1 to 3, wherein the polyamic acid (A) has a repeating unit consisting of the following chemical formula (2).
５． ２５℃における溶液粘度が、０．１〜３０００ポイズの範囲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溶液組成物。 5. Item 5. The polyimide precursor solution composition according to any one of Items 1 to 4, wherein the solution viscosity at 25 ° C is in the range of 0.1 to 3000 poise.
本発明によって、溶液の粘度調節が容易であり、溶液粘度が安定しており、且つ比較的低温或いは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得ることができるポリイミド前駆体溶液組成物を提供することができる。 According to the present invention, the viscosity of the solution can be easily adjusted, the solution viscosity is stable, and a polyimide film having physical properties equivalent to or better than linear polyimide by heat treatment at a relatively low temperature or in a short time The polyimide precursor solution composition which can obtain suitably the polyimide resin molding can be provided.
本発明で用いられるメリット酸化合物は、前記化学式（１）で示されるメリット酸及びそのエステル化物である。すなわち、化学式（１）中のＡ１〜Ａ６としては、メリット酸のときの水素原子、及びそのエステル化物のときのメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ヒドロキシエチル基、メトキシエチル基などの脂肪族基、好ましくは炭素数が１〜６の水酸基やエーテル結合を含んでもよい脂肪族基、またフェニル基、ベンジル基などの芳香族基、好ましくは炭素数が６〜１２の芳香族基を挙げることができる。これらのうち、取り扱いやすさや入手のしやすさから、特にＡ１〜Ａ６のすべてが水素原子であるメリット酸、及び少なくとも一部がメチル基、エチル基のエステル化物が好ましい。 The merit acid compound used in the present invention is merit acid represented by the chemical formula (1) and its esterified product. That is, as A 1 to A 6 in the chemical formula (1), a hydrogen atom at the time of merit acid, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hydroxyethyl group at the time of its esterified product, An aliphatic group such as a methoxyethyl group, preferably an aliphatic group having 1 to 6 carbon atoms or an aliphatic group which may contain an ether bond, an aromatic group such as a phenyl group or a benzyl group, preferably 6 to 12 carbon atoms The aromatic group can be mentioned. Among these, from the viewpoint of ease of handling and availability, merit acid in which all of A 1 to A 6 are hydrogen atoms and esterified products having at least a methyl group and an ethyl group are particularly preferable.
具体的化合物としては、メリット酸、メリット酸メチルエステル、メリット酸ジメチルエステル、メリット酸トリメチルエステル、メリット酸エチルエステル、メリット酸ジエチルエステル、メリット酸トリエチルエステル、メリット酸プロピルエステル、メリット酸ジプロピルエステル、メリット酸トリプロピルエステル、メリット酸ブチルエステル、メリット酸ジブチルエステル、メリット酸トリブチルエステル、メリット酸フェニルエステル、メリット酸ジフェニルエステル、メリット酸トリフェニルエステルなどを好適に挙げることができる。
これらのメリット酸化合物は単独あるいは混合して用いることができる。なお、メリット酸化合物が、無水化して、酸二無水物基や酸三無水物基などを全カルボキシル基数のうちの５％特に１０％以上含むようになるとポリアミド酸溶液組成物の粘度が不安定になることや、ゲル化することから好ましくない。
Specific compounds include merit acid, merit acid methyl ester, merit acid dimethyl ester, merit acid trimethyl ester, merit acid ethyl ester, merit acid diethyl ester, merit acid triethyl ester, merit acid propyl ester, merit acid dipropyl ester, Preferred examples include merit acid tripropyl ester, merit acid butyl ester, merit acid dibutyl ester, merit acid tributyl ester, merit acid phenyl ester, merit acid diphenyl ester, merit acid triphenyl ester, and the like.
These merit acid compounds can be used alone or in combination. The viscosity of the polyamic acid solution composition becomes unstable when the merit acid compound is dehydrated to contain acid dianhydride groups, acid dianhydride groups, or the like in 5%, particularly 10% or more of the total number of carboxyl groups. It is not preferable because of becoming or gelling.
本発明に用いられるポリアミド酸（Ａ）は、テトラカルボン酸成分とジアミン成分とをイミド化を抑制しながら反応させることによって好適に得ることができる。テトラカルボン酸成分の具体例として、例えばピロメリット酸二無水物、４，４’−オキシジフタル酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、１，１，１，３，３，３−ヘキサフルオロプロパン−２，２−ジフタル酸二無水物、３，３'，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物、１，２，３，４−ベンゼンテトラカルボン酸二無水物、３，６−トリフルオロ−１，２，４，５−ベンゼンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物、１，４−ジメトキシ−２，３，５，６−ベンゼンテトラカルボン酸二無水物、１，４−ジトリメチルシリル−２，３，５，６−ベンゼンテトラカルボン酸二無水物、１，４−ビス（３，４−ジカルボキシルフェノキシ）ベンゼン二無水物、１，３−ビス（３，４−ジカルボキシルフェノキシ）ベンゼン二無水物、３，３’，４，４’−ジフェニルメタンテトラカルボン酸二無水物、ビス（３，４−ジカルボキシルフェノキシ）ジメチルシラン二無水物、ビス（３，４−ジカルボキシルフェノキシ）メチルアミン二無水物、４，４’−ビス（３，４−ジカルボキシルフェノキシ）ビフェニル二無水物、４，４’−ビス（３，４−ジカルボキシルフェノキシ）ジフェニルスルホン二無水物、２，３，５，６−ナフタレンテトラカルボン酸二無水物、２，３，５，６−ピリジンテトラカルボン酸二無水物、２，３，６，７−キノリンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルフィドテトラカルボン酸二無水物、３，３，４，４’−ジフェニルスルホキシドテトラカルボン酸二無水物、１，２，８，９−アントラセンテトラカルボン酸二無水物、１，４−ビス（３，４−ジカルボキシルフェニルスルフォニル）ベンゼン二無水物、１，４−ビス（３，４−ジカルボキシルフェニルチオ）ベンゼン二無水物、３，３’’，４，４’’−タ−フェニルテトラカルボン酸二無水物、４−フェニルベンゾフェノン−３，３’’，４，４’’−テトラカルボン酸二無水物、１，４−ビス（３，４−ジカルボキシルベンゾイル）−ベンゼン二無水物、３，３’’’，４，４’’’−クアチルフェニルテトラカルボン酸二無水物、４，４’−ビス（３，４−ジカルボキシルフェノキシ）ベンゾフェノン二無水物、４，４’−ビス（３，４−ジカルボキシルフェノキシ）ジフェニルスルホキシド二無水物、ナフタレンテトラカルボン酸二無水物、ビナフタレンテトラカルボン酸二無水物などの芳香族テトラカルボン酸二無水物、あるいは、下記化学式（５）で表される芳香族テトラカルボン酸二無水物を例示できる。これらの芳香族テトラカルボン酸二無水物は単独或いは２種類以上を混合して使用しても構わない。また、これらの芳香族テトラカルボン酸二無水物は、そのエステル化物などの誘導体で代替することもできる。 The polyamic acid (A) used in the present invention can be suitably obtained by reacting a tetracarboxylic acid component and a diamine component while suppressing imidization. Specific examples of the tetracarboxylic acid component include pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′. , 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoropropane-2,2-diphthalic dianhydride, 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1,2,3 , 4-Benzenetetracarboxylic dianhydride, 3,6-trifluoro-1,2,4,5-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 1,4-dimension Toxi-2,3,5,6-benzenetetracarboxylic dianhydride, 1,4-ditrimethylsilyl-2,3,5,6-benzenetetracarboxylic dianhydride, 1,4-bis (3,4 -Dicarboxylphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxylphenoxy) benzene dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, bis (3 , 4-Dicarboxylphenoxy) dimethylsilane dianhydride, bis (3,4-dicarboxylphenoxy) methylamine dianhydride, 4,4′-bis (3,4-dicarboxylphenoxy) biphenyl dianhydride, 4 , 4′-bis (3,4-dicarboxylphenoxy) diphenylsulfone dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5 6-pyridinetetracarboxylic dianhydride, 2,3,6,7-quinolinetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3,4 , 4'-diphenylsulfoxide tetracarboxylic dianhydride, 1,2,8,9-anthracene tetracarboxylic dianhydride, 1,4-bis (3,4-dicarboxylphenylsulfonyl) benzene dianhydride, 1 , 4-bis (3,4-dicarboxylphenylthio) benzene dianhydride, 3,3 ″, 4,4 ″ -terphenyltetracarboxylic dianhydride, 4-phenylbenzophenone-3,3 ′ ', 4,4 ″ -tetracarboxylic dianhydride, 1,4-bis (3,4-dicarboxylbenzoyl) -benzene dianhydride, 3,3 ′ ″, 4,4 ′ ″-quartylf Nyltetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxylphenoxy) benzophenone dianhydride, 4,4′-bis (3,4-dicarboxylphenoxy) diphenyl sulfoxide dianhydride, naphthalene Examples thereof include aromatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride and binaphthalene tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydrides represented by the following chemical formula (5). These aromatic tetracarboxylic dianhydrides may be used alone or in admixture of two or more. Moreover, these aromatic tetracarboxylic dianhydrides can be replaced by derivatives such as esterified products thereof.
また、非芳香族のテトラカルボン酸成分を用いてもよい。非芳香族のテトラカルボン酸成分としては、例えばブタン−１，２，３，４−テトラカルボン酸二無水物、ペンタン−１，２，４，５−テトラカルボン酸二無水物、シクロブタンテトラカルボン酸二無水物、シクロペンタン−１，２，３，４−テトラカルボン酸二無水物、シクロヘキサン−１，２，４，５−テトラカルボン酸二無水物、シクロヘキサ−１−エン−２，３，５，６−テトラカルボン酸二無水物、３−エチルシクロヘキサ−１−エン−３−（１，２），５，６−テトラカルボン酸二無水物、１−メチル−３−エチルシクロヘキサン−３−（１，２），５，６−テトラカルボン酸二無水物、１−メチル−３−エチルシクロヘキサ−１−エン−３−（１，２），５，６−テトラカルボン酸二無水物、１−エチルシクロヘキサン−１−（１，２），３，４−テトラカルボン酸二無水物、１−プロピルシクロヘキサン−１−（２，３），３，４−テトラカルボン酸二無水物、１，３−ジプロピルシクロヘキサン−１−（２，３），３−（２，３）−テトラカルボン酸二無水物、ジシクロヘキシル−３，４，３’，４’−テトラカルボン酸二無水物、ビシクロ［２．２．１］ヘプタン−２，３，５，６ラカルボン酸二無水物、１−プロピルシクロヘキサン−１−（２，３），３，４−テトラカルボン酸二無水物、１，３−ジプロピルシクロヘキサン−１−（２，３），３−（２，３）−テトラカルボン酸二無水物、ジシクロヘキシル−３，４，３’，４’−テトラカルボン酸二無水物、ビシクロ［２．２．１］ヘプタン−２，３，５，６−テトラカルボン酸二無水物、ビシクロ［２．２．２］オクタン−２，３，５，６−テトラカルボン酸二無水物、ビシクロ［２．２．２］オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物などのテトラカルボン酸二無水物を例示できる。これらのテトラカルボン酸二無水物は単独或いは２種類以上を混合して使用しても構わない。また、これらのテトラカルボン酸二無水物は、そのエステル化物などの誘導体で代替することもできる。 Further, a non-aromatic tetracarboxylic acid component may be used. Non-aromatic tetracarboxylic acid components include, for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutanetetracarboxylic acid Dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3,5 , 6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- 1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane- 2,3,5,6 lacarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2, 3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3 , 5,6-tetracarboxylic dianhydride, bicyclo [ .2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride And tetracarboxylic dianhydrides such as These tetracarboxylic dianhydrides may be used alone or in admixture of two or more. Further, these tetracarboxylic dianhydrides can be replaced by derivatives such as esterified products thereof.
本発明において、比較的低温あるいは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド樹脂成形体を好適に得るためには、これらのテトラカルボン酸成分のなかで芳香族テトラカルボン酸二無水物またはそのエステル化物などの誘導体を用いることが好ましい。さらに入手のしやすさ、取り扱いやすさ、優れた耐熱性や機械的物性を考慮すると、特にピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物など、或いはそれらのエステル化物などの誘導体を用いることが好ましい。 In the present invention, in order to suitably obtain a polyimide resin molded article having physical properties equivalent to or better than linear polyimide by heat treatment at a relatively low temperature or in a short time, among these tetracarboxylic acid components, It is preferable to use a derivative such as an aromatic tetracarboxylic dianhydride or an esterified product thereof. Furthermore, considering the availability, ease of handling, excellent heat resistance and mechanical properties, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 , 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, or derivatives thereof such as esterified products thereof are preferably used.
本発明で用いられるジアミン成分としては、例えばパラフェニレンジアミン、３，３'−ジメチル−４，４’−ジアミノビフェニル、２，２'−ジメチル−４，４'−ジアミノビフェニル、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、９，１０−ビス（４−アミノフェニル）アントラセン、４，４'−ジアミノベンゾフェノン、４，４'−ジアミノジフェニルスルホン、３，３'−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フォキシド、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〕スルホン、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−（４−アミノフェノキシ）フェニル〕エーテル、２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（４−アミノフェニル）プロパン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（３−アミノ−４−メチルフェニル）プロパン、メタフェニレンジアミン、４，４'−ジアミノジフェニルエーテル、４，４'−ジアミノジフェニルスルフィド、３，４'−ジアミノジフェニルエーテル、１，４−ビス（４− アミノフェノキシ）ベンゼン、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（３−アミノフェノキシ）ベンゼン、５−アミノ−２−（ｐ−アミノフェニル）ベンズオキサゾール、６−アミノ−２−（ｐ−アミノフェニル）ベンズオキサゾール、５−アミノ−２−（ｍ−アミノフェニル）ベンズオキサゾール、６−アミノ−２−（ｍ−アミノフェニル）ベンズオキサゾール、トルイジンジアミン、ジアミノポリシロキサンなどを挙げることができる。これらは、単独あるいは２種類以上混合して使用することができる。 Examples of the diamine component used in the present invention include paraphenylenediamine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, and 3,3′-. Dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4′-diaminobenzophenone, 4,4 ′ -Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl Sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxybiphenyl), [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2 -Bis (4-aminophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3 , 3,3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) propane, metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4 ′ -Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) ben 1,4-bis (3-aminophenoxy) benzene, 5-amino-2- (p-aminophenyl) benzoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, 5-amino-2 -(M-aminophenyl) benzoxazole, 6-amino-2- (m-aminophenyl) benzoxazole, toluidinediamine, diaminopolysiloxane, etc. These may be used alone or in combination of two or more. can do.
本発明において、比較的低温あるいは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド樹脂成形体を好適に得るためには、これらのジアミン成分うちで芳香族ジアミンを用いることが好ましい。さらに入手のしやすさ、取り扱いやすさ、優れた耐熱性や機械的物性を考慮すると、特にメタフェニレンジアミン、パラフェニレンジアミン、４，４’−ジアミノジフェニルエーテル、トルイジンジアミンなどを用いることが好ましい。 In the present invention, an aromatic diamine among these diamine components is preferably used in order to suitably obtain a polyimide resin molded article having physical properties equivalent to or better than linear polyimide by heat treatment at a relatively low temperature or in a short time. Is preferably used. Further, in view of easy availability, ease of handling, excellent heat resistance and mechanical properties, it is particularly preferable to use metaphenylene diamine, paraphenylene diamine, 4,4'-diaminodiphenyl ether, toluidine diamine and the like.
テトラカルボン酸成分とジアミン成分との組み合わせは、特に制限はないが、その組み合わせから得られたポリアミド酸を加熱処理して得られたポリイミドのガラス転移温度が２５０℃以上、より好ましくは２５５℃以上、さらに好ましくは２６０℃以上、特に好ましくは２７０℃以上になり得るものである。ガラス転移温度は、例えば示差走査熱量測定（ＤＳＣ）、動的粘弾性測定、熱機械分析（ＴＭＡ）などの方法で好適に測定することができる。 The combination of the tetracarboxylic acid component and the diamine component is not particularly limited, but the glass transition temperature of the polyimide obtained by heat treatment of the polyamic acid obtained from the combination is 250 ° C. or higher, more preferably 255 ° C. or higher. More preferably, it can be 260 ° C or higher, particularly preferably 270 ° C or higher. The glass transition temperature can be suitably measured by methods such as differential scanning calorimetry (DSC), dynamic viscoelasticity measurement, and thermomechanical analysis (TMA).
すなわち、本発明において、ポリアミド酸（Ａ）は、好ましくは芳香族テトラカルボン酸成分と芳香族ジアミン成分とからなる芳香族ポリアミド酸であり、より好ましくはポリアミド酸を加熱処理して得られたポリイミドのガラス転移温度が２５０℃以上、より好ましくは２５５℃以上、さらに好ましくは２６０℃以上、特に好ましくは２７０℃以上になり得るものであり、さらに好ましくは前記化学式（２）の繰り返し単位を有するものである。 That is, in the present invention, the polyamic acid (A) is preferably an aromatic polyamic acid composed of an aromatic tetracarboxylic acid component and an aromatic diamine component, and more preferably a polyimide obtained by heat-treating the polyamic acid. The glass transition temperature of the resin is such that it can be 250 ° C. or higher, more preferably 255 ° C. or higher, more preferably 260 ° C. or higher, particularly preferably 270 ° C. or higher, and more preferably having the repeating unit of the chemical formula (2). It is.
本発明に用いられるポリアミド酸の調製方法に制限はなく公知の方法を好適に用いることができる。例えば、テトラカルボン酸二無水物とジアミンとを、不活性雰囲気ガス下、ポリアミド酸濃度が５〜６０質量％となるような濃度で、有機溶媒中で０．５〜７８時間反応させることにより好適に得ることができる。その際、例えばイ）ジアミンを溶解した溶液に酸二無水物を一度にあるいは数回に分割して加えて反応させる、ロ）溶媒にジアミンと酸二無水物を一度に加えて反応させる、ハ）ジアミンと酸二無水物をおのおの数回に分割して加えて反応させる、ことにより好適に調製できる。反応温度はイミド化反応を抑制できる温度範囲であればよく、好ましくは５〜８０℃、より好ましくは１０〜７０℃、さらに好ましくは１０〜６５℃の温度範囲である。５℃より低いと反応が遅くなり長時間かかり、８０℃より高いとイミド化反応が進行して析出などを生じる恐れがあることから好ましくない。 There is no restriction | limiting in the preparation method of the polyamic acid used for this invention, A well-known method can be used suitably. For example, tetracarboxylic dianhydride and diamine are preferably reacted in an organic solvent for 0.5 to 78 hours in an inert atmosphere at a concentration such that the polyamic acid concentration is 5 to 60% by mass. Can get to. In this case, for example, a) acid dianhydride is added to a solution in which diamine is dissolved at a time or divided into several times for reaction, and b) diamine and acid dianhydride are added to the solvent at a time for reaction. ) A diamine and an acid dianhydride can be suitably prepared by adding them in several portions and reacting them. The reaction temperature should just be a temperature range which can suppress imidation reaction, Preferably it is 5-80 degreeC, More preferably, it is 10-70 degreeC, More preferably, it is a temperature range of 10-65 degreeC. If it is lower than 5 ° C., the reaction is delayed and takes a long time. If it is higher than 80 ° C., the imidization reaction may proceed to cause precipitation, which is not preferable.
ポリアミド酸の調製に用いられる有機溶剤は、ポリアミド酸の調製に用いられる公知の溶剤を好適に用いることができるが、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，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチルカプロラクタム、ヘキサメチルホスホロトリアミド、１，２−ジメトキシエタン、ビス（２−メトキシエチル）エーテル、１，２−ビス（２−メトキシエトキシ）エタン、テトラヒドロフラン、ビス［２−（２−メトキシエトキシ）エチル］エーテル、１，４−ジオキサン、ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソールなどが挙げられる。これらの溶剤は、単独または２種以上混合して使用しても差し支えない。 As the organic solvent used for the preparation of the polyamic acid, known solvents used for the preparation of the polyamic acid can be preferably used. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethyl Acetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, 1,2-dimethoxyethane, bis ( 2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, Sulfolane, diphenylsulfone, tetramethylurine , Such as anisole, and the like. These solvents may be used alone or in combination of two or more.
本発明のポリアミド酸を構成するジアミン成分とテトラカルボン酸成分とのモル比［ジアミン成分のモル数／テトラカルボン酸成分のモル数］は、０．９８〜１．０５、好ましくは０．９８５〜１．０４５、より好ましくは０．９８５〜０．９９９或いは１．００１〜１．０４０、さらに好ましくは０．９９０〜０．９９９或いは１．００１〜１．０４０の範囲である。この範囲外では加熱処理の際のポリイミドの分子量の増加が十分でなくなり、得られるポリイミド樹脂成形体の物性が低下することがあるので好ましくない。
本発明のポリアミド酸は対数粘度（Ｎ−メチル−２−ピロリドン溶媒中、濃度０．５ｇ／１００ｍｌ、３０℃）で０．０１〜４の範囲が好適である。
The molar ratio [number of moles of diamine component / number of moles of tetracarboxylic acid component] of the diamine component and the tetracarboxylic acid component constituting the polyamic acid of the present invention is 0.98 to 1.05, preferably 0.985. The range is 1.045, more preferably 0.985 to 0.999 or 1.001 to 1.040, and still more preferably 0.990 to 0.999 or 1.001 to 1.040. Outside this range, the increase in the molecular weight of the polyimide during the heat treatment is not sufficient, and the physical properties of the resulting polyimide resin molded article may be lowered, which is not preferable.
The polyamic acid of the present invention preferably has a logarithmic viscosity (concentration of 0.5 g / 100 ml, 30 ° C. in N-methyl-2-pyrrolidone solvent) in the range of 0.01 to 4.
本発明のポリイミド前駆体溶液組成物は、前記のようにして調製したポリアミド酸（Ａ）溶液に、メリット酸化合物（Ｂ）を添加し、比較的低温好ましくは常温で必要に応じて攪拌・溶解することによって好適に得ることができる。
なお、ポリイミド前駆体溶液組成物を調製する際に用いるポリアミド酸溶液は、調製したポリアミド酸溶液をそのまま用いてもよく、また有機溶剤を除去して単離したポリアミド酸を再度有機溶剤に溶解させて用いても構わない。
The polyimide precursor solution composition of the present invention is obtained by adding the merit acid compound (B) to the polyamic acid (A) solution prepared as described above, and stirring and dissolving as necessary at a relatively low temperature, preferably at normal temperature. By doing so, it can be suitably obtained.
The polyamic acid solution used for preparing the polyimide precursor solution composition may be the prepared polyamic acid solution as it is, or the polyamic acid isolated by removing the organic solvent is dissolved again in the organic solvent. May be used.
ポリイミド前駆体溶液組成物を調製する際に用いるポリアミド酸（Ａ）溶液の濃度は、３〜６０質量％、好ましくは５〜５０質量％、より好ましくは５〜４０質量％、さらに好ましくは５〜３５質量％の範囲である。濃度が５質量％未満では、加熱処理によって除去する有機溶媒の量が多くなるから好ましくなく、一方６０質量％を越えると、溶液の粘度が高くなって成形が難くなることから好ましくない。また、有機溶剤は、ポリアミド酸の調製に用いられる前述の有機溶剤を好適に用いることができる。 The concentration of the polyamic acid (A) solution used when preparing the polyimide precursor solution composition is 3 to 60% by mass, preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 5% by mass. It is in the range of 35% by mass. If the concentration is less than 5% by mass, the amount of the organic solvent to be removed by heat treatment increases, which is not preferable. On the other hand, if it exceeds 60% by mass, the viscosity of the solution increases and molding becomes difficult. Moreover, the above-mentioned organic solvent used for preparation of a polyamic acid can be used suitably as an organic solvent.
メリット酸化合物の添加量は、ポリアミド酸（Ａ）を構成するジアミン成分のモル数を１としたときに、０．００１〜０．０５倍モル、より好ましくは０．００１〜０．０４倍モル、さらに好ましくは０．００１５〜０．０３倍モルの範囲である。添加量が０．００１倍モルより少ないと本発明の効果を得るのが難しくなり、一方０．０５倍モルより多いと、得られるポリイミド樹脂成形体の物性が低下することがあるので好ましくない。 The addition amount of the merit acid compound is 0.001 to 0.05 times mol, more preferably 0.001 to 0.04 times mol, when the number of moles of the diamine component constituting the polyamic acid (A) is 1. More preferably, it is in the range of 0.0015 to 0.03 moles. If the addition amount is less than 0.001 mol, it is difficult to obtain the effect of the present invention. On the other hand, if the addition amount is more than 0.05 mol, the physical properties of the resulting polyimide resin molded product may be deteriorated.
本発明のポリイミド前駆体溶液組成物では、前記ポリアミド酸（Ａ）の調製に好適に用いることができる溶剤以外でも、溶解性を損なわない範囲で、ポリアミド酸の貧溶媒を添加してもよい。貧溶媒の具体例としては、例えばキシレン、エチルセロソルブ、ジグライム、ジオキサンや、メタノ−ル、エタノ−ル、ｎ−プロパノ−ル、ｉｓｏ−プロパノ−ル、ｎ−ブタノ−ル、ｓｅｃ−ブタノ−ル、ｎ−アミルアルコ−ル、ｎ−ヘキサノ−ル、ｎ−ヘプタノ−ル等のアルコ−ル類を挙げることができる。 In the polyimide precursor solution composition of this invention, you may add the poor solvent of a polyamic acid in the range which does not impair solubility other than the solvent which can be used suitably for preparation of the said polyamic acid (A). Specific examples of the poor solvent include xylene, ethyl cellosolve, diglyme, dioxane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol. , N-amyl alcohol, n-hexanol, n-heptanol and the like.
本発明のポリイミド前駆体溶液組成物は、低粘度化などの粘度調節や高濃度化が容易である。さらに溶液粘度は安定しており、且つ比較的低温或いは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得ることができる。加熱処理の方法は、通常のポリイミドを得る公知の方法を用いることができるが、例えば基材上にポリイミド前駆体溶液組成物を塗布・流延した後、得られた塗膜を例えば熱風乾燥機を用いて比較的低温で加熱処理して溶媒を除去した後、そのままの状態で、或いは必要に応じて基材から剥離して、さらに高温で加熱処理することによりポリイミド樹脂成形体（ポリイミド膜）とすることができる。このとき、加熱処理の最高温度は、好ましくは１８０〜５００℃、より好ましくは１９０〜４８０℃、さらに好ましくは２００〜４７０℃、特に好ましくは２１０〜４６０℃の範囲である。加熱処理の最高温度が１８０℃より低いとイミド化に長時間を必要とすること、またポリイミド樹脂成形体の物性が低くなることから好ましくなく、一方、５００℃を越えるとポリイミド樹脂の熱分解が進行し、物性の低下をもたらすことがあるから好ましくない。 The polyimide precursor solution composition of the present invention can be easily adjusted in viscosity such as lowering viscosity or increased in concentration. Furthermore, a polyimide resin molded body such as a polyimide film having a stable property viscosity and a physical property equivalent to or superior to that of linear polyimide can be suitably obtained by heat treatment at a relatively low temperature or in a short time. . As the heat treatment method, a known method for obtaining a normal polyimide can be used. For example, after applying and casting a polyimide precursor solution composition on a substrate, the obtained coating film is subjected to, for example, a hot air dryer. After removing the solvent by heat treatment at a relatively low temperature using a polyimide resin molded body (polyimide film) as it is or after peeling from the substrate as necessary, and heat treatment at a higher temperature It can be. At this time, the maximum temperature of the heat treatment is preferably in the range of 180 to 500 ° C, more preferably 190 to 480 ° C, still more preferably 200 to 470 ° C, and particularly preferably 210 to 460 ° C. When the maximum temperature of the heat treatment is lower than 180 ° C., it is not preferable because it requires a long time for imidization, and the physical properties of the polyimide resin molded article are lowered. On the other hand, when the temperature exceeds 500 ° C., the thermal decomposition of the polyimide resin is not preferable. This is not preferable because it may progress and cause a decrease in physical properties.
本発明のポリイミド前駆体溶液組成物は、限定するものではないが、ポリアミック酸濃度が３〜６０質量％、好ましくは５〜５０質量％、より好ましくは５〜３５質量％であって、溶液粘度は、限定するものではないが、２５℃において０．１〜３０００ポイズ、好ましくは０．１〜１０００ポイズ、より好ましくは０．５〜５００ポイズ、特に好ましくは１〜２００ポイズである。また、本発明のポリイミド前駆体溶液組成物は、その用途に応じて、有機あるいは無機の添加剤、例えば増量剤、充填剤、強化材、顔料、染料、剥離剤などを好適に含有することができる。 The polyimide precursor solution composition of the present invention is not limited, but the polyamic acid concentration is 3 to 60% by mass, preferably 5 to 50% by mass, more preferably 5 to 35% by mass, and the solution viscosity. Although it does not limit, it is 0.1-3000 poise in 25 degreeC, Preferably it is 0.1-1000 poise, More preferably, it is 0.5-500 poise, Most preferably, it is 1-200 poise. Further, the polyimide precursor solution composition of the present invention may suitably contain an organic or inorganic additive such as a filler, a filler, a reinforcing material, a pigment, a dye, a release agent, etc., depending on the application. it can.
以下、本発明を実施例により更に具体的に説明するが、これら実施例に限定されるものではない。実施例で用いた特性の測定方法を以下に示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to these Examples. A method for measuring the characteristics used in the examples is shown below.
＜溶液粘度＞
ポリアミド酸溶液組成物或いはポリイミド前駆体溶液組成物の溶液粘度は、２５℃でＥ型粘度計を用いて測定した。
<Viscosity of solution>
The solution viscosity of the polyamic acid solution composition or the polyimide precursor solution composition was measured at 25 ° C. using an E-type viscometer.
＜機械的物性（引張試験）＞
引張試験は、２５℃、５０％ＲＨの雰囲気で、島津製作所社製 ＥＺＴｓｅｔを用いて、ダンベル型の試験片を５ｍｍ／分の速度で引っ張ることにより行った。引っ張り破断データから弾性率、破断伸び、破断強度を求めた。試験片は、標点間距離２６．３２ｍｍ、幅４ｍｍのものを用いた。各試料に関して、ｎ数を５以上となるように測定を行い、その算術平均を求めた。
<Mechanical properties (tensile test)>
The tensile test was performed by pulling a dumbbell-shaped test piece at a speed of 5 mm / min using EZTset manufactured by Shimadzu Corporation in an atmosphere of 25 ° C. and 50% RH. The elastic modulus, elongation at break, and strength at break were determined from the tensile break data. The test piece used was a distance between gauge points of 26.32 mm and a width of 4 mm. About each sample, it measured so that n number might be set to 5 or more, and calculated | required the arithmetic mean.
〔実施例１〕
４，４’−ジアミノジフェニルエーテル（以下、ＯＤＡと略記することもある）２０．０２ｇ（０．１００モル）を、Ｎ−メチル−２−ピロリドン（以下、ＮＭＰと略記することもある）２２１ｇに溶解した溶液に、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（以下、ＢＰＤＡと略記することもある）２８．５４ｇ（０．０９７モル）を添加し、２５℃で、ＢＰＤＡが溶解して粘調溶液となるまで２４時間攪拌して、ポリアミド酸溶液を得た。この溶液のポリアミド酸濃度は１８質量％であり、粘度は４１ポイズであった。この溶液に、メリット酸を０．６８ｇ（０．００２モル、ＯＤＡに対して０．０２倍モル）を添加して、ポリアミド酸溶液組成物を調整した。得られたポリイミド前駆体溶液組成物の粘度は４１ポイズで、室温で３日間保存してもほとんど変化しなかった。
得られたポリイミド前駆体溶液組成物を、ガラス板上に流延し、１２０℃で３０分間熱風乾燥した。さらに、ガラス板から剥離後、金属枠に固定して、２５０℃で１０分間加熱して厚みが４０μｍのポリイミド膜を得た。更にそのポリイミド膜を３５０℃で１０分間加熱したポリイミド膜も得た。得られたポリイミド膜の特性を表１に示す。
[Example 1]
Dissolve 20.02 g (0.100 mol) of 4,4′-diaminodiphenyl ether (hereinafter also abbreviated as ODA) in 221 g of N-methyl-2-pyrrolidone (hereinafter also abbreviated as NMP). 28.54 g (0.097 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as BPDA) was added to the solution, and BPDA was added at 25 ° C. Was dissolved for 24 hours until it became a viscous solution to obtain a polyamic acid solution. The polyamic acid concentration of this solution was 18% by mass, and the viscosity was 41 poise. To this solution, 0.68 g (0.002 mol, 0.02 mol per mol of ODA) of merit acid was added to prepare a polyamic acid solution composition. The viscosity of the obtained polyimide precursor solution composition was 41 poise, and hardly changed even when stored for 3 days at room temperature.
The obtained polyimide precursor solution composition was cast on a glass plate and dried with hot air at 120 ° C. for 30 minutes. Furthermore, after peeling from the glass plate, it was fixed to a metal frame and heated at 250 ° C. for 10 minutes to obtain a polyimide film having a thickness of 40 μm. Furthermore, the polyimide film which heated the polyimide film for 10 minutes at 350 degreeC was also obtained. The properties of the obtained polyimide film are shown in Table 1.
〔比較例１〕
メリット酸を添加せず、代わりに３，３’，４，４’−ビフェニルテトラカルボン酸（以下、ＢＰＴＡと略記することがある）を１．１０ｇ（０．００３モル）添加したこと以外は、実施例１と同様にしてポリイミド前駆体溶液組成物を調製した。このときのアミン成分に対するＢＰＴＡのカルボン酸基の割合は、実施例１のアミン成分に対するメリット酸のカルボン酸基の割合と同じである。
得られたポリイミド前駆体溶液組成物を用いて、実施例1と同様にしてポリイミド膜を得た。得られたポリイミド膜の特性を表１に示す。
[Comparative Example 1]
Instead of adding merit acid, instead of adding 1.10 g (0.003 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic acid (hereinafter sometimes abbreviated as BPTA), A polyimide precursor solution composition was prepared in the same manner as in Example 1. The ratio of the carboxylic acid group of BPTA to the amine component at this time is the same as the ratio of the carboxylic acid group of merit acid to the amine component of Example 1.
A polyimide film was obtained in the same manner as Example 1 using the obtained polyimide precursor solution composition. The properties of the obtained polyimide film are shown in Table 1.
比較例１で得られるポリイミドは実施例１で用いられたポリアミド酸（Ａ）のテトラカルボン酸成分とジアミン成分とを略等モルにして得られた直鎖状ポリイミドである。
実施例１のポリイミド膜の物性は、比較例１と比較して低温加熱時に特に高く、また３５０℃で熱処理した場合でも比較例１と同等か上回った。
The polyimide obtained in Comparative Example 1 is a linear polyimide obtained by making the tetracarboxylic acid component and the diamine component of the polyamic acid (A) used in Example 1 substantially equimolar.
The physical properties of the polyimide film of Example 1 were particularly high when heated at a low temperature as compared with Comparative Example 1, and even when heat-treated at 350 ° C., the physical properties were equal to or higher than those of Comparative Example 1.
本発明によって、溶液の粘度調節が容易であり、溶液粘度が安定しており、且つ比較的低温或いは短時間の加熱処理によって直鎖状ポリイミドと同等あるいはそれ以上に優れた物性を有するポリイミド膜などのポリイミド樹脂成形体を好適に得ることができるポリイミド前駆体溶液組成物を提供することができる。 According to the present invention, the viscosity of the solution can be easily adjusted, the solution viscosity is stable, and a polyimide film having physical properties equivalent to or better than linear polyimide by heat treatment at a relatively low temperature or in a short time The polyimide precursor solution composition which can obtain suitably the polyimide resin molding can be provided.
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| US13/125,451 US9334368B2 (en) | 2008-10-31 | 2009-10-28 | Polyimide precursor solution composition |
| KR1020117008423A KR101657113B1 (en) | 2008-10-31 | 2009-10-28 | Polyimide precursor solution composition |
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| JP2017106027A (en) * | 2013-10-23 | 2017-06-15 | アクロン ポリマー システムズ，インク． | Resin composition, method for manufacturing resin composition, substrate for manufacturing electronic element, and electronic device |
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