JP5916498B2 - ポリイミド多孔質体及びその製造方法 - Google Patents
ポリイミド多孔質体及びその製造方法 Download PDFInfo
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- JP5916498B2 JP5916498B2 JP2012100163A JP2012100163A JP5916498B2 JP 5916498 B2 JP5916498 B2 JP 5916498B2 JP 2012100163 A JP2012100163 A JP 2012100163A JP 2012100163 A JP2012100163 A JP 2012100163A JP 5916498 B2 JP5916498 B2 JP 5916498B2
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- JP
- Japan
- Prior art keywords
- porous body
- phase separation
- polyimide
- polyamic acid
- carbon dioxide
- 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.)
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- 239000004642 Polyimide Substances 0.000 title claims description 70
- 229920001721 polyimide Polymers 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000005191 phase separation Methods 0.000 claims description 68
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 64
- 229920005575 poly(amic acid) Polymers 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 32
- 239000001569 carbon dioxide Substances 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000012024 dehydrating agents Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 33
- 229920001451 polypropylene glycol Polymers 0.000 description 17
- 239000011148 porous material Substances 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 239000006260 foam Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- -1 2,3-dicarboxyphenyl Chemical group 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 238000006358 imidation reaction Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000000126 substance 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
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 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 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-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
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- VDOKWPVSGXHSNP-UHFFFAOYSA-N 2-methylprop-1-en-1-one Chemical compound CC(C)=C=O VDOKWPVSGXHSNP-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IFYXKXOINSPAJQ-UHFFFAOYSA-N 4-(4-aminophenyl)-5,5-bis(trifluoromethyl)cyclohexa-1,3-dien-1-amine Chemical group FC(F)(F)C1(C(F)(F)F)CC(N)=CC=C1C1=CC=C(N)C=C1 IFYXKXOINSPAJQ-UHFFFAOYSA-N 0.000 description 1
- ZNDJZRZZTPORNT-UHFFFAOYSA-N 4-(4-aminophenyl)-5,5-dimethylcyclohexa-1,3-dien-1-amine Chemical group CC1(C)CC(N)=CC=C1C1=CC=C(N)C=C1 ZNDJZRZZTPORNT-UHFFFAOYSA-N 0.000 description 1
- YPGXCJNQPKHBLH-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=CC=C1OC1=CC=C(N)C=C1 YPGXCJNQPKHBLH-UHFFFAOYSA-N 0.000 description 1
- AJYDKROUZBIMLE-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C=CC(N)=CC=2)C=1C(C)(C)C1=CC=CC=C1OC1=CC=C(N)C=C1 AJYDKROUZBIMLE-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
- 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
- FJVIHKKXPLPDSV-UHFFFAOYSA-N 4-phenoxybenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=CC=C1 FJVIHKKXPLPDSV-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 208000030984 MIRAGE syndrome Diseases 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BYVCTYDTPSKPRM-UHFFFAOYSA-N naphthalene-1-carbonyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(OC(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 BYVCTYDTPSKPRM-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
(平均孔径の測定)
作製したポリイミド多孔質体を液体窒素で冷却し、刃物を用いてシート面に対して垂直に切断してサンプルを作製した。サンプルの切断面にAu蒸着処理を施し、該切断面をSEMで観察した。その画像を画像処理ソフト(三谷商事(株)製、WinROOF)で二値化処理し、気泡部と樹脂部とに分離して気泡の直径を測定した。50個の気泡について直径をそれぞれ測定し、その平均値を平均孔径とした。
電子比重計(アルファーミラージュ社製、MD−300S)を用いて作製したポリイミド多孔質体と無孔質体の比重をそれぞれ測定し、下記式により体積空孔率を計算した。
体積空孔率(%)={1−(ポリイミド多孔質体の比重)/(無孔質体の比重)}×100
作製したポリイミド多孔質体を、JIS K6251の規格に準拠した3号形のダンベル形状に打ち抜いたサンプルを用い、100mm/minの速度で引張試験を行って引張弾性率を測定した。測定機器として、引張圧縮試験機(エー・アンド・ディー社製、テンシロン RTG1210)を使用した。サンプルの体積空孔率を補正するため、下記式を用いてバルク弾性率を算出した。
バルク弾性率(MPa)=測定値/(1−体積空孔率/100)
JlS C2110の規格に準拠した方法により、作製したポリイミド多孔質体の絶縁破壊電圧試験を行った。昇圧速度は1kV/secとした。
空洞共振器摂動法により、周波数1GHzにおける複素誘電率を測定し、その実数部を比誘電率とした。測定機器は、円筒空洞共振機(アジレント・テクノロジー社製「ネットワークアナライザ N5230C」、関東電子応用開発社製「空洞共振器1GHz」)を用い、短冊状のサンプル(サンプルサイズ2mm×70mm長さ)を用いて測定した。
1000mlの4つ口フラスコに、N−メチル−2−ピロリドン(NMP)785.3g、p−フェニレンジアミン(PDA)44.1g、及び4,4’−ジアミノジフェニルエーテル(DDE)20.4gを加え、常温で撹拌しながら溶解させた。次いで、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(BPDA)150.2gを加え、25℃で1時間反応させた後、75℃で25時間加熱することによりB型粘度計による溶液粘度が160Pa・sのポリアミド酸溶液(固形分濃度20wt%)を得た。得られたポリアミド酸溶液に、イミド化触媒として2−メチルイミダゾール0.832g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)、及び脱水剤として安息香酸無水物2.32g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)を添加した。
実施例1において、重量平均分子量400のポリプロピレングリコールの代わりに重量平均分子量250のポリプロピレングリコールを添加した以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
実施例1において、イミド化触媒として2−メチルイミダゾールの代わりにイソキノリン1.308g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)を添加し、また重量平均分子量400のポリプロピレングリコールの代わりに重量平均分子量250のポリプロピレングリコールを添加した以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
実施例1において、イミド化触媒として2−メチルイミダゾールの代わりにトリエチルアミン1.026g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)を添加し、また重量平均分子量400のポリプロピレングリコールの代わりに重量平均分子量250のポリプロピレングリコールを添加した以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
実施例1において、イミド化触媒として2−メチルイミダゾールの代わりにイソキノリン1.308g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)、及び脱水剤として安息香酸無水物の代わりに無水酢酸1.034g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)を添加し、また重量平均分子量400のポリプロピレングリコールの代わりに重量平均分子量250のポリプロピレングリコールを添加した以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
実施例1において、脱水剤として安息香酸無水物の代わりに無水酢酸1.034g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)を添加し、また重量平均分子量400のポリプロピレングリコールの代わりに重量平均分子量250のポリプロピレングリコールを添加した以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
実施例1において、イミド化触媒として2−メチルイミダゾールの代わりにトリエチルアミン1.026g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)、及び脱水剤として安息香酸無水物の代わりに無水酢酸1.034g(ポリアミド酸ユニット1モル当量に対して0.2モル当量)を添加し、また重量平均分子量400のポリプロピレングリコールの代わりに重量平均分子量250のポリプロピレングリコールを添加した以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
実施例1において、ポリアミド酸溶液にイミド化触媒及び脱水剤を添加しなかった以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
実施例1において、ポリアミド酸溶液にイミド化触媒及び脱水剤を添加せず、重量平均分子量400のポリプロピレングリコールの代わりに重量平均分子量250のポリプロピレングリコールを添加した以外は実施例1と同様の方法でポリイミド多孔質体を作製した。
Claims (4)
- ポリアミド酸、該ポリアミド酸と相分離する相分離化剤、イミド化触媒、及び脱水剤を含有するポリマー溶液を基板上に塗布し、乾燥させてミクロ相分離構造を有する相分離構造体を作製する工程、相分離構造体から前記相分離化剤を除去して多孔質体を作製する工程、及び多孔質体中のポリアミド酸を300〜400℃でイミド化させてポリイミドを合成する工程を含むポリイミド多孔質体の製造方法。
- 相分離化剤を溶剤抽出により除去する請求項1記載のポリイミド多孔質体の製造方法。
- 溶剤が液化二酸化炭素、亜臨界二酸化炭素、又は超臨界二酸化炭素である請求項2記載のポリイミド多孔質体の製造方法。
- 相分離化剤を加熱により除去する請求項1記載のポリイミド多孔質体の製造方法。
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JP2012100163A JP5916498B2 (ja) | 2011-06-06 | 2012-04-25 | ポリイミド多孔質体及びその製造方法 |
PCT/JP2012/063633 WO2012169383A1 (ja) | 2011-06-06 | 2012-05-28 | ポリイミド多孔質体及びその製造方法 |
CN201280027845.9A CN103597016B (zh) | 2011-06-06 | 2012-05-28 | 聚酰亚胺多孔体及其制造方法 |
US14/123,695 US20140127494A1 (en) | 2011-06-06 | 2012-05-28 | Polyimide porous body and method for producing same |
KR1020147000136A KR20140025569A (ko) | 2011-06-06 | 2012-05-28 | 폴리이미드 다공질체 및 그의 제조 방법 |
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KR20180112927A (ko) | 2017-04-05 | 2018-10-15 | 에스케이이노베이션 주식회사 | 폴리이미드 미세다공막 및 그 제조 방법 |
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JP2012182116A (ja) * | 2011-02-03 | 2012-09-20 | Nitto Denko Corp | モーター用電気絶縁性樹脂シート及びその製造方法 |
JP6135665B2 (ja) * | 2012-03-23 | 2017-05-31 | 東レ株式会社 | ポリオレフィン多孔性フィルムおよび蓄電デバイス |
JP5458137B2 (ja) * | 2012-03-29 | 2014-04-02 | 日東電工株式会社 | 電気絶縁性樹脂シート |
JP6342891B2 (ja) * | 2013-06-07 | 2018-06-13 | 東京応化工業株式会社 | ワニス、それを用いて製造した多孔質ポリイミド膜、及びその製造方法 |
JP6440092B2 (ja) * | 2013-09-06 | 2018-12-19 | 宇部興産株式会社 | ポリイミド多孔質膜及び多孔質膜製造用のポリイミド前駆体反応生成物溶液 |
CN104157630B (zh) * | 2014-09-09 | 2017-10-17 | 西华大学 | 一种超低介电常数聚酰亚胺薄膜及其制备方法 |
CA3002391C (en) | 2015-10-30 | 2021-01-05 | Blueshift Materials, Inc. | Highly branched non-crosslinked aerogel, methods of making, and uses thereof |
WO2017078888A1 (en) | 2015-11-03 | 2017-05-11 | Blueshift International Materials, Inc. | Internally reinforced aerogel and uses thereof |
CA3016132A1 (en) | 2016-06-08 | 2017-12-14 | Blueshift Materials, Inc. | Polymer aerogel with improved mechanical and thermal properties |
JP6747091B2 (ja) * | 2016-06-23 | 2020-08-26 | 富士ゼロックス株式会社 | 多孔質フィルム、及びその製造方法 |
KR20220158872A (ko) * | 2016-07-25 | 2022-12-01 | 닛토덴코 가부시키가이샤 | 밀리파 안테나용 필름 |
US20190263995A1 (en) * | 2016-07-25 | 2019-08-29 | Nitto Denko Corporation | Low-dielectric porous polymer film and film for millimeter-wave antenna |
JP6567722B2 (ja) * | 2017-04-06 | 2019-08-28 | 日東電工株式会社 | ミリ波アンテナ用フィルム |
JP7024225B2 (ja) * | 2017-06-29 | 2022-02-24 | 富士フイルムビジネスイノベーション株式会社 | ポリイミド積層膜、及びポリイミド積層膜の製造方法 |
CN111433265B (zh) * | 2017-12-05 | 2023-09-29 | 蓝移材料有限公司 | 经热处理的聚酰胺酰胺气凝胶 |
CN108565331A (zh) * | 2018-04-22 | 2018-09-21 | 佛山市领卓科技有限公司 | 一种热电材料 |
JP2022165324A (ja) * | 2021-04-19 | 2022-10-31 | 日東電工株式会社 | 金属層積層板用フィルム |
CN113353925B (zh) * | 2021-05-12 | 2022-12-20 | 浙江中科玖源新材料有限公司 | 一种高导热聚酰亚胺基石墨膜的制备方法 |
CN114716859B (zh) * | 2022-04-24 | 2022-11-15 | 住井科技(深圳)有限公司 | 绝缘清漆及绝缘电线 |
CN115746385B (zh) * | 2022-11-24 | 2023-10-24 | 华东理工大学 | 一种聚酰亚胺泡沫材料及其制备方法 |
CN118480208B (zh) * | 2024-07-12 | 2024-11-05 | 富优特(山东)新材料科技有限公司 | 两亲性聚合物调控的聚酰亚胺纳米多孔薄膜的制备方法 |
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JP2903704B2 (ja) * | 1990-11-27 | 1999-06-14 | 宇部興産株式会社 | 芳香族ポリイミドフィルムの製造法 |
JP4110669B2 (ja) * | 1999-05-13 | 2008-07-02 | 宇部興産株式会社 | 多孔質絶縁材料およびその積層体 |
JP4159199B2 (ja) * | 1999-09-16 | 2008-10-01 | 日東電工株式会社 | 多孔質体及び多孔質体の製造方法 |
KR100683086B1 (ko) * | 2001-07-09 | 2007-02-16 | 가부시키가이샤 가네카 | 수지 조성물 |
JP4896309B2 (ja) * | 2001-07-13 | 2012-03-14 | 日東電工株式会社 | 多孔質ポリイミド樹脂の製造方法 |
JP4302342B2 (ja) * | 2001-11-01 | 2009-07-22 | 宇部興産株式会社 | ポリイミド多孔質膜及びその製造方法 |
JP2003026849A (ja) * | 2001-07-23 | 2003-01-29 | Ube Ind Ltd | ポリイミド多孔質膜 |
JP2011001434A (ja) * | 2009-06-17 | 2011-01-06 | Ube Industries Ltd | ポリイミド多孔質体の製造方法、及びポリイミド多孔質体 |
KR101747462B1 (ko) * | 2009-10-09 | 2017-06-14 | 우베 고산 가부시키가이샤 | 착색 폴리이미드 성형체 및 그의 제조 방법 |
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- 2012-05-28 KR KR1020147000136A patent/KR20140025569A/ko not_active Application Discontinuation
- 2012-05-28 CN CN201280027845.9A patent/CN103597016B/zh active Active
- 2012-05-28 WO PCT/JP2012/063633 patent/WO2012169383A1/ja active Application Filing
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KR20180112927A (ko) | 2017-04-05 | 2018-10-15 | 에스케이이노베이션 주식회사 | 폴리이미드 미세다공막 및 그 제조 방법 |
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WO2012169383A1 (ja) | 2012-12-13 |
KR20140025569A (ko) | 2014-03-04 |
JP2013014742A (ja) | 2013-01-24 |
US20140127494A1 (en) | 2014-05-08 |
CN103597016A (zh) | 2014-02-19 |
CN103597016B (zh) | 2016-05-18 |
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