WO2013137260A1 - 高分子超薄膜及び多孔質高分子超薄膜 - Google Patents
高分子超薄膜及び多孔質高分子超薄膜 Download PDFInfo
- Publication number
- WO2013137260A1 WO2013137260A1 PCT/JP2013/056823 JP2013056823W WO2013137260A1 WO 2013137260 A1 WO2013137260 A1 WO 2013137260A1 JP 2013056823 W JP2013056823 W JP 2013056823W WO 2013137260 A1 WO2013137260 A1 WO 2013137260A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- film
- ultra
- porous
- solvent
- Prior art date
Links
- 229920006254 polymer film Polymers 0.000 title claims abstract description 230
- 229920000642 polymer Polymers 0.000 claims abstract description 442
- 239000002904 solvent Substances 0.000 claims abstract description 288
- 239000000758 substrate Substances 0.000 claims abstract description 205
- 238000000034 method Methods 0.000 claims abstract description 116
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- 239000010408 film Substances 0.000 claims description 356
- 239000011148 porous material Substances 0.000 claims description 150
- 239000004793 Polystyrene Substances 0.000 claims description 132
- 229920002223 polystyrene Polymers 0.000 claims description 126
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 84
- 239000010419 fine particle Substances 0.000 claims description 77
- 239000002131 composite material Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000010409 thin film Substances 0.000 claims description 47
- 238000009826 distribution Methods 0.000 claims description 44
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 44
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 37
- 239000012528 membrane Substances 0.000 claims description 33
- -1 polysaccharide ester Chemical class 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 20
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 17
- 239000004626 polylactic acid Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000454 talc Substances 0.000 claims description 8
- 229910052623 talc Inorganic materials 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 229920002307 Dextran Polymers 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001282 polysaccharide Polymers 0.000 claims description 5
- 239000005017 polysaccharide Substances 0.000 claims description 5
- 239000011118 polyvinyl acetate Substances 0.000 claims description 5
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229920000936 Agarose Polymers 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 102000009027 Albumins Human genes 0.000 claims description 3
- 108010088751 Albumins Proteins 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 109
- 239000000243 solution Substances 0.000 description 101
- 239000002135 nanosheet Substances 0.000 description 87
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- 239000004372 Polyvinyl alcohol Substances 0.000 description 37
- 229920002451 polyvinyl alcohol Polymers 0.000 description 37
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 36
- 238000004528 spin coating Methods 0.000 description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
- 238000000089 atomic force micrograph Methods 0.000 description 33
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- 239000010703 silicon Substances 0.000 description 30
- 229910052710 silicon Inorganic materials 0.000 description 30
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 229920000954 Polyglycolide Polymers 0.000 description 13
- 239000004633 polyglycolic acid Substances 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000003247 decreasing effect Effects 0.000 description 12
- 238000000149 argon plasma sintering Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229920001610 polycaprolactone Polymers 0.000 description 11
- 229920002959 polymer blend Polymers 0.000 description 11
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 10
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 229920002472 Starch Polymers 0.000 description 8
- 239000012620 biological material Substances 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000004310 lactic acid Substances 0.000 description 8
- 235000014655 lactic acid Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 102000008186 Collagen Human genes 0.000 description 7
- 108010035532 Collagen Proteins 0.000 description 7
- 229930182843 D-Lactic acid Natural products 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 7
- 229920001436 collagen Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000004584 polyacrylic acid Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 6
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004113 cell culture Methods 0.000 description 6
- 238000007646 gravure printing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002120 nanofilm Substances 0.000 description 6
- 239000004632 polycaprolactone Substances 0.000 description 6
- 229920000193 polymethacrylate Polymers 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 6
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 5
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000008272 agar Substances 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000000661 sodium alginate Substances 0.000 description 5
- 235000010413 sodium alginate Nutrition 0.000 description 5
- 229940005550 sodium alginate Drugs 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- 239000004373 Pullulan Substances 0.000 description 4
- 229920001218 Pullulan Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 4
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 description 4
- 239000000622 polydioxanone Substances 0.000 description 4
- 235000019423 pullulan Nutrition 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIFCOORMJVPBTN-UHFFFAOYSA-N 2-methylidene-1,3,6-trioxocane Chemical compound C=C1OCCOCCO1 JIFCOORMJVPBTN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 229940081735 acetylcellulose Drugs 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920002961 polybutylene succinate Polymers 0.000 description 3
- 239000004631 polybutylene succinate Substances 0.000 description 3
- 229920000921 polyethylene adipate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010079 rubber tapping Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229940008099 dimethicone Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- JETSKDPKURDVNI-UHFFFAOYSA-N [C].[Ca] Chemical compound [C].[Ca] JETSKDPKURDVNI-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000000601 blood cell Anatomy 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002674 endoscopic surgery Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002350 laparotomy Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 210000004165 myocardium Anatomy 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 210000000130 stem cell Anatomy 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 230000009278 visceral effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/122—Separate manufacturing of ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/48—Polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
- B29C67/202—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising elimination of a solid or a liquid ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/06—Surface irregularities
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
- C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/21—Circular sheet or circular blank
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
Definitions
- the present invention relates to a polymer ultrathin film, a self-supporting porous polymer ultrathin film, and the like.
- Organic ultra-thin films have been conventionally produced using spin coating, electrolytic polymerization, vapor deposition, and vapor deposition polymerization.
- LB Langmuir-Blodgett
- This method is a method in which an amphiphilic molecule is dissolved in a volatile organic solvent and developed on a gas-liquid interface, and a monomolecular film obtained by compressing the solvent after evaporation is transferred onto a solid substrate. The number of thin films and the stacking order can be controlled.
- self-supporting ultra-thin polymer films of any shape can be formed by, for example, forming a self-assembled monolayer on a patterned gold substrate obtained by microlithography technology, and then adsorbing polymerizable molecules in water. Then, the ultrathin polymer film is peeled off from the gold substrate, or the polymer electrolyte is alternately laminated on the substrate to form the ultrathin polymer film, and the ultrathin film is formed using a water-soluble support film.
- a method of preparing an ultrathin film having the same size as the substrate by peeling from the substrate is known (for example, see Patent Document 1: WO 2006/025592, Patent Document 2: WO2008 / 050913, etc.).
- composite membranes composed of a plurality of polymers and block copolymers are known to have a microphase separation structure, and there are sphere-like, column-like, lamellar, and gyroid-like structures.
- a microphase separation structure in the form of a column using an amphiphilic block copolymer plasma, light, electron beam, heat, acid, base, reducing agent, etc. are used as the polymer constituting the column.
- Patent Document 3 Japanese Patent Laid-Open No. 2003-155365
- Patent Document 4 Japanese Patent Special Publication No. 2004-502554, Patent Document 5: Japanese Patent Laid-Open No. 2004).
- Patent Document 6 Japanese Patent Laid-Open No. 2010-116463, etc.
- a polymer having a special structure such as a block copolymer or an amphiphilic polymer is used, and the versatility is poor.
- a porous polymer ultrathin film in which a plurality of pores are opened in a self-supporting organic polymer ultrathin film using a general-purpose polymer has not been known.
- a method for producing such a porous ultra-thin polymer film has not been known.
- claim 1 of Patent Document 8 includes a step of applying a coating liquid containing an organic compound and a hydrophobic organic solvent on a support to form a coating film, and aggregating water vapor on the coating film.
- a method for producing a porous film including a condensation / drying step for drying a coating film is described.
- claims 1 and 10 of Patent Documents 9 and 10 have a microphase separation structure composed of a continuous phase mainly composed of a water-insoluble polymer A and a cylindrical microdomain mainly composed of a water-soluble polymer B.
- a porous membrane is described in which pores having a cylindrical structure with an average pore diameter of 1 to 1000 nm are present in a cylindrical microdomain.
- Example 2 of Patent Document 11 a product formed by PMMA degradation is removed from an asymmetric diblock copolymer film of polystyrene (PS) and polymethyl methacrylate (PMMA) formed on a gold film, and PS nano Making a pore template is described.
- PS polystyrene
- PMMA polymethyl methacrylate
- An object of the present invention is to provide a self-supporting porous ultra-thin polymer film, a method for producing a porous ultra-thin polymer film, and the like.
- the present inventors have mixed a poor solvent having a higher boiling point than that of a high-boiling solvent that is compatible with the solvent of the polymer solution.
- Two types that can be obtained by casting a polymer ultra-thin film that is phase-separated into a sea-island structure, and by further evaporating the poor solvent that composes the island, or not mixing in the solid state Is dissolved in a common solvent and cast onto a substrate to obtain an ultra-thin polymer film that is phase-separated into a sea-island structure and treated with a good solvent for the polymer that forms the island.
- the inventors have conceived that only the islands are removed from the thin film to produce a porous ultra-thin polymer film, and the present invention has been completed.
- the present invention provides the following self-supporting porous ultra-thin polymer film and a method for producing the same.
- a self-supporting porous polymer ultrathin film having a thickness of 10 nm to 1000 nm.
- the ultra-thin porous polymer film according to item 1. [4a] Any of [2a], [2b] and [3a] above, wherein the ratio of the pore diameter to the film thickness of the porous ultra-thin polymer film (pore diameter ( ⁇ m) / film thickness ( ⁇ m)) is 0.1 to 50 2.
- Polymer is polyhydroxyalkanoic acid, copolymer of polyhydroxyalkanoic acid, poly (ester-ether), polyester of aliphatic dicarboxylic acid and aliphatic diol, polyamide, polyurethane, polysaccharide ester, poly (acrylate) Any one of [1], [2], [3] and [4] above, which is at least one selected from the group consisting of poly (methacrylate), polystyrene, polyvinyl acetate, and polysiloxane Porous polymer ultrathin film.
- Polymer is polyhydroxyalkanoic acid, copolymer of polyhydroxyalkanoic acid, poly (ester-ether), polyester of aliphatic dicarboxylic acid and aliphatic diol, polyamide, polyurethane, polysaccharide ester, poly (acrylate) Any one of the above-mentioned [2a], [2b], [3a] and [4a], which is at least one selected from the group consisting of poly (methacrylate), polystyrene, polyvinyl acetate, and polysiloxane Porous polymer ultrathin film.
- a process for obtaining a self-supporting porous ultra-thin polymer film is a self-supporting porous ultra-thin polymer film.
- the islands of the sea-island structure have a size in the range of greater than 1 ⁇ m and less than or equal to 25 ⁇ m, and exist on the surface at a density of 5 ⁇ 10 ⁇ 3 pieces / ⁇ m 2 to 50 pieces / ⁇ m 2
- [6-3] The method according to [6-2] above, wherein the size of the island part of the sea-island structure is in a range of 15 ⁇ m or less.
- [6-4] The method according to any one of [6], [6-2] and [6-3] above, wherein the ultrathin polymer film has a thickness of 10 nm to 1000 nm.
- a combination of the first polymer that forms the island part of the sea-island structure and the second polymer that forms the sea part is selected from the following group, [6], [6-2 ], [6-3] and the method according to any one of [6-4]: (i) first polymer: polystyrene, second polymer: polymethyl methacrylate; (ii) first polymer: polystyrene, second polymer: poly D, L-lactic acid; (iii) first polymer: polymethyl methacrylate, second polymer: polystyrene; (iv) first polymer: polyethylene glycol, second polymer: polystyrene; (v) first polymer: polyvinyl pyrrolidone, second polymer: polystyrene; and (vi) first polymer: poly D, L-lactic acid, second polymer: polystyrene.
- a method for producing a porous ultra-thin polymer film is
- the uneven substrate is a substrate having a polymer thin film in which fine particles are dispersed and fixed.
- the substrate having the polymer thin film in which fine particles are dispersed and fixed is removed by dissolving in a solvent that does not dissolve the polymer ultrathin film.
- the fine particles are polystyrene particles, silica particles, dextran particles, polylactic acid particles, polyurethane fine particles, polyacrylic particles, polyethyleneimine particles, albumin particles, agarose particles, iron oxide particles, titanium oxide fine particles, alumina fine particles, talc fine particles,
- the method according to [9] above which is at least one particle selected from the group consisting of kaolin fine particles, montmorillonite fine particles, and hydroxyapatite fine particles.
- a step of dissolving a polymer in a solvent to obtain a solution A step of dispersing fine particles in a solution to obtain a dispersion; After applying the dispersion to a substrate, and then removing the solvent from the dispersion applied to the substrate to obtain an ultra-thin polymer film; A step of obtaining a self-supporting porous ultra-thin polymer film having a thickness of 10 nm to 1000 nm by immersing the obtained ultra-thin polymer film in a solvent capable of dissolving the fine particles to remove the fine particles.
- a method for producing a porous ultra-thin polymer film A method for producing a porous ultra-thin polymer film.
- a composite of a substrate, a water-soluble sacrificial film, and a porous ultra-thin polymer film having an ultra-thin film [16a] A water-soluble sacrificial film is provided on the substrate, and the porous high-fluidic material according to any one of [2a], [2b], [3a], [4a] and [5a] is provided on the sacrificial film. A composite of a substrate, a water-soluble sacrificial film, and a porous ultra-thin polymer film having an ultra-thin molecular film. [17] The porous polymer ultrathin film according to any one of [1], [2], [3], [4] and [5] above is provided on a substrate.
- a composite of a substrate, a porous ultra-thin polymer film, and a water-soluble support film, having a water-soluble support film on the thin film [17a]
- the porous ultra-thin polymer film according to any one of [2a], [2b], [3a], [4a] and [5a] described above is provided on a substrate, A composite of a substrate, a porous ultra-thin polymer film, and a water-soluble support film, having a water-soluble support film on the thin film.
- a porous high membrane having a water-soluble support film on the porous polymer ultrathin film according to any one of [1], [2], [3], [4] and [5] A composite of an ultra-thin molecular film and a water-soluble support membrane.
- [18a] A porous high membrane having a water-soluble support film on the porous polymer ultrathin film according to any one of [2a], [2b], [3a], [4a] and [5a] A composite of an ultra-thin molecular film and a water-soluble support membrane.
- the porous ultra-thin polymer film is scraped off on another substrate, and water is removed from the scavenged porous ultra-thin polymer film to obtain a dry ultra-thin polymer film.
- [20a] The porous ultra-thin polymer film is scraped on another substrate, and water is removed from the scavenged porous ultra-thin polymer film to obtain a dry ultra-thin polymer film.
- the self-supporting porous polymer ultrathin film produced by the method according to [19] above is scooped with a mesh to produce a composite of a porous polymer ultrathin film and a mesh, A method for producing a composite of a mesh and a porous ultra-thin polymer film.
- a self-supporting porous polymer ultrathin film produced by the method described in [19a] above is scraped with a mesh to produce a composite of a porous polymer ultrathin film and a mesh, A method for producing a composite of a mesh and a porous ultra-thin polymer film.
- One or more porous polymer ultrathin films according to any one of [1], [2], [3], [4] and [5] above, and one or more polymers having no pores A composite of a porous ultra-thin polymer film and an ultra-thin polymer film without pores.
- this invention provides the polymer ultrathin film phase-separated into the following sea-island structures.
- Two types of polymers, a first polymer and a second polymer that are not mixed with each other, are dissolved in a solvent at an arbitrary ratio to obtain a solution, and the obtained solution is applied to a substrate, and then the substrate A polymer ultrathin film phase-separated into a sea-island structure obtained on the substrate by removing the solvent from the solution applied to the substrate.
- the “first polymer” is a polymer that forms an island when phase-separated into a sea-island structure
- the “second polymer” is a polymer that forms a portion other than the island (the sea). It is.
- the present invention also provides the following substantially circular ultra-thin polymer film (sometimes referred to herein as “nanodisk”) and a method for producing the same.
- a substantially circular ultra-thin polymer film having a thickness of 10 nm to 1000 nm and a size in the range of 30 nm to 50 ⁇ m or less.
- the substantially circular polymer ultrathin film according to [B1] wherein the size is in the range of 1 ⁇ m to 25 ⁇ m.
- [B3] The substantially circular ultra-thin polymer film according to [B2] above, wherein the size is in a range of 15 ⁇ m or less.
- [B4] The substantially circular polymer ultrathin film according to any one of [B1] to [B3], wherein the polymer is poly D, L-lactic acid.
- [C1] A step of dissolving two kinds of polymers that are not mixed with each other in a first solvent at an arbitrary ratio to obtain a solution; Applying the obtained solution to the substrate, and then removing the first solvent from the solution applied to the substrate to obtain a polymer ultrathin film phase-separated into a sea-island structure; The polymer ultrathin film is immersed in a second solvent that is a good solvent for the sea part polymer and a poor solvent for the polymer other than the sea part, and the sea part is removed to obtain a film thickness of 10 nm to 1000 nm.
- the present invention can provide a self-supporting porous polymer ultrathin film and a method for producing the same.
- AFM image of PDLLA / PS nanosheet and porous PS nanosheet It is an AFM image of PDLLA / PS nanosheet and porous PS nanosheet.
- FIG. 8 (a) shows an example of the porous polymer ultrathin film 1 of the present invention.
- the porous ultra-thin polymer film of the present invention is a self-supporting ultra-thin film.
- the “self-supporting property” is a property that the ultra-thin film has, and means that the ultra-thin film does not require a support to maintain the film structure. However, this does not deny that the ultrathin film of the present invention forms a composite with the support.
- Porous means that a plurality of pores are provided in the ultrathin film. Furthermore, the hole may or may not penetrate through the ultra-thin polymer film.
- the porous ultra-thin polymer film of the present invention may have only through-holes, only non-through-holes, or through-holes and non-through-holes as shown in FIG. It may have both of the holes. What is necessary is just to set suitably the form of such a hole according to a use.
- the shape of the pores can be any shape such as a substantially circular shape, an elliptical shape, a rectangular shape, or a square shape when the surface of the membrane is viewed from above. Shape.
- the substantially circular holes may be fused together.
- the porous ultra-thin polymer film of the present invention has a thickness of 10 nm to 1000 nm.
- the film thickness of the porous ultra-thin polymer film of the present invention may be 10 nm to 1000 nm, and the film thickness can be appropriately set according to the use, but the film thickness is preferably 20 nm to 800 nm, More preferably, it is 30 nm to 600 nm, still more preferably 40 nm to 400 nm, and particularly preferably 50 nm to 200 nm.
- the porous ultra-thin polymer film of the present invention has a plurality of pores on the surface.
- the “surface” means the upper surface or the lower surface of the ultrathin film.
- the surface pore density may be plural, and the surface pore density can be appropriately set according to the application, but the surface pore density (pieces / ⁇ m 2 ) is usually 0.005 pieces / ⁇ m 2 to 100 / ⁇ m 2 , preferably 0.05 / ⁇ m 2 to 50 / ⁇ m 2 , more preferably 0.1 / ⁇ m 2 to 30 / ⁇ m 2 , and still more preferably 0.5 / ⁇ m 2 to 20 pieces / ⁇ m 2 .
- the hole diameter is not particularly limited, and the hole diameter can be appropriately set according to the use, but the hole diameter is preferably 0.01 ⁇ m to 500 ⁇ m, more preferably 0.03 ⁇ m. -100 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m.
- the pore diameter is in the range of 1 ⁇ m to 25 ⁇ m, more preferably in the range of 1 ⁇ m to 20 ⁇ m, more preferably in the range of 1 ⁇ m to 18 ⁇ m, particularly preferably in excess of 1 ⁇ m. The range is 15 ⁇ m or less.
- a plurality of holes having the same hole diameter may be provided, or a plurality of holes having different hole diameters may be provided.
- the hole diameter distribution is, for example, ⁇ 10% or more.
- the pore size distribution is ⁇ 20% or greater, preferably ⁇ 25% or greater, more preferably ⁇ 30% or greater, and even more preferably ⁇ 35% or greater (e.g., ⁇ 35% or more, ⁇ 40% or more, ⁇ 45% or more, or ⁇ 50% or more).
- the pore size distribution is from the above lower limit ⁇ 10% or more, for example, ⁇ 200% or less, ⁇ 150% or less, ⁇ 100% or less, ⁇ 50% or less Range, ⁇ 40% or less, ⁇ 30% or less, ⁇ 20% or less, or ⁇ 15% or less.
- the pore size distribution is the above lower limit value ⁇ 20% or more (for example, ⁇ 20% or more, ⁇ 25% or more, ⁇ 30% or more, ⁇ 35% or more, ⁇ 40% or more, ⁇ 45% or more, or ⁇ 50% or more) to ⁇ 200% or less, or ⁇ 150% or less.
- pore diameter distribution means a value obtained by calculation as follows. That is, if the pore size distribution is approximated as a normal distribution, the average is ⁇ , and the variance is ⁇ 2 , the pore size distribution is calculated as ⁇ / ⁇ .
- the hole diameter difference between the hole having the maximum hole diameter and the hole having the minimum hole diameter is usually 0.01 ⁇ m to 500 ⁇ m, preferably 0.03 ⁇ m to 100 ⁇ m. More preferably, it is 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m.
- the ratio of the pore diameter to the film thickness of the porous ultrathin polymer film is, for example, 0.1 to 50, preferably 0.2. Is 40, more preferably 0.3 to 20, and particularly preferably 0.5 to 15.
- the holes may be provided on both the upper and lower surfaces of the porous polymer ultrathin film, or may be provided on only one surface (only the upper surface or only the lower surface).
- the hole density may be the same on the upper surface and the lower surface, or may be different. What is necessary is just to set suitably arrangement
- the porous ultra-thin polymer film of the present invention can have any size and shape.
- the size is 0.05 mm to 50 cm, preferably 0.1 mm to 10 cm, more preferably 0.3 mm to 5 cm.
- the shape is not particularly limited, but for example, a flat shape such as a circle, an ellipse, a rectangle, a hexagon, a ribbon, a string, a multi-branch, and a star, a solid such as a tube, a convex, a face mask, and a hand And so on. What is necessary is just to set the shape of a porous polymer ultrathin film suitably according to a use.
- the polymer constituting the porous ultra-thin polymer film of the present invention is not particularly limited, and can be appropriately selected according to its use.
- Examples of the polymer constituting the ultrathin porous polymer film of the present invention include, for example, “Biomaterials for Regenerative Medicine” edited by Yasuhiko Tabata, “Corona Inc.”, and supervised by Sadao Anazawa. Biomaterials Society “Biomaterial Basics”, Biological Materials Society Journal Special Feature “Biomaterials Used in Contact with Blood”, Biomaterials, 22, 78-139 (2004), Special Feature “Used in Contact with Blood” Biomaterials (Vol. 2) ”, Biomaterials, 23, 178-238 (2005), literature“ Biomedical Applications of Biodegradable Polymers ”, Journal of Science, Science Part B: Polymer Physics, 49, 832-864 (2011) ).
- the polymers described in etc. can be used.
- the polymer constituting the porous ultra-thin polymer film of the present invention is preferably (i) polyhydroxyalkanoic acids such as poly D, L lactic acid, polyglycolic acid, hydroxybutyric acid, polycaprolactone; (ii) a copolymer of lactic acid and glycolic acid, a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, a copolymer of trimethylene carbonate and glycolide, a copolymer of polyglycolic acid and poly ⁇ caprolactone, etc.
- polyhydroxyalkanoic acids such as poly D, L lactic acid, polyglycolic acid, hydroxybutyric acid, polycaprolactone
- a copolymer of lactic acid and glycolic acid a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid
- trimethylene carbonate and glycolide a copolymer of trimethylene carbonate and glycolide
- poly (ester-ether) such as polydioxanone, poly (2-methylene-1,3,6-trioxocane);
- Polyesters of aliphatic dicarboxylic acids and aliphatic diols such as polybutylene succinate, polyethylene adipate, polyethylene succinate;
- Polyamides such as polyesteramide, polyamide 4, polyaspartic acid ester, polyglutamic acid ester, polyurethane;
- polysaccharides or polysaccharide esters such as acetylcellulose, polyglucuronic acid, alginic acid, chitosan;
- poly (acrylates) such as polymethyl acrylate, polyethyl acrylate, polybutyl acrylate;
- Poly (methacrylates) such as polymethyl methacrylate, polyethyl methacrylate, polycaprylyl methacrylate, polyglyceryl methacrylate, polyglu
- the polymer is poly (methacrylate), preferably polymethyl methacrylate, polyethyl methacrylate, or polypropyl methacrylate, more preferably polymethyl methacrylate. is there.
- the polymer is a polyhydroxyalkanoic acid, a copolymer with polyhydroxyalkanoic acid, preferably poly D, L lactic acid, polyglycolic acid, or lactic acid and glycolic acid.
- poly D and L lactic acid are more preferable.
- the porous polymer ultrathin film according to a preferred embodiment of the present invention can be used as, for example, a cell culture support, a nano / micro filter, a high light scattering film, a cell separation filter, and the like.
- Using a porous ultra-thin polymer film as a cell support means using as a scaffold that allows entry and exit of a substance.
- a super-thin polymer film is used as follows. Say that. It is used as a scaffold for culturing cells from stem cells to form tissues such as skin, cornea, heart muscle, and nerves. Cells are cultured in a petri dish, but efficient supply of oxygen and nutrients and waste products cannot be discharged from the substrate side. For this reason, there is a concern that the tissue may have a different property from the original cellular tissue.
- a porous polymer ultra-thin film can be used as a scaffolding material that allows substances to enter and exit.
- the polymer of the porous ultra-thin polymer is preferably a polyhydroxyalkanoic acid such as poly-D, L-lactic acid, polyglycolic acid, hydroxybutyric acid, polycaprolactone, or a combination of lactic acid and glycolic acid.
- a polyhydroxyalkanoic acid such as poly-D, L-lactic acid, polyglycolic acid, hydroxybutyric acid, polycaprolactone, or a combination of lactic acid and glycolic acid.
- the thickness of the porous ultra-thin polymer film is preferably 30 nm to 1000 nm, more preferably 50 nm to 1000 nm, still more preferably 100 nm to 1000 nm, and particularly preferably. Is between 200 nm and 1000 nm.
- the pore density (number / ⁇ m 2 ) of the surface of the porous polymer ultrathin film is usually 0.005 / ⁇ m 2 to 100 / ⁇ m 2 , preferably 0.05 / ⁇ m 2. -50 / ⁇ m 2 , more preferably 0.1 / ⁇ m 2 to 30 / ⁇ m 2 , and still more preferably 0.5 / ⁇ m 2 to 20 / ⁇ m 2 .
- the pore size is a pore size suitable for adsorbing the target cells without permeation, preferably 0.01 ⁇ m to 50 ⁇ m, more preferably 0.03 ⁇ m to 10 ⁇ m, More preferably, it is 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m.
- the porous polymer ultrathin film when used as a cell culture support, it is preferable to provide pores on both the upper and lower surfaces of the porous polymer ultrathin film, but the pore density may be the same on the upper surface and the lower surface or may be different.
- the porous ultra-thin polymer film preferably has only through holes, but may have both through holes and non-through holes.
- the shape of the porous ultra-thin polymer film is preferably substantially circular or elliptical.
- Using a porous ultra-thin polymer film as a nano / micro filter specifically means using a super-thin polymer film as follows.
- a porous ultra-thin film is spread on a coarse support and used to control the permeation of various polymers, proteins, viruses, and particles. For example, it can be used as a virus removal membrane or a protein removal membrane.
- the polymer of the porous ultra-thin polymer film is poly (methacrylate), preferably polymethyl methacrylate, polyethyl methacrylate, or polypropyl methacrylate, more preferably Polymethyl methacrylate.
- the film thickness of the porous ultra-thin polymer film is 30 nm to 1000 nm, more preferably 50 nm to 1000 nm, still more preferably 100 nm to 1000 nm, particularly preferably 200 nm to 1000 nm.
- the pore density (number / ⁇ m 2 ) of the surface of the porous ultra-thin polymer film is made as high as possible while maintaining the film strength.
- 0.01 / ⁇ m 2 to 100 / ⁇ m 2 preferably 0.05 / ⁇ m 2 to 100 / ⁇ m 2 , more preferably 0.1 / ⁇ m 2 to 100 / ⁇ m 2 More preferably, the number is 1 / ⁇ m 2 to 100 / ⁇ m 2 .
- the pore size is a pore size suitable for blocking the target substance or particles, preferably 0.001 ⁇ m to 50 ⁇ m, and more preferably 0.01 ⁇ m to 10 ⁇ m.
- the porous polymer ultrathin film when used as a nano / micro filter, it is preferable to provide pores on both the upper and lower surfaces of the porous polymer ultrathin film, but the pore density may be the same on the upper surface and the lower surface or may be different.
- the porous ultra-thin polymer film preferably has only through holes, but may have both through holes and non-through holes.
- the pore size distribution is preferably as narrow as possible. More specifically, the pore size distribution is, for example, in the range of ⁇ 10% to ⁇ 40%, preferably in the range of ⁇ 10% to ⁇ 30%, and more The range is preferably ⁇ 10% to ⁇ 20%, and more preferably ⁇ 10% to ⁇ 15%.
- the shape of the porous ultra-thin polymer film is preferably substantially circular or square.
- cell culture and use of a filter may be combined to form, for example, a bag shape or a cylinder shape, and cultivate floating cells or blood cells therein, or may be used for the purpose of separating them by size.
- Using a porous ultra-thin polymer film as a high light scattering film specifically means that the ultra-thin polymer film is used as follows.
- the porous ultra-thin polymer film of the present invention has a plurality of holes that can scatter light.
- Such a high light scattering film is used by being attached to a patch.
- the patch is, for example, the surface of an ex vivo tissue (skin, nail, hair, etc.), the surface of an in vivo tissue (eg, viscera, blood vessel, tumor, etc.).
- the porous ultra-thin polymer film of some embodiments of the present invention can be used by sticking to the skin for the purpose of hiding skin spots, aza, moles, and wrinkles.
- the porous ultra-thin polymer film according to another embodiment of the present invention can be used by being attached to a visceral surface for the purpose of marking during laparotomy or endoscopic surgery.
- the porous ultra-thin polymer film according to still another embodiment of the present invention can be used by being applied to the skin, nails and hair for the purpose of body painting, nail art, hair coloring and the like.
- the porous ultra-thin polymer film of the present invention is used by sticking to the skin for the purpose of hiding skin spots, aza, moles and wrinkles.
- the shape and size of the porous ultra-thin polymer film is selected to achieve its purpose, and is preferably circular, polygonal, or tape-like. Further, a fine dispersion liquid of a high light scattering film may be prepared and used in the form of spray or cream.
- the polymer of the porous ultra-thin polymer is preferably a polyhydroxyalkanoic acid such as poly-D, L-lactic acid, polyglycolic acid, hydroxybutyric acid, polycaprolactone, or the co-polymerization of lactic acid and glycolic acid.
- a polyhydroxyalkanoic acid such as poly-D, L-lactic acid, polyglycolic acid, hydroxybutyric acid, polycaprolactone, or the co-polymerization of lactic acid and glycolic acid.
- Copolymers copolymers, copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, copolymers of trimethylene carbonate and glycolide, copolymers of polyglycolic acid and poly ⁇ caprolactone, polydioxanone, poly (2- A poly (ester-ether) such as methylene-1,3,6-trioxocan), a polybutylene succinate, a polyethylene adipate, a polyethylene succinate, and the like, and more preferably a polyester of an aliphatic dicarboxylic acid and an aliphatic diol.
- D L lactic acid, polyglycolic acid, hydroxybutyric acid, poly Polyhydroxyalkanoic acid such as caprolactone, copolymer of lactic acid and glycolic acid, copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, copolymer of trimethylene carbonate and glycolide, polyglycolic acid and poly ⁇ caprolactone Copolymers such as copolymers.
- polyhydroxyalkanoic acid such as caprolactone
- copolymer of lactic acid and glycolic acid copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid
- copolymer of trimethylene carbonate and glycolide copolycolic acid and poly ⁇ caprolactone Copolymers such as copolymers.
- the thickness of the porous ultra-thin polymer film is selected with emphasis on adhesion to a patch (for example, skin), preferably 20 nm to 900 nm, more preferably 30 nm. It is ⁇ 500 nm, more preferably 40 nm to 300 nm, and particularly preferably 50 nm to 200 nm.
- the pore density (number / ⁇ m 2 ) on the surface of the porous ultra-thin polymer film is usually 0.01 / ⁇ m 2 to 100 / ⁇ m 2 , preferably 0.05 / ⁇ m 2. -80 / ⁇ m 2 , more preferably 0.1 / ⁇ m 2 to 50 / ⁇ m 2 , and even more preferably 1 / ⁇ m 2 to 30 / ⁇ m 2 .
- the pore size is a pore size suitable for efficiently scattering light in a wide wavelength region in a random direction, preferably 0.01 ⁇ m to 50 ⁇ m, more preferably 0.03 ⁇ m to 10 ⁇ m. More preferably, the thickness is 0.1 ⁇ m to 5 ⁇ m.
- a plurality of holes having the same hole diameter may be provided, or a plurality of holes having different hole diameters may be provided, but it is preferable to provide a plurality of holes having different hole diameters.
- the difference in hole diameter between the hole having the maximum hole diameter and the hole having a small hole diameter is usually 0.01 ⁇ m to 500 ⁇ m, preferably 0.03 ⁇ m to 100 ⁇ m. More preferably, the thickness is 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m.
- the pore distribution is preferably as wide as possible to obtain random light scattering. More specifically, the pore size distribution is, for example, in the range of ⁇ 20% to ⁇ 200%, preferably ⁇ 30% to ⁇ 200. %, More preferably in the range of ⁇ 50% to ⁇ 150%, and still more preferably in the range of ⁇ 50% to ⁇ 100%.
- the hole density may be the same on the upper surface and the lower surface, or may be different.
- the porous ultra-thin polymer film preferably has only through holes, but may have both through holes and non-through holes.
- Using a porous ultra-thin polymer film as a filter for cell separation specifically refers to using a super-thin polymer film as follows. That is, a porous ultra-thin film is spread on a coarse support and used for the purpose of controlling the permeation of various cells.
- the polymer of the porous ultra-thin polymer film is poly (methacrylate), preferably polymethyl methacrylate, polyethyl methacrylate, or polypropyl methacrylate, more preferably Polymethyl methacrylate.
- the thickness of the porous ultra-thin polymer film is 30 nm to 1000 nm, more preferably 50 nm to 1000 nm, still more preferably 100 nm to 1000 nm, and particularly preferably 200 nm to 1000 nm.
- the pore density (number / ⁇ m 2 ) on the surface of the porous ultra-thin polymer film is made as high as possible while maintaining the membrane strength.
- 0.01 / ⁇ m 2 to 100 / ⁇ m 2 preferably 0.05 / ⁇ m 2 to 100 / ⁇ m 2 , more preferably 0.1 / ⁇ m 2 to 100 / ⁇ m 2 More preferably, the number is 1 / ⁇ m 2 to 100 / ⁇ m 2 .
- the pore size is a pore size suitable for preventing permeation of the target cells, preferably in the range of 1 to 25 ⁇ m, more preferably 1 to 20 ⁇ m. More preferably, it is in the range of more than 1 ⁇ m and not more than 18 ⁇ m, and particularly preferably in the range of more than 1 ⁇ m and not more than 15 ⁇ m.
- pores are preferably provided on both the upper and lower surfaces of the porous polymer ultrathin film, but the pore density may be the same on the upper surface and the lower surface, or may be different.
- the porous ultra-thin polymer film preferably has only through holes, but may have both through holes and non-through holes.
- the pore size distribution is preferably as narrow as possible. More specifically, the pore size distribution is, for example, in the range of ⁇ 10% to ⁇ 40%, preferably in the range of ⁇ 10% to ⁇ 30%, and more The range is preferably ⁇ 10% to ⁇ 20%, and more preferably ⁇ 10% to ⁇ 15%.
- the shape of the porous ultra-thin polymer film is preferably substantially circular or square.
- a composite may be formed together with the sacrificial film.
- the composite has a water-soluble sacrificial film 2 on a substrate 3 as shown in FIG. 8 (b), and a porous polymer ultrathin film 1 of the present invention on the substrate and the water-soluble sacrificial film. And a composite 4 of an ultrathin porous polymer film.
- the porous ultra-thin polymer film of the present invention may form a composite together with the substrate and the water-soluble support film.
- the composite has a porous polymer ultrathin film 1 of the present invention on a substrate 3 and a water-soluble support film 5 on the substrate and a porous polymer as shown in FIG. 8 (c). It is a composite 6 of an ultrathin film and a water-soluble support membrane.
- the substrate is not particularly limited as long as it can support a porous ultra-thin polymer film, but is usually a silicon substrate, glass substrate, metal substrate, polyester, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, ethylene vinyl acetate.
- Polymer ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer, nylon film, etc., preferably silicon substrate, polyester, polypropylene, polyethylene, etc., more preferably silicon substrate, For example, polyester.
- the film thickness of the substrate is usually 1 ⁇ m to 5000 ⁇ m, preferably 5 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, still more preferably 30 ⁇ m to 300 ⁇ m, and particularly preferably 50 ⁇ m to 100 ⁇ m. It is.
- the porous ultra-thin polymer film of the present invention is as described above.
- the water-soluble sacrificial film and the water-soluble support film are not limited as long as they are soluble in water, but usually a polyvinyl alcohol film, a polyacrylic acid film, a polymethacrylic acid film, a sodium alginate film, a polyethylene oxide film, and a polyacrylamide film.
- the film thickness of the water-soluble sacrificial film is usually 5 nm to 1000 nm, preferably 5 nm to 500 nm, more preferably 10 nm to 300 nm, still more preferably 10 nm to 200 nm, and particularly preferably 10 nm to 100 nm.
- the film thickness of the water-soluble support membrane is usually 50 nm to 20000 nm, preferably 100 nm to 10000 nm, more preferably 200 nm to 5000 nm, still more preferably 500 nm to 5000 nm, and particularly preferably 700 nm to 5000 nm.
- the porous polymer ultrathin film of the present invention may form a complex together with the water-soluble support membrane.
- the complex has a water-soluble support film 5 on the porous polymer ultra-thin film 1 of the present invention, and is a composite of a porous polymer ultra-thin film and a water-soluble support film. 7.
- this composite is immersed in water, the water-soluble support film is dissolved, and a porous polymer ultrathin film is obtained.
- the resulting porous polymer ultrathin film is self-supporting.
- the “self-supporting type” means a form in which the porous ultra-thin polymer film exists independently without a support.
- porous polymer ultrathin film and the water-soluble support film of the present invention are as described above.
- the porous ultra-thin film is attached to the adherend by removing the water-soluble support film by washing with water. Can do.
- the porous polymer ultrathin film of the present invention may form a complex together with the mesh.
- the composite is a composite 9 of a mesh and a porous ultra-thin polymer film having the porous ultra-thin polymer film 1 of the present invention on a mesh 8 as shown in FIG. 8 (e).
- the porous ultra-thin polymer film of the present invention is as described above. Any mesh may be used as long as the mesh can support the porous ultra-thin polymer film of the present invention and can be easily peeled off from the porous ultra-thin polymer film.
- the mesh examples include a mesh formed from a material selected from the group consisting of nylon, polyester, Teflon (registered trademark), polypropylene, silk, and the like.
- the mesh size is usually 1 to 4000 ⁇ m, preferably 5 to 400 ⁇ m, more preferably 10 to 200 ⁇ m, and particularly preferably 40 to 100 ⁇ m.
- the thickness of the mesh is usually 5 ⁇ m to 1000 ⁇ m, preferably 7 ⁇ m to 700 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, still more preferably 30 ⁇ m to 300 ⁇ m, and particularly preferably 50 ⁇ m to 100 ⁇ m. It is.
- the ultra-thin porous polymer film can be easily attached to the adherend by peeling off the mesh from the ultra-thin porous polymer film. Can do.
- the porous polymer ultrathin film of the present invention may form a composite together with an ultrathin film having no pores. “No pores” means that no pores are provided in the ultrathin film, such as those provided by the porous polymer ultrathin film.
- the composite has the porous polymer ultrathin film 1 of the present invention on the ultrathin film 10 having no pores, and the ultrathin film without pores and the ultrathin film without pores. It is the complex 11.
- the composite may contain at least one porous polymer ultrathin film (for example, 1 to 20 layers, 1 to 10 layers, or 1 to 5 layers), and at least one ultrathin film without pores.
- the order of lamination of the porous ultra-thin polymer film and the ultra-thin film without pores is not particularly limited, and when the composite has three or more layers, the ultra-thin porous polymer film starts from the bottom layer. It may be included in any one or more of the uppermost layers.
- the thickness of each ultra-thin polymer film, pore size, pore density, pore size distribution, ratio of pore diameter to film thickness, material Etc. may be different, or all or some of them may be the same.
- the ultrathin film thickness, material, etc. may be different between the ultrathin films, or all or part of them may be the same.
- the thickness of the ultrathin film having no pores is usually 10 nm to 1000 nm, preferably 20 nm to 800 nm, more preferably 30 nm to 600 nm, still more preferably 40 nm to 400 nm, and particularly preferably 50 nm to 200 nm.
- the material of the ultrathin film having no pores can be appropriately selected according to the use.
- polylactic acid a copolymer of lactic acid and glycolic acid, polyglycolic acid, polycaprolactone, silicon, dimethicone, polyvinyl acetate
- Acrylic polymers such as carboxymethyl cellulose, polyvinyl pyrrolidone, collagen, (alkyl acrylate / diacetone acrylamide) copolymer, (alkyl acrylate / dimethicone) copolymer, methacrylic polymers, polyurethane, etc., preferably polylactic acid, lactic acid It is a copolymer of glycolic acid, carboxymethylcellulose, polyurethane, and acrylic polymer.
- the ultrathin film having no holes can be produced, for example, by the method described in WO 2006/025592, WO2008 / 050913, Adv. Mater. 2009, 21, 4388-4392, or the like.
- a composite of a porous ultra-thin polymer film and an ultra-thin film without pores may be manufactured by sequentially forming a porous ultra-thin polymer film (layer) and an ultra-thin film (layer) without pores from the beginning. Or you may manufacture by bonding together the porous polymer ultrathin film manufactured separately, and the ultrathin film without a hole.
- the complex can be used, for example, as the high light scattering film.
- porous polymer ultrathin film of the present invention can be produced, for example, by the following method.
- “Arbitrary ratio” means that the ratio of polymer 1 to polymer 2 (w / w) is arbitrary, and the ratio of polymer 1 to polymer 2 (w / w) is, for example, 1 : 9 to 5: 5.
- the ratio of polymer 1 to polymer 2 (w / w) is preferably 1: 9 to 4: 6, more preferably 1: 9 to 3: 7.
- the first solvent is not limited as long as it can dissolve the two kinds of polymers, but in general, dichloromethane, diethyl ether, methyl acetate, acetone, chloroform, methyl alcohol, tetrahydrofuran, dioxane, Ethyl acetate, methyl ethyl ketone, benzene, acetonitrile, isopropyl alcohol, dimethoxyethane, ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), ethylene glycol mono-normal-butyl ether (also known as butyl cellosolve) , Ethylene glycol monomethyl ether (also known as methyl cellosolve) selected from the group consisting of toluene, N, N-dimethylformamide, and dimethylacetamide At least one solvent that can be given.
- the first solvent is preferably from dichloromethane, diethyl ether, acetone, chloroform, tetrahydrofuran, dioxane, ethyl acetate, methyl ethyl ketone, acetonitrile, isopropyl alcohol, dimethoxyethane, N, N-dimethylformamide, and dimethylacetamide.
- At least one solvent more preferably at least one solvent selected from the group consisting of dichloromethane, tetrahydrofuran, and ethyl acetate.
- the total weight concentration of the polymer in the solution is usually 0.1 wt% to 20 wt%, preferably 0.3 wt% to 10 wt%, more preferably 0.5 wt% to 2 wt%.
- the polymer ultrathin film phase-separated into the sea island structure is obtained by removing the 1st solvent from the solution apply
- the method for applying the solution to the substrate is not particularly limited, but for example, the solution is applied to the substrate by a conventional method such as spin coating, spray coating, bar coating, or dip coating. Alternatively, the solution is thinly applied to the substrate by a conventional printing method such as gravure printing, screen printing, or ink jet printing.
- the first solvent is removed from the solution applied to the substrate.
- the method for removing the first solvent is not particularly limited.
- the first solvent can be evaporated and removed by continuing the rotation as it is. .
- the first solvent can be evaporated and removed by heating.
- the first solvent can be removed by reducing the pressure.
- the first solvent may be removed by combining two or more of these first solvent removal methods.
- the ultrathin polymer film phase-separated into a sea-island structure is immersed in a second solvent that is a good solvent for the polymer 1 in the island and a poor solvent for the polymer 2 other than the island. By removing it, a porous ultra-thin polymer film is obtained.
- the combination of the solubility parameter calculation by the method described in the document “SP Value Basics / Applications and Calculation Methods”, Hideki Yamamoto, Information Mechanism can be mentioned.
- the combination of the polymer 1, the polymer 2, and the second solvent is determined according to the following guidelines. That is, the Hansen solubility parameter for a certain polymer is plotted in a three-dimensional space, and a sphere is created using the interaction radius of the polymer as a center.
- the target solvent is a good solvent for the polymer, and if it is outside the sphere, it is a poor solvent. to decide. From this guideline, the first solvent is a good solvent for polymer 1 and polymer 2, and the second solvent is a good solvent for polymer 1 and a poor solvent for polymer 2.
- polymer 1 polystyrene, polymer 2: polymethyl methacrylate, second solvent: cyclohexane
- polymer 1 polystyrene, polymer 2: poly D, L-lactic acid, second solvent: cyclohexane
- polymer 1 polymethyl methacrylate, polymer 2: polystyrene, second solvent: ethyl acetate
- polymer 1 polyethylene glycol, polymer 2: polystyrene, second solvent: water
- polymer 1 polyvinylpyrrolidone, polymer 2: polystyrene, second solvent: water
- polymer 1 poly D, L-lactic acid, polymer 2: polystyrene, second solvent: acetic acid ethyl.
- the second solvent is a good solvent for the polymer 1 and a poor solvent for the polymer 2. Therefore, when the ultrathin polymer phase separated into the sea-island structure is immersed in the second solvent, Only part of the polymer 1 is dissolved in the second solvent, whereby the islands are selectively removed. The removed area becomes a hole. As a result, a porous ultra-thin polymer film is obtained.
- the pore diameter and the pore density are adjusted by adjusting the mixing ratio (w / w) of the two types of polymer when preparing a solution in which the two types of polymer are dissolved, and the method of applying the solution to the substrate
- the spin coating method it can be controlled by adjusting the number of rotations, adjusting the boiling point of the first solvent, and the like.
- the hole diameter can be reduced and the hole density can be increased by increasing the number of rotations.
- the hole diameter can be increased and the hole density can be decreased.
- the temperature during spin coating by heating can be increased, the pore diameter can be increased, and the pore density can be decreased.
- the pore diameter can be reduced and the pore density can be increased.
- the pore diameter and the pore density in the porous polymer ultrathin film can be freely controlled.
- the pore size distribution can be controlled as follows. For example, when the spin coating method is used, the pore size distribution can be increased by reducing the rotation speed during spin coating. On the other hand, the pore size distribution can be reduced by increasing the rotational speed during spin coating.
- Examples of the combination of the polymer, the good solvent, and the poor solvent include a combination from the calculation of the solubility parameter according to the method described in the literature “SP value basics / application and calculation method”, Hideki Yamamoto, information mechanism. .
- the combination of polymer, good solvent, and poor solvent is determined according to the following guidelines. That is, the Hansen solubility parameter for a certain polymer is plotted in a three-dimensional space, and a sphere is created using the interaction radius of the polymer as a center.
- the target solvent is a good solvent for the polymer, and if it is outside the sphere, it is a poor solvent. to decide. From this guideline, a good solvent group and a poor solvent group for a certain polymer are created, and a combination of a good solvent and a poor solvent having a boiling point higher than that of the good solvent is selected.
- polymer poly D, L lactic acid, good solvent: ethyl acetate, poor solvent: dimethyl sulfoxide;
- polymer polyglycolic acid, good solvent: 1,1,1,3,3,3-hexafluoro-2-propanol, poor solvent: ethyl acetate;
- polymer polycaprolactone, good solvent: tetrahydrofuran (THF), poor solvent: isopropyl alcohol;
- Polymer polydioxanone, good solvent: dichloromethane, poor solvent: ethylene glycol;
- Polymer cellulose acetate, good solvent: THF, poor solvent: water;
- Polymer cellulose acetate, good solvent: THF, poor solvent: water;
- Polymer cellulose acetate, good solvent: THF, poor solvent: toluene; or
- any ratio means that the ratio of good solvent to poor solvent (v / v) is arbitrary, and the ratio of good solvent to poor solvent (v / v) is, for example, 100: 1 to 100 : 10.
- the ratio of good solvent to poor solvent (v / v) is preferably 100: 1 to 100: 7, more preferably 100: 1 to 100: 5.
- the concentration of the polymer in the solution is usually 1 mg / ml to 1000 mg / ml, preferably 3 mg / ml to 100 mg / ml, more preferably 5 mg / ml to 50 mg / ml.
- a porous polymer ultrathin film is obtained by removing a mixed solvent from the solution apply
- the method for applying the solution to the substrate is the same as described above.
- the method for removing the mixed solvent from the solution applied to the substrate is the same as the method for removing the first solvent.
- an ultra-thin polymer film in which the poor solvent having a high boiling point is dispersed is temporarily obtained. Therefore, a porous ultra-thin polymer film can be obtained by removing the poor solvent in the ultra-thin polymer film.
- the pore diameter and the pore density are adjusted when the content of the poor solvent in the mixed solvent of the good solvent and the poor solvent is adjusted, and when the spin coating method is used as a method of applying the solution in which the polymer is dissolved to the substrate. It can be controlled by adjusting the number, adjusting the difference between the boiling points of the good solvent and the poor solvent, the solubility of the polymer in the poor solvent, and the temperature at the time of preparation.
- the pore diameter can be increased and the pore density can be increased by increasing the content of the poor solvent in the mixed solvent of the good solvent and the poor solvent.
- the pore diameter can be reduced and the pore density can be lowered.
- the hole diameter can be reduced and the hole density can be increased by increasing the number of rotations.
- the hole diameter can be increased and the hole density can be decreased.
- the pore diameter By increasing the difference between the boiling points of the good solvent and the poor solvent, the pore diameter can be increased and the pore density can be decreased. On the other hand, by reducing the difference in boiling point between the good solvent and the poor solvent, the pore diameter can be reduced and the pore density can be increased.
- the pore diameter can be reduced and the pore density can be increased.
- the pore diameter can be increased and the pore density can be decreased.
- the pore diameter and the pore density in the porous polymer ultrathin film can be freely controlled.
- the pore size distribution can be controlled as follows. For example, when the spin coating method is used, the pore size distribution can be increased by reducing the rotational speed during spin coating. On the other hand, the pore size distribution can be reduced by increasing the rotational speed during spin coating. .
- a polymer is dissolved in a solvent to obtain a solution.
- the polymer is a polymer constituting the porous ultra-thin polymer film of the present invention, and specific examples are as described above.
- the solvent may be any solvent that can dissolve the polymer, for example, ethyl acetate, dichloromethane, diethyl ether, methyl acetate, acetone, chloroform, methyl alcohol, tetrahydrofuran, dioxane, methyl ethyl ketone, benzene, acetonitrile, isopropyl alcohol, dimethoxyethane, Ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), ethylene glycol mono-normal-butyl ether (also known as butyl cellosolve), ethylene glycol monomethyl ether (also known as methyl cellosolve), toluene, N, N -Dimethylformamide, dimethylacetamide, etc., preferably ethyl acetate, dichloromethane, diethyl ether Acetone, chlor
- the concentration of the polymer in the solution is usually 1 mg / ml to 1000 mg / ml, preferably 3 mg / ml to 100 mg / ml, more preferably 5 mg / ml to 50 mg / ml. .
- the obtained solution is applied to an uneven substrate, and the solvent is removed from the solution applied to the substrate to obtain a porous ultra-thin polymer film.
- the uneven substrate is, for example, a substrate having a polymer thin film in which fine particles are dispersed and fixed, or a substrate having an uneven pattern formed by other methods.
- the method for applying the solution to the substrate is the same as described above.
- the method for removing the solvent from the solution applied to the substrate is the same as the method for removing the first solvent.
- a porous ultra-thin polymer film in which the uneven shape on the substrate is copied is obtained.
- the “substrate having a polymer thin film in which fine particles are dispersed and fixed” exemplified as an uneven substrate can be produced, for example, as follows. First, a polymer is dissolved in a solvent to obtain a solution. The fine particle dispersion is diluted with the resulting solution and stirred. After applying the obtained diluted solution to the substrate, the solvent is removed from the diluted solution applied to the substrate. Thereby, a substrate having a polymer thin film in which fine particles are dispersed and fixed can be produced.
- the fine particles are usually 20 nm to 3000 nm in diameter (preferably 100 nm to 2000 nm in diameter, more preferably 500 nm to 1500 nm in diameter).
- polystyrene particles, silica particles, dextran particles, polylactic acid particles, polyurethane fine particles, polyacryl particles, Polyethyleneimine particles, albumin particles, agarose particles, iron oxide particles, titanium oxide particles, alumina particles, talc particles, kaolin particles, montmorillonite particles, hydroxyapatite particles, etc. preferably polystyrene particles, silica particles, dextran particles, titanium oxide particles) , Talc fine particles, montmorillonite fine particles, etc.
- the dispersion is obtained by dispersing these fine particles in a solvent that dissolves a polymer that forms the following polymer thin film.
- Polymers used to form polymer thin films in which fine particles are dispersed and fixed include, for example, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, sodium alginate, polyethylene oxide, polyacrylamide, polyvinylpyrrolidone, starch, collagen, pullulan, agar Preferred are polyvinyl alcohol, polyacrylic acid, sodium alginate, polyethylene oxide, polyacrylamide, polyvinyl pyrrolidone, starch and the like, and more preferred are polyvinyl alcohol, polyacrylic acid and starch.
- the solvent for dissolving the polymer is, for example, water, acidic water, alkaline water, methanol, ethanol or the like, preferably water, alkaline water or the like.
- the density of the fine particles in the dispersion is usually 0.1 wt% to 20 wt%, preferably 0.5 wt% to 10 wt%, more preferably 1 wt% to 5 wt%.
- the method for applying the dispersion liquid to the substrate is not particularly limited.
- the dispersion liquid is applied to the substrate by a conventional method such as a spin coating method, a spray coating method, a bar coating method, or a dip coating method.
- the solution is thinly applied to the substrate by a conventional printing method such as gravure printing, screen printing, or ink jet printing.
- the solvent is removed from the diluted solution applied to the substrate.
- the method for removing the solvent is not limited, but, for example, if the diluent is applied to the substrate by a spin coating method, the solvent can be removed by evaporation by continuing to rotate as it is. Alternatively, the solvent can be removed by evaporation by heating. Alternatively, the solvent can be removed by reducing the pressure. Alternatively, the solvent may be removed by combining two or more of these solvent removal methods.
- the film thickness of the polymer thin film in which fine particles are dispersed and fixed is usually 50 nm to 1500 nm, preferably 100 nm to 1000 nm, more preferably 200 nm to 800 nm.
- “Substrate with irregularities formed by other methods” is prepared, for example, by forming a pattern by a method such as lithography, printing, spraying, etc., on the polymer thin film used for dispersing and fixing the fine particles. Can do.
- the uneven substrate is a substrate having a polymer thin film in which fine particles are dispersed and fixed
- the fine particles are dispersed and fixed.
- a self-supporting porous polymer ultrathin film can be obtained by dissolving the polymer thin film in a solvent and peeling the porous polymer ultrathin film from the uneven substrate. Even in a substrate having irregularities formed by other methods, a self-supporting porous ultra-thin polymer film can be obtained by forming the ultra-thin polymer film and then dissolving the substrate itself.
- the solvent for dissolving the polymer thin film or the substrate may be any solvent that dissolves the polymer thin film but does not dissolve the porous polymer ultra-thin film, such as water, acidic water, alkaline water, methanol, and ethanol. Preferably, water, alkaline water or the like is used.
- the pore size, the pore density, and the pore size distribution can be freely controlled by adjusting the size, density, and size distribution of the fine particles used.
- a polymer is dissolved in a solvent to obtain a solution.
- the polymer is a polymer constituting the porous ultra-thin polymer film of the present invention, and specific examples are as described above.
- the solvent may be any solvent that can dissolve the polymer, and specific examples are as described above.
- the concentration of the polymer in the solution is usually 1 mg / ml to 1000 mg / ml, preferably 3 mg / ml to 100 mg / ml, more preferably 5 mg / ml to 50 mg / ml. .
- fine particles are precipitated at the time of concentration using a difference in solubility from a solution in which a salt is dissolved, or insoluble fine particles are dispersed in advance to obtain a dispersion.
- the fine particles usually have a diameter of 20 nm to 3000 nm (preferably a diameter of 100 nm to 2000 nm, more preferably a diameter of 500 nm to 1500 nm), and are not dissolved in a solvent for forming a porous ultra-thin polymer film. There is no limitation as long as it can be dissolved in a solvent that does not dissolve the thin film.
- the fine particles are, for example, inorganic salts (for example, lithium bromide, sodium chloride, sodium iodide, ammonium chloride, sodium hydrogen sulfate, sodium dihydrogen phosphate, calcium chloride, sodium acetate, sodium carbonate, sodium hydrogen carbonate, hydrogen phosphate.
- inorganic salts for example, lithium bromide, sodium chloride, sodium iodide, ammonium chloride, sodium hydrogen sulfate, sodium dihydrogen phosphate, calcium chloride, sodium acetate, sodium carbonate, sodium hydrogen carbonate, hydrogen phosphate.
- polymer eg, polystyrene, dextran, polyphenol, polyamide, acrylic, polyethyleneimine, agarose, etc.
- Metal oxides eg, alumina, iron oxide, titanium oxide, etc.
- metals eg, silver, copper, iron, zinc, aluminum, etc.
- the solvent is removed from the dispersion applied to the substrate to obtain an ultra-thin polymer film.
- the method for applying the dispersion liquid to the substrate is not particularly limited, but for example, the dispersion liquid is applied to the substrate by a conventional method such as a spin coating method, a spray coating method, a bar coating method, or a dip coating method.
- the solution is thinly applied to the substrate by a conventional printing method such as gravure printing, screen printing, or ink jet printing.
- the solvent is removed from the dispersion applied to the substrate.
- the method for removing the solvent is not limited, but, for example, if the dispersion is applied to the substrate by spin coating, the solvent can be removed by evaporation by continuing to rotate as it is. Alternatively, the solvent can be removed by evaporation by heating. Alternatively, the solvent can be removed by reducing the pressure. Alternatively, the solvent may be removed by combining two or more of these solvent removal methods.
- the “solvent capable of dissolving fine particles” is a solvent that does not dissolve the polymer ultrathin film but can dissolve the fine particles.
- the solvent can be appropriately selected according to the type of polymer and the type of fine particles. Specific examples of the solvent are water, acidic water, alkaline water, alcohol, dimethylformamide, cyclohexane, acetone, ethyl acetate and the like.
- sodium bromide dissolves in acetone
- potassium thiocyanide dissolves in dimethylformamide
- metal and calcium carbonate dissolve in acidic water
- silica dissolves in alkaline water.
- Fine particles are dissolved and removed by the solvent.
- the portion from which the fine particles have been removed becomes a hole.
- a porous ultra-thin polymer film is obtained.
- the pore size, the pore density, and the pore size distribution can be freely controlled by adjusting the size, density, and size distribution of the fine particles used.
- a polymer as a raw material is dissolved in a solvent to obtain a solution, the microbubbles are dispersed in the obtained solution, and the solution in which the microbubbles are dispersed is applied to the substrate. Then, the porous polymer ultrathin film is obtained by removing the solvent from the solution applied to the substrate.
- the polymer, solvent, substrate and the like are the same as described above.
- a method of dispersing microbubbles in the solution can be performed by a known method. After removing the solvent, the microbubbles become pores. As a result, a porous ultra-thin polymer film is obtained.
- a water-soluble sacrificial film is provided in advance between the porous polymer ultra-thin film and the substrate, and water is used to The porous ultra-thin polymer film can be peeled from the substrate by removing the film.
- the water-soluble sacrificial film include polyvinyl alcohol film, polyacrylic acid film, polymethacrylic acid film, sodium alginate film, polyethylene oxide film, polyacrylamide film, polyvinylpyrrolidone film, starch film, carboxymethylcellulose film, collagen film, pullulan. Examples thereof include at least one film selected from the group consisting of a film, an agar film, a silicon film, and the like.
- a polystyrene film or a polyolefin film is previously provided between the porous polymer ultrathin film and the substrate.
- the porous ultra-thin polymer film can be peeled from the substrate.
- the film thickness of the water-soluble sacrificial film or other sacrificial film is usually 5 nm to 1000 nm, preferably 5 nm to 500 nm, more preferably 10 nm to 300 nm, and further preferably 10 nm to 200 nm. Particularly preferably, the thickness is 10 nm to 100 nm.
- the water-soluble sacrificial film or other sacrificial film can be formed by a known method.
- a self-supporting porous ultra-thin polymer film can be obtained by removing the water-soluble sacrificial film of the composite of the substrate, the water-soluble sacrificial film, and the porous ultra-thin polymer film with water. That is, the water-soluble sacrificial film is dissolved by water, and a self-supporting porous polymer ultrathin film can be obtained in water.
- the self-supporting porous polymer ultrathin film thus obtained is spread on another substrate, and water is removed from the porous polymer ultrathin film thus obtained to obtain a dry porous polymer ultrathin film. You can also.
- “Another substrate” is the same as the substrate.
- the obtained free-standing porous polymer ultrathin film may be scraped with a mesh to produce a composite of the porous polymer ultrathin film and the mesh.
- Mesh is as described above.
- water-soluble support film examples include polyvinyl alcohol film, polyacrylic acid film, polymethacrylic acid film, sodium alginate film, polyethylene oxide film, polyacrylamide film, polyvinylpyrrolidone film, starch film, carboxymethylcellulose film, collagen film, pullulan.
- examples thereof include at least one film selected from the group consisting of a film, an agar film, a silicon film, and the like.
- the film thickness of the water-soluble support membrane is usually 50 nm to 20000 nm, preferably 100 nm to 10000 nm, more preferably 200 nm to 5000 nm, still more preferably 500 nm to 5000 nm, and particularly preferably 700 nm to 5000 nm.
- the water-soluble support membrane can be formed by a known method.
- the present invention provides a solution by dissolving two kinds of polymers, a first polymer and a second polymer that are not mixed with each other, in a solvent at an arbitrary ratio, After the obtained solution is applied to the substrate, the solvent is removed from the solution applied to the substrate, and the polymer ultrathin film phase-separated into a sea-island structure obtained on the substrate (hereinafter referred to as “the present invention”). Molecular ultrathin film ").
- first solvent the solvent in which the first polymer and the second polymer are dissolved may be referred to as “first solvent”.
- the two types of polymers, the first polymer and the second polymer that are not mixed with each other refer to two types of polymers that are not mixed with each other in the solid state.
- a polymer that forms an island when phase-separated into a sea-island structure is referred to as a first polymer
- a polymer other than the island is referred to as a second polymer.
- Examples of the combination of the first polymer and the second polymer include the combinations described later.
- the film thickness of the polymer ultrathin film of the present invention is usually from 10 nm to 1000 nm, like the porous polymer ultrathin film of the present invention.
- the film thickness of the ultra-thin polymer film of the present invention can be appropriately set according to the application, but the film thickness is preferably 20 nm to 800 nm, more preferably 30 nm to 600 nm. More preferably, it is 40 nm to 400 nm, and particularly preferably 50 nm to 200 nm.
- the “surface” means the upper surface or the lower surface of the ultrathin film.
- the density of the islands on the surface may be plural, and the density of the islands on the surface can be appropriately set according to the application, but the density of islands on the surface (pieces / ⁇ m 2 ) is usually 0.005 / ⁇ m 2 to 100 / ⁇ m 2 , preferably 0.05 / ⁇ m 2 to 50 / ⁇ m 2 , more preferably 0.1 / ⁇ m 2 to 30 / ⁇ m 2 , The number is preferably 0.5 / ⁇ m 2 to 20 / ⁇ m 2 .
- the shape of the island portion can be formed in any shape such as a substantially circular shape, an elliptical shape, a rectangular shape, and a square shape when viewed from above the film surface. It is.
- the substantially circular islands may be merged.
- the size of the island part of the sea-island structure is not particularly limited and can be appropriately selected according to the purpose, but usually the same size as the pore diameter of the porous ultra-thin polymer film of the present invention. is there. Therefore, the size of the island part of the sea-island structure is preferably 0.01 ⁇ m to 500 ⁇ m, more preferably 0.03 ⁇ m to 100 ⁇ m, still more preferably 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m.
- the size of the island part of the sea-island structure is preferably in the range of 1 ⁇ m to 25 ⁇ m, more preferably in the range of 1 ⁇ m to 20 ⁇ m, and still more preferably in the range of 1 ⁇ m to 18 ⁇ m. In particular, the range is more than 1 ⁇ m and not more than 15 ⁇ m.
- a plurality of island portions having the same size may be provided, or a plurality of island portions having different sizes may be provided.
- the size distribution of the island portions is, for example, ⁇ 10% or more.
- the size distribution of the islands is ⁇ 20% or more, preferably ⁇ 25% or more, more preferably ⁇ 30% or more, and even more preferably ⁇ 35% or more ( For example, ⁇ 35% or more, ⁇ 40% or more, ⁇ 45% or more, or ⁇ 50% or more).
- the size distribution is from the above lower limit ⁇ 10% or more, for example, ⁇ 200% or less, ⁇ 150% or less, ⁇ 100% or less, ⁇ 50% or less. Range, ⁇ 40% or less, ⁇ 30% or less, ⁇ 20% or less, or ⁇ 15% or less. In some other embodiments of the present invention, the size distribution is the above lower limit value ⁇ 20% or more (for example, ⁇ 20% or more, ⁇ 25% or more, ⁇ 30% or more, ⁇ 35% or more, ⁇ 40% or more, ⁇ 45% or more, or ⁇ 50% or more) to ⁇ 200% or less, or ⁇ 150% or less.
- “size distribution” in this specification means a value obtained by calculation as follows.
- the size difference between the island portion having the maximum size and the island portion having the minimum size is usually 0.01 ⁇ m to 500 ⁇ m, preferably 0.03 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m.
- the ratio of the island part size to the film thickness of the polymer ultrathin film is, for example, 0.1 to 50, preferably 0.2 to 40, more preferably 0.3 to 20, and particularly preferably 0.5 to 15.
- the island portions may be provided on both the upper and lower surfaces of the ultra-thin polymer film, or may be provided only on one surface (only the upper surface or only the lower surface), similar to the holes in FIG. 8 (a).
- the density of the island portions may be the same on the upper surface and the lower surface, or may be different. What is necessary is just to set suitably the arrangement
- the ultra-thin polymer film of the present invention can have any size and shape.
- the size is 0.05 mm to 50 cm, preferably 0.1 mm to 10 cm, more preferably 0.3 mm to 5 cm.
- the shape is not particularly limited, but for example, a flat shape such as a circle, an ellipse, a rectangle, a hexagon, a ribbon, a string, a multi-branch, and a star, a solid such as a tube, a convex, a face mask, and a hand And so on. What is necessary is just to set the shape of the polymer ultrathin film of this invention suitably according to a use.
- a porous ultra-thin polymer film can also be produced using the ultra-thin polymer film of the present invention.
- the polymer ultrathin film phase-separated into a sea-island structure is immersed in a second solvent that is a good solvent for the first polymer in the island and a poor solvent for the second polymer other than the island.
- the porous polymer ultrathin film is obtained by removing the island part.
- the first polymer, the second polymer, and the second solvent at this time for example, according to the method described in the document “SP Value Basics / Applications and Calculation Methods”, Hideki Yamamoto, Information Organization Combinations can be mentioned from the calculation of solubility parameters.
- the combination of the first polymer, the second polymer, and the third solvent is determined according to the following guidelines. That is, the Hansen solubility parameter for a certain polymer is plotted in a three-dimensional space, and a sphere is created using the interaction radius of the polymer as a center.
- the Hansen solubility parameter of the target solvent is plotted in a three-dimensional space, if the plot is inside the sphere, the target solvent is a good solvent for the polymer, and if it is outside the sphere, it is a poor solvent. to decide. From this guideline, the first solvent is a good solvent for the first polymer and the second polymer 2, and the second solvent is a good solvent for the first polymer and a poor solvent for the second polymer. Choose something.
- first polymer polystyrene, second polymer: polymethyl methacrylate
- first polymer polystyrene, second polymer: poly D, L-lactic acid
- first polymer polymethyl methacrylate, second polymer: polystyrene
- first polymer polyethylene glycol, second polymer: polystyrene
- first polymer polyvinylpyrrolidone, second polymer: polystyrene
- first polymer poly D, L-lactic acid, second polymer: polystyrene.
- the second solvent is, for example, cyclohexane.
- the second solvent is, for example, cyclohexane.
- the second solvent is, for example, ethyl acetate.
- the second solvent is, for example, water.
- the second solvent is, for example, water.
- the second solvent is, for example, ethyl acetate.
- the second solvent is a good solvent for the first polymer and a poor solvent for the second polymer
- the polymer ultrathin film phase-separated into a sea-island structure is used as the second solvent.
- the first polymer in the island is dissolved in the second solvent, thereby selectively removing the island.
- the removed area becomes a hole.
- a porous ultra-thin polymer film is obtained.
- the ultra-thin polymer film of the present invention can be produced as follows. First, two kinds of polymers that are not mixed with each other are dissolved in a solvent at an arbitrary ratio to obtain a solution. “Any ratio” means that the ratio of the first polymer to the second polymer (w / w) is arbitrary, and the ratio of the first polymer to the second polymer (w / w) is, for example, 1: 9 to 5: 5.
- the ratio (w / w) of the first polymer to the second polymer is preferably 1: 9 to 4: 6, more preferably 1: 9 to 3: 7.
- the first solvent is not limited as long as it can dissolve the two kinds of polymers, but in general, dichloromethane, diethyl ether, methyl acetate, acetone, chloroform, methyl alcohol, tetrahydrofuran, dioxane, Ethyl acetate, methyl ethyl ketone, benzene, acetonitrile, isopropyl alcohol, dimethoxyethane, ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), ethylene glycol mono-normal-butyl ether (also known as butyl cellosolve) , Ethylene glycol monomethyl ether (also known as methyl cellosolve) selected from the group consisting of toluene, N, N-dimethylformamide, and dimethylacetamide At least one solvent that can be given.
- the solvent is preferably from the group consisting of dichloromethane, diethyl ether, acetone, chloroform, tetrahydrofuran, dioxane, ethyl acetate, methyl ethyl ketone, acetonitrile, isopropyl alcohol, dimethoxyethane, N, N-dimethylformamide, and dimethylacetamide.
- At least one solvent selected more preferably at least one selected from the group consisting of dichloromethane, acetone, tetrahydrofuran, ethyl acetate, methyl ethyl ketone, acetonitrile, isopropyl alcohol, and N, N-dimethylformamide. More preferably, it is at least one solvent selected from the group consisting of dichloromethane, tetrahydrofuran, and ethyl acetate.
- the total weight concentration of the polymer in the solution is usually 0.1 wt% to 20 wt%, preferably 0.3 wt% to 10 wt%, more preferably 0.5 wt% to 2 wt%.
- the solvent is removed from the solution apply
- the method for applying the solution to the substrate is not particularly limited, but for example, the solution is applied to the substrate by a conventional method such as spin coating, spray coating, bar coating, or dip coating. Alternatively, the solution is thinly applied to the substrate by a conventional printing method such as gravure printing, screen printing, or ink jet printing.
- the solvent is removed from the solution applied to the substrate.
- the method for removing the solvent is not particularly limited.
- the solvent can be removed by evaporation by continuing the rotation.
- the solvent can be removed by evaporation by heating.
- the solvent can be removed by reducing the pressure.
- the solvent may be removed by combining two or more of these solvent removal methods.
- the island size and island density are adjusted by adjusting the mixing ratio (w / w) of the two types of polymers when preparing a solution in which the two types of polymers are dissolved.
- the spin coating method it can be controlled by adjusting the number of rotations, adjusting the boiling point of the solvent, and the like.
- the size can be increased and the island density can be reduced.
- the island size is reduced.
- the island density can be increased.
- the island size can be reduced and the island density can be increased by increasing the number of rotations.
- the island size can be increased and the island density can be reduced.
- the island size can be increased, and the island density can be decreased.
- the island size can be reduced and the island density can be increased.
- the island size distribution can be controlled as follows. For example, when the spin coating method is used, the island size distribution can be increased by reducing the rotation speed during spin coating. On the other hand, the island size distribution can be reduced by increasing the rotation speed during spin coating.
- Nanodisk which is an ultra-thin polymer film on the island obtained by dissolving the sea part of the sea-island structure
- the first polymer described in “7.” By reversing the ratio of the two polymers, the composition of the sea-island polymer can be reversed.
- first polymer poly D, L-lactic acid
- second polymer polystyrene
- second solvent cyclohexane the example of FIG.
- the disk-shaped ultra-thin polymer film shown can be obtained.
- the second solvent which is a poor solvent for the first polymer and a good solvent for the second polymer
- the ultrathin polymer film phase-separated into a sea-island structure is selected as the second solvent.
- the second solvent which is a poor solvent for the first polymer and a good solvent for the second polymer
- the resulting nanodisk has the dimensions of the islands described in “7. Ultra-thin polymer phase separated into Bohai Island structure”.
- Example 1-1 Method Using Two Kinds of Polymer Polystyrene (PS) and polymethyl methacrylate (PMMA) were purchased from Chemco Scientific Co., Ltd. and Sigma-Aldrich, respectively. Table 1 shows their characteristics.
- Polyvinyl alcohol (PVA, 10 mg / mL) having a molecular weight (Mw ca. 22 kDa) was purchased from Kanto Chemicals Co. These polymers were used without purification.
- a 200 nm thick silicon (100) wafer with an oxide film layer was purchased from KST World Co., cut into 20 ⁇ 20 mm 2 and used as a substrate.
- the substrate was immersed in sulfuric acid and 30% hydrogen peroxide (3: 1, v / v) at 120 ° C for 10 minutes, washed with ion-exchanged water (18 M ⁇ cm), and dried under a nitrogen stream. It was confirmed with a contact angle measuring machine (DM-301, Kyowa Interface Science Co., Ltd.) that the contact angle of water was 44.5 °.
- the total weight concentration of the polymer in the solution was 10 mg / mL, and a polymer blend nanosheet was prepared using a spin coater MS-A100 (MIKASA Co., Ltd.).
- a sacrificial film is created by spin-coating a PVA aqueous solution (1.0 wt%) ⁇ on a silicon substrate at a rotation speed of 3000 rpm, and a polymer blend solution is formed on it at a rotation speed of 1000, 3000, 5000, 7000 rpm. Spin coated for 60 seconds. If this is immersed in ion-exchanged water together with the substrate, the PVA sacrificial membrane will dissolve and the self-supporting polymer blend nanosheet will peel off, so that it can be manipulated with tweezers so that the top or bottom surface is on the silicon substrate. Crawled. Cyclohexane is a good solvent for PS but a poor solvent for PMMA.
- an intermolecular force microscope (KEYENCE VN-8000 NANOSCALE hybrid microscope) and a field emission scanning electron microscope (FE-SEM, Hitachi S-5500) were used.
- the former scanned the nanosheet surface in a tapping mode ( ⁇ ⁇ ⁇ ⁇ 1.67-3.33 Hz) using a silicon cantilever (KEYENCE, OP-75041).
- AFM images were processed with VN Analyzer (KEYENCE) and ImageJ (NIH) software. The latter was used for observation of the nanosheet cross section.
- the nanosheet was immersed in liquid nitrogen for 10 minutes, frozen and cleaved.
- the cross section was sputtered with gold-palladium (Au-Pd) and observed at an acceleration voltage of 5 kV.
- the images were processed with ImageJ software.
- Figure 1 shows a typical AFM image with a polymer blend solution with a PS: PMMA ratio of (0:10, 1: 9, 2: 8 and 3: 7 w / w) and a rotation speed of 5000 rpm.
- the upper (a1) to (d1) of FIG. 1 are AFM images of polymer blend nanosheets composed of PS and PMMA.
- the bright region is the PS region that is phase separated.
- the middle steps (a2) to (d2) in FIG. 1 are AFM images of the surface of the nanosheet when the PMMA region is left by solubilizing the PS region using cyclohexane. It can be seen that the upper bright area is darker. This is a hole due to the removal of the PS region.
- the lower (a3) to (d3) of FIG. 1 are AFM images of the back surface of the nanosheet when the PMMA region is left by solubilizing the PS region using cyclohexane. Since the front and back surfaces show similar structures, it is suggested that the hole penetrates.
- the AFM image of the nanosheet with PS PMMA ratios of (a) 0:10, (b) 1: 9, (c) 2: 8, (d) 3: 7 (w / w) Yes.
- the surface is smooth and no phase separation structure is observed.
- no porous structure was observed even after cyclohexane treatment.
- the PS / PMMA blend nanosheet a phase-separated structure was observed, and the total area of the phase-separated PS region increased as the PS ratio increased.
- FIG. 2 is an AFM image of a nanosheet prepared from a polymer blend solution with a PS: PMMA ratio of 2: 8 (w / w) ⁇ at each rotation speed (1000, 3000, 5000, 7000 rpm), upper, middle,
- the lower definition is the same as in FIG.
- the total area of the phase-separated PS was not changed, but it was observed that the number of rotations increased and the number decreased with increasing number of rotations with respect to the hole density and size of 1000 rpm. This is considered to be a result of drying and fixing before the PS regions separated by phase merge and become larger because the nanosheet dries faster at higher rotation speeds.
- the average size of the top and bottom holes is 187.2 ⁇ 33.9 / 194.1 ⁇ 72.9 (top / bottom) at 1000rpm, and 105.4 ⁇ 25.1 / 108.2 ⁇ 20.9 nm ⁇ (top / bottom) at 7000rpm there were.
- Table 2 summarizes the film thickness, pore diameter, and pore density of nanosheets prepared at PS, PMMA ratios of 1: 9 and 2: 8 at 1000, 3000, 5000, and 7000 rpm, respectively. .
- the film thickness tends to change with the rotational speed.
- the mixing ratio of 2: 8 tended to be slightly thicker.
- the pore diameter was larger at 2: 8 than 1: 9, and a tendency to decrease with the rotation speed was observed.
- the pore density was lower at 2: 8 than 1: 9, and it tended to increase with the number of rotations.
- the pore size distribution tended to increase as the rotational speed during spin coating decreased.
- a scanning electron microscope (SEM) was used to collect information on the cross section of the porous nanosheet obtained by treating the PS / PMMA blend nanosheet with cyclohexane and the depth direction of the pores (FIG. 3).
- the PS region is a flat ellipsoidal structure distributed in the nanosheet.
- a hole is formed, and one PS region is a nanosheet.
- through-holes are formed.
- the total weight concentration of the polymer in the solution was 10 mg / mL, and a polymer blend nanosheet was prepared with a spin coater MS-A100 (MIKASA Co., Ltd.).
- a sacrificial film is created by spin-coating a PVA aqueous solution (10 mg / mL) ⁇ on a silicon substrate at a rotation speed of 3000 rpm, and a polymer blend solution on the silicon substrate at a rotation speed of 1000, 3000, 5000, 7000 rpm. Spin coated for 60 seconds. When this is immersed in ion-exchanged water together with the substrate, the PVA sacrificial membrane will dissolve and the self-supporting polymer blend nanosheet will peel off, so it can be manipulated with tweezers and scraped onto the silicon substrate so that the top surface is on top. It was.
- Cyclohexane is a good solvent for PS but a poor solvent for poly D and L lactic acid.
- the polymer blend nanosheet on the silicon substrate was immersed in cyclohexane together with the substrate, only the PS region was selectively removed. All operations were performed in a clean room (class: 10,000 conditions) at room temperature (25 ° C) and humidity (35% RH).
- FIG. 4 shows the phase separation state of the nanosheet before being treated with cyclohexane
- the lower part is the nanosheet with holes formed by the treatment with cyclohexane.
- the nanosheets created at 1000, 3000, 5000, and 7000 rpm from the left are arranged. From Table 2, it can be seen that the film thickness decreases with increasing rotation speed. Further, it can be confirmed that the hole diameter decreases and the hole density tends to increase as the rotational speed increases. In addition, the pore size distribution tended to increase as the rotational speed during spin coating decreased.
- Example 2 Method Using Two Kinds of Solvents All operations were performed with a spin coater (Opticoat MS-A 100, MIKASA) installed in a clean room (class 10,000). Cut silicon substrate (KST World) into 2.0cm x 2.0cm, soak in sulfuric acid / 30% hydrogen peroxide (3/1, v / v) at 120 ° C for 10 minutes, and then deionized water (resistivity 18M ⁇ cm).
- Polyvinyl alcohol aqueous solution (Mw: 22,000, manufactured by Kanto Chemical Co., Inc., 100 mg / mL) is dropped on the poly D, L lactic acid nanosheet on the silicon substrate, and a PVA film is used as a support film on the poly D, L lactic acid nanosheet.
- a hot plate HAT PLATE NHP-M20, NISSIN
- the poly D and L lactic acid nanosheets were peeled off from the silicon substrate together with the PVA film, and vacuum dried using a vacuum dryer (KVO-300, AS ONE) (all night).
- the surface structure was scanned in a tapping mode (1.67-3.33 Hz) using an intermolecular force microscope (KEYENCE VN-8000 NANOSCALE hybrid microscope) and a silicon cantilever (KEYENCE, OP-75041).
- AFM images were processed with VN Analyzer (KEYENCE) and ImageJ (NIH) software. From the top of Fig.
- the first stage (a1) to (c1) and the second stage (a2) to (c2) are the top and bottom surfaces of ethyl acetate: DMSO 100: 1 respectively
- the third stage (d1) to (f1), 4th stage (d2) to (f2) are the top and bottom surfaces of ethyl acetate: DMSO 100: 3
- 5th stage (g1) to (i1), 6th stage (g2) to ( i2) are the upper and lower surfaces of ethyl acetate: DMSO 100: 5, respectively.
- the number of rotations during preparation is 1000, 3000, and 5000 rpm.
- Table 4 summarizes the characteristics of the nanosheets obtained when the number of rotations was changed for three types of systems with different mixed solvent ratios.
- the film thickness decreased as the number of rotations increased, or the film thickness increased as the amount of DMSO increased.
- the ethyl acetate: DMSO ratio was 100: 1, it was found that the pore density was considerably low and the number of rotations increased and the formation of pores became difficult.
- the ethyl acetate: DMSO ratio is 100: 3, the pore density is 0.075 / ⁇ m 2 (1000 rpm), 0.090 / ⁇ m 2 (3000 rpm), and 0.11 / ⁇ m 2 (5000 rpm), all of which provide good quality porous nanosheets. It was confirmed that the hole density increased with the rotation speed.
- the pore diameters were 2.1 ⁇ m (1000 rpm), 1.8 ⁇ m (3000 rpm), and 1.6 ⁇ m (5000 rpm), and a tendency to decrease as the number of rotations increased was observed.
- 100: 5 when the number of rotations was low, the large holes were fused together, making it difficult to measure the hole density.
- the hole diameter and hole density could be measured.
- the conditions of the holes on the upper surface and the lower surface were different, and the upper surface had a larger hole density and diameter, and the upper surface of the upper surface and the lower surface had a larger total area of the holes. This seems to be due to DMSO missing from the top surface.
- the low boiling point good solvent is first removed.
- a nanosheet in which the poor solvent was dispersed was obtained, and then the poor solvent was removed to obtain a porous nanosheet.
- Example 3 Method of Using Fine Particles as Convex / Concavity Polymer Film Mold All operations were performed by installing a spin coater (Opticoat MS-A 100, MIKASA) in a clean room (class 10,000). A silicon substrate (manufactured by KST World) was cut into 2 cm ⁇ 2 cm, immersed in sulfuric acid / 30% hydrogen peroxide solution at 120 ° C. for 10 minutes, and then washed with deionized water (resistivity 18 M ⁇ cm).
- Polystyrene (PS) fine particle (diameter 913 nm) dispersion (Polysciences) was diluted 10 times with aqueous polyvinyl alcohol (Mw: 22,000, Kanto Chemical, 125 mg / mL), vortex mixer (VOATEX-2-GENIE, The mixture was stirred using G-560 (Scientific Industries). The substrate was placed on a spin coater, and the prepared solution was dropped, followed by spin coating (1000, 2000 mm, 3000 mm, 5000 mm rpm) and rotating for 60 seconds (room temperature 28 ° C., humidity 23%).
- aqueous polyvinyl alcohol Mw: 22,000, Kanto Chemical, 125 mg / mL
- vortex mixer VOATEX-2-GENIE
- poly D, L lactic acid (Mw: 300 kDa) was adjusted to a final concentration of 30 mg / ml.
- the prepared poly D and L lactic acid solution was spin-coated (3000 rpm, 60 seconds) on the PS soot fine particle fixed PVA film prepared earlier (room temperature 28 ° C., soot humidity 26%).
- the composite nanosheet was immersed in pure water to dissolve the PVA film and the PS fine particles to obtain porous poly D, L lactic acid nanosheets.
- the porous membrane was free-standing in water and dried over a silicon substrate so that the upper surface or the lower surface was on top.
- the film thickness of the PVA film was 1043 nm (1000 rpm), 782 nm (2000 rpm), 642 nm (3000 rpm), and 533 nm (5000 rpm). Moreover, the film thickness of only the poly D, L lactic acid nanosheet was about 200 nm. Fig.
- the PS fine particles had a diameter of 900 nm, the tip end was exposed as the film thickness became thinner, and it was confirmed that pores were opened in the poly D and L lactic acid nanosheets according to the degree of exposure. Specifically, the PS fine particles were only slightly exposed at a rotation speed of 1000 nm, and small holes were formed on the back surface of the poly D and L lactic acid nanosheets, but only a few penetrated to the top surface. Above 2000 rpm, the PS fine particles are exposed enough to penetrate the poly D, L lactic acid nanosheets, because the size of the PVA film and the poly D, L lactic acid nanosheets is less than the size of the PS fine particles. On the front and back surfaces, similar hole formation, that is, through holes were observed.
- Lithium bromide which had been dissolved when ethyl acetate was evaporated by spin coating, was precipitated, and a nanosheet in which microcrystals were mixed was obtained.
- the porous ultrathin film was peeled from the silicon substrate while dissolving lithium bromide by immersing this in pure water. This was scraped onto a silicon substrate for AFM observation and observed with AFM. A portion where the precipitated lithium bromide was dissolved was observed as porous. The results are summarized in FIG. 7 and Table 6.
- Figure 7 shows poly D, L lactic acid: lithium bromide ratio from the top: 10: 1, 10: 2, 10: 3, 10: 4, 10: 5 (v / v), first from the left (a1) ⁇ (E1) is the photo before removing lithium bromide, the second (a2) ⁇ (e2) is the lithium bromide removed by washing, and the third (a2) ' ⁇ (e2)' is a small porous region This is a photograph that is magnified 10 times, and the fourth (a2) ''-(e2) '' is a photograph that magnifies a large porous region 10 times.
- the mixing ratio of lithium bromide increased, the pore size distribution increased and the number increased.
- Example 5 Ratio of pore diameter to film thickness
- the ratio of pore diameter to film thickness was determined as follows.
- the aspect range of the porous nanosheet obtained in each example is as follows.
- Example 6 Method using two types of polymers (2) Polyvinyl alcohol (PVA) (manufactured by Kanto Chemical Co., Inc.) was dissolved in water by 2.0% by weight. The obtained PVA solution was applied to one side of a base film made of polyethylene terephthalate (PET) so that the film thickness after drying was about 60 nm by gravure printing. The PVA solution was dried at 80 ° C. for 10 seconds in a hot air drying dryer to prepare a laminated film including a PVA layer on the base film.
- PVA Polyvinyl alcohol
- PET polyethylene terephthalate
- poly D, L-lactic acid ( PDLLA ) PURSORB PDL20
- polystyrene (PS) manufactured by Chemco Co., Ltd.
- PDLLA: PS ratio 1: It dissolved so that it might become 9, 2: 8, and 3: 7 (w / w).
- the obtained PDLLA / PS solution was applied on the PVA layer by gravure printing so that the film thickness after drying was 190 nm.
- the PDLLA / PS solution was dried at 50 ° C. for 10 seconds in a hot air drying dryer to prepare a laminated film in which a PDLLA / PS nanosheet was provided on the PVA layer.
- Table 8 and FIG. 9 summarize the characteristics for three types of systems with different mixing ratios.
- PS ratio 1: 9, 2: 8 (w / w)
- the island shape is circular
- PDLLA: PS ratio is 3: 7 (w / w)
- a ribbon shape is obtained. It was.
- FIG. 10 shows typical AFM images of the obtained PDLLA / PS nanosheet and porous PS nanosheet.
- the upper (a) and (b) of FIG. 10 are AFM images of PDLLA / PS nanosheets.
- the bright region is the PS region that is phase separated.
- the lower (b1) and (b2) of FIG. 10 are AFM images of the surface of the porous PS nanosheet when the PDLLA region is solubilized using ethyl acetate to leave the PS region.
- FIG. 11 is a schematic view of the porous PS nanosheet of FIGS. 10 (a ′) and (b ′).
- the obtained porous PS nanosheet has a film thickness of 190 nm, and has an average size of 10 ⁇ m (about 5 ⁇ m to about 20 ⁇ m, pore size distribution value: ⁇ 60%) with a density of 6 ⁇ 10 ⁇ 3 / ⁇ m 2.
- the aspect range of the porous PS nanosheet obtained by the method of Example 5 was about 10 to 100.
- Cyclohexane is a poor solvent for PDLLA, but a good solvent for PS.
- FIG. (A), (b) and (c) in FIG. 12 are AFM images of PDLLA nanodisks obtained on the same silicon substrate.
- (a) and (c) are AFM images of a single-layer structure of a PDLLA nanodisk on a silicon substrate, and (b) are two-layer structures of a PDLLA nanodisk.
- the obtained PDLLA nanodisk had a thickness of 59 nm and an average diameter of 8 ⁇ m (3 to 12 ⁇ m).
- a blended nanosheet phase-separated into a sea-island structure As described above, two types of polymers that do not mix with each other in the solid state are dissolved in a common solvent and cast to obtain a blended nanosheet phase-separated into a sea-island structure.
- a porous nanosheet is obtained by processing.
- a nanodisk can be obtained by treatment with a good solvent for a polymer constituting the sea.
Abstract
Description
また、特許文献9、10の請求項1には、水不溶性ポリマーAを主成分とする連続相と、水溶性ポリマーBを主成分とするシリンダ状ミクロドメインとからなるミクロ相分離構造を有し、シリンダ状ミクロドメイン内に平均孔径1~1000nmのシリンダ状構造の細孔が存在する多孔質膜が記載されている。
さらに、特許文献11の実施例2には、金膜上に形成されたポリスチレン(PS)とポリメチルメタクリレート(PMMA)の非対称ジブロック・コポリマー膜から、PMMA劣化による生成物質を除去し、PSナノ細孔鋳型を作製することが記載されている。
[1] 膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜。
[2] 30nm~50μmのサイズの孔が5x10-3個/μm2~50個/μm2の密度で表面に存在する上記[1]記載の多孔質高分子超薄膜。
[2a] 前記孔のサイズが、1μmより大きく25μm以下の範囲である、上記[1]記載の多孔質高分子超薄膜。
[2b] 前記孔のサイズが、15μm以下の範囲である、上記[2a]記載の多孔質高分子超薄膜。
[3] 孔径分布が少なくとも±20%である、上記[1]又は[2]記載の多孔質高分子超薄膜。
[3a] 孔径分布が少なくとも±20%である、上記[2a]又は[2b]記載の多孔質高分子超薄膜。
[4] 多孔質高分子超薄膜の膜厚に対する孔径の比(孔径 (μm)/膜厚(μm))が0.1~50である、上記[1]、[2]及び[3]のいずれか1項に記載の多孔質高分子超薄膜。
[4a] 多孔質高分子超薄膜の膜厚に対する孔径の比(孔径 (μm)/膜厚(μm))が0.1~50である、上記[2a]、[2b]及び[3a]のいずれか1項に記載の多孔質高分子超薄膜。
[5] 高分子がポリヒドロキシアルカン酸、ポリヒドロキシアルカン酸の共重合体、ポリ(エステル-エーテル)、脂肪族ジカルボン酸と脂肪族ジオールのポリエステル、ポリアミド、ポリウレタン、多糖類エステル、ポリ(アクリレート)、ポリ(メタクリレート)、ポリスチレン、ポリ酢酸ビニル、およびポリシロキサンからなる群から選択される少なくとも1つである、上記[1]、[2]、 [3]及び[4]のいずれか1項記載の多孔質高分子超薄膜。
[5a] 高分子がポリヒドロキシアルカン酸、ポリヒドロキシアルカン酸の共重合体、ポリ(エステル-エーテル)、脂肪族ジカルボン酸と脂肪族ジオールのポリエステル、ポリアミド、ポリウレタン、多糖類エステル、ポリ(アクリレート)、ポリ(メタクリレート)、ポリスチレン、ポリ酢酸ビニル、およびポリシロキサンからなる群から選択される少なくとも1つである、上記[2a]、[2b]、[3a]及び[4a]のいずれか1項記載の多孔質高分子超薄膜。
[6] 互いに混ざらない2種類の高分子を任意の割合で第1の溶媒に溶解させて溶液を得る工程と、
得られた溶液を基体に塗布した後、該基体に塗布した溶液中から第1の溶媒を除去することによって、海島構造に相分離した高分子超薄膜を得る工程と、
島部の高分子の良溶媒であるとともに島部以外の高分子の貧溶媒である第2の溶媒に前記高分子超薄膜を浸漬させて、島部を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得る工程と
を含む、多孔質高分子超薄膜の製造方法。
[6-2] 前記海島構造の島部が、1μmより大きく25μm以下の範囲のサイズであり、5x10-3個/μm2~50個/μm2の密度で表面に存在する、上記[6]に記載の方法。
[6-3] 前記海島構造の島部のサイズが、15μm以下の範囲である、上記[6-2]に記載の方法。
[6-4] 前記高分子超薄膜の膜厚が10nm~1000nmである、上記[6]、[6-2]及び[6-3]のいずれか1項に記載の方法。
[6-5] 前記海島構造の島部を形成する第1の高分子と海部を形成する第2の高分子の組み合わせが、下記の群から選択される、上記[6]、[6-2]、[6-3]及び[6-4]のいずれか1項に記載の方法:
(i)第1の高分子:ポリスチレン、第2の高分子:ポリメタクリル酸メチル;
(ii)第1の高分子:ポリスチレン、第2の高分子:ポリD,L-乳酸;
(iii) 第1の高分子:ポリメタクリル酸メチル、第2の高分子:ポリスチレン;
(iv) 第1の高分子:ポリエチレングリコール、第2の高分子:ポリスチレン;
(v) 第1の高分子:ポリビニルピロリドン、第2の高分子:ポリスチレン;及び
(vi) 第1の高分子:ポリD,L-乳酸、第2の高分子:ポリスチレン。
[7] 原料となる高分子を、該高分子の良溶媒とその良溶媒よりも沸点の高い貧溶媒との任意の割合の混合溶媒に溶解させて溶液を得る工程と、
得られた溶液を基体に塗布し、該基体に塗布した溶液中から混合溶媒を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得る工程と
を含む、多孔質高分子超薄膜の製造方法。
[8] 高分子を溶媒に溶解させて溶液を得る工程と、
溶液を凹凸のある基体に塗布した後、該基体に塗布した溶液中から溶媒を除去することにより高分子超薄膜を得る工程と、
凹凸のある基体を、高分子超薄膜を溶解させない溶媒にて溶解させることにより除去する工程、
を含む、膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜の製造方法。
[9] 凹凸のある基体が、微粒子を分散固定した高分子薄膜を有する基体であり、
前記基体に塗布した溶液中から溶媒を除去することにより高分子超薄膜を得た後、微粒子を分散固定した高分子薄膜を有する基体を、高分子超薄膜を溶解させない溶媒に溶解させることにより除去して多孔質高分子超薄膜を得る、上記[8]に記載の方法。
[10] 微粒子が、ポリスチレン粒子、シリカ粒子、デキストラン粒子、ポリ乳酸粒子、ポリウレタン微粒子、ポリアクリル粒子、ポリエチレンイミン粒子、アルブミン粒子、アガロース粒子、酸化鉄粒子、酸化チタン微粒子、アルミナ微粒子、タルク微粒子、カオリン微粒子、モンモリロナイト微粒子、及びハイドロキシアパタイト微粒子からなる群から選択される少なくとも1つの粒子である、上記 [9]に記載の方法。
[11] 微粒子が20nm~3000nmの直径を有する上記[9]又は[10]に記載の方法。
[12] 高分子を溶媒に溶解させて溶液を得る工程と、
溶液に微粒子を分散させて分散液を得る工程と、
前記分散液を基体に塗布した後、該基体に塗布した分散液中から溶媒を除去することにより高分子超薄膜を得る工程と、
得られた高分子超薄膜を、前記微粒子を溶解できる溶剤中に浸漬させて該微粒子を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得る工程と
を含む、多孔質高分子超薄膜の製造方法。
[13] 微粒子が、無機塩、シリカ、タルク、カオリン、モンモリロナイト、ポリマー、金属酸化物、及び金属からなる群から選択される少なくとも1つである、上記[12]に記載の方法。
[14] 基体の上に構築した高分子超薄膜をガラス転移温度以上に加温した後、該高分子超薄膜を別に用意した凹凸のある基体で圧迫することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得ることを特徴とする、多孔質高分子超薄膜の製造方法。
[15] 原料となる高分子を溶解して溶液を得、得られた溶液に微小気泡を分散させ、微小気泡を分散させた溶液を基体に塗布し、基体に塗布した溶液から溶媒を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得ることを特徴とする、多孔質高分子超薄膜の製造方法。
[16] 基体の上に水溶性犠牲膜を有し、その上に上記[1]、[2]、[3]、[4]及び[5]のいずれか1項に記載の多孔質高分子超薄膜を有する、基体と水溶性犠牲膜と多孔質高分子超薄膜の複合体。
[16a] 基体の上に水溶性犠牲膜を有し、その上に、上記[2a]、[2b]、[3a]、[4a]及び[5a]のいずれか1項に記載の多孔質高分子超薄膜を有する、基体と水溶性犠牲膜と多孔質高分子超薄膜の複合体。
[17] 基体の上に上記[1]、[2]、[3]、[4]及び[5]のいずれか1項に記載の多孔質高分子超薄膜を有し、多孔質高分子超薄膜の上に水溶性支持膜を有する、基体と多孔質高分子超薄膜と水溶性支持膜の複合体。
[17a] 基体の上に上記[2a]、[2b]、[3a]、[4a]及び[5a]のいずれか1項に記載の多孔質高分子超薄膜を有し、多孔質高分子超薄膜の上に水溶性支持膜を有する、基体と多孔質高分子超薄膜と水溶性支持膜の複合体。
[18]上記[1]、[2]、[3]、[4]及び[5]のいずれか1項に記載の多孔質高分子超薄膜の上に水溶性支持膜を有する、多孔質高分子超薄膜と水溶性支持膜の複合体。
[18a]上記[2a]、[2b]、[3a]、[4a]及び[5a]のいずれか1項に記載の多孔質高分子超薄膜の上に水溶性支持膜を有する、多孔質高分子超薄膜と水溶性支持膜の複合体。
[19] 上記[16]、[17]及び[18]のいずれか1項に記載の複合体の水溶性犠牲膜又は水溶性支持膜を水を用いて除去することによって水中にて多孔質高分子超薄膜を得ることを特徴とする、自己支持性の多孔質高分子超薄膜の製造方法。
[19a] 上記[16a]、[17a]及び[18a]のいずれか1項に記載の複合体の水溶性犠牲膜又は水溶性支持膜を水を用いて除去することによって水中にて多孔質高分子超薄膜を得ることを特徴とする、自己支持性の多孔質高分子超薄膜の製造方法。
[20] 前記多孔質高分子超薄膜を別の基体に掬い取り、掬い取った多孔質高分子超薄膜から水を除去して乾燥状態の多孔質高分子超薄膜を得ることを特徴とする、上記[19]に記載の多孔質高分子超薄膜の製造方法。
[20a] 前記多孔質高分子超薄膜を別の基体に掬い取り、掬い取った多孔質高分子超薄膜から水を除去して乾燥状態の多孔質高分子超薄膜を得ることを特徴とする、上記[19a]に記載の多孔質高分子超薄膜の製造方法。
[21] メッシュの上に上記[1]、[2]、[3]、[4]及び[5]のいずれか1項に記載の多孔質高分子超薄膜を有する、メッシュと多孔質高分子超薄膜の複合体。
[21a] メッシュの上に上記[2a]、[2b]、[3a]、[4a]及び[5a]のいずれか1項に記載の多孔質高分子超薄膜を有する、メッシュと多孔質高分子超薄膜の複合体。
[22] 上記[19]に記載の方法で製造した自己支持性の多孔質高分子超薄膜をメッシュで掬い取り、多孔質高分子超薄膜とメッシュの複合体を製造することを特徴とする、メッシュと多孔質高分子超薄膜の複合体の製造方法。
[22a] 上記[19a]に記載の方法で製造した自己支持性の多孔質高分子超薄膜をメッシュで掬い取り、多孔質高分子超薄膜とメッシュの複合体を製造することを特徴とする、メッシュと多孔質高分子超薄膜の複合体の製造方法。
[23] 上記[1]、[2]、[3]、[4]及び[5]のいずれか1項に記載の1以上の多孔質高分子超薄膜と、孔のない1以上の高分子超薄膜とを有する、多孔質高分子超薄膜と孔のない高分子超薄膜の複合体。
[23a] 上記上記[2a]、[2b]、[3a]、[4a]及び[5a]のいずれか1項に記載の1以上の多孔質高分子超薄膜と、孔のない1以上の高分子超薄膜とを有する、多孔質高分子超薄膜と孔のない高分子超薄膜の複合体。
[A1] 互いに混ざらない第1の高分子と第2の高分子の2種類の高分子を任意の割合で溶媒に溶解させて溶液を得、得られた溶液を基体に塗布した後、該基体に塗布した溶液中から前記溶媒を除去することによって基体上に得られる、海島構造に相分離した高分子超薄膜。ここで、「第1の高分子」は海島構造に相分離したときに島部を形成する高分子であり、「第2の高分子」は島部以外の部分(海部)を形成する高分子である。
[A2] 前記海島構造の島部が、1μmより大きく25μm以下の範囲のサイズであり、5x10-3個/μm2~50個/μm2の密度で表面に存在する、上記[A1]に記載の高分子超薄膜。
[A3] 前記孔のサイズが、15μm以下の範囲である、上記[A2]に記載の高分子超薄膜。
[A4] 前記高分子超薄膜の膜厚が10nm~1000nmである、上記[A1]~[A3]のいずれか1項に記載の高分子超薄膜。
[A5] 前記第1の高分子と第2の高分子の組み合わせが、下記の群から選択される、上記[A1]~[A4]のいずれか1項に記載の高分子超薄膜:
(i)第1の高分子:ポリスチレン、第2の高分子:ポリメタクリル酸メチル;
(ii)第1の高分子:ポリスチレン、第2の高分子:ポリD,L-乳酸;
(iii) 第1の高分子:ポリメタクリル酸メチル、第2の高分子:ポリスチレン;
(iv) 第1の高分子:ポリエチレングリコール、第2の高分子:ポリスチレン;
(v) 第1の高分子:ポリビニルピロリドン、第2の高分子:ポリスチレン;及び
(vi) 第1の高分子:ポリD,L-乳酸、第2の高分子:ポリスチレン。
[B1] 膜厚が10nm~1000nmであり、サイズが30nm~50μm以下の範囲である、略円形状高分子超薄膜。
[B2] 前記サイズが1μmより大きく25μm以下の範囲である、上記[B1]に記載の略円形状高分子超薄膜。
[B3] 前記サイズが15μm以下の範囲である、上記[B2]に記載の略円形状高分子超薄膜。
[B4] 前記高分子がポリD,L-乳酸である、上記[B1]~[B3]のいずれか1項に記載の略円形状高分子超薄膜。
[C1] 互いに混ざらない2種類の高分子を任意の割合で第1の溶媒に溶解させて溶液を得る工程と、
得られた溶液を基体に塗布した後、該基体に塗布した溶液中から第1の溶媒を除去することによって、海島構造に相分離した高分子超薄膜を得る工程と、
海部の高分子の良溶媒であるとともに海部以外の高分子の貧溶媒である第2の溶媒に前記高分子超薄膜を浸漬させて、海部を除去することにより膜厚が10nm~1000nmであり、サイズが30nm~50μm以下の範囲である、略円形状高分子超薄膜を得る工程と
を含む、略円形状高分子超薄膜の製造方法。
本明細書中では、超薄膜を、「ナノシート」という場合がある。
図8(a)に、本発明の多孔質高分子超薄膜1の一例を示す。
本発明の多孔質高分子超薄膜は、自己支持性の超薄膜である。「自己支持性」とは、超薄膜が有する性質であり、超薄膜が膜構造を維持するのに支持体を必要としない性質のことを意味する。ただし、これは、本発明の超薄膜が支持体と複合体を形成することを否定するものではない。
あるいは、孔径は、1μmより大きく25μm以下の範囲であり、より好ましくは、1μmより大きく20μm以下の範囲であり、さらに好ましくは、1μmより大きく18μm以下の範囲であり、特に好ましくは、1μmより大きく15μm以下の範囲である。
孔径の異なる複数の孔が設けられている場合、孔径分布は、例えば、±10%以上である。本発明のいくつかの態様では、孔径分布は、±20%以上であり、好ましくは±25%以上であり、より好ましくは±30%以上であり、さらに好ましくは±35%以上(例えば、±35%以上、±40%以上、±45%以上、又は±50%以上)である。
また孔径分布は、本発明のいくつかの態様では、上記下限値±10%以上から、例えば、±200%以下の範囲、±150%以下の範囲、±100%以下の範囲、±50%以下の範囲、±40%以下の範囲、±30%以下の範囲、±20%以下の範囲、又は±15%以下の範囲である。
孔径分布は、本発明の別のいくつかの態様では、上記下限値±20%以上(例えば、±20%以上、±25%以上、±30%以上、±35%以上、±40%以上、±45%以上、又は±50%以上)から、±200%以下の範囲、又は±150%以下の範囲である。
ここで、本明細書において「孔径分布」は、次のようにして計算して求めた値のことを意味する。すなわち、孔径の分布を正規分布として近似し、平均を μ、分散を σ2とすると孔径分布はσ/μとして計算される。
また、孔径の異なる複数の孔が設けられている場合、最大の孔径を有する孔と最小の孔径を有する孔との孔径差は、通常、0.01μm~500μmであり、好ましくは、0.03μm~100μmであり、さらに好ましくは、0.1μm~5μmであり、特に好ましくは、0.5μm~3μmである。
(i) ポリD,L乳酸、ポリグリコール酸、ヒドロキシ酪酸、ポリカプロラクトンなどのポリヒドロキシアルカン酸;
(ii)乳酸とグリコール酸の共重合体、3-ヒドロキシ酪酸と3-ヒドロキシ吉草酸の共重合体、トリメチレンカーボネートとグリコリドの共重合体、ポリグリコール酸とポリεカプロラクトンの共重合体などの共重合体;
(iii) ポリジオキサノン、ポリ(2-メチレンー1,3,6-トリオキソカン)などのポリ(エステル-エーテル);
(iv) ポリブチレンサクシネート、ポリエチレンアジペート、ポリエチレンサクシネートなどの脂肪族ジカルボン酸と脂肪族ジオールのポリエステル;
(v) ポリエステルアミド、ポリアミド4、ポリアスパラギン酸エステル、ポリグルタミン酸エステルなどのポリアミド、ポリウレタン;
(vi) アセチルセルロース、ポリグルクロン酸、アルギン酸、キトサンなどの多糖類あるいは多糖類エステル;
(vii) ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ブチルなどのポリ(アクリレート);
(viii) ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸カプリリル、ポリメタクリル酸グリセリル、ポリメタクリル酸グルコシルエチル、ポリメタクリル酸ブチル、ポリメタクリル酸プロピル、ポリメタクリロイルオキシエチルホスホリルコリンなどのポリ(メタクリレート);
(ix) ポリスチレン、ポリ酢酸ビニル;及び
(x) ポリジメチルシロキサンなどポリシロキサン;
からなる群から選択される少なくとも1つである。
多孔質高分子超薄膜の形状は、略円形、四角形などとするのが好ましい。
また、細胞培養とフィルターの用途を組み合わせて、例えば袋状、筒状にしてその中に浮遊細胞、血液細胞を培養したり、大きさで分離する目的で使用しても良い。
本発明のいくつかの態様の多孔質高分子超薄膜は、肌のシミ、アザ、ホクロ、皺を隠す目的で皮膚に貼付して使用することができる。
本発明の別のいくつかの態様の多孔質高分子超薄膜は、開腹あるいは内視鏡手術の際のマーキングの目的で内臓表面に貼付して使用することができる。
本発明のさらに別のいくつかの態様の多孔質高分子超薄膜は、ボディペインティング、ネイルアート、ヘアカラーなどの目的で皮膚、爪、毛髪に貼付して使用することができる。
好ましくは、本発明の多孔質高分子超薄膜は、肌のシミ、アザ、ホクロ、皺を隠す目的で皮膚に貼付して使用する。
多孔質高分子超薄膜の形状は、略円形、四角形などとするのが好ましい。
本発明の多孔質高分子超薄膜は、基体、及び水溶性犠牲膜とともに、複合体を形成していてもよい。当該複合体は、図8(b)に示すように基体3の上に水溶性犠牲膜2を有し、その上に本発明の多孔質高分子超薄膜1を有する、基体と水溶性犠牲膜と多孔質高分子超薄膜の複合体4である。
基体は、多孔質高分子超薄膜を支持できる限り特に制限されないが、通常、シリコン基板、ガラス基板、金属基板、ポリエステル、ポリプロピレン、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリアクリロニトリル、 ポリカーボネート、エチレン酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体、エチレン-メタクリル酸共重合体、ナイロンフィルムなどのフィルムどであり、好ましくは、シリコン基板、ポリエステル、ポリプロピレン、ポリエチレンなどであり、より好ましくは、シリコン基板、ポリエステルなどである。
基体の膜厚は、通常、1μm~5000μmであり、好ましくは、5μm~1000μmであり、より好ましくは、10μm~500μmであり、さらに好ましくは、30μm~300μmであり、特に好ましくは、50μm~100μmである。
水溶性犠牲膜や水溶性支持膜は、水で溶解するものである限り限定されないが、通常、ポリビニルアルコール膜、ポリアクリル酸膜、ポリメタクリル酸膜、アルギン酸ナトリウム膜、ポリエチレンオキサイド膜、ポリアクリルアミド膜、ポリビニルピロリドン膜、デンプン膜、カルボキシメチルセルロース膜、コラーゲン膜、プルラン膜、寒天膜、シリコン膜などであり、好ましくは、ポリビニルアルコール膜、ポリアクリル酸膜、デンプン膜、コラーゲン膜、寒天膜などであり、より好ましくは、ポリビニルアルコール膜、デンプン膜、コラーゲン膜などであり、さらに好ましくは、ポリビニルアルコール膜である。
水溶性犠牲膜の膜厚は、通常、5nm~1000nmであり、好ましくは、5nm~500nmであり、より好ましくは、10nm~300nmであり、さらに好ましくは、10nm~200nmであり、特に好ましくは、10nm~100nmである。
水溶性支持膜の膜厚は、通常、50nm~20000nmであり、好ましくは、100nm~10000nmであり、より好ましくは、200nm~5000nmであり、さらに好ましくは、500nm~5000nmであり、特に好ましくは、700nm~5000nmである。
本発明の多孔質高分子超薄膜は、水溶性支持膜とともに、複合体を形成していてもよい。
当該複合体は、図8(d)に示すように、本発明の多孔質高分子超薄膜1の上に水溶性支持膜5を有する、多孔質高分子超薄膜と水溶性支持膜の複合体7である。
この複合体を水中にて浸漬させると水溶性支持膜が溶解し、多孔質高分子超薄膜が得られる。得られる多孔質高分子超薄膜は自立型である。ここで、「自立型」とは、多孔質高分子超薄膜が支持体なしで独立して存在する形態のことを意味する。
本発明の多孔質高分子超薄膜、及び水溶性支持膜は、前記の通りである。
例えば、多孔質高分子超薄膜と水溶性支持膜の複合体を被貼付体に貼付した後、水溶性支持膜を水洗により除去することにより多孔質高分子超薄膜を被貼付体に貼付することができる。
本発明の多孔質高分子超薄膜は、メッシュとともに、複合体を形成していてもよい。
当該複合体は、図8(e)に示すように、メッシュ8の上に本発明の多孔質高分子超薄膜1を有する、メッシュと多孔質高分子超薄膜の複合体9である。
本発明の多孔質高分子超薄膜は前記の通りである。
メッシュは、本発明の多孔質高分子超薄膜を支持することができ、また、貼付する際に、容易に多孔質高分子超薄膜から剥がすことができるものであればいずれのものでもよい。メッシュとしては、例えば、ナイロン、ポリエステル、テフロン(登録商標)、ポリプロピレン、シルクなどからなる群から選択されるものから形成されたメッシュが挙げられる。メッシュサイズは、通常、1~4000μm、好ましくは、5~400μm、より好ましくは、10~200μm、特に好ましくは40~100μmである。
メッシュの膜厚は、通常、5μm~1000μmであり、好ましくは、7μm~700μmであり、より好ましくは、10μm~500μmであり、さらに好ましくは、30μm~300μmであり、特に好ましくは、50μm~100μmである。
例えば、メッシュと多孔質高分子超薄膜の複合体を被貼付体に貼付した後、多孔質高分子超薄膜からメッシュを剥がすことにより多孔質高分子超薄膜を容易に被貼付体に貼付することができる。
本発明の多孔質高分子超薄膜は、孔のない超薄膜とともに、複合体を形成していてもよい。「孔のない」とは、前記多孔質高分子超薄膜で設けたような孔を超薄膜に設けていないことを意味する。
当該複合体は、図8(f)に示すように、孔のない超薄膜10の上に本発明の多孔質高分子超薄膜1を有する、多孔質高分子超薄膜と孔のない超薄膜との複合体11である。
複合体中、多孔質高分子超薄膜は1以上含まれていればよく(例えば、1層~20層、1層~10層、又は1層~5層)、孔のない超薄膜も1以上含まれていればよい(例えば、1層~20層、1層~10層、又は1層~5層)。
複合体中、多孔質高分子超薄膜と孔のない超薄膜の積層の順番は、特に制限されず、複合体が3層以上の層を有する場合、多孔質高分子超薄膜は、最下層から最上層のいずれか1以上の層に含まれていればよい。
複合体中に2以上の多孔質高分子超薄膜が含まれる場合、各多孔質高分子超薄膜間で超薄膜の膜厚、孔サイズ、孔密度、孔径分布、膜厚に対する孔径の比、材質などは異なっていてもよく、あるいは、それらの全部又は一部が同じでもよい。
複合体中に孔のない2以上の超薄膜が含まれる場合、各超薄膜間で超薄膜の膜厚、材質などは異なっていてもよく、あるいは、それらの全部又は一部が同じでもよい。
孔のない超薄膜の膜厚は、通常、10nm~1000nmであり、好ましくは、20nm~800nmであり、より好ましくは、30nm~600nmであり、さらに好ましくは、40nm~400nmであり、特に好ましくは、50nm~200nmである。
孔のない超薄膜の材質は、用途に応じて適宜選択することができるが、例えば、ポリ乳酸、乳酸とグリコール酸の共重合体、ポリグリコール酸、ポリカプロラクトン、シリコン、ジメチコン、ポリ酢酸ビニル、カルボキシメチルセルロース、ポリビニルピロリドン、コラーゲン、(アクリル酸アルキル/ジアセトンアクリルアミド)コポリマー、(アクリル酸アルキル/ジメチコン)コポリマーなどのアクリル系ポリマーやメタクリル系ポリマー、ポリウレタンなどであり、好ましくは、ポリ乳酸、乳酸とグリコール酸の共重合体、カルボキシメチルセルロース、ポリウレタン、アクリル系ポリマーである。
孔のない超薄膜は、例えば、WO 2006/025592号、WO2008/050913号、Adv. Mater. 2009, 21, 4388-4392などに記載の方法又はそれに準ずる方法により製造することができる。
多孔質高分子超薄膜と孔のない超薄膜の複合体は、最初から多孔質高分子超薄膜(層)と孔のない超薄膜(層)を順次形成していくことにより製造してもよいし、あるいは、別々に製造した多孔質高分子超薄膜と孔のない超薄膜を、貼り合わせることにより製造してもよい。
当該複合体は、例えば、前記高光散乱膜として使用することができる。
本発明の多孔質高分子超薄膜は、例えば、下記の方法にて製造することができる。
本方法では、先ず、互いに混ざらない2種類の高分子を任意の割合で第1の溶媒に溶解させて溶液を得る。
「互いに混ざらない2種類の高分子」とは、固体状態では互いに混ざりあわない2種類の高分子のことをいう。以下では、2種類の高分子のうち、海島構造に相分離したときに島部を形成する高分子を高分子1といい、島部以外の高分子を高分子2という。そのような高分子の組み合わせとしては、後述の組み合わせが挙げられる。
「任意の割合」とは、高分子1:高分子2の比(w/w)が任意であることを意味し、高分子1:高分子2の比(w/w)は、例えば、1:9~5:5である。高分子1:高分子2の比(w/w)は、好ましくは、1:9~4:6であり、より好ましくは、1:9~3:7である。
溶液を基体に塗布する方法は、特に限定されないが、例えば、スピンコーティング法、スプレーコーティング法、バーコーティング法、ディップコーティング法などの常法により溶液を基体に塗布する。あるいは、グラビア印刷、スクリーン印刷、インクジェット印刷などの常法の印刷法により溶液を薄く基体に塗布する。
(i)高分子1:ポリスチレン、高分子2:ポリメタクリル酸メチル、第2の溶媒:シクロヘキサン;
(ii)高分子1:ポリスチレン、高分子2:ポリD,L-乳酸、第2の溶媒:シクロヘキサン;
(iii) 高分子1:ポリメタクリル酸メチル、高分子2:ポリスチレン、第2の溶媒:酢酸エチル;
(iv) 高分子1:ポリエチレングリコール、高分子2:ポリスチレン、第2の溶媒:水;
(v) 高分子1:ポリビニルピロリドン、高分子2:ポリスチレン、第2の溶媒:水;又は
(vi) 高分子1:ポリD,L-乳酸、高分子2:ポリスチレン、第2の溶媒:酢酸エチル。
第2の溶媒は高分子1に対しては良溶媒であるとともに高分子2に対しては貧溶媒であるので、海島構造に相分離した高分子超薄膜を第2の溶媒に浸漬すると、島部の高分子1のみが第2の溶媒に溶解し、それにより、島部が選択的に除去される。そして、除去された領域は、孔となる。結果として、多孔質高分子超薄膜が得られる。
また、孔径分布は次のようにして制御することができる。例えば、スピンコーティング法を用いる場合には、スピンコーティング時の回転速度を低下させることで孔径分布を増大させることができる。一方、スピンコーティング時の回転速度を上げることで孔径分布を小さくすることができる。
本方法では、先ず、原料となる高分子を、該高分子の良溶媒とその良溶媒よりも沸点の高い貧溶媒との任意の割合の混合溶媒に溶解させて溶液を得る。
(i) 高分子:ポリD, L乳酸、良溶媒:酢酸エチル、貧溶媒:ジメチルスルホキシド;
(ii) 高分子:ポリグリコール酸、良溶媒:1,1,1,3,3,3-ヘキサフルオロ-2-プロパノール、貧溶媒:酢酸エチル;
(iii) 高分子:ポリカプロラクトン、良溶媒:テトラヒドロフラン(THF)、貧溶媒:イソプロピルアルコール;
(iv) 高分子:ポリジオキサノン、良溶媒:ジクロロメタン、貧溶媒:エチレングリコール;
(v) 高分子:ポリメタクリル酸メチル、良溶媒:アセトン、貧溶媒:水;
(vi) 高分子:酢酸セルロース、良溶媒:THF、貧溶媒:水;
(vii) 高分子:酢酸セルロース、良溶媒:THF、貧溶媒:トルエン;又は、
(viii) 高分子:ポリスチレン、良溶媒:THF、貧溶媒:ジメチルスルホキシド(DMSO)。
溶液中の高分子の濃度は、通常、1mg/ml~1000mg/mlであり、好ましくは、3 mg/ml ~100 mg/mlであり、より好ましくは、5mg/ml ~50 mg/mlである。
溶液を基体に塗布する方法は、前記と同様である。
また、孔径分布は次のようにして制御することができる。例えば、スピンコーティング法を用いる場合には、孔径分布はスピンコーティング時の回転速度を低下させることで孔径分布を増大させることができる。一方、スピンコーティング時の回転速度を上げることで孔径分布を小さくすることができる。。
本方法では、先ず、高分子を溶媒に溶解させて溶液を得る。
高分子は、本発明の多孔質高分子超薄膜を構成する高分子であり、具体例は、前記の通りである。
溶媒は、高分子を溶解できるものであればよく、例えば、酢酸エチル、ジクロロメタン、ジエチルエーテル、酢酸メチル、アセトン、クロロホルム、メチルアルコール、テトラヒドロフラン、ジオキサン、メチルエチルケトン、ベンゼン、アセトニトリル、イソプロピルアルコール、ジメトキシエタン、エチレングリコールモノエチルエーテル(別名 セロソルブ)、エチレングリコールモノエチルエーテルアセタート(別名 セロソルブアセタート)、エチレングリコールモノ―ノルマル―ブチルエーテル(別名 ブチルセロソルブ)、エチレングリコールモノメチルエーテル(別名 メチルセロソルブ)トルエン、N,N-ジメチルホルミアミド、及びジメチルアセタミドなどであり、好ましくは、酢酸エチル、ジクロロメタン、ジエチルエーテル、アセトン、クロロホルム、テトラヒドロフラン、ジオキサン、メチルエチルケトン、アセトニトリル、イソプロピルアルコール、ジメトキシエタン、N,N-ジメチルホルミアミド、及びジメチルアセタミドなどであり、より好ましくは、酢酸エチル、ジクロロメタン、アセトン、テトラヒドロフラン、メチルエチルケトン、アセトニトリル、イソプロピルアルコール、及びN,N-ジメチルホルミアミドなどである。
溶液を基体に塗布する方法は、前記と同様である。
基体に塗布した溶液中から溶媒を除去する方法も、前記第1の溶媒を除去する方法と同様である。
基体に塗布した溶液中から溶媒を除去すると、基体上の凹凸形状が写し取られた多孔質高分子超薄膜が得られる。
微粒子を分散固定した高分子薄膜の膜厚は、通常50nm~1500nmであり、好ましくは100nm~1000nmであり、より好ましくは、200nm~800nmである。
孔径、孔密度、及び孔径分布は、用いる微粒子のサイズ、密度、及びサイズ分布を調整することで、自在に制御することができる。
本方法では、先ず、高分子を溶媒に溶解させて溶液を得る。
高分子は、本発明の多孔質高分子超薄膜を構成する高分子であり、具体例は、前記の通りである。
溶媒は、高分子を溶解できるものであればよく、具体例は、前記の通りである。
溶液中の高分子の濃度は、通常、1mg/ml~1000mg/mlであり、好ましくは、3 mg/ml ~100 mg/mlであり、より好ましくは、5mg/ml ~50 mg/mlである。
微粒子は、通常、直径20nm~3000nm (好ましくは直径100nm~2000nm、より好ましくは直径500nm~1500nm)であり、多孔質高分子超薄膜を作成する溶剤には溶解せずに、多孔質高分子超薄膜を溶解させない溶剤にて溶解できるものであれば限定されない。微粒子は、例えば、無機塩(例えば、臭化リチウム、塩化ナトリウム、ヨウ化ナトリウム、塩化アンモニウム、硫酸水素ナトリウム、リン酸二水素ナトリウム、塩化カルシウム、酢酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、リン酸水素二ナトリウム、炭酸カルシウム、酸化カルシウム、水酸化カルシウム、チオシアン酸カリウム、ハイドロキシアパタイトなど)、シリカ、タルク、カオリン、モンモリロナイト、ポリマー(例えば、ポリスチレン、デキストラン、ポリフェノール、ポリアミド、アクリル、ポリエチレンイミン、アガロースなど)、金属酸化物(例えば、アルミナ、酸化鉄、酸化チタンなど)、及び金属(例えば、銀、銅、鉄、亜鉛、アルミニウムなど)から形成されたものであり、好ましくは、臭化リチウム、炭酸カルシウム、シリカ、タルク、酸化チタンなどから形成されたものである。
分散液を基板に塗布する方法は、特に限定されないが、例えば、スピンコーティング法、スプレーコーティング法、バーコーティング法、ディップコーティング法などの常法により分散液を基体に塗布する。あるいは、グラビア印刷、スクリーン印刷、インクジェット印刷などの常法の印刷法により溶液を薄く基体に塗布する。
「微粒子を溶解できる溶剤」は、高分子超薄膜を溶解しないが、微粒子を溶解することができる溶剤である。溶剤は、高分子の種類及び微粒子の種類に応じて適宜選択することができる。溶剤の具体例は、水、酸性水、アルカリ性水、アルコール、ジメチルホルムアミド、シクロヘキサン、アセトン、酢酸エチルなどである。例えば、臭化ナトリウムはアセトン、チオシアン化カリウムはジメチルホルムアミド、金属や炭酸カルシウムは酸性水、シリカはアルカリ性水に溶解する。
孔径、孔密度、及び孔径分布は、用いる微粒子のサイズ、密度、及びサイズ分布を調整することで、自在に制御することができる。
本方法では、基体の上に構築した高分子超薄膜をガラス転移温度以上に加温した後、該高分子超薄膜を別に用意した凹凸のある基体で圧迫することにより多孔質高分子超薄膜を得る。
基体、高分子、及び凹凸のある基体は、前記と同様である。
ガラス転移温度以上に加温した高分子超薄膜を凹凸のある基体で圧迫することにより、基体の凹凸形状が写し取られた多孔質高分子超薄膜が得られる。
本方法では、原料となる高分子を溶媒に溶解して溶液を得、得られた溶液に微小気泡を分散させ、微小気泡を分散させた溶液を基体に塗布し、基体に塗布した溶液から溶媒を除去することにより多孔質高分子超薄膜を得る。
高分子、溶媒、基体等は、前記と同様である。
溶液に微小気泡を分散させる方法は、公知の方法により行うことができる。
溶媒を除去後、微小気泡部分が孔となる。結果として、多孔質高分子超薄膜が得られる。
前記各方法により多孔質高分子超薄膜が基体との複合体の形で得られた場合、多孔質高分子超薄膜を、基体から剥離させることにより、自立型多孔質高分子超薄膜を得ることができる。
多孔質高分子超薄膜を基体から剥離させる方法としては、例えば、多孔質高分子超薄膜と基体の間に水溶性犠牲膜を設けておく方法、多孔質高分子超薄膜と基体の間に多孔質高分子超薄膜が溶解しない溶剤に溶解する犠牲膜(以下、「その他の犠牲膜」という場合がある)を設けておく方法などがある。
このようにして得られた自立型多孔質高分子超薄膜を別の基体に掬い取り、掬い取った多孔質高分子超薄膜から水を除去して乾燥状態の多孔質高分子超薄膜を得ることもできる。
「別の基体」は、前記基体と同様である。
あるいは、得られた自立型多孔質高分子超薄膜をメッシュで掬い取り、多孔質高分子超薄膜とメッシュの複合体を製造するようにしてもよい。
「メッシュ」は前記の通りである。
前記各方法により本発明の多孔質高分子超薄膜が基体との複合体の形で得られた場合、その多孔質高分子超薄膜の上に、さらに水溶性支持膜を設けてもよい。これにより、基体の上に多孔質高分子超薄膜を有し、多孔質高分子薄膜の上に水溶支持膜を有する、基体と多孔質高分子超薄膜と水溶性支持膜の複合体を得ることができる。
本発明は、互いに混ざらない第1の高分子と第2の高分子の2種類の高分子を任意の割合で溶媒に溶解させて溶液を得、得られた溶液を基体に塗布した後、該基体に塗布した溶液中から前記溶媒を除去することによって基体上に得られる、海島構造に相分離した高分子超薄膜(以下、「本発明の高分子超薄膜」)を提供する。
以下、第1の高分子と第2の高分子を溶解させる溶媒を、「第1の溶媒」と言う場合がある。
あるいは、海島構造の島部のサイズは、好ましくは、1μmより大きく25μm以下の範囲であり、より好ましくは、1μmより大きく20μm以下の範囲であり、さらに好ましくは、1μmより大きく18μm以下の範囲であり、特に好ましくは、1μmより大きく15μm以下の範囲である。
サイズの異なる複数の島部が設けられている場合、島部のサイズ分布は、例えば、±10%以上である。本発明のいくつかの態様では、島部のサイズ分布は、±20%以上であり、好ましくは±25%以上であり、より好ましくは±30%以上であり、さらに好ましくは±35%以上(例えば、±35%以上、±40%以上、±45%以上、又は±50%以上)である。
またサイズ分布は、本発明のいくつかの態様では、上記下限値±10%以上から、例えば、±200%以下の範囲、±150%以下の範囲、±100%以下の範囲、±50%以下の範囲、±40%以下の範囲、±30%以下の範囲、±20%以下の範囲、又は±15%以下の範囲である。
サイズ分布は、本発明の別のいくつかの態様では、上記下限値±20%以上(例えば、±20%以上、±25%以上、±30%以上、±35%以上、±40%以上、±45%以上、又は±50%以上)から、±200%以下の範囲、又は±150%以下の範囲である。
ここで、本明細書において「サイズ分布」は、次のようにして計算して求めた値のことを意味する。すなわち、サイズの分布を正規分布として近似し、平均を μ、分散を σ2とすると島部サイズ分布はσ/μとして計算される。
また、サイズの異なる複数の島部が設けられている場合、最大のサイズを有する島部と最小のサイズを有する島部とのサイズ差は、通常、0.01μm~500μmであり、好ましくは、0.03μm~100μmであり、さらに好ましくは、0.1μm~5μmであり、特に好ましくは、0.5μm~3μmである。
本発明の好ましい態様の高分子超薄膜では、高分子超薄膜の膜厚に対する島部サイズの比(島部サイズ(μm)/膜厚(μm))が、例えば0.1~50であり、好ましくは、0.2~40であり、より好ましくは、0.3~20であり、特に好ましくは、0.5~15である。
この時の第1の高分子、第2の高分子、及び第2の溶媒の組み合わせとしては、例えば、文献「SP値 基礎・応用と計算方法」、山本秀樹著、情報機構に記載の方法により溶解度パラメーターの計算から組み合わせを挙げることができる。この場合、次の指針により第1の高分子、第2の高分子、及び第3の溶媒の組み合わせを決める。すなわち、ある高分子に対するHansen溶解度パラメーターを3次元空間にプロットし、それを中心にその高分子の相互作用半径を用いて球をつくる。対象となる溶媒のHansen溶解度パラメーターを3次元空間にプロットした際に、そのプロットが球の内側にあると対象溶媒はその高分子の良溶媒であり、球の外側にあると貧溶媒であると判断する。この指針から第1の溶媒は第1の高分子と第2の高分子2の良溶媒であり、第2の溶媒は第1の高分子の良溶媒であり第2の高分子の貧溶媒であるものを選択する。
(i)第1の高分子:ポリスチレン、第2の高分子:ポリメタクリル酸メチル;
(ii)第1の高分子:ポリスチレン、第2の高分子:ポリD,L-乳酸;
(iii) 第1の高分子:ポリメタクリル酸メチル、第2の高分子:ポリスチレン;
(iv) 第1の高分子:ポリエチレングリコール、第2の高分子:ポリスチレン;
(v) 第1の高分子:ポリビニルピロリドン、第2の高分子:ポリスチレン;又は
(vi) 第1の高分子:ポリD,L-乳酸、第2の高分子:ポリスチレン。
上記(ii)の組み合わせのとき、第2の溶媒は、例えば、シクロヘキサンである。
上記(iii)の組み合わせのとき、第2の溶媒は、例えば、酢酸エチルである。
上記(iv)の組み合わせのとき、第2の溶媒は、例えば、水である。
上記(v)の組み合わせのとき、第2の溶媒は、例えば、水である。
上記(vi)の組み合わせのとき、第2の溶媒は、例えば、酢酸エチルである。
先ず、互いに混ざらない2種類の高分子を任意の割合で溶媒に溶解させて溶液を得る。
「任意の割合」とは、第1の高分子:第2の高分子の比(w/w)が任意であることを意味し、第1の高分子:第2の高分子の比(w/w)は、例えば、1:9~5:5である。第1の高分子:第2の高分子の比(w/w)は、好ましくは、1:9~4:6であり、より好ましくは、1:9~3:7である。
溶液を基体に塗布する方法は、特に限定されないが、例えば、スピンコーティング法、スプレーコーティング法、バーコーティング法、ディップコーティング法などの常法により溶液を基体に塗布する。あるいは、グラビア印刷、スクリーン印刷、インクジェット印刷などの常法の印刷法により溶液を薄く基体に塗布する。
また、島部サイズ分布は次のようにして制御することができる。例えば、スピンコーティング法を用いる場合には、スピンコーティング時の回転速度を低下させることで島部サイズ分布を増大させることができる。一方、スピンコーティング時の回転速度を上げることで島部サイズ分布を小さくすることができる。
前述の「7. 海島構造に相分離した高分子超薄膜」に記載した第1の高分子:第2の高分子の比を逆転することによって、海島の高分子の組成を逆転することができる。
ポリスチレン(PS)とポリメタクリル酸メチル(PMMA)は各々Chemco Scientific Co., Ltd. と Sigma-Aldrichから購入した。表1にそれらの特徴を示す。ポリビニルアルコール(PVA, 10mg/mL )として分子量(Mw = ca. 22 kDa)のものをKanto Chemicals Co.から購入した。これらの高分子は精製せずに用いた。
また、孔径分布は、スピンコーティング時の回転速度を低下させると増大する傾向が見られた。
PS(Mw:170kD)およびポリD,L乳酸(Mw:300kD)を酢酸エチルに異なる重量比(PS: ポリD,L乳酸= 3:7 w/w)で溶解させて混合溶液とした。溶液中の高分子の総重量濃度は10mg/mLとし、スピンコーターMS-A100 (MIKASA Co., Ltd.)にて高分子ブレンドナノシートを調製した。
また、孔径分布は、スピンコーティング時の回転速度を低下させると増大する傾向が見られた。
全ての操作は、クリーンルーム(クラス10,000)内にスピンコーター(Opticoat MS-A 100、MIKASA)を設置して行った。シリコン基板(KST World社製)を2.0cm x 2.0cmに切り、硫酸/30%過酸化水素水(3/1, v/v)に120℃で10分間浸漬した後、脱イオン水(抵抗率18MΩcm)にて洗浄した。酢酸エチルおよびジメチルスルホキシド(DMSO)からなる混合溶媒(酢酸エチル:DMSO=100:1, 100:3, 100:5, v/v)にて、ポリD,L乳酸(Mw:300kDa)を終濃度が各30 mg/mLとなるように調整した。基板をスピンコーターに設置し、調整した各溶液を滴下後、スピンコーティングの回転数(1000, 3000, 5000,7000 rpm)し60秒回転させた(室温32℃, 湿度32%)。作製後のナノシートは目視にて白濁が確認できた。
また、孔径分布は、スピンコーティング時の回転速度を低下させると増大する傾向が見られた。
全ての操作は、クリーンルーム(クラス10,000)内にスピンコーター(Opticoat MS-A 100、MIKASA)を設置して行った。シリコン基板(KST World社製)を2cm x 2cmに切り、硫酸/30%過酸化水素水に120℃で10分間浸漬した後、脱イオン水(抵抗率 18MΩcm)にて洗浄した。
ポリD,L乳酸を酢酸エチルに溶解させ終濃度を30mg/mLになる様に調整し、別に臭化リチウムの微粒子を酢酸エチルに終濃度60mg/mLになる様に加えて溶解させ、溶液を調製した。この2つの溶液10mg/mLをポリD,L乳酸:臭化リチウム比=5:1, 5:2, 5:3, 5:4, 5:5 (w/w)の割合で混合した。犠牲膜としてPVA(Mw: 22kD, 1wt%)をシリコン基板上に製膜後、各溶液をスピンコーティング(3000 rpm, 60秒)した。スピンコーティングにより酢酸エチルが蒸発して行く際に溶けていた臭化リチウムが析出し、微結晶が混在したナノシートが得られた。これを純水中に浸漬させることにより臭化リチウムを溶解させながら、シリコン基板から多孔質超薄膜を剥離させた。これをAFM観察用のシリコン基板に掬い取りAFM観察した。析出した臭化リチウムが溶解した部分が多孔質として観察された。結果を図7と表6にまとめた。
上記各実施例で得られた多孔質ナノシートについて、膜厚(film thickness)に対する孔径 (pore diameter)の比(aspect)を次のようにして求めた。
ポリビニルアルコール(PVA)(関東化学社製)を水に2.0重量%溶解した。得られたPVA溶液を、ポリエチレンテレフタレート(PET)からなる基材フィルムの片面に、グラビア印刷にて乾燥後の膜厚が約60 nmになるように塗布した。PVA溶液を、熱風乾燥式ドライヤー内にて80℃で10秒間乾燥し、基材フィルムの上にPVA層を含む積層フィルムを作成した。
さらに、ポリD,L-乳酸(PDLLA)(PURSORB PDL20)及びポリスチレン(PS)(Chemco Co., Ltd.製)を酢酸エチルに高分子の総量2.0重量%で、かつPDLLA:PS比=1:9,2:8,3:7(w/w)となるように溶解した。得られたPDLLA/PS溶液を、上記PVA層の上にグラビア印刷にて、乾燥後の膜厚が190nmになるように塗布した。PDLLA/PS溶液を、熱風乾燥式ドライヤー内にて50℃で10秒間乾燥し、PVA層の上にPDLLA/PSナノシートを設けた積層フィルムを作成した。表8、図9に混合比の異なる3種類の系に対して特徴をまとめた。
図11は、図10(a’)及び(b’)の多孔質PSナノシートの模式図である。
得られた多孔質PSナノシートは、膜厚190nmであり、平均10μm(約5μm~約20μm、孔径分布値:±60%)のサイズの孔を6×10-3個/μm2の密度で有していた。
実施例5の方法で求めた多孔質PSナノシートのアスペクト範囲は、約10~100であった。
(a)及び(c)ではシリコン基板上にPDLLAナノディスクの一層構造の、(b)ではPDLLAナノディスクの二層構造のAFM像である。
得られたPDLLAナノディスクは、膜厚59nmであり、直径平均8μm(3~12μm)であった。
Claims (35)
- 互いに混ざらない第1の高分子と第2の高分子の2種類の高分子を任意の割合で溶媒に溶解させて溶液を得、得られた溶液を基体に塗布した後、該基体に塗布した溶液中から前記溶媒を除去することによって基体上に得られる、海島構造に相分離した高分子超薄膜。
- 前記海島構造の島部が、1μmより大きく25μm以下の範囲のサイズであり、5x10-3個/μm2~50個/μm2の密度で表面に存在する、請求項1に記載の高分子超薄膜。
- 前記海島構造の島部のサイズが、15μm以下の範囲である、請求項2に記載の高分子超薄膜。
- 前記高分子超薄膜の膜厚が10nm~1000nmである、請求項1~3のいずれか1項に記載の高分子超薄膜。
- 前記第1の高分子と第2の高分子の組み合わせが、下記の群から選択される、請求項1~4のいずれか1項に記載の高分子超薄膜:
(i)第1の高分子:ポリスチレン、第2の高分子:ポリメタクリル酸メチル;
(ii)第1の高分子:ポリスチレン、第2の高分子:ポリD,L-乳酸;
(iii) 第1の高分子:ポリメタクリル酸メチル、第2の高分子:ポリスチレン;
(iv) 第1の高分子:ポリエチレングリコール、第2の高分子:ポリスチレン;
(v) 第1の高分子:ポリビニルピロリドン、第2の高分子:ポリスチレン;及び
(vi) 第1の高分子:ポリD,L-乳酸、第2の高分子:ポリスチレン。 - 膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜。
- 30nm~50μmのサイズの孔が5x10-3個/μm2~50個/μm2の密度で表面に存在する請求項6に記載の多孔質高分子超薄膜。
- 前記孔のサイズが、1μmより大きく25μm以下の範囲である、請求項7に記載の多孔質高分子超薄膜。
- 前記孔のサイズが、15μm以下の範囲である、請求項8に記載の多孔質高分子超薄膜。
- 孔径分布が少なくとも±20%である、請求項6~9のいずれか1項に記載の多孔質高分子超薄膜。
- 多孔質高分子超薄膜の膜厚に対する孔径の比(孔径 (μm)/膜厚(μm))が0.1~50である、請求項6~10のいずれか1項に記載の多孔質高分子超薄膜。
- 高分子がポリヒドロキシアルカン酸、ポリヒドロキシアルカン酸の共重合体、ポリ(エステル-エーテル)、脂肪族ジカルボン酸と脂肪族ジオールのポリエステル、ポリアミド、ポリウレタン、多糖類エステル、ポリ(アクリレート)、ポリ(メタクリレート)、ポリスチレン、ポリ酢酸ビニル、およびポリシロキサンからなる群から選択される少なくとも1つである、請求項6~11のいずれか1項記載の多孔質高分子超薄膜。
- 互いに混ざらない2種類の高分子を任意の割合で第1の溶媒に溶解させて溶液を得る工程と、
得られた溶液を基体に塗布した後、該基体に塗布した溶液中から第1の溶媒を除去することによって、海島構造に相分離した高分子超薄膜を得る工程と、
島部の高分子の良溶媒であるとともに島部以外の高分子の貧溶媒である第2の溶媒に前記高分子超薄膜を浸漬させて、島部を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得る工程と
を含む、多孔質高分子超薄膜の製造方法。 - 原料となる高分子を、該高分子の良溶媒とその良溶媒よりも沸点の高い貧溶媒との任意の割合の混合溶媒に溶解させて溶液を得る工程と、
得られた溶液を基体に塗布し、該基体に塗布した溶液中から混合溶媒を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得る工程と
を含む、多孔質高分子超薄膜の製造方法。 - 高分子を溶媒に溶解させて溶液を得る工程と、
溶液を凹凸のある基体に塗布した後、該基体に塗布した溶液中から溶媒を除去することにより高分子超薄膜を得る工程と、
凹凸のある基体を、高分子超薄膜を溶解させない溶媒にて溶解させることにより除去する工程、
を含む、膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜の製造方法。 - 凹凸のある基体が、微粒子を分散固定した高分子薄膜を有する基体であり、
前記基体に塗布した溶液中から溶媒を除去することにより高分子超薄膜を得た後、微粒子を分散固定した高分子薄膜を有する基体を、高分子超薄膜を溶解させない溶媒に溶解させることにより除去して多孔質高分子超薄膜を得る、請求項15に記載の方法。 - 微粒子が、ポリスチレン粒子、シリカ粒子、デキストラン粒子、ポリ乳酸粒子、ポリウレタン微粒子、ポリアクリル粒子、ポリエチレンイミン粒子、アルブミン粒子、アガロース粒子、酸化鉄粒子、酸化チタン微粒子、アルミナ微粒子、タルク微粒子、カオリン微粒子、モンモリロナイト微粒子、及びハイドロキシアパタイト微粒子からなる群から選択される少なくとも1つの粒子である、請求項16に記載の方法。
- 微粒子が20nm~3000nmの直径を有する請求項16又は17に記載の方法。
- 高分子を溶媒に溶解させて溶液を得る工程と、
溶液に微粒子を分散させて分散液を得る工程と、
前記分散液を基体に塗布した後、該基体に塗布した分散液中から溶媒を除去することにより高分子超薄膜を得る工程と、
得られた高分子超薄膜を、前記微粒子を溶解できる溶剤中に浸漬させて該微粒子を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得る工程と
を含む、多孔質高分子超薄膜の製造方法。 - 微粒子が、無機塩、シリカ、タルク、カオリン、モンモリロナイト、ポリマー、金属酸化物、及び金属からなる群から選択される少なくとも1つである、請求項19に記載の方法。
- 基体の上に構築した高分子超薄膜をガラス転移温度以上に加温した後、該高分子超薄膜を別に用意した凹凸のある基体で圧迫することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得ることを特徴とする、多孔質高分子超薄膜の製造方法。
- 原料となる高分子を溶解して溶液を得、得られた溶液に微小気泡を分散させ、微小気泡を分散させた溶液を基体に塗布し、基体に塗布した溶液から溶媒を除去することにより膜厚が10nm~1000nmである自己支持性の多孔質高分子超薄膜を得ることを特徴とする、多孔質高分子超薄膜の製造方法。
- 基体の上に水溶性犠牲膜を有し、その上に請求項6~12のいずれか1項に記載の多孔質高分子超薄膜を有する、基体と水溶性犠牲膜と多孔質高分子超薄膜の複合体。
- 基体の上に請求項6~12のいずれか1項に記載の多孔質高分子超薄膜を有し、多孔質高分子超薄膜の上に水溶性支持膜を有する、基体と多孔質高分子超薄膜と水溶性支持膜の複合体。
- 請求項6~12のいずれか1項に記載の多孔質高分子超薄膜の上に水溶性支持膜を有する、多孔質高分子超薄膜と水溶性支持膜の複合体。
- 請求項23~25のいずれか1項に記載の複合体の水溶性犠牲膜又は水溶性支持膜を水を用いて除去することによって水中にて多孔質高分子超薄膜を得ることを特徴とする、自己支持性の多孔質高分子超薄膜の製造方法。
- 前記多孔質高分子超薄膜を別の基体に掬い取り、掬い取った多孔質高分子超薄膜から水を除去して乾燥状態の多孔質高分子超薄膜を得ることを特徴とする、請求項26に記載の多孔質高分子超薄膜の製造方法。
- メッシュの上に請求項6~12のいずれか1項に記載の多孔質高分子超薄膜を有する、メッシュと多孔質高分子超薄膜の複合体。
- 請求項26に記載の方法で製造した自己支持性の多孔質高分子超薄膜をメッシュで掬い取り、多孔質高分子超薄膜とメッシュの複合体を製造することを特徴とする、メッシュと多孔質高分子超薄膜の複合体の製造方法。
- 請求項6~12のいずれか1項に記載の1以上の多孔質高分子超薄膜と、孔のない1以上の高分子超薄膜とを有する、多孔質高分子超薄膜と孔のない高分子超薄膜の複合体。
- 膜厚が10nm~1000nmであり、サイズが30nm~50μm以下の範囲である、略円形状高分子超薄膜。
- 前記サイズが1μmより大きく25μm以下の範囲である、請求項31に記載の略円形状高分子超薄膜。
- 前記サイズが15μm以下の範囲である、請求項32に記載の略円形状高分子超薄膜。
- 前記高分子がポリD,L-乳酸である、請求項31~33のいずれか1項に記載の略円形状高分子超薄膜。
- 互いに混ざらない2種類の高分子を任意の割合で第1の溶媒に溶解させて溶液を得る工程と、
得られた溶液を基体に塗布した後、該基体に塗布した溶液中から第1の溶媒を除去することによって、海島構造に相分離した高分子超薄膜を得る工程と、
海部の高分子の良溶媒であるとともに海部以外の高分子の貧溶媒である第2の溶媒に前記高分子超薄膜を浸漬させて、海部を除去することにより膜厚が10nm~1000nmであり、サイズが30nm~50μm以下の範囲である、略円形状高分子超薄膜を得る工程と
を含む、略円形状高分子超薄膜の製造方法。
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147027657A KR102096286B1 (ko) | 2012-03-12 | 2013-03-12 | 고분자 초박막 및 다공질 고분자 초박막 |
EP13761776.7A EP2826815B1 (en) | 2012-03-12 | 2013-03-12 | Ultra-thin polymer film disk and method of preparation |
CN201380012758.0A CN104321375B (zh) | 2012-03-12 | 2013-03-12 | 高分子超薄膜和多孔高分子超薄膜 |
US14/383,191 US9938384B2 (en) | 2012-03-12 | 2013-03-12 | Ultra-thin polymer film, and porous ultra-thin polymer film |
SG11201405484UA SG11201405484UA (en) | 2012-03-12 | 2013-03-12 | Ultra-thin polymer film, and porous ultra-thin polymer film |
JP2014504931A JP6322571B2 (ja) | 2012-03-12 | 2013-03-12 | 高分子超薄膜及び多孔質高分子超薄膜 |
CA2866749A CA2866749C (en) | 2012-03-12 | 2013-03-12 | Ultra-thin polymer film and porous ultra-thin polymer film |
US15/902,501 US10858490B2 (en) | 2012-03-12 | 2018-02-22 | Ultra-thin polymer film and porous ultra-thin polymer film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-054255 | 2012-03-12 | ||
JP2012054255 | 2012-03-12 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/383,191 A-371-Of-International US9938384B2 (en) | 2012-03-12 | 2013-03-12 | Ultra-thin polymer film, and porous ultra-thin polymer film |
US15/902,501 Division US10858490B2 (en) | 2012-03-12 | 2018-02-22 | Ultra-thin polymer film and porous ultra-thin polymer film |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013137260A1 true WO2013137260A1 (ja) | 2013-09-19 |
Family
ID=49161166
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/056823 WO2013137260A1 (ja) | 2012-03-12 | 2013-03-12 | 高分子超薄膜及び多孔質高分子超薄膜 |
Country Status (8)
Country | Link |
---|---|
US (2) | US9938384B2 (ja) |
EP (1) | EP2826815B1 (ja) |
JP (1) | JP6322571B2 (ja) |
KR (1) | KR102096286B1 (ja) |
CN (2) | CN106432761B (ja) |
CA (1) | CA2866749C (ja) |
SG (2) | SG11201405484UA (ja) |
WO (1) | WO2013137260A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014140978A (ja) * | 2013-01-22 | 2014-08-07 | Nanotheta Co Ltd | シート状積層体およびシート状積層体の製造方法 |
WO2014133136A1 (ja) * | 2013-03-01 | 2014-09-04 | 富士フイルム株式会社 | フィルム及びその製造方法、複合体、フィルム積層体、エッチング方法 |
JP2014213550A (ja) * | 2013-04-26 | 2014-11-17 | リンテック株式会社 | 非水溶性高分子薄膜転写用部材および非水溶性高分子薄膜転写用部材の製造方法 |
JP2016056317A (ja) * | 2014-09-11 | 2016-04-21 | 国立大学法人 東京大学 | マイクロバブル含有ポリマー溶液及び該ポリマー溶液製造方法 |
JP2016539215A (ja) * | 2013-10-23 | 2016-12-15 | 東麗先端材料研究開発(中国)有限公司 | 微多孔ポリ乳酸配向フィルムおよびその応用 |
JP2016214148A (ja) * | 2015-05-20 | 2016-12-22 | 住友電気工業株式会社 | 細胞培養担体及びこれを備える細胞シート |
WO2023054591A1 (ja) * | 2021-09-30 | 2023-04-06 | 古河電気工業株式会社 | 紫外線、可視光線および/または赤外線を拡散反射する物品およびその製造方法 |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015073980A (ja) * | 2013-10-11 | 2015-04-20 | 富士フイルム株式会社 | ガス分離膜およびガス分離膜モジュール |
EP4321860A3 (en) | 2015-02-03 | 2024-04-24 | Siemens Healthcare Diagnostics Inc. | Improved magnesium ion selective membranes |
DK3056260T3 (da) * | 2015-02-16 | 2020-04-27 | Helmholtz Zentrum Geesthacht | Fremgangsmåde til fremstilling af en separeringsmembran og en separeringsmembran der kan fremstilles ved nævnte fremgangsmåde |
CN104774342A (zh) * | 2015-03-04 | 2015-07-15 | 南昌航空大学 | 一种利用微相分离法制备聚氨酯多孔薄膜的方法 |
WO2016149394A1 (en) * | 2015-03-17 | 2016-09-22 | President And Fellows Of Harvard College | Automated membrane fabrication system |
KR102536494B1 (ko) * | 2015-05-11 | 2023-05-25 | 도레이 카부시키가이샤 | 고분자막 및 그것을 사용한 분산액과 집적체 |
KR101714621B1 (ko) * | 2015-05-21 | 2017-03-09 | 충남대학교산학협력단 | 스루포어 구조의 마이크로 기공을 갖는 프리스탠딩 고분자필름의 제조방법 |
CN105632892A (zh) * | 2015-11-30 | 2016-06-01 | 东莞酷派软件技术有限公司 | Ito图案的制备方法、基板的制备方法及基板和终端 |
EP3178873A1 (en) | 2015-12-08 | 2017-06-14 | ETH Zurich | Waterproof and breathable, porous membranes |
EP3463790B1 (en) | 2016-06-05 | 2020-05-13 | Okinawa Institute of Science and Technology School Corporation | Method of nanoscale patterning based on controlled pinhole formation |
CN108452689A (zh) * | 2017-03-06 | 2018-08-28 | 青岛致用新材料科技有限公司 | 一种高选择性全脂环族聚酰胺纳滤膜及其制备方法 |
CN109575538B (zh) * | 2017-09-29 | 2023-04-07 | 东丽先端材料研究开发(中国)有限公司 | 一种微多孔取向聚乳酸薄膜 |
EP3723956B1 (de) * | 2017-12-14 | 2023-03-01 | Basf Se | Vorrichtung und verfahren zur imprägnierung von einzelfasern, einzelfäden oder einzelrovings |
CN111491719B (zh) | 2017-12-18 | 2022-11-29 | 香港科技大学 | 柔性多功能高孔隙率超薄聚乙烯膜的合成方法 |
CN112105447B (zh) * | 2018-05-16 | 2022-12-23 | 日产化学株式会社 | 气体分离膜的制造方法 |
US11298663B2 (en) | 2018-08-28 | 2022-04-12 | Molecule Works Inc. | Thin metal/ceramic hybrid membrane sheet and filter |
CN109722004B (zh) * | 2018-12-24 | 2020-12-18 | 中国科学院兰州化学物理研究所 | 一种可控自卷曲聚氨酯膜及其制备和应用 |
WO2020153805A1 (en) * | 2019-01-25 | 2020-07-30 | Seoul National University R&Db Foundation | Method of preparing a free standing ultrathin porous membrane and free standing ultrathin porous membrane manufactured using the same |
CN110201554A (zh) * | 2019-07-08 | 2019-09-06 | 安徽农业大学 | 一种蒙脱土增强型疏水/超亲油聚氨酯膜材料的制备方法 |
JP7240608B2 (ja) * | 2019-08-29 | 2023-03-16 | トヨタ自動車株式会社 | 非水溶性高分子の多孔質体の製造方法 |
JP7281086B2 (ja) * | 2019-10-09 | 2023-05-25 | トヨタ自動車株式会社 | 多孔質体の製造方法 |
CN112795042A (zh) * | 2021-01-29 | 2021-05-14 | 赵春富 | 一种玉米秸秆纤维素抗菌膜的制备方法 |
CN113200523B (zh) * | 2021-03-25 | 2022-11-22 | 华南师范大学 | 一种大面积层状二维材料的剥离及其转移方法 |
CN113694743A (zh) * | 2021-08-17 | 2021-11-26 | 安徽智泓净化科技股份有限公司 | 高盐废水处理用反渗透膜及其制备方法 |
CN113851704B (zh) * | 2021-09-24 | 2023-12-15 | 中化学南方建设投资有限公司 | 一种聚合物电解质膜的制备方法 |
CN114114755B (zh) * | 2021-12-03 | 2024-04-02 | 宁波长阳科技股份有限公司 | 反射膜的制备方法、反射膜及其应用 |
CN115445456B (zh) * | 2022-09-30 | 2024-03-19 | 沃顿科技股份有限公司 | 一种高通量反渗透复合膜的制备方法 |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61231227A (ja) * | 1978-06-17 | 1986-10-15 | Asahi Chem Ind Co Ltd | 熱可塑性重合体未延伸連続繊維 |
JP2002221608A (ja) * | 2001-01-26 | 2002-08-09 | Daicel Chem Ind Ltd | 光散乱シートおよび液晶表示装置 |
JP2003155365A (ja) | 2001-11-22 | 2003-05-27 | Toshiba Corp | 加工方法及び成形体 |
JP2004502554A (ja) | 2000-03-22 | 2004-01-29 | ユニバーシティー オブ マサチューセッツ | ナノシリンダー・アレイ |
JP2004124088A (ja) | 2002-09-11 | 2004-04-22 | Rikogaku Shinkokai | ブロック共重合体、及びミクロ相分離構造膜の製造方法 |
JP2005082746A (ja) * | 2003-09-10 | 2005-03-31 | Kawamura Inst Of Chem Res | 三次元周期構造体、三次元周期多孔質構造体、およびこれらの製造方法 |
WO2006025592A1 (ja) | 2004-08-31 | 2006-03-09 | Oxygenix Co., Ltd. | 薄膜状高分子構造体とその調製方法 |
JP2006070254A (ja) | 2004-08-06 | 2006-03-16 | Fuji Photo Film Co Ltd | フィルムの製造方法 |
JP2007279372A (ja) * | 2006-04-06 | 2007-10-25 | Toei Sangyo Kk | 画像形成装置用帯電ブラシ |
JP2008036491A (ja) * | 2006-08-03 | 2008-02-21 | Nippon Telegr & Teleph Corp <Ntt> | パターン形成方法及びモールド |
WO2008050913A1 (fr) | 2006-10-27 | 2008-05-02 | Shinji Takeoka | Structure polymère de type film et son procédé de préparation |
JP2009256592A (ja) | 2008-03-18 | 2009-11-05 | Fujifilm Corp | 多孔質膜 |
JP2010116463A (ja) | 2008-11-12 | 2010-05-27 | Nippon Oil Corp | ミクロ相分離構造膜、ナノ多孔質膜、およびそれらの製造方法 |
JP2010138286A (ja) | 2008-12-11 | 2010-06-24 | Fujifilm Corp | 多孔質膜およびその製造方法 |
JP2011105780A (ja) | 2009-11-12 | 2011-06-02 | Lintec Corp | 多孔質膜の製造方法、多孔質膜、多孔質膜製造装置 |
JP2011186056A (ja) * | 2010-03-05 | 2011-09-22 | Fujifilm Corp | 防眩性フィルムの製造方法 |
JP2011236412A (ja) * | 2010-04-12 | 2011-11-24 | Nitto Denko Corp | 樹脂成形体およびその製造方法 |
JP2012054255A (ja) | 2002-06-05 | 2012-03-15 | Eveready Battery Co Inc | 改善されたエネルギー密度を有する非水性電気化学電池 |
Family Cites Families (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3695989A (en) | 1970-08-12 | 1972-10-03 | Robert E Albert | Cold water soluble foam plastic package |
US3933561A (en) * | 1974-03-27 | 1976-01-20 | North Star Research Institute | Process for manufacturing ultrathin polymer membranes and products derived therefrom |
DE3148312A1 (de) | 1981-12-07 | 1983-06-09 | Hoechst Ag, 6230 Frankfurt | Folie zum trennen fluessiger oder gasfoermiger mehrkomponentensysteme |
JPS61186576A (ja) | 1985-02-14 | 1986-08-20 | Toray Ind Inc | 人工皮革シ−トおよびその製造方法 |
US5394868A (en) * | 1992-06-25 | 1995-03-07 | Schering Corporation | Inhalation device for powdered medicaments |
US5962544A (en) * | 1995-12-07 | 1999-10-05 | 3M | Microporous materials of ethylene-vinyl alcohol copolymer and methods for making same |
EP0889080A1 (en) | 1996-12-10 | 1999-01-07 | Daicel Chemical Industries, Ltd. | Porous films, process for producing the same, and laminate films and recording sheets made with the use of the porous films |
DE19803362A1 (de) * | 1998-01-29 | 1999-08-05 | Sartorius Gmbh | Geschäumte poröse Membranen aus thermoplastischen Polymeren sowie Verfahren und Vorrichtung zu ihrer Herstellung |
US6365173B1 (en) * | 1999-01-14 | 2002-04-02 | Efrat Biopolymers Ltd. | Stereocomplex polymeric carriers for drug delivery |
DE10058258B4 (de) * | 2000-11-23 | 2005-01-27 | Goedel, Werner Andreas | Poröse Membranen, deren Herstellung und Verwendung |
US6824680B2 (en) * | 2001-05-07 | 2004-11-30 | New Jersey Institute Of Technology | Preparation of microporous films from immiscible blends via melt processing and stretching |
US20030186405A1 (en) | 2002-04-01 | 2003-10-02 | The Ohio State University Research Foundation | Micro/nano-embossing process and useful applications thereof |
ES2323492T3 (es) * | 2002-11-30 | 2009-07-17 | Gambro Lundia Ab | Membrana espumada. |
US20060210785A1 (en) * | 2003-07-18 | 2006-09-21 | Oji Paper Co., Ltd. | Foamed product in a sheet form and method for production thereof |
US7761130B2 (en) * | 2003-07-25 | 2010-07-20 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US7959780B2 (en) | 2004-07-26 | 2011-06-14 | Emporia Capital Funding Llc | Textured ion exchange membranes |
US8043480B2 (en) | 2004-11-10 | 2011-10-25 | The Regents Of The University Of Michigan | Methods for forming biodegradable nanocomponents with controlled shapes and sizes via electrified jetting |
JP2006321852A (ja) | 2005-05-17 | 2006-11-30 | Kyoto Institute Of Technology | 深さ方向の傾斜構造を有する共連続構造体および光照射を用いた共連続構造体の生産方法 |
JP5216995B2 (ja) | 2006-02-03 | 2013-06-19 | 国立大学法人北海道大学 | ブロック共重合体からなるナノディスク |
JP2007260817A (ja) | 2006-03-28 | 2007-10-11 | Toray Ind Inc | 研磨材料 |
JP5207467B2 (ja) * | 2006-04-21 | 2013-06-12 | 独立行政法人理化学研究所 | ポリマー薄膜の製造方法およびポリマー薄膜 |
JP4778410B2 (ja) * | 2006-12-15 | 2011-09-21 | 三菱レイヨン株式会社 | 脱気用複合中空糸膜 |
JP2008254146A (ja) | 2007-04-09 | 2008-10-23 | Toray Ind Inc | 研磨用シート |
JP5278939B2 (ja) * | 2007-07-11 | 2013-09-04 | 独立行政法人物質・材料研究機構 | 柔らかで自立性があるタンパク質ナノ薄膜、その製造法及び応用 |
WO2009029859A2 (en) * | 2007-08-31 | 2009-03-05 | Board Of Regents, The University Of Texas | Nanodisks and methods of fabrication of nanodisks |
US8409450B2 (en) | 2008-03-24 | 2013-04-02 | The Regents Of The University Of California | Graphene-based structure, method of suspending graphene membrane, and method of depositing material onto graphene membrane |
WO2009140441A2 (en) | 2008-05-13 | 2009-11-19 | Nanoink, Inc. | Height sensing cantilever |
JP2010065151A (ja) * | 2008-09-11 | 2010-03-25 | Fujifilm Corp | 三次元網目状構造を有する多孔質膜 |
EP2344683A2 (en) * | 2008-09-11 | 2011-07-20 | Ramot at Tel-Aviv University Ltd. | Nanostructures and process of preparing same |
EP2366449A4 (en) * | 2008-11-11 | 2012-05-30 | Snu R&Db Foundation | MEMBRANE WITH STRUCTURED SURFACE, MANUFACTURING METHOD AND WATER TREATMENT PROCESS THEREFOR |
US20100155325A1 (en) | 2008-12-24 | 2010-06-24 | General Electric Company | Particle-templated membranes, and related processes for their preparation |
JP2010254815A (ja) | 2009-04-24 | 2010-11-11 | Asahi Kasei Chemicals Corp | ブロックポリマー及びその製造方法 |
JP5394857B2 (ja) | 2009-08-27 | 2014-01-22 | 富士フイルム株式会社 | 高分子膜の製造方法 |
JP5600304B2 (ja) | 2010-03-03 | 2014-10-01 | 富士フイルム株式会社 | 光散乱シート及びその製造方法 |
JP2011236110A (ja) | 2010-04-12 | 2011-11-24 | Nitto Denko Corp | 有機無機複合粒子、粒子分散液、粒子分散樹脂組成物および有機無機複合粒子の製造方法 |
US8377182B2 (en) * | 2010-05-14 | 2013-02-19 | Brady Worldwide, Inc. | Gas anti diffusion assemblies |
-
2013
- 2013-03-12 WO PCT/JP2013/056823 patent/WO2013137260A1/ja active Application Filing
- 2013-03-12 US US14/383,191 patent/US9938384B2/en active Active
- 2013-03-12 KR KR1020147027657A patent/KR102096286B1/ko active IP Right Grant
- 2013-03-12 JP JP2014504931A patent/JP6322571B2/ja active Active
- 2013-03-12 SG SG11201405484UA patent/SG11201405484UA/en unknown
- 2013-03-12 SG SG10201610281SA patent/SG10201610281SA/en unknown
- 2013-03-12 CN CN201610592439.7A patent/CN106432761B/zh active Active
- 2013-03-12 EP EP13761776.7A patent/EP2826815B1/en active Active
- 2013-03-12 CN CN201380012758.0A patent/CN104321375B/zh active Active
- 2013-03-12 CA CA2866749A patent/CA2866749C/en active Active
-
2018
- 2018-02-22 US US15/902,501 patent/US10858490B2/en active Active
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61231227A (ja) * | 1978-06-17 | 1986-10-15 | Asahi Chem Ind Co Ltd | 熱可塑性重合体未延伸連続繊維 |
JP2004502554A (ja) | 2000-03-22 | 2004-01-29 | ユニバーシティー オブ マサチューセッツ | ナノシリンダー・アレイ |
JP2002221608A (ja) * | 2001-01-26 | 2002-08-09 | Daicel Chem Ind Ltd | 光散乱シートおよび液晶表示装置 |
JP2003155365A (ja) | 2001-11-22 | 2003-05-27 | Toshiba Corp | 加工方法及び成形体 |
JP2012054255A (ja) | 2002-06-05 | 2012-03-15 | Eveready Battery Co Inc | 改善されたエネルギー密度を有する非水性電気化学電池 |
JP2004124088A (ja) | 2002-09-11 | 2004-04-22 | Rikogaku Shinkokai | ブロック共重合体、及びミクロ相分離構造膜の製造方法 |
JP2005082746A (ja) * | 2003-09-10 | 2005-03-31 | Kawamura Inst Of Chem Res | 三次元周期構造体、三次元周期多孔質構造体、およびこれらの製造方法 |
JP2006070254A (ja) | 2004-08-06 | 2006-03-16 | Fuji Photo Film Co Ltd | フィルムの製造方法 |
WO2006025592A1 (ja) | 2004-08-31 | 2006-03-09 | Oxygenix Co., Ltd. | 薄膜状高分子構造体とその調製方法 |
JP2007279372A (ja) * | 2006-04-06 | 2007-10-25 | Toei Sangyo Kk | 画像形成装置用帯電ブラシ |
JP2008036491A (ja) * | 2006-08-03 | 2008-02-21 | Nippon Telegr & Teleph Corp <Ntt> | パターン形成方法及びモールド |
WO2008050913A1 (fr) | 2006-10-27 | 2008-05-02 | Shinji Takeoka | Structure polymère de type film et son procédé de préparation |
JP2009256592A (ja) | 2008-03-18 | 2009-11-05 | Fujifilm Corp | 多孔質膜 |
JP2010116463A (ja) | 2008-11-12 | 2010-05-27 | Nippon Oil Corp | ミクロ相分離構造膜、ナノ多孔質膜、およびそれらの製造方法 |
JP2010138286A (ja) | 2008-12-11 | 2010-06-24 | Fujifilm Corp | 多孔質膜およびその製造方法 |
JP2011105780A (ja) | 2009-11-12 | 2011-06-02 | Lintec Corp | 多孔質膜の製造方法、多孔質膜、多孔質膜製造装置 |
JP2011186056A (ja) * | 2010-03-05 | 2011-09-22 | Fujifilm Corp | 防眩性フィルムの製造方法 |
JP2011236412A (ja) * | 2010-04-12 | 2011-11-24 | Nitto Denko Corp | 樹脂成形体およびその製造方法 |
Non-Patent Citations (10)
Title |
---|
"Biomaterial for Regenerative Medicine", CORONA PUBLISHING |
"Biomaterials utilized by making contact with blood (second series", BIOMATERIALS, vol. 23, 2005, pages 178 - 238 |
"Biomaterials utilized by making contact with blood", BIOMATERIALS, vol. 22, 2004, pages 78 - 139 |
"Biomedical Applications of Biodegradable Polymers", JOURNAL OF POLYMER SCIENCE, PART B: POLYMER PHYSICS, vol. 49, 2011, pages 832 - 864 |
"Dressing: New Wound Management", HERUSU SHUPPAN |
"Journal of Biomaterials", article "Basis of Biomaterials" |
ADV. MATER., vol. 21, 2009, pages 4388 - 4392 |
HIDEKI YAMAMOTO, JOHOKIKO, SP VALUES, BASIS, APPLICATIONS AND CALCULATION METHODS |
HIDEKI YAMAMOTO, SP VALUES, BASIS, APPLICATIONS AND CALCULATION METHODS |
See also references of EP2826815A4 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014140978A (ja) * | 2013-01-22 | 2014-08-07 | Nanotheta Co Ltd | シート状積層体およびシート状積層体の製造方法 |
WO2014133136A1 (ja) * | 2013-03-01 | 2014-09-04 | 富士フイルム株式会社 | フィルム及びその製造方法、複合体、フィルム積層体、エッチング方法 |
JP2014193989A (ja) * | 2013-03-01 | 2014-10-09 | Fujifilm Corp | フィルム,複合体,フィルム積層体,フィルムの製造方法,及びエッチング方法 |
JP2014213550A (ja) * | 2013-04-26 | 2014-11-17 | リンテック株式会社 | 非水溶性高分子薄膜転写用部材および非水溶性高分子薄膜転写用部材の製造方法 |
JP2016539215A (ja) * | 2013-10-23 | 2016-12-15 | 東麗先端材料研究開発(中国)有限公司 | 微多孔ポリ乳酸配向フィルムおよびその応用 |
JP2016056317A (ja) * | 2014-09-11 | 2016-04-21 | 国立大学法人 東京大学 | マイクロバブル含有ポリマー溶液及び該ポリマー溶液製造方法 |
JP2016214148A (ja) * | 2015-05-20 | 2016-12-22 | 住友電気工業株式会社 | 細胞培養担体及びこれを備える細胞シート |
WO2023054591A1 (ja) * | 2021-09-30 | 2023-04-06 | 古河電気工業株式会社 | 紫外線、可視光線および/または赤外線を拡散反射する物品およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US20150056399A1 (en) | 2015-02-26 |
CN104321375B (zh) | 2019-05-10 |
CN106432761B (zh) | 2021-02-12 |
SG10201610281SA (en) | 2017-01-27 |
CN106432761A (zh) | 2017-02-22 |
EP2826815B1 (en) | 2023-05-24 |
KR102096286B1 (ko) | 2020-04-02 |
SG11201405484UA (en) | 2014-10-30 |
US20180179352A1 (en) | 2018-06-28 |
JPWO2013137260A1 (ja) | 2015-08-03 |
KR20150008060A (ko) | 2015-01-21 |
US10858490B2 (en) | 2020-12-08 |
CA2866749C (en) | 2021-06-15 |
CN104321375A (zh) | 2015-01-28 |
CA2866749A1 (en) | 2013-09-19 |
JP6322571B2 (ja) | 2018-05-09 |
EP2826815A4 (en) | 2016-04-06 |
EP2826815A1 (en) | 2015-01-21 |
US9938384B2 (en) | 2018-04-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6322571B2 (ja) | 高分子超薄膜及び多孔質高分子超薄膜 | |
EP2082869B1 (en) | Thin film-like polymer structure and method for preparing the same | |
Kustandi et al. | Fabrication of a gecko-like hierarchical fibril array using a bonded porous alumina template | |
JP5997068B2 (ja) | シート状積層体およびシート状積層体の製造方法 | |
Badmus et al. | Hierarchically electrospun nanofibers and their applications: A review | |
US10590247B2 (en) | Process for preparing free-standing films of conductive polymers | |
JP5580671B2 (ja) | 複合ナノファイバ | |
CN1511625A (zh) | 无机纳米多孔膜及其形成方法 | |
WO2004048064A1 (ja) | 微細突起構造体及びその製造方法 | |
JP5830381B2 (ja) | 高分子超薄膜分散体及びその調製方法 | |
JP2013136550A (ja) | 肌貼付用ナノファイバ積層体 | |
Shi et al. | Highly permeable nanoporous block copolymer membranes by machine-casting on nonwoven supports: An upscalable route | |
Taylor et al. | Fabrication of 2D arrays of giant liposomes on solid substrates by microcontact printing | |
Tuntanatewin et al. | One-pot fabrication of polymer micro/nano-discs via phase separation and a roll-to-roll coating process | |
JP4815496B2 (ja) | ナノポーラス表面を有する立体製品の製造方法 | |
Huang et al. | Nanotubings of titania/polymer composite: template synthesis and nanoparticle inclusion | |
Matsuyama et al. | Hydrophobic modification of fibers by pressure-induced phase-separation coupled with ultrasonic irradiation in high-pressure liquid carbon dioxide | |
Rojjanapinun et al. | Low-cost nanofabrication of isoporous nanomembranes using hybrid lithography | |
Koley et al. | Tunable morphology from 2D to 3D in the formation of hierarchical architectures from a self-assembling dipeptide: thermal-induced morphological transition to 1D nanostructures | |
JP2010065151A (ja) | 三次元網目状構造を有する多孔質膜 | |
Wei | Self-Assembled Bio-Nanomaterials: Synthesis, Characterization, and Applications | |
JP4526597B1 (ja) | 細胞培養足場の製造方法 | |
Lu et al. | Nano-modification of textile surfaces using layer-by-layer deposition methods | |
Banta | Development of biopolymeric patterned thin films | |
Muñoz-Bonilla et al. | Breath Figures: Fabrication of Honeycomb Porous Films Induced by Marangoni Instabilities |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13761776 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014504931 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2866749 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14383191 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20147027657 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013761776 Country of ref document: EP |