JPH03167306A - Extra fine fibrous substance - Google Patents
Extra fine fibrous substanceInfo
- Publication number
- JPH03167306A JPH03167306A JP1302040A JP30204089A JPH03167306A JP H03167306 A JPH03167306 A JP H03167306A JP 1302040 A JP1302040 A JP 1302040A JP 30204089 A JP30204089 A JP 30204089A JP H03167306 A JPH03167306 A JP H03167306A
- Authority
- JP
- Japan
- Prior art keywords
- fibrous material
- polymer
- fine fibrous
- solution
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000126 substance Substances 0.000 title abstract description 16
- 239000002657 fibrous material Substances 0.000 claims description 91
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000000149 argon plasma sintering Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000004745 nonwoven fabric Substances 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 61
- 239000000243 solution Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 30
- 238000001704 evaporation Methods 0.000 description 28
- 230000008020 evaporation Effects 0.000 description 28
- 239000002904 solvent Substances 0.000 description 25
- -1 take-up conditions Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 238000009987 spinning Methods 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000010041 electrostatic spinning Methods 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000001523 electrospinning Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CMVNWVONJDMTSH-UHFFFAOYSA-N 7-bromo-2-methyl-1h-quinazolin-4-one Chemical compound C1=CC(Br)=CC2=NC(C)=NC(O)=C21 CMVNWVONJDMTSH-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JHGGYGMFCRSWIZ-UHFFFAOYSA-N 2,2-dichloro-1-(4-phenoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C(Cl)Cl)=CC=C1OC1=CC=CC=C1 JHGGYGMFCRSWIZ-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- QNSFQIRYXVVLGT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(C)(C)CO.CCC(CO)(CO)CO QNSFQIRYXVVLGT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- YMRDPCUYKKPMFC-UHFFFAOYSA-N 4-hydroxy-2,2,5,5-tetramethylhexan-3-one Chemical compound CC(C)(C)C(O)C(=O)C(C)(C)C YMRDPCUYKKPMFC-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 238000011907 photodimerization Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、実質的に無配向な微細繊維状物質に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a substantially non-oriented fine fibrous material.
更に詳細に説明すると、本発明による微細繊維状物質は
、その微細性と分子配向性のないことを利用し、電気光
学的特性のすぐれた、液晶物質に浸透された微細繊維状
集合体を主体とする光散乱型液晶表示素子及び装置、プ
ラスチックレンズなどの光学的等方性透明光学部品の補
強材、耐衝撃性付与剤、或いは耐熱収縮性のすぐれた高
強力繊維、更には酵素固定化などの機能性繊維や不織布
などに用いられるものである。More specifically, the fine fibrous material according to the present invention utilizes its fineness and lack of molecular orientation to mainly consist of fine fibrous aggregates penetrated by a liquid crystal material with excellent electro-optical properties. Light scattering type liquid crystal display elements and devices, reinforcing materials for optically isotropic transparent optical parts such as plastic lenses, impact resistance agents, high strength fibers with excellent heat shrinkage resistance, and enzyme immobilization, etc. It is used in functional fibers and nonwoven fabrics.
通常の紡糸法、例えば、溶融紡糸法にて、微細繊維状物
質を作製しようとすると、押出し量の減少、或いはノズ
ルの小孔径化などにより、不安定性が増大し、連続した
紡糸が困難になる。したがって、微細繊維状物質を得る
ための試みは、独自に長期にわたってなされてきた。When attempting to produce a fine fibrous material using a normal spinning method, such as a melt spinning method, instability increases due to a decrease in the extrusion rate or a smaller pore size of the nozzle, making continuous spinning difficult. . Therefore, attempts to obtain fine fibrous materials have been made independently and for a long time.
例えば、溶融紡糸法にて、ノズル孔径の他に、口金濾過
紡糸雰囲気、引取り条件、溶剤付与条件，平均径はせい
ぜい４μｍ程度である。For example, in the melt spinning method, in addition to the nozzle hole diameter, the spinneret filtration spinning atmosphere, take-up conditions, solvent application conditions, and average diameter are about 4 μm at most.
また、ポリエチレンテレフタレートなどの、特定のボリ
マーにおいて、延伸温度を見掛け怯最大６
結晶化温度プラス２０〜６０℃にて延伸すると通常の方
法での延伸倍率のｌＯ倍以上の高倍率延伸が可能になる
ことを利用し、微細繊維を作製する方法が開発されてい
る。但し、この方法では、微細繊維状物質に大きな複屈
折が生じる。In addition, in certain polymers such as polyethylene terephthalate, if the stretching temperature is set to a maximum of 6 degrees Celsius, the crystallization temperature plus 20 to 60 degrees Celsius, it becomes possible to stretch at a high stretching ratio of more than 10 times the stretching ratio in the normal method. A method for producing fine fibers using this fact has been developed. However, with this method, large birefringence occurs in the fine fibrous material.
更にポリマー溶液をその溶媒の沸点以上にて、高圧側か
ら低圧側、或いは常圧中へ爆発的に噴出させることによ
り微細繊維状物質を得る方法も知られている。この方法
では、繊維状物質に大きな複屈折が生じ、かつ微細化の
程度も大きくない。Furthermore, a method of obtaining a fine fibrous material by explosively ejecting a polymer solution from a high pressure side to a low pressure side or into normal pressure at a temperature higher than the boiling point of the solvent is also known. In this method, large birefringence occurs in the fibrous material, and the degree of refinement is not large.
更に、微細な繊維状物質を得る方法として、ノズルから
押し出された溶融ボリマーを加熱空気にて噴出させるメ
ルトブロー法が開発されている。Furthermore, as a method for obtaining fine fibrous materials, a melt blow method has been developed in which heated air is used to blow out a molten polymer extruded from a nozzle.
この方法にては、ｌμｍ以下の比較的、微細な繊維状物
質が得られるが、平均径の不均一性が大きい他に、繊維
状物質に複屈折を生じる。微細化の程度も、まだ、不充
分である。In this method, a relatively fine fibrous material of 1 μm or less can be obtained, but in addition to the large non-uniformity of the average diameter, birefringence occurs in the fibrous material. The degree of miniaturization is still insufficient.
平均径の均一な微細繊維状物質を得る方法としてポリマ
ーの相分離を利用した高分子相互配列体繊維溶解法が発
表されている。本方法の繊維状物質は、１本のノズルか
ら複数本の微細繊維状物質を形成する“島”ポリマー成
分とその“島”ボリマー成分を内部に均一に分配されて
いる“海”ポリマー成分を紡糸し、そののち、′海１ポ
リマー成分のみを溶解、除去する方法にて得るものであ
り、充分な機械強度を有する微細繊維状物質は更に延伸
して得られる。この方法は、好みの平均径及び形状を有
する均一な繊維状物質を得ることができる。As a method for obtaining fine fibrous materials with a uniform average diameter, a polymer interlayer fiber dissolution method using phase separation of polymers has been announced. The fibrous material produced by this method consists of an "island" polymer component that forms multiple fine fibrous materials from a single nozzle, and a "sea" polymer component in which the "island" polymer component is uniformly distributed inside. It is obtained by spinning and then dissolving and removing only the polymer component, and a fine fibrous material having sufficient mechanical strength can be obtained by further stretching. This method can yield a uniform fibrous material with a desired average diameter and shape.
しかしながら平均径０．５μｍ未満の微細繊維状物質を
得るためには、不充分であり、更に延伸による細化が行
なわれている。このため、繊維状物質に大きな複屈折が
生じるという問題を生じる。However, this is insufficient to obtain a fine fibrous material with an average diameter of less than 0.5 μm, and further thinning by stretching is performed. This causes the problem that large birefringence occurs in the fibrous material.
また、高電圧をノズルを介してポリマー、或いはポリマ
ー溶液に印加する静電紡糸法も別用途を目的に開発され
てきたが、微細繊維状物質の観点からも、有望と思われ
る。しかしながら今までに知られている静電紡糸法から
得られる繊維状物質は多くの点で問題を有している。Furthermore, an electrospinning method in which a high voltage is applied to a polymer or a polymer solution through a nozzle has been developed for other purposes, but it also seems to be promising from the viewpoint of fine fibrous materials. However, the fibrous materials obtained from the electrospinning methods known up to now have many problems.
例えば、特公昭５３− ２８５４８においては、無端の
電極を用いた静電紡糸法により繊維フィルターを目的と
して最少０．４μｍの微細繊維状物質が得られているが
、繊維状物質の外径のバラツキが大きく、また繊維状物
質の長さ方向の均一性も不充分である。For example, in Japanese Patent Publication No. 53-28548, a fine fibrous material with a minimum size of 0.4 μm was obtained for the purpose of fiber filters by electrostatic spinning using an endless electrode, but the variation in the outer diameter of the fibrous material is large, and the uniformity of the fibrous material in the longitudinal direction is also insufficient.
この主因は、溶媒としあて、塩化メチレン、クロロホル
ム、四塩化炭素、ジメチルホルムアミド、などを使うた
め、蒸発速度が、速すぎるため、或いは、表面張力が大
きすぎるため等と考えられる。The main reason for this is thought to be that methylene chloride, chloroform, carbon tetrachloride, dimethylformamide, etc. are used as the solvent, so the evaporation rate is too fast, or the surface tension is too large.
また特公昭６２− １１８６１号、同６２− ６１７０
３号、同６３−５４３号、特開昭５５− ７６１５６号
、同６３− ８９１６５号に記載の繊維状物質はいずれ
もその直径が細くともｌμｍであり、応用される分野か
らの要求より太い。Also, Special Publication No. 62-11861, No. 62-6170
The fibrous materials described in Japanese Patent Application Laid-open No. 3, No. 63-543, JP-A-55-76156, and JP-A-63-89165 all have a diameter of 1 μm at the smallest, which is larger than required by the field of application.
また、この場合も溶媒はジメチルホルムアミド、ジメチ
ルホルムアミド／ブタノン（３ ： ２）等の高い表面
張力を有するもののみを用いるという問題点を有してい
る。Further, in this case as well, there is a problem in that only solvents having high surface tension such as dimethylformamide or dimethylformamide/butanone (3:2) are used.
また、特開昭５６− ５０１３２５号においては、加熱
することによりポリマーを溶融させて静電紡糸するもの
で、溶媒を使用していない。この場合は紡糸繊維状物質
の平均径も５μｍと大きく、形成された繊維状物質の複
屈折が大きくなる。Furthermore, in JP-A-56-501325, electrostatic spinning is performed by melting the polymer by heating, and no solvent is used. In this case, the average diameter of the spun fibrous material is as large as 5 μm, and the birefringence of the formed fibrous material becomes large.
以上、述べたように、ボリマー溶液を用いた静電紡糸法
は実質的に無配向の微細繊維状物質を得るには、適切な
方法と考えられるが、現状では、多くの点で不充分であ
った。As mentioned above, the electrospinning method using a polymer solution is considered to be an appropriate method for obtaining a substantially non-oriented fine fibrous material, but at present it is insufficient in many respects. there were.
本発明は、これら従来技術の有する欠点を解消し、実質
的に無配向な（即ち、複屈折の小さな）巾広い実際の用
途に供せられる微細未延伸繊維状物質を提供することで
ある。The object of the present invention is to overcome these drawbacks of the prior art and to provide a fine undrawn fibrous material that is substantially unoriented (that is, has low birefringence) and can be used in a wide range of practical applications.
本発明者らは、上記の様な課題を解決すべく、種々検討
を重ねた結果、本発明に到達した。即ち、本発明は、静
電紡糸法を用いて平均径が０．５μｍ本発明について、
更に詳細に検討する。The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have arrived at the present invention. That is, in the present invention, the average diameter is 0.5 μm using the electrospinning method,
Let's consider this in more detail.
本発明の微細繊維状物質作製に用いる静電紡糸装置の基
本的構成の一例を第１図を用いて説明する。An example of the basic configuration of an electrostatic spinning apparatus used for producing the fine fibrous material of the present invention will be explained with reference to FIG.
内部に金属端子ｌを設けたノズル２にポンブ３にて制御
された一定量のポリマー溶液４が、絶縁物質からなるチ
ューブ５により供給される。ボリマー溶液４には、ノズ
ル２を通して一端６を接地した高電圧発生装置７により
高電圧が印加される。A fixed amount of polymer solution 4 controlled by a pump 3 is supplied to a nozzle 2 having a metal terminal 1 therein through a tube 5 made of an insulating material. A high voltage is applied to the polymer solution 4 through the nozzle 2 by a high voltage generator 7 whose one end 6 is grounded.
ノズル先端８より押し出されたポリマー溶液は、高荷電
のため、＝その一端を接地された対向電極９に引き出さ
れ、この引力及びボリマー溶液内部の静電気的反撥、更
には溶媒の揮散にて微細繊維状物質ｌＯが形成され、対
向電極上９に巻き取られる。Because the polymer solution pushed out from the nozzle tip 8 is highly charged, it is drawn out to the counter electrode 9 whose one end is grounded, and due to this attraction, electrostatic repulsion inside the polymer solution, and further evaporation of the solvent, fine fibers are formed. A substance lO is formed and wound onto the counter electrode 9.
なお、形成された微細繊維状物質ｌＯは、第２図に示す
ように対向電極上９に堆積され、不織布状の繊維状集合
体１１を形成することもある。Note that the formed fine fibrous material IO may be deposited on the counter electrode 9 to form a nonwoven fabric-like fibrous aggregate 11, as shown in FIG.
実質的に無配向な微細繊維状物質を得るために紡糸に用
いられたポリマー溶液は、適切な範囲の粘度、表面張力
及び蒸発速度を有する。本発明で用いられるポリマー溶
液の表面張力は２７． ５ｄｙｎｅｓ／印以下、好まし
くは、２７． Ｏｄｙｎｅｓ／ｃｍ以下である。The polymer solution used for spinning to obtain the substantially unoriented microfibrous material has a suitable range of viscosity, surface tension, and evaporation rate. The surface tension of the polymer solution used in the present invention is 27. 5 dynes/mark or less, preferably 27. Odynes/cm or less.
２７． ５ｄｙｎｅｓ／ｃｍ以上では、形成される繊維
状物質中に粒子状の凸部を含み、均一な繊維状物質とは
ならない。27. If it is 5 dynes/cm or more, the fibrous material formed will contain particulate convex portions and will not be a uniform fibrous material.
また、蒸発速度は、酢酸ブチルを１００としたとき２４
０以下、好ましくは、２３０以下である。蒸発速度が２
４０より速くなると、繊維状物質の平均径が大きくなり
、平均径が０．５μｍ未満の微細な繊維状物質が得られ
ないと同時に、形成された繊維状物質に分子配向が生じ
るようになる。In addition, the evaporation rate is 24 when butyl acetate is taken as 100.
It is 0 or less, preferably 230 or less. Evaporation rate is 2
If the speed is higher than 40, the average diameter of the fibrous material becomes large, and a fine fibrous material with an average diameter of less than 0.5 μm cannot be obtained, and at the same time, molecular orientation occurs in the formed fibrous material.
また、本発明で用いられるポリマー溶液の溶液粘度は３
００ＣＰＳ〜２５ＣＰＳ 、好ましくは２９０ＣＰＳ〜
３０ＣＰＳである。Furthermore, the solution viscosity of the polymer solution used in the present invention is 3
00CPS~25CPS, preferably 290CPS~
It is 30CPS.
溶液粘度が３００ＣＰＳより大きくなると繊維状物質の
直径が大きくなり、平均径が０．５μｍ以下の微細な繊
維状物質が得られなくなると同時に、形成凸部を生じ、
均一性のすぐれた繊維とはならない。When the solution viscosity is greater than 300 CPS, the diameter of the fibrous material becomes large, making it impossible to obtain a fine fibrous material with an average diameter of 0.5 μm or less, and at the same time forming convex portions.
This does not result in fibers with excellent uniformity.
更にはなはだしい場合には、球状の粒子のみが、形成さ
れ繊維が形成されないことも有る。Furthermore, in extreme cases, only spherical particles may be formed and no fibers may be formed.
本発明で用いられる分子配同性を示す複屈折率範囲は、
５ Ｘ １０−”以下、好ましくは４ Ｘ １０−２
以下である。５ Ｘ １０−”以上では、通過光が繊
維状物質を通過するときに生じる位相差が無視できない
ほどになり、また、加熱時の寸法収縮も同様に生じる。The birefringence range indicating molecular conformation used in the present invention is:
5 X 10-” or less, preferably 4 X 10-2
It is as follows. When the diameter is 5 x 10-'' or more, the phase difference that occurs when the transmitted light passes through the fibrous material becomes non-negligible, and dimensional shrinkage also occurs during heating.
上記の表面張力、蒸発速度、粘度は、何れも繊％匙
維状物質書署時の環境条件における紡糸液の値であり、
液環境条件は、通常０〜１２０℃好ましくはｌＯ〜１０
０℃、湿度３０〜９０％、好ましくは４０〜６５％、気
圧０．８気圧〜１．１気圧、好ましくは０，９〜１．０
気圧を意味する。The above surface tension, evaporation rate, and viscosity are all values of the spinning solution under the environmental conditions at the time of printing the fibrous material.
The liquid environment conditions are usually 0 to 120°C, preferably lO to 10°C.
0°C, humidity 30-90%, preferably 40-65%, atmospheric pressure 0.8 atm-1.1 atm, preferably 0.9-1.0
means atmospheric pressure.
また、本発明で用いられる紡糸に用いられるボリマー溶
液の表面張力、蒸発速度、粘度、及び複屈折は以下のよ
うに定義される。Further, the surface tension, evaporation rate, viscosity, and birefringence of the polymer solution used for spinning used in the present invention are defined as follows.
ポリマー溶液の表面張力とは、ボリマ成分が全溶液中で
占める重量が比較的少ないことから、溶媒の表面張力を
もってその値とする。また混合溶媒においては、（各溶
媒の重量比（％）×各溶媒の表面張力）の総和を混合溶
媒を用いたボリマー溶液の表面張力とする。The surface tension of a polymer solution is determined by the surface tension of the solvent, since the weight of the polymer component in the entire solution is relatively small. In addition, in the case of a mixed solvent, the sum of (weight ratio (%) of each solvent x surface tension of each solvent) is taken as the surface tension of the polymer solution using the mixed solvent.
該ポリマー溶液の蒸発速度とは、当然、ポリマー溶液中
の溶媒の蒸発速度を指すが、蒸発速度の定義が簡単では
ない。本発明においては溶剤ハンドブック（産業図書、
松田種光、箱島勝、鎌苅藤行）による近似式
蒸発速度＝（蒸気圧×分子量） ／１１により蒸発速度
を定義する。したがって、真の蒸発速度を用いていると
は言えないが、本発明では蒸発速度と称して、蒸気圧×
分子量を問題にしていると考えてよい。また、混合溶媒
においては表面張力と同様で、（各溶媒の重量比（％）
×各溶媒の蒸発速度）の総和で定義される。The evaporation rate of the polymer solution naturally refers to the evaporation rate of the solvent in the polymer solution, but the definition of the evaporation rate is not easy. In the present invention, the solvent handbook (industrial book),
The evaporation rate is defined by the approximate formula evaporation rate = (vapor pressure x molecular weight) /11 according to the following formula (Tanemitsu Matsuda, Masaru Hakoshima, Fujiyuki Kamakari). Therefore, although it cannot be said that the true evaporation rate is used, in the present invention, it is referred to as the evaporation rate,
It can be thought that molecular weight is the issue. In addition, in mixed solvents, it is similar to surface tension, (weight ratio (%) of each solvent)
x evaporation rate of each solvent).
該ポリマー溶液の粘度とは、ポリマー溶液を東京計器製
Ｂ型粘度計ＢＬ−５０により測定した値とする。The viscosity of the polymer solution is a value measured using a B-type viscometer BL-50 manufactured by Tokyo Keiki.
複屈折（Δｎ）は、鋭敏色検板を装着した偏光顕微鏡に
て、得た軸方向に並べられた複数本（ｎ本）の繊維状物
質のレターデーション値（Ｒ：ｎｍ）Δｎ＝Ｒ／ＤＸｎ
複屈折は分子の配付性のパラメーターとして使われる。Birefringence (Δn) is the retardation value (R:nm) of a plurality of fibrous materials (n fibers) arranged in the axial direction obtained using a polarizing microscope equipped with a sensitive color detector plate.Δn=R/ DXn Birefringence is used as a parameter for molecular distribution.
本発明のポリマー溶液は、上記の表面張力、蒸発速度、
粘度に関する限定を満足するポリマー組成物、溶剤、硬
化剤及び光重合開始剤からなり、本発明のポリマー溶液
を構成するポリマー組成物は、溶媒、或いはモノマーに
溶解するポリマーオリゴマー或いは／及びモノマー及び
それらの混合物などである。The polymer solution of the present invention has the above surface tension, evaporation rate,
The polymer composition that composes the polymer solution of the present invention, which is composed of a polymer composition that satisfies the limitations regarding viscosity, a solvent, a curing agent, and a photopolymerization initiator, is composed of a polymer oligomer and/or monomer that is dissolved in the solvent or monomer, and such as a mixture of
本発明のポリマー組成物の特徴は、その紡糸過程にてポ
リマー組成物そのもの、或いは溶剤或いはモノマーで希
釈された溶液状態にて適当な流動性を示すことが不可欠
であると同時に、第１図、第２図の対向電極上では、形
成された繊維状物質は、すでに粘着性を示さない固体状
の性質を示すで
ことかある。The characteristics of the polymer composition of the present invention are that it is essential that the polymer composition itself or a solution state diluted with a solvent or monomer exhibits appropriate fluidity during the spinning process; On the counter electrode shown in FIG. 2, the formed fibrous material already exhibits solid-like properties that do not exhibit stickiness.
このような、性質は、ポリマー或いはポリマー混合物の
場合は、何ら問題はないが、オリゴマー或いはモノマー
は、液体或いは粘稠固体を示すことが多いため、しばし
ば問題を生じる。したがって上記のオリゴマー、或いは
モノマーは、例えば、上記、オリゴマー、或いはモノマ
ーを単独で、或いは溶媒に溶解したあとで、紡糸し、形
成された繊維状物質が第ｌ図または第２図の対向電極９
に到達する直前の空間にて、紫外線架僑などの方法にて
硬化させられる。Although such properties pose no problem in the case of polymers or polymer mixtures, they often pose a problem since oligomers or monomers are often liquids or viscous solids. Therefore, the above oligomer or monomer can be spun, for example, alone or after being dissolved in a solvent, and the formed fibrous material can be used as the counter electrode 9 in FIG. 1 or 2.
In the space just before the material reaches the surface, it is cured using methods such as ultraviolet rays.
なお、上記オリゴマー、或いはモノマーは、紡揮 糸条件下にて爆発しないものを選ぶことは当然である。In addition, the above oligomer or monomer is It is natural to choose a material that will not explode under thread conditions.
また、直径の細い微細繊維状物質を得るためには、ポリ
マー溶液中のポリマー組成物濃度が低い方が適切な場合
もあり、該ポリマー組成物濃度は、該溶液の粘度にも依
存するが、４０％以下が好ましい。In addition, in order to obtain a fine fibrous substance with a small diameter, it may be appropriate to have a low concentration of the polymer composition in the polymer solution, and the concentration of the polymer composition also depends on the viscosity of the solution. It is preferably 40% or less.
用いられるポリマーとしては、例えば、ポリビニルアル
コール、ポリビニルブチラール、ポリ塩化ビニル、種々
のセルロース誘導体、ポリメチルメタクリレート、ポリ
カーポネート、ポリアクリロニトリル、ポリアミド、ポ
リエチレンテレフタレート、ボリスルホン、ポリエーテ
ルスルホン、ポリエーテルイミドなどの熱可塑性ポリマ
ーが挙げられる。Examples of polymers used include polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, various cellulose derivatives, polymethyl methacrylate, polycarbonate, polyacrylonitrile, polyamide, polyethylene terephthalate, borisulfone, polyethersulfone, polyetherimide, etc. Thermoplastic polymers may be mentioned.
オリゴマー或いはモノマーとしては、上記熱可塑性ポリ
マーの低分子量オリゴマーの他に、ポリマー形成性硬化
性ビニル化合物、ポリマー形成性硬化性エポキシ化合物
、ポリマー形成性硬化性ウレタン化合物などが挙げられ
る。Examples of oligomers or monomers include, in addition to the low molecular weight oligomers of the thermoplastic polymers mentioned above, polymer-forming curable vinyl compounds, polymer-forming curable epoxy compounds, polymer-forming curable urethane compounds, and the like.
ポリマー形成性硬化性ビニル化合物としては、例えば、
スチレン、酢酸ビニルなど、ラジカルにより重合硬化す
るものであれば特に制限はないが、特に好適な例として
、次のような分子の末端ないし側面に（メタ）アクリロ
イル基を１個または２個以上有する硬化型アクリル系化
合物を挙げることができる。Examples of the polymer-forming curable vinyl compound include:
There are no particular restrictions on materials that can be polymerized and cured by radicals, such as styrene and vinyl acetate, but particularly preferred examples include the following molecules that have one or more (meth)acryloyl groups at the end or side of the molecule. Examples include curable acrylic compounds.
その第ｌは、ポリオール（メタ）アクリレート類であり
、ボリオール例えばエチレングリコール、ジエチレング
リコール、トリメチロールプロパンネオペンチルグリコ
ール、ペンタエリスリトールなどと、（メタ）アクリル
酸との反応生成物である。The first are polyol (meth)acrylates, which are reaction products of polyols such as ethylene glycol, diethylene glycol, trimethylolpropane neopentyl glycol, pentaerythritol, etc., and (meth)acrylic acid.
その第２は、ジオールとジカルボン酸とを縮合してえら
れる繰返し単位が２〜２０の末端ヒドロキシル基を有す
るポリエステルと（メタ）アクリル酸との反応生威物で
あるポリエステルジ（メタ）アクリレート類である。The second type is polyester di(meth)acrylate, which is a reaction product of a polyester whose repeating unit has 2 to 20 terminal hydroxyl groups obtained by condensing a diol and a dicarboxylic acid, and (meth)acrylic acid. It is.
その第３は、ポリエボキシ化合物の（メタ）アＡなどの
ヒドロキシル基含有化合物とエビクロルヒドリンとから
誘導されるポリグリ井シジルエーテル類あるいは多価カ
ルボン酸とエビクロルヒドリンとから誘−導されるポリ
グリシジルエーテル類などのポリエポキシ化合物類が挙
げられる。The third type is polyglycidyl ethers derived from a hydroxyl group-containing compound such as (meth)A of a polyepoxy compound and shrimp chlorohydrin, or polyhydric acid derivatives derived from a polyhydric carboxylic acid and shrimp chlorohydrin. Examples include polyepoxy compounds such as polyglycidyl ethers.
その第４は、多官能ウレタンアクリレート類であり、こ
れらはポリイソシアネート化合物とヒドロキシル基含有
（メタ）アクリル系モノマーまたは（メタ）アクリロイ
ル基とヒドロキシル基とを含有するオリゴマーとを反応
させてえられるものである。The fourth type is polyfunctional urethane acrylates, which are obtained by reacting a polyisocyanate compound with a (meth)acrylic monomer containing a hydroxyl group or an oligomer containing a (meth)acryloyl group and a hydroxyl group. It is.
その第５は、（メタ）アクリル系モノマー類であり、そ
の例としては、，（メタ）アクリル酸エチル、（メタ）
アクリル酸プロビル、（メタ）アクリル酸ヘキシルなど
である。The fifth is (meth)acrylic monomers, examples of which are (meth)ethyl acrylate, (meth)acrylate, and (meth)acrylic monomers.
These include probyl acrylate and hexyl (meth)acrylate.
その第６は、無水マレイン酸などの不飽和多価カルボン
酸と他の多価カルポン酸および多価アルコールとを縮合
してえられる、いわゆる不飽和ポリエステルである。The sixth type is a so-called unsaturated polyester obtained by condensing an unsaturated polycarboxylic acid such as maleic anhydride with another polycarboxylic acid and a polyhydric alcohol.
更に光二量化することにより重合硬化するその他の、例
えば、ポリケイ酸ビニル、ポリシンナミリデン酢酸ビニ
ル、フェニレンジアクリル酸エステルなどが挙げられる
。Furthermore, other materials that are polymerized and cured by photodimerization, such as polyvinyl silicate, polycinnamylidene vinyl acetate, and phenylene diacrylic acid ester, may be mentioned.
また、本発明に用いる光重合開始剤としては、ベンゾイ
ンメチルエーテル、ベンゾイルｎ−プチルエーテル、ペ
ンゾインフェニルエーテル、ナフトキノン、ペンゾフエ
ノン、ピバロインエチルエーテル、ペンゾイルバーオキ
シド、ｐ−ｔ−プチルジクロロネアセトフェノン、２，
２−ジエトキシアセトフェノン、２，２−ジクロルー４
−フエノキシアセトフェノン、α−ヒドロキシブチルフ
エノン、ジベンゾスロン、ペンゾフエノンアミン系（Ｎ
−メチルジエタノールアミン、トリエチルアミンなど）
などがあげられ、その配合量は組成物中おおよそ１−１
０重量％の範回から適宜適量選択する。The photopolymerization initiators used in the present invention include benzoin methyl ether, benzoyl n-butyl ether, penzoin phenyl ether, naphthoquinone, penzophenone, pivaloin ethyl ether, penzoyl peroxide, pt-butyl dichloromethane, Acetophenone, 2,
2-diethoxyacetophenone, 2,2-dichloro-4
-Phenoxyacetophenone, α-hydroxybutylphenone, dibenzothrone, penzophenone amines (N
-methyldiethanolamine, triethylamine, etc.)
etc., and the blending amount is approximately 1-1 in the composition.
An appropriate amount is selected from a range of 0% by weight.
また、ボリマー形成性硬化性エボキシ化合物【よ、繊維
状集合体形成時に固体状を呈するものが好ましく、例え
ば、エポキシ当量が１５０〜５０００の範囲であるあビ
スフェノールＡジグリシジルエーテノレ、ビスフェノー
ルＦジグリシジルエーテル、ヘキサヒド口ビスフェノー
ルＡジグリシジルエーテノレ、ネオペンチルグリコール
ジグリシジルエーテル、フタル酸ジグリシジルエステル
、ポリプロピレングリコールジグリシジルエーテルなど
の２官能性エポキシ化合物、エポキシ当量が１３０〜３
５０の範囲であるトリグリシジルイソシアヌレート、テ
トラグリシジルジアミノジフエニルメタン、テトラグリ
シジルメタキシレンジアミンなどの多官能性エボキシ樹
脂が例示される。In addition, polymer-forming curable epoxy compounds (such as bisphenol A diglycidyl ether, bisphenol F diglycidyl) having an epoxy equivalent in the range of 150 to 5,000 are preferred. Difunctional epoxy compounds such as ether, hexahydride, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, phthalic acid diglycidyl ester, polypropylene glycol diglycidyl ether, etc., with an epoxy equivalent of 130 to 3
Polyfunctional epoxy resins such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, and tetraglycidyl metaxylene diamine, which have a range of 50 to 50, are exemplified.
また、本発明に用いられるボリマー形成性硬化性エポキ
シ化合物の硬化剤は、該エポキシ化合物と共に、繊維状
集合体形成時に固体状を呈するものが好ましく、例えば
、重付加型としては、ジエチレントリアミン、トリエチ
レンテトラミン、テトラエチレンベンタミン、ジエチル
アミノブロピルアミン、及びそれらの変性物など、メン
センジアミン、インホロンジアミン、Ｎ−アミノエチル
ピペラジン、ビス（４−アミノー３−メチルシクロヘキ
シル）メタン及びその変性物、ｍ−キシレンアミン、ジ
アミノジフェニルメタン、ジアミノジフエニルスルホン
及びその変性物などのポリアミン、無水フタル酸、テト
ラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メ
チルテトラヒド口無水フタル酸、無水メチルナジック酸
、無水クロレンディック酸、無水ピロメリット酸、ペン
ゾフェノンテトラカルボン酸無水物、エチレングリコー
ルビス（アンヒドロトリメート）、メチルシクロヘキセ
ンテトラカルボン酸無水物などの酸無水物、フェノール
ノボラック、ポリメルカプトンなどが挙げられる。また
触媒型としては、２．４．６−トリス（ジメチルアミノ
メチル）フェノール、２−エチル−４−メチルイミダゾ
ール、ＢＰ．モノエチルアミン錯体などが挙げられる。Further, the curing agent for the polymer-forming curable epoxy compound used in the present invention is preferably one that exhibits a solid state when forming a fibrous aggregate together with the epoxy compound. For example, as a polyaddition type, diethylene triamine, triethylene Tetramine, tetraethylenebentamine, diethylaminopropylamine, and modified products thereof, etc., menzendiamine, inphorondiamine, N-aminoethylpiperazine, bis(4-amino-3-methylcyclohexyl)methane and modified products thereof, m - Polyamines such as xylene amine, diaminodiphenylmethane, diaminodiphenylsulfone and modified products thereof, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, chlorendic anhydride Examples include acids, acid anhydrides such as pyromellitic anhydride, penzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimate), and methylcyclohexenetetracarboxylic anhydride, phenol novolak, and polymercapton. Catalytic types include 2.4.6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, BP. Examples include monoethylamine complex.
本発明では、上に挙げたポリマー形成性硬化性ビニル化
合物及び光重合開始剤、或いはポリマ−形成性硬化性エ
ポキシ化合物及び硬化剤、或いはボリマー形或性硬化性
イソシアネート化合物及び硬化剤は、形成繊維状物質の
使用目的を考慮して、それぞれ単独、或いは複数個の組
合わせを行なえばよい。In the present invention, the above-mentioned polymer-forming curable vinyl compound and photopolymerization initiator, or polymer-forming curable epoxy compound and curing agent, or polymer-forming curable isocyanate compound and curing agent are used to form fibers. Each of these substances may be used alone or in combination, taking into consideration the intended use of the substance.
本発明に用いる溶剤は、前述したごとく、紡糸後、繊維
状物質を形成する直前の空間中で、蒸発、飛散すること
が不可欠であり、この目的から沸点温度が１５０℃以上
の揮発しにくい溶媒を単独で、或いは、そのような溶媒
が混合比２０％以上を占める混合溶媒では、使用するこ
とは好ましくない。As mentioned above, it is essential for the solvent used in the present invention to evaporate and scatter in the space immediately before forming the fibrous material after spinning, and for this purpose, a solvent with a boiling point temperature of 150°C or higher that is difficult to volatilize. It is not preferable to use these alone or in a mixed solvent in which such a solvent accounts for 20% or more of the mixing ratio.
本発明に用いられる溶剤としては、水、メタノール、エ
タノール、ｎ−プロパノール、イソブロパノール、ｎ−
ブタノール、ｓｅｅ−ブタノール、ジアセトンアルコー
ルなどのアルコール類、ギ酸メチル、酢酸メチル、酢酸
エチル、酢酸イソブロビル、酢酸ｎ−ブチルなどのエス
テル類、アセトン、メチルエチルケトン、メチルイソブ
チルケトン、シクロヘキサノン、イソホロンなどのケト
ン類、メチルセロソルブ、エチルセロソルブ、ブチルセ
ロソルブなどのセロソルブ類、テトラヒドロフラ．ン．
、ジオキサンなどのエーテル類、Ｎ，Ｎ’一ジメチルア
セトアミドなどのアミド類、メチレンクロライド、クロ
ロホルムなどの塩素系溶媒などの溶媒の中から蒸発速度
、表面張力などを考慮して単独もしくは、多成分混合系
で使用できる。Solvents used in the present invention include water, methanol, ethanol, n-propanol, isopropanol, n-
Alcohols such as butanol, see-butanol, diacetone alcohol, esters such as methyl formate, methyl acetate, ethyl acetate, isobrobyl acetate, n-butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, etc. , cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and tetrahydrofura. hmm.
, ethers such as dioxane, amides such as N,N'-dimethylacetamide, chlorine-based solvents such as methylene chloride, chloroform, etc., either singly or as a multi-component mixture, taking into consideration evaporation rate, surface tension, etc. Can be used in the system.
また、本発明で用いられるポリマー溶液は、繊維状物質
形成時、或いは、使用時に必要な改良を折はＩＯＸＩＯ
−１と極めて大きかった。In addition, the polymer solution used in the present invention may be modified with IOXIO at the time of fibrous material formation or use.
-1, which was extremely large.
以上のボリマー溶液を、第１図にて、概説した静電紡糸
装置を用いて紡糸し、繊維状物質を形成する。チューブ
５を通してノズル２に供給されるボリマー溶液の量は、
ノズルの先端８の孔径、印加電圧量などに依存するが、
通常０．２−〜４０−／ｈ『好ましくは０． ５ｄ 〜
２０ｇ／ ／ ｈｒである。４０ｔｄ／ｈｒ以上では、
ボリマー溶液に充分な電荷が得られず、細化が不充分に
なり、結果的に、平均径０．５μｍ以上の繊維状物質と
なり、微細繊維状物質は得られない。他方ｏ．２ｍ／／
ｈｒ 以下の場合は、ノズル先端にて細化前のポリマ
ー溶液からの溶媒の蒸発、飛散が大きく、表面が部分的
に乾燥し、粒子状凸部を有する不均一な繊維状物質が得
られる。The above polymer solution is spun using the electrostatic spinning apparatus outlined in FIG. 1 to form a fibrous material. The amount of polymer solution supplied to the nozzle 2 through the tube 5 is
It depends on the hole diameter of the nozzle tip 8, the amount of applied voltage, etc.
Usually 0.2-40-/h (preferably 0.2-40-/h) 5d~
20g//hr. At 40td/hr or more,
A sufficient charge cannot be obtained in the polymer solution, resulting in insufficient thinning, resulting in a fibrous material with an average diameter of 0.5 μm or more, and a fine fibrous material cannot be obtained. On the other hand o. 2m//
hr or less, the evaporation and scattering of the solvent from the polymer solution before thinning at the nozzle tip is large, the surface is partially dried, and a non-uniform fibrous material having particulate convex portions is obtained.
金属端子ｌを通してノズル２に印加される高電圧は、使
用する繊維状物質の用途に依存するが、５ｋｖ 〜４５
ｋｖの範囲であり、好ましくは１０ｋｖ 〜４０ｋｖで
ある。The high voltage applied to the nozzle 2 through the metal terminal l depends on the application of the fibrous material used, but is between 5 kv and 45 kv.
kv, preferably 10 kv to 40 kv.
１０ｋｖ〜４０ｋｖの範囲では、形成される繊維状物質
の直径に大きな影響を与えない。４５ｋｖ以上では、電
荷が多すぎるためか紡糸状態が不安定になる。In the range of 10kv to 40kv, the diameter of the fibrous material formed is not significantly affected. At 45 kV or more, the spinning state becomes unstable, probably because there are too many charges.
５ｋｖ以下では、細化が生じず、繊維状物質は形成され
ず、液滴が落下する。Below 5 kV, no attenuation occurs, no fibrous material is formed, and droplets fall.
以下に、実施例に基いて説明するが、本発明はこれらに
限定されるものではない。The present invention will be explained below based on Examples, but the present invention is not limited thereto.
実施例ｌ
繊維状物質を形成するためのポリマーとしてポリビニル
ブチラール（***ヘキスト社製、Ｂ６０Ｔ）を用い、こ
れをｎ−プロビルアルコールとアセトニトリルとの重量
比でｌ＝１の混合溶媒に溶解し１０％溶液を得た。この
溶液の２５℃での蒸発速度は２３４，表面張力は２１．
５ｄｙｎｅｓ／ｃｍ ，粘度は７０ＣＰＳであった。Example 1 Polyvinyl butyral (manufactured by Hoechst AG, West Germany, B60T) was used as a polymer for forming a fibrous substance, and it was dissolved in a mixed solvent of n-propyl alcohol and acetonitrile in a weight ratio of l=1. % solution was obtained. The evaporation rate of this solution at 25°C is 234, and the surface tension is 21.
The viscosity was 5 dynes/cm 2 and 70 CPS.
その後、静電紡糸装置を用いて上記ボリた。Thereafter, the above-mentioned yarn was spun using an electrostatic spinning device.
得られた繊維状物質を走査型電子顕微鏡を用いて測定し
たところ平均直径は０．２０μｍであり、また０．５μ
ｍ未満の繊維状物質は、頻度、確率的測定の結果、確率
的に９５％であった。When the obtained fibrous material was measured using a scanning electron microscope, the average diameter was 0.20 μm and 0.5 μm.
As a result of frequency and probability measurements, the probability of fibrous substances having a diameter of less than m was 95%.
また、粒子状凸部の体積比率は４％であった。Further, the volume ratio of the particulate convex portions was 4%.
偏光顕微鏡にて測定した繊維状物質の複屈折はｌ．２Ｘ
１０−’であった。The birefringence of a fibrous material measured with a polarizing microscope is l. 2X
It was 10-'.
更に、この繊維状物質の浸漬法による屈折率評価法にて
得た屈折率は１．５１５であった。Furthermore, the refractive index obtained by the refractive index evaluation method using the immersion method of this fibrous material was 1.515.
比較例ｌ
実施例ｌにおいて、使用した混合溶媒の代りに、！−
溶媒としてセ４ブロビルアルコールを用い、６％溶液を
得た。このポリマー溶液の２５℃での蒸発速度は２００
、表面張力は２１． ７ｄｙｎｅｓ／ｃｍ ，粘度は１
５０ＣＰＳであった。Comparative Example 1 In Example 1, instead of the mixed solvent used,! - Using sebrovir alcohol as a solvent, a 6% solution was obtained. The evaporation rate of this polymer solution at 25°C is 200
, the surface tension is 21. 7dynes/cm, viscosity is 1
It was 50 CPS.
以下実施例ｌと同様に静電紡糸法で繊維状物質を得た。Thereafter, a fibrous material was obtained using the electrostatic spinning method in the same manner as in Example 1.
得られた繊維状物質の平均直径は０．３１μｍで、粒子
状凸部の体積比率は４０％と増加した。The average diameter of the obtained fibrous material was 0.31 μm, and the volume ratio of particulate convex portions increased to 40%.
比較例２
比較例ｌにおいて、ポリマー濃度を６％とした代りに、
９％のポリマー溶液を用いた。このポリマー溶液の蒸発
速度、表面張力は比較例１とほぼ同じであり、粘度は１
７０ＣＰＳであった。得られた繊維状物質の平均直径は
０．６０μと大きくなり、粒子状凸部の体積比率は、５
％であった。また直径０．５μｍ未満の繊維状物質は確
率的に２５％であった。Comparative Example 2 In Comparative Example 1, instead of setting the polymer concentration to 6%,
A 9% polymer solution was used. The evaporation rate and surface tension of this polymer solution are almost the same as those of Comparative Example 1, and the viscosity is 1
It was 70CPS. The average diameter of the obtained fibrous material was as large as 0.60μ, and the volume ratio of the particulate convex portions was 5.
%Met. Furthermore, the probability of fibrous substances having a diameter of less than 0.5 μm was 25%.
実施例２
繊維状物質を形成するためのポリマーとしてポリビニル
ブチラール（積水化学工業（ｍ製、ＢＭ５）を用い、こ
れをシクロヘキサノンとアセトニトリルとの重量比で１
＝１の混合溶媒に溶解し７％溶液を得た。この溶液の２
５℃での蒸発速度は１８３、表面張力は２７． Ｏｄｙ
ｎｅｓ／ｃｍ、粘度は６４ＣＰＳであった。Example 2 Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd. (M), BM5) was used as a polymer for forming a fibrous material, and it was mixed with cyclohexanone and acetonitrile in a weight ratio of 1.
=1 to obtain a 7% solution. 2 of this solution
The evaporation rate at 5°C is 183, and the surface tension is 27. Ody
nes/cm, and the viscosity was 64 CPS.
以下、実施例ｌと同様に静電紡糸法で繊維状物質を得た
。Thereafter, a fibrous material was obtained using the electrostatic spinning method in the same manner as in Example 1.
得られた繊維状物質の平均直径は０．４５μｍで、粒子
状凸部の体積比率は５％であった。また、直径０．５μ
ｍ未満の繊維状物質は確率的に８６％であった。偏光顕
微鏡にて測定した繊維状物質の複屈折幸は、 ｌ．３Ｘ
１０−”であった。The average diameter of the obtained fibrous material was 0.45 μm, and the volume ratio of particulate convex portions was 5%. Also, the diameter is 0.5μ
The probability of fibrous material having a diameter of less than m was 86%. The birefringence of the fibrous material measured with a polarizing microscope is: l. 3X
It was 10-”.
比較例３
実施例２において、使用した混合溶媒の代りに溶媒とし
てシクロヘキサノン、メタノール、アセトンを重量比４
６：５３：ｌで混合した溶媒を用い、８％溶液を得た。Comparative Example 3 In Example 2, cyclohexanone, methanol, and acetone were used as solvents in a weight ratio of 4 instead of the mixed solvent used.
An 8% solution was obtained using a 6:53:l mixed solvent.
このポリマー溶液の２５℃での蒸発速度は１８２、表面
張力は２８． ３ｄｙｎｅｓ／ｃｍ ，粘度は３５ＣＰ
Ｓであった。The evaporation rate of this polymer solution at 25°C is 182, and the surface tension is 28. 3dynes/cm, viscosity is 35CP
It was S.
以下実施例２と同様に静電紡糸法で繊維状物質を得た。Thereafter, a fibrous material was obtained by electrospinning in the same manner as in Example 2.
得られた繊維状物質の平均直径は０．３０μｍで、粒子
状凸部の体積比率は４５％と増加した。The average diameter of the obtained fibrous material was 0.30 μm, and the volume ratio of particulate convex portions increased to 45%.
比較例４
比較例３において、ポリマー濃度を８％とした代りに、
１１％のポリマー溶液を用いた。このポリマー溶液の蒸
発速度、表面張力は比較例３とほぼ同じであり、粘度は
１８５ｃＰｓであった。得られた繊維状物質の平均直径
は０．５０μｍと大きくなり、粒子状凸部の体積比率は
５％であった。また直径０．５μｍ未満の繊維状物質は
確率的に３５％であった。Comparative Example 4 In Comparative Example 3, instead of setting the polymer concentration to 8%,
An 11% polymer solution was used. The evaporation rate and surface tension of this polymer solution were almost the same as those of Comparative Example 3, and the viscosity was 185 cPs. The average diameter of the obtained fibrous material was as large as 0.50 μm, and the volume ratio of particulate convex portions was 5%. Furthermore, the probability of fibrous substances having a diameter of less than 0.5 μm was 35%.
実施例３
繊維状物質を形成するための固体ボリマーとして、べヘ
ニルメタクリレート５０部、エポキシエステル３００２
Ａ （共栄社油脂製：ビスフェノールＡボリオキシエ
チレン←１１モル付加物のジグリシジルエーテルのアク
リル酸付加物）２５部、ペンタエリスリトールテトラア
クリレートｌＯ部、ポリメチルメタクリレート（住友化
学製：スミペックスＢＭ｝１０） １５部の混合物を用
い、これをｎ−プロビルアルコールとアセトニトリルと
の重量比でｌ：ｌの混合溶媒に溶解しｌＯ％溶液を得た
。この溶液の２５℃での蒸発速度は２３４、表面張力は
２１． ５ｄｙｎｅｓ／ｃｍ，粘度は７０ＣＰＳであっ
た。Example 3 50 parts of behenyl methacrylate, 3002 parts of epoxy ester as solid polymers to form fibrous material
A (manufactured by Kyoeisha Yushi: acrylic acid adduct of diglycidyl ether of bisphenol A polyoxyethylene ← 11 mole adduct) 25 parts, 10 parts of pentaerythritol tetraacrylate, polymethyl methacrylate (manufactured by Sumitomo Chemical: Sumipex BM} 10) 15 This was dissolved in a mixed solvent of n-propyl alcohol and acetonitrile in a weight ratio of 1:1 to obtain a 10% solution. The evaporation rate of this solution at 25°C is 234, and the surface tension is 21. The viscosity was 5 dynes/cm and 70 CPS.
光重合開始剤として、ベンゾインエチルエーテル０．１
ｇを１００ｇの上記硬化性ビニル化合物溶液に加え、一
様に溶解するまでかきまぜた。As a photopolymerization initiator, benzoin ethyl ether 0.1
g was added to 100 g of the above curable vinyl compound solution and stirred until uniformly dissolved.
以下、実施例ｌと同様に静電紡糸法で繊維状物質を得た
。その後、この繊維状物質を高圧水銀灯（理工化学社製
： ＵＶＬ−４００Ｐ）により約１分間露光し架橋処理
を行なった。Thereafter, a fibrous material was obtained using the electrostatic spinning method in the same manner as in Example 1. Thereafter, this fibrous material was exposed to light for about 1 minute using a high-pressure mercury lamp (manufactured by Riko Kagaku Co., Ltd.: UVL-400P) to perform a crosslinking treatment.
得られた繊維状物質の平均直径は０．２７μｍで、粒子
状凸部の体積比率は０％であった。また、直径０．５μ
ｍ未満の繊維状物質は確率的に９０％であった。偏光顕
微鏡にて測定した繊維状物質の複屈折は１．ＯＸｌＯ−
”であった。The average diameter of the obtained fibrous material was 0.27 μm, and the volume ratio of particulate convex portions was 0%. Also, the diameter is 0.5μ
The probability of the fibrous material being less than m was 90%. The birefringence of the fibrous material measured with a polarizing microscope is 1. OXlO-
"Met.
更に、この繊維状物質の浸漬法による屈折率評価法にて
得た屈折率は１． ４９９であった。Furthermore, the refractive index obtained by the refractive index evaluation method using the immersion method of this fibrous material was 1. It was 499.
実施例４
繊維状物質を形成するためのポリマーとして、ポリアク
リロニトリル（ＳＣＩＮＴＩＦＩＣ ＰＯＬＹＭＥＲ
ＰＲＯＤＵＣＴ社製）を用い、これをＮ，Ｎ−２−メチ
ルホルムアルデヒドとアセトニトリルとの重量比を４＝
６の混合溶媒に溶解し７％溶液を得た。この溶液の２５
℃での蒸発速度は２０８、表面張力は２５， ５ｄｙｎ
ｅ５／ｃｍ，粘度は８７ＣＰＳであった。Example 4 Polyacrylonitrile (SCINTIFIC POLYMER) was used as a polymer for forming a fibrous material.
(manufactured by PRODUCT), and the weight ratio of N,N-2-methylformaldehyde and acetonitrile was set to 4=
6 to obtain a 7% solution. 25 of this solution
The evaporation rate at °C is 208, and the surface tension is 25.5 dyn.
e5/cm, and the viscosity was 87 CPS.
以下、実施例ｌと同様に静電紡糸法で繊維状物質を得た
。得られた繊維状物質の平均直径は０．４５μｍで、粒
子状凸部の体積比率は４％であった。Thereafter, a fibrous material was obtained using the electrostatic spinning method in the same manner as in Example 1. The average diameter of the obtained fibrous material was 0.45 μm, and the volume ratio of particulate convex portions was 4%.
また、直径０．５μｍ未満の繊維状物質は確率的に８１
％であった。偏光顕微鏡にて測定した繊維状物質の複屈
折は２３Ｘ １０−’であった。Furthermore, fibrous substances with a diameter of less than 0.5 μm have a probability of 81
%Met. The birefringence of the fibrous material measured using a polarizing microscope was 23×10-'.
実施例５
繊維状物質を形成するためのポリマーとしてポＮ，Ｎ−
ジメチルホルムアミド、ｉ−ブタノールとの重量比で１
８：３２：５０の混合溶媒に溶解し、参軒６％溶液を得
た。この溶液のｌＯ℃での蒸発速度は２２９、表面張力
は２６． ６ｄｙｎｅｓ／ｃｍ ，粘度は１０５ＣＰＳ
であった。Example 5 Po-N,N- as a polymer for forming fibrous material
Dimethylformamide, weight ratio of i-butanol: 1
It was dissolved in a mixed solvent of 8:32:50 to obtain a 6% Sanxeon solution. The evaporation rate of this solution at lO°C is 229, and the surface tension is 26. 6dynes/cm, viscosity is 105CPS
Met.
以下実施例１と同様に静電紡糸法で繊維状物嘗を得た。Thereafter, a fibrous material was obtained using the electrostatic spinning method in the same manner as in Example 1.
得られた繊維状物質の平均直径は０．４４４ｍで、粒子
状凸部の体積比率は６％であった。また、直径０，５μ
ｍ未満の繊維状物質は確率的に８％であった。偏光顕微
鏡にて測定した繊維状物負の複屈折は３ Ｘ １０−”
であった。The average diameter of the obtained fibrous material was 0.444 m, and the volume ratio of particulate convex portions was 6%. Also, the diameter is 0.5μ
The probability of fibrous substances less than m was 8%. The negative birefringence of the fibrous material measured using a polarizing microscope is 3 x 10-"
Met.
比較例５
繊維状物質を形成するためのポリマーとしてべヘニルメ
タクリレート７５部、エポキシエステル３００２Ａ（共
栄社油脂製：ビスフェノールＡポリオキシエチレン←弓
２モル付加物のシグリシジルエーテルへのアクリル酸付
加物）２５部、ペンタエリスリールテトラアクリレート
ｌｏ部、を用いた。Comparative Example 5 As a polymer for forming a fibrous substance, 75 parts of behenyl methacrylate and epoxy ester 3002A (manufactured by Kyoeisha Yushi Co., Ltd.: bisphenol A polyoxyethylene ← acrylic acid adduct of 2 mole adduct of bow to siglycidyl ether) 25 1 part and 1 part of pentaerythryl tetraacrylate were used.
なお、光重合開始剤としてベンゾイルエチルエーテル１
部を上記ペンタエリスリトールテトラアクリレート中に
溶解してある。In addition, benzoylethyl ether 1 is used as a photopolymerization initiator.
part of the pentaerythritol tetraacrylate described above.
上記硬化製ビニル化合物を８０℃に加温し液状にした上
で撹拌混合した。この温度に保った状態で融ポリマーを
流量１．０ｃｃ／時、ノズル電圧２５ＫＶＦ？で紡糸し
、繊維状物質を得た。The above-mentioned cured vinyl compound was heated to 80° C. to make it into a liquid state, and then stirred and mixed. While maintaining this temperature, the flow rate of the molten polymer is 1.0cc/hour, and the nozzle voltage is 25KVF? A fibrous material was obtained by spinning.
その後、実施例３と同様にして該繊維状物質の架僑処理
を行なった。Thereafter, the fibrous material was subjected to cross-dressing treatment in the same manner as in Example 3.
得られた繊維状物質の平均直径は０．４０μｍで粒子状
凸部の体積比率は０であった。また、直径０．５μｍ未
満の繊維状物質は確率的に６０％であった。但し偏光顕
微鏡にて測定した繊維状物質の複屈折はＩＯＸＩＯ−”
と極めて大きかった。The average diameter of the obtained fibrous material was 0.40 μm, and the volume ratio of particulate convex portions was 0. Furthermore, the probability of fibrous substances having a diameter of less than 0.5 μm was 60%. However, the birefringence of the fibrous material measured with a polarizing microscope is IOXIO-"
It was extremely large.
以上に述べたように本発明の蒸発速度、表面張力、或い
は粘度を調整したボリマー溶液を用いて静電紡糸法にて
得た繊維状物質は、平均径が０．５μｍ以下であり、ま
た実質的に複屈折を生じないため、更に、延伸してより
微細繊維状物質を製造することができるとともに、巾広
い種々の用途に用いられる。As described above, the fibrous material obtained by electrospinning using the polymer solution with adjusted evaporation rate, surface tension, or viscosity of the present invention has an average diameter of 0.5 μm or less and a substantially Because it does not produce birefringence, it can be drawn to produce finer fibrous materials, and is used in a wide variety of applications.
（１） 液晶に浸透された微細繊維状集合体を主体と
する被浸透性物体層を有する散乱型液晶装置。(1) A scattering type liquid crystal device having a permeable object layer mainly composed of fine fibrous aggregates permeated with liquid crystal.
この方式は、基本的には液晶分子の常光屈折率と支持媒
体の屈折率とを一致させ、電圧を印加して液晶分子の配
向が揃うときには透明状態を表示し、電圧無印加のとき
には液晶分子の配向の乱れによる光散乱状態を表示する
ものである。無配向性のかつ、可視光線の波長以下の直
径の微細繊維状物質を用いることにより、上記の屈折率
の一致を、緩和させ、かつ電圧印加時の透明性を格段に
向上させることができる。This method basically matches the ordinary refractive index of the liquid crystal molecules with the refractive index of the supporting medium, and when a voltage is applied and the alignment of the liquid crystal molecules is aligned, a transparent state is displayed, and when no voltage is applied, the liquid crystal molecules It displays the state of light scattering due to disordered orientation. By using a fine fibrous material that is non-oriented and has a diameter less than the wavelength of visible light, it is possible to relax the above-mentioned matching of refractive indexes and to significantly improve transparency when voltage is applied.
（２）光学的等方性透明材料
細繊維状物質はマトリックス材料との屈折率一致を厳密
にしなくても、微細繊維状物質とマトリックス材料との
間での光散乱を生じず、また、光の位相を変化させない
ため、光学部品としてのプラスチックレンズ、或いはコ
ンタクトレンズなどの光学的等方性透明光学部品の補強
材、柔軟性付与材、或いは耐衝撃性付与材に用いられる
。(2) Optically isotropic transparent material The fine fibrous material does not cause light scattering between the fine fibrous material and the matrix material, even if the refractive index does not match strictly with the matrix material. Since it does not change the phase of optical components, it is used as a reinforcing material, a flexibility imparting material, or an impact resistance imparting material for optically isotropic transparent optical components such as plastic lenses or contact lenses.
その他、寸法安定性のすぐれた高強度繊維状物質或いは
繊維表面に結合された酵素、微生物、或いは機能性官能
基を利用した不織布、或いは繊維状集合体などに用いら
れる。In addition, it is used for high-strength fibrous materials with excellent dimensional stability, nonwoven fabrics, fibrous aggregates, etc. that utilize enzymes, microorganisms, or functional groups bonded to the fiber surface.
第１図及び第２図は、本発明による微細繊維状物資を製
造する方法を略図的に示した図である。
第２図
手続？ｒ１３正書
（方式）
平成２年３月２２日1 and 2 are diagrams schematically illustrating a method for manufacturing a fine fibrous material according to the present invention. Figure 2 procedure? r13 official book (method) March 22, 1990
Claims (1)
細繊維状物質。Substantially non-oriented fine fibrous material having an average diameter of less than 0.5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1302040A JPH03167306A (en) | 1989-11-22 | 1989-11-22 | Extra fine fibrous substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1302040A JPH03167306A (en) | 1989-11-22 | 1989-11-22 | Extra fine fibrous substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03167306A true JPH03167306A (en) | 1991-07-19 |
Family
ID=17904186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1302040A Pending JPH03167306A (en) | 1989-11-22 | 1989-11-22 | Extra fine fibrous substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03167306A (en) |
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| WO2006101175A1 (en) * | 2005-03-24 | 2006-09-28 | Kuraray Co., Ltd. | Nonwoven fabrics and laminates made by using the same |
| EP1867771A4 (en) * | 2005-03-24 | 2012-04-04 | Kuraray Co | Nonwoven fabrics and laminates made by using the same |
| EP1867771A1 (en) * | 2005-03-24 | 2007-12-19 | Kuraray Co., Ltd. | Nonwoven fabrics and laminates made by using the same |
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| JP2010185146A (en) * | 2009-02-10 | 2010-08-26 | Japan Vilene Co Ltd | Structural coloring fiber assembly, and method for producing the same |
| JP2013023804A (en) * | 2011-07-15 | 2013-02-04 | Samsung Electro-Mechanics Co Ltd | Porous sheet and method for producing the same |
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