JP5822064B2 - Method for producing aromatic polyimide seamless belt - Google Patents
Method for producing aromatic polyimide seamless belt Download PDFInfo
- Publication number
- JP5822064B2 JP5822064B2 JP2011154912A JP2011154912A JP5822064B2 JP 5822064 B2 JP5822064 B2 JP 5822064B2 JP 2011154912 A JP2011154912 A JP 2011154912A JP 2011154912 A JP2011154912 A JP 2011154912A JP 5822064 B2 JP5822064 B2 JP 5822064B2
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- JP
- Japan
- Prior art keywords
- seamless belt
- aromatic
- aromatic polyimide
- producing
- polyimide seamless
- Prior art date
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- 239000004642 Polyimide Substances 0.000 title claims description 165
- 229920001721 polyimide Polymers 0.000 title claims description 165
- 125000003118 aryl group Chemical group 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- 239000002243 precursor Substances 0.000 claims description 85
- 239000000203 mixture Substances 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 229920005575 poly(amic acid) Polymers 0.000 claims description 42
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 39
- 239000003960 organic solvent Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 23
- 150000002460 imidazoles Chemical class 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 19
- 150000004984 aromatic diamines Chemical class 0.000 claims description 18
- 239000003125 aqueous solvent Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- QEFLNYXPYKZGEX-UHFFFAOYSA-N 4-ethyl-1-methylimidazole Chemical compound CCC1=CN(C)C=N1 QEFLNYXPYKZGEX-UHFFFAOYSA-N 0.000 claims description 3
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims description 3
- 238000001175 rotational moulding Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 61
- 239000002904 solvent Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 239000007810 chemical reaction solvent Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 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 5
- 239000011231 conductive filler Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 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 3
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 3
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical class 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 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- 229920001780 ECTFE Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-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
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000003756 stirring Methods 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
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- QRUWUSOUUMPANJ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-carboxyphenyl)methyl]benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1CC1=CC=C(N)C(C(O)=O)=C1 QRUWUSOUUMPANJ-UHFFFAOYSA-N 0.000 description 1
- UINDRJHZBAGQFD-UHFFFAOYSA-N 2-ethyl-1-methylimidazole Chemical compound CCC1=NC=CN1C UINDRJHZBAGQFD-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical class 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
- 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
- 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
- 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
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- QQPYIXJPRJQUDC-UHFFFAOYSA-N 5-(3-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=C(C=CC=2)C=2C=CC=CC=2)=C1C(O)=O QQPYIXJPRJQUDC-UHFFFAOYSA-N 0.000 description 1
- JJJDAERKXDTMPH-UHFFFAOYSA-N 5-(4-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=C1C(O)=O JJJDAERKXDTMPH-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Fixing For Electrophotography (AREA)
- Electrophotography Configuration And Component (AREA)
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、ポリイミド前駆体水溶液組成物を用いた芳香族ポリイミドシームレスベルトの製造方法に関する。このポリイミド前駆体水溶液組成物を用いて得られる芳香族ポリイミドシームレスベルトの製造方法は、ポリイミド前駆体のポリアミック酸を有機溶媒に溶解したポリイミド前駆体溶液組成物を用いた場合に較べて環境適応性が高いので好適である。しかも、このポリイミド前駆体水溶液組成物を加熱処理して得られる芳香族ポリイミドシームレスベルトは、好ましくは結晶性が高く、耐熱性、機械的強度、電気特性、耐溶剤性などの優れた特性を有することができる。したがって、特に耐熱性、電気抵抗の安定性、高い強靭性が要求される電子写真装置の中間転写用シームレスベルト或いは定着用シームレスベルトとして好適に用いることができる。 The present invention relates to a method for producing an aromatic polyimide seamless belt using a polyimide precursor aqueous solution composition. The method for producing an aromatic polyimide seamless belt obtained using this polyimide precursor aqueous solution composition is more environmentally friendly than using a polyimide precursor solution composition obtained by dissolving a polyamic acid of a polyimide precursor in an organic solvent. Is preferable. Moreover, the aromatic polyimide seamless belt obtained by heat-treating this polyimide precursor aqueous solution composition preferably has high crystallinity and has excellent characteristics such as heat resistance, mechanical strength, electrical characteristics, and solvent resistance. be able to. Accordingly, it can be suitably used as a seamless belt for intermediate transfer or a seamless belt for fixing of an electrophotographic apparatus that requires particularly heat resistance, stability of electric resistance, and high toughness.
芳香族テトラカルボン酸二無水物と芳香族ジアミンから得られる芳香族ポリイミドは、耐熱性、機械的強度、電気特性、耐溶剤性などの特性が優れるために、電気電子産業分野などで広く用いられている。しかし、芳香族ポリイミドは有機溶媒への溶解性が悪いので、通常は、ポリイミド前駆体のポリアミック酸を有機溶媒に溶解した溶液組成物を、例えば基材表面上に塗布し、次いで高温で加熱して脱水閉環（イミド化）させることで芳香族ポリイミドを得ている。このように有機溶媒を用いることや高温での加熱処理が必要なことから環境面で必ずしも好適ではなく、場合によっては用途が限定されることもあった。 Aromatic polyimides obtained from aromatic tetracarboxylic dianhydrides and aromatic diamines have excellent heat resistance, mechanical strength, electrical properties, solvent resistance, and other properties, so they are widely used in the electrical and electronics industries. ing. However, since aromatic polyimides have poor solubility in organic solvents, a solution composition in which a polyimide precursor polyamic acid is dissolved in an organic solvent is usually applied onto a substrate surface, and then heated at a high temperature. Thus, aromatic polyimide is obtained by dehydration ring closure (imidization). As described above, the use of an organic solvent and the heat treatment at a high temperature are necessary, so that it is not necessarily suitable in terms of the environment, and the use may be limited in some cases.
このため、水溶性ポリイミド前駆体が提案されている。特許文献１には、有機溶媒中で得られたポリアミド酸を加水分解した後で水中に投入してポリアミド酸粉末を得、そのポリアミド酸粉末をさらに温水中で粉砕したり洗浄したりした後で、２−メチルアミノジエタノールなどの特定のアミン化合物と混合して水溶性ポリアミド酸塩を得ることが提案されている。しかし、この水溶性ポリアミド酸塩からなるポリイミド前駆体組成物は、高分子量化し難く、また得られるポリイミドの特性も改良の余地があった。 For this reason, a water-soluble polyimide precursor has been proposed. In Patent Document 1, after the polyamic acid obtained in an organic solvent is hydrolyzed and then poured into water to obtain a polyamic acid powder, the polyamic acid powder is further pulverized and washed in warm water. It has been proposed to obtain a water-soluble polyamic acid salt by mixing with a specific amine compound such as 2-methylaminodiethanol. However, the polyimide precursor composition comprising this water-soluble polyamic acid salt is difficult to achieve a high molecular weight, and there is room for improvement in the properties of the resulting polyimide.
特許文献２には、有機溶媒中で得られたポリアミック酸と１，２−ジメチルイミダゾ−ル及び／又は１−メチル−２−エチルイミダゾ−ルとの反応混合物から分離取得した水溶性ポリイミド前駆体が提案されている。しかし、この水溶性ポリイミド前駆体は、有機溶媒中で水溶性ポリイミド前駆体を調製後、分離することによって得られる。得られた水溶性ポリイミド前駆体は水溶媒に溶解されて水溶液組成物が得られるが、有機溶媒中で調製された水溶性ポリイミド前駆体から有機溶媒を完全に除去できない（完全に除去しようとして加熱処理するとイミド化が起こり溶解性がなくなる）ために、水溶液組成物中に有機溶媒が同伴するなどの問題があった。さらに、ここで提案された水溶性ポリイミド前駆体は、得られるポリイミドが非結晶性で熱融着性を有しており、有機あるいは無機繊維製の織物あるいは不織布の結合剤として好適に用いられるものである。すなわち、ポリイミド前駆体水溶性組成物を用いて芳香族ポリイミドシームレスベルトを製造することについては記載されていない。 Patent Document 2 discloses a water-soluble polyimide precursor obtained separately from a reaction mixture of a polyamic acid obtained in an organic solvent and 1,2-dimethylimidazole and / or 1-methyl-2-ethylimidazole. Has been proposed. However, this water-soluble polyimide precursor can be obtained by preparing a water-soluble polyimide precursor in an organic solvent and then separating it. The obtained water-soluble polyimide precursor is dissolved in an aqueous solvent to obtain an aqueous solution composition, but the organic solvent cannot be completely removed from the water-soluble polyimide precursor prepared in the organic solvent (heating to remove completely). When treated, imidization occurs and the solubility is lost), and there is a problem that an organic solvent is accompanied in the aqueous solution composition. Furthermore, the water-soluble polyimide precursor proposed here has a non-crystalline and heat-fusible polyimide, and is suitably used as a binder for woven or non-woven fabrics made of organic or inorganic fibers. It is. That is, there is no description about producing an aromatic polyimide seamless belt using a polyimide precursor water-soluble composition.
本発明の目的は、水溶媒からなる環境適応性が良好なポリイミド前駆体水溶液組成物を用いた芳香族ポリイミドシームレスベルトの製造方法を提案することである。このポリイミド前駆体水溶液組成物は、好ましくは高分子量のポリアミック酸からなり、また溶媒が水以外の有機溶媒を含まない。また、本発明の製造方法によって得られる芳香族ポリイミドシームレスベルトは、好ましくは結晶性が高く、耐熱性、機械的強度、電気特性、耐溶剤性などの優れた特性を有するために、電子写真装置の中間転写用或いは定着用シームレスベルトとして好適に用いることができる。 An object of the present invention is to propose a method for producing an aromatic polyimide seamless belt using a polyimide precursor aqueous solution composition having an excellent environmental adaptability comprising an aqueous solvent. This polyimide precursor aqueous solution composition preferably comprises a high molecular weight polyamic acid, and the solvent does not contain an organic solvent other than water. The aromatic polyimide seamless belt obtained by the production method of the present invention preferably has high crystallinity, and has excellent characteristics such as heat resistance, mechanical strength, electrical characteristics, and solvent resistance. Can be suitably used as a seamless belt for intermediate transfer or fixing.
本発明は、特に以下の各項に関する。 The present invention particularly relates to the following items.
１． テトラカルボン酸成分とジアミン成分とが反応して得られる、下記化学式（１）で表される繰返し単位からなるポリアミック酸が、前記ポリアミック酸のテトラカルボン酸成分に対して１．６倍モル以上のイミダゾール類と共に、水溶媒中に溶解してなるポリイミド前駆体水溶液組成物を加熱処理する工程を含むことを特徴とする芳香族ポリイミドシームレスベルトの製造方法。 1. A polyamic acid comprising a repeating unit represented by the following chemical formula (1) obtained by reacting a tetracarboxylic acid component and a diamine component is 1.6 times mol or more with respect to the tetracarboxylic acid component of the polyamic acid. The manufacturing method of the aromatic polyimide seamless belt characterized by including the process of heat-processing the polyimide precursor aqueous solution composition melt | dissolved in a water solvent with imidazole.
２． イミダゾール類が、置換基として２個以上のアルキル基を有するイミダゾール類であることを特徴とする前記項１に記載の芳香族ポリイミドシームレスベルトの製造方法。 2. Item 2. The method for producing an aromatic polyimide seamless belt according to Item 1, wherein the imidazole is an imidazole having two or more alkyl groups as a substituent.
３． イミダゾール類が、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、４−エチル−２−メチルイミダゾール、及び１−メチル−４−エチルイミダゾールからなる群から選択されるイミダゾール類であることを特徴とする前記項１または２に記載の芳香族ポリイミドシームレスベルトの製造方法。 3. The imidazole is an imidazole selected from the group consisting of 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, and 1-methyl-4-ethylimidazole. Item 3. The method for producing an aromatic polyimide seamless belt according to Item 1 or 2, wherein
４． ポリイミド前駆体水溶液組成物が、水以外の有機溶媒を実質的に含まないことを特徴とする前記項１〜３のいずれかに記載の芳香族ポリイミドシームレスベルトの製造方法。 4). Item 4. The method for producing an aromatic polyimide seamless belt according to any one of Items 1 to 3, wherein the polyimide precursor aqueous solution composition contains substantially no organic solvent other than water.
５． ポリアミック酸の対数粘度が０．２以上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芳香族ポリイミドシームレスベルトの製造方法。 5. Item 5. The method for producing an aromatic polyimide seamless belt according to any one of Items 1 to 4, wherein the polyamic acid has a logarithmic viscosity of 0.2 or more.
６． Ａが、下記化学式（２）〜（７）のいずれか或いはそれらの混合物であることを特徴とする前記項１〜５のいずれかに記載の芳香族ポリイミドシームレスベルトの製造方法。 6). A is any one of following chemical formula (2)-(7), or those mixtures, The manufacturing method of the aromatic polyimide seamless belt in any one of said claim | item 1-5 characterized by the above-mentioned.
７． Ｂが、１〜２個の芳香族環を有する芳香族ジアミンからアミノ基を除いた２価の基であることを特徴とする前記項１〜６のいずれかに記載の芳香族ポリイミドシームレスベルトの製造方法。 7). The aromatic polyimide seamless belt according to any one of Items 1 to 6, wherein B is a divalent group obtained by removing an amino group from an aromatic diamine having 1 to 2 aromatic rings. Production method.
８． Ｂが、下記化学式（８）〜（９）のいずれか或いはそれらの混合物であることを特徴とする前記項１〜７のいずれかに記載の芳香族ポリイミドシームレスベルトの製造方法。 8). The manufacturing method of the aromatic polyimide seamless belt according to any one of Items 1 to 7, wherein B is any one of the following chemical formulas (8) to (9) or a mixture thereof.
９． 得られるシームレスベルトが中間転写ベルトであることを特徴とする前記項１〜８のいずれかに記載の芳香族ポリイミドシームレスベルトの製造方法。 9. Item 9. The method for producing an aromatic polyimide seamless belt according to any one of Items 1 to 8, wherein the obtained seamless belt is an intermediate transfer belt.
１０． 得られるシームレスベルトが定着ベルトであることを特徴とする前記項１〜８のいずれかに記載の芳香族ポリイミドシームレスベルトの製造方法。 10. Item 9. The method for producing an aromatic polyimide seamless belt according to any one of Items 1 to 8, wherein the obtained seamless belt is a fixing belt.
１１． 回転成形法で芳香族ポリイミドシームレスベルトを製造することを特徴とする前記項１〜１０のいずれかに記載の芳香族ポリイミドシームレスベルトの製造方法。 11. Item 11. The method for producing an aromatic polyimide seamless belt according to any one of Items 1 to 10, wherein an aromatic polyimide seamless belt is produced by a rotational molding method.
本発明によって、水溶媒からなる環境適応性が良好なポリイミド前駆体水溶液組成物を用いた芳香族ポリイミドシームレスベルトの製造方法を提案することができる。このポリイミド前駆体水溶液組成物は、好ましくはポリアミック酸が高分子量であり、また溶媒が水以外の有機溶媒を含まない。また、本発明の製造方法によって得られる芳香族ポリイミドシームレスベルトは、好ましくは結晶性が高く、耐熱性、機械的強度、電気特性、耐溶剤性などの優れた特性を有するために、電子写真装置の中間転写用シームレスベルト或いは定着用シームレスベルトとして好適に用いることができる。 According to the present invention, it is possible to propose a method for producing an aromatic polyimide seamless belt using a polyimide precursor aqueous solution composition having good environmental adaptability, which comprises an aqueous solvent. In this polyimide precursor aqueous solution composition, the polyamic acid preferably has a high molecular weight, and the solvent does not contain an organic solvent other than water. The aromatic polyimide seamless belt obtained by the production method of the present invention preferably has high crystallinity, and has excellent characteristics such as heat resistance, mechanical strength, electrical characteristics, and solvent resistance. The intermediate transfer seamless belt or the fixing seamless belt can be suitably used.
本発明の芳香族ポリイミドシームレスベルトの製造方法は、前記化学式（１）で表される繰返し単位からなるポリアミック酸が、前記ポリアミック酸のカルボキシル基に対して０．８倍当量以上のイミダゾール類と共に、水溶媒中に均一に溶解してなるポリイミド前駆体水溶液組成物を、基材の表面に塗布或いは吹き付けしてポリイミド前駆体水溶液組成物層からなる塗膜を形成し、そのポリイミド前駆体水溶液組成物を加熱処理することを特徴とする。 In the method for producing an aromatic polyimide seamless belt of the present invention, the polyamic acid composed of the repeating unit represented by the chemical formula (1) is 0.8 times equivalent or more imidazoles with respect to the carboxyl group of the polyamic acid, A polyimide precursor aqueous solution composition that is uniformly dissolved in an aqueous solvent is applied or sprayed onto the surface of a substrate to form a coating film composed of a polyimide precursor aqueous solution composition layer, and the polyimide precursor aqueous solution composition Is heat-treated.
本発明のポリイミド前駆体水溶液組成物を構成するポリアミック酸は、化学式（１）で表される繰返し単位からなる。
The polyamic acid which comprises the polyimide precursor aqueous solution composition of this invention consists of a repeating unit represented by Chemical formula (1).
化学式（１）のＡは、テトラカルボン酸からカルボキシル基を除いた４価の基であって、好ましくは前記化学式（２）〜（７）或いはそれらの混合物である。すなわち、本発明で用いるポリアミック酸のテトラカルボン酸成分は、テトラカルボン酸類（テトラカルボン酸、その二無水物或いはエステル化物など）であって、例えば、３，３’，４，４’−ビフェニルテトラカルボン酸類、２，３，３’，４’−ビフェニルテトラカルボン酸類、２，２’，３，３’−ビフェニルテトラカルボン酸類、４，４’−オキシジフタル酸類、３，３’，４，４’−ベンゾフェノンテトラカルボン酸類、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸類、ｐ−ターフェニルテトラカルボン酸類、ｍ−ターフェニルテトラカルボン酸類など、及びそれらの混合物を好適に例示することができる。この中で好ましくは、３，３’，４，４’−ビフェニルテトラカルボン酸類、３，３’，４，４’−ベンゾフェノンテトラカルボン酸類、４，４’−オキシジフタル酸類であり、３，３’，４，４’−ビフェニルテトラカルボン酸類、４，４’−オキシジフタル酸類、及びそれらの混合物がより好ましい。これら以外のテトラカルボン酸成分を用いると、水溶性のポリイミド前駆体を得るのが難しくなったり、得られるポリイミドの結晶性が低下して高い特性が得られなくなったりする場合がある。 A in the chemical formula (1) is a tetravalent group obtained by removing a carboxyl group from tetracarboxylic acid, and is preferably the chemical formulas (2) to (7) or a mixture thereof. That is, the tetracarboxylic acid component of the polyamic acid used in the present invention is a tetracarboxylic acid (tetracarboxylic acid, dianhydride or esterified product thereof), for example, 3,3 ′, 4,4′-biphenyltetra Carboxylic acids, 2,3,3 ′, 4′-biphenyltetracarboxylic acids, 2,2 ′, 3,3′-biphenyltetracarboxylic acids, 4,4′-oxydiphthalic acids, 3,3 ′, 4,4 ′ -Preferred examples include benzophenone tetracarboxylic acids, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acids, p-terphenyl tetracarboxylic acids, m-terphenyl tetracarboxylic acids, and mixtures thereof. it can. Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic acids, 3,3 ′, 4,4′-benzophenonetetracarboxylic acids, and 4,4′-oxydiphthalic acids are preferable. 4,4′-biphenyltetracarboxylic acids, 4,4′-oxydiphthalic acids, and mixtures thereof are more preferred. If a tetracarboxylic acid component other than these is used, it may be difficult to obtain a water-soluble polyimide precursor, or the crystallinity of the resulting polyimide may be reduced, and high characteristics may not be obtained.
また、得られるポリアミック酸が水に対して十分な溶解性を有すると共に、得られる芳香族ポリイミドの結晶性をより高くして高い特性の芳香族ポリイミドシームレスベルトを容易に得るためには、好ましくは２〜３個の芳香族環を有するテトラカルボン酸、さらに好ましくは前記化学式（２）〜（３）のいずれか或いはそれらの混合物であることが好適である。 Further, in order to easily obtain a high-quality aromatic polyimide seamless belt by making the resulting polyamic acid sufficiently soluble in water and making the obtained aromatic polyimide more crystalline, it is preferable that A tetracarboxylic acid having 2 to 3 aromatic rings, more preferably any one of the chemical formulas (2) to (3) or a mixture thereof is suitable.
化学式（１）のＢは、ポリアミック酸のジアミン成分に由来する化学構造であるが、本発明においては、２５℃の水に対する溶解度が０．１ｇ／Ｌ以上、好ましくは１ｇ／Ｌ以上である芳香族ジアミンからアミノ基を除いた２価の基である。２５℃における水に対する溶解度が０．１ｇ／Ｌ以上である芳香族ジアミンであることは、均一に溶解したポリイミド前駆体水溶液組成物を得るために特に必要な特性であって、水に対する溶解度が０．１ｇ／Ｌ未満では、均一に溶解したポリイミド前駆体水溶液組成物を得るのが難しくなるので好ましくない。 B in the chemical formula (1) is a chemical structure derived from the diamine component of the polyamic acid. In the present invention, B is an aromatic having a solubility in water at 25 ° C. of 0.1 g / L or more, preferably 1 g / L or more. It is a divalent group obtained by removing an amino group from a group diamine. The aromatic diamine having a solubility in water at 25 ° C. of 0.1 g / L or more is a characteristic particularly necessary to obtain a uniformly dissolved polyimide precursor aqueous solution composition, and the solubility in water is 0. If it is less than 1 g / L, it is difficult to obtain a uniformly dissolved polyimide precursor aqueous solution composition, which is not preferable.
化学式（１）のＢは、芳香族ジアミンの２５℃における水に対する溶解度が０．１ｇ／Ｌ以上のものであって、好ましくは１〜２個の芳香族環を有する芳香族ジアミンからアミノ基を除いた２価の基である。すなわち、本発明で用いるポリアミック酸の芳香族ジアミン成分は、芳香族ジアミンの２５℃における水に対する溶解度が０．１ｇ／Ｌ以上のものであって、好ましくは１〜２個の芳香族環を有する芳香族ジアミンある。
芳香族ジアミンが２個を越える芳香族環を持つ場合には、通常芳香族ジアミン分子中に複数の屈曲性が高い結合が含まれるので、その様な芳香族ジアミンから得られる芳香族ポリイミドは結晶性が低下して高い特性を得ることが難しくなる。
B in the chemical formula (1) is an aromatic diamine having a solubility in water at 25 ° C. of 0.1 g / L or more, and preferably an amino group from an aromatic diamine having 1 to 2 aromatic rings. Excluded divalent groups. That is, the aromatic diamine component of the polyamic acid used in the present invention has an aromatic diamine solubility in water at 25 ° C. of 0.1 g / L or more, and preferably has 1 to 2 aromatic rings. There is an aromatic diamine.
When the aromatic diamine has more than two aromatic rings, since the aromatic diamine molecule usually contains a plurality of highly flexible bonds, the aromatic polyimide obtained from such an aromatic diamine is crystalline. It becomes difficult to obtain high characteristics due to a decrease in properties.
すなわち、本発明で用いる好ましい芳香族ジアミン成分としては、ｐ−フェニレンジアミン（２５℃における水に対する溶解度は１２０ｇ／Ｌ、以下同様）、ｍ−フェニレンジアミン（７７ｇ／Ｌ）、４，４’−ジアミノジフェニルエーテル（０．１９ｇ／Ｌ）、３，４’−ジアミノジフェニルエーテル（０．２４ｇ／Ｌ）、４，４’−ジアミノジフェニルメタン（０．５４ｇ／Ｌ）、２，４−トルエンジアミン（６２ｇ／Ｌ）、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル（１．３ｇ／Ｌ）、ビス（４−アミノ−３−カルボキシフェニル）メタン（２００ｇ／Ｌ）などを例示できるが、水溶性が高く、得られるポリイミドの結晶性が高くて優れた特性を得ることができるので、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、及びそれらの混合物が好ましく、さらにｐ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテル、及びそれらの混合物がより好ましい。
なお、２５℃おける水に対する溶解度は、当該物質が、２５℃の水１Ｌ（リットル）に溶解する限界量（ｇ）を意味する。この値は、ケミカル・アブストラクトなどのベータベースに基づいた検索サービスとして知られるＳｃｉＦｉｎｄｅｒ（登録商標）によって容易に検索することができる。ここでは、種々の条件下での溶解度のうち、Ａｄｖａｎｃｅｄ Ｃｈｅｍｉｓｔｒｙ Ｄｅｖｅｌｏｐｍｅｎｔ（ＡＣＤ／Ｌａｂｓ）Ｓｏｆｔｗａｒｅ Ｖ１１．０２（Ｃｏｐｙｒｉｇｈｔ １９９４−２０１１ ＡＣＤ／Ｌａｂｓ）によって算出されたｐＨが７における値を採用した。
That is, as a preferable aromatic diamine component used in the present invention, p-phenylenediamine (the solubility in water at 25 ° C. is 120 g / L, the same applies hereinafter), m-phenylenediamine (77 g / L), 4,4′-diamino Diphenyl ether (0.19 g / L), 3,4'-diaminodiphenyl ether (0.24 g / L), 4,4'-diaminodiphenylmethane (0.54 g / L), 2,4-toluenediamine (62 g / L) 3,3′-dihydroxy-4,4′-diaminobiphenyl (1.3 g / L), bis (4-amino-3-carboxyphenyl) methane (200 g / L), etc. Since the resulting polyimide has high crystallinity and excellent characteristics, p-phenylenediamine, m-phenylenediamine, 4 4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and mixtures thereof are preferred, and p- phenylenediamine, 4,4'-diaminodiphenyl ether, and mixtures thereof are more preferred.
In addition, the solubility with respect to the water in 25 degreeC means the limit amount (g) which the said substance melt | dissolves in 1 L (liter) of water of 25 degreeC. This value can be easily searched by SciFinder (registered trademark) known as a search service based on a beta base such as a chemical abstract. Here, among the solubility under various conditions, the value at pH 7 calculated by Advanced Chemistry Development (ACD / Labs) Software V11.02 (Copyright 1994-2011 ACD / Labs) was adopted.
本発明で用いるイミダゾール類（化合物）としては、下記化学式（６）の化合物を好適に挙げることができる。 As the imidazoles (compound) used in the present invention, a compound represented by the following chemical formula (6) can be preferably exemplified.
本発明で用いるイミダゾール類としては、２５℃における水に対する溶解度が０．１ｇ／Ｌ以上特に１ｇ／Ｌ以上であることが好ましい。化学式（６）のイミダゾール類においては、Ｘ１〜Ｘ４が、それぞれ独立に、水素原子、或いは炭素数が１〜５のアルキル基であって、Ｘ１〜Ｘ４のうち少なくとも２個が、炭素数が１〜５のアルキル基であるイミダゾール類、すなわち置換基として２個以上のアルキル基を有するイミダゾール類がより好ましい。 The imidazoles used in the present invention preferably have a solubility in water at 25 ° C. of 0.1 g / L or more, particularly 1 g / L or more. In the imidazoles of the chemical formula (6), X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and at least two of X 1 to X 4 are Imidazoles that are alkyl groups having 1 to 5 carbon atoms, that is, imidazoles having two or more alkyl groups as substituents are more preferred.
置換基として２個以上のアルキル基を有するイミダゾール類は水に対する溶解性が高いので、それらを用いることによって、加熱処理をして芳香族ポリイミドシームレスベルトとなるポリイミド前駆体水溶液組成物を容易に製造することができる。これらのイミダゾール類としては、１，２−ジメチルイミダゾール（２５℃における水に対する溶解度は２３９ｇ／Ｌ、以下同様）、２−エチル−４−メチルイミダゾール（１０００ｇ／Ｌ）、４−エチル−２−メチルイミダゾール（１０００ｇ／Ｌ）、及び１−メチル−４−エチルイミダゾール（５４ｇ／Ｌ）などが好適である。
なお、２５℃おける水に対する溶解度は、当該物質が、２５℃の水１Ｌ（リットル）に溶解する限界量（ｇ）を意味する。この値は、ケミカル・アブストラクトなどのベータベースに基づいた検索サービスとして知られるＳｃｉＦｉｎｄｅｒ（登録商標）によって容易に検索することができる。ここでは、種々の条件下での溶解度のうち、Ａｄｖａｎｃｅｄ Ｃｈｅｍｉｓｔｒｙ Ｄｅｖｅｌｏｐｍｅｎｔ（ＡＣＤ／Ｌａｂｓ）Ｓｏｆｔｗａｒｅ Ｖ１１．０２（Ｃｏｐｙｒｉｇｈｔ １９９４−２０１１ ＡＣＤ／Ｌａｂｓ）によって算出されたｐＨが７における値を採用した。
Since imidazoles having two or more alkyl groups as substituents are highly soluble in water, using them makes it easy to produce a polyimide precursor aqueous solution composition that becomes an aromatic polyimide seamless belt by heat treatment. can do. As these imidazoles, 1,2-dimethylimidazole (solubility in water at 25 ° C. is 239 g / L, hereinafter the same), 2-ethyl-4-methylimidazole (1000 g / L), 4-ethyl-2-methyl Imidazole (1000 g / L), 1-methyl-4-ethylimidazole (54 g / L), and the like are preferable.
In addition, the solubility with respect to the water in 25 degreeC means the limit amount (g) which the said substance melt | dissolves in 1 L (liter) of water of 25 degreeC. This value can be easily searched by SciFinder (registered trademark) known as a search service based on a beta base such as a chemical abstract. Here, among the solubility under various conditions, the value at pH 7 calculated by Advanced Chemistry Development (ACD / Labs) Software V11.02 (Copyright 1994-2011 ACD / Labs) was adopted.
本発明で用いるイミダゾール類の使用量は、ポリアミック酸のカルボキシル基に対して０．８倍当量以上、好ましくは１．０倍当量以上、より好ましくは１．２倍当量以上である。イミダゾール類の使用量がポリアミック酸のカルボキシル基に対して０．８倍当量未満では、均一に溶解したポリイミド前駆体水溶液組成物を得るのが難しくなるので好ましくない。また、イミダゾール類の使用量の上限は、特に限定されないが、通常は１０倍当量未満、好ましくは５倍当量未満、より好ましくは３倍当量未満である。イミダゾール類の使用量が多過ぎると、非経済的になるし、且つポリイミド前駆体水溶液組成物の保存安定性が悪くなることがある。
本発明において、イミダゾール類の量を規定するポリアミック酸のカルボキシル基に対する倍当量とは、ポリアミック酸のアミド酸基を形成するカルボキシル基１個に対して何個（何分子）の割合でイミダゾール類を用いるかを表す。なお、ポリアミック酸のアミド酸基を形成するカルボキシル基の数は、原料のテトラカルボン酸成分１分子当たり２個のカルボキシル基を形成するものとして計算される。
The amount of imidazoles used in the present invention is 0.8 times equivalent or more, preferably 1.0 times equivalent or more, more preferably 1.2 times equivalent or more with respect to the carboxyl group of the polyamic acid. If the amount of the imidazole used is less than 0.8 equivalent to the carboxyl group of the polyamic acid, it is not preferable because it is difficult to obtain a uniformly dissolved polyimide precursor aqueous solution composition. Moreover, although the upper limit of the usage-amount of imidazoles is not specifically limited, Usually, it is less than 10 times equivalent, Preferably it is less than 5 times equivalent, More preferably, it is less than 3 times equivalent. If the amount of imidazole used is too large, it may become uneconomical and the storage stability of the polyimide precursor aqueous solution composition may be deteriorated.
In the present invention, the double equivalent to the carboxyl group of the polyamic acid that defines the amount of imidazoles is the number (number of molecules) of imidazoles in one carboxyl group that forms the amic acid group of the polyamic acid. Indicates whether to use. Note that the number of carboxyl groups forming the amic acid group of the polyamic acid is calculated as forming two carboxyl groups per molecule of the starting tetracarboxylic acid component.
本発明で用いるイミダゾール類の特徴は、ポリアミック酸のカルボキシル基と塩を形成して水に対する溶解性を高めるだけでなく、さらにポリイミド前駆体をイミド化（脱水閉環）してポリイミドにする際に、極めて高い触媒的な作用を有することにある。この結果、本発明のポリイミド前駆体水溶液組成物を用いると、例えばより低温且つ短時間の加熱処理によっても、容易に極めて高い物性を有する芳香族ポリイミドシームレスベルトを製造することが可能になる。 The characteristics of imidazoles used in the present invention are not only to increase the solubility in water by forming a salt with a carboxyl group of polyamic acid, but also when imidizing (dehydrating cyclization) the polyimide precursor into a polyimide, It has an extremely high catalytic action. As a result, when the polyimide precursor aqueous solution composition of the present invention is used, an aromatic polyimide seamless belt having extremely high physical properties can be easily produced, for example, even by heat treatment at a lower temperature for a shorter time.
本発明のポリイミド前駆体水溶液組成物は、特許文献１，２などの方法に準じ、
(i) 有機溶媒を反応溶媒とし、テトラカルボン酸成分とジアミン成分とを反応して得られたポリアミド酸を水中に投入してポリアミド酸粉末を得、そのポリアミド酸粉末を水溶媒中でイミダゾール類（好ましくは２個以上のアルキル基を有するイミダゾール類）と共に混合溶解して水溶液組成物を得る方法、
(ii) 有機溶媒を反応溶媒とし、イミダゾール類（好ましくは２個以上のアルキル基を有するイミダゾール類）の存在下にテトラカルボン酸成分とジアミン成分とを反応して水溶性ポリイミド前駆体を得、それを分離後、水溶媒に溶解する方法、或いは、
(iii) 有機溶媒を反応溶媒とし、テトラカルボン酸成分とジアミン成分とを反応してポリアミック酸を得、そのポリアミック酸を、有機溶媒を反応溶媒として、イミダゾール類（好ましくは２個以上のアルキル基を有するイミダゾール類）と反応して水溶性ポリイミド前駆体を得、それを分離後、水溶媒に溶解する方法
などでも得ることができる。但し、前述の通り、有機溶媒の含有量が極めて少ない、さらには有機溶媒を含まないポリイミド前駆体水溶液組成物を得るためには、ポリイミド前駆体を有機溶媒中で調製することは好ましくない。
The polyimide precursor aqueous solution composition of the present invention conforms to the methods of Patent Documents 1 and 2,
(i) Polyamic acid obtained by reacting a tetracarboxylic acid component with a diamine component using an organic solvent as a reaction solvent is poured into water to obtain a polyamic acid powder, and the polyamic acid powder is imidazoles in an aqueous solvent. (Preferably a method of obtaining an aqueous solution composition by mixing and dissolving together with imidazoles having two or more alkyl groups),
(ii) A water-soluble polyimide precursor is obtained by reacting a tetracarboxylic acid component and a diamine component in the presence of imidazoles (preferably imidazoles having two or more alkyl groups) using an organic solvent as a reaction solvent, A method of dissolving it in an aqueous solvent after separating it, or
(iii) A polyamic acid is obtained by reacting a tetracarboxylic acid component and a diamine component using an organic solvent as a reaction solvent, and the polyamic acid is converted into an imidazole (preferably two or more alkyl groups) using the organic solvent as a reaction solvent. It can also be obtained by a method in which a water-soluble polyimide precursor is obtained by reacting with an imidazole having a solvent, and is separated and then dissolved in an aqueous solvent. However, as described above, it is not preferable to prepare the polyimide precursor in an organic solvent in order to obtain a polyimide precursor aqueous solution composition having an extremely small organic solvent content and further not containing an organic solvent.
本発明のポリイミド前駆体水溶液組成物は、好ましくは、水を反応溶媒として、イミダゾール類の存在下に、好ましくは置換基として２個以上のアルキル基を有するイミダゾール類の存在下に、テトラカルボン酸成分と芳香族ジアミン成分とを反応することによって、極めて簡便に（直接的に）製造することが可能である。 The aqueous polyimide precursor solution composition of the present invention is preferably tetracarboxylic acid in the presence of imidazoles having water as a reaction solvent, preferably in the presence of imidazoles having two or more alkyl groups as substituents. By reacting the component with the aromatic diamine component, it can be produced very simply (directly).
この反応は、テトラカルボン酸成分と芳香族ジアミン成分を略等モル用い、イミド化反応を抑制するために１００℃以下好ましくは８０℃以下の比較的低温で行なわれる。限定するものではないが、通常の反応温度は２５℃〜１００℃、好ましくは４０℃〜８０℃、より好ましくは５０℃〜８０℃であり、反応時間は０．１〜２４時間程度、好ましくは２〜１２時間程度である。反応温度及び反応時間を前記範囲内とすることによって、生産効率よく高分子量のポリイミド前駆体水溶液組成物を容易に得ることができる。なお、反応は、空気雰囲気間でも構わないが、通常は不活性ガス好ましくは窒素ガス雰囲気下で好適に行われる。
また、テトラカルボン酸成分と芳香族ジアミン成分を略等モルとは、具体的にはモル比［テトラカルボン酸成分／ジアミン成分］で０．９０〜１．１０程度、好ましくは０．９５〜１．０５程度である。
This reaction is carried out at a relatively low temperature of 100 ° C. or less, preferably 80 ° C. or less in order to suppress the imidization reaction, using approximately equimolar amounts of a tetracarboxylic acid component and an aromatic diamine component. Although it does not limit, normal reaction temperature is 25 to 100 degreeC, Preferably it is 40 to 80 degreeC, More preferably, it is 50 to 80 degreeC, Reaction time is about 0.1 to 24 hours, Preferably It is about 2 to 12 hours. By setting the reaction temperature and reaction time within the above ranges, a high-molecular weight polyimide precursor aqueous solution composition can be easily obtained with high production efficiency. The reaction may be performed in an air atmosphere, but is usually suitably performed in an inert gas atmosphere, preferably a nitrogen gas atmosphere.
Further, the substantially equimolar amount of the tetracarboxylic acid component and the aromatic diamine component specifically refers to a molar ratio [tetracarboxylic acid component / diamine component] of about 0.90 to 1.10, preferably 0.95 to 1. .05 or so.
本発明のポリイミド前駆体水溶液組成物においては、ポリイミド前駆体（実質的にポリアミック酸）に起因する固形分濃度に基づいて温度３０℃、濃度０．５ｇ／１００ｍＬ（水溶解）で測定した対数粘度が０．２以上、好ましくは０．４以上、より好ましくは０．６以上、さらに好ましくは０．８以上、特に好ましくは１．０以上または超の高分子量であることが好適である。対数粘度が前記範囲よりも低くい場合には、ポリイミド前駆体の分子量が低いことから、本発明のポリイミド前駆体水溶液組成物を用いても、高い特性の芳香族ポリイミドシームレスベルトを得ることが難しくなることがある。 In the polyimide precursor aqueous solution composition of the present invention, the logarithmic viscosity measured at a temperature of 30 ° C. and a concentration of 0.5 g / 100 mL (dissolved in water) based on the solid content concentration resulting from the polyimide precursor (substantially polyamic acid). Is 0.2 or more, preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.8 or more, and particularly preferably 1.0 or more, or a high molecular weight. When the logarithmic viscosity is lower than the above range, the molecular weight of the polyimide precursor is low, so it is difficult to obtain an aromatic polyimide seamless belt having high characteristics even when using the polyimide precursor aqueous solution composition of the present invention. May be.
本発明のポリイミド前駆体水溶液組成物は、水溶媒を用いるが、水以外のポリアミック酸を調製する際に用いられる公知の有機溶媒を全溶媒中５０質量％以下、好ましくは３０質量％以下、より好ましくは１０質量％以下の割合で用いても構わない。 The polyimide precursor aqueous solution composition of the present invention uses an aqueous solvent, but a known organic solvent used when preparing a polyamic acid other than water is 50% by mass or less, preferably 30% by mass or less, based on the total solvent. Preferably, you may use in the ratio of 10 mass% or less.
「水を反応溶媒として」とは、溶媒の主成分として水を用いることを意味する。したがって、本発明のポリイミド前駆体水溶液組成物は、水溶媒を用いるが、水以外のポリアミック酸を調製する際に用いられる公知の有機溶媒を全溶媒中５０質量％以下、好ましくは３０質量％以下、より好ましくは１０質量％以下の割合で用いてもよい。なお、ここで言う有機溶媒には、テトラカルボン酸二無水物等のテトラカルボン酸成分、ジアミン成分、ポリアミック酸等のポリイミド前駆体、及びイミダゾール類は含まれない。 “Water as a reaction solvent” means that water is used as a main component of the solvent. Therefore, the polyimide precursor aqueous solution composition of the present invention uses a water solvent, but a known organic solvent used when preparing a polyamic acid other than water is 50% by mass or less, preferably 30% by mass or less in the total solvent. More preferably, you may use in the ratio of 10 mass% or less. The organic solvent mentioned here does not include tetracarboxylic acid components such as tetracarboxylic dianhydride, diamine components, polyimide precursors such as polyamic acid, and imidazoles.
前記有機溶媒とは、例えばＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，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、ｍ−クレゾール、フェノール、γ−ブチロラクトンなどが挙げられる。 Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, 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, diphenyl sulfone, tetramethyl urea, anisole, m-cresol, phenol, γ-butyrolactone, and the like. .
本発明のポリイミド前駆体水溶液組成物の製造方法においては、環境適応性が高いので、反応溶媒が、有機溶媒の含有量が５％未満である溶媒であることが好ましく、水以外の有機溶媒を含まない水溶媒であることが特に好ましい。反応溶媒の組成は、製造するポリイミド前駆体水溶液組成物の所望の溶媒組成に応じて適宜選択することができ、ポリイミド前駆体水溶液組成物の所望の溶媒組成と同一であることが好ましい場合がある。 In the manufacturing method of the polyimide precursor aqueous solution composition of the present invention, since the environmental adaptability is high, the reaction solvent is preferably a solvent having an organic solvent content of less than 5%, and an organic solvent other than water is used. It is particularly preferable that the aqueous solvent does not contain. The composition of the reaction solvent can be appropriately selected according to the desired solvent composition of the polyimide precursor aqueous solution composition to be produced, and may be preferably the same as the desired solvent composition of the polyimide precursor aqueous solution composition. .
本発明のポリイミド前駆体水溶液組成物は、ポリイミド前駆体（実質的にポリアミック酸）に起因する固形分濃度が、限定されないが、ポリイミド前駆体と溶媒との合計量に対して、好ましくは５質量％〜４５質量％、より好ましくは７質量％〜４０質量％、さらに好ましくは１０質量％超〜３０質量％であることが好適である。固形分濃度が５質量％より低いと著しく生産性が悪くなることがあり、４５質量％より高いと溶液の流動性がなくなることがある。また本発明のポリイミド前駆体水溶液組成物の３０℃における溶液粘度は、限定されないが、好ましくは１０００Ｐａ・ｓｅｃ以下、より好ましくは０．５〜５００Ｐａ・ｓｅｃ、さらに好ましくは１〜３００Ｐａ・ｓｅｃ、特に好ましくは３〜２００Ｐａ・ｓｅｃであることが取り扱い上好適である。
溶液粘度が１０００Ｐａ・ｓｅｃを超えると、流動性がなくなるため金属やガラスなどへの均一な塗布が困難となり、また、０．５Ｐａ・ｓｅｃよりも低いと、金属やガラスなどへの塗布時にたれやハジキなどが生じるので好ましくなく、また高い特性の芳香族ポリイミドシームレスベルトを得ることが難しくなることがある。
In the polyimide precursor aqueous solution composition of the present invention, the solid content concentration resulting from the polyimide precursor (substantially polyamic acid) is not limited, but is preferably 5 mass with respect to the total amount of the polyimide precursor and the solvent. % To 45% by mass, more preferably 7% to 40% by mass, and further preferably more than 10% by mass to 30% by mass. If the solid content concentration is lower than 5% by mass, the productivity may be remarkably deteriorated, and if it is higher than 45% by mass, the fluidity of the solution may be lost. The solution viscosity at 30 ° C. of the polyimide precursor aqueous solution composition of the present invention is not limited, but is preferably 1000 Pa · sec or less, more preferably 0.5 to 500 Pa · sec, still more preferably 1 to 300 Pa · sec, The handling is preferably 3 to 200 Pa · sec.
If the solution viscosity exceeds 1000 Pa · sec, the fluidity is lost, so that uniform application to metal or glass becomes difficult, and if it is lower than 0.5 Pa · sec, it may sag during application to metal or glass. Since repelling and the like occur, it is not preferable, and it may be difficult to obtain an aromatic polyimide seamless belt having high characteristics.
本発明の芳香族ポリイミドシームレスベルトの製造方法において、ポリイミド前駆体水溶液組成物は、加熱処理によって水溶媒を除去するとともにイミド化（脱水閉環）することによって好適に芳香族ポリイミドシームレスベルトを得ることができる。加熱処理条件は、特に限定されないが、概ね１００℃以上、好ましくは１２０℃〜６００℃、より好ましくは１５０℃〜５００℃で、更に好ましくは１５０℃〜３５０℃で、好ましくは段階的に温度を上げながら、０．０１時間〜３０時間、好ましくは０．０１〜１０時間である。
この加熱処理は、常圧下で好適に行うこともできるが、水溶媒を効率よく除去するために減圧下で行っても構わない。また初期段階で減圧下比較的低温で加熱処理して脱泡処理しても構わない。いきなり加熱処理温度を高くすると、発泡などの不具合が生じて好適なシームレスベルトを得ることができないことがある。
本発明の芳香族ポリイミドシームレスベルトの製造方法においては、比較的低温（例えば１５０℃〜３００℃、好ましくは２００℃〜２８０℃）で加熱処理しただけで、通常の有機溶媒を用いたポリイミド前駆体（ポリアミック酸）溶液組成物を用いた場合に較べて遜色ない優れた特性を容易に得ることができる。
In the method for producing an aromatic polyimide seamless belt of the present invention, the polyimide precursor aqueous solution composition can be suitably obtained by removing an aqueous solvent by heat treatment and imidizing (dehydrating ring closure). it can. The heat treatment conditions are not particularly limited, but are generally 100 ° C. or higher, preferably 120 ° C. to 600 ° C., more preferably 150 ° C. to 500 ° C., still more preferably 150 ° C. to 350 ° C., preferably in steps. While increasing, it is 0.01 to 30 hours, preferably 0.01 to 10 hours.
This heat treatment can be suitably performed under normal pressure, but may be performed under reduced pressure in order to efficiently remove the aqueous solvent. Further, the defoaming treatment may be performed by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, problems such as foaming may occur and a suitable seamless belt may not be obtained.
In the method for producing an aromatic polyimide seamless belt of the present invention, a polyimide precursor using an ordinary organic solvent is merely heated at a relatively low temperature (for example, 150 ° C. to 300 ° C., preferably 200 ° C. to 280 ° C.). Compared with the case of using a (polyamic acid) solution composition, excellent characteristics comparable to those obtained can be easily obtained.
シームレスベルトの成形方法は、従来公知の方法を好適に用いることができる。例えば回転成形法、すなわち基材の役割をする円筒形の金型を回転させながら金型（内側乃至外側）表面にポリアミック酸水溶液組成物からなる塗膜を塗布や吹き付けなどの手段によって形成し、比較的低温で加熱処理して水溶媒除去を行って自己支持性膜（皮膜の流動が発生しない状態、水溶媒の除去と共に重合及び一部イミド化反応が進んでいる）を形成し、次いで自己支持性膜をそのままの状態、或いは必要に応じて基材から剥がした状態で加熱処理して脱水・イミド化する方法によってシームレスベルトを好適に得ることができる。ここで用いた「水溶媒除去」或いは「脱水・イミド化」は、当該工程で、それぞれ水溶媒除去のみ或いは脱水・イミド化のみが進行することを意味しない。水溶媒除工程でも相当程度の脱水・イミド化は進行するし、脱水・イミド化工程でも残存水溶媒の除去が進行する。 As a method for forming the seamless belt, a conventionally known method can be suitably used. For example, a rotational coating method, that is, by forming a coating film composed of a polyamic acid aqueous solution composition on the surface of the mold (inside to outside) while rotating a cylindrical mold that serves as a base material, by means such as coating or spraying, Heat treatment is carried out at a relatively low temperature to remove the water solvent to form a self-supporting membrane (in the state where the film does not flow, polymerization and partial imidization reaction proceed with removal of the water solvent), and then self A seamless belt can be suitably obtained by a method of dehydrating and imidizing by heat-treating the supporting film as it is or after peeling from the substrate as necessary. “Water solvent removal” or “dehydration / imidization” used here does not mean that only water solvent removal or only dehydration / imidation proceeds in the step. A considerable amount of dehydration and imidization proceeds even in the water solvent removal step, and removal of the remaining water solvent proceeds in the dehydration and imidization step.
本発明のポリイミド前駆体水溶液組成物は、得られる芳香族ポリイミドシームレスベルトの用途に応じて、他の添加成分を含有していてもよい。また、得られる芳香族ポリイミドシームレスベルトは、さらに他の樹脂層や金属層を積層したものであってもよい。
本発明の芳香族ポリイミドシームレスベルトの厚みは、使用する目的に応じて適宜選択すればよいが、通常２０〜２００μｍ程度である。
The polyimide precursor aqueous solution composition of the present invention may contain other additive components depending on the use of the resulting aromatic polyimide seamless belt. Moreover, the obtained aromatic polyimide seamless belt may be obtained by further laminating other resin layers and metal layers.
The thickness of the aromatic polyimide seamless belt of the present invention may be appropriately selected according to the purpose of use, but is usually about 20 to 200 μm.
本発明の製造方法によって得られる芳香族ポリイミドシームレスベルトは、好ましくは結晶性が高く、耐熱性、機械的強度、電気特性、耐溶剤性などの優れた特性を有するために、電子写真装置の中間転写用或いは定着用シームレスベルトとして好適に用いることができる。 The aromatic polyimide seamless belt obtained by the production method of the present invention preferably has high crystallinity and has excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance. It can be suitably used as a transfer or fixing seamless belt.
芳香族ポリイミドシームレスベルトを、電子写真装置の中間転写用ベルトとして使用する場合には、導電性フィラーを含有させて、表面抵抗率が１０８〜１０１６Ω／□、体積抵抗率が１０８〜１０１６Ω・ｃｍの半導電性を付与することが好適である。
本発明における導電性フィラーとしては、通常の中間転写シームレスベルトに用いられる導電性もしくは半導電性の微粉末が使用でき、特に制限はないが、ケッチエンブラック、アセチレンブラック等のカーボンブラック、アルミニウムやニッケル等の金属、酸化錫等の酸化金属化合物、チタン酸カリウム等が例示できる。そしてこれらを単独、あるいは併用して使用してもよい。本発明では、カーボンブラックを導電性フィラーとして使用するのが好ましいが、特に、平均一次粒子径が、５〜１００ｎｍのものが好ましく、特に１０〜５０ｎｍのものが好ましい。平均一次粒子径が１００ｎｍを超えるものは、機械特性や電気抵抗値の均一性が不十分になり易い傾向がある。
導電性フィラーの配合量はフィラーの種類、粒子径、分散状態によっても異なるが、ポリイミド（固形分）１００重量部に対して、１〜５０重量部の範囲が好ましく、２〜３０重量部がより好ましい。本発明では、導電性フィラーを選択することと適当な配合量の組み合わせにより、中間転写ベルトに適した表面抵抗率（１０８〜１０１６Ω／□）と体積抵抗率（１０８〜１０１６Ω・ｃｍ）の範囲に調整される。
When the aromatic polyimide seamless belt is used as an intermediate transfer belt of an electrophotographic apparatus, a conductive filler is contained, the surface resistivity is 10 8 to 10 16 Ω / □, and the volume resistivity is 10 8 to. It is preferable to impart a semiconductivity of 10 16 Ω · cm.
As the conductive filler in the present invention, a conductive or semiconductive fine powder used in a normal intermediate transfer seamless belt can be used, and there is no particular limitation, but carbon black such as Ketchen Black and Acetylene Black, aluminum, Examples thereof include metals such as nickel, metal oxide compounds such as tin oxide, and potassium titanate. These may be used alone or in combination. In the present invention, carbon black is preferably used as the conductive filler. In particular, the average primary particle diameter is preferably 5 to 100 nm, and particularly preferably 10 to 50 nm. When the average primary particle size exceeds 100 nm, the uniformity of mechanical properties and electrical resistance tends to be insufficient.
Although the compounding quantity of an electroconductive filler changes also with the kind of filler, particle diameter, and a dispersion state, the range of 1-50 weight part is preferable with respect to 100 weight part of polyimides (solid content), and 2-30 weight part is more. preferable. In the present invention, the surface resistivity (10 8 to 10 16 Ω / □) and the volume resistivity (10 8 to 10 16 Ω) suitable for the intermediate transfer belt are selected by selecting a conductive filler and combining it in an appropriate amount.・ Adjusted to the range of cm).
芳香族ポリイミドシームレスベルトを、電子写真装置の定着用ベルトとして使用する場合には、熱伝導性を付与するためにシリカ、窒化ホウ素、窒化アルミニウム、窒化ケイ素、アルミナなどの充填材が添加されたり、ゴム弾性を付与するために例えばフッ素樹脂粉末を添加したり、発熱体である金属箔と好適に積層したりすることが好適である。充填剤の添加量はポリイミド（固形分）１００重量部に対して、１〜５０重量部の範囲が好ましく、２〜３０重量部がより好ましい。
熱伝導率に関しては、０．１５Ｗ／ｍＫ以上、好ましくは０．２０Ｗ／ｍＫ以上とすることが好適である。
When an aromatic polyimide seamless belt is used as a fixing belt for an electrophotographic apparatus, a filler such as silica, boron nitride, aluminum nitride, silicon nitride, or alumina is added to impart thermal conductivity, In order to impart rubber elasticity, for example, it is preferable to add fluororesin powder or to suitably laminate with a metal foil as a heating element. The addition amount of the filler is preferably in the range of 1 to 50 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the polyimide (solid content).
With respect to the thermal conductivity, it is suitable to be 0.15 W / mK or more, preferably 0.20 W / mK or more.
さらに、芳香族ポリイミドシームレスベルトを、電子写真装置の定着用ベルトとして使用する場合には、表面にゴム弾性層或いは離型層を積層したシームレスベルトとして好適に用いられる。離型層（剥離層）は、シームレスベルトの表面の剥離性を向上させるものであれば特に限定するものではなく、それ自身公知の、例えばポリテトラフルオロエチレン（ＰＴＦＥ）、もしくはその変性物であるテトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−エチレン共重合体（ＥＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−フッ化ビニリデン共重合体（ＴＦＥ／ＶｄＦ）、テトラフルオロエチレン−ヘキサフルオロプロピレン−パーフルオロアルキルビニルエーテル共重合体（ＥＰＡ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、クロロトリフルオロエチレン−エチレン共重合体（ＥＣＴＦＥ）、クロロトリフルオロエチレン−フッ化ビニリデン共重合体（ＣＴＦＥ／ＶｄＦ）、ポリフッ化ビニリデン（ＰＶｄＦ）、ポリフッ化ビニル（ＰＶＦ）などを用いて好適に構成できる。また、ゴム弾性も同様の材料で構成することが可能であり、それらの表面層に導電性フィラーを含有することも好適である。 Further, when the aromatic polyimide seamless belt is used as a fixing belt of an electrophotographic apparatus, it is suitably used as a seamless belt having a rubber elastic layer or a release layer laminated on the surface. The release layer (release layer) is not particularly limited as long as it improves the peelability of the surface of the seamless belt, and is known per se, for example, polytetrafluoroethylene (PTFE) or a modified product thereof. Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-vinylidene fluoride copolymer Polymer (TFE / VdF), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPA), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), copolymer B trifluoroethylene - vinylidene fluoride copolymer (CTFE / VdF), polyvinylidene fluoride (PVdF), can be suitably configured by using a polyvinyl fluoride (PVF). Moreover, rubber elasticity can also be comprised with the same material, and it is also suitable to contain a conductive filler in those surface layers.
以下、本発明を実施例により更に具体的に説明するが、本発明は、これら実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
以下の例で用いた特性の測定方法を以下に示す。
＜固形分濃度＞
試料溶液（その質量をｗ１とする）を、熱風乾燥機中１２０℃で１０分間、２５０℃で１０分間、次いで３５０℃で３０分間加熱処理して、加熱処理後の質量（その質量をｗ２とする）を測定する。固形分濃度［質量％］は、次式によって算出した。
固形分濃度［質量％］＝（ｗ２／ｗ１）×１００
A method for measuring the characteristics used in the following examples is shown below.
<Concentration of solid content>
The sample solution (whose mass is designated as w1) is heat-treated in a hot air dryer at 120 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then at 350 ° C. for 30 minutes. Measure). Solid content concentration [mass%] was computed by the following formula.
Solid content concentration [% by mass] = (w2 / w1) × 100
＜対数粘度＞
試料溶液を、固形分濃度に基づいて濃度が０．５ｇ／ｄｌ（溶媒は水）になるように希釈した。この希釈液を、３０℃にて、キャノンフェンスケＮｏ．１００を用いて流下時間（Ｔ１）を測定した。対数粘度は、ブランクの水の流下時間（Ｔ０）を用いて、次式から算出した。
対数粘度＝｛ｌｎ（Ｔ１／Ｔ０）｝／０．５
<Logarithmic viscosity>
The sample solution was diluted to a concentration of 0.5 g / dl (solvent is water) based on the solid content concentration. This diluted solution was added to Cannon Fenceke No. The flow-down time (T 1 ) was measured using 100. The logarithmic viscosity was calculated from the following equation using the flow time (T 0 ) of blank water.
Logarithmic viscosity = {ln (T 1 / T 0 )} / 0.5
＜溶液粘度（回転粘度）＞
トキメック社製Ｅ型粘度計を用いて３０℃で測定した。
<Solution viscosity (rotational viscosity)>
It measured at 30 degreeC using the Tokimec E-type viscosity meter.
＜芳香族ポリイミドシームレスベルトの製造＞
ポリイミド前駆体水溶液組成物を、内径１５０ｍｍ、長さ３００ｍｍの円筒金型の内側表面に、回転数１００ｒｐｍで回転させながら均一に塗布し、その後回転数が２００ｒｐｍでこの塗膜を、８０℃で３０分間、１２０℃で３０分間、２００℃で１０分間、次いで２５０℃で１０分間加熱処理して、厚さが５０μｍの芳香族ポリイミドシームレスベルトを得た。
得られた芳香族シームレスベルトについて目視により状態観察を行った。また、この芳香族ポリイミドシームレスベルトの特性を評価した。
<Manufacture of aromatic polyimide seamless belt>
The polyimide precursor aqueous solution composition was uniformly applied to the inner surface of a cylindrical mold having an inner diameter of 150 mm and a length of 300 mm while being rotated at a rotation speed of 100 rpm. Heat treatment was performed at 120 ° C. for 30 minutes, 200 ° C. for 10 minutes, and then at 250 ° C. for 10 minutes to obtain an aromatic polyimide seamless belt having a thickness of 50 μm.
The state of the obtained aromatic seamless belt was visually observed. Moreover, the characteristic of this aromatic polyimide seamless belt was evaluated.
＜芳香族ポリイミドシームレスベルトの状態観察＞
発泡または割れなどの不具合が全くないものを○、発泡または割れなどの不具合がある領域が全体の３０％以下のものを△、発泡または割れなどの不具合がある領域が３０％を越えているものを×とした。
<Observation of aromatic polyimide seamless belt>
○ where there are no defects such as foaming or cracking, △ the area where there is a defect such as foaming or cracking is 30% or less △, and the area where there is a defect such as foaming or cracking is over 30% Was marked with x.
＜機械的特性（引張試験）＞
引張り試験機（オリエンテック社製ＲＴＣ−１２２５Ａ）を用いて、ＡＳＴＭ Ｄ８８２に準拠して引張試験を行い、引張弾性率、引張破断伸び、引張破断強度を求めた。
<Mechanical properties (tensile test)>
Using a tensile tester (Orientec RTC-1225A), a tensile test was performed in accordance with ASTM D882 to determine the tensile modulus, tensile break elongation, and tensile break strength.
＜ガラス転移温度測定＞
ＴＡインスツルメンツ（株）製 固体粘弾性アナライザー ＲＳＡIII（圧縮モード 動的測定、周波数６２．８ｒａｄ／ｓｅｃ（１０Ｈｚ）、歪量はサンプル高さの３％に設定）を用い、雰囲気窒素気流中、−１４０℃から４５０℃まで温度ステップ３℃で、各温度到達後３０秒後に測定を行ない次の温度に昇温して測定を繰り返す方法で、損失弾性率（Ｅ''）の極大点を求め、その温度をガラス転移点（Ｔｇ）として求めた。
<Glass transition temperature measurement>
TA Instruments Co., Ltd. solid viscoelasticity analyzer RSAIII (compression mode dynamic measurement, frequency 62.8 rad / sec (10 Hz), strain amount set to 3% of sample height), −140 Measure from 30 ° C to 450 ° C at a temperature step of 3 ° C, measure 30 seconds after reaching each temperature, raise the temperature to the next temperature and repeat the measurement to obtain the maximum point of loss elastic modulus (E ''), The temperature was determined as the glass transition point (Tg).
以下の例で使用した化合物の略号について説明する。
ｓ−ＢＰＤＡ：３，３’，４，４’−ビフェニルテトラカルボン酸二無水物
ＯＤＰＡ：４，４’−オキシジフタル酸二無水物
ａ−ＢＰＤＡ：２，３’，３，４’−ビフェニルテトラカルボン酸二無水物
ＰＰＤ：ｐ−フェニレンジアミン（２５℃における水に対する溶解度：１２０ｇ／Ｌ、以下同様）
ＯＤＡ：４，４’−ジアミノジフェニルエーテル（０．１９ｇ／Ｌ）
ＢＡＰＰ：２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン（０．００００１９ｇ／Ｌ）
ＴＰＥ−Ｒ：１，３−ビス（４−アミノフェノキシ）ベンゼン（０．００１８ｇ／Ｌ）
１，２−ＤＭＺ：１，２−ジメチルイミダゾ−ル
２Ｅ４ＭＺ：２−エチル−４−メチルイミダゾール
ＮＭＰ：Ｎ−メチル−２−ピロリドン
The abbreviations of the compounds used in the following examples are described.
s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ODPA: 4,4′-oxydiphthalic dianhydride a-BPDA: 2,3 ′, 3,4′-biphenyltetracarboxylic Acid dianhydride PPD: p-phenylenediamine (solubility in water at 25 ° C .: 120 g / L, the same applies hereinafter)
ODA: 4,4′-diaminodiphenyl ether (0.19 g / L)
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane (0.000019 g / L)
TPE-R: 1,3-bis (4-aminophenoxy) benzene (0.0018 g / L)
1,2-DMZ: 1,2-dimethylimidazole 2E4MZ: 2-ethyl-4-methylimidazole NMP: N-methyl-2-pyrrolidone
〔実施例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＰＰＤの１３．４４ｇ（０．１２４モル）と、１，２−ＤＭＺの２９．８７ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にｓ−ＢＰＤＡの３６．５６ｇ（０．１２４モル）を加え、７０℃で４時間撹拌して、固形分濃度９．１質量％、溶液粘度６３．０Ｐａ・ｓ、対数粘度１．８６のポリイミド前駆体水溶液組成物を得た。
このポリイミド前駆体水溶液組成物を用いて、前記の芳香族ポリイミドシームレスベルトの製造に従って芳香族ポリイミドシームレスベルトを製造した。
得られたポリイミド前駆体水溶液組成物及びポリイミドシームレスベルトについて、状態観察及び特性の評価結果を表１に示した。
[Example 1]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 1,2-DMZ were added thereto. Of 29.87 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.56 g (0.124 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 9.1% by mass, the solution viscosity was 63.0 Pa · s, and the logarithmic viscosity was 1.86. The polyimide precursor aqueous solution composition was obtained.
Using this polyimide precursor aqueous solution composition, an aromatic polyimide seamless belt was produced according to the production of the aromatic polyimide seamless belt.
Regarding the obtained polyimide precursor aqueous solution composition and polyimide seamless belt, the results of state observation and property evaluation are shown in Table 1.
〔実施例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＰＰＤの１３．４４ｇ（０．１２４モル）と、２Ｅ４ＭＺの３４．２３ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にｓ−ＢＰＤＡの３６．５６ｇ（０．１２４モル）を加え、７０℃で４時間撹拌して、固形分濃度９．６質量％、溶液粘度１０．３Ｐａ・ｓ、対数粘度０．６４のポリイミド前駆体水溶液組成物を得た。
このポリイミド前駆体水溶液組成物を用いて、前記の芳香族ポリイミドシームレスベルトの製造に従って芳香族ポリイミドシームレスベルトを製造した。
得られたポリイミド前駆体水溶液組成物及びポリイミドシームレスベルトについて、状態観察及び特性の評価結果を表１に示した。
[Example 2]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 34.23 g of 2E4MZ were added thereto. (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 36.56 g (0.124 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours to obtain a solid content concentration of 9.6% by mass, a solution viscosity of 10.3 Pa · s, and a logarithmic viscosity of 0.64. The polyimide precursor aqueous solution composition was obtained.
Using this polyimide precursor aqueous solution composition, an aromatic polyimide seamless belt was produced according to the production of the aromatic polyimide seamless belt.
Regarding the obtained polyimide precursor aqueous solution composition and polyimide seamless belt, the results of state observation and property evaluation are shown in Table 1.
〔実施例３〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＯＤＡの２０．２５ｇ（０．１０１モル）と、１，２−ＤＭＺの２４．３１ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にｓ−ＢＰＤＡの２９．７５ｇ（０．１０１モル）を加え、７０℃で４時間撹拌して、固形分濃度８．７質量％、溶液粘度３２．０Ｐａ・ｓ、対数粘度０．４２のポリイミド前駆体水溶液組成物を得た。
このポリイミド前駆体水溶液組成物を用いて、前記の芳香族ポリイミドシームレスベルトの製造に従って芳香族ポリイミドシームレスベルトを製造した。
得られたポリイミド前駆体水溶液組成物及びポリイミドシームレスベルトについて、状態観察及び特性の評価結果を表１に示した。
Example 3
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 20.25 g (0.101 mol) of ODA and 1,2-DMZ were added thereto. Of 24.31 g (1.25 times equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 29.75 g (0.101 mol) of s-BPDA was added and stirred at 70 ° C. for 4 hours. The solid content concentration was 8.7% by mass, the solution viscosity was 32.0 Pa · s, and the logarithmic viscosity was 0.42. The polyimide precursor aqueous solution composition was obtained.
Using this polyimide precursor aqueous solution composition, an aromatic polyimide seamless belt was produced according to the production of the aromatic polyimide seamless belt.
Regarding the obtained polyimide precursor aqueous solution composition and polyimide seamless belt, the results of state observation and property evaluation are shown in Table 1.
〔実施例４〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＯＤＡの１０．９７ｇ（０．０５５モル）及びＰＰＤの５．９２ｇ（０．０５５モル）と、１，２−ＤＭＺの２０．４３ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にｓ−ＢＰＤＡの１６．１２ｇ（０．０５５モル）及びＯＤＰＡの１６．９９ｇ（０．０５５モル）を加え、７０℃で４時間撹拌して、固形分濃度９．１質量％、溶液粘度６．５Ｐａ・ｓ、対数粘度０．５０のポリイミド前駆体水溶液組成物を得た。
このポリイミド前駆体水溶液組成物を用いて、前記の芳香族ポリイミドシームレスベルトの製造に従って芳香族ポリイミドシームレスベルトを製造した。
得られたポリイミド前駆体水溶液組成物及びポリイミドシームレスベルトについて、状態観察及び特性の評価結果を表１に示した。
Example 4
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 10.97 g (0.055 mol) of ODA and 5.92 g of PPD ( 0.055 mol) and 20.43 g of 1,2-DMZ (1.25 times equivalent to the carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 16.12 g (0.055 mol) of s-BPDA and 16.99 g (0.055 mol) of ODPA were added and stirred at 70 ° C. for 4 hours to obtain a solid content concentration of 9.1% by mass. A polyimide precursor aqueous solution composition having a viscosity of 6.5 Pa · s and a logarithmic viscosity of 0.50 was obtained.
Using this polyimide precursor aqueous solution composition, an aromatic polyimide seamless belt was produced according to the production of the aromatic polyimide seamless belt.
Regarding the obtained polyimide precursor aqueous solution composition and polyimide seamless belt, the results of state observation and property evaluation are shown in Table 1.
〔実施例５〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＯＤＡの１４．８６ｇ（０．０７４モル）及びＰＰＤの３．４４ｇ（０．０３２モル）と、１，２−ＤＭＺの２０．４３ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にｓ−ＢＰＤＡの２１．８３ｇ（０．０７４モル）及びＯＤＰＡの９．８７ｇ（０．０３２モル）を加え、７０℃で４時間撹拌して、固形分濃度９．０質量％、溶液粘度５．２Ｐａ・ｓ、対数粘度０．４６のポリイミド前駆体水溶液組成物を得た。
このポリイミド前駆体水溶液組成物を用いて、前記の芳香族ポリイミドシームレスベルトの製造に従って芳香族ポリイミドシームレスベルトを製造した。
得られたポリイミド前駆体水溶液組成物及びポリイミドシームレスベルトについて、状態観察及び特性の評価結果を表１に示した。
Example 5
450 g of water was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 14.86 g (0.074 mol) of ODA and 3.44 g of PPD ( 0.032 mol) and 20.43 g of 1,2-DMZ (1.25 times equivalent to carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 21.83 g (0.074 mol) of s-BPDA and 9.87 g (0.032 mol) of ODPA were added and stirred at 70 ° C. for 4 hours to obtain a solid content of 9.0% by mass. A polyimide precursor aqueous solution composition having a viscosity of 5.2 Pa · s and a logarithmic viscosity of 0.46 was obtained.
Using this polyimide precursor aqueous solution composition, an aromatic polyimide seamless belt was produced according to the production of the aromatic polyimide seamless belt.
Regarding the obtained polyimide precursor aqueous solution composition and polyimide seamless belt, the results of state observation and property evaluation are shown in Table 1.
〔参考例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＰＰＤの１３．４４ｇ（０．１２４モル）と、１，２−ＤＭＺの１７．９２ｇ（カルボキシル基に対して０．７５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にｓ−ＢＰＤＡの３６．５６ｇ（０．１２４モル）を加え、７０℃で４時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶液組成物を得ることができなかった。
結果を表２に示した。
[Reference Example 1]
450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 13.44 g (0.124 mol) of PPD and 1,2-DMZ were added thereto. Of 17.92 g (0.75 equivalent to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and a polyimide precursor aqueous solution composition could not be obtained.
The results are shown in Table 2.
〔参考例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＢＡＰＰの２９．１３ｇ（０．０７１モル）と、１，２−ＤＭＺの１７．０５ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にｓ−ＢＰＤＡの２０．８７ｇ（０．０７１モル）を加え、７０℃で４時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶液組成物を得ることができなかった。
結果を表２に示した。
[Reference Example 2]
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 29.13 g (0.071 mol) of BAPP and 1,2-DMZ were added thereto. Of 17.05 g (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 20.87 g (0.071 mol) of s-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and a polyimide precursor aqueous solution composition could not be obtained.
The results are shown in Table 2.
〔参考例３〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＴＰＥ−Ｒの２４．９２ｇ（０．０８５モル）と、１，２−ＤＭＺの２０．４９ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にａ−ＢＰＤＡの２５．０８ｇ（０．０８５モル）を加え、７０℃で４時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶液組成物を得ることができなかった。
結果を表２に示した。
[Reference Example 3]
450 g of water was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 24.92 g (0.085 mol) of TPE-R was added to the reaction vessel. -20.49 g of DMZ (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. 25.08 g (0.085 mol) of a-BPDA was added to this solution and stirred for 4 hours at 70 ° C., but it did not dissolve uniformly, and a polyimide precursor aqueous solution composition could not be obtained.
The results are shown in Table 2.
〔参考例４〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒として水の４５０ｇを加え、これにＴＰＥ−Ｒの２４．２６ｇ（０．０８３モル）と、１，２−ＤＭＺの１９．９５ｇ（カルボキシル基に対して１．２５倍当量）とを加え２５℃で１時間攪拌し、溶解させた。この溶液にＯＤＰＡの２５．７４ｇ（０．０８３モル）を加え、７０℃で４時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶液組成物を得ることができなかった。
結果を表２に示した。
[Reference Example 4]
450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 24.26 g (0.083 mol) of TPE-R was added to the reaction vessel. -19.95 g of DMZ (1.25 equivalents relative to the carboxyl group) was added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 25.74 g (0.083 mol) of ODPA was added and stirred at 70 ° C. for 4 hours. However, the solution did not dissolve uniformly and a polyimide precursor aqueous solution composition could not be obtained.
The results are shown in Table 2.
〔参考例５〕
ＴＰＥ−Ｒの２９．２３ｇ（０．１モル）とＤＭＡｃの２３４．６０ｇとを、攪拌機、還流冷却器（水分分離器付き）、温度計、窒素導入管を備えた１０００ｍＬのガラス製反応容器に、２５℃において添加し、その混合液に窒素ガス流通下攪拌しながら、ａ−ＢＰＤＡの２９．４２ｇ（０．１モル）を添加し、２時間反応させポリイミド前駆体溶液を得た。そして、この溶液をＤＭＡｃの２９３．２５ｇで希釈し３０℃において１．３ポイズとした。この溶液にＤＭＺの５．８７ｇ（０．０６モル）を添加し、この溶液を、ホモジナイザーを備えたアセトン（６．５Ｌ）に徐々に加えポリイミド前駆体粉末を析出させた。この懸濁液を濾過し、アセトン洗浄し、４０℃で１０時間真空乾燥して、６０．５２ｇのポリイミド前駆体の粉末を得た。
[Reference Example 5]
29.23 g (0.1 mol) of TPE-R and 234.60 g of DMAc were placed in a 1000 mL glass reaction vessel equipped with a stirrer, a reflux condenser (with a water separator), a thermometer, and a nitrogen introduction tube. The mixture was added at 25 ° C., and 29.42 g (0.1 mol) of a-BPDA was added to the mixed solution while stirring under a nitrogen gas flow, and reacted for 2 hours to obtain a polyimide precursor solution. This solution was then diluted with 293.25 g of DMAc to 1.3 poise at 30 ° C. To this solution, 5.87 g (0.06 mol) of DMZ was added, and this solution was gradually added to acetone (6.5 L) equipped with a homogenizer to precipitate a polyimide precursor powder. This suspension was filtered, washed with acetone, and vacuum-dried at 40 ° C. for 10 hours to obtain 60.52 g of polyimide precursor powder.
このポリイミド前駆体粉末３ｇに対して、水の２６．１０ｇおよび１，２−ＤＭＺの０．９ｇ（０．００９４モル）を加え、６０℃で攪拌しながら２時間で溶解し均一なポリイミド前駆体水溶液を得た。この水溶液をＧＣ−ＭＳを用いて発生ガスの分析を行ったところ、６．２８％のＤＭＡｃが検出された。 To 3 g of this polyimide precursor powder, 26.10 g of water and 0.9 g (0.0094 mol) of 1,2-DMZ were added and dissolved in 2 hours while stirring at 60 ° C. to obtain a uniform polyimide precursor An aqueous solution was obtained. When this aqueous solution was analyzed for evolved gas using GC-MS, 6.28% DMAc was detected.
本発明によって、水溶媒からなる環境適応性が良好なポリイミド前駆体水溶液組成物を用いた芳香族ポリイミドシームレスベルトの製造方法を提案することができる。このポリイミド前駆体水溶液組成物は、好ましくはポリアミック酸が高分子量であり、また溶媒が水以外の有機溶媒を含まない。また、本発明の製造方法によって得られる芳香族ポリイミドシームレスベルトは、好ましくは結晶性が高く、耐熱性、機械的強度、電気特性、耐溶剤性などの優れた特性を有するために、電子写真装置の中間転写用シームレスベルト或いは定着用シームレスベルトとして好適に用いることができる。 According to the present invention, it is possible to propose a method for producing an aromatic polyimide seamless belt using a polyimide precursor aqueous solution composition having good environmental adaptability, which comprises an aqueous solvent. In this polyimide precursor aqueous solution composition, the polyamic acid preferably has a high molecular weight, and the solvent does not contain an organic solvent other than water. The aromatic polyimide seamless belt obtained by the production method of the present invention preferably has high crystallinity, and has excellent characteristics such as heat resistance, mechanical strength, electrical characteristics, and solvent resistance. The intermediate transfer seamless belt or the fixing seamless belt can be suitably used.
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| JP2011154912A JP5822064B2 (en) | 2010-12-15 | 2011-07-13 | Method for producing aromatic polyimide seamless belt |
| EP11806873.3A EP2594609B1 (en) | 2010-07-14 | 2011-07-14 | Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition |
| US13/809,768 US20130171520A1 (en) | 2010-07-14 | 2011-07-14 | Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition |
| PCT/JP2011/066144 WO2012008543A1 (en) | 2010-07-14 | 2011-07-14 | Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition |
| CN201180044187.XA CN103097463B (en) | 2010-07-14 | 2011-07-14 | Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition |
| TW100125005A TWI496816B (en) | 2010-07-14 | 2011-07-14 | Polyimide precursor aqueous composition and method for preparing the same |
| KR1020137003518A KR101831009B1 (en) | 2010-07-14 | 2011-07-14 | Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition |
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| JP6007809B2 (en) * | 2013-01-31 | 2016-10-12 | 富士ゼロックス株式会社 | Method for producing polyimide molded body, polyimide molded body, liquid crystal alignment film, passivation film, wire coating material, and adhesive film |
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