JP5380662B2 - Functional polyamic acid composite particles and method for producing functional polyimide composite particles - Google Patents
Functional polyamic acid composite particles and method for producing functional polyimide composite particles Download PDFInfo
- Publication number
- JP5380662B2 JP5380662B2 JP2005317992A JP2005317992A JP5380662B2 JP 5380662 B2 JP5380662 B2 JP 5380662B2 JP 2005317992 A JP2005317992 A JP 2005317992A JP 2005317992 A JP2005317992 A JP 2005317992A JP 5380662 B2 JP5380662 B2 JP 5380662B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- carrier
- varnish
- polyimide
- functional
- 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.)
- Expired - Fee Related
Links
- 229920005575 poly(amic acid) Polymers 0.000 title claims description 128
- 229920001721 polyimide Polymers 0.000 title claims description 81
- 239000004642 Polyimide Substances 0.000 title claims description 80
- 239000011246 composite particle Substances 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 47
- 239000002966 varnish Substances 0.000 claims description 104
- -1 tetracarboxylic anhydride Chemical class 0.000 claims description 89
- 239000002904 solvent Substances 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 54
- 125000000524 functional group Chemical group 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000000010 aprotic solvent Substances 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 239000011147 inorganic material Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000006358 imidation reaction Methods 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 3
- 230000003100 immobilizing effect Effects 0.000 claims 5
- 230000001476 alcoholic effect Effects 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 63
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 57
- 239000000741 silica gel Substances 0.000 description 47
- 229910002027 silica gel Inorganic materials 0.000 description 47
- 239000002245 particle Substances 0.000 description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 125000003277 amino group Chemical group 0.000 description 35
- 239000011325 microbead Substances 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 32
- 239000011347 resin Substances 0.000 description 26
- 229920005989 resin Polymers 0.000 description 26
- 239000002002 slurry Substances 0.000 description 22
- 239000011148 porous material Substances 0.000 description 20
- 235000010724 Wisteria floribunda Nutrition 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000002411 thermogravimetry Methods 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 9
- 150000003983 crown ethers Chemical group 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 230000009102 absorption Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 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 7
- 238000000926 separation method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 125000003172 aldehyde group Chemical group 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- IQGYCVKWCYGVBK-UHFFFAOYSA-N 5,6-diamino-1h-pyrimidine-2,4-dithione Chemical compound NC=1NC(=S)NC(=S)C=1N IQGYCVKWCYGVBK-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 description 3
- CQNGAZMLFIMLQN-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-trien-17-amine Chemical compound O1CCOCCOCCOCCOC2=CC(N)=CC=C21 CQNGAZMLFIMLQN-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 238000004807 desolvation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- DDAPSNKEOHDLKB-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)naphthalen-2-amine Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=C(N)C=CC2=C1 DDAPSNKEOHDLKB-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- RXCOGDYOZQGGMK-UHFFFAOYSA-N (3,4-diaminophenyl)-phenylmethanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=CC=C1 RXCOGDYOZQGGMK-UHFFFAOYSA-N 0.000 description 1
- HQDYNFWTFJFEPR-UHFFFAOYSA-N 1,2,3,3a-tetrahydropyrene Chemical compound C1=C2CCCC(C=C3)C2=C2C3=CC=CC2=C1 HQDYNFWTFJFEPR-UHFFFAOYSA-N 0.000 description 1
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- ODANWMOQWMHGCY-UHFFFAOYSA-N 1,4-diaminobutan-2-one Chemical compound NCCC(=O)CN ODANWMOQWMHGCY-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- FKBDSZNRJFOVHK-UHFFFAOYSA-N 2,5-bis(ethoxycarbonyl)terephthalic acid Chemical compound CCOC(=O)C1=CC(C(O)=O)=C(C(=O)OCC)C=C1C(O)=O FKBDSZNRJFOVHK-UHFFFAOYSA-N 0.000 description 1
- UQFHLJKWYIJISA-UHFFFAOYSA-N 2,6-dimethyl-1h-pyrimidin-4-one Chemical compound CC1=CC(O)=NC(C)=N1 UQFHLJKWYIJISA-UHFFFAOYSA-N 0.000 description 1
- YENVMPPRTXICRT-UHFFFAOYSA-N 2-(2,6-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C1=C(C(O)=O)C=CC=C1C(O)=O YENVMPPRTXICRT-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- FUJGQJMITCJTFA-UHFFFAOYSA-N 3-[3-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=C(OC=3C(=C(C(O)=O)C=CC=3)C(O)=O)C=CC=2)=C1C(O)=O FUJGQJMITCJTFA-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- KHDSXXRHWXXXBY-UHFFFAOYSA-N 3-[4-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC(OC=3C(=C(C(O)=O)C=CC=3)C(O)=O)=CC=2)=C1C(O)=O KHDSXXRHWXXXBY-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- 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
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical group C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 1
- QVMOHNTZLKZWNT-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]ethoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCOCCOCCOC1=CC=C(N)C=C1 QVMOHNTZLKZWNT-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-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
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 101150052439 Qdpr gene Proteins 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 description 1
- 229960004012 amifampridine Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling 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
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- RBMTXFLUVLIQGN-UHFFFAOYSA-N dodecane-1,10-diamine Chemical compound CCC(N)CCCCCCCCCN RBMTXFLUVLIQGN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002211 flavins Chemical class 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002339 glycosphingolipids Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229930013032 isoflavonoid Natural products 0.000 description 1
- 150000003817 isoflavonoid derivatives Chemical class 0.000 description 1
- 235000012891 isoflavonoids Nutrition 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 1
- 229930014802 neoflavonoid Natural products 0.000 description 1
- 150000002804 neoflavonoids Chemical class 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 125000003835 nucleoside group Chemical group 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、機能性ポリアミド酸複合粒子及び機能性ポリイミド複合粒子の製造方法に関する。 The present invention relates to a method for producing functional polyamic acid composite particles and functional polyimide composite particles.
ポリアミド酸あるいはポリイミドの粒子を製造する方法としては、これまでいくつかの方法が提案されている。 Several methods have been proposed for producing polyamic acid or polyimide particles.
例えば、特許文献１では、ポリイミド前駆体であるポリアミド酸のワニスを調製し、これを貧溶媒中に滴下し、沈殿法により粒子を製造する方法が開示されている。 For example, Patent Document 1 discloses a method in which a polyamic acid varnish that is a polyimide precursor is prepared, this is dropped into a poor solvent, and particles are produced by a precipitation method.
また、特許文献２には、ポリアミド酸の溶液をポリマー不溶溶媒中に入れて加熱して閉環させることによりイミド化を行い、生成した粒子状重合体を回収する方法が提案されている。 Patent Document 2 proposes a method in which a solution of a polyamic acid is placed in a polymer-insoluble solvent and heated to cause ring closure to perform imidization, and the produced particulate polymer is recovered.
特許文献３には、芳香族テトラカルボン酸二無水物（Ｉ）、芳香族ジアミン（II）を、（Ｉ）及び（II）は溶解するが、生成するポリアミド酸は溶解しない有機溶媒（III）中で、（Ｉ）及び（II）の総量を（III）に対して１０重量％以下として反応させることを特徴とするポリアミド酸微粒子の製造法が開示されている。
しかしながら、いずれの方法によっても、所望の粒径に制御されたポリアミド酸粒子又はポリイミド粒子を製造することは困難である。 However, it is difficult to produce polyamic acid particles or polyimide particles controlled to have a desired particle size by any method.
また、ポリアミド酸又はポリイミドの粒子を種々の用途に用いる場合、その用途によってはいろいろな機能性（反応性等）が要求されるが、前記の従来技術ではそれらの提案がなされていない。 Further, when polyamic acid or polyimide particles are used in various applications, various functions (reactivity, etc.) are required depending on the application, but no proposals have been made in the above prior art.
従って、本発明の主な目的は、所望の粒径に制御され、かつ、機能性を兼ね備えたポリアミド酸粒子又はポリイミド粒子を工業的規模で生産できる方法を提供することにある。 Accordingly, a main object of the present invention is to provide a method capable of producing polyamic acid particles or polyimide particles having a controlled particle size and functionality, on an industrial scale.
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定の方法により上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by a specific method, and has completed the present invention.
すなわち、本発明は、下記の機能性ポリアミド酸複合粒子及び機能性ポリイミド複合粒子の製造方法に係るものである。
１． 少なくとも無水テトラカルボン酸と多官能ジアミン化合物を反応させることにより機能性ポリアミド酸を調製する工程に際し、前記工程のいずれかの段階で担体を混合することにより、機能性基を有するポリアミド酸が担体に担持された複合粒子を製造する方法。
２． （ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸が溶解せず、かつ、前記非プロトン性極性溶媒と相溶性のある溶媒に前記混合物を分散することにより、ポリアミド酸を担体上に析出させる析出工程を含む、前記項１に記載の製造方法。
３． （ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程を含む、前記項１に記載の製造方法。
４． （ａ）無水テトラカルボン酸と多官能ジアミン化合物をアルコール系溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程、（ｄ）混合物中に含まれる溶媒を除去する溶媒除去工程を含む、前記項１に記載の製造方法。
５． 少なくとも無水テトラカルボン酸と多官能ジアミン化合物を反応させることにより機能性ポリアミド酸を調製し、次いで前記ポリアミド酸をイミド化することにより機能性ポリイミドを調製する工程に際し、前記工程のいずれかの段階で担体を混合することにより、機能性基を有するポリイミドが担体に担持された複合粒子を製造する方法。
６． （ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸が溶解せず、かつ、前記非プロトン性極性溶媒と相溶性のある溶媒に前記混合物を分散することにより、ポリアミド酸を担体上に析出させる析出工程、（ｄ）ポリアミド酸をイミド化するイミド化工程を含む、前記項５に記載の製造方法。
７． （ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程、（ｄ）ポリアミド酸をイミド化するイミド化工程
を含む、前記項５に記載の製造方法。
８． （ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸をイミド化するイミド化工程、（ｄ）ポリイミドが溶解せず、かつ、前記非プロトン性極性溶媒と相溶性のある溶媒に、前記イミド化工程で得られた混合物を分散することにより、ポリイミドを担体上に析出させる析出工程、
を含むことを特徴とする、前記項５に記載の製造方法。
９． （ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸をイミド化するイミド化工程、（ｄ）前記イミド化工程で得られた混合物から溶媒を除去する溶媒除去工程を含む、前記項５に記載の製造方法。
１０． （ａ）無水テトラカルボン酸と多官能ジアミン化合物をアルコール系溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程、（ｄ）ポリアミド酸をイミド化するイミド化工程を含む、前記項５に記載の製造方法。
１１． 担体が無機材料により構成されている、前記項１〜１０のいずれかに記載の製造方法。
１２． 担体があらかじめシランカップリング剤で処理されたものである、前記項１〜１１のいずれかに記載の製造方法。
That is, the present invention relates to the following method for producing functional polyamic acid composite particles and functional polyimide composite particles.
1. In the step of preparing a functional polyamic acid by reacting at least tetracarboxylic anhydride and a polyfunctional diamine compound, the polyamic acid having a functional group is added to the carrier by mixing the carrier at any stage of the above step. A method for producing a supported composite particle.
2. (A) a varnish preparation step for preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an aprotic solvent; (b) a mixture for obtaining a mixture by mixing a carrier with the varnish; A preparation step, (c) including a precipitation step in which the polyamic acid is not dissolved and the polyamic acid is precipitated on a support by dispersing the mixture in a solvent compatible with the aprotic polar solvent, Item 2. The manufacturing method according to Item 1.
3. (A) a varnish preparation step for preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an aprotic solvent; (b) a mixture for obtaining a mixture by mixing a carrier with the varnish; Item 2. The production method according to Item 1, comprising a preparation step and (c) a solvent removal step of removing the solvent contained in the mixture.
4). (A) a varnish preparation step of preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an alcohol solvent; (b) preparing a mixture by mixing a carrier with the varnish; Item 2. The production method according to Item 1, comprising a step, (c) a solvent removal step of removing the solvent contained in the mixture, and (d) a solvent removal step of removing the solvent contained in the mixture.
5. In the process of preparing a functional polyamic acid by reacting at least a tetracarboxylic anhydride and a polyfunctional diamine compound, and then preparing a functional polyimide by imidizing the polyamic acid, at any stage of the process A method for producing composite particles in which a polyimide having a functional group is supported on a carrier by mixing the carrier.
6). (A) a varnish preparation step for preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an aprotic solvent; (b) a mixture for obtaining a mixture by mixing a carrier with the varnish; A preparation step, (c) a precipitation step in which the polyamic acid is not dissolved and the mixture is dispersed in a solvent compatible with the aprotic polar solvent, thereby precipitating the polyamic acid on the support, (d) Item 6. The production method according to Item 5, comprising an imidization step of imidizing polyamic acid.
7). (A) a varnish preparation step for preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an aprotic solvent; (b) a mixture for obtaining a mixture by mixing a carrier with the varnish; Item 6. The production method according to Item 5, comprising a preparation step, (c) a solvent removal step of removing the solvent contained in the mixture, and (d) an imidization step of imidizing the polyamic acid.
8). (A) a varnish preparation step for preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an aprotic solvent; (b) a mixture for obtaining a mixture by mixing a carrier with the varnish; Preparation step, (c) imidization step for imidizing polyamic acid, (d) mixture obtained in the imidization step in a solvent in which polyimide does not dissolve and is compatible with the aprotic polar solvent A precipitation step of precipitating polyimide on the carrier by dispersing
The manufacturing method of said claim | item 5 characterized by including.
9. (A) a varnish preparation step for preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an aprotic solvent; (b) a mixture for obtaining a mixture by mixing a carrier with the varnish; Item 6. The production method according to Item 5, comprising a preparation step, (c) an imidization step in which the polyamic acid is imidized, and (d) a solvent removal step in which the solvent is removed from the mixture obtained in the imidization step.
10. (A) a varnish preparation step of preparing a polyamic acid-containing varnish by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound in an alcohol solvent; (b) preparing a mixture by mixing a carrier with the varnish; Item 6. The production method according to Item 5, comprising a step, (c) a solvent removal step of removing the solvent contained in the mixture, and (d) an imidization step of imidizing the polyamic acid.
11. Item 11. The method according to any one of Items 1 to 10, wherein the carrier is composed of an inorganic material.
12 Item 12. The production method according to any one of Items 1 to 11, wherein the carrier has been previously treated with a silane coupling agent.
本発明の製造方法によれば、特に、無水テトラカルボン酸と多官能ジアミン化合物との反応系において担体を存在させることによって、所望の粒径に制御された機能性複合粒子を製造することができる。この場合、担体の種類、多官能ジアミン化合物の種類等を変えることによって、さまざまな用途に適した複合粒子を作製することが可能である。例えば、クロマトグラフ（医薬品の分離精製、金属イオンの分離精製、同位体の分離精製、有機化合物の分離精製）、イオン交換（純水の製造、液体中のイオンの除去、燃料電池のイオン交換膜）
気体及び液体の浄化（脱臭、脱色、不純物の除去）、建材（断熱、防音、吸音、化学物質の除去）、プラスチック成形材及びフィルム（ガス分離、絶縁、光拡散、光拡散ディスプレイ材、ポリイミドフィルムへの添加、強度、靭性、耐熱性、難燃性の向上）、プラスチックやゴムへの添加剤（強度、靭性、耐熱性、難燃性の向上）等に用いることができる。
According to the production method of the present invention, functional composite particles controlled to have a desired particle size can be produced, particularly by allowing a carrier to be present in the reaction system of tetracarboxylic anhydride and a polyfunctional diamine compound. . In this case, composite particles suitable for various applications can be produced by changing the type of carrier, the type of polyfunctional diamine compound, and the like. For example, chromatograph (separation and purification of pharmaceuticals, separation and purification of metal ions, separation and purification of isotopes, separation and purification of organic compounds), ion exchange (production of pure water, removal of ions in liquid, ion exchange membrane of fuel cell) )
Gas and liquid purification (deodorization, decolorization, removal of impurities), building materials (heat insulation, sound insulation, sound absorption, chemical removal), plastic molding materials and films (gas separation, insulation, light diffusion, light diffusion display materials, polyimide films) And additives for plastics and rubber (improvement of strength, toughness, heat resistance, flame retardancy) and the like.
本発明の製造方法は、下記の１）機能性ポリアミド酸複合粒子の製造方法、２）機能性ポリイミド複合粒子の製造方法を包含する。 The production method of the present invention includes the following 1) production method of functional polyamic acid composite particles and 2) production method of functional polyimide composite particles.
前記１）は、無水テトラカルボン酸と多官能ジアミン化合物を反応させることにより機能性ポリアミド酸を調製する工程に際し、前記工程のいずれかの段階で担体を混合することにより、機能性基を有するポリアミド酸が担体に担持された複合粒子を製造する方法である。 The above 1) is a polyamide having a functional group by mixing a carrier at any stage of the above process in the process of preparing a functional polyamic acid by reacting a tetracarboxylic anhydride with a polyfunctional diamine compound. This is a method for producing composite particles in which an acid is supported on a carrier.
前記２）は、無水テトラカルボン酸と多官能ジアミン化合物を反応させることにより機能性ポリアミド酸を調製し、次いで前記ポリアミド酸をイミド化することにより機能性ポリイミドを調製する工程に際し、前記工程のいずれかの段階で担体を混合することにより、機能性基を有するポリイミドが担体に担持された複合粒子を製造する方法である。 The above 2) is a step in which a functional polyamic acid is prepared by reacting a tetracarboxylic anhydride and a polyfunctional diamine compound, and then a functional polyimide is prepared by imidizing the polyamic acid. This is a method for producing composite particles in which a polyimide having a functional group is supported on a carrier by mixing the carrier at such a stage.
このように、本発明の製造方法は、担体をいずれの段階で混合しても良い。また、用いる担体を１回にまとめて混合しても良いし、あるいは２回以上に分けて混合しても良い。 Thus, in the production method of the present invention, the carrier may be mixed at any stage. Further, the carriers to be used may be mixed all at once, or may be mixed in two or more times.
担体
担体は、機能性ポリアミド酸及び機能性ポリイミドの製造中に変質しないものであれば限定的でなく、例えば活性炭、シリカ等の無機系担体（無機材料から構成されるもの）、樹脂類、ゴム類等の有機系担体（有機材料から構成されるもの）を使用することができる。
The carrier carrier is not limited as long as it does not change during the production of the functional polyamic acid and the functional polyimide. For example, inorganic carrier (made of inorganic material) such as activated carbon and silica, resin, rubber An organic carrier (made of an organic material) such as an organic material can be used.
また、担体の形態も粉末状であれば限定されない。粒子形状も限定されず、例えば球状、針状、鱗片状等のいずれであっても良い。平均粒子径は一般的には０．５ｎｍ〜１ｍｍ程度とすれば良い。 Further, the form of the carrier is not limited as long as it is powdery. The particle shape is not limited, and may be any shape such as a spherical shape, a needle shape, and a scale shape. The average particle size may generally be about 0.5 nm to 1 mm.
担体は、多孔体であることが好ましい。この場合のＢＥＴ比表面積は１０〜４０００ｍ２／ｇ程度の範囲内で用途等に応じて適宜決定すれば良い。また、平均細孔径は限定的でないが、一般的には０．２ｎｍ〜０．１ｍｍ程度の範囲内で適宜設定すれば良い。 The carrier is preferably a porous body. In this case, the BET specific surface area may be appropriately determined in accordance with the application within the range of about 10 to 4000 m 2 / g. Further, the average pore diameter is not limited, but generally it may be appropriately set within a range of about 0.2 nm to 0.1 mm.
担体（特に無機系担体）は、あらかじめシランカップリング剤で処理（特に表面処理）されたものを用いることもできる。上記処理により、１）担体とポリイミドとの接着性又は密着性をより強固なものとすることができ、担体からの樹脂成分の脱落等を効果的に抑制することができる、２）被覆するポリイミドの低分子量化あるいはオリゴイミドの担持が可能となる（低分子量化により官能基の反応性を高めることができる）等の効果を得ることができる。 As the carrier (particularly, the inorganic carrier), one that has been previously treated with a silane coupling agent (particularly surface treatment) can also be used. By the above treatment, 1) the adhesiveness or adhesion between the carrier and the polyimide can be strengthened, and the resin component can be effectively prevented from dropping from the carrier. 2) The polyimide to be coated It is possible to obtain effects such as lowering the molecular weight or supporting oligoimide (reducing the molecular weight can increase the reactivity of the functional group).
シランカップリング剤は、担体の種類等に応じて公知又は市販のものから適宜選ぶことができる。例えば、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン等のアミン系シランカップリング剤；２−（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン等のエポキシ系シランカップリング剤；３−イソシアネートプロピルトリエトキシシラン等のイソシアネートシランカップリング剤等が挙げられる。この中でも、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン等の少なくとも１種が好ましい。 The silane coupling agent can be appropriately selected from known or commercially available ones according to the type of carrier. For example, N-phenyl-3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) ) Amine-based silane coupling agents such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycol Epoxy silane coupling agents such as cidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane And the like. Among these, at least one of 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like is preferable. .
シランカップリング剤による処理方法は、一般的な乾式法又は湿式法により実施することができる。乾式法は、担体（粒子）を撹拌機で高速攪拌し、シランカップリング剤の原液又は溶液を均一に分散させて処理する方法である。より具体的には、ミキサーに担体（粒子）を仕込み、攪拌した後、シラン化合物を滴下又は噴霧し、さらに攪拌すれば良い。また、湿式法は、シランカップリング剤の希薄溶液で担体をスラリー化したり、あるいは前記希薄溶液に担体を直接浸漬する方法である。より具体的には、撹拌機に水（又は１重量％酢酸水溶液）を充填し、攪拌し、シランカップリング剤を添加（担体に対して０．５〜１重量％が一般的）し、攪拌 しながら担体（粒子）を添加し、ろ過し、乾燥（１００〜１５０℃程度）すれば良い。いずれの場合も、シランカップリング剤の一般的な処理量（付与量）は、担体１００重量部に対して０．５〜２重量部程度とすれば良い。 The treatment method using a silane coupling agent can be carried out by a general dry method or wet method. The dry method is a method in which a carrier (particles) is stirred at high speed with a stirrer, and a stock solution or a solution of a silane coupling agent is uniformly dispersed and treated. More specifically, after the carrier (particles) is charged into the mixer and stirred, the silane compound is dropped or sprayed and further stirred. The wet method is a method in which a carrier is slurried with a dilute solution of a silane coupling agent, or a carrier is directly immersed in the dilute solution. More specifically, a stirrer is filled with water (or 1 wt% acetic acid aqueous solution), stirred, a silane coupling agent is added (generally 0.5 to 1 wt% with respect to the carrier), and stirred. The carrier (particles) may be added while being filtered, and dried (about 100 to 150 ° C.). In any case, the general processing amount (applied amount) of the silane coupling agent may be about 0.5 to 2 parts by weight with respect to 100 parts by weight of the carrier.
担体の使用量は、複合粒子の用途、担体の形態、使用形態当に応じて適宜設定することができる。例えば、機能性ポリアミド酸又は機能性ポリイミドの含有量が０．１〜３０重量％程度となるように適宜調整すれば良い。 The amount of the carrier used can be appropriately set according to the application of the composite particles, the form of the carrier, and the usage form. For example, what is necessary is just to adjust suitably so that content of a functional polyamic acid or a functional polyimide may be about 0.1 to 30 weight%.
以下、機能性ポリアミド酸及び機能性ポリイミドの製造方法に従って、本発明の製造方法を説明する。なお、機能性ポリイミドは、機能性ポリアミド酸から製造されるので、機能性ポリアミド酸の製法はまとめて説明する。 Hereinafter, the production method of the present invention will be described according to the production method of functional polyamic acid and functional polyimide. In addition, since functional polyimide is manufactured from functional polyamic acid, the manufacturing method of functional polyamic acid is demonstrated collectively.
１．機能性ポリアミド酸が担体に担持された複合粒子の製造
機能性ポリアミド酸は、無水テトラカルボン酸と多官能ジアミン化合物を反応させることにより製造される。
1. Production of composite particles in which functional polyamic acid is supported on a carrier Functional polyamic acid is produced by reacting tetracarboxylic anhydride with a polyfunctional diamine compound.
無水テトラカルボン酸
無水テトラカルボン酸は、特に制限されず、例えば従来のポリイミド合成で用いられているものと同様のものも使用できる。例えば、３，３'，４，４'−ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、３，３'，４，４'−ビフェニルテトラカルボン酸二無水物、２，３，３'，４'−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、１，３−ビス（２，３−ジカルボキシフェノキシ）ベンゼン二無水物、１，４−ビス（２，３−ジカルボキシフェノキシ）ベンゼン二無水物、２，３，３'，４'−ベンゾフェノンテトラカルボン酸二無水物、２，２'，３，３'−ベンゾフェノンテトラカルボン酸二無水物、２，２'，３，３'−ビフェニルテトラカルボン酸二無水物、２，２'，６，６'−ビフェニルテトラカルボン酸二無水物、ナフタレン−１，２，４，５−テトラカルボン酸二無水物、アントラセン−２，３，６，７−テトラカルボン酸二無水物、フェナンスレン−１，８，９，１０−テトラカルボン酸二無水物等の芳香族テトラカルボン酸無水物；ブタン−１，２，３，４−テトラカルボン酸二無水物等の脂肪族テトラカルボン酸無水物；シクロブタン−１，２，３，４−テトラカルボン酸二無水物等の脂環族テトラカルボン酸無水物；チオフェン−２，３，４，５−テトラカルボン酸無水物、ピリジン−２，３，５，６−テトラカルボン酸無水物等の複素環族テトラカルボン酸無水物等を使用することができる。これらは、１種又は２種以上を用いることができる。本発明では、特にＢＴＤＡ、ピロメリット酸二無水物等が好ましい。
Tetracarboxylic anhydride Tetracarboxylic anhydride is not particularly limited, and for example, those similar to those used in conventional polyimide synthesis can be used. For example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene Dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, anthracene-2,3,6 , 7-Tetracarboxylic dianhydride Aromatic tetracarboxylic anhydrides such as phenanthrene-1,8,9,10-tetracarboxylic dianhydride; aliphatic tetracarboxylic anhydrides such as butane-1,2,3,4-tetracarboxylic dianhydride Alicyclic tetracarboxylic anhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic anhydride, pyridine-2,3 , 5,6-tetracarboxylic acid anhydrides and the like can be used. These can use 1 type (s) or 2 or more types. In the present invention, BTDA, pyromellitic dianhydride and the like are particularly preferable.
また、本発明では、無水テトラカルボン酸の一部を酸クロライドで置換したものを使用することができる。酸クロライドで置換すれば、条件によって反応速度を大きくしたり、得られる粒子の粒径をより微細化できる等の効果が得られる。酸クロライドとしては、例えばジエチルピロメリテイトジアシルクロライド等を用いることができる。 Moreover, in this invention, what substituted a part of tetracarboxylic anhydride with the acid chloride can be used. By substituting with acid chloride, it is possible to obtain effects such as increasing the reaction rate depending on conditions and making the particle size of the particles obtained finer. As the acid chloride, for example, diethyl pyromellitate diacyl chloride and the like can be used.
多官能ジアミン化合物
多官能ジアミン化合物は、得られる複合粒子表面上に所望の機能を付与できるものであれば良い。機能性基としては、例えば水酸基（−ＯＨ）、カルボキシル基（−ＣＯＯＨ）、アミノ基（−ＮＨ２）、アルケン類（−ＣＨ＝ＣＨ−）、アルキン類（−Ｃ≡Ｃ−）、ビニルエーテル類（−ＣＨ＝ＣＨ−Ｏ−）、アミド基（−ＣＯＮＨ２）、ニトリル基（−Ｃ≡Ｎ）、イソシアネート基（−Ｎ＝Ｃ＝Ｏ）、ニトロ基（−ＮＯ２）、スルホン基（−ＳＯ３Ｈ）、チオール基（−ＳＨ）、アルデヒド基（−ＣＯＨ）、エポキシ基、クラウンエーテル基、無水カルボキシル基、エステル基、シアン基、エポキシ基、イミド基、ハロゲノ基、エーテル基等の官能基のほか、−ＣＦ３基、−ＣＣｌ３基、−ＣＢｒ３等を挙げることができる。また、有機金属も挙げることができる。
Polyfunctional diamine compound The polyfunctional diamine compound is not particularly limited as long as it can provide a desired function on the surface of the obtained composite particles. Examples of functional groups include hydroxyl groups (—OH), carboxyl groups (—COOH), amino groups (—NH 2 ), alkenes (—CH═CH—), alkynes (—C≡C—), vinyl ethers. (—CH═CH—O—), amide group (—CONH 2 ), nitrile group (—C≡N), isocyanate group (—N═C═O), nitro group (—NO 2 ), sulfone group (— SO 3 H), thiol group (—SH), aldehyde group (—COH), epoxy group, crown ether group, anhydrous carboxyl group, ester group, cyan group, epoxy group, imide group, halogeno group, ether group, etc. other groups, -CF 3 group, -CCl 3 group, can be exemplified -CBr 3, and the like. Moreover, an organic metal can also be mentioned.
多官能ジアミン化合物として、具体的には１，３−ジアミノ−２−プロピルアルコール（ＤＨＰｒ）、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン（ＢＩＳ．Ａ．ＡＦ）、３，５−ジアミノ安息香酸、（３．５．ＤＢＡ）、２，４−ジメチル−６−ヒドロキシピリミジン（２．４．Ｄ．６．ＨＰ）、２，４，６−トリアミノピリミジン（２．４．６．ＴＡＰＭ）等が例示できる。これらは、１種又は２種以上を用いることができる。本発明では、特に３．５．ＤＢＡ、２．４．６．ＴＡＰＭ等が好ましい。 Specific examples of the polyfunctional diamine compound include 1,3-diamino-2-propyl alcohol (DHPr), 2,2-bis (4-aminophenyl) hexafluoropropane (BIS.A.AF), 3,5- Diaminobenzoic acid, (3.5.DBA), 2,4-dimethyl-6-hydroxypyrimidine (2.4.D.6.HP), 2,4,6-triaminopyrimidine (2.4.6. TAPM) and the like. These can use 1 type (s) or 2 or more types. In the present invention, particularly 3.5. DBA, 2.4.6. TAPM and the like are preferable.
また、本発明では、必要に応じて通常のジアミン化合物も併用することができる。例えば、４，４’−ジアミノジフェニルメタン（ＤＤＭ）、４，４’−ジアミノジフェニルエーテル（ＤＰＥ）、４，４’−ビス（４−アミノフェノキシ）ビフェニル（ＢＡＰＢ）、４，４’−ビス（３−アミノフェノキシ）ビフェニル、１，４’−ビス（４−アミノフェノキシ）ベンゼン（ＴＰＥ−Ｑ）、１，３’−ビス（４−アミノフェノキシ）ベンゼン（ＴＰＥ−Ｒ）、１，３−ビス（３−アミノフェノキシ）ベンゼン、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルフォン、３，４−ジアミノジフェニルスルフォン、３，３'−ジアミノジフェニルスルフォン、ビス［４−（３−アミノフェノキシ）フェニル］スルフォン（ＢＡＰＳ−Ｍ）、４，４’−メチレン−ビス（２−クロロアニリン）、３，３’−ジメチル−４，４’−ジアミノビフェニル、４，４’−ジアミノジフェニルスルフィド、２，６’−ジアミノトルエン、２，４−ジアミノクロロベンゼン、１，２−ジアミノアントラキノン、１，４−ジアミノアントラキノン、３，３’−ジアミノベンゾフェノン、３，４−ジアミノベンゾフェノン、４，４’−ジアミノベンゾフェノン、４，４’−ジアミノビベンジル、Ｒ（＋）−２，２’−ジアミノ−１，１’−ビナフタレン、Ｓ（＋）−２，２’−ジアミノ−１，１’−ビナフタレン、１，３−ビス（４−アミノフェノキシ）アルカン、１，４−ビス（４−アミノフェノキシ）アルカン、１，５−ビス（４−アミノフェノキシ）アルカン等の１，ｎ−ビス（４−アミノフェノキシ）アルカン（ｎは、３〜１０）、１，２−ビス［２−（４−アミノフェノキシ）エトキシ］エタン、９，９−ビス（４−アミノフェニル）フルオレン等の芳香族ジアミン；１，２−ジアミノメタン、１，４−ジアミノブタン、テトラメチレンジアミン、１，５−ジアミノペンタン、１，６−ジアミノヘキサン、１，８−ジアミノオクタン、１，１０−ジアミノドデカン、１，１１−ジアミノウンデカン等の脂肪族ジアミン；１，４−ジアミノシクロヘキサン、１，２−ジアミノシクロヘキサン、ビス（４−アミノシクロヘキシル）メタン、４，４’−ジアミノジシクロヘキシルメタン等の脂環族ジアミンのほか、３，４−ジアミノピリジン、１，４−ジアミノ−２−ブタノン等を使用することができる。これらは、１種又は２種以上を用いることができる。本発明では、特にＤＰＥ、ＴＰＥ−Ｒ、ＢＡＰＳ−Ｍ等が好ましい。 Moreover, in this invention, a normal diamine compound can also be used together as needed. For example, 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenyl ether (DPE), 4,4′-bis (4-aminophenoxy) biphenyl (BAPB), 4,4′-bis (3- Aminophenoxy) biphenyl, 1,4′-bis (4-aminophenoxy) benzene (TPE-Q), 1,3′-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3 -Aminophenoxy) benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3 ' -Diaminodiphenylsulfone, bis [4- (3-aminophenoxy) phenyl] sulfone ( BAPS-M), 4,4′-methylene-bis (2-chloroaniline), 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminodiphenyl sulfide, 2,6′-diamino Toluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3′-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4 ′ -Diaminobibenzyl, R (+)-2,2'-diamino-1,1'-binaphthalene, S (+)-2,2'-diamino-1,1'-binaphthalene, 1,3-bis (4 1, n-bi, such as -aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane Aromatics such as (4-aminophenoxy) alkane (n is 3 to 10), 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminododecane, 1, In addition to aliphatic diamines such as 11-diaminoundecane; alicyclic diamines such as 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 4,4′-diaminodicyclohexylmethane, 3,4-diaminopyridine, 1,4-diamino-2-butanone and the like can be used. These can use 1 type (s) or 2 or more types. In the present invention, DPE, TPE-R, BAPS-M and the like are particularly preferable.
また、本発明では、機能性ポリアミド酸及び機能性ポリイミド（又はこれらの複合粒子）の機能性基と、機能性を有する化合物とをさらに反応させて二次的に新たな機能性を付与することもできる。機能性を有する化合物としては、例えばクラウンエーテル類、ジグリシジルエーテル類、ジアルデヒド類、イオン交換機能、炭水化物（単糖類、オリゴ糖、多糖類など）、ステロイド類、テルペノイド類、アルカロイド類、テトラピロール類、グリコスフィンゴ脂質、フラボノイド、イソフラボノイド、ネオフラボノイド、ヌクレオシドとヌクレオチド、フラビン、ビタミンＢ−６類、フラーレン、複素環化合物、有機環状化合物、色素、顔料、有機ＬＥＤ等を挙げることができる。 In the present invention, the functional group of functional polyamic acid and functional polyimide (or composite particles thereof) and a functional compound are further reacted to impart secondary functionality. You can also. Examples of functional compounds include crown ethers, diglycidyl ethers, dialdehydes, ion exchange functions, carbohydrates (monosaccharides, oligosaccharides, polysaccharides, etc.), steroids, terpenoids, alkaloids, tetrapyrrole And glycosphingolipids, flavonoids, isoflavonoids, neoflavonoids, nucleosides and nucleotides, flavins, vitamin B-6s, fullerenes, heterocyclic compounds, organic cyclic compounds, dyes, pigments, organic LEDs and the like.
無水カルボン酸と多官能ジアミンとの反応
無水テトラカルボン酸と多官能ジアミン化合物を反応で使用する溶媒は特に制限されない。例えば、２−プロパノン、３−ペンタノン、テトラヒドロピレン、エピクロロヒドリン、アセトン、メチルエチルケトン（ＭＥＫ）、テトラヒドロフラン（ＴＨＦ）、酢酸エチル、アセトアニリド、メタノール、エタノール、イソプロパノール等の少なくとも１種を含む溶媒を使用できる。また、例えばＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）等の非プロトン性極性溶媒のように、ポリアミド酸が溶解する溶媒を使用することもできる。さらに、例えばアセトン、酢酸エチル、ＭＥＫ、トルエン、キシレン等のポリアミド酸の貧溶媒を混合してポリアミド酸が沈殿するように調整することもできる。
Reaction of carboxylic anhydride and polyfunctional diamine The solvent in which the tetracarboxylic anhydride and the polyfunctional diamine compound are used in the reaction is not particularly limited. For example, a solvent containing at least one of 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, acetanilide, methanol, ethanol, isopropanol and the like is used. it can. In addition, a solvent in which polyamic acid dissolves, such as an aprotic polar solvent such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), etc. Can also be used. Furthermore, it can also adjust so that polyamic acid may precipitate by mixing the poor solvent of polyamic acids, such as acetone, ethyl acetate, MEK, toluene, and xylene.
この場合、例えば無水カルボン酸と多官能ジアミン化合物とを１つの溶媒中に添加し、反応させても良いし、あるいは別々の溶液として調製した後に両溶液を混合することにより反応させても良い。前者の場合は、溶媒中に担体を混合することができる。また、後者の場合は、いずれかの溶液の少なくとも一方に担体を混合することができる。 In this case, for example, the carboxylic anhydride and the polyfunctional diamine compound may be added and reacted in one solvent, or may be reacted by mixing both solutions after prepared as separate solutions. In the former case, the carrier can be mixed in the solvent. In the latter case, the carrier can be mixed with at least one of the solutions.
無水カルボン酸と多官能ジアミン化合物との配合比率は、無水テトラカルボン酸・ジアミン化合物の種類、各溶液の濃度等によって適宜変更できるが、通常は無水テトラカルボン酸：ジアミン化合物＝１：０．５〜１．５程度（モル比）、好ましくは１：０．９〜１．１となるように混合すれば良い。 The mixing ratio of the carboxylic anhydride and the polyfunctional diamine compound can be appropriately changed depending on the kind of the tetracarboxylic anhydride / diamine compound, the concentration of each solution, etc., but usually the tetracarboxylic anhydride: diamine compound = 1: 0.5. It is sufficient to mix so as to be about ~ 1.5 (molar ratio), preferably 1: 0.9 to 1.1.
無水カルボン酸と多官能ジアミン化合物との反応によって、機能性基（官能基）を有するポリアミド酸が生成する。両者を溶媒中で反応させる場合は、反応生成物としてワニス（ポリアミド酸含有ワニス）の形態で得ることができる。 A polyamic acid having a functional group (functional group) is generated by the reaction between the carboxylic anhydride and the polyfunctional diamine compound. When both are reacted in a solvent, the reaction product can be obtained in the form of a varnish (polyamic acid-containing varnish).
反応生成物としてのポリアミド酸は、機能性基（官能基）を有するポリアミド酸として得られるが、必要に応じてこの機能性基（第一の機能性基）に第二の機能性基（又は前記の機能性を有する化合物）を付与することもできる。例えば、第一の機能性基がアミノ基である場合、それにＢＴＤＡを反応させることにより、第二の機能性基として無水カルボン酸を有するポリアミド酸を得ることができる。このような工程も本発明の製造方法に包含される。 The polyamic acid as the reaction product is obtained as a polyamic acid having a functional group (functional group). If necessary, the functional group (first functional group) may be replaced with a second functional group (or The compound having the above-mentioned functionality can also be imparted. For example, when the first functional group is an amino group, polyamic acid having a carboxylic anhydride as the second functional group can be obtained by reacting BTDA with the first functional group. Such a process is also included in the production method of the present invention.
本発明では、上記ワニスが生成した段階で、これを担体に担持させることが好ましい。すなわち、ポリアミド酸含有ワニスに担体を混合することが好ましい。混合方法としては、例えばポリアミド酸含有ワニスと担体とを公知の攪拌機、混合機等を用いて混合すれば良い。この場合に得られる混合物は、用いる溶媒量に応じて固形状から液状（流動体）までの形態をとり得る。いずれも本発明に包含される。 In the present invention, it is preferable to support the varnish on the carrier when the varnish is formed. That is, it is preferable to mix a carrier with the polyamic acid-containing varnish. As a mixing method, for example, the polyamic acid-containing varnish and the carrier may be mixed using a known stirrer, mixer or the like. The mixture obtained in this case can take a form from solid to liquid (fluid) depending on the amount of solvent used. Both are included in the present invention.
例えば、上記混合物が液状（溶媒量が相対的に多い場合）は、ポリアミド酸が溶解せず、かつ、前記ワニスの溶媒と相溶性のある溶媒に前記混合物を分散することにより、ポリアミド酸を担体上に析出させる方法（析出工程）を採用することが好ましい。例えば、溶媒として、ＤＭＦ、ＤＭＡｃ、ＮＭＰ等の非プロトン性極性溶媒を用いた場合は、前記混合物をアセトン、酢酸エチル、ＭＥＫ、トルエン、キシレン等の溶媒に分散させれば良い。ここで使用される溶媒の量は、ポリアミド酸が析出するのに十分な量とすれば良い。その後、例えば静置分離、遠心分離等の方法により固液分離すれば良い。 For example, when the mixture is liquid (when the amount of the solvent is relatively large), the polyamic acid is not dissolved, and the polyamic acid is dispersed in a solvent compatible with the solvent of the varnish, thereby supporting the polyamic acid. It is preferable to employ a method of precipitation on top (precipitation step). For example, when an aprotic polar solvent such as DMF, DMAc, or NMP is used as the solvent, the mixture may be dispersed in a solvent such as acetone, ethyl acetate, MEK, toluene, or xylene. The amount of the solvent used here may be a sufficient amount for the polyamic acid to precipitate. Thereafter, solid-liquid separation may be performed by a method such as stationary separation or centrifugation.
また例えば、上記混合物が固体状（溶媒量が相対的に少ない場合）は、混合物中に含まれる溶媒を除去する方法（溶媒除去工程）を採用することが好ましい。溶媒を除去する方法は限定的でなく、例えば、減圧脱溶媒、常圧加熱脱溶媒、減圧加熱脱溶媒等の方法を採用することができる。 For example, when the mixture is solid (when the amount of the solvent is relatively small), it is preferable to employ a method (solvent removal step) for removing the solvent contained in the mixture. The method for removing the solvent is not limited. For example, methods such as vacuum desolvation, atmospheric pressure heating desolvation, and vacuum heating desolvation can be employed.
２．機能性ポリイミドが担体に担持された複合粒子の製造
機能性ポリイミドが担体に担持された複合粒子を製造する場合は、（１）前記１．のポリアミド酸含有ワニスに担体を共存させた状態でイミド化を行う方法、（２）前記１．のポリアミド酸含有ワニスを製造し、さらにポリアミド酸をイミド化した後に、得られたポリイミドを担体に担持する方法等のいずれも採用することができる。
2. Production of composite particles in which functional polyimide is supported on carrier When producing composite particles in which functional polyimide is supported on carrier, (1) A method of imidization in a state in which a carrier is allowed to coexist with the polyamic acid-containing varnish of (2). Any of the methods for producing a polyamic acid-containing varnish of this and further imidizing the polyamic acid and then supporting the obtained polyimide on a carrier can be employed.
上記（１）の方法は、さらに１）析出工程又は溶媒除去工程を経たものをイミド化する方法、２）前記１．の析出工程又は溶媒除去工程を経ていないものをイミド化する方法がある。 The above-mentioned method (1) further includes 1) a method for imidizing the product subjected to the precipitation step or the solvent removal step, and 2) the above-mentioned 1. There is a method of imidizing those that have not undergone the precipitation step or solvent removal step.
前記１）の析出工程又は溶媒除去工程は、前記１．の方法と同様にして実施することができる。 The precipitation step or the solvent removal step of 1) is the same as described in 1. above. The method can be carried out in the same manner as described above.
前記２）では、ポリアミド酸をイミド化した後に、析出工程又は溶媒除去工程を実施すれば良い。この場合、溶媒除去工程は、前記１．の方法と同様にすれば良い。また、析出工程は、ポリイミドが溶解せず、かつ、前記溶媒（例えば、非プロトン性極性溶媒）と相溶性のある溶媒に分散する方法を採用でき、例えば前記１．の析出工程と同様に実施することができる。 In 2), after imidizing the polyamic acid, a precipitation step or a solvent removal step may be performed. In this case, the solvent removal step is performed as described in 1. above. It may be done in the same way as above. The precipitation step can employ a method in which polyimide is not dissolved and is dispersed in a solvent compatible with the solvent (for example, aprotic polar solvent). It can carry out similarly to the precipitation process.
前記（１）（２）の方法において、ポリアミド酸をイミド化する方法は特に制限されないが、特に（i）有機溶媒中で加熱してイミド化する方法（湿式熱閉環）、（ii）有機溶媒中における化学反応によりイミド化する方法（化学閉環）、又は（iii）乾式（無溶媒下）で加熱することによりイミド化する方法（乾式熱閉環）を採用することが望ましい。 In the methods (1) and (2), the method for imidizing the polyamic acid is not particularly limited, but in particular (i) the method for imidizing by heating in an organic solvent (wet thermal ring closure), (ii) the organic solvent It is desirable to employ a method of imidization by chemical reaction in the inside (chemical ring closure) or (iii) a method of imidization by heating in a dry mode (without solvent) (dry thermal ring closure).
上記（ｉ）の加熱による方法は、例えばポリアミド酸を有機溶媒中に分散させ、通常１３０℃以上、好ましくは１３０〜２５０℃程度の温度で加熱すれば良い。有機溶媒としては、ポリアミド酸の貧溶媒であり、かつ、イミド化反応に必要な温度以上の沸点を有するものであれば制限されない。特に、本発明では、上記有機溶媒中に水と共沸混合物を構成し得る溶媒（以下「共沸溶媒」ともいう）を含むことが好ましい。すなわち、本発明では、共沸溶媒を上記有機溶媒の一部又は全部として用いることが好ましい。共沸溶媒としては、例えばキシレン、エチルベンゼン、オクタン、シクロヘキサン、ジフェニルエーテル、ノナン、ピリジン、ドデカン等を用いることができる。これらは１種又は２種以上を用いることができる。本発明では、共沸溶媒は上記有機溶媒中１０容積％以上含むことが好ましい。共沸溶媒を使用することによって、特に副生する水（主に縮合水）を共沸させ、これを還流等により反応系外へ除去できることから、未反応のアミド結合の加水分解を抑制し、粒子の形態の変化、分子量の低下等を防止できる結果、単分散性に優れたポリイミド微粒子がより確実に得られる。 In the method (i) by heating, for example, polyamic acid is dispersed in an organic solvent and heated at a temperature of usually 130 ° C. or higher, preferably about 130 to 250 ° C. The organic solvent is not limited as long as it is a poor solvent for polyamic acid and has a boiling point equal to or higher than the temperature required for the imidization reaction. In particular, in the present invention, the organic solvent preferably contains a solvent capable of forming an azeotrope with water (hereinafter also referred to as “azeotropic solvent”). That is, in the present invention, it is preferable to use an azeotropic solvent as a part or all of the organic solvent. As the azeotropic solvent, for example, xylene, ethylbenzene, octane, cyclohexane, diphenyl ether, nonane, pyridine, dodecane and the like can be used. These can use 1 type (s) or 2 or more types. In the present invention, the azeotropic solvent is preferably contained in the organic solvent in an amount of 10% by volume or more. By using an azeotropic solvent, water produced as a by-product (mainly condensed water) can be azeotropically removed and removed from the reaction system by refluxing, etc., thereby suppressing hydrolysis of unreacted amide bonds, As a result of preventing changes in particle shape, lowering of molecular weight, and the like, polyimide fine particles having excellent monodispersibility can be obtained more reliably.
有機溶媒中に分散させるポリアミド酸の割合は、有機溶媒の種類等に応じて適宜設定すれば良いが、通常は１〜５０ｇ／リットル程度、好ましくは５〜１０ｇ／リットルとすれば良い。 The ratio of the polyamic acid dispersed in the organic solvent may be appropriately set according to the type of the organic solvent, but is usually about 1 to 50 g / liter, preferably 5 to 10 g / liter.
上記（ii）の化学反応による方法では、公知の化学閉環方法を適用することができる。例えば、ポリアミド酸微粒子をピリジン及び無水酢酸からなる有機溶媒中に分散させ、撹拌しながら通常１５〜１１５℃程度の温度で２４時間程度加熱すれば良い。両溶媒の配合割合は適宜設定すれば良い。
上記（iii）による方法では、例えばポリアミド酸を空気中、真空中、不活性ガス中等の雰囲気下で上記微粒子を流動させながら加熱すれば良い。加熱温度は、一般的には１３０〜３００℃程度とすれば良い。また、流動方法は、公知の攪拌流動装置等を用いることによって実施することができる。この方法によっても、粒子を凝集させることなくイミド化することが可能である。特に、この方法では、溶媒が実質的に存在しない条件下でイミド化を行うので、加熱効率が良く、また安全性等においても有利である。
In the method based on the chemical reaction (ii), a known chemical ring closure method can be applied. For example, polyamic acid fine particles may be dispersed in an organic solvent composed of pyridine and acetic anhydride and heated at a temperature of usually about 15 to 115 ° C. for about 24 hours while stirring. What is necessary is just to set the mixture ratio of both solvents suitably.
In the method according to (iii), for example, polyamic acid may be heated while flowing the fine particles in an atmosphere such as air, vacuum, or inert gas. The heating temperature may generally be about 130 to 300 ° C. Further, the flow method can be carried out by using a known stirring flow device or the like. Also by this method, it is possible to imidize without agglomerating particles. In particular, in this method, since imidization is performed under a condition in which a solvent is not substantially present, heating efficiency is good and safety is advantageous.
生成したポリイミドは、公知の方法により回収し、必要に応じて石油エーテル、メタノール、アセトン等の有機溶剤で洗浄すれば良い。 The produced polyimide may be recovered by a known method and washed with an organic solvent such as petroleum ether, methanol, acetone or the like as necessary.
以下に実施例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。 The features of the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the examples.
実施例１
ＢＴＤＡ（１．０１ｇ）をメタノール５００ｍＬに溶かし、ＤＰＥ（０．５４ｇ）を添加して溶解した後、２．４．６．ＴＡＰＭ（０．０９ｇ）を添加することにより、ワニスを得た。マイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ７０００−６０／１００ｍｅｓｈ」富士シリシア化学製、ＢＥＴ比表面積３４．５２７ｍ２／ｇ、平均細孔径７２９ｎｍ）１０ｇを前記ワニス１５０ｍＬに分散し、常温減圧下で溶媒を揮発させて乾燥した。
次いで、乾燥物（ポリアミド酸とシリカゲルの複合粒子）を２００℃で４時間熱処理してイミド化することによって、表面にアミノ基を有するシリカ−ポリイミド複合粒子を得た。
イミド化させた粒子をアセトン（５０ｍＬ）中に分散し、ＢＴＤＡ（１ｇ）を加え、振とう器にて室温下２４時間攪拌した。その後、ろ過し、繰り返しアセトンで洗浄した後、乾燥し、２００℃で４時間処理してイミド化することによって、表面に無水テトラカルボン酸を有するシリカ−ポリイミド複合粒子を得た。
Example 1
BTDA (1.01 g) was dissolved in 500 mL of methanol, and DPE (0.54 g) was added and dissolved, then 2.4.6. Varnish was obtained by adding TAPM (0.09 g). 10 g of microbead silica gel (“Micro Bead Silica Gel MB7000-60 / 100 mesh” manufactured by Fuji Silysia Chemical Ltd., BET specific surface area 34.527 m 2 / g, average pore size 729 nm) is dispersed in 150 mL of the varnish, and the solvent is removed under reduced pressure at room temperature. Volatilized and dried.
Next, the dried product (composite particles of polyamic acid and silica gel) was heat-treated at 200 ° C. for 4 hours to imidize to obtain silica-polyimide composite particles having amino groups on the surface.
The imidized particles were dispersed in acetone (50 mL), BTDA (1 g) was added, and the mixture was stirred with a shaker at room temperature for 24 hours. Then, after filtering and wash | cleaning repeatedly with acetone, it dried, and it processed at 200 degreeC for 4 hours, and obtained the silica-polyimide composite particle which has an anhydrous tetracarboxylic acid on the surface.
４’−アミノベンゾ−１５−クラウン−５−エーテル（０．１２ｇ）をアセトン５０ｍＬに溶解した溶液に、上記の表面に無水テトラカルボン酸を有するシリカ−ポリイミド複合粒子（約５ｇ）を分散し、振とう器にて室温下２４時間攪拌した。ろ別し、アセトンで繰り返し洗浄した後、１５０℃で５時間熱処理してイミド化することによって、クラウンエーテル担持シリカ−ポリイミド複合粒子を得た。 Silica-polyimide composite particles (about 5 g) having tetracarboxylic anhydride on the surface are dispersed in a solution of 4′-aminobenzo-15-crown-5-ether (0.12 g) in 50 mL of acetone. The mixture was stirred for 24 hours at room temperature in a stirrer. After filtration and washing repeatedly with acetone, the mixture was heat treated at 150 ° C. for 5 hours to imidize to obtain crown ether-supported silica-polyimide composite particles.
実施例２
ＢＴＤＡ（３２．２ｇ）をＤＭＦ１０００ｍＬに溶かし、ＤＰＥ（１６．０ｇ）を添加して溶解した後、２．４．６．ＴＡＰＭ（２．５ｇ）を添加することにより、アミノ基を有するポリアミド酸ワニス（Ａ）を得た。このワニス２００ｍＬにＢＴＤＡ（１．２９ｇ）を添加し、２４時間攪拌することにより、無水カルボン酸を有するポリアミド酸ワニス（Ｂ）を得た。前記ワニス（Ｂ）２００ｍＬにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ７０００−６０／１００ｍｅｓｈ」富士シリシア化学製、ＢＥＴ比表面積３４．５２７ｍ２／ｇ、平均細孔径７２９ｎｍ）１２０ｇを分散した（嵩の比率＝およそ１：１）。脱気してから振とう器で２４時間攪拌した後、ろ過することによりシリカを分離し、多量のアセトンに分散した。シリカ粒子の細孔に含まれていたポリアミド酸は相分離し、シリカの細孔中に残り、それ以外のものは微細なフリーのポリアミド酸粒子になると考えられる。シリカ−ポリアミド酸複合粒子は、デカンテーションにより分離し、繰り返しアセトンで洗浄した。乾燥後、２００℃で４時間熱処理してイミド化し、シリカ−表面に無水カルボン酸を有するポリイミドの複合粒子とした。
Example 2
BTDA (32.2 g) was dissolved in 1000 mL of DMF, DPE (16.0 g) was added and dissolved, and then 2.4.6. TAPM (2.5 g) was added to obtain a polyamic acid varnish (A) having an amino group. BTDA (1.29 g) was added to 200 mL of this varnish and stirred for 24 hours to obtain a polyamic acid varnish (B) having carboxylic anhydride. In 200 mL of the varnish (B), 120 g of microbead silica gel (“Micro Bead Silica Gel MB7000-60 / 100 mesh” manufactured by Fuji Silysia Chemical Ltd., BET specific surface area 34.527 m 2 / g, average pore diameter 729 nm) was dispersed (volume ratio). = Approximately 1: 1). After deaeration, the mixture was stirred with a shaker for 24 hours, and then the silica was separated by filtration and dispersed in a large amount of acetone. The polyamic acid contained in the pores of the silica particles is phase-separated and remains in the pores of the silica, and the others are considered to be fine free polyamic acid particles. Silica-polyamic acid composite particles were separated by decantation and repeatedly washed with acetone. After drying, it was heat-treated at 200 ° C. for 4 hours to imidize to obtain polyimide composite particles having a carboxylic anhydride on the silica surface.
次に、表面に無水カルボン酸を有するシリカ−ポリイミド複合粒子をアセトン４００ｍＬ中に分散させてスラリーをつくり、そこに４’−アミノベンゾ−１５−クラウン−５−エーテル（１ｇ）を添加し、振とう器にて室温下２４時間攪拌した。その後、ろ過し、繰り返しアセトンで洗浄した後、乾燥し、１５０℃で５時間処理してイミド化することによって、表面にクラウンエーテル担持シリカ−ポリイミド複合粒子を得た。このときの複合粒子における樹脂含有率は５．１２重量％、ＢＥＴ比表面積は３５．０６３ｍ２／ｇであった。 Next, a silica-polyimide composite particle having carboxylic anhydride on the surface is dispersed in 400 mL of acetone to form a slurry, to which 4′-aminobenzo-15-crown-5-ether (1 g) is added and shaken. The mixture was stirred at room temperature for 24 hours. Then, after filtering and washing | cleaning repeatedly with acetone, it dried and processed at 150 degreeC for 5 hours, and obtained the crown ether carrying | support silica-polyimide composite particle on the surface. The resin content in the composite particles at this time was 5.12% by weight, and the BET specific surface area was 35.063 m 2 / g.
粒子表面のクラウンエーテルの亜鉛吸着能力を評価した。１００ｍｌのスクリュー管の中に入れた試料の２０ｍｌ（８．２８ｇ）に亜鉛イオン濃度１．７７２５ppに調製した５０ｍｌを加えて密封し、４８時間しんとう器で撹拌した後、塩化亜鉛水溶液をろ過した。ろ液を蒸留水で２倍に希釈したものを原子吸光測定により亜鉛の濃度を求めた。その結果を以下に示す。
・標準液の亜鉛濃度：０．８８４５４ｐｐｍ（実測値）
・処理後の亜鉛濃度：０．２３２８１ｐｐｍ（実測値）
７３．７％の亜鉛イオンを吸着した。
The zinc ether adsorption capacity of crown ether on the particle surface was evaluated. 50 ml of a zinc ion concentration of 1.7725 pp was added to 20 ml (8.28 g) of the sample placed in a 100 ml screw tube, sealed, and stirred for 48 hours in a shaker, and then the aqueous zinc chloride solution was filtered. The filtrate was diluted twice with distilled water, and the zinc concentration was determined by atomic absorption measurement. The results are shown below.
-Zinc concentration of standard solution: 0.884454 ppm (actual value)
-Zinc concentration after treatment: 0.23281 ppm (actual value)
73.7% zinc ions were adsorbed.
実施例３
ＢＴＤＡ（３．２２ｇ）をＤＭＦ１００ｍＬに溶かし、ＢＡＰＳ−Ｍ（３．４６ｇ）を添加して溶解した後、２．４．６．ＴＡＰＭ（０．２５ｇ）を添加し、常温で２４時間攪拌することにより、表面にアミノ基を有するポリアミド酸ワニス（Ａ）を得た。このワニス（Ａ）２００ｍＬにトルエン２０ｍＬを添加し、共沸により副生する水を反応系外に留去しながら４時間環流し、官能基を有するポリイミドのワニス（Ｂ）（可溶性ポリイミドのワニス）を得た。得られたワニス（Ｂ）１００ｇにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ７０００−６０／１００ｍｅｓｈ」富士シリシア化学製、ＢＥＴ比表面積３４．５２７ｍ２／ｇ、平均細孔径７２９ｎｍ）５０ｇを加え、スラリー（嵩の比率＝およそ１：１）とした。このスラリーに対して超音波処理及び常温減圧処理を施すことにより脱泡した。このスラリーを多量のアセトンに分散させ、ポリアミド酸を相分離させた。すなわち、ＤＭＦはメタノールに溶解し、ポリイミドは相分離させた。アセトンで繰り返し洗浄し、乾燥することにより、表面にアミノ酸を有するポリイミド−シリカ複合粒子を得た。このときの複合粒子における樹脂含有率は５．８重量％、ＢＥＴ比表面積は３３．７３４ｍ２／ｇであった。
Example 3
BTDA (3.22 g) was dissolved in 100 mL of DMF, BAPS-M (3.46 g) was added and dissolved, and then 2.4.6. TAPM (0.25 g) was added and stirred at room temperature for 24 hours to obtain a polyamic acid varnish (A) having an amino group on the surface. 20 mL of toluene is added to 200 mL of this varnish (A) and refluxed for 4 hours while distilling off the water by-produced by azeotropic distillation outside the reaction system, and a polyimide varnish (B) having a functional group (soluble polyimide varnish) Got. To 100 g of the obtained varnish (B), 50 g of microbead silica gel (“Micro Bead Silica Gel MB7000-60 / 100 mesh” manufactured by Fuji Silysia Chemical Ltd., BET specific surface area 34.527 m 2 / g, average pore diameter 729 nm) was added, and a slurry ( Bulk ratio = approximately 1: 1). The slurry was degassed by subjecting it to ultrasonic treatment and room temperature vacuum treatment. This slurry was dispersed in a large amount of acetone, and the polyamic acid was phase-separated. That is, DMF was dissolved in methanol and polyimide was phase-separated. By repeatedly washing with acetone and drying, polyimide-silica composite particles having amino acids on the surface were obtained. The resin content in the composite particles at this time was 5.8% by weight, and the BET specific surface area was 33.734 m 2 / g.
実施例４
ＢＴＤＡ（３２．２２ｇ、０．１ｍｏｌ）をＤＭＦ（５００ｍＬ）に溶解し、ＤＰＥ（１２.０１ｇ ０.０６ｍｏｌ）を添加した。ＤＰＥが溶解した後、約１時間撹拌してから２．４．６．ＴＡＰＭ（５．０１ｇ，０．０４ｍｏｌ）を加えてから４時間室温で撹拌し、アミノ基を有するポリアミド酸ワニスを調整した。
Example 4
BTDA (32.22 g, 0.1 mol) was dissolved in DMF (500 mL) and DPE (12.01 g 0.06 mol) was added. After DPE is dissolved, it is stirred for about 1 hour and then 2.4.6. TAPM (5.01 g, 0.04 mol) was added and stirred at room temperature for 4 hours to prepare a polyamic acid varnish having an amino group.
このワニスの２５ｍＬにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）５０ｇを加え、スラリー（パサパサ状）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。その後、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った。ＴＧＡの測定結果では樹脂含有量が１０．１９重量％であった。計算では樹脂１００ｇ中に存在するアミノ基の数は０．５３×１０２３個である。従って、粒子１００ｇ中に存在するアミノ基の数は約５．４×１０２１個となる。また、比表面積（ＢＥＴ法）は２２．６４２ｍ２／ｇであった。 To 25 mL of this varnish, 50 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm” manufactured by Fuji Silysia Chemical Co., Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm) was added, and a slurry (papasa-form) The pressure was reduced while heating (about 100 ° C.) with a rotary evaporator, and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure. After completion of imidization, it was repeatedly washed with acetone and then dried under reduced pressure. According to the TGA measurement result, the resin content was 10.19% by weight. In the calculation, the number of amino groups present in 100 g of the resin is 0.53 × 10 23 . Therefore, the number of amino groups present in 100 g of particles is about 5.4 × 10 21 . The specific surface area (BET method) was 22.642 m 2 / g.
実施例５
ＢＴＤＡ（３２.２２ｇ ０.１ｍｏｌ）をＤＭＦ（５００ｍＬ）に溶解し、ＤＰＥ（１２.０１ｇ ０.０６ｍｏｌ）を添加し、ＤＰＥが溶解後、約１時間撹拌してから２．４．６．ＴＡＰＭ（５.０１ｇ ０.０４ｍｏｌ）を加えた。２．４．６．ＴＡＰＭ溶解後４時間室温で撹拌してアミノ基を有するポリアミド酸ワニスを調整した。このワニスの２５ｍＬにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）２０ｇを加えスラリー（パサパサ状態）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。そのあと、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った。
Example 5
BTDA (32.22 g 0.1 mol) was dissolved in DMF (500 mL), DPE (12.01 g 0.06 mol) was added, and after DPE was dissolved, the mixture was stirred for about 1 hour and then 2.4.6. TAPM (5.01 g 0.04 mol) was added. 2.4.6. After the TAPM was dissolved, the polyamic acid varnish having an amino group was prepared by stirring at room temperature for 4 hours. To 25 mL of this varnish, 20 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm) was added, and the slurry (pumped state) The pressure was reduced while heating (about 100 ° C.) with a rotary evaporator, and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure. After completion of imidization, it was repeatedly washed with acetone and then dried under reduced pressure.
上記の粒子を「エピオールＮＰＧ−１００」（ネオペンチルグリコールジグリシジルエーテル、日本油脂製）２０ｇをアセトン（８０ｍＬ）で希釈した溶液に添加し、スラリー化した。次に、減圧下でスラリーのアセトンを留去した後、１７０〜１８０℃で１時間加熱し、ジグリシジルである「エピオールＮＰＧ−１００」を反応させた。反応終了後、過剰の「エピオールＮＰＧ-１００」をアセトンで繰り返し洗浄して洗い落とした。洗浄後、減圧乾燥を行い、表面にエポキシ基を有するポリイミドとシリカゲルの複合体を得た。 The above particles were slurried by adding 20 g of “Epiol NPG-100” (neopentyl glycol diglycidyl ether, manufactured by NOF Corporation) diluted with acetone (80 mL). Next, after acetone of the slurry was distilled off under reduced pressure, the slurry was heated at 170 to 180 ° C. for 1 hour to react with “Epiol NPG-100” which is diglycidyl. After completion of the reaction, excess “Epiol NPG-100” was washed with acetone repeatedly. After washing, drying under reduced pressure was performed to obtain a composite of polyimide and silica gel having an epoxy group on the surface.
ポリイミドとシリカゲルの複合体と表面にエポキシ基を有するポリイミドとシリカゲルの複合体のＦＴ−ＩＲを測定し、両者の差スペクトルをとるとグリシジルエーテルを示す吸収が３０５１ｃｍ-１、２９２０ｃｍ-１、１９５６ ｃｍ-１、１１０５ｃｍ-１に認められた。 When the FT-IR of the polyimide / silica gel composite and the polyimide / silica gel composite having an epoxy group on the surface is measured and the difference spectrum between the two is taken, the absorptions indicating glycidyl ether are 3051 cm −1 , 2920 cm −1 and 1956 cm. -1 and 1105 cm -1 .
ＴＧＡの測定結果ではエピオールＮＰＧ−１００（分子量２１６.２７）の分解曲線とポリイミドの分解曲線との明確な分離はできないが、４５０℃における２者の重量減少の差（エポキシ成分は無くなっているがポリイミドは残っている）からエポキシ成分の比率を求めると樹脂成分の２４.１８％（重量）であることが確認された。本樹脂成分のアミノ基（１級アミン）に１分子に反応するエピオールＮＰＧ−１００は８.６％（重量、計算値）である。したがって、アミノ基（１級）以外に、ポリイミドの末端のアミノ基および無水カルボキシル基、グリシジルが反応した後に生じた２級のアミノ基などが反応に関与していると考えられる。 Although the TGA measurement result does not clearly separate the decomposition curve of Epiol NPG-100 (molecular weight 216.27) from the decomposition curve of polyimide, the difference in weight loss between the two at 450 ° C. (although the epoxy component has disappeared) When the ratio of the epoxy component was determined from the remaining polyimide), it was confirmed to be 24.18% (weight) of the resin component. Epiol NPG-100 which reacts with one molecule of amino group (primary amine) of the resin component is 8.6% (weight, calculated value). Therefore, in addition to the amino group (primary), it is considered that the amino group at the end of the polyimide, the anhydrous carboxyl group, the secondary amino group generated after the reaction of glycidyl, and the like are involved in the reaction.
また、シリカとの複合体中における樹脂含有率はＴＧＡの結果より１３.０２％で、エピオールＮＰＧ−１００成分の含有率は３.１５％（１００×０.１３０２×０.２４１８）、１.４６×１０-２（ｍｏｌ/複合粒子１００ｇ）、８.７７×１０２１（個/複合粒子１００ｇ）である。また、比表面積（ＢＥＴ法）は３４.９０３ｍ２/ｇであった。 Moreover, the resin content in the composite with silica is 13.02% from the result of TGA, and the content of the epiol NPG-100 component is 3.15% (100 × 0.1302 × 0.2418), 1. They are 46 × 10 −2 (mol / composite particle 100 g) and 8.77 × 10 21 (piece / composite particle 100 g). The specific surface area (BET method) was 34.903 m 2 / g.
実施例６
ＢＴＤＡ（３２.２２ｇ ０.１ｍｏｌ）をＤＭＦ（５００ｍＬ）に溶解し、ＤＰＥ（１２.０１ｇ， ０.０６ｍｏｌ）を添加する。ＤＰＥが溶解後、約１時間撹拌してから２．４．６．ＴＡＰＭ（５.０１ｇ， ０.０４ｍｏｌ）を加えてから４時間室温で撹拌し、アミノ基を有するポリアミド酸ワニスを調整した。
Example 6
BTDA (32.22 g 0.1 mol) is dissolved in DMF (500 mL) and DPE (12.01 g, 0.06 mol) is added. After the DPE is dissolved, the mixture is stirred for about 1 hour and then 2.4.6. TAPM (5.01 g, 0.04 mol) was added and stirred at room temperature for 4 hours to prepare a polyamic acid varnish having an amino group.
このワニス２５０ｍＬにＢＴＤＡ（６.４４ｇ，０.００２ｍｏｌ）を加え、４時間室温で撹拌した。次にこのワニス１００ｍＬをとり、４'−アミノベンゾ−１５−クラウン−５−エーテル（２.３ｇ，０.００８ｍｏｌ）を加えて２４時間室温で撹拌し、１５−クラウン−５−エーテルを有するポリアミド酸を調整した。このワニス１００ｍＬにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）９０ｇを加え、スラリー（実際はパサパサ）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。そのあと、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った（収量約８３ｇ）。 BTDA (6.44 g, 0.002 mol) was added to 250 mL of this varnish, and the mixture was stirred at room temperature for 4 hours. Next, 100 mL of this varnish was taken, 4'-aminobenzo-15-crown-5-ether (2.3 g, 0.008 mol) was added, and the mixture was stirred for 24 hours at room temperature to give polyamic acid having 15-crown-5-ether. Adjusted. To 100 mL of this varnish, 90 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm) was added, and a slurry (actually papasa) The pressure was reduced while heating (about 100 ° C.) with a rotary evaporator, and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure. After completion of imidation, after repeatedly washing with acetone, drying under reduced pressure was performed (yield: about 83 g).
ポリイミドとシリカゲルの複合体と表面にクラウンエーテルを有するポリイミドとシリカゲルの複合体のＦＴ−ＩＲを測定し、両者の差スペクトルをとるとエーテル結合及び環状エーテル結合を示す吸収が２８６５ｃｍ-１、１１２０ｃｍ-１、１０９０ ｃｍ-１、９４０ｃｍ-１に認められた。 When the FT-IR of the polyimide / silica gel composite and the polyimide / silica gel composite having crown ether on the surface is measured and the difference spectrum between the two is taken, the absorption indicating the ether bond and the cyclic ether bond is 2865 cm −1 , 1120 cm −. 1, 1090 cm -1, was found to 940cm -1.
ＴＧＡの測定結果では樹脂含有量が１４.２２％（重量）であった。計算では樹脂１００ｇ中に存在するクラウンエーテルの数は０.３５×１０２３個である。従って、粒子１００ｇ中に存在するクラウンエーテルの数は約５.０×１０２１個となる。また、比表面積（ＢＥＴ法）は２０.８９６ｍ２/ｇであった。 According to the TGA measurement result, the resin content was 14.22% (weight). In the calculation, the number of crown ethers present in 100 g of the resin is 0.35 × 10 23 . Therefore, the number of crown ethers present in 100 g of particles is about 5.0 × 10 21 . The specific surface area (BET method) was 20.896 m 2 / g.
次いで、粒子表面のクラウンエーテルの亜鉛吸着能力を評価した。試料（クラウンエーテル担持粒子２０ｍＬ、９.１６ｇ）と塩化亜鉛水溶液（亜鉛濃度１.７７２５ｐｐｍ）５０ｍＬとをサンプル管（１００ｍＬ）に入れ、しんとう器で４８時間処理し、塩化亜鉛水溶液をろ別した。この亜鉛水溶液液を蒸留水で２分の１に薄めて原子吸光で亜鉛の濃度を定量分析した。以下に結果を示す。
・標準液の亜鉛濃度：０.８７６９８ｐｐｍ（実測値）
・処理後の亜鉛濃度：０.３０５５８ｐｐｍ（実測値）
約６５.２％の亜鉛イオンが粒子に吸着された。
Subsequently, the zinc adsorption ability of the crown ether on the particle surface was evaluated. A sample (20 mL of crown ether-carrying particles, 9.16 g) and 50 mL of an aqueous zinc chloride solution (zinc concentration of 1.7725 ppm) were placed in a sample tube (100 mL), treated with a stirrer for 48 hours, and the aqueous zinc chloride solution was separated by filtration. This zinc aqueous solution was diluted to half with distilled water, and the zinc concentration was quantitatively analyzed by atomic absorption. The results are shown below.
-Zinc concentration of standard solution: 0.887698 ppm (actual value)
-Zinc concentration after treatment: 0.3558 ppm (actual value)
About 65.2% zinc ions were adsorbed on the particles.
実施例７
ＢＴＤＡ（３２.２２ｇ ０.１ｍｏｌ）をＤＭＦ（５００ｍＬ）に溶解し、ＤＰＥ（１２.０１ｇ，０.０６ｍｏｌ）を添加する。ＤＰＥが溶解後、約１時間撹拌してから２．４．６．ＴＡＰＭ（５.０１ｇ ０.０４ｍｏｌ）を加えてから４時間室温で撹拌し、アミノ基を有するポリアミド酸ワニスを調整した。
Example 7
BTDA (32.22 g 0.1 mol) is dissolved in DMF (500 mL) and DPE (12.01 g, 0.06 mol) is added. After the DPE is dissolved, the mixture is stirred for about 1 hour and then 2.4.6. TAPM (5.01 g 0.04 mol) was added and stirred at room temperature for 4 hours to prepare a polyamic acid varnish having an amino group.
このワニスの２５ｍＬにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）２０ｇを加えスラリー（パサパサ状）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。その後、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行い、表面にアミノ基を有するポリイミドとシリカゲルの複合体を得た。 20 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm” manufactured by Fuji Silysia Chemical Co., Ltd., BET specific surface area of 31.798 m 2 / g, average pore diameter of 95.1 nm) was added to 25 mL of this varnish, and a slurry (pumped) The pressure was reduced while heating (about 100 ° C.) with a rotary evaporator, and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure. After completion of imidization, after repeatedly washing with acetone, drying under reduced pressure was performed to obtain a composite of a polyimide having an amino group on the surface and silica gel.
次に、この粒子１０ｇをグルタルアルデヒド（１５０ｍＬ）、水（２８４０ｍＬ）、リン酸二水素カリウム（４.０ｇ）、１Ｎ水酸化ナトリウム水溶液（１２ｍＬ）の混合液に分散させ、液温を３７℃に保持し、スターラーで２時間撹拌した。反応終了後、濾過し蒸留水で繰り返し洗浄し、表面にアルデヒド基を有するポリイミドとシリカゲルの複合体を得た（収量１０ｇ、約１００％）。表面にアミノ基を有するポリイミドとシリカゲルの複合体と表面にアルデヒド基を有するポリイミドとシリカゲルの複合体のＦＴ−ＩＲを測定し、両者の差スペクトルをとるとアルデヒド基を示す強い吸収が１７２０ｃｍ-１に認められた。 Next, 10 g of the particles are dispersed in a mixed solution of glutaraldehyde (150 mL), water (2840 mL), potassium dihydrogen phosphate (4.0 g), and 1N aqueous sodium hydroxide solution (12 mL), and the liquid temperature is 37 ° C. Hold and stir with a stirrer for 2 hours. After completion of the reaction, the mixture was filtered and washed repeatedly with distilled water to obtain a composite of polyimide and silica gel having an aldehyde group on the surface (yield 10 g, about 100%). When the FT-IR of a composite of a polyimide having an amino group on the surface and a silica gel and a composite of a polyimide having an aldehyde group on the surface and a silica gel is measured and a difference spectrum between the two is taken, strong absorption indicating an aldehyde group is 1720 cm −1. Recognized by
実施例８
ＢＴＤＡ（３２.２２ｇ ０.１ｍｏｌ）をＤＭＦ（５００ｍＬ）に溶解し、ＤＰＥ（１２.０１ｇ ０.０６ｍｏｌ）を添加する。ＤＰＥが溶解後、約１時間撹拌してから２．４．６．ＴＡＰＭ（５.０１ｇ ０.０４ｍｏｌ）を加えてから４時間室温で撹拌し、アミノ基を有するポリアミド酸ワニスを調整した。
Example 8
BTDA (32.22 g 0.1 mol) is dissolved in DMF (500 mL) and DPE (12.01 g 0.06 mol) is added. After the DPE is dissolved, the mixture is stirred for about 1 hour and then 2.4.6. TAPM (5.01 g 0.04 mol) was added and stirred at room temperature for 4 hours to prepare a polyamic acid varnish having an amino group.
このワニス２５０ｍＬにＢＴＤＡ（６.４４ｇ ０.００２ｍｏｌ）を加え、４時間室温で撹拌した。次に、このワニスの１００ｍＬにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）９０ｇを加えスラリー（パサパサ状）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。そのあと、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥し無水カルボキシル基を有するポリイミドとシリカゲルとの複合粒子を得た。次に、この複合粒子１０ｇをＤＭＦ１００ｍＬに分散させ液にオリゴ糖の一種であるβ−シクロデキストリン（１１.３５ｇ ０.０１ｍｏｌ）を加えて４時間還流し、β−シクロデキストリンの水酸基と複合粒子の表面に存在する無水カルボン酸とのエステル化反応によって担持した。反応終了後、濾過して分離し、蒸留水で繰り返し洗浄して精製した。 BTDA (6.44 g 0.002 mol) was added to 250 mL of this varnish and stirred at room temperature for 4 hours. Next, 90 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm” manufactured by Fuji Silysia Chemical Ltd., BET specific surface area of 31.798 m 2 / g, average pore diameter of 95.1 nm) was added to 100 mL of this varnish, and a slurry ( The pressure was reduced while heating with a rotary evaporator (about 100 ° C.), and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure. After completion of imidation, the mixture was repeatedly washed with acetone and then dried under reduced pressure to obtain composite particles of polyimide having an anhydrous carboxyl group and silica gel. Next, 10 g of the composite particles are dispersed in 100 mL of DMF, β-cyclodextrin (11.35 g 0.01 mol), which is a kind of oligosaccharide, is added to the liquid, and the mixture is refluxed for 4 hours. It was supported by an esterification reaction with carboxylic anhydride present on the surface. After completion of the reaction, it was separated by filtration, and purified by repeatedly washing with distilled water.
ポリイミドとシリカゲルの複合体と表面にβ−シクロデキストリンを有するポリイミドとシリカゲルの複合体のＦＴ−ＩＲを測定し、両者の差スペクトルをとるとシクロデキストリンの存在を示す吸収が３４１０ｃｍ-１、１０７９ｃｍ-１、１０３０ｃｍ-１に認められた。 The FT-IR of the polyimide / silica gel composite and the polyimide / silica gel composite having β-cyclodextrin on the surface was measured, and when the difference spectrum between the two was taken, absorption indicating the presence of cyclodextrin was 3410 cm −1 , 1079 cm −. 1 and 1030 cm −1 .
実施例９
ＢＴＤＡ（３．２２ｇ）をＤＭＦ１００ｍＬに溶かし、ＢＡＰＳ−Ｍ（３.４６ｇ）を添加し溶解した後、２．４．６．ＴＡＰＭ（０.２５ｇ）を添加し２４時間常温で撹拌して表面にアミノ基を有するポリアミド酸ワニスを調製した。このワニスにトルエン２０ｍＬを加え共沸により副成する水を反応系外に留去しながら４時間還流し、官能基を有するポリイミドのワニス得た（可溶性ポリイミドのワニス）。得られたワニス１００ｇにマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）９０ｇを加えスラリーとし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。ＴＧＡの測定結果では樹脂含有量が５.０１％（重量）であった。また、比表面積（ＢＥＴ法）は２８.６５６ｍ２/ｇであった。また、上記の方法で、得られた複合体粒子の細孔内は閉塞しておらず、気体や液体を容易に通過させることができることが判明した。
Example 9
BTDA (3.22 g) was dissolved in 100 mL of DMF, BAPS-M (3.46 g) was added and dissolved, and then 2.4.6. TAPM (0.25 g) was added and stirred at room temperature for 24 hours to prepare a polyamic acid varnish having an amino group on the surface. To this varnish, 20 mL of toluene was added and refluxed for 4 hours while distilling out water formed by azeotropic distillation out of the reaction system to obtain a polyimide varnish having a functional group (soluble polyimide varnish). 90 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm” manufactured by Fuji Silysia Chemical Ltd., BET specific surface area of 31.798 m 2 / g, average pore diameter of 95.1 nm) was added to 100 g of the obtained varnish to obtain a slurry, and the rotary The pressure was reduced while heating with an evaporator (about 100 ° C.) to distill off DMF. According to the TGA measurement result, the resin content was 5.01% (weight). The specific surface area (BET method) was 28.656 m 2 / g. Further, it has been found that the pores of the obtained composite particles are not closed by the above method, and gas or liquid can be easily passed.
実施例１０
（１）マイクロビーズシリカゲルのシランカップリング処理
マイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）５０ｇをシランカップリング剤（０．５ｇ、信越化学工業株式会社製、製品名「KBE−903」、(C2H5O)3SiC3H6NH2）をイオン交換水６２５ｍｌに溶解した液に分散し、室温で２４時間攪拌してから濾過し、水洗、乾燥後、１１０℃で２時間加熱してシランカップリング処理を行った。
Example 10
(1) Silane coupling treatment of microbead silica gel 50 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm” manufactured by Fuji Silysia Chemical, BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm) Disperse silane coupling agent (0.5 g, manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBE-903”, (C 2 H 5 O) 3 SiC 3 H 6 NH 2 ) in 625 ml of ion-exchanged water The mixture was stirred at room temperature for 24 hours, filtered, washed with water, dried, and then heated at 110 ° C. for 2 hours for silane coupling treatment.
他の無機粒子に対しても、あるいは他のシランカップリング剤を用いても同様の方法でシランカップリング処理を行うことができる。
（２）複合粒子の製造
ＢＴＤＡ（３２．２２ｇ、０．１ｍｏｌ）をＤＭＦ（５００ｍＬ）に溶解し、ＤＰＥ（１２.０１ｇ ０.０６ｍｏｌ）を添加した。ＤＰＥが溶解した後、約１時間撹拌してから２．４．６．ＴＡＰＭ（５．０１ｇ，０．０４ｍｏｌ）を加えてから４時間室温で撹拌し、アミノ基を有するポリアミド酸ワニスを調整した。
The silane coupling treatment can be performed in the same manner with respect to other inorganic particles or using another silane coupling agent.
(2) Production of composite particles BTDA (32.22 g, 0.1 mol) was dissolved in DMF (500 mL), and DPE (12.01 g 0.06 mol) was added. After DPE is dissolved, it is stirred for about 1 hour and then 2.4.6. TAPM (5.01 g, 0.04 mol) was added and stirred at room temperature for 4 hours to prepare a polyamic acid varnish having an amino group.
このワニスの２５ｍＬに上記の方法でシランカップリング処理したマイクロビーズシリカゲル５０ｇを加え、スラリー（実際はパサパサ）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。その後、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った。ＴＧＡの測定結果では樹脂含有量が１０．２１重量％であった。計算では樹脂中に存在するアミノ基の数は０．５３×１０２３個である（但し、シランカップリング剤の処理量を無視して計算した）。従って、粒子１００ｇ中に存在するアミノ基の数は約５．４０×１０２１個となる。また、比表面積（ＢＥＴ法）は２２．２９ｍ２／ｇであった。 To 25 mL of this varnish, 50 g of microbead silica gel treated with silane coupling by the above method was added to form a slurry (actually Pasapasa), and the pressure was reduced while heating (about 100 ° C.) with a rotary evaporator to distill off DMF. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure. After completion of imidization, it was repeatedly washed with acetone and then dried under reduced pressure. According to the TGA measurement result, the resin content was 10.21% by weight. In the calculation, the number of amino groups present in the resin is 0.53 × 10 23 (however, calculation was performed ignoring the treatment amount of the silane coupling agent). Therefore, the number of amino groups present in 100 g of particles is about 5.40 × 10 21 . The specific surface area (BET method) was 22.29 m 2 / g.
実施例１１
4,5-Diamino-2,6-dimercaptopyrimidine（略称ＤＡＤＭＰ ３．８７ｇ、純度９０％、０．０２ｍｏｌ、分子量１７４．２５）をＤＭＦ（１００ｍｌ）に溶解し、ＢＴＤＡ(６．４４ｇ、０．０２ｍｏｌ)を添加し、２４時間室温で撹拌し、チオール基を有するポリアミド酸ワニスを調製した。
Example 11
4,5-Diamino-2,6-dimercaptopyrimidine (abbreviation DADMP 3.87 g, purity 90%, 0.02 mol, molecular weight 174.25) was dissolved in DMF (100 ml) and BTDA (6.44 g, 0.02 mol) Was added and stirred at room temperature for 24 hours to prepare a polyamic acid varnish having a thiol group.
このワニスの２５ｍｌを多孔性シリカゲルであるマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）の２０ｇに加えスラリー（パサパサ状）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。その後、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。 25 ml of this varnish was added to 20 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical Co., Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm). The slurry was added to form a slurry (pasapasa), and the pressure was reduced while heating (about 100 ° C.) with a rotary evaporator, and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure.
イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った。ＴＧＡの測定結果では樹脂含有量が１１．０３重量％であった。計算では樹脂中に存在するアミノ基の数は２．６１×１０２１個／ｇ個である。従って、粒子中に存在するアミノ基の数は約２．８８×１０２０個／ｇとなる。 After completion of imidization, it was repeatedly washed with acetone and then dried under reduced pressure. According to the TGA measurement result, the resin content was 11.03 wt%. In the calculation, the number of amino groups present in the resin is 2.61 × 10 21 / g. Therefore, the number of amino groups present in the particles is about 2.88 × 10 20 / g.
実施例１２
4,5-Diamino-2,6-dimercaptopyrimidine(略称ＤＡＤＭＰ ３．３６ｇ、純度９０％、０．０２ｍｏｌ、分子量１７４．２５)をＤＭＦ（１００ｍｌ）に溶解し、ＢＴＤＡ（６．４４ｇ，０．０２ｍｏｌ）を添加し、２４時間室温で撹拌し、ＳＨ基を有するポリアミド酸ワニスを調製した。
Example 12
4,5-Diamino-2,6-dimercaptopyrimidine (abbreviation DADMP 3.36 g, purity 90%, 0.02 mol, molecular weight 174.25) was dissolved in DMF (100 ml) to obtain BTDA (6.44 g, 0.02 mol). Was added and stirred at room temperature for 24 hours to prepare a polyamic acid varnish having an SH group.
このワニスの２５ｍｌを多孔性シリカゲルであるマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）の２０ｇに加えスラリー（パサパサ状）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。その後、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。 25 ml of this varnish was added to 20 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical Co., Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm). The slurry was added to form a slurry (pasapasa), and the pressure was reduced while heating (about 100 ° C.) with a rotary evaporator, and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure.
イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った。ＴＧＡの測定結果では樹脂含有量が１０．２４重量％であった。計算では樹脂中に存在するアミノ基の数は２．７５×１０２１個／ｇである。従って、粒子中に存在するアミノ基の数は約２．８２×１０２０個／ｇとなる。 After completion of imidization, it was repeatedly washed with acetone and then dried under reduced pressure. The TGA measurement result showed that the resin content was 10.24% by weight. In calculation, the number of amino groups present in the resin is 2.75 × 10 21 / g. Therefore, the number of amino groups present in the particles is about 2.82 × 10 20 / g.
実施例１３
4,5-Diamino-2,6-dimercaptopyrimidine(略称ＤＡＤＭＰ ３．８７ｇ、純度９０％、０．０２ｍｏｌ、分子量１７４．２５)をＤＭＦ（６５ｍｌ）に溶解し、ピロメリット酸無水物PMDA(４．５９ｇ、純度９５％、０．０２ｍｏｌ)を添加し、24時間室温で撹拌し、ＳＨ基を有するポリアミド酸ワニスを調製した。
Example 13
4,5-Diamino-2,6-dimercaptopyrimidine (abbreviation DADMP 3.87 g, purity 90%, 0.02 mol, molecular weight 174.25) was dissolved in DMF (65 ml) and pyromellitic anhydride PMDA (4.59 g , Purity 95%, 0.02 mol) was added, and the mixture was stirred for 24 hours at room temperature to prepare a polyamic acid varnish having SH groups.
このワニスの２５ｍｌを多孔性シリカゲルであるマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）の２０ｇに加えスラリー（パサパサ状）とし、ロータリーエバポレーターで加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。その後、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。 25 ml of this varnish was added to 20 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical Co., Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm). The slurry was added to form a slurry (pasapasa), and the pressure was reduced while heating (about 100 ° C.) with a rotary evaporator, and DMF was distilled off. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure.
イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った。ＴＧＡの測定結果では樹脂含有量が１１．７０重量％であった。計算では樹脂中に存在するアミノ基の数は３．２２×１０２１個／ｇである。従って、粒子中に存在するアミノ基の数は約３．７６×１０２０個／ｇとなる。 After completion of imidization, it was repeatedly washed with acetone and then dried under reduced pressure. According to the TGA measurement result, the resin content was 11.70% by weight. In the calculation, the number of amino groups present in the resin is 3.22 × 10 21 / g. Therefore, the number of amino groups present in the particles is about 3.76 × 10 20 / g.
実施例１４
無官能のポリイミドとのブレンドと多孔性シリカを複合させた。
（１）4,5-Diamino-2,6-dimercaptopyrimidine(略称ＤＡＤＭＰ ３．８７ｇ、純度９０％、０．０２ｍｏｌ、分子量１７４．２５)をＤＭＦ（６５ｍｌ）に溶解したものに、ピロメリット酸無水物ＰＭＤＡ(４．５９ｇ、純度９５％、０．０２ｍｏｌ)を添加し、２４時間室温で撹拌し、ＳＨ基を有するポリアミド酸ワニスを調製した。
（２）DME（２０．０１ｇ，０．１ｍｏｌ）をＤＭＦ（５００ｍｌ）に溶解したものに、ＢＴＤＡ（３２．２２ｇ，０．１ｍｏｌ）を添加し、２４時間室温で撹拌して無官能のポリアミド酸ワニスを調製した。
Example 14
A blend of nonfunctional polyimide and porous silica were combined.
(1) 4,5-Diamino-2,6-dimercaptopyrimidine (abbreviation DADMP 3.87 g, purity 90%, 0.02 mol, molecular weight 174.25) dissolved in DMF (65 ml), pyromellitic anhydride PMDA (4.59 g, purity 95%, 0.02 mol) was added and stirred at room temperature for 24 hours to prepare a polyamic acid varnish having SH groups.
(2) BTDA (32.22 g, 0.1 mol) was added to DME (20.01 g, 0.1 mol) dissolved in DMF (500 ml), and the mixture was stirred at room temperature for 24 hours to obtain a non-functional polyamic acid. A varnish was prepared.
（１）と（２）のワニスをそれぞれ１２．５ｍｌずつ混合して均一にした後、多孔性シリカゲルであるマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）の２０ｇに加えスラリーとし、加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。そのあと、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。 After mixing 12.5 ml each of the varnishes of (1) and (2) and making them uniform, microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical, BET ratio) The slurry was added to 20 g having a surface area of 31.798 m 2 / g and an average pore diameter of 95.1 nm, and the pressure was reduced while heating (about 100 ° C.) to distill off DMF. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure.
ＴＧＡの測定結果では樹脂含有量が１０．９５重量％であった。計算では樹脂中に存在するアミノ基の数は１．８０×１０２１個／ｇである。従って、粒子中に存在するアミノ基の数は約１．９７×１０２０個／ｇとなる。 As a result of TGA measurement, the resin content was 10.95% by weight. In the calculation, the number of amino groups present in the resin is 1.80 × 10 21 / g. Therefore, the number of amino groups present in the particles is about 1.97 × 10 20 / g.
実施例１５
ＢＴＤＡ(３２．２２ｇ，０．１ｍｏｌ)をＤＭＦ（５００ｍｌ）に溶解し、ＤＰＥ（１２．０１ｇ，０．０６ｍｏｌ）を添加し、ＤＰＥが溶解後、約１時間撹拌してから2,4,6-トリアミノピリミジン(５．０１ｇ，０．０４ｍｏｌ)を加えて４時間室温で撹拌し、アミノ基を有するポリアミド酸ワニスを調製した。
Example 15
BTDA (32.22 g, 0.1 mol) was dissolved in DMF (500 ml), DPE (12.01 g, 0.06 mol) was added, and after DPE was dissolved, the mixture was stirred for about 1 hour, and then 2,4,6 -Triaminopyrimidine (5.01 g, 0.04 mol) was added and stirred at room temperature for 4 hours to prepare a polyamic acid varnish having an amino group.
このワニスにＢＴＤＡ（１２．８８ｇ，０．０４ｍｏｌ）を加え、4時間室温で撹拌してからワニス１００ｍｌに対して4-アミノチオフェノール(０．２５ｇ，０．００２ｍｏｌ)を加え２４時間室温で撹拌しチオールを有するポリアミド酸を調製した。 BTDA (12.88 g, 0.04 mol) was added to this varnish and stirred for 4 hours at room temperature, then 4-aminothiophenol (0.25 g, 0.002 mol) was added to 100 ml of varnish and stirred for 24 hours at room temperature. A polyamic acid having a thiol was prepared.
このワニスの２５ｍｌを多孔性シリカゲルであるマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）の２０ｇに加えスラリー（パサパサ状）とし、加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。そのあと、加熱温度を１８０℃まで上げ、減圧を保持したまま４時間かけてイミド化した。イミド化終了後、アセトンで繰り返し洗浄した後、減圧加熱乾燥を行った。 25 ml of this varnish was added to 20 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical Co., Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm). The slurry was added (pulverized), and the pressure was reduced while heating (about 100 ° C.) to distill off DMF. Thereafter, the heating temperature was raised to 180 ° C., and imidization was performed for 4 hours while maintaining the reduced pressure. After completion of imidization, it was repeatedly washed with acetone and then dried under reduced pressure.
ＴＧＡの測定結果では樹脂含有量が１３．２３重量％であった。計算では樹脂中に存在するアミノ基の数は３．８８×１０２０個／ｇである。従って、粒子中に存在するアミノ基の数は約４．７４２×１０１９個／ｇとなる。 According to the TGA measurement result, the resin content was 13.23 wt%. In the calculation, the number of amino groups present in the resin is 3.88 × 10 20 / g. Therefore, the number of amino groups present in the particles is about 4.742 × 10 19 / g.
実施例１６
ＢＴＤＡ(３２．２２ｇ，０．１ｍｏｌ)をＤＭＦ(５００ｍｌ)に溶解し、ＤＰＥ(１２．０１ｇ，０．０６ｍｏｌ)を添加し、ＤＰＥが溶解後、約１時間撹拌してから2,4,6-トリアミノピリミジン(５．０１ｇ，０．０４ｍｏｌ)を加えて４時間室温で撹拌し、アミノ基を有するポリアミド酸ワニスを調製した。
Example 16
BTDA (32.22 g, 0.1 mol) was dissolved in DMF (500 ml), DPE (12.01 g, 0.06 mol) was added, and after DPE was dissolved, the mixture was stirred for about 1 hour, and then 2,4,6 -Triaminopyrimidine (5.01 g, 0.04 mol) was added and stirred at room temperature for 4 hours to prepare a polyamic acid varnish having an amino group.
このワニスの５０ｍｌを多孔性シリカゲルであるマイクロビーズシリカゲル（「Micro Bead Silica Ｇel ＭＢ１０００−４０／７５μｍ」富士シリシア化学製、ＢＥＴ比表面積３１．７９８ｍ２／ｇ、平均細孔径９５．１ｎｍ）の４０ｇに加えスラリー（パサパサ状）とし、加熱（約１００℃）しながら減圧し、ＤＭＦを留去した。そのあと、加熱温度を１６５℃まで上げ、減圧を保持したまま４時間かけてイミド化し、表面にアミノ基を有する多孔性シリカゲル−ポリイミド複合粒子を調製した。 50 ml of this varnish was added to 40 g of microbead silica gel (“Micro Bead Silica Gel MB1000-40 / 75 μm”, manufactured by Fuji Silysia Chemical Co., Ltd., BET specific surface area 31.798 m 2 / g, average pore diameter 95.1 nm). The slurry was added (pulverized), and the pressure was reduced while heating (about 100 ° C.) to distill off DMF. Thereafter, the heating temperature was raised to 165 ° C., and imidization was carried out for 4 hours while maintaining the reduced pressure to prepare porous silica gel-polyimide composite particles having amino groups on the surface.
次に、グルタル酸アルデヒド（５０％）３０ｍｌ、水２８４ｍｌ、リン酸二水素カリウム０．４ｇ、１Ｎ-水酸化ナトリウム水溶液１２ｍｌの溶液に上記のアミノ基を有する複合粒子を３７℃で２時間、浸漬し、デカンテーションで粒子を分離した後水で洗浄後、室温で４日間減圧乾燥した。 Next, the composite particles having the amino group are immersed in a solution of 30 ml of glutaric aldehyde (50%), 284 ml of water, 0.4 g of potassium dihydrogen phosphate and 12 ml of 1N aqueous sodium hydroxide solution at 37 ° C. for 2 hours. The particles were separated by decantation, washed with water, and dried under reduced pressure at room temperature for 4 days.
ＴＧＡの測定結果では樹脂含有量が11.30重量％であった。計算では樹脂中に存在するアルデヒドの数は３．８８×１０２０個／ｇである。従って、粒子中に存在するアルデヒド基の数は約４．３８×１０１９個／ｇとなる。 The TGA measurement result showed that the resin content was 11.30% by weight. In the calculation, the number of aldehydes present in the resin is 3.88 × 10 20 / g. Therefore, the number of aldehyde groups present in the particles is about 4.38 × 10 19 / g.
Claims (13)
前記担体は、多孔体により構成されており、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸が溶解せず、かつ、前記非プロトン性極性溶媒と相溶性のある溶媒に前記混合物を分散することにより、ポリアミド酸を担体上に析出させる析出工程を含む、製造方法。 In the step of preparing a functional polyamic acid by reacting at least a tetracarboxylic anhydride and a polyfunctional diamine compound, a composite particle in which the polyamic acid having a functional group is supported on the carrier is produced by mixing the carrier. A method,
The carrier is composed of a porous body,
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by reacting an anhydride tetracarboxylic acid polyfunctional diamine compound in an aprotic solvent, by mixed-powdered carrier (b) the varnish Mixture preparation step for obtaining a mixture, (c) Precipitation step for precipitating polyamic acid on a support by dispersing the mixture in a solvent in which the polyamic acid is not dissolved and is compatible with the aprotic polar solvent Manufacturing method.
前記担体は、多孔体により構成されており、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程を含む、製造方法。 In the step of preparing a functional polyamic acid by reacting at least a tetracarboxylic anhydride and a polyfunctional diamine compound, a composite particle in which the polyamic acid having a functional group is supported on the carrier is produced by mixing the carrier. A method,
The carrier is composed of a porous body,
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by reacting an anhydride tetracarboxylic acid polyfunctional diamine compound in an aprotic solvent, by mixed-powdered carrier (b) the varnish A production method comprising a mixture preparation step for obtaining a mixture, and (c) a solvent removal step for removing the solvent contained in the mixture.
前記担体は、多孔体により構成されており、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物をアルコール系溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程を含む、製造方法。 In the step of preparing a functional polyamic acid by reacting at least a tetracarboxylic anhydride and a polyfunctional diamine compound, a composite particle in which the polyamic acid having a functional group is supported on the carrier is produced by mixing the carrier. A method,
The carrier is composed of a porous body,
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by anhydride tetracarboxylic acid and a polyfunctional diamine compounds are reacted in an alcoholic solvent, a mixture by mixed-powdered carrier (b) the varnish (C) The solvent preparation process including the solvent removal process of removing the solvent contained in a mixture.
前記担体は、多孔体により構成されており、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸が溶解せず、かつ、前記非プロトン性極性溶媒と相溶性のある溶媒に前記混合物を分散することにより、ポリアミド酸を担体上に析出させる析出工程、（ｄ）ポリアミド酸をイミド化するイミド化工程を含む、製造方法。 A functional polyamic acid is prepared by reacting at least tetracarboxylic anhydride and a polyfunctional diamine compound, and then the functional polyimide is mixed by immobilizing the polyamic acid to prepare a functional polyimide. A method for producing composite particles in which a polyimide having a functional group is supported on a carrier,
The carrier is composed of a porous body,
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by reacting an anhydride tetracarboxylic acid polyfunctional diamine compound in an aprotic solvent, by mixed-powdered carrier (b) the varnish Mixture preparation step for obtaining a mixture, (c) Precipitation step for precipitating polyamic acid on a support by dispersing the mixture in a solvent in which the polyamic acid is not dissolved and is compatible with the aprotic polar solvent (D) The manufacturing method including the imidation process of imidating a polyamic acid.
前記担体は、多孔体により構成されており、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程、（ｄ）ポリアミド酸をイミド化するイミド化工程
を含む、製造方法。 A functional polyamic acid is prepared by reacting at least tetracarboxylic anhydride and a polyfunctional diamine compound, and then the functional polyimide is mixed by immobilizing the polyamic acid to prepare a functional polyimide. A method for producing composite particles in which a polyimide having a functional group is supported on a carrier,
The carrier is composed of a porous body,
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by reacting an anhydride tetracarboxylic acid polyfunctional diamine compound in an aprotic solvent, by mixed-powdered carrier (b) the varnish A production method comprising a mixture preparation step for obtaining a mixture, (c) a solvent removal step for removing a solvent contained in the mixture, and (d) an imidization step for imidizing polyamic acid.
前記担体は、無機材料からなる多孔体により構成されており、且つ、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに前記粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸をイミド化するイミド化工程、（ｄ）ポリイミドが溶解せず、かつ、前記非プロトン性極性溶媒と相溶性のある溶媒に、前記イミド化工程で得られた混合物を分散することにより、ポリイミドを担体上に析出させる析出工程、
を含む、製造方法。 A functional polyamic acid is prepared by reacting at least tetracarboxylic anhydride and a polyfunctional diamine compound, and then the functional polyimide is mixed by immobilizing the polyamic acid to prepare a functional polyimide. A method for producing composite particles in which a polyimide having a functional group is supported on the carrier,
The carrier is composed of a porous body made of an inorganic material, and
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by reacting anhydrous tetracarboxylic acid and a polyfunctional diamine compound in an aprotic solvent, (b) the powdered carrier to mixed-to the varnish (C) imidization step for imidizing polyamic acid, (d) the imidization step in a solvent in which polyimide does not dissolve and is compatible with the aprotic polar solvent. A precipitation step of precipitating polyimide on the carrier by dispersing the mixture obtained in
Manufacturing method.
前記担体は、無機材料からなる多孔体により構成されており、且つ、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物を非プロトン性溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに前記粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）ポリアミド酸をイミド化するイミド化工程、（ｄ）前記イミド化工程で得られた混合物から溶媒を除去する溶媒除去工程を含む、製造方法。 A functional polyamic acid is prepared by reacting at least tetracarboxylic anhydride and a polyfunctional diamine compound, and then the functional polyimide is mixed by immobilizing the polyamic acid to prepare a functional polyimide. A method for producing composite particles in which a polyimide having a functional group is supported on the carrier,
The carrier is composed of a porous body made of an inorganic material, and
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by reacting anhydrous tetracarboxylic acid and a polyfunctional diamine compound in an aprotic solvent, (b) the powdered carrier to mixed-to the varnish (C) an imidization step for imidizing polyamic acid, and (d) a solvent removal step for removing the solvent from the mixture obtained in the imidization step.
前記担体は、無機材料からなる多孔体により構成されており、且つ、
（ａ）無水テトラカルボン酸と多官能ジアミン化合物をアルコール系溶媒中で反応させることによりポリアミド酸含有ワニスを調製するワニス調製工程、（ｂ）前記ワニスに前記粉末状の担体を混合することにより混合物を得る混合物調製工程、（ｃ）混合物中に含まれる溶媒を除去する溶媒除去工程、（ｄ）ポリアミド酸をイミド化するイミド化工程を含む、製造方法。 A functional polyamic acid is prepared by reacting at least tetracarboxylic anhydride and a polyfunctional diamine compound, and then the functional polyimide is mixed by immobilizing the polyamic acid to prepare a functional polyimide. A method for producing composite particles in which a polyimide having a functional group is supported on the carrier,
The carrier is composed of a porous body made of an inorganic material, and
(A) the varnish preparation step of preparing a polyamic acid-containing varnish by anhydride tetracarboxylic acid and a polyfunctional diamine compounds are reacted in an alcoholic solvent, by mixed-said powdered carrier (b) the varnish A production method comprising a mixture preparation step for obtaining a mixture, (c) a solvent removal step for removing a solvent contained in the mixture, and (d) an imidization step for imidizing polyamic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005317992A JP5380662B2 (en) | 2005-03-29 | 2005-11-01 | Functional polyamic acid composite particles and method for producing functional polyimide composite particles |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005093608 | 2005-03-29 | ||
| JP2005093608 | 2005-03-29 | ||
| JP2005317992A JP5380662B2 (en) | 2005-03-29 | 2005-11-01 | Functional polyamic acid composite particles and method for producing functional polyimide composite particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006307146A JP2006307146A (en) | 2006-11-09 |
| JP5380662B2 true JP5380662B2 (en) | 2014-01-08 |
Family
ID=37474386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005317992A Expired - Fee Related JP5380662B2 (en) | 2005-03-29 | 2005-11-01 | Functional polyamic acid composite particles and method for producing functional polyimide composite particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5380662B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5103598B2 (en) * | 2007-03-13 | 2012-12-19 | 地方独立行政法人大阪府立産業技術総合研究所 | Method for producing functional polyimide fine particles |
| KR101116753B1 (en) * | 2009-05-19 | 2012-02-22 | 한국화학연구원 | High dielectric polyimide-inorganic composites and its Preparation |
| TWI492970B (en) | 2013-01-28 | 2015-07-21 | Taimide Technology Inc | Colored delustrant powder, polyimide film incorporating the same, and its manufacture methods |
| KR101728100B1 (en) * | 2015-01-21 | 2017-04-18 | 에스케이씨코오롱피아이 주식회사 | Method for preparation of polyimide film using porous particles and polyimide film having low permittivity |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61281150A (en) * | 1985-06-05 | 1986-12-11 | Nitto Electric Ind Co Ltd | Polyimide powder and production thereof |
| JPS62224382A (en) * | 1986-03-26 | 1987-10-02 | 日東電工株式会社 | Golf club face and its production |
| JPS6487307A (en) * | 1987-09-30 | 1989-03-31 | Nitto Denko Corp | Polyimide powder and manufacture thereof |
| JPH09176317A (en) * | 1995-12-27 | 1997-07-08 | Unitika Ltd | Powdery or granular material for molding and its production |
| JPH09194723A (en) * | 1996-01-25 | 1997-07-29 | Du Pont Kk | Production of polyimide composite material and production of formed polyimide composite material |
| JPH09208823A (en) * | 1996-01-29 | 1997-08-12 | Toyota Central Res & Dev Lab Inc | Powdery polyimide composite material and its production |
| JP4025943B2 (en) * | 1999-02-26 | 2007-12-26 | 大阪府 | Functional polyamic acid fine particles, functional polyimide fine particles and methods for producing them |
| JP2004010653A (en) * | 2002-06-04 | 2004-01-15 | Osaka Prefecture | Composite fine particle and method for producing the same |
-
2005
- 2005-11-01 JP JP2005317992A patent/JP5380662B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006307146A (en) | 2006-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5530178B2 (en) | Porous polyimide | |
| JP4025943B2 (en) | Functional polyamic acid fine particles, functional polyimide fine particles and methods for producing them | |
| CN109414645B (en) | Method for producing gas separation membrane | |
| CN106987019A (en) | A kind of polyimide aerogels of functionalisation of surfaces nano-particle crosslinking and preparation method thereof | |
| JP7003914B2 (en) | Polyimide resin, polyimide resin composition, and polyimide film | |
| US11760738B2 (en) | Anisotropic copoly(imide oxetane) coatings and articles of manufacture, copoly(imide oxetane)s containing pendant fluorocarbon moieties, oligomers and processes therefor | |
| JP2014500393A (en) | Curable silicate-siloxane mixed matrix film composition | |
| CN105237645B (en) | Macromolecules cross-linking agent, its gelatin film and preparation method based on oxycellulose | |
| JPWO2006025327A1 (en) | Hyperbranched polyimide hybrid material | |
| JP5263749B2 (en) | Polyamide composite particles, polyamic acid composite particles, polyimide composite particles, and production methods thereof | |
| JP5380662B2 (en) | Functional polyamic acid composite particles and method for producing functional polyimide composite particles | |
| JP2013109842A (en) | Manufacturing method of separator for lithium ion battery | |
| CN109021233A (en) | The high thermal stability composite polyimide material and preparation method thereof of the material of boron nitride nanometer containing amino functional | |
| CN105001413B (en) | A kind of preparation method of polyethylene glycol diazonium polymer | |
| JP4661282B2 (en) | Method for producing polyamic acid fine particles and polyimide fine particles | |
| Wu et al. | In-situ preparation of poly (ether imide)/amino functionalized silica mixed matrix membranes for application in enzyme separation | |
| JP4752993B2 (en) | POLYIMIDE POROUS MEMBRANE AND METHOD FOR PRODUCING THE SAME | |
| JP4284451B2 (en) | Polyimide fine particles and method for producing the same | |
| JP2004010653A (en) | Composite fine particle and method for producing the same | |
| JP4621852B2 (en) | Polyimide porous body and method for producing fine particles | |
| JP5883566B2 (en) | Manufacturing method of hyperbranched polyimide hybrid material | |
| JPH07300524A (en) | Production of particulate polyimide, and particulate polyimide | |
| JP5103598B2 (en) | Method for producing functional polyimide fine particles | |
| JP2006182845A (en) | Method for producing polyamic acid particulate and polyimide particulate | |
| Sribala et al. | Structural, Thermal, Morphological, Adsorption and Catalytic Properties of Poly (BPDAH-co-ODA/PPDA)-Ag/V2O5 Nanocomposites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080729 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20080729 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110217 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110405 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110606 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120131 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120402 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20120613 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20120806 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20120814 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121218 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130214 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130813 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130903 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5380662 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |