JP4054497B2 - Cellulose aqueous composition - Google Patents
Cellulose aqueous composition Download PDFInfo
- Publication number
- JP4054497B2 JP4054497B2 JP35521399A JP35521399A JP4054497B2 JP 4054497 B2 JP4054497 B2 JP 4054497B2 JP 35521399 A JP35521399 A JP 35521399A JP 35521399 A JP35521399 A JP 35521399A JP 4054497 B2 JP4054497 B2 JP 4054497B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- component
- water
- aqueous
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920002678 cellulose Polymers 0.000 title claims description 29
- 239000001913 cellulose Substances 0.000 title claims description 29
- 239000000203 mixture Substances 0.000 title claims description 18
- 235000001014 amino acid Nutrition 0.000 claims description 11
- 150000001413 amino acids Chemical class 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000004627 regenerated cellulose Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000013535 sea water Substances 0.000 claims description 3
- 239000004475 Arginine Substances 0.000 claims description 2
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004473 Threonine Substances 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005016 bacterial cellulose Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 11
- 229940024606 amino acid Drugs 0.000 description 10
- 238000002156 mixing Methods 0.000 description 6
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960003767 alanine Drugs 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960002429 proline Drugs 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 1
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 1
- 229930064664 L-arginine Natural products 0.000 description 1
- 235000014852 L-arginine Nutrition 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 229930182821 L-proline Natural products 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229950010030 dl-alanine Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- JFJBBPQJSGKGLB-UHFFFAOYSA-N manganese(2+) dinitrate dihydrate Chemical compound O.[N+](=O)([O-])[O-].[Mn+2].O.[N+](=O)([O-])[O-] JFJBBPQJSGKGLB-UHFFFAOYSA-N 0.000 description 1
- MQVIVNNXPOSYDA-UHFFFAOYSA-N manganese(2+) dinitrate trihydrate Chemical compound O.O.O.[Mn++].[O-][N+]([O-])=O.[O-][N+]([O-])=O MQVIVNNXPOSYDA-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
- HBTFASPVVFSRRI-UHFFFAOYSA-N manganese(2+);dinitrate;hydrate Chemical compound O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O HBTFASPVVFSRRI-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LFMTUFVYMCDPGY-UHFFFAOYSA-N n,n-diethylethanamine oxide Chemical compound CC[N+]([O-])(CC)CC LFMTUFVYMCDPGY-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- -1 nitric acid Manganese tetrahydrate Chemical compound 0.000 description 1
- 229940038580 oat bran Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 235000013930 proline Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 235000015099 wheat brans Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Jellies, Jams, And Syrups (AREA)
- Medicinal Preparation (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、再生セルロース繊維，再生セルロースフィルムや粒子などの再生セルロース成型体製造用の原液として、また医薬品，化粧品，食品等の基剤や、セルロース誘導体合成の中間体として有用な、セルロースの水性組成物に関する。
【０００２】
【従来の技術】
セルロースは、分子鎖の凝集性が強く、特定の溶媒、あるいは特定の条件下でしか溶解しない。これまで水性媒質への分散溶解に関しては種々の試みがなされている。例えば、工業的に使用されている再生セルロース成型品の製造方法は、主に二硫化炭素を用いるビスコース法と、銅アンモニア溶液に溶解する銅安法の２つの方法に限られている。しかし、どちらの方法も溶液を調製する過程や成型品を製造する過程で、毒性気体の発生や重金属の排出を避けることができず、作業環境面や地球環境的見地から見ても問題点がないとはいえない。
【０００３】
セルロース溶液の溶媒系としては他に、第三級アミンＮ−オキシドと水の混合溶媒系がセルロースを溶解することが古くから知られており、特にＮ−メチルモルホリンＮ−オキシドと水とから成る溶媒系（H.Chanzy et al.,J.Polym.Sci.:Polym.Phys.Ed.,18,1137(1980)）はセルロースの溶解力が高いため、工業利用が有力視されているが、環境面での問題点があった。また類似の溶媒系としては、ジメチルスルホキシドとテトラアルキルアンモニウム塩とＮ−メチルモルホリンＮ−オキシド若しくはトリエチルアミンＮ−オキシドとの溶媒系が知られている（特開平１−１９３３３８号公報）が、溶媒系が複雑であり、セルロース製品を製造した後の溶媒回収が難しいという問題点があった。
【０００４】
【発明が解決しようとする課題】
本発明においては、上記先行技術の問題点を鑑み、特別な前処理を行うことなく、穏和な条件下で、簡便な溶媒を用いてセルロース水性組成物を得ることを目的とした。
【０００５】
【課題を解決するための手段】
本発明者は、上記目的を達成するため研究を行った結果、水溶性アミノ酸、水溶液中で二価の陽イオンと陰イオンに解離する水溶性無機塩類、水から成る溶媒系を用いてセルロースを分散させることにより、上記課題を解決できることを見いだし、本発明を完成するに至った。
【０００６】
【発明の実施の形態】
本発明の実施の形態を説明する。
【０００７】
本発明で用いられるセルロースは、セルロースを含有する素材を表すものであり、その種類，起源，分子量，結晶系は問わない。例えば、木材パルプ，リンターパルプ，竹パルプのような脱リグニン処理を施した精製パルプ、綿繊維，麻繊維のようなセルロース系天然繊維又はそれらに脱リグニン処理を施した精製天然繊維、ビスコースやセルロース銅アンモニア溶液から凝固再生された再生セルロース成形物、小麦フスマ，えん麦フスマ，とうもろこし外皮，米糠，ビール粕，ダイズ粕，えんどう豆繊維，おから，リンゴ繊維，ビート繊維等の穀物又は果実由来の食物繊維、木材及び麦わらの様なリグノセルロース、微生物由来のバクテリアセルロース等が挙げられる。
【０００８】
本発明で用いる水溶性アミノ酸としては、水溶性のアミノ酸であれば種類，基源，立体構造は問わず、例えばプロリン，アルギニン，リジン，アラニン，グリシン，ヒスチジン，トレオニン等が挙げられ、これらを単独で、若しくは２種以上を選択して用いることができる。これらのアミノ酸の中でも、溶媒への溶解度の点からＬ−プロリン，Ｌ−アルギニン，Ｌ−リジン，Ｌ−アラニン，ＤＬ−アラニンから選択される１種又は２種以上を用いることが好ましい。
【０００９】
本発明で用いられる水溶液中で二価の陽イオンと陰イオンに解離する水溶性無機塩類としては、カルシウム，マグネシウム，銅，亜鉛，鉄，ニッケル等の二価の電荷を有する金属と、塩素，硫酸，硝酸などとの塩が用いられる。具体的には、塩化カルシウム，硝酸カルシウム無水物，硝酸カルシウム四水和物，塩化鉄，硫酸鉄七水和物，硝酸鉄六水和物，硝酸鉄九水和物，塩化バリウム，塩化マグネシウム，硫酸マグネシウム，硝酸マグネシウム，塩化ニッケル，硫酸ニッケル七水和物，硝酸ニッケル，塩化マンガン，硫酸マンガン，硝酸マンガン，硝酸マンガン一水和物，硝酸マンガン二水和物，硝酸マンガン三水和物，硝酸マンガン四水和物，硝酸マンガン六水和物，塩化亜鉛，硝酸亜鉛，硫酸亜鉛などが挙げられ、安全性，環境への影響面から酸化カルシウム，塩化マグネシウムが好ましい例として挙げられる。本発明においては、これらの無機塩を単独で、若しくは２種以上を組み合わせて配合する。本発明においてこれらの無機塩の基原は特に問わず、化学的に合成されたものを用いることもでき、また天然物由来のものをそのまま、若しくは精製したものを用いることもできる。さらに、海水を脱塩化ナトリウム処理した後乾燥させてなる海水乾燥物が、望ましい例として挙げられる。
【００１０】
本発明において、各必須成分の配合比は、特に限定されないが、セルロース１gに対して、無機塩０．０１〜５モル、アミノ酸０．０１〜５モル、精製水１０〜１０,０００ｇが好ましく、無機塩とアミノ酸の配合比はモル比で１：１０〜１０：１の範囲が好ましい。
【００１１】
本発明において、セルロース水性組成物は、セルロースが水性溶媒中に均一に分散若しくは溶解している状態をいい、液状，ゲル状の外観を呈する。
【００１２】
本発明のセルロース水性組成物は、精製水にアミノ酸，無機塩類，セルロースを添加して、常温で撹拌，均一化することにより容易に調製することができる。本発明においては、さらに目的に応じて、防腐剤，紫外線吸収剤などの添加剤を併用することができる。
【００１３】
【実施例】
さらに実施例により、本発明の特徴について詳細に説明する。
【００１４】
表１に示した処方にて、全成分を室温で混合，均一化することにより、セルロース水性組成物を調製した。調製したセルロース水性組成物を２５℃にて一昼夜保存した後、組成物の状態及び透明度の評価を行った。状態は溶液状，ゲル状として目視で評価した。また透明性については、「透明で白濁，沈殿が認められない：◎」，「わずかに白濁が認められるが沈殿は認められない：○」，「あきらかな白濁が認められるが沈殿は認められない：△」，「白濁，沈殿ともに認められる：×」として、目視で評価した。また、同時に無機塩若しくはアミノ酸を配合せずに同様にセルロース水性組成物を調製し、比較例１及び比較例２として、状態及び透明度の評価を行った。
【００１５】
【表１】
表１に示したように、本発明の実施例１〜実施例３においては、特別な前処理もなく、穏和な条件下での混合により、透明度の高い良好なセルロース水性組成物を得ることができ、またアミノ酸濃度を変化させることにより粘度の異なる組成物を得ることができることが示された。それに対し、アミノ酸若しくは無機塩を配合していない比較例１又は比較例２においては、セルロースが均一に分散若しくは溶解せず、２５℃で一昼夜保存することによりセルロースの沈殿が認められていた。
【００１７】
本発明の他の実施例４〜実施例６を表２〜表４に示した処方により調製した。これらのセルロース水性組成物は、常温ですべての成分を混合，均一化することにより調製した。これらの実施例においても、２５℃で一昼夜保存後に、状態及び透明度の評価を行った。
【００１８】
【表２】
【表３】
【表４】
表２〜表４に示したとおり、本発明の実施例４〜実施例６においても、穏和な条件下で、簡便な溶媒を用いて、透明度の高いセルロース水性組成物を得ることができることが示された。
【００２２】
【発明の効果】
以上詳述したように、本発明により、特別な前処理を行うことなく、穏和な条件下で、簡便な溶媒を用いてセルロース水性組成物を得ることをができた。[0001]
BACKGROUND OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention is an aqueous cellulose solution useful as a stock solution for the production of regenerated cellulose molded bodies such as regenerated cellulose fibers, regenerated cellulose films and particles, as a base for pharmaceuticals, cosmetics, foods, etc., and as an intermediate for cellulose derivative synthesis. Relates to the composition.
[0002]
[Prior art]
Cellulose has strong cohesiveness of molecular chains, and dissolves only in a specific solvent or under specific conditions. Various attempts have been made so far for dispersion and dissolution in aqueous media. For example, industrially used methods for producing regenerated cellulose molded products are limited to two methods, a viscose method using mainly carbon disulfide and a copper ammonium method dissolving in a copper ammonia solution. However, both methods cannot avoid the generation of toxic gases and the discharge of heavy metals in the process of preparing solutions and manufacturing molded products, and there are problems from the viewpoint of work environment and global environment. It cannot be said that there is no.
[0003]
As another solvent system for cellulose solution, it has been known for a long time that a mixed solvent system of tertiary amine N-oxide and water dissolves cellulose, and particularly comprises N-methylmorpholine N-oxide and water. Although the solvent system (H. Chanzy et al., J. Polym. Sci .: Polym. Phys. Ed., 18 , 1137 (1980)) has high dissolving power of cellulose, industrial use is considered to be promising. There was an environmental problem. As a similar solvent system, a solvent system of dimethyl sulfoxide, a tetraalkylammonium salt and N-methylmorpholine N-oxide or triethylamine N-oxide is known (Japanese Patent Laid-Open No. 1-193338). However, there is a problem that it is difficult to recover the solvent after producing the cellulose product.
[0004]
[Problems to be solved by the invention]
In the present invention, in view of the above-mentioned problems of the prior art, an object is to obtain a cellulose aqueous composition using a simple solvent under mild conditions without performing a special pretreatment.
[0005]
[Means for Solving the Problems]
As a result of researches to achieve the above object, the present inventor has found that cellulose is produced using a water-soluble amino acid, a water-soluble inorganic salt dissociated into a divalent cation and an anion in an aqueous solution, and a solvent system comprising water. It was found that the above-mentioned problems can be solved by dispersing, and the present invention has been completed.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
An embodiment of the present invention will be described.
[0007]
Cellulose used in the present invention represents a material containing cellulose, and its type, origin, molecular weight, and crystal system are not limited. For example, refined pulp subjected to delignification treatment such as wood pulp, linter pulp, bamboo pulp, cellulosic natural fiber such as cotton fiber and hemp fiber, or purified natural fiber subjected to delignification treatment on these, viscose, Regenerated cellulose moldings coagulated and regenerated from cellulose copper ammonia solution, wheat bran, oat bran, corn hull, rice bran, beer lees, soybean lees, pea fiber, okara, apple fiber, beet fiber, etc. Dietary fiber, lignocellulose such as wood and straw, and bacterial cellulose derived from microorganisms.
[0008]
The water-soluble amino acid used in the present invention is not limited in its type, base source and steric structure as long as it is a water-soluble amino acid, and examples thereof include proline, arginine, lysine, alanine, glycine, histidine, threonine, etc. Or, two or more types can be selected and used. Among these amino acids, it is preferable to use one or more selected from L-proline, L-arginine, L-lysine, L-alanine and DL-alanine from the viewpoint of solubility in a solvent.
[0009]
Examples of water-soluble inorganic salts that dissociate into divalent cations and anions in the aqueous solution used in the present invention include divalent charge metals such as calcium, magnesium, copper, zinc, iron, nickel, chlorine, Salts with sulfuric acid, nitric acid, etc. are used. Specifically, calcium chloride, calcium nitrate anhydrous, calcium nitrate tetrahydrate, iron chloride, iron sulfate heptahydrate, iron nitrate hexahydrate, iron nitrate nonahydrate, barium chloride, magnesium chloride, Magnesium sulfate, magnesium nitrate, nickel chloride, nickel sulfate heptahydrate, nickel nitrate, manganese chloride, manganese sulfate, manganese nitrate, manganese nitrate monohydrate, manganese nitrate dihydrate, manganese nitrate trihydrate, nitric acid Manganese tetrahydrate, manganese nitrate hexahydrate, zinc chloride, zinc nitrate, zinc sulfate and the like can be mentioned, and calcium oxide and magnesium chloride are preferable examples from the viewpoint of safety and environmental impact. In this invention, these inorganic salts are mix | blended individually or in combination of 2 or more types. In the present invention, the base of these inorganic salts is not particularly limited, and those chemically synthesized can be used, or those derived from natural products can be used as they are or after purification. A desirable example is a seawater dried product obtained by desalinating seawater and then drying it.
[0010]
In the present invention, the mixing ratio of each essential component is not particularly limited, but is preferably 0.01 to 5 mol of inorganic salt, 0.01 to 5 mol of amino acid, and 10 to 10,000 g of purified water with respect to 1 g of cellulose. The mixing ratio of the inorganic salt and the amino acid is preferably in the range of 1:10 to 10: 1 by molar ratio.
[0011]
In the present invention, the aqueous cellulose composition refers to a state in which cellulose is uniformly dispersed or dissolved in an aqueous solvent, and exhibits a liquid and gel-like appearance.
[0012]
The aqueous cellulose composition of the present invention can be easily prepared by adding amino acids, inorganic salts and cellulose to purified water and stirring and homogenizing at room temperature. In the present invention, additives such as preservatives and ultraviolet absorbers can be used in combination according to the purpose.
[0013]
【Example】
Further, the features of the present invention will be described in detail by way of examples.
[0014]
A cellulose aqueous composition was prepared by mixing and homogenizing all components at room temperature with the formulation shown in Table 1. The prepared aqueous cellulose composition was stored at 25 ° C. all day and night, and then the state and transparency of the composition were evaluated. The state was visually evaluated as a solution and a gel. In addition, regarding transparency, “transparent, cloudiness and precipitation are not recognized: ◎”, “slight cloudiness is observed but precipitation is not recognized: ○”, “clear cloudiness is observed but precipitation is not observed : Δ ”,“ both cloudiness and precipitation are recognized: × ”, and visually evaluated. At the same time, an aqueous cellulose composition was similarly prepared without blending an inorganic salt or amino acid, and as Comparative Example 1 and Comparative Example 2, the state and transparency were evaluated.
[0015]
[Table 1]
As shown in Table 1, in Examples 1 to 3 of the present invention, there is no special pretreatment, and a good cellulose aqueous composition having high transparency can be obtained by mixing under mild conditions. It was shown that compositions with different viscosities can be obtained by changing the amino acid concentration. On the other hand, in Comparative Example 1 or Comparative Example 2 in which no amino acid or inorganic salt was blended, cellulose was not uniformly dispersed or dissolved, and precipitation of cellulose was observed when stored at 25 ° C. overnight.
[0017]
Other Examples 4 to 6 of the present invention were prepared according to the formulations shown in Tables 2 to 4. These cellulose aqueous compositions were prepared by mixing and homogenizing all components at room temperature. Also in these examples, the state and transparency were evaluated after storage at 25 ° C. all day and night.
[0018]
[Table 2]
[Table 3]
[Table 4]
As shown in Tables 2 to 4, also in Examples 4 to 6 of the present invention, it is shown that a highly transparent aqueous cellulose composition can be obtained using a simple solvent under mild conditions. It was done.
[0022]
【The invention's effect】
As described above in detail, according to the present invention, an aqueous cellulose composition can be obtained using a simple solvent under mild conditions without performing a special pretreatment.
Claims (1)
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| JP35521399A JP4054497B2 (en) | 1999-12-15 | 1999-12-15 | Cellulose aqueous composition |
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