JPWO2015093589A1 - Fiber, composition for producing the fiber, and biocompatible material containing the fiber - Google Patents
Fiber, composition for producing the fiber, and biocompatible material containing the fiber Download PDFInfo
- Publication number
- JPWO2015093589A1 JPWO2015093589A1 JP2015553616A JP2015553616A JPWO2015093589A1 JP WO2015093589 A1 JPWO2015093589 A1 JP WO2015093589A1 JP 2015553616 A JP2015553616 A JP 2015553616A JP 2015553616 A JP2015553616 A JP 2015553616A JP WO2015093589 A1 JPWO2015093589 A1 JP WO2015093589A1
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- carbon atoms
- fiber
- composition
- condensation product
- Prior art date
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- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 145
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000000560 biocompatible material Substances 0.000 title claims abstract description 19
- 239000002657 fibrous material Substances 0.000 title 1
- 239000007859 condensation product Substances 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 115
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 49
- -1 butoxymethyl group Chemical group 0.000 claims description 47
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 39
- 238000001523 electrospinning Methods 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000003342 alkenyl group Chemical group 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 125000003277 amino group Chemical group 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000007380 fibre production Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 claims description 12
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 11
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229920001410 Microfiber Polymers 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 239000003658 microfiber Substances 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 5
- 210000004027 cell Anatomy 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 238000004113 cell culture Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000002609 medium Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002953 phosphate buffered saline Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229940116333 ethyl lactate Drugs 0.000 description 5
- 239000012091 fetal bovine serum Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000006145 Eagle's minimal essential medium Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- GLNADSQYFUSGOU-GPTZEZBUSA-J Trypan blue Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(/N=N/C3=CC=C(C=C3C)C=3C=C(C(=CC=3)\N=N\C=3C(=CC4=CC(=CC(N)=C4C=3O)S([O-])(=O)=O)S([O-])(=O)=O)C)=C(O)C2=C1N GLNADSQYFUSGOU-GPTZEZBUSA-J 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VSIVTUIKYVGDCX-UHFFFAOYSA-M sodium;4-[2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)tetrazol-2-ium-5-yl]benzene-1,3-disulfonate Chemical compound [Na+].COC1=CC([N+]([O-])=O)=CC=C1[N+]1=NC(C=2C(=CC(=CC=2)S([O-])(=O)=O)S([O-])(=O)=O)=NN1C1=CC=C([N+]([O-])=O)C=C1 VSIVTUIKYVGDCX-UHFFFAOYSA-M 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000006285 cell suspension Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 210000003292 kidney cell Anatomy 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QTENRWWVYAAPBI-YZTFXSNBSA-N Streptomycin sulfate Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@H]1[C@H](N=C(N)N)[C@@H](O)[C@H](N=C(N)N)[C@@H](O)[C@@H]1O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@H]1[C@H](N=C(N)N)[C@@H](O)[C@H](N=C(N)N)[C@@H](O)[C@@H]1O QTENRWWVYAAPBI-YZTFXSNBSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000001605 fetal effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 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
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005815 pentoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012192 staining solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Materials For Medical Uses (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
本発明の目的は、安全性に優れ、簡便に製造可能で、且つ有機溶剤耐性を有する繊維、該繊維を製造するための原料組成物及び該繊維を含む生体適合材料を提供することにある。(A)一般式(1)で表される化合物の1種又は2種以上を縮合して得られる縮合生成物、および(B)酸化合物を含有する組成物を紡糸して製造される繊維。〔式中の各記号は、明細書に記載のとおりである。〕An object of the present invention is to provide a fiber that is excellent in safety, can be easily produced, and has resistance to organic solvents, a raw material composition for producing the fiber, and a biocompatible material containing the fiber. (A) A fiber produced by spinning a composition containing a condensation product obtained by condensing one or more of the compounds represented by formula (1) and (B) an acid compound. [Each symbol in the formula is as described in the specification. ]
Description
本発明は、特定のトリアジン化合物を縮合して得られる縮合生成物及び酸化合物を含有する繊維製造用組成物、該組成物を紡糸して製造される繊維、並びに該繊維を含む生体適合材料に関する。 The present invention relates to a composition for producing a fiber containing a condensation product obtained by condensing a specific triazine compound and an acid compound, a fiber produced by spinning the composition, and a biocompatible material containing the fiber. .
近年、ナノメートルオーダー乃至マイクロメートルオーダーの直径を持つ極細繊維が注目されており、電池・情報、環境・エネルギー、医療(例、生体適合材料等)・福祉のようなさまざまな分野に活用されることが期待されている。 In recent years, ultrafine fibers with a diameter of nanometer order to micrometer order have attracted attention, and are used in various fields such as batteries / information, environment / energy, medical treatment (eg, biocompatible materials) / welfare. It is expected that.
その極細繊維を形成する素材として、ナイロン等の有機高分子、TiO2やSiO2等の無機物質、セルロースやコラーゲン等の生物由来の高分子等のように、多岐にわたる素材が検討されている。As materials for forming the ultrafine fibers, various materials such as organic polymers such as nylon, inorganic substances such as TiO 2 and SiO 2 , and polymers derived from living organisms such as cellulose and collagen have been studied.
ナノメートルオーダー乃至マイクロメートルオーダーの直径を持つ極細繊維を紡糸する技術として、メルトブロー法、複合溶融紡糸法、電界紡糸法等が知られているが、特に電界紡糸法は、今まで扱えなかった素材も繊維化可能な方法として注目されている。例えば、前記したセルロースやコラーゲン等の生物由来の高分子に加えて、ポリ乳酸等の医療用高分子、ポリビニルアルコール等の水溶性高分子も数多く検討されている(特許文献1〜7、非特許文献1)。 Melt blowing, composite melt spinning, electrospinning, etc. are known as technologies for spinning ultrafine fibers with nanometer order to micrometer order diameters. Is also attracting attention as a method for making fibers. For example, in addition to the above-mentioned bio-derived polymers such as cellulose and collagen, many medical polymers such as polylactic acid and water-soluble polymers such as polyvinyl alcohol have been studied (Patent Documents 1 to 7, Non-patent Documents). Reference 1).
一方、細胞培養足場材料等の生体適合材料は、近年、安全性の問題から、生物由来の素材(特に、ウシ由来のゼラチン等)の使用は避けられる傾向にあり、非生物由来の素材(例、合成ポリマー等)を使用して製造されることが求められている。 On the other hand, biocompatible materials such as cell culture scaffolds have recently been evaded from the use of biological materials (especially bovine gelatin) due to safety issues. , Synthetic polymers, etc.).
また、細胞培養足場材料等の生体適合材料は、滅菌処理としてエタノール等の有機溶剤が使用される。そのため、上記の極細繊維を生体適合材料へ適用する場合、有機溶剤への耐性も必要である。上記特許文献及び非特許文献においては、繊維の耐久性を向上させる手段として、ポリマー同士を架橋剤により架橋させる方法等が用いられているが、ポリマーの種類が異なると架橋条件が異なり、UV照射や塩化水素ガス処理等の煩雑な処理が必要となる場合もある(例えば、特許文献3、7及び非特許文献1)。そのため、簡易な処理のみ(例えば、加熱処理のみ、好ましくは、低温短時間の加熱処理のみ)で有機溶剤耐性を有する繊維を製造できる方法が求められている。 In addition, biocompatible materials such as cell culture scaffold materials use an organic solvent such as ethanol as a sterilization treatment. Therefore, when applying the above ultrafine fibers to biocompatible materials, resistance to organic solvents is also necessary. In the above patent document and non-patent document, as a means for improving the durability of the fiber, a method of cross-linking polymers with a cross-linking agent, etc. is used. In some cases, complicated processing such as hydrogen chloride gas processing is required (for example, Patent Documents 3 and 7 and Non-Patent Document 1). Therefore, there is a demand for a method capable of producing a fiber having resistance to organic solvents only by simple treatment (for example, only heat treatment, preferably only low-temperature and short-time heat treatment).
本発明の目的は、安全性に優れ、簡便に製造可能で、且つ有機溶剤耐性を有する繊維、該繊維を製造するための原料組成物(繊維製造用組成物)及び該繊維を含む生体適合材料を提供することである。 An object of the present invention is to provide a fiber that is excellent in safety, can be easily manufactured, and has resistance to organic solvents, a raw material composition for manufacturing the fiber (a composition for manufacturing a fiber), and a biocompatible material including the fiber Is to provide.
本発明者らが鋭意検討した結果、特定のトリアジン化合物を縮合して得られる縮合生成物及び酸化合物を含有する組成物を紡糸して製造した繊維は、十分な有機溶媒耐性を有し、更には優れた生体適合性、具体的な一例としては細胞培養足場としての機能を有するため、生体適合材料として有用であることを見出し、本発明を完成するに至った。
また、本発明者らは、本発明の繊維は、加熱処理を施すことより、より優れた有機溶剤耐性を発現すること、また生産効率が向上することを見出した。As a result of intensive studies by the present inventors, a fiber produced by spinning a composition containing a condensation product obtained by condensing a specific triazine compound and an acid compound has sufficient organic solvent resistance, and Has been found to be useful as a biocompatible material because it has excellent biocompatibility and, as a specific example, a function as a cell culture scaffold, has led to the completion of the present invention.
Further, the present inventors have found that the fiber of the present invention expresses better organic solvent resistance and the production efficiency is improved by performing heat treatment.
即ち、本発明は以下の通りである。 That is, the present invention is as follows.
[1](A)一般式(1)で表される化合物の1種又は2種以上を縮合して得られる縮合生成物、および
(B)酸化合物
を含有する組成物を紡糸して製造される繊維。[1] (A) produced by spinning a condensation product obtained by condensing one or more compounds represented by formula (1), and (B) an acid compound. Fiber.
〔式中、
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕
[2]上記組成物がさらに(C)溶剤を含む、[1]記載の繊維。
[3]上記R1が、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、ビニル基、プロペニル基、ブテニル基、フェニル基及びナフチル基から選ばれ、
上記R2、R3、R4およびR5が、同一又は異なって、水素原子、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、ビニル基、プロペニル基、ブテニル基、メチル基、エチル基、プロピル基及びブチル基から選ばれる、[1]又は[2]記載の繊維。
[4](A)縮合生成物が、一般式(1A):[Where,
R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. Represents an aryl group of formula 6-14;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ]
[2] The fiber according to [1], wherein the composition further contains (C) a solvent.
[3] R 1 is an amino group, a vinyl group, a propenyl group, a butenyl group, a phenyl group or a naphthyl group which may be substituted with a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or a hydroxymethyl group. Chosen from the group,
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a vinyl group, a propenyl group, or a butenyl group. The fiber according to [1] or [2], selected from methyl group, ethyl group, propyl group and butyl group.
[4] (A) The condensation product is represented by the general formula (1A):
〔式中、
R1Aは、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物、及び/又は
一般式(1B):[Where,
R 1A represents an amino group which may be substituted with an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. And / or general formula (1B):
〔式中、
R1Bは、炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物を縮合して得られる縮合生成物である、[1]又は[2]記載の繊維。
[5](A)縮合生成物の重量平均分子量が、1,000〜1,000,000である、[1]〜[4]のいずれか1つに記載の繊維。
[6]上記紡糸が、電界紡糸である、[1]〜[5]のいずれか1つに記載の繊維。
[7]ナノ繊維及び/又はマイクロ繊維である、[1]〜[6]のいずれか1つに記載の繊維。
[8](A)一般式(1)で表される化合物の1種又は2種以上を縮合して得られる縮合生成物、および
(B)酸化合物
を含有する繊維製造用組成物。[Where,
R 1B represents an aryl group having 6 to 14 carbon atoms;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ] The fiber as described in [1] or [2] which is a condensation product obtained by condensing the compound represented by this.
[5] The fiber according to any one of [1] to [4], wherein the condensation product (A) has a weight average molecular weight of 1,000 to 1,000,000.
[6] The fiber according to any one of [1] to [5], wherein the spinning is electrospinning.
[7] The fiber according to any one of [1] to [6], which is a nanofiber and / or a microfiber.
[8] A composition for fiber production containing (A) a condensation product obtained by condensing one or more compounds represented by formula (1), and (B) an acid compound.
〔式中、
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕
[9]さらに(C)溶剤を含む、[8]記載の組成物。
[10](A)縮合生成物が、一般式(1A):[Where,
R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. Represents an aryl group of formula 6-14;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ]
[9] The composition according to [8], further comprising (C) a solvent.
[10] The condensation product (A) is represented by the general formula (1A):
〔式中、
R1Aは、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物、及び/又は
一般式(1B):[Where,
R 1A represents an amino group which may be substituted with an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. And / or general formula (1B):
〔式中、
R1Bは、炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物を縮合して得られる縮合生成物である、[8]又は[9]記載の組成物。
[11](A)縮合生成物の重量平均分子量が、1,000〜1,000,000である、[8]〜[10]のいずれか1つに記載の組成物。
[12](A)縮合生成物の固形分の含有割合が、1〜90重量%である、[8]〜[11]のいずれか1つに記載の組成物。
[13](第一工程)一般式(1)で表される化合物を1種又は2種以上含む単量体組成物を縮合して(A)縮合生成物溶液を得る工程、
(第二工程)前記(A)縮合生成物溶液に(B)酸化合物及び(C)溶剤を添加して繊維製造用組成物を得る工程、および
(第三工程)前記繊維製造用組成物を紡糸する工程
を含む、繊維の製造方法。[Where,
R 1B represents an aryl group having 6 to 14 carbon atoms;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ] The composition of [8] or [9] which is a condensation product obtained by condensing the compound represented by this.
[11] The composition according to any one of [8] to [10], wherein the condensation product (A) has a weight average molecular weight of 1,000 to 1,000,000.
[12] The composition according to any one of [8] to [11], wherein the solid content of the (A) condensation product is 1 to 90% by weight.
[13] (First step) (A) A step of obtaining a condensation product solution by condensing a monomer composition containing one or more compounds represented by general formula (1),
(Second step) (A) A step of adding an acid compound and (C) solvent to the condensation product solution to obtain a composition for fiber production, and (Third step) a composition for fiber production. A method for producing a fiber, comprising a step of spinning.
〔式中、
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕
[14]紡糸した繊維を、50〜300℃の範囲で加熱する工程をさらに含む、[13]記載の方法。
[15]上記紡糸が、電界紡糸である、[13]又は[14]記載の方法。
[16][1]〜[7]のいずれか1つに記載の繊維を含む、生体適合材料。[Where,
R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. Represents an aryl group of formula 6-14;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ]
[14] The method according to [13], further comprising a step of heating the spun fiber in the range of 50 to 300 ° C.
[15] The method according to [13] or [14], wherein the spinning is electrospinning.
[16] A biocompatible material comprising the fiber according to any one of [1] to [7].
本発明によれば、安全性に優れ、簡便に製造可能で、且つ有機溶剤耐性を有する繊維、該繊維を製造するための原料組成物、及び該繊維を含む生体適合材料を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in safety, can manufacture easily, and can provide the fiber which has organic solvent tolerance, the raw material composition for manufacturing this fiber, and the biocompatible material containing this fiber.
本発明の繊維は、(A)一般式(1)で表される化合物の1種又は2種以上を縮合して得られる縮合生成物(以下、「成分Aの縮合生成物」又は単に「成分A」とも称する)、および(B)酸化合物(以下、「成分Bの酸化合物」又は単に「成分B」とも称する)を含有する組成物を紡糸(好ましくは電界紡糸)して製造されることが主たる特徴である。 The fiber of the present invention comprises (A) a condensation product obtained by condensing one or more compounds represented by the general formula (1) (hereinafter referred to as “condensation product of component A” or simply “component”). A "), and (B) an acid compound (hereinafter also referred to as" component B acid compound "or simply" component B "). Is the main feature.
本発明の繊維の直径は、繊維の用途等に応じて適宜調整でき、特に限定されないが、細胞の足場となる基材への適用、医療用材料、化粧用材料等に適用する観点から、本発明の繊維は直径がナノメートルオーダー(例、1〜1000nm)の繊維(ナノ繊維)及び/またはマイクロメートルオーダー(例、1〜1000μm)の繊維(マイクロ繊維)であることが好ましい。本発明において、繊維の直径は、走査型電子顕微鏡(SEM)にて測定される。 The diameter of the fiber of the present invention can be appropriately adjusted according to the use of the fiber and the like, and is not particularly limited. However, from the viewpoint of application to a substrate serving as a cell scaffold, medical material, cosmetic material, etc. The fiber of the invention is preferably a fiber (nanofiber) having a diameter of nanometer order (eg, 1 to 1000 nm) and / or a fiber (microfiber) having a micrometer order (eg, 1 to 1000 μm). In the present invention, the diameter of the fiber is measured with a scanning electron microscope (SEM).
[成分A]
成分Aは、一般式(1):[Component A]
Component A has the general formula (1):
〔式中、
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕
で表される化合物の1種又は2種以上を縮合して得られる縮合生成物である。[Where,
R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. Represents an aryl group of formula 6-14;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ]
It is a condensation product obtained by condensing 1 type (s) or 2 or more types of the compound represented by these.
一般式(1)における各基の定義について、以下に詳述する。 The definition of each group in General formula (1) is explained in full detail below.
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示す。R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. The aryl group of number 6-14 is shown.
R1で示される「炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基」における「炭素原子数2〜6のアルコキシメチル基」は、直鎖状又は分岐鎖状のいずれでもよく、その具体例としては、メトキシメチル基、エトキシメチル基、プロポキシメチル基、イソプポキシメチル基、ブトキシメチル基、イソブトキシメチル基、sec−ブトキシメチル基、tert−ブトキシメチル基、ペントキシメチル基、イソペントキシメチル基、ネオペントキシメチル基、tert−ペントキシメチル基、1−エチルプロポキシメチル基、2−メチルブトキシメチル基等が挙げられる。該アルコキシメチル基の炭素原子数は、好ましくは2〜5であり、より好ましくは2〜4である。The “alkoxymethyl group having 2 to 6 carbon atoms” in the “amino group optionally substituted with an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group” represented by R 1 is linear or branched. Any of a chain may be used. Specific examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, an isobutoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. Pentoxymethyl group, isopentoxymethyl group, neopentoxymethyl group, tert-pentoxymethyl group, 1-ethylpropoxymethyl group, 2-methylbutoxymethyl group and the like. The number of carbon atoms of the alkoxymethyl group is preferably 2-5, more preferably 2-4.
R1で示される「炭素原子数1〜6のアルキル基」は、直鎖状又は分岐鎖状のいずれでもよく、その具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、tert−ペンチル基、1−エチルプロピル基、ヘキシル基、イソヘキシル基、1,1−ジメチルブチル基、2,2−ジメチルブチル基、3,3−ジメチルブチル基、2−エチルブチル基等が挙げられる。該アルキル基の炭素原子数は、好ましくは1〜5であり、より好ましくは1〜4である。The “alkyl group having 1 to 6 carbon atoms” represented by R 1 may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2, 2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group and the like can be mentioned. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 4.
R1で示される「炭素原子数2〜6のアルケニル基」は、直鎖状又は分岐鎖状のいずれでもよく、その具体例としては、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等が挙げられる。該アルケニル基の炭素原子数は、好ましくは2〜5であり、より好ましくは2〜4である。The “alkenyl group having 2 to 6 carbon atoms” represented by R 1 may be either linear or branched, and specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, and a pentenyl group. Hexenyl group and the like. The number of carbon atoms of the alkenyl group is preferably 2 to 5, and more preferably 2 to 4.
R1で示される「炭素原子数6〜14のアリール基」は、単環式又は縮合多環式のいずれでもよく、その具体例としては、フェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、アントリル基、フェナントリル基、アセナフチレニル基等が挙げられる。該アリール基の炭素原子数は、好ましくは6〜12であり、より好ましくは6〜10である。The “aryl group having 6 to 14 carbon atoms” represented by R 1 may be monocyclic or condensed polycyclic, and specific examples thereof include phenyl group, naphthyl group, azulenyl group, indenyl group, indanyl. Group, anthryl group, phenanthryl group, acenaphthylenyl group and the like. The number of carbon atoms of the aryl group is preferably 6-12, more preferably 6-10.
R1は、縮合反応の反応性の観点から、好ましくは、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基であり、より好ましくはメトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、ビニル基、プロペニル基、ブテニル基、フェニル基又はナフチル基であり、特に好ましくはメトキシメチル基、エトキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基又はフェニル基である。From the viewpoint of the reactivity of the condensation reaction, R 1 is preferably an amino group optionally substituted with an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkenyl group having 2 to 6 carbon atoms, or An aryl group having 6 to 14 carbon atoms, more preferably an amino group, a vinyl group, a propenyl group, which may be substituted with a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or a hydroxymethyl group, A butenyl group, a phenyl group or a naphthyl group, particularly preferably an amino group or a phenyl group which may be substituted with a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group or a hydroxymethyl group.
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6.
R2、R3、R4又はR5で示される「炭素原子数2〜6のアルコキシメチル基」、「炭素原子数2〜6のアルケニル基」及び「炭素原子数1〜6のアルキル基」は、それぞれ上記R1における「炭素原子数2〜6のアルコキシメチル基」、「炭素原子数2〜6のアルケニル基」及び「炭素原子数1〜6のアルキル基」と同義である。“Alkoxymethyl group having 2 to 6 carbon atoms”, “alkenyl group having 2 to 6 carbon atoms” and “alkyl group having 1 to 6 carbon atoms” represented by R 2 , R 3 , R 4 or R 5 is "alkoxymethyl group having 2 to 6 carbon atoms" in the above R 1, respectively, is synonymous with "alkenyl group having 2 to 6 carbon atoms" and "alkyl group having 1 to 6 carbon atoms."
R2、R3、R4およびR5は、縮合反応を行うアルコキシメチル基やヒドロキシメチル基との反応性の観点から、同一又は異なって、好ましくは、水素原子、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、ビニル基、プロペニル基、ブテニル基、メチル基、エチル基、プロピル基又はブチル基であり、より好ましくはメトキシメチル基、エトキシメチル基、ブトキシメチル基又はヒドロキシメチル基である。R 2 , R 3 , R 4 and R 5 are the same or different from the viewpoint of reactivity with an alkoxymethyl group or a hydroxymethyl group for performing a condensation reaction, preferably a hydrogen atom, a hydroxymethyl group or a methoxymethyl group. , Ethoxymethyl group, propoxymethyl group, butoxymethyl group, vinyl group, propenyl group, butenyl group, methyl group, ethyl group, propyl group or butyl group, more preferably methoxymethyl group, ethoxymethyl group, butoxymethyl group Or it is a hydroxymethyl group.
一般式(1)で表される化合物は、
R1が、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、ビニル基、プロペニル基、ブテニル基、フェニル基及びナフチル基(より好ましくはメトキシメチル基、エトキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基及びフェニル基、特に好ましくはメトキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基及びフェニル基)から選ばれ;
R2、R3、R4およびR5が、同一又は異なって、水素原子、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、ビニル基、プロペニル基、ブテニル基、メチル基、エチル基、プロピル基及びブチル基(より好ましくはメトキシメチル基、エトキシメチル基、ブトキシメチル基及びヒドロキシメチル基、特に好ましくはメトキシメチル基、ブトキシメチル基及びヒドロキシメチル基)から選ばれることが好ましい。The compound represented by the general formula (1) is:
R 1 is an amino group, vinyl group, propenyl group, butenyl group, phenyl group and naphthyl group (more preferably) which may be substituted with a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or a hydroxymethyl group. Is an amino group and a phenyl group which may be substituted with a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group or a hydroxymethyl group, particularly preferably a methoxymethyl group, a butoxymethyl group or a hydroxymethyl group. Amino groups and phenyl groups);
R 2 , R 3 , R 4 and R 5 are the same or different and each represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a vinyl group, a propenyl group, a butenyl group, It is selected from a methyl group, an ethyl group, a propyl group and a butyl group (more preferably a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group and a hydroxymethyl group, particularly preferably a methoxymethyl group, a butoxymethyl group and a hydroxymethyl group). Is preferred.
一般式(1)で表される化合物は、自体公知の方法又はそれに準ずる方法によって製造することができる。また、市販品を使用してもよい。 The compound represented by the general formula (1) can be produced by a method known per se or a method analogous thereto. Moreover, you may use a commercial item.
成分Aの縮合生成物は、一般式(1)で表される化合物の1種を縮合したものであってよく、又は一般式(1)で表される化合物の2種以上を縮合したものであってもよいが、一般式(1)で表される化合物の4種以下を縮合したものが好ましく、一般式(1)で表される化合物の3種以下を縮合したものがより好ましく、一般式(1)で表される化合物の2種以下を縮合したものが特に好ましい。 The condensation product of component A may be a product obtained by condensing one type of compound represented by the general formula (1), or a product obtained by condensing two or more types of compounds represented by the general formula (1). However, it is preferable to condense 4 or less of the compound represented by the general formula (1), more preferable to condense 3 or less of the compound represented by the general formula (1). What condensed 2 or less types of compounds represented by Formula (1) is especially preferable.
成分Aの一態様としては、例えば、一般式(1A): As one mode of component A, for example, general formula (1A):
〔式中、
R1Aは、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基を示し;
R2、R3、R4およびR5は、上記と同義である。〕で表される化合物、及び/又は
一般式(1B):[Where,
R 1A represents an amino group which may be substituted with an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group;
R 2 , R 3 , R 4 and R 5 are as defined above. And / or general formula (1B):
〔式中、
R1Bは、炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、上記と同義である。〕で表される化合物を縮合して得られる縮合生成物等が挙げられる。[Where,
R 1B represents an aryl group having 6 to 14 carbon atoms;
R 2 , R 3 , R 4 and R 5 are as defined above. ] The condensation product obtained by condensing the compound represented by this, etc. are mentioned.
R1Aで示される「炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基」における「炭素原子数2〜6のアルコキシメチル基」、及びR1Bで示される「炭素原子数6〜14のアリール基」は、それぞれ上記R1における「炭素原子数2〜6のアルコキシメチル基」及び「炭素原子数6〜14のアリール基」と同義である。“Alkoxymethyl group having 2 to 6 carbon atoms” in “amino group optionally substituted with alkoxymethyl group having 2 to 6 carbon atoms or hydroxymethyl group” represented by R 1A , and represented by R 1B The “aryl group having 6 to 14 carbon atoms” has the same meaning as the “alkoxymethyl group having 2 to 6 carbon atoms” and the “aryl group having 6 to 14 carbon atoms” in R 1 .
一般式(1A)で表される化合物は、
R1Aが、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基(より好ましくはメトキシメチル基、エトキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、特に好ましくはメトキシメチル基、ブトキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基)から選ばれ;
R2、R3、R4およびR5が、同一又は異なって、水素原子、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、ビニル基、プロペニル基、ブテニル基、メチル基、エチル基、プロピル基及びブチル基(より好ましくはメトキシメチル基、エトキシメチル基、ブトキシメチル基及びヒドロキシメチル基、特に好ましくはメトキシメチル基、ブトキシメチル基及びヒドロキシメチル基)から選ばれることが好ましい。The compound represented by the general formula (1A) is
R 1A is an amino group which may be substituted with a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or a hydroxymethyl group (more preferably, a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group or a hydroxymethyl group). An amino group optionally substituted with a group, particularly preferably an amino group optionally substituted with a methoxymethyl group, a butoxymethyl group or a hydroxymethyl group;
R 2 , R 3 , R 4 and R 5 are the same or different and each represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a vinyl group, a propenyl group, a butenyl group, It is selected from a methyl group, an ethyl group, a propyl group and a butyl group (more preferably a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group and a hydroxymethyl group, particularly preferably a methoxymethyl group, a butoxymethyl group and a hydroxymethyl group). Is preferred.
一般式(1B)で表される化合物は、
R1Bが、フェニル基及びナフチル基(より好ましくはフェニル基)から選ばれ;
R2、R3、R4およびR5が、同一又は異なって、水素原子、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、ビニル基、プロペニル基、ブテニル基、メチル基、エチル基、プロピル基及びブチル基(より好ましくはメトキシメチル基、エトキシメチル基、ブトキシメチル基及びヒドロキシメチル基、特に好ましくはメトキシメチル基、ブトキシメチル基及びヒドロキシメチル基)から選ばれることが好ましい。The compound represented by the general formula (1B) is:
R 1B is selected from a phenyl group and a naphthyl group (more preferably a phenyl group);
R 2 , R 3 , R 4 and R 5 are the same or different and each represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a vinyl group, a propenyl group, a butenyl group, It is selected from a methyl group, an ethyl group, a propyl group and a butyl group (more preferably a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group and a hydroxymethyl group, particularly preferably a methoxymethyl group, a butoxymethyl group and a hydroxymethyl group). Is preferred.
一般式(1A)で表される化合物と一般式(1B)で表される化合物とを縮合する場合、用いられる各化合物の重量比(1A:1B)は特に制限されないが、例えば1:10〜10:1である。 When the compound represented by the general formula (1A) and the compound represented by the general formula (1B) are condensed, the weight ratio (1A: 1B) of each compound used is not particularly limited. 10: 1.
成分Aは、自体公知の方法又はそれに準ずる方法によって製造することができる。例えば、一般式(1)で表される化合物の1種又は2種以上を、適当な溶媒(例、乳酸エチル等)中で、適当な縮合開始剤(例、p−トルエンスルホン酸等)を使用して重合すること等により製造できるが、これに限定されない。また、市販品を使用してもよい。 Component A can be produced by a method known per se or a method analogous thereto. For example, an appropriate condensation initiator (eg, p-toluenesulfonic acid) is added to one or more compounds represented by the general formula (1) in an appropriate solvent (eg, ethyl lactate). Although it can manufacture by superposing | polymerizing using, etc., it is not limited to this. Moreover, you may use a commercial item.
一般式(1)で表される化合物の1種又は2種以上を重合する際、本発明の目的を損なわない限り、一般式(1)で表される化合物と重合可能な他の化合物を一緒に重合させてもよい。当該他の化合物としては、例えば、公知のアクリル化合物、公知のメタクリル化合物が挙げられるが、これらに限定されない。当該他の化合物は、単独で用いても、2種以上を併用してもよい。重合される全ての化合物に対する一般式(1)で表される化合物の割合は、通常10モル%以上であり、好ましくは30モル%以上、特に好ましくは50モル%以上である。 When one or more of the compounds represented by the general formula (1) are polymerized, the compound represented by the general formula (1) and other polymerizable compounds are combined together unless the purpose of the present invention is impaired. May be polymerized. Examples of the other compounds include, but are not limited to, known acrylic compounds and known methacrylic compounds. The other compounds may be used alone or in combination of two or more. The ratio of the compound represented by the general formula (1) to all the compounds to be polymerized is usually 10 mol% or more, preferably 30 mol% or more, particularly preferably 50 mol% or more.
上記公知のアクリル化合物又は公知のメタクリル化合物としては、例えば下記一般式(2): Examples of the known acrylic compound or the known methacrylic compound include the following general formula (2):
〔式中、
R6及びR7は、同一又は異なって、水素原子又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物が好ましい。
R6及びR7で示される「炭素原子数1〜6のアルキル基」は上記と同義である。[Where,
R 6 and R 7 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ] The compound represented by this is preferable.
The “alkyl group having 1 to 6 carbon atoms” represented by R 6 and R 7 has the same meaning as described above.
成分Aの重量平均分子量は、紡糸性の観点から、好ましくは1,000〜1,000,000の範囲であり、より好ましくは5,000〜500,000の範囲であり、特に好ましくは10,000〜200,000の範囲であり、最も好ましくは10,000〜100,000の範囲である。本発明において「重量平均分子量」とは、ゲルパーミエーションクロマトグラフィー(GPC)にて測定される、ポリスチレン換算の分子量をいう。 The weight average molecular weight of component A is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 5,000 to 500,000, and particularly preferably 10, from the viewpoint of spinnability. The range is from 000 to 200,000, and most preferably from 10,000 to 100,000. In the present invention, “weight average molecular weight” means a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
成分Aは単独で用いても、2種以上を併用してもよいが、好ましくは4種以下、更に好ましくは3種以下、特に好ましくは2種以下である。 Component A may be used alone or in combination of two or more, but is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less.
[成分B]
成分Bは酸化合物であり、成分A同士、さらに本発明の目的を損なわない限り、一般式(1)で表される化合物以外の他の化合物の縮合生成物がさらに縮合した成分A同士が反応するための触媒として作用する。当該成分Bを含む繊維は、加熱処理を施した場合であっても良好な繊維形状を維持でき、また良好な有機溶剤耐性を有する。成分Bは塩の態様であってもよく、即ち、本発明における「酸化合物」なる用語は、塩をも包含する概念である。[Component B]
Component B is an acid compound, and the components A are reacted with each other as long as the condensation products of compounds other than the compound represented by the general formula (1) are further condensed unless the object of the present invention is impaired. It acts as a catalyst for Even if the fiber containing the said component B is a case where heat processing is performed, it can maintain a favorable fiber shape, and has the favorable organic solvent tolerance. Component B may be in the form of a salt, that is, the term “acid compound” in the present invention is a concept including a salt.
成分Bの酸化合物としては、例えば、スルホン酸化合物、カルボン酸化合物、リン酸化合物等の有機酸化合物;塩酸、リン酸、硫酸、硝酸、臭化水素酸等の無機酸化合物等が挙げられる。 Examples of the acid compound of component B include organic acid compounds such as sulfonic acid compounds, carboxylic acid compounds, and phosphoric acid compounds; inorganic acid compounds such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, and hydrobromic acid.
成分Bは、好ましくは有機酸化合物であり、より好ましくはスルホン酸化合物である。スルホン酸化合物としては、例えば、p−トルエンスルホン酸、ピリジニウム−p−トルエンスルホナート、トリフルオロメタンスルホン酸等が挙げられ、好ましくはp−トルエンスルホン酸又はピリジニウム−p−トルエンスルホナートである。 Component B is preferably an organic acid compound, and more preferably a sulfonic acid compound. Examples of the sulfonic acid compound include p-toluenesulfonic acid, pyridinium-p-toluenesulfonate, trifluoromethanesulfonic acid, and the like, preferably p-toluenesulfonic acid or pyridinium-p-toluenesulfonate.
成分Bの酸化合物は単独で用いても、2種以上を併用してもよい。 The acid compound of component B may be used alone or in combination of two or more.
成分Bの酸化合物は、自体公知の方法又はそれに準ずる方法によって製造することができる。また、市販品を用いてもよい。 The acid compound of component B can be produced by a method known per se or a method analogous thereto. Moreover, you may use a commercial item.
本発明の繊維は、好適には、成分Aの縮合生成物及び成分Bの酸化合物に、さらに(C)溶剤(以下、「成分Cの溶剤」又は単に「成分C」とも称する)を含有する組成物(すなわち、本発明の繊維製造用組成物(以下、単に「本発明の組成物」とも称する))を調製し、該組成物を紡糸して、製造される。 The fiber of the present invention preferably contains (C) a solvent (hereinafter also referred to as “solvent of component C” or simply “component C”) in addition to the condensation product of component A and the acid compound of component B. A composition (that is, a composition for producing a fiber of the present invention (hereinafter also simply referred to as “the composition of the present invention”)) is prepared, and the composition is spun to produce.
より詳細には、本発明の繊維は、
(第一工程)一般式(1)で表される化合物を1種又は2種以上含む単量体組成物を縮合して(A)縮合生成物溶液を得る工程、
(第二工程)前記(A)縮合生成物溶液に(B)酸化合物及び(C)溶剤を添加して繊維製造用組成物を得る工程、および
(第三工程)前記繊維製造用組成物を紡糸する工程
を含む製造方法により製造されることが好ましい。More particularly, the fiber of the present invention comprises:
(First step) (A) A step of obtaining a condensation product solution by condensing a monomer composition containing one or more compounds represented by general formula (1),
(Second step) (A) A step of adding an acid compound and (C) solvent to the condensation product solution to obtain a composition for fiber production, and (Third step) a composition for fiber production. It is preferably produced by a production method including a spinning step.
成分Cの溶剤は、成分A及び成分Bを均一に溶解又は分散し得、且つ、各成分と反応しないものであれば特に制限されないが、成分A及びBの溶解性の観点から、極性溶剤が好ましい。
当該極性溶剤としては、例えば、水、メタノール、エタノール、2−プロパノール、プロピレングリコールモノメチルエーテル、アセトン、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン、乳酸エチル等が挙げられ、成分A及びBの溶解性の観点から、好ましくは乳酸エチルである。The solvent of component C is not particularly limited as long as it can uniformly dissolve or disperse component A and component B and does not react with each component, but from the viewpoint of solubility of components A and B, a polar solvent is used. preferable.
Examples of the polar solvent include water, methanol, ethanol, 2-propanol, propylene glycol monomethyl ether, acetone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl lactate, etc., and solubility of components A and B From this viewpoint, ethyl lactate is preferable.
成分Cは単独で用いても、2種以上を併用してもよい。 Component C may be used alone or in combination of two or more.
本発明の組成物における成分Aの固形分の含有割合は、紡糸性の観点から、1〜90重量%が好ましく、1〜70重量%がより好ましい。ここで、成分Aの固形分の含有割合は、後記の実施例に示されるように、メトラー・トレド株式会社製ハロゲン水分計(HR83)を用いて測定される。 The solid content of component A in the composition of the present invention is preferably 1 to 90% by weight and more preferably 1 to 70% by weight from the viewpoint of spinnability. Here, the solid content of component A is measured by using a halogen moisture meter (HR83) manufactured by METTLER TOLEDO Co., Ltd. as shown in the examples described later.
本発明の組成物における成分Bの含有割合は、架橋反応時の反応効率の観点から、1〜10重量%が好ましく、1〜5重量%がより好ましい。 The content of Component B in the composition of the present invention is preferably 1 to 10% by weight and more preferably 1 to 5% by weight from the viewpoint of reaction efficiency during the crosslinking reaction.
本発明の組成物に含まれる成分Aの固形分と成分Bの重量比(成分Aの固形分の重量/成分Bの重量)は、架橋反応時の反応効率の観点から、5〜40が好ましく、10〜30がより好ましい。 The weight ratio of the solid content of component A and the component B contained in the composition of the present invention (weight of solid content of component A / weight of component B) is preferably 5 to 40 from the viewpoint of reaction efficiency during the crosslinking reaction. 10-30 are more preferable.
本発明の組成物における成分Cの含有割合は、繊維製造用組成物の紡糸性の観点から、5〜80重量%が好ましく、10〜50重量%がより好ましい。 The content ratio of Component C in the composition of the present invention is preferably 5 to 80% by weight and more preferably 10 to 50% by weight from the viewpoint of spinnability of the composition for fiber production.
本発明の組成物は、本発明の目的を損なわない限り、成分A〜C以外に、繊維製造用組成物の分野で慣用の添加剤を必要に応じて含んでもよい。当該添加剤としては、例えば、架橋剤、界面活性剤、レオロジー調整剤、薬剤、微粒子、成分A以外の縮合生成物等が挙げられる。 As long as the object of the present invention is not impaired, the composition of the present invention may contain, in addition to the components A to C, additives that are commonly used in the field of composition for fiber production, if necessary. Examples of the additive include a crosslinking agent, a surfactant, a rheology modifier, a drug, fine particles, a condensation product other than Component A, and the like.
上記(第二工程)において、本発明の組成物は、成分Aに成分B及び成分Cを混合し、又はこれらに上記の添加剤をさらに混合して調製される。混合方法は特に制限されず、自体公知の方法又はそれに準ずる方法によって混合すればよい。 In the above (second step), the composition of the present invention is prepared by mixing Component A with Component B and Component C, or further mixing the above additives with them. The mixing method is not particularly limited, and may be mixed by a method known per se or a method analogous thereto.
上記(第三工程)において、本発明の組成物を紡糸する方法は、繊維を形成できるものであれば特に制限されず、例えば、メルトブロー法、複合溶融紡糸法、電界紡糸法等が挙げられるが、極細繊維(ナノ繊維、マイクロ繊維)の形成能の観点から、電界紡糸法が好ましい。 In the above (third step), the method for spinning the composition of the present invention is not particularly limited as long as it can form fibers, and examples thereof include a melt blow method, a composite melt spinning method, an electrospinning method, and the like. From the viewpoint of the ability to form ultrafine fibers (nanofibers and microfibers), the electrospinning method is preferred.
電界紡糸法は、公知の紡糸方法であり、公知の電界紡糸装置を用いて行うことができる。本発明の組成物をノズル(例、ニードル等)の先端から吐出する速度(吐出速度);印加電圧;本発明の組成物を吐出するノズルの先端から、これを受け取る基板までの距離(吐出距離)等の各種条件は、製造する繊維の直径等に応じて適宜設定できる。吐出速度は、通常0.1〜100μl/minであり、好ましくは0.5〜50μl/minであり、より好ましくは1〜20μl/minである。印加電圧は、通常0.5〜80kVであり、好ましくは1〜60kVであり、より好ましくは3〜40kVである。吐出距離は、通常1〜60cmであり、好ましくは2〜40cmであり、より好ましくは3〜30cmである。
また電界紡糸法は、ドラムコレクター等を用いて行ってもよい。ドラムコレクター等を用いることにより、繊維の配向性を制御することができる。例えば、ドラムを低速回転した場合は不織布等を得ることができ、高速回転した場合は配向性繊維シート等を得ることができる。The electrospinning method is a known spinning method and can be performed using a known electrospinning apparatus. Speed (discharge speed) at which the composition of the present invention is discharged from the tip of a nozzle (eg, needle); applied voltage; distance from the tip of the nozzle that discharges the composition of the present invention to the substrate that receives it (discharge distance) ) And the like can be appropriately set according to the diameter of the fiber to be produced. The discharge speed is usually 0.1 to 100 μl / min, preferably 0.5 to 50 μl / min, and more preferably 1 to 20 μl / min. The applied voltage is usually 0.5 to 80 kV, preferably 1 to 60 kV, more preferably 3 to 40 kV. A discharge distance is 1-60 cm normally, Preferably it is 2-40 cm, More preferably, it is 3-30 cm.
The electrospinning method may be performed using a drum collector or the like. By using a drum collector or the like, the orientation of the fibers can be controlled. For example, a nonwoven fabric or the like can be obtained when the drum is rotated at a low speed, and an oriented fiber sheet or the like can be obtained when the drum is rotated at a high speed.
電界紡糸法によって製造された本発明の繊維の直径は、従来の他の紡糸方法によって製造されたものに比べてより一層小さくすることが可能であり、通常1nm〜3μmであり、好ましくは1nm〜1μmである。 The diameter of the fiber of the present invention produced by the electrospinning method can be made much smaller than that produced by other conventional spinning methods, and is usually 1 nm to 3 μm, preferably 1 nm to 1 μm.
本発明の繊維の製造方法は、上述の紡糸工程に加えて、紡糸した繊維を、特定の温度で加熱する工程を更に含んでもよい。 The fiber manufacturing method of the present invention may further include a step of heating the spun fiber at a specific temperature in addition to the above-described spinning step.
紡糸した繊維を加熱する温度は、通常50〜300℃の範囲であり、成分Aの耐熱性の観点から、好ましくは80〜250℃であり、より好ましくは90〜220℃である。当該温度が50℃未満であると、成分A同士の架橋反応が不十分となり、製造した繊維の有機溶剤耐性が低くなる傾向があり、300℃を超えると、成分Aが熱による分解又は溶解等を起こし繊維が形成できない場合がある。 The temperature at which the spun fiber is heated is usually in the range of 50 to 300 ° C., and preferably 80 to 250 ° C., more preferably 90 to 220 ° C. from the viewpoint of the heat resistance of Component A. When the temperature is less than 50 ° C., the crosslinking reaction between the components A becomes insufficient, and the resistance of the produced fiber to the organic solvent tends to be low. When the temperature exceeds 300 ° C., the component A is decomposed or dissolved by heat. In some cases, fibers cannot be formed.
紡糸した繊維の加熱方法は、上記の加熱温度で加熱し得るものであれば特に制限されず、自体公知の方法又はそれに準ずる方法で適宜加熱することができる。該加熱方法の具体例としては、大気下にてホットプレート又はオーブン等を使用する方法等が挙げられる。 The method for heating the spun fiber is not particularly limited as long as it can be heated at the above heating temperature, and can be appropriately heated by a method known per se or a method analogous thereto. Specific examples of the heating method include a method using a hot plate or an oven in the atmosphere.
紡糸した繊維を加熱する時間は、加熱温度等に応じて適宜設定し得るが、架橋反応速度、生産効率の観点から、1分〜48時間が好ましく、5分〜36時間がより好ましく、5分〜24時間が特に好ましい。 The time for heating the spun fiber can be appropriately set according to the heating temperature and the like, but from the viewpoint of the crosslinking reaction rate and production efficiency, 1 minute to 48 hours is preferable, 5 minutes to 36 hours are more preferable, and 5 minutes are preferable. ˜24 hours is particularly preferred.
本発明の繊維の用途は特に制限されないが、後述の実施例に示されるように、本発明の繊維は優れた有機溶剤耐性を有し、且つ、非生物由来の素材であるにも関わらず、安全性に優れ、生体適合材料に適している。また、本発明の繊維は、細胞培養足場として十分な機能を有することから、細胞培養足場材料にも適している。
従って、本発明は、本発明の繊維を含む生体適合材料(以下、単に「本発明の生体適合材料」とも称する)も提供する。本発明において「生体適合材料」とは、生体に対して悪影響を及ぼさず、医療用材料、化粧用材料等として利用可能な材料をいう。Although the use of the fiber of the present invention is not particularly limited, as shown in the examples below, the fiber of the present invention has excellent organic solvent resistance and is a non-biological material, Excellent safety and suitable for biocompatible materials. Moreover, since the fiber of the present invention has a sufficient function as a cell culture scaffold, it is also suitable as a cell culture scaffold material.
Accordingly, the present invention also provides a biocompatible material comprising the fiber of the present invention (hereinafter also simply referred to as “the biocompatible material of the present invention”). In the present invention, the “biocompatible material” refers to a material that does not adversely affect a living body and can be used as a medical material, a cosmetic material, or the like.
本発明の生体適合材料の種類は特に制限されないが、例えば、細胞培養足場材料、創傷被覆材料、フェイスマスク(美容用、衛生管理用)等が挙げられる。中でも、本発明の繊維は細胞培養足場として十分な機能を有することから、細胞培養足場材料として用いられることが好ましい。 The type of the biocompatible material of the present invention is not particularly limited, and examples thereof include cell culture scaffold materials, wound covering materials, face masks (for cosmetics and hygiene management), and the like. Especially, since the fiber of this invention has sufficient function as a cell culture scaffold, it is preferable to be used as a cell culture scaffold material.
本発明の生体適合材料は、本発明の繊維を原材料の一つとして使用し、自体公知の方法又はそれに準ずる方法によって製造することができる。 The biocompatible material of the present invention can be produced by a method known per se or a method analogous thereto, using the fiber of the present invention as one of the raw materials.
以下、本発明に係る具体例を説明するが、これによって本発明は何ら限定されるものではない。 Hereinafter, although the specific example which concerns on this invention is demonstrated, this invention is not limited at all by this.
<縮合生成物溶液の調製>
ヘキサメトキシメチルメラミン化合物(三井サイテック株式会社製、商品名「Cymel303」)10.0gと、テトラメトキシメチルベンゾグアナミン化合物(三井サイテック株式会社製、商品名「Cymel1123」)10.0gとを、乳酸エチル100gに溶解させた後、p−トルエンスルホン酸0.5gを添加し、120℃で24時間反応させ、これらのトリアジン化合物の縮合生成物(縮合生成物1)を含む縮合生成物溶液1を得た。
その後、50℃の湯浴を用いて縮合生成物溶液1から溶媒を適宜留去し、更に自体公知のカチオン系イオン交換樹脂によるイオン交換により縮合生成物溶液1中の酸、イオンを除去した。溶媒留去後の縮合生成物溶液1における縮合生成物1の固形分の含有割合は、79重量%であった。また、縮合生成物1の重量平均分子量は、ポリスチレン換算で16,000であった。
縮合生成物溶液1における縮合生成物1の固形分の含有割合の測定、及び縮合生成物1の重量平均分子量の測定は、それぞれ以下の通りに行った。<Preparation of condensation product solution>
10.0 g of hexamethoxymethyl melamine compound (trade name “Cymel 303” manufactured by Mitsui Cytec Co., Ltd.) and 10.0 g of tetramethoxymethyl benzoguanamine compound (trade name “Cymel 1123” manufactured by Mitsui Cytec Co., Ltd.) Then, 0.5 g of p-toluenesulfonic acid was added and reacted at 120 ° C. for 24 hours to obtain a condensation product solution 1 containing a condensation product (condensation product 1) of these triazine compounds. .
Thereafter, the solvent was appropriately distilled off from the condensation product solution 1 using a 50 ° C. hot water bath, and the acid and ions in the condensation product solution 1 were removed by ion exchange with a known cationic ion exchange resin. The solid content of the condensation product 1 in the condensation product solution 1 after distilling off the solvent was 79% by weight. Moreover, the weight average molecular weight of the condensation product 1 was 16,000 in terms of polystyrene.
The measurement of the content rate of the solid content of the condensation product 1 in the condensation product solution 1 and the measurement of the weight average molecular weight of the condensation product 1 were performed as follows.
[縮合生成物溶液1における縮合生成物1の固形分の含有割合の測定]
縮合生成物溶液1における縮合生成物1の固形分の含有割合は、測定装置としてメトラー・トレド株式会社製ハロゲン水分計(HR83)を用いて、以下の手順により測定した。
(1)メトラー・トレド株式会社製アルミニウムサンプル皿(HA−D90)上にワットマン(登録商標)ガラス繊維ろ紙(GF/D、直径70mm)を重ね、装置内に設置する。
(2)装置をゼログラムに校正した後、縮合生成物溶液1を1.0g秤量し、120℃で加熱する。
(3)縮合生成物溶液1に含まれている溶媒が全て留去されると、測定は自動的に終了し、縮合生成物1の固形分の含有割合(単位:重量%)が示される。[Measurement of solid content of condensation product 1 in condensation product solution 1]
The solid content of the condensation product 1 in the condensation product solution 1 was measured by the following procedure using a halogen moisture meter (HR83) manufactured by METTLER TOLEDO Co., Ltd. as a measuring device.
(1) Whatman (registered trademark) glass fiber filter paper (GF / D, diameter 70 mm) is stacked on an aluminum sample pan (HA-D90) manufactured by METTLER TOLEDO Co., Ltd., and installed in the apparatus.
(2) After calibrating the apparatus to zero grams, 1.0 g of the condensation product solution 1 is weighed and heated at 120 ° C.
(3) When all the solvent contained in the condensation product solution 1 is distilled off, the measurement is automatically terminated, and the solid content (unit: wt%) of the condensation product 1 is indicated.
[縮合生成物1の重量平均分子量の測定]
縮合生成物1の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定した。測定に用いた装置、測定条件は次の通りである。
装置:TOSOH HLC−8320GPC system
カラム:Shodex(登録商標)KF−803L、KF−802及びKF−801
カラム温度:40℃
溶離液:DMF
流量:0.6ml/分
検出器:RI
標準試料:ポリスチレン[Measurement of weight average molecular weight of condensation product 1]
The weight average molecular weight of the condensation product 1 was measured by gel permeation chromatography (GPC). The apparatus and measurement conditions used for the measurement are as follows.
Equipment: TOSOH HLC-8320GPC system
Column: Shodex® KF-803L, KF-802 and KF-801
Column temperature: 40 ° C
Eluent: DMF
Flow rate: 0.6 ml / min Detector: RI
Standard sample: Polystyrene
<繊維製造用組成物(溶液)の調製>
(実施例1)
縮合生成物溶液1 2.5g(縮合生成物1の固形分:2.0g)、p−トルエンスルホン酸 0.10g及び乳酸エチル 0.44gを混合した後、ミックスローターVMR−5(アズワン株式会社製)にて溶解するまで80rpmで攪拌し、実施例1の繊維製造用組成物を得た。実施例1の繊維製造用組成物における縮合生成物1の固形分の含有割合は、約65重量%である。<Preparation of composition for fiber production (solution)>
Example 1
After mixing 2.5 g of the condensation product solution 1 (solid content of the condensation product 1: 2.0 g), 0.10 g of p-toluenesulfonic acid and 0.44 g of ethyl lactate, a mixed rotor VMR-5 (As One Corporation) The composition for fiber production of Example 1 was obtained by stirring at 80 rpm until dissolved. The content rate of the solid content of the condensation product 1 in the composition for producing fibers of Example 1 is about 65% by weight.
(比較例1)
縮合生成物溶液1 2.5g(縮合生成物1の固形分:2.0g)及び乳酸エチル 0.54gを混合した後、ミックスローターVMR−5(アズワン株式会社製)にて溶解するまで80rpmで攪拌し、比較例1の繊維製造用組成物を得た。比較例1の繊維製造用組成物における縮合生成物1の固形分の含有割合は、約65重量%である。(Comparative Example 1)
After mixing 2.5 g of the condensation product solution 1 (solid content of the condensation product 1: 2.0 g) and 0.54 g of ethyl lactate, the mixture is dissolved at 80 rpm until dissolved in the mix rotor VMR-5 (manufactured by ASONE Corporation). Stirring was performed to obtain the fiber manufacturing composition of Comparative Example 1. The content rate of the solid content of the condensation product 1 in the composition for producing fibers of Comparative Example 1 is about 65% by weight.
<試験例1:加熱処理及び溶剤耐性試験>
実施例1及び比較例1の繊維製造用組成物を、それぞれ電界紡糸法により、アルミ箔上に紡糸した後、得られた各繊維に加熱処理(加熱温度:80℃、160℃、205℃、加熱時間:各10分)を施し、当該加熱処理後の繊維形状を確認した。
また加熱処理を施した繊維をアセトンに10秒間浸漬した後、再び繊維形状を確認し、繊維の直径を測定した。
電界紡糸法による繊維の製造、繊維形状の確認及び繊維の直径の測定は、それぞれ以下の通りに行った。<Test Example 1: Heat treatment and solvent resistance test>
The fiber production compositions of Example 1 and Comparative Example 1 were each spun onto an aluminum foil by an electrospinning method, and then the resulting fibers were subjected to heat treatment (heating temperatures: 80 ° C., 160 ° C., 205 ° C., Heating time: 10 minutes each), and the fiber shape after the heat treatment was confirmed.
Moreover, after the fiber which heat-processed was immersed in acetone for 10 second, the fiber shape was confirmed again and the diameter of the fiber was measured.
Production of the fiber by electrospinning, confirmation of the fiber shape, and measurement of the fiber diameter were performed as follows.
[電界紡糸法による繊維の製造]
電界紡糸法による繊維の製造は、エスプレイヤーES−2000(株式会社フューエンス製)を用いて実施した。繊維製造用組成物は、1mlのロック式ガラス注射筒(アズワン株式会社製)に注入し、針長13mmのロック式金属製ニードル22G(武蔵エンジニアリング株式会社製)を取り付けた。ニードル先端から繊維を受け取る基板までの距離(吐出距離)は20cmとした。印加電圧は25kVとし、吐出速度は10μl/minとした。[Production of fibers by electrospinning]
The production of the fiber by the electrospinning method was carried out using Esplayer ES-2000 (manufactured by Fuence Co., Ltd.). The composition for fiber production was poured into a 1 ml lock-type glass syringe (manufactured by As One Co., Ltd.), and a lock-type metal needle 22G (manufactured by Musashi Engineering Co., Ltd.) having a needle length of 13 mm was attached. The distance (discharge distance) from the tip of the needle to the substrate that receives the fibers was 20 cm. The applied voltage was 25 kV, and the ejection speed was 10 μl / min.
[繊維形状の確認]
繊維形状の確認は、イオンスパッター(E−1030、株式会社日立ハイテクノロジーズ製)にてPt−Pdを繊維に1分間蒸着した後、走査型電子顕微鏡(SEM)(S−4800、株式会社日立ハイテクノロジーズ製)を使用して、拡大倍率10,000倍で観察することにより行った。[Confirmation of fiber shape]
The fiber shape was confirmed by depositing Pt-Pd on the fiber for 1 minute by ion sputtering (E-1030, manufactured by Hitachi High-Technologies Corporation), and then scanning electron microscope (SEM) (S-4800, Hitachi High Corporation). (Manufactured by Technologies) and observed at an enlargement magnification of 10,000 times.
[繊維の直径の測定]
繊維径(繊維の太さ)の測定は、走査型電子顕微鏡(SEM)を使用して、拡大倍率10,000倍の画像を保存した後、付属の測長ツールにより行った。[Measurement of fiber diameter]
The fiber diameter (fiber thickness) was measured using an attached length measuring tool after storing an image with a magnification of 10,000 times using a scanning electron microscope (SEM).
結果を表1(加熱処理後の形状)、表2(アセトン浸漬後の形状及び繊維の直径)及び図1〜14(加熱処理前、加熱処理後、アセトン浸漬後のSEM写真)に示す。 The results are shown in Table 1 (shape after heat treatment), Table 2 (shape after immersion in acetone and fiber diameter) and FIGS. 1 to 14 (SEM photographs before heat treatment, after heat treatment, and after acetone immersion).
実施例1の繊維製造用組成物を電界紡糸して得られた繊維は、加熱温度が80℃〜205℃のいずれの条件においても良好な形状であった。比較例1の繊維製造用組成物を電界紡糸して得られた繊維は、加熱温度が80℃では形状をかろうじて保持し網目状の固化物となったが、160℃と205℃においては形状を維持できず溶解し、フィルム状の膜となった(表1)。
更に、実施例1の繊維製造用組成物を電界紡糸して得られた繊維は、いずれの加熱温度条件においても良好な有機溶剤(アセトン)耐性を保持していたが、比較例1の繊維製造用組成物を電界紡糸後、80℃で加熱処理して得られた網目状の固化物はアセトンに溶解し、アルミ箔上から消失した(表2)。The fiber obtained by electrospinning the fiber manufacturing composition of Example 1 had a good shape under any conditions of heating temperatures of 80 ° C to 205 ° C. The fiber obtained by electrospinning the fiber production composition of Comparative Example 1 barely retained its shape at a heating temperature of 80 ° C. and became a network solidified product, but did not have a shape at 160 ° C. and 205 ° C. It could not be maintained and dissolved to form a film-like membrane (Table 1).
Further, the fiber obtained by electrospinning the fiber production composition of Example 1 maintained good organic solvent (acetone) resistance under any heating temperature conditions, but the fiber production of Comparative Example 1 After the electrospinning, the network solidified product obtained by heat treatment at 80 ° C. was dissolved in acetone and disappeared from the aluminum foil (Table 2).
<試験例2:細胞培養評価>
実施例1の繊維製造用組成物を電界紡糸法により紡糸した後、得られた繊維上にて細胞培養評価を行った。なお、以下において、CO2インキュベーターにおけるCO2の濃度(%)は、雰囲気中のCO2の体積%で示した。また、PBSはリン酸緩衝生理食塩水(シグマアルドリッチジャパン社製)を意味し、FBSは牛胎児血清(Biological Industries社製)を意味する。<Test Example 2: Cell culture evaluation>
After spinning the composition for producing fibers of Example 1 by electrospinning, cell culture evaluation was performed on the obtained fibers. In the following, the concentration (%) of CO 2 in the CO 2 incubator is indicated by volume% of CO 2 in the atmosphere. PBS means phosphate buffered saline (manufactured by Sigma Aldrich Japan), and FBS means fetal bovine serum (manufactured by Biological Industries).
[細胞の調製]
細胞は、ヒト胎児腎細胞株Hek293(DSファーマバイオメディカル社製)を用いた。細胞の培養に用いた培地は、10%(v/v)FBS及び1%(v/v)NEAA(GIBCO社製)を含むEMEM培地(和光純薬工業株式会社製)を用いた。細胞は、37℃CO2インキュベーター内にて5%二酸化炭素濃度を保った状態で、直径10cmシャーレ(培地10mL)を用いて2日間以上静置培養した。引き続き、本細胞をPBS10mLで洗浄した後、トリプシン−EDTA溶液(和光純薬工業株式会社製)1mLを添加して細胞を剥がし、上記の培地10mLにて懸濁した。本懸濁液を遠心分離(トミー精工社製、LC−200、1000rpm/3分、室温)後、上清を除き、上記の培地を添加して細胞懸濁液を調製した。[Preparation of cells]
As a cell, a human fetal kidney cell line Hek293 (manufactured by DS Pharma Biomedical) was used. The medium used for cell culture was EMEM medium (Wako Pure Chemical Industries, Ltd.) containing 10% (v / v) FBS and 1% (v / v) NEAA (GIBCO). The cells were statically cultured for 2 days or more using a 10 cm diameter petri dish (medium 10 mL) in a state where 5% carbon dioxide concentration was maintained in a 37 ° C. CO 2 incubator. Subsequently, after washing the cells with 10 mL of PBS, 1 mL of trypsin-EDTA solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to separate the cells, and the cells were suspended in 10 mL of the above medium. The suspension was centrifuged (Tomy Seiko Co., Ltd., LC-200, 1000 rpm / 3 minutes, room temperature), the supernatant was removed, and the above medium was added to prepare a cell suspension.
[実施例1の繊維の製造]
実施例1の繊維製造用組成物を、試験例1と同様に電界紡糸法により紡糸し、ガラス基板上に10分間吹付けた後、205℃10分間加熱処理した。ガラス基板には、TEMPAX Float(登録商標)(Φ12mm、厚さ1mm)を使用した。得られた繊維をエタノールで洗浄して風乾した後、繊維形状を走査型電子顕微鏡(SEM)で確認した。実施例1の繊維製造用組成物から得られた繊維の直径は約1μmであった。
尚、以下において、実施例1の繊維製造用組成物を紡糸して繊維を形成したガラス基板を、便宜上「実施例1の繊維基板」と称する。[Production of fiber of Example 1]
The fiber manufacturing composition of Example 1 was spun by electrospinning as in Test Example 1, sprayed on a glass substrate for 10 minutes, and then heat-treated at 205 ° C. for 10 minutes. For the glass substrate, TEMPAX Float (registered trademark) (Φ12 mm, thickness 1 mm) was used. The obtained fiber was washed with ethanol and air-dried, and then the fiber shape was confirmed with a scanning electron microscope (SEM). The diameter of the fiber obtained from the fiber manufacturing composition of Example 1 was about 1 μm.
In the following, the glass substrate on which fibers are formed by spinning the composition for fiber production of Example 1 is referred to as “fiber substrate of Example 1” for convenience.
[細胞培養]
24穴平底マイクロプレート(コーニング社製)に、実施例1の繊維基板、及び対照として未処理のガラス基板を配置し、1%(v/v)ペニシリン/ストレプトマイシン溶液(GIBCO社製)を含むEMEM培地(和光純薬工業株式会社製)に15分浸漬した。この培地を除いた後、1.0×105cells/wellに調製したHek293(ヒト胎児腎細胞)の細胞懸濁液を各1mL加えた。その後、5%二酸化炭素濃度を保った状態で、37℃で24時間CO2インキュベーター内にて静置した。[Cell culture]
An EMEM containing a 1% (v / v) penicillin / streptomycin solution (GIBCO) containing the fiber substrate of Example 1 and an untreated glass substrate as a control on a 24-hole flat bottom microplate (Corning). It was immersed in a medium (Wako Pure Chemical Industries, Ltd.) for 15 minutes. After removing this medium, 1 mL each of a cell suspension of Hek293 (human embryonic kidney cells) prepared to 1.0 × 10 5 cells / well was added. Then, it was allowed to stand in a CO 2 incubator at 37 ° C. for 24 hours while maintaining a 5% carbon dioxide concentration.
[トリパンブルーを用いた細胞数計測]
24時間の細胞培養の後、細胞培養を行った実施例1の繊維基板、及びガラス基板の上清を除き、PBS2mLで洗浄した。PBSを除いた後、トリプシン−EDTA溶液(和光純薬工業株式会社製)300μLを添加した。37℃で5分間CO2インキュベーター内にて静置した後、10%(v/v)FBSを含むEMEM培地を1mL添加し、ピペッティングにて細胞を剥がした。剥がした細胞を1.5mLマイクロテストチューブ(エッペンドルフ社製)に移し、培養液の一部にトリパンブルー染色液(GIBCO社製)を同量添加後、セルカウンター(Bio−Rad社製、TC20)にて生細胞数を計測した。[Cell count using trypan blue]
After 24 hours of cell culture, the fiber substrate of Example 1 where the cell culture was performed and the supernatant of the glass substrate were removed, and the plate was washed with 2 mL of PBS. After removing PBS, 300 μL of trypsin-EDTA solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After leaving still in a CO 2 incubator at 37 ° C. for 5 minutes, 1 mL of EMEM medium containing 10% (v / v) FBS was added, and the cells were detached by pipetting. The peeled cells were transferred to a 1.5 mL micro test tube (Eppendorf), the same amount of trypan blue staining solution (GIBCO) was added to a part of the culture solution, and then a cell counter (Bio-Rad, TC20). The number of viable cells was counted.
[WST−8を用いた細胞数計測]
24時間の細胞培養の後、細胞培養を行った実施例1の繊維基板、及びガラス基板の上清を除き、PBS2mLで洗浄した。PBSを除いた後、10%(v/v)FBS及び1%(v/v)NEAA(GIBCO社製)を含むEMEM培地を1mL添加し、さらに100μLのWST−8試薬(キシダ化学社製)を添加した。37℃で100分間CO2インキュベーター内にて静置した後、反応溶液100μLを96穴平底マイクロプレートに移し、吸光度計(モレキュラーデバイス社製、SpectraMax)にて450nmの吸光度を測定した。[Counting the number of cells using WST-8]
After 24 hours of cell culture, the fiber substrate of Example 1 where the cell culture was performed and the supernatant of the glass substrate were removed, and the plate was washed with 2 mL of PBS. After removing PBS, 1 mL of EMEM medium containing 10% (v / v) FBS and 1% (v / v) NEAA (GIBCO) was added, and 100 μL of WST-8 reagent (Kishida Chemical) was added. Was added. After standing at 37 ° C. for 100 minutes in a CO 2 incubator, 100 μL of the reaction solution was transferred to a 96-well flat bottom microplate, and the absorbance at 450 nm was measured with an absorptiometer (SpectraMax, manufactured by Molecular Devices).
各細胞数計測の結果(n=2)の平均値)を表3に示す。 Table 3 shows the result of each cell count (average value of n = 2).
表3の結果から、実施例1の繊維基板上で細胞増殖することが分かり、実施例1の繊維製造用組成物により形成した繊維は、生体に対して無害であることが示された。さらに、実施例1の繊維基板上で培養した場合、ガラス基板上に比べて、細胞数の増加を示した。特に、WST−8による細胞数計測では、30%の細胞数増加が認められた。トリパンブルーによる細胞数計測では、全ての細胞を回収して細胞数を測定できた訳ではないが、約20%の細胞数増加が認められた。 From the results of Table 3, it was found that cells proliferated on the fiber substrate of Example 1, and it was shown that the fiber formed by the fiber manufacturing composition of Example 1 was harmless to the living body. Furthermore, when it culture | cultivated on the fiber substrate of Example 1, the increase in the number of cells was shown compared with the glass substrate. In particular, in the cell count measurement with WST-8, a 30% increase in cell count was observed. In the cell count measurement using trypan blue, not all cells were recovered and the cell count could be measured, but an increase of about 20% was observed.
本発明によれば、安全性に優れ、簡便に製造可能で、且つ有機溶剤耐性を有する繊維、該繊維を製造するための原料組成物、及び該繊維を含む生体適合材料を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in safety, can manufacture easily, and can provide the fiber which has organic-solvent tolerance, the raw material composition for manufacturing this fiber, and the biocompatible material containing this fiber.
本出願は、日本で出願された特願2013-264435(出願日:2013年12月20日)を基礎としており、その内容は本明細書に全て包含されるものである。 This application is based on Japanese Patent Application No. 2013-264435 filed in Japan (filing date: December 20, 2013), the contents of which are incorporated in full herein.
Claims (16)
(B)酸化合物
を含有する組成物を紡糸して製造される繊維。
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕(A) A condensation product obtained by condensing one or more compounds represented by general formula (1), and (B) a fiber produced by spinning a composition containing an acid compound.
R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. Represents an aryl group of formula 6-14;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ]
上記R2、R3、R4およびR5が、同一又は異なって、水素原子、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、ビニル基、プロペニル基、ブテニル基、メチル基、エチル基、プロピル基及びブチル基から選ばれる、請求項1又は2記載の繊維。R 1 is selected from an amino group, a vinyl group, a propenyl group, a butenyl group, a phenyl group, and a naphthyl group, which may be substituted with a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or a hydroxymethyl group. And
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a vinyl group, a propenyl group, or a butenyl group. The fiber according to claim 1, wherein the fiber is selected from methyl group, ethyl group, propyl group, and butyl group.
R1Aは、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物、及び/又は
一般式(1B):
R1Bは、炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物を縮合して得られる縮合生成物である、請求項1又は2記載の繊維。(A) The condensation product is represented by the general formula (1A):
R 1A represents an amino group which may be substituted with an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. And / or general formula (1B):
R 1B represents an aryl group having 6 to 14 carbon atoms;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. The fiber of Claim 1 or 2 which is a condensation product obtained by condensing the compound represented by this.
(B)酸化合物
を含有する繊維製造用組成物。
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕(A) A condensation product obtained by condensing one or more of the compounds represented by the general formula (1), and (B) a composition for fiber production containing an acid compound.
R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. Represents an aryl group of formula 6-14;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ]
R1Aは、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物、及び/又は
一般式(1B):
R1Bは、炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕で表される化合物を縮合して得られる縮合生成物である、請求項8又は9記載の組成物。(A) The condensation product is represented by the general formula (1A):
R 1A represents an amino group which may be substituted with an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. And / or general formula (1B):
R 1B represents an aryl group having 6 to 14 carbon atoms;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. The composition of Claim 8 or 9 which is a condensation product obtained by condensing the compound represented by this.
(第二工程)前記(A)縮合生成物溶液に(B)酸化合物及び(C)溶剤を添加して繊維製造用組成物を得る工程、および
(第三工程)前記繊維製造用組成物を紡糸する工程
を含む、繊維の製造方法。
R1は、炭素原子数2〜6のアルコキシメチル基若しくはヒドロキシメチル基で置換されていてもよいアミノ基、炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基又は炭素原子数6〜14のアリール基を示し;
R2、R3、R4およびR5は、同一又は異なって、水素原子、ヒドロキシメチル基、炭素原子数2〜6のアルコキシメチル基、炭素原子数2〜6のアルケニル基又は炭素原子数1〜6のアルキル基を示す。〕(First step) (A) A step of obtaining a condensation product solution by condensing a monomer composition containing one or more compounds represented by general formula (1),
(Second step) (A) A step of adding an acid compound and (C) solvent to the condensation product solution to obtain a composition for fiber production, and (Third step) a composition for fiber production. A method for producing a fiber, comprising a step of spinning.
R 1 is an amino group optionally substituted by an alkoxymethyl group having 2 to 6 carbon atoms or a hydroxymethyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom. Represents an aryl group of formula 6-14;
R 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom, a hydroxymethyl group, an alkoxymethyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group of ˜6. ]
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JP2015553616A Expired - Fee Related JP6701733B2 (en) | 2013-12-20 | 2014-12-19 | FIBER, COMPOSITION FOR PRODUCING THE FIBER, AND BIOCOMPATIBLE MATERIAL CONTAINING THE FIBER |
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US (1) | US20160305044A1 (en) |
EP (1) | EP3085817A4 (en) |
JP (1) | JP6701733B2 (en) |
CN (1) | CN105829590A (en) |
SG (1) | SG11201605038QA (en) |
TW (1) | TW201529620A (en) |
WO (1) | WO2015093589A1 (en) |
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JPS5319425A (en) * | 1976-08-09 | 1978-02-22 | Asahi Chem Ind Co Ltd | Production of alcohol-modified melamine resin fibers |
US4145371A (en) * | 1976-10-01 | 1979-03-20 | Toray Industries, Inc. | Flame-retardant fiber having an excellent color-fastness and preparative method thereof |
JPS56128310A (en) * | 1980-02-09 | 1981-10-07 | British Industrial Plastics | Fiber containing cationic amino-formaldehyde resin and method |
JPS61136533A (en) * | 1984-12-03 | 1986-06-24 | フイリツプス ペトロリユーム コンパニー | Composition |
JPH03231957A (en) * | 1989-07-11 | 1991-10-15 | Basf Ag | High-modulus melamine resin molding |
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- 2014-12-19 US US15/106,463 patent/US20160305044A1/en not_active Abandoned
- 2014-12-19 TW TW103144639A patent/TW201529620A/en unknown
- 2014-12-19 CN CN201480069424.1A patent/CN105829590A/en active Pending
- 2014-12-19 EP EP14870890.2A patent/EP3085817A4/en not_active Withdrawn
- 2014-12-19 SG SG11201605038QA patent/SG11201605038QA/en unknown
- 2014-12-19 JP JP2015553616A patent/JP6701733B2/en not_active Expired - Fee Related
- 2014-12-19 WO PCT/JP2014/083658 patent/WO2015093589A1/en active Application Filing
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JPS5319425A (en) * | 1976-08-09 | 1978-02-22 | Asahi Chem Ind Co Ltd | Production of alcohol-modified melamine resin fibers |
US4145371A (en) * | 1976-10-01 | 1979-03-20 | Toray Industries, Inc. | Flame-retardant fiber having an excellent color-fastness and preparative method thereof |
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WO2013044014A1 (en) * | 2011-09-21 | 2013-03-28 | Donaldson Company, Inc. | Fibers made from soluble polymers |
CN102800490A (en) * | 2012-08-16 | 2012-11-28 | 黑龙江大学 | Method for directly preparing carbon fiber electrode containing nitrogen with melamine formaldehyde resin/polyvinyl accohol water solution through high-voltage electrostatic spinning technology |
Also Published As
Publication number | Publication date |
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CN105829590A (en) | 2016-08-03 |
WO2015093589A1 (en) | 2015-06-25 |
EP3085817A1 (en) | 2016-10-26 |
EP3085817A4 (en) | 2017-08-02 |
SG11201605038QA (en) | 2016-07-28 |
JP6701733B2 (en) | 2020-05-27 |
TW201529620A (en) | 2015-08-01 |
US20160305044A1 (en) | 2016-10-20 |
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