WO2022210141A1 - 分散液及び複合体、並びにこれらの製造方法 - Google Patents
分散液及び複合体、並びにこれらの製造方法 Download PDFInfo
- Publication number
- WO2022210141A1 WO2022210141A1 PCT/JP2022/013379 JP2022013379W WO2022210141A1 WO 2022210141 A1 WO2022210141 A1 WO 2022210141A1 JP 2022013379 W JP2022013379 W JP 2022013379W WO 2022210141 A1 WO2022210141 A1 WO 2022210141A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cnf
- cnc
- dispersion
- cellulose
- layer
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 187
- 239000002131 composite material Substances 0.000 title claims abstract description 185
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 69
- 239000001913 cellulose Substances 0.000 claims abstract description 69
- 239000002159 nanocrystal Substances 0.000 claims abstract description 26
- 239000002121 nanofiber Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims description 80
- 239000010419 fine particle Substances 0.000 claims description 56
- 239000000758 substrate Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 229920001971 elastomer Polymers 0.000 claims description 21
- 239000005060 rubber Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 239000002612 dispersion medium Substances 0.000 claims description 20
- 238000010008 shearing Methods 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 27
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 26
- 230000004888 barrier function Effects 0.000 abstract description 25
- 238000001035 drying Methods 0.000 abstract description 23
- 230000000704 physical effect Effects 0.000 abstract description 5
- 239000002134 carbon nanofiber Substances 0.000 description 252
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 216
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 113
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 96
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 80
- 239000000203 mixture Substances 0.000 description 63
- 239000000123 paper Substances 0.000 description 44
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 40
- 239000000377 silicon dioxide Substances 0.000 description 39
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 38
- 239000004810 polytetrafluoroethylene Substances 0.000 description 38
- 229920002451 polyvinyl alcohol Polymers 0.000 description 36
- 239000007787 solid Substances 0.000 description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 description 27
- 239000012153 distilled water Substances 0.000 description 26
- 230000008859 change Effects 0.000 description 20
- -1 hydrogen ions Chemical class 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- 239000012528 membrane Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010586 diagram Methods 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000006259 organic additive Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000004497 NIR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011111 cardboard Substances 0.000 description 3
- 239000012611 container material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002009 alkene group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 1
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 229920006347 Elastollan Polymers 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical group CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002609 medium 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
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
- C08B5/14—Cellulose sulfate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/16—Esters of inorganic acids
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
- D21H17/27—Esters thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/16—Esters of inorganic acids
Definitions
- the present invention relates to dispersions and composites, and methods for producing them.
- CNF Cellulose nanofibers
- CNC Cellulose nanocrystals
- Raphael Bardet et al. "Substitution of nanoclay in high gas barrier films of cellulose nanofibrils with cellulose nanocrystals and thermal treatment," Cellulose 2015, 21-22, 22 Xiuxuan Sun et al., "Nanocellulose films with combined cellulose nanofibers and nanocrystals: tailored thermal, optical and mechanical properties", Cellulose 2018, 25, 1103-111 Pedro Claro et al., “Curaua and eucalyptus nanofiber films by continuous casting: mixture of cellulose nanocrystals and nanofibrils," Cellulose 2019, 26, 2453-2470
- a composite containing CNF and CNC as described in Non-Patent Documents 1 to 3 is manufactured by applying and/or filtering a dispersion containing CNF and CNC and drying the resulting product.
- the dispersion liquid is dried to remove the dispersion medium to obtain a dry body, which is transported and / or stored, and the dispersion medium is added to the dry body to obtain the dispersion liquid again. is obtained and used for the manufacture of the composite. Therefore, it is desirable that the dispersion has little change in its physical properties (specifically, viscosity) even after being dried and re-dispersed. It is also desirable that the dispersion have a long pot life.
- composites containing CNF and CNC are required to have higher breaking strength and oxygen gas barrier properties when used as packaging materials or container materials.
- the present invention provides a CNF and CNC dispersion that maintains its physical properties even after drying and redispersion and has a long pot life.
- the present invention also provides composites of CNF and CNC having higher breaking strength and oxygen gas barrier properties. Further, the present invention provides methods of making such dispersions and composites.
- a dispersion containing cellulose nanofibers having sulfate ester groups and cellulose nanocrystals having sulfate ester groups is provided.
- a composite that includes cellulose nanofibers having sulfate ester groups and cellulose nanocrystals having sulfate ester groups.
- a dispersion of cellulose nanofibers having a sulfate ester group and a dispersion of cellulose nanocrystals having a sulfate ester group are subjected to a shear force.
- a method is provided comprising mixing while adding the
- a method for producing the composite of the above aspect comprising: (a) forming a first layer comprising one of cellulose nanofibers having sulfate groups or cellulose nanocrystals having sulfate groups and a liquid; (b) supplying a dispersion containing the other of cellulose nanofibers having sulfate ester groups or cellulose nanocrystals having sulfate ester groups onto the first layer to form a second layer on the first layer; , (c) removing liquid from the first layer and the second layer;
- a method is provided, comprising: This specification includes the disclosure of Japanese Patent Application No. 2021-059274, which is the basis of priority of this application.
- the dispersion of the present invention maintains its physical properties even after drying and redispersion, and has a long pot life. Also, the composite of the present invention has higher breaking strength and oxygen gas barrier properties.
- FIG. 1 is a diagram showing an example of sulfated CNF.
- FIG. 2 is a diagram showing an example of a sulfated CNC.
- FIG. 3 is a diagram schematically showing a composite according to one embodiment.
- FIG. 4 is a diagram schematically showing a composite according to one embodiment.
- FIG. 5 is a diagram schematically showing a composite according to one embodiment.
- FIG. 6 is a diagram schematically showing a composite according to one embodiment.
- FIG. 7 is a diagram schematically showing a composite according to one embodiment.
- FIG. 8 is a diagram schematically showing a composite according to one embodiment.
- FIG. 9 is a diagram schematically showing a composite according to one embodiment.
- FIG. 10 is a diagram schematically showing a composite according to one embodiment.
- FIG. 11 is a diagram schematically showing a composite according to one embodiment.
- FIG. 12 is a diagram schematically showing a composite according to one embodiment.
- FIG. 13 is a diagram schematically showing
- Dispersion contains CNF having a sulfate ester group (also referred to as sulfate esterified CNF) and CNC having a sulfate ester group (also referred to as sulfate esterified CNC) as dispersoids.
- CNF having a sulfate ester group
- CNC having a sulfate ester group
- dispersoids also referred to as sulfate esterified CNC
- CNF is a fiber composed of cellulose.
- Cellulose is a polysaccharide in which glucose is ⁇ -1,4-glycosidically linked and is represented by (C 6 H 10 O 5 ) n .
- CNF usually has a fiber width (fiber diameter (equivalent projected area diameter)) within the range of 4 nm to 100 nm and a fiber length within the range of 0.5 ⁇ m to 100 ⁇ m.
- an atomic force microscope SPM-9700HT, manufactured by Shimadzu Corporation
- SPM-9700HT is used to measure the fiber width and fiber length of 50 arbitrarily selected CNFs, and the addition average is obtained. It can be obtained by calculation.
- a CNC is a needle-like crystal composed of cellulose.
- CNCs typically have a minor axis length in the range of 4 nm to 100 nm and a major axis length in the range of 50 nm to less than 0.5 ⁇ m.
- the length of the short axis and the long axis is measured using, for example, an atomic force microscope (SPM-9700HT, manufactured by Shimadzu Corporation), the length of the long axis and the short axis of 50 arbitrarily selected CNCs. can be obtained by calculating the addition average of each.
- Sulfated CNF is CNF in which at least one OH group in cellulose constituting CNF is substituted with a sulfate ester group.
- a sulfated CNC is a CNC in which at least one OH group in cellulose constituting the CNC is substituted with a sulfate ester group.
- the sulfate ester group is represented by formula (1): (wherein M represents a monovalent to trivalent cation). When M is a divalent or trivalent cation, M ionically bonds to two or three -OSO 3 - .
- Examples of monovalent to trivalent cations include hydrogen ions, metal ions, and ammonium ions.
- Metal ions include alkali metal ions, alkaline earth metal ions, transition metal ions, and other metal ions.
- Alkali metals include lithium, sodium, potassium, rubidium, cesium and the like.
- Alkaline earth metals include calcium, strontium, and the like.
- Transition metals include iron, nickel, palladium, copper, silver, and the like. Other metals include beryllium, magnesium, zinc, and aluminum.
- ammonium ions not only NH 4 + but also ammonium ions derived from various amines in which one or more hydrogen atoms of NH 4 + are replaced with organic groups (e.g., quaternary ammonium cations, alkanolamine ions, pyridinium ions ) are also included.
- the cation may be one of the listed cations, or may be two or more.
- FIGS. 1 and 2 Examples of sulfated CNF and sulfated CNC are shown in FIGS. 1 and 2, respectively.
- both the sulfated CNF and the sulfated CNC have sulfate ester groups on the surface, so a large electrostatic repulsion acts on each other. Therefore, the dispersion according to the embodiment has high easy dispersibility and high dispersion stability.
- the sulfated CNF and the sulfated CNC have similar surface states, and thus have high affinity for each other. Therefore, in the dispersion liquid according to the embodiment, the sulfated CNF and the sulfated CNC are uniformly mixed, and microphase separation into a CNF-rich phase and a CNC-rich phase is unlikely to occur. Due to these, the dispersion according to the embodiment maintains its physical properties even after drying and redispersion, and has a long pot life. Furthermore, the dispersions according to embodiments can be used to produce composites in which CNF and CNC are uniformly mixed, and such composites can have high breaking strength and oxygen gas barrier properties.
- At least one of the sulfated CNF and the sulfated CNC may have other substituents in addition to the sulfate group.
- At least one of the OH groups in the cellulose constituting CNF or CNC may be substituted with other substituents.
- Other substituents may be, for example, anionic substituents and salts thereof, ester groups, ether groups, acyl groups, aldehyde groups, alkyl groups, alkylene groups, aryl groups, or may include two or more of these. good.
- the other substituent may be an anionic substituent or a salt thereof, or an acyl group.
- Anionic substituents include a carboxy group, a phosphate group, a phosphite group, and a xanthate group.
- the salt of the anionic substituent may be sodium salt, potassium salt, or calcium salt.
- the acyl group may be an acetyl group.
- the sulfate esterification modification rate in the sulfate esterified CNF can be set to any appropriate value depending on the application.
- the sulfate esterification modification rate in the sulfate esterified CNF can be represented by the sulfur content (% by mass) in the sulfate esterified CNF.
- the sulfur content (mass%) in the sulfated CNF is not limited, but is usually 0.05% to 30% by weight, preferably 0.1% to 25% by weight, more preferably 0.5% by weight. ⁇ 22% by weight.
- Sulfuric esterified CNF having a sulfur content of 30% by weight or less can have sufficient crystallinity and heat resistance.
- Sulfuric esterified CNF having a sulfur content of 0.05% by weight or more can be produced efficiently. This is because such CNFs electrostatically repel each other due to their sufficient amount of sulfate ester groups, and this causes the sulfate esterified pulp to defibrate and sulfate ester as described later in the manufacturing process. This is to reduce the energy required to obtain the compounded CNF.
- the sulfate esterification modification rate in the sulfate esterification CNC can be set to any appropriate value depending on the application.
- the sulfate esterification modification rate in the sulfate esterified CNC can be represented by the sulfur content (% by mass) in the sulfate esterified CNC, and is usually in the range of 0.05% by mass to 15% by mass. is not limited to
- the sulfur content (% by mass) of sulfated CNF and sulfate CNC can be determined as follows, for example, by combustion absorption-ion chromatography (IC) method.
- IC combustion absorption-ion chromatography
- ⁇ Measuring device ICS-1500 manufactured by Nippon Dionex Co., Ltd.
- ⁇ Measurement conditions A sample is weighed on a magnetic board, burned in an oxygen atmosphere (flow rate: 1.5 L / min) in a tubular furnace (1350 ° C.), and the generated gas component is added to 3% hydrogen peroxide water (20 mL). Absorption liquid is obtained by absorption.
- the resulting absorption liquid is diluted with pure water to 100 mL, and the diluted liquid is subjected to ion chromatography.
- the sulfated CNF can be produced by sulfate-esterifying raw material pulp and defibrating the obtained sulfate-esterified pulp.
- the sulfated CNF thus obtained has a crystalline portion and an amorphous portion.
- the degree of crystallinity of sulfated CNF depends on its raw material (cotton, wood, etc.).
- the sulfated CNF typically has a crystallinity of 20% to 99%, preferably 30% to 95%, more preferably 40% to 90%, even more preferably 50% to 85%.
- Sulfuric esterified CNF having a crystallinity of 20% or more can have sufficient heat resistance and rigidity. Sulfated CNF with crystallinity greater than 99% tend to be difficult to manufacture with sufficient fiber length.
- Sulfate-esterified CNC can be obtained by hydrolyzing the amorphous portion of raw pulp with sulfuric acid.
- the crystallinity of sulfated CNC is usually 85-100%, especially 90% or more.
- the crystallinity of sulfated CNF and sulfated CNC is obtained by dividing the peak area derived from cellulose crystals in the X-ray diffraction pattern by the sum of the halo area derived from amorphous and the peak area derived from crystals. , can be calculated.
- the mass ratio of the sulfated CNF and the sulfated CNC contained in the dispersion according to the embodiment may be within the range of 1:99 to 99:1. Thereby, the breaking strength and oxygen gas barrier properties of the composite produced using the dispersion liquid are further improved, as shown in the examples described later.
- the dispersion according to the embodiment further contains a dispersion medium.
- the dispersion medium can be a polar medium such as water, dimethylsulfoxide, dimethylformamide, ethylene glycol, diethyl ether, dioxane, tetrahydrofuran, methyltetrahydrofuran, or mixtures thereof.
- the dispersion medium may contain a liquid having a dielectric constant of 38 or higher in an amount within the range of 50 to 100% by volume, preferably 75 to 100% by volume, based on the total volume of the dispersion medium.
- the dispersion medium may contain a liquid having a dielectric constant of 38 or higher in an amount within the range of 80 to 100% by volume based on the total volume of the dispersion medium. This results in a longer pot life of the dispersion, as shown in the examples below.
- the dispersion according to the embodiment may optionally further contain an additive as a dispersoid.
- Additives may be inorganic additives or organic additives.
- Inorganic additives include silica, mica, talc, clay, carbon, carbonates (e.g. calcium carbonate, magnesium carbonate), oxides (e.g. aluminum oxide, titanium oxide, zinc oxide, iron oxide), ceramics (e.g. ferrite), or It may be an inorganic particulate such as a particulate of a mixture of these.
- the inorganic fine particles may be contained in an amount of 0.09-5% by mass based on the total weight of the dispersoid. As a result, the breaking strength of the composite produced using the dispersion is further improved, as shown in the examples described later.
- Organic additives include organic fine particles and functional compounds.
- the organic fine particles include fine particles of at least one substance selected from the group consisting of resins and rubbers, such as phenol resins, melamine resins, urea resins, alkyd resins, epoxy resins, unsaturated polyester resins, polyurethane resins, and polyethylene resins. (eg, high-density polyethylene, medium-density polyethylene, low-density polyethylene), polypropylene resin, polystyrene resin, acrylic resin, polyvinyl alcohol, acrylamide resin, silicone resin, natural rubber, synthetic rubber, or fine particles of mixtures thereof.
- Functional compounds include dyes, UV absorbers, antioxidants, antistatic agents, and surfactants.
- the dispersion liquid according to the embodiment can be dried by any method such as freeze-drying or spray-drying, if necessary.
- a dispersion liquid can be obtained again by adding a dispersion medium to the dried product and mixing them.
- a method of preparing a dispersion comprising sulfated CNF and sulfated CNC includes mixing a sulfated CNF dispersion and a sulfated CNC dispersion.
- the sulfated CNF dispersion may be prepared by any method. For example, a solution containing at least one of acetic anhydride or propionic anhydride, dimethyl sulfoxide, and sulfuric acid is mixed with raw material pulp to obtain sulfate-esterified pulp. The sulfated pulp is then stirred together with the dispersion medium described above. Agitation may be performed, for example, by sonication. Thereby, the sulfated pulp is defibrated to obtain a sulfated CNF dispersion.
- the sulfated CNC dispersion may be prepared by any method.
- a sulfuric acid-esterified CNC dispersion can be obtained by hydrolyzing the amorphous portion of cellulose in raw material pulp with sulfuric acid, washing the obtained solid content, and stirring it together with an appropriate dispersion medium. can.
- the sulfated CNF dispersion and the sulfated CNC dispersion are mixed together. You may further add the additive mentioned above here. Mixing may be performed while applying shear forces. Thereby, the sulfated CNF and the sulfated CNC are well mixed.
- a composite manufactured using such a well-mixed dispersion can have higher breaking strength and oxygen gas barrier properties, as shown in the examples below.
- devices such as stirrers, three-roll mills, twin-screw kneaders, three-screw planetary kneaders, dispersers, paint shakers, bead mills, cutter mixers, and planetary mixers may be used.
- Mixing may be performed under any conditions, for example, at 20°C to 150°C for 5 minutes to 1 hour.
- the composite according to the embodiment includes sulfated CNF and sulfated CNC.
- the composite is a mixed composite in which sulfated CNF and sulfated CNC are mixed, as shown schematically in FIG.
- the composite comprises at least one layer of CNF containing sulfated CNF and at least one layer of CNC and a layer.
- the mass ratio of the sulfated CNF and the sulfated CNC contained in the mixed complex may be within the range of 1:99 to 99:1. As a result, the breaking strength and oxygen gas barrier properties of the mixed composite are further improved, as shown in the examples described later.
- the mixed composite may further contain an additive mixed with the sulfated CNF and the sulfated CNC.
- Additives may be inorganic additives or organic additives.
- the mixed composite may contain inorganic fine particles as an inorganic additive, as shown in FIG.
- inorganic fine particles include silica, mica, talc, clay, carbon, carbonates (e.g. calcium carbonate, magnesium carbonate), oxides (e.g. aluminum oxide, titanium oxide, zinc oxide, iron oxide), ceramics (e.g. ferrite), or fine particles of mixtures thereof.
- the mixed composite may contain inorganic fine particles in an amount within the range of 0.09 to 5% by weight based on the total weight of the mixed composite, thereby further improving the breaking strength of the mixed composite.
- the mixed composite may contain at least one substance selected from the group consisting of resins and rubbers as an organic additive, as shown in FIG.
- resins and rubbers include phenolic resins, melamine resins, urea resins, alkyd resins, epoxy resins, unsaturated polyester resins, polyurethane resins, polyethylene resins (e.g., high-density polyethylene, medium-density polyethylene, low-density polyethylene), and polypropylene.
- At least one substance selected from the group consisting of resins and rubbers can further improve the breaking strength of the mixed composite.
- the mixed composite may contain functional compounds as organic additives. Functional compounds include dyes, UV absorbers, antioxidants, antistatic agents, and surfactants.
- the mixed complex may have a crosslinked structure as shown in FIG. Specifically, cross-linking is formed between at least one of the sulfated CNF and at least one substance selected from the group consisting of the sulfated CNF, the sulfated CNC, or the resin and rubber. may be Additionally or alternatively, between at least one of the sulfated CNC and at least one of the sulfated CNF, the sulfated CNC, or at least one material selected from the group consisting of resin and rubber. , a cross-link may be formed.
- Crosslinking is performed by combining a hydroxy group of cellulose with another hydroxy group of cellulose, or a reactive site (e.g., hydroxy group, aldehyde group, carboxy group, methoxy group) of at least one substance selected from the group consisting of resins and rubbers. , carbonyl group, alkene moiety, ether moiety) can be formed by combining with each other through a condensation reaction or an addition reaction.
- the type of bond is not particularly limited, but examples include urethane bond, ester bond, ether bond, amide bond, and urea bond.
- cross-linking containing urethane bonds can improve the oxygen gas barrier properties of the mixed composite.
- the mixed composite having a crosslinked structure may contain the inorganic fine particles described above, as shown in FIG.
- crosslinks can be confirmed by any method such as infrared spectroscopy, near-infrared spectroscopy, Raman spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, gel permeation chromatography, and differential scanning calorimetry.
- the types of chemical bonds that form crosslinks can be identified by any method such as infrared spectroscopy, near-infrared spectroscopy, Raman spectroscopy, and nuclear magnetic resonance spectroscopy.
- the mixed composite may be supported by a substrate, as shown in FIG. That is, a composite according to one embodiment may include a mixed composite containing the above-described sulfated CNF and sulfated CNC, and a substrate supporting the mixed composite.
- the substrate may be a paper substrate containing cellulose as a main component, such as filter paper, western paper, Japanese paper, pulp sheet, kraft paper, and base paper for corrugated board.
- the paper substrate may contain inorganic fine particles such as talc, a fluorescent agent, a resin such as polyethylene, and the like.
- the OH group of cellulose which is the main component of the paper base material, forms a very strong hydrogen bond with the sulfate ester group. Therefore, the mixed composite containing the sulfated CNF and the sulfated CNC and the paper substrate can be bonded with sufficient strength. Also, a composite comprising a paper substrate and a mixed composite supported thereon can have higher gas barrier properties and higher breaking strength than the paper substrate alone. Accordingly, such composites can be used as replacements with enhanced functionality for paper products such as wrapping materials, packing materials (eg corrugated board), container materials and the like.
- (3-2) Laminate Composite In the laminate composite, at least one CNF layer and at least one CNC layer are adjacent to each other. At least one CNF layer and at least one CNC layer may be alternately stacked.
- the laminated composite has one CNF layer 1 and one CNC layer 3 thereon, as shown in FIG.
- the laminate composite has two CNF layers 1 with one CNC layer 3 therebetween, as shown in FIG.
- the laminated composite has two CNC layers 3 with one CNF layer 1 therebetween, as shown in FIG.
- Sulfate-esterified CNF and sulfate-esterified CNC both have sulfate ester groups on their surfaces and have similar surface states, so they have high affinity for each other. Therefore, the adhesive strength between the CNF layer and the CNC layer is high, so the mixed composite can have high breaking strength and oxygen gas barrier properties.
- At least one of the CNF layer and the CNC layer may further contain additives.
- the additive may be an inorganic additive or an organic additive as described above.
- At least one of the CNF layer and the CNC layer may contain inorganic fine particles in an amount within the range of 0.09 to 5% by weight based on the total weight of the layer. This further improves the breaking strength of the laminated composite.
- the interface between the layer containing the inorganic fine particles and the layer adjacent to that layer has irregularities due to the presence of the inorganic fine particles, and this increases the adhesive strength between these mutually adjacent layers due to the anchor effect.
- At least one of the CNF layer and the CNC layer may further contain at least one substance selected from the group consisting of resin and rubber. This further improves the breaking strength of the laminated composite.
- resins and rubbers include phenolic resins, melamine resins, urea resins, alkyd resins, epoxy resins, unsaturated polyester resins, polyurethane resins, polyethylene resins (e.g., high-density polyethylene, medium-density polyethylene, low-density polyethylene), and polypropylene.
- At least one of the CNF layer and the CNC layer may have a crosslinked structure.
- crosslinks may be formed between at least one of the sulfated CNFs and at least one of the sulfated CNFs or at least one substance selected from the group consisting of resins and rubbers.
- the CNC layer between at least one of the sulfated CNC and at least one of the sulfated CNC or at least one material selected from the group consisting of resin and rubber, Crosslinks may be formed.
- Crosslinking is performed by combining a hydroxy group of cellulose with another hydroxy group of cellulose, or a reactive site (e.g., hydroxy group, aldehyde group, carboxy group, methoxy group) of at least one substance selected from the group consisting of resins and rubbers. , carbonyl group, alkene moiety, ether moiety) can be formed by combining with each other through a condensation reaction or an addition reaction.
- the type of bond is not particularly limited, but examples include urethane bond, ester bond, ether bond, amide bond, and urea bond.
- a crosslinked structure containing urethane bonds can improve the oxygen gas barrier properties of the laminated composite.
- crosslinks can be confirmed by any method such as infrared spectroscopy, near-infrared spectroscopy, Raman spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, gel permeation chromatography, and differential scanning calorimetry.
- the types of chemical bonds that form crosslinks can be identified by any method such as infrared spectroscopy, near-infrared spectroscopy, Raman spectroscopy, and nuclear magnetic resonance spectroscopy.
- the laminated composite may be supported by a substrate. That is, as shown in FIG. 13, the composite according to one embodiment includes a laminated composite 10 including at least one CNF layer 1 and at least one CNC layer 3, and a substrate 5 that supports it. may contain.
- the substrate 5 may be a paper substrate containing cellulose as a main component, such as filter paper, western paper, Japanese paper, pulp sheet, kraft paper, and cardboard base paper.
- the paper substrate may contain inorganic fine particles such as talc, a fluorescent agent, a resin such as polyethylene, and the like.
- the OH group of cellulose which is the main component of the paper base material, forms a very strong hydrogen bond with the sulfate ester group of sulfate-esterified CNF and sulfate-esterified CNC.
- the laminated composite can adhere with sufficient strength to the paper substrate.
- a composite comprising a paper substrate and a laminated composite supported thereon can have higher gas barrier properties and higher breaking strength than the paper substrate alone. Accordingly, such composites can be used as replacements with enhanced functionality for paper products such as wrapping materials, packing materials (eg corrugated board), container materials and the like.
- the mixed composite contains at least one substance selected from the group consisting of resins and rubbers
- the mixed composite further contains fine particles of at least one substance selected from the group consisting of resins and rubbers. It can be produced by drying the liquid. During drying, the dispersion may be heated and/or pressurized. The dried body after drying may be heated and/or pressurized.
- a mixed composite containing at least one substance selected from the group consisting of resins and rubbers is obtained by drying a dispersion containing sulfated CNF and sulfated CNC to obtain sulfated CNF and sulfated It can also be produced by obtaining a CNC mixed powder, adding at least one substance selected from the group consisting of resins and rubbers, mixing the mixture, and heating and/or pressurizing the mixture.
- the mixed composite When the mixed composite has a crosslinked structure, the mixed composite is obtained by adding a cross-linking agent to the dispersion containing the above-mentioned sulfated CNF and sulfated CNC to cause a cross-linking reaction, and then drying the dispersion. , can be manufactured.
- the mixed composite may be molded into a desired shape depending on the application.
- the dispersion may be dried on a substrate as described above, especially a paper substrate. Thereby, a composite is produced that includes the mixed composite and the substrate that supports it. Such composites can be produced in a short time because dispersions on paper substrates can dry quickly.
- a method of manufacturing a laminated composite comprises: (a) forming a first layer comprising one of sulfated CNF or sulfated CNC and a liquid; and (b) on the first layer, sulfated CNF or providing a dispersion comprising the other of the sulfated CNCs to form a second layer on the first layer; and (c) removing liquid from the first and second layers.
- a layer of a dispersion containing either sulfated CNF or sulfated CNC is formed to form a first layer.
- the liquid content of the first layer may be greater than 0% by mass, particularly 5% by mass or more. This improves the adhesion between the first layer and the second layer formed thereon, as shown in the examples below. It is considered that this is because the sulfated CNF and the sulfated CNC are mixed and entangled to a predetermined depth or more at the interface between the first layer and the second layer.
- the liquid content of the first layer may be 30% by mass or less, particularly 20% by mass or less. The liquid content of the first layer can be adjusted by forming a dispersion layer and then drying this layer to reduce the dispersion medium.
- step (b) a dispersion containing the other of sulfated CNF or sulfated CNC is supplied onto the first layer to form a second layer on the first layer.
- Step (a) and step (b) may be alternately repeated to form a total of three or more first layers and second layers.
- the second layer in step (b), the second layer may be dried to adjust the liquid content of the second layer.
- the liquid content of the second layer after drying may be more than 0% by mass, particularly 5% by mass or more. This improves the adhesion between the second layer and the first layer formed thereon. Further, the liquid content of the second layer after drying may be 30% by mass or less, particularly 20% by mass or less.
- step (c) the first layer and the second layer are dried to remove the dispersion medium contained in the first layer and the second layer.
- a drying method any method such as natural drying, reduced pressure drying, warm air drying, or the like can be used.
- a laminated mixture as described above is obtained.
- the first layer may be formed on the base material described above, particularly a paper base material.
- a composite including the laminated composite and the substrate supporting it is manufactured.
- Such composites can be produced in a short time because dispersions on paper substrates can dry quickly.
- Sample A Sulfate-esterified CNF dispersion in water 300 g of dimethyl sulfoxide, 33.3 g of acetic anhydride, and 4.3 g of sulfuric acid having a concentration of 98% by weight are mixed in a 1 L flask with a stirrer tip. Stir to mix. Subsequently, 10 g of softwood bleached kraft pulp (NBKP) (“CARIBOO” manufactured by Cariboo Pulp and Paper Company) was added and stirred at room temperature for 4 hours to sulfate the NBKP. After that, a 5% sodium hydroxide aqueous solution was added dropwise to adjust the pH of the reaction mixture to 7.0.
- NNKP softwood bleached kraft pulp
- the reaction mixture was filtered through a nylon mesh (“PA-11 ⁇ ” manufactured by AS ONE Co., Ltd.) and rinsed with distilled water at the same time.
- a sulfate esterified pulp was obtained.
- the sulfate esterified pulp was transferred to a 1 L flask, distilled water was added so that the solid content concentration was 1%, and ultrasonic treatment was performed. Thereby, a sulfated CNF dispersion in water (Sample A) having a solid content concentration of 1% by mass was obtained.
- Sample B Sulfuric esterified CNF dispersion in N,N-dimethylformamide (DMF) In the same manner as Sample A, except that DMF was used instead of distilled water, the solid content concentration was 1% by mass, in DMF. A sulfated CNF dispersion (Sample B) was obtained.
- DMF N,N-dimethylformamide
- Sample C Sulfate-esterified CNF dispersion in ethylene glycol Sulfate-esterified CNF dispersion in ethylene glycol having a solid content concentration of 1% by mass in the same manner as sample A, except that ethylene glycol was used instead of distilled water. A liquid (Sample C) was obtained.
- Sample H Sulfate-esterified CNF dispersion in formamide A sulfate-esterified CNF dispersion in formamide having a solid content concentration of 1% by mass (sample H) was obtained.
- Sample L TEMPO-oxidized CNF dispersion in water 0.25 mmol 2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO) and 20 mmol sodium bromide were dissolved in water to give a 500 mL aqueous solution.
- 10 g of absolutely dry NBKP (“CARIBOO” manufactured by Cariboo Pulp and Paper Company) was added and stirred until the pulp was uniformly dispersed. After the temperature of the mixture was brought to 20° C., 64 mmol of an aqueous sodium hypochlorite solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to initiate an oxidation reaction.
- the temperature of the reaction system was kept at 20° C., and the pH was maintained at 10 by successively adding 3N sodium hydroxide aqueous solution. After reacting for 3 hours, the resulting product was filtered through a glass filter and washed thoroughly with water. Thereby, an oxidized pulp was obtained.
- Sample M Phosphated CNF dispersion in water 10 g urea, 5.53 g sodium dihydrogen phosphate dihydrate, and 4.13 g disodium hydrogen phosphate were dissolved in 10.9 g water and phosphorylated Reagents were prepared.
- a dried NBKP (“CARIBOO” manufactured by Cariboo Pulp and Paper Company) sheet was processed with a cutter mill and a pin mill to obtain cotton-like fibers.
- the phosphorylation reagent was evenly sprayed on cotton-like fibers having an absolute dry weight of 10 g, and kneaded by hand to obtain an impregnated pulp.
- the impregnated pulp was heat-treated for 80 minutes in a blower dryer with a damper heated to 140°C. A phosphorylated pulp was thereby obtained.
- the sheet and 1 L of ion-exchanged water were stirred until they were uniformly dispersed, and the dispersion was filtered and dehydrated.
- the resulting sheet was treated in the same way two more times.
- the obtained sheet and ion-exchanged water were mixed to obtain a slurry of 0.5% by mass.
- This slurry was defibrated for 180 minutes at 6900 rpm using a fibrillation treatment apparatus (“CLEARMIX-11S” manufactured by M-Technic Co., Ltd.).
- Ion-exchanged water was added to adjust the solid content concentration of the slurry to 1% by mass. Thereby, a phosphorylated CNF dispersion in water (Sample M) having a solid content concentration of 1% by mass was obtained.
- Sample N Sulfated CNC Dispersion in Water 800 mL of 58% sulfuric acid was heated to 50° C. in a 2 L flask. 100 g of absolute dry NBKP (“CARIBOO” manufactured by Cariboo Pulp and Paper Company) was added to the flask and stirred for 3 hours. The resulting product was treated at 20,000 G for 10 minutes with a centrifuge ("CT18R" manufactured by Eppendorf Himac Technologies). Subsequently, the supernatant was removed by decantation, and 400 mL of distilled water was added to suspend the pellets. Similar centrifugation, decantation, addition of distilled water, and suspension were performed twice more. A sulfated CNC dispersion in water (Sample N) was thereby obtained.
- CARIBOO absolute dry NBKP
- Sample O Sulfuric Acid Esterified CNC Dispersion in DMF Sample N was dried with a freeze dryer (“FDU-12AS” manufactured by AS ONE) to obtain CNC powder. DMF was added to the CNC powder so that the solid content concentration was 1% by mass, and treated with Primix Homodisper 2.5 type for 2 minutes. A CNC dispersion in DMF (Sample O) was thereby obtained with a solids concentration of 1% by weight.
- FDU-12AS freeze dryer
- Sample P CNC Dispersion in Ethylene Glycol A CNC dispersion in ethylene glycol (Sample P) having a solid content concentration of 1% by mass was obtained in the same manner as Sample O, except that ethylene glycol was used instead of DMF. rice field.
- Sample U CNC Dispersion in Formamide A CNC dispersion in formamide (Sample U) having a solid content concentration of 1% by mass was obtained in the same manner as Sample O, except that formamide was used instead of DMF.
- This dispersion liquid was poured into a rectangular PTFE container with internal dimensions of 20 cm x 20 cm x 5 cm, and allowed to air dry at room temperature for 2 weeks to form a film.
- Remove the membrane from the PTFE container, cut it with a sample cutter ("SDL200" manufactured by Dumbbell Co.), and prepare a dumbbell-shaped sample containing sulfated CNF and sulfated CNC (CNF: CNC 50: 50 (mass ratio)).
- the tested part of the composite had a thickness of 25 ⁇ m, a width of 10 mm and a length of 100 mm.
- silica fine particles (“HS-208” manufactured by Nippon Steel Chemical & Materials Co., Ltd.)
- M-110EH microfluidizer
- FDU-12AS freeze dryer
- Example 26 4.68 mL of a dispersion of CNF and CNC prepared in the same manner as in Example 1, 1.5 g of polyvinyl alcohol fine particles ("Kuraray Poval” manufactured by Kuraray), and 100 mL of distilled water were stirred in a beaker for 24 hours. , to obtain a dispersion.
- a radical generator (“Perhexa 25B-40” manufactured by NOF Corporation) was added thereto, and the mixture was placed in a Teflon (registered trademark) tray and dried at 80° C. for 3 days.
- the resulting product was rolled four times at 100° C. using a three-roll rolling machine (manufactured by Imoto Seisakusho Co., Ltd., model 1983).
- SDL200 sample cutting machine manufactured by Dumbbell Co.
- Example 28 4.68 mL of a dispersion of CNF and CNC prepared in the same manner as in Example 1, 1.5 g of polyvinyl alcohol fine particles ("Kuraray Poval" manufactured by Kuraray), and 100 mL of distilled water were stirred in a beaker for 24 hours. , to obtain a dispersion. To the resulting dispersion were added 0.01 g of 1N hydrochloric acid and 0.3 g of a 37 mass % formaldehyde aqueous solution. Thereby, a crosslinked structure was formed via an acetal bond. A dumbbell-shaped composite was produced in the same manner as in Example 1 using the dispersion after the cross-linking reaction.
- Kuraray Poval manufactured by Kuraray
- Example 29 41 g of diphenylmethane diisocyanate was added to 150 g of a dispersion of CNF and CNC prepared in the same manner as in Example 9, and the mixture was stirred at 50° C. for 3 hours. Thereby, the OH groups of CNF, CNC, and ethylene glycol reacted with the NCO groups of diphenylmethane diisocyanate to form urethane linkages. As a result, a crosslinked product in which CNF, CNC, and urethane resins are crosslinked via urethane bonds was obtained.
- the dispersion liquid after the reaction was rolled four times at 100° C. using a three-roll rolling mill (manufactured by Imoto Seisakusho Co., Ltd., model 1983). The resulting membrane was cut with a sample cutter ("SDL200" manufactured by Dumbbell Co.) to prepare a dumbbell-shaped composite.
- SDL200 sample cutter
- Example 30 4.68 mL of a CNF and CNC dispersion liquid prepared in the same manner as in Example 1, 1.5 g of polyvinyl alcohol fine particles ("Kuraray Poval” manufactured by Kuraray), 100 mL of distilled water, and 0.05 g of diphenylmethane diisocyanate were added to 50 C. for 24 hours. Thereby, a crosslinked structure was formed via urethane bonds.
- a dumbbell-shaped composite was produced in the same manner as in Example 1 using the dispersion after the cross-linking reaction.
- Example 31 20.5 g of diphenylmethane diisocyanate was added to 150 g of a dispersion of CNF and CNC prepared in the same manner as in Example 16, and the mixture was stirred at 50° C. for 3 hours. Thereby, the OH groups of CNF, CNC, and ethylene glycol reacted with the NCO groups of diphenylmethane diisocyanate to form urethane linkages. As a result, a crosslinked product in which CNF, CNC, and urethane resins are crosslinked via urethane bonds was obtained.
- the dispersion liquid after the reaction was rolled four times at 100° C. using a three-roll rolling mill (manufactured by Imoto Seisakusho Co., Ltd., Model 1983). The resulting membrane was cut with a sample cutter ("SDL200" manufactured by Dumbbell Co.) to prepare a dumbbell-shaped composite.
- SDL200 sample cutter
- Example 32 75 mL of sample A was poured into a rectangular PTFE container with internal dimensions of 20 cm ⁇ 20 cm ⁇ 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change. 75 mL of sample N was further poured into this PTFE container and air-dried for two weeks. The membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 33 50 mL of sample A was poured into a rectangular PTFE container with internal dimensions of 20 cm ⁇ 20 cm ⁇ 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change. 50 mL of sample N was further poured into this PTFE container and air-dried until the liquid content reached 20% by mass. 50 mL of sample A was further poured into this PTFE container and air-dried for two weeks. The membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 34 50 mL of sample N was poured into a rectangular PTFE container with internal dimensions of 20 cm ⁇ 20 cm ⁇ 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change. 50 mL of sample A was further poured into this PTFE container and air-dried until the liquid content reached 20% by mass. 50 mL of sample N was further poured into this PTFE container and air-dried for two weeks. The membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 35 500 mL of sample A and 0.0025 g of silica fine particles (“HS-208” manufactured by Nippon Steel Chemical & Materials Co., Ltd.) were mixed for 5 minutes with Primix Homo Disper 2.5 type, and CNF and silica fine particles were dissolved in water. A fine dispersion was obtained. In addition, 500 mL of sample N and 0.0025 g of silica fine particles (“HS-208” manufactured by Nippon Steel Chemical & Materials Co., Ltd.) were mixed for 5 minutes in a Primix Homo Disper 2.5 type, and the CNC and silica fine particles were mixed. A dispersion in water was obtained.
- a 75 mL dispersion of CNF and fine silica particles was poured into a rectangular PTFE container with internal dimensions of 20 cm x 20 cm x 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change. 75 mL of dispersion liquid of CNC and fine silica particles was further poured into this PTFE container and air-dried for two weeks. The membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 36 Dumbbell-shaped composites were produced in the same manner as in Example 35, except that the amount of silica fine particles mixed in each of sample A and sample N was 0.005 g.
- Example 37 Dumbbell-shaped composites were produced in the same manner as in Example 35, except that the amount of silica fine particles mixed in each of sample A and sample N was 0.125 g.
- Example 38 Dumbbell-shaped composites were produced in the same manner as in Example 35, except that the amount of silica fine particles mixed in each of sample A and sample N was 0.25 g.
- Example 39 Dumbbell-shaped composites were produced in the same manner as in Example 35, except that the amount of silica fine particles mixed in each of sample A and sample N was set to 0.30 g.
- Example 40 A dumbbell-shaped composite was produced in the same manner as in Example 35, except that the amount of silica fine particles mixed in sample A was 0.005 g, and the silica fine particles were not mixed in sample N.
- Example 41 A dumbbell-shaped composite was produced in the same manner as in Example 35, except that sample A was not mixed with silica fine particles and sample N was not mixed with 0.005 g of silica fine particles.
- Example 42 2.34 mL of sample A, 0.75 g of polyvinyl alcohol fine particles (“Kuraray Poval” manufactured by Kuraray), and 100 mL of distilled water were stirred in a beaker for 24 hours to obtain a dispersion containing CNF and polyvinyl alcohol. .
- the resulting dispersion was poured into a rectangular PTFE container with internal dimensions of 20 cm x 20 cm x 5 cm and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change. 75 mL of sample N was further poured into this PTFE container and air-dried for two weeks. The membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 43 2.34 mL of Sample N, 0.75 g of polyvinyl alcohol fine particles ("Kuraray Poval” manufactured by Kuraray), and 100 mL of distilled water were stirred in a beaker for 24 hours to obtain a dispersion containing CNC and polyvinyl alcohol. .
- sample A 75 mL was poured into a rectangular PTFE container with internal dimensions of 20 cm x 20 cm x 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change.
- the dispersion liquid containing the above CNC and polyvinyl alcohol was further poured into this PTFE container and air-dried for two weeks.
- the membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 44 A dispersion containing CNF and polyvinyl alcohol was prepared in the same manner as in Example 42. Further, in the same manner as in Example 43, a dispersion containing CNC and polyvinyl alcohol was prepared.
- a dispersion liquid containing CNF and polyvinyl alcohol was poured into a rectangular PTFE container with internal dimensions of 20 cm x 20 cm x 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change.
- the dispersion liquid containing the above CNC and polyvinyl alcohol was further poured into this PTFE container and air-dried for two weeks.
- the membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 45 2.34 mL of sample A, 0.75 g of polyvinyl alcohol fine particles (“Kuraray Poval” manufactured by Kuraray), and 100 mL of distilled water were stirred in a beaker for 24 hours to obtain a dispersion containing CNF and polyvinyl alcohol. . To the resulting dispersion were added 0.01 g of 1N hydrochloric acid and 0.3 g of a 37 mass % formaldehyde aqueous solution. Thereby, a crosslinked structure was formed via an acetal bond.
- polyvinyl alcohol fine particles (“Kuraray Poval” manufactured by Kuraray)
- the dispersion liquid containing CNF and polyvinyl alcohol after the cross-linking reaction was poured into a rectangular PTFE container with internal dimensions of 20 cm x 20 cm x 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change.
- a dispersion containing the CNC and polyvinyl alcohol after the cross-linking reaction was further poured into this PTFE container and air-dried for two weeks.
- the membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 46 2.34 mL of sample A, 0.75 g of polyvinyl alcohol fine particles (“Kuraray Poval” manufactured by Kuraray Co., Ltd.), 100 mL of distilled water, and 0.025 g of diphenylmethane diisocyanate were stirred at 50° C. for 3 hours. Thereby, a crosslinked structure was formed via urethane bonds.
- the dispersion liquid containing CNF and polyvinyl alcohol after the cross-linking reaction was poured into a rectangular PTFE container with internal dimensions of 20 cm x 20 cm x 5 cm, and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change.
- a dispersion containing the CNC and polyvinyl alcohol after the cross-linking reaction was further poured into this PTFE container and air-dried for two weeks.
- the membrane formed in the PTFE container was taken out, and a dumbbell-shaped composite was produced in the same manner as in Example 1.
- Example 47 A dumbbell-shaped composite was produced in the same manner as in Example 32, except that sample A was naturally dried to a liquid content of 5% by mass instead of being naturally dried to a liquid content of 20% by mass. did.
- Example 48 In the same manner as in Example 32, except that sample A was dried at 105 ° C. for 3 hours to make the liquid content 0% by mass instead of air drying until the liquid content was 20% by mass. A composite was produced.
- a sample cutter manufactured by Dumbbell Co.
- Example 50 A dumbbell-shaped composite was produced in the same manner as in Example 49, except that corrugated board base paper (“LCC120” manufactured by Rengo Co., Ltd.) was used as the paper substrate.
- corrugated board base paper (“LCC120” manufactured by Rengo Co., Ltd.) was used as the paper substrate.
- Example 51 A paper base material (qualitative filter paper No. 1, manufactured by Advantech Co., Ltd.) was cut into squares of 19.5 cm ⁇ 19.5 cm and placed in a rectangular PTFE container with internal dimensions of 20 cm ⁇ 20 cm ⁇ 5 cm. 75 mL of sample A was poured into this PTFE container and air-dried until the liquid content reached 20% by mass. Liquid content was monitored by mass change. An additional 75 mL of sample N was poured into the PTFE container and allowed to air dry for two weeks. The paper substrate and membrane were taken out from the PTFE container and cut with a sample cutter ("SDL200" manufactured by Dumbbell Co.). As a result, a dumbbell-shaped composite consisting of a paper substrate, a CNF layer, and a CNC layer was obtained.
- SDL200 sample cutter
- Example 52 A dumbbell-shaped composite was produced in the same manner as in Example 51, except that cardboard base paper ("LCC120" manufactured by Rengo Co., Ltd.) was used as the paper base material.
- cardboard base paper (“LCC120” manufactured by Rengo Co., Ltd.) was used as the paper base material.
- Tables 1 and 2 simply represent various conditions in Examples 1 to 52 and Comparative Examples 1 and 2.
- each of the dispersion liquids of Examples 1 to 7, 18 to 24 and Comparative Examples 1 and 2 were frozen at -18°C and dried with a freeze dryer ("FDU1110" manufactured by Tokyo Rika).
- each of the dispersions of Examples 8 to 17 was centrifuged ("Heraeus Megafuge 8R centrifuge” manufactured by Thermo Fisher) at 10,000 G for 5 minutes, the supernatant was removed, and distilled water was added. This operation was repeated to replace the dispersion medium with water. Thereafter, 100 g of each dispersion liquid was frozen at -18°C and dried with a freeze dryer ("FDU1110" manufactured by Tokyo Rika Kikai Co., Ltd.).
- a dispersion medium was added to each dry body so that the composition would be the same as when the initial viscosity was measured, and treated with a disper (Homo Disper 2.5 type manufactured by Primix) for 2 minutes to obtain a dispersion liquid.
- the viscosity of the resulting dispersion was measured three times with a Brookfield viscometer (“TVB10” manufactured by Toki Sangyo Co., Ltd.), and the average was obtained.
- Viscosity change rate after drying re-dispersion is less than 10%
- Viscosity change rate after drying re-dispersion is 10% or more and less than 30%
- Viscosity change rate after drying re-dispersion is 30% or more
- Viscosity change rate after 3 months is less than 10%
- Viscosity change rate after 2 months is less than 10%
- viscosity change rate after 3 months is more than 10%
- Viscosity after 2 months More than 10% change
- the oxygen gas barrier properties of the composites of Examples 1 to 52 and Comparative Examples 1 and 2 were evaluated based on the following criteria. The results are shown in Table 3.
- ⁇ Oxygen gas permeability less than 0.5 ml/m 2 /day/atm
- ⁇ Oxygen gas permeability 0.5 ml/m 2 /day/atm or more and less than 2.5 ml/m 2 /day/atm
- ⁇ Oxygen gas permeability of 2.5 ml/m 2 /day/atm or more and less than 4.5 ml/m 2 /day/atm
- Adhesion of the composites of Examples 32-52 was evaluated based on the following criteria. The results are shown in Table 3. ⁇ : The number of squares where film peeling was observed is less than 3 ⁇ : The number of squares in which film peeling was observed was 3 or more and less than 7 ⁇ : The number of squares in which film peeling was observed was 7 or more and less than 11 ⁇ : The number of squares in which film peeling was observed was 11 or more
- the dispersions of Examples 1-24 exhibited better dry redispersibility and longer pot life than the dispersions of Comparative Examples 1 and 2.
- the composites of Examples 1 to 48 exhibited higher breaking strength and higher oxygen gas barrier properties than the composites of Comparative Examples 1 and 2. From this, it was shown that the combination of sulfated CNF and sulfated CNC provides good dry redispersibility, long pot life, high breaking strength, and high oxygen gas barrier properties.
- the dispersion medium of the dispersion liquid has a dielectric constant of 38 or more, such as water, DMF, ethylene glycol, and formamide, and the total volume of the dispersion medium is An amount within the range of 80-100% by volume as a basis has been shown to result in longer pot life.
- the composites contained inorganic fine particles such as silica in an amount within the range of 0.09 to 5% by mass based on the total mass of the composites. was shown to provide higher breaking strength.
- the evaluation results of the composites of Examples 1, 9, 25-31 showed that the addition of resins such as polyurethane and PVA or rubbers such as natural rubber improved the breaking strength of the composites.
- the composite may have a crosslinked structure, and it was shown that crosslinkage via urethane bonds in particular improves the oxygen gas barrier properties of the composite.
- Composites having multiple laminated layers such as those of Examples 32 to 48 also exhibited high breaking strength and high oxygen gas barrier properties.
- At least one of the multiple layers of the composite contains, based on the total weight of the layer, an amount within the range of 0.09 to 5% by weight It was shown that the inclusion of inorganic fine particles brings about higher breaking strength and improves adhesion between layers.
- the evaluation results of the composites of Examples 32 and 42-46 showed that the addition of resin or rubber improved the breaking strength of the composite.
- the composite may have a crosslinked structure, and it was shown that crosslinkage via urethane bonds in particular improves the oxygen gas barrier properties of the composite.
- the lower layer containing liquid (particularly, more than 0% by mass and 30% by mass or less, or 5% by mass
- the liquid in the lower layer was completely removed by supplying the dispersion liquid for forming the upper layer on the lower layer containing the liquid in an amount exceeding and not more than 25% by mass, and then removing the liquid in the upper layer and the lower layer. It was shown that the adhesion between the top layer and the bottom layer is better than when the top layer is formed later.
- composites containing biomass-derived paper substrates such as filter paper and cardboard and CNCs and CNFs supported on the paper substrates have high breaking strength and gas barrier properties. , and adhesiveness.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
(a)硫酸エステル基を有するセルロースナノファイバー又は硫酸エステル基を有するセルロースナノクリスタルの一方、及び液体を含む第1層を形成することと、
(b)第1層上に、硫酸エステル基を有するセルロースナノファイバー又は硫酸エステル基を有するセルロースナノクリスタルの他方を含む分散液を供給して、第1層上に第2層を形成することと、
(c)第1層及び第2層から液体を除去することと、
を含む、方法が提供される。
本明細書は本願の優先権の基礎となる日本国特許出願番号2021-059274号の開示内容を包含する。
実施形態に係る分散液は、硫酸エステル基を有するCNF(硫酸エステル化CNFともいう)及び硫酸エステル基を有するCNC(硫酸エステル化CNCともいう)を分散質として含む。
・測定装置:日本ダイオネクス株式会社製のICS-1500
・測定条件:磁性ボードに試料を秤量し、酸素雰囲気下(流量:1.5L/分)、環状炉(1350℃)で燃焼させ、発生したガス成分を3%過酸化水素水(20mL)に吸収させて吸収液を得る。得られた吸収液を純水で希釈して100mLにし、希釈液をイオンクロマトグラフィーに供する。測定結果から、試料の硫酸イオン濃度(質量%)を算出し、下記式:
硫黄含有率(質量%)=硫酸イオン濃度(質量%)×32/96
により、硫黄含有率を計算する。
上記のような硫酸エステル化CNF及び硫酸エステル化CNCを含む分散液の調製方法の例を説明する。実施形態に係る硫酸エステル化CNF及び硫酸エステル化CNCを含む分散液の調製方法は、硫酸エステル化CNF分散液と硫酸エステル化CNC分散液を混合することを含む。
実施形態に係る複合体は、硫酸エステル化CNF、及び硫酸エステル化CNCを含む。一実施形態において、複合体は、図3に模式的に示されるように、硫酸エステル化CNFと硫酸エステル化CNCが混合されている混合複合体である。別の実施形態において、複合体は、図4に模式的に示されるように、硫酸エステル化CNFを含有する、少なくとも1層のCNF層と、硫酸エステル化CNCを含有する、少なくとも1層のCNC層と、を含む積層複合体である。以下、各実施形態を説明する。
硫酸エステル化CNF及び硫酸エステル化CNCは、上で詳細に説明したため、ここでは詳細な説明は省略する。硫酸エステル化CNF及び硫酸エステル化CNCは、いずれも表面に硫酸エステル基を有し、同様の表面状態を有することから、互いに高い親和性を有する。そのため、混合複合体において、硫酸エステル化CNFと硫酸エステル化CNCは、相分離することなく均一に混合された状態であることが可能である。それにより、混合複合体は、高い破断強度及び酸素ガスバリア性を有することができる。
積層複合体において、少なくとも1層のCNF層と少なくとも1層のCNC層は、互いに隣接している。少なくとも1層のCNF層と少なくとも1層のCNC層は、交互に積層されていてよい。例えば、一実施形態において、積層複合体は、図10に示すように、1層のCNF層1と、その上に設けられた1層のCNC層3を有する。別の実施形態において、積層複合体は、図11に示すように、2層のCNF層1と、それらの間に設けられた1層のCNC層3を有する。さらに別の実施形態において、積層複合体は、図12に示すように、2層のCNC層3と、それらの間に設けられた1層のCNF層1を有する。
(4-1)混合複合体の製造方法
上述のような混合複合体は、上述の硫酸エステル化CNF及び硫酸エステル化CNCを含む分散液を乾燥させて、分散媒を除去することにより製造することができる。
上記のような積層複合体の製造方法の例を説明する。積層複合体の製造方法は、(a)硫酸エステル化CNF又は硫酸エステル化CNCの一方、及び液体を含む第1層を形成することと、(b)第1層上に、硫酸エステル化CNF又は硫酸エステル化CNCの他方を含む分散液を供給して、第1層上に第2層を形成することと、(c)第1層及び第2層から液体を除去することと、を含む。
試料A:水中の硫酸エステル化CNF分散液
ジメチルスルホキシド300g、無水酢酸33.3g、及び濃度98質量%の硫酸4.3gを、1Lフラスコ中で、スターラーチップで撹拌して混合した。続いて、針葉樹晒クラフトパルプ(NBKP)(Cariboo Pulp and Paper Company製「CARIBOO」)10gを添加し、室温で4時間撹拌して、NBKPを硫酸エステル化した。その後、5%水酸化ナトリウム水溶液を滴下して、反応混合物のpHを7.0にした。続いて、反応混合物をナイロンメッシュ(アズワン株式会社製「PA-11μ」)でろ過し、同時に蒸留水でリンスした。それにより、硫酸エステル化パルプを得た。硫酸エステル化パルプを1Lフラスコに移し、固形分濃度が1%となるように蒸留水を加え、超音波処理を行った。それにより、固形分濃度1質量%の、水中の硫酸エステル化CNF分散液(試料A)を得た。
蒸留水の代わりにDMFを用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、DMF中の硫酸エステル化CNF分散液(試料B)を得た。
蒸留水の代わりにエチレングリコールを用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、エチレングリコール中の硫酸エステル化CNF分散液(試料C)を得た。
蒸留水の代わりに水とエタノールの混合物(水:エタノール(体積比)=80:20)を用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、水とエタノールの混合物中の硫酸エステル化CNF分散液(試料D)を得た。
蒸留水の代わりに水とエタノールの混合物(水:エタノール(体積比)=75:25)を用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、水とエタノールの混合物中の硫酸エステル化CNF分散液(試料E)を得た。
蒸留水の代わりにエチレングリコールとエタノールの混合物(エチレングリコール:エタノール(体積比)=80:20)を用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、エチレングリコールとエタノールの混合物中の硫酸エステル化CNF分散液(試料F)を得た。
蒸留水の代わりにエチレングリコールとエタノールの混合物(エチレングリコール:エタノール(体積比)=75:25)を用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、エチレングリコールとエタノールの混合物中の硫酸エステル化CNF分散液(試料G)を得た。
蒸留水の代わりにホルムアミドを用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、ホルムアミド中の硫酸エステル化CNF分散液(試料H)を得た。
蒸留水の代わりにホルムアミドとエチレングリコールの混合物(ホルムアミド:エチレングリコール(体積比)=50:50)を用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、ホルムアミドとエチレングリコールの混合物(ホルムアミド:エチレングリコール(体積比)=50:50)中の硫酸エステル化CNF分散液(試料I)を得た。
蒸留水の代わりに蒸留水とエチレングリコールの混合物(水:エチレングリコール(体積比)=50:50)を用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、水とエチレングリコールの混合物中の硫酸エステル化CNF分散液(試料J)を得た。
蒸留水の代わりに蒸留水とエチレングリコールの混合物(水:エチレングリコール(体積比)=80:20)を用いたこと以外は試料Aと同様にして、固形分濃度1質量%の、水とエチレングリコールの混合物中の硫酸エステル化CNF分散液(試料K)を得た。
2,2,6,6-テトラメチルピペリジン-N-オキシド(TEMPO)0.25mmol及び臭化ナトリウム20mmolを水に溶解させて、500mLの水溶液を得た。この水溶液に、絶対乾燥状態(すなわち、含水率0%)のNBKP(Cariboo Pulp and Paper Company製「CARIBOO」)10gを加え、パルプが均一に分散するまで撹拌した。混合物の温度を20℃にした後、次亜塩素酸ナトリウム水溶液(富士フイルム和光純薬株式会社製)64mmolを添加して酸化反応を開始させた。反応中、反応系の温度を20℃に保ち、3N水酸化ナトリウム水溶液を逐次添加することによりpHを10に維持した。3時間反応させた後、結果物をガラスフィルターでろ過し、ろ物を十分に水洗した。それにより、酸化処理されたパルプを得た。
尿素10g、リン酸二水素ナトリウム二水和物5.53g、及びリン酸水素二ナトリウム4.13gを、水10.9gに溶解させて、リン酸化試薬を調製した。乾燥状態のNBKP(Cariboo Pulp and Paper Company製「CARIBOO」)の抄上げシートを、カッターミル及びピンミルで処理し、綿状繊維を得た。絶乾質量10gの綿状繊維にリン酸化試薬をまんべんなくスプレーし、手で練り合わせて含浸パルプを得た。140℃に加熱したダンパー付きの送風乾燥機で含浸パルプを80分間加熱処理した。それにより、リン酸化パルプを得た。
2Lフラスコ中で58%硫酸800mLを50℃に加熱した。絶対乾燥状態のNBKP(Cariboo Pulp and Paper Company製「CARIBOO」)100gをフラスコに投入し、3時間撹拌した。結果物を、遠心分離機(エッペンドルフ・ハイマック・テクノロジーズ株式会社製「CT18R」)で、20,000Gで10分間処理した。続いて、上澄み液をデカンテーションで除去し、蒸留水400mLを添加してペレットを懸濁させた。同様の遠心分離処理、デカンテーション、蒸留水の添加、及び懸濁をさらに二回行った。それにより、水中の硫酸エステル化CNC分散液(試料N)を得た。
試料Nを、凍結乾燥機(アズワン製「FDU-12AS」)で乾燥し、CNC粉体を得た。固形分濃度が1質量%になるようにCNC粉体にDMFを添加し、Primix製のホモディスパー2.5型で2分間処理した。それにより、固形分濃度1質量%の、DMF中のCNC散液(試料O)を得た。
DMFの代わりにエチレングリコールを用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、エチレングリコール中のCNC分散液(試料P)を得た。
DMFの代わりに水とエタノールの混合物(水:エタノール(体積比)=80:20)を用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、水とエタノールの混合物中の硫酸エステル化CNC分散液(試料Q)を得た。
DMFの代わりに水とエタノールの混合物(水:エタノール(体積比)=75:25)を用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、水とエタノールの混合物中の硫酸エステル化CNC分散液(試料R)を得た。
DMFの代わりにエチレングリコールとエタノールの混合物(エチレングリコール:エタノール(体積比)=80:20)を用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、エチレングリコールとエタノールの混合物中の硫酸エステル化CNC分散液(試料S)を得た。
DMFの代わりにエチレングリコールとエタノールの混合物(エチレングリコール:エタノール(体積比)=75:25)を用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、エチレングリコールとエタノールの混合物中の硫酸エステル化CNC分散液(試料T)を得た。
DMFの代わりにホルムアミドを用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、ホルムアミド中のCNC分散液(試料U)を得た。
DMFの代わりにホルムアミドとエチレングリコールの混合物(ホルムアミド:エチレングリコール(体積比)=50:50)を用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、ホルムアミドとエチレングリコールの混合物中の硫酸エステル化CNC分散液(試料V)を得た。
DMFの代わりに水とエチレングリコールの混合物(水:エチレングリコール(体積比)=50:50)を用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、水とエチレングリコールの混合物中の硫酸エステル化CNC分散液(試料W)を得た。
DMFの代わりに水とエチレングリコールの混合物(水:エチレングリコール(体積比)=80:20)を用いたこと以外は試料Oと同様にして、固形分濃度1質量%の、水とエチレングリコールの混合物中の硫酸エステル化CNC分散液(試料X)を得た。
実施例1
300mLのポリプロピレン製ビーカー中で、75mLの試料A及び75mLの試料NをPrimix製のホモディスパー2.5型で5分間混合して、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水(比誘電率80.4)中で分散した分散液を得た。
75mLの試料A及び75mLの試料Nに代えて、0.75mLの試料A及び149.25mLの試料Nを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=0.5:99.5(質量比))が水中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=0.5:99.5(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、1.5mLの試料A及び148.5mLの試料Nを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=1:99(質量比))が水中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=1:99(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、37.5mLの試料A及び112.5mLの試料Nを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=25:75(質量比))が水中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=25:75(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、112.5mLの試料A及び37.5mLの試料Nを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=75:25(質量比))が水中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=75:25(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、148.5mLの試料A及び1.5mLの試料Nを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=99:1(質量比))が水中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=99:1(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、149.25mLの試料A及び0.75mLの試料Nを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=99.5:0.5(質量比))が水中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=99.5:0.5(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、75mLの試料B及び75mLの試料Oを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))がDMF(比誘電率38)中で分散した分散液を得た。この分散液を用いて、自然乾燥の代わりに、真空乾燥機(ヤマト科学製「APD200」)で、減圧下、150℃で5時間乾燥を行ったこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料B及び75mLの試料Oに代えて、75mLの試料C及び75mLの試料Pを使用したこと以外は実施例8と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))がエチレングリコール(比誘電率38.7)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、75mLの試料D及び75mLの試料Qを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水(比誘電率80.4)とエタノール(比誘電率25.3)の混合物(水:エタノール(体積比)=80:20)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、75mLの試料E及び75mLの試料Rを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水とエタノールの混合物(水:エタノール(体積比)=75:25)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料B及び75mLの試料Oに代えて、75mLの試料F及び75mLの試料Sを使用したこと以外は実施例8と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))がエチレングリコールとエタノールの混合物(エチレングリコール:エタノール(体積比)=80:20)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料B及び75mLの試料Oに代えて、75mLの試料G及び75mLの試料Tを使用したこと以外は実施例8と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))がエチレングリコールとエタノールの混合物(エチレングリコール:エタノール(体積比)=75:25)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料A及び75mLの試料Nに代えて、75mLの試料H及び75mLの試料Uを使用したこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))がホルムアミド(比誘電率110)中で分散した分散液を得た。この分散液を用いて、自然乾燥の代わりに、真空乾燥機(ヤマト科学製「APD200」)で、減圧下、150℃で10時間乾燥を行ったこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料H及び75mLの試料Uに代えて、75mLの試料I及び75mLの試料Vを使用したこと以外は実施例14と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))がホルムアミドとエチレングリコールの混合物(ホルムアミド:エチレングリコール(体積比)=50:50)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料H及び75mLの試料Uに代えて、75mLの試料J及び75mLの試料Wを使用したこと以外は実施例14と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水とエチレングリコールの混合物(水:エチレングリコール(体積比)=50:50)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
75mLの試料H及び75mLの試料Uに代えて、75mLの試料K及び75mLの試料Xを使用したこと以外は実施例14と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水とエチレングリコールの混合物(水:エチレングリコール(体積比)=80:20)中で分散した分散液、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
300mLのポリプロピレン製ビーカー中で、150mLの試料A、150mLの試料N、及び0.0015gのシリカ微粒子(日鉄ケミカル&マテリアル株式会社製「HS-208」)をPrimix製のホモディスパー2.5型で5分間混合して、硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:0.05(質量比))が水中で分散した分散液を得た。この分散液の半量を用いて、実施例1と同様にして、硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:0.05(質量比))を含むダンベル型の複合体を作製した。
0.003gのシリカ微粒子を用いたこと以外は実施例18と同様にして、硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:0.1(質量比))が水中で分散した分散液、及び硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:0.1(質量比))を含むダンベル型の複合体を得た。
0.075gのシリカ微粒子を用いたこと以外は実施例18と同様にして、硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:2.5(質量比))が水中で分散した分散液、及び硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:2.5(質量比))を含むダンベル型の複合体を得た。
0.15gのシリカ微粒子を用いたこと以外は実施例18と同様にして、硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC=50:50:5.0(質量比))が水中で分散した分散液、及び硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:5.0(質量比))を含むダンベル型の複合体を得た。
0.18gのシリカ微粒子を用いたこと以外は実施例18と同様にして、硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:6.0(質量比))が水中で分散した分散液、及び硫酸エステル化CNF、硫酸エステル化CNC、及びシリカ微粒子(CNF:CNC:シリカ=50:50:6.0(質量比))を含むダンベル型の複合体を得た。
375mLの試料A及び375mLの試料Nを、マイクロフルイダイザー(Microfluidics製「M-110EH」)を用いて150MPaで3回処理して混合した。それにより、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水中で分散した分散液を得た。150mLのこの分散液を用いて、実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を作製した。
75mLの試料A及び75mLの試料Nを、500mLのポリプロピレン製のボトルに入れて密閉し、ボトルを80℃のウォーターバスに24時間静置した。試料A及び試料Nは、熱対流により混合された。それにより、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水中で分散した分散液を得た。この分散液の全量を用いて、実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を作製した。
試料Aに代えて試料Lを用いたこと以外は実施例1と同様にして、TEMPO酸化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水中で分散した分散液、及びTEMPO酸化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
試料Aに代えて試料Mを用いたこと以外は実施例1と同様にして、リン酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水中で分散した分散液、及びリン酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含むダンベル型の複合体を得た。
実施例1と同様にして調製したCNF及びCNCの分散液を、凍結乾燥機(アズワン製「FDU-12AS」)で乾燥させて、乾燥粉体を得た。乾燥粉体3gとポリウレタンペレット(BASF製「エラストラン」)97gとを併せて、三本ロール圧延装置(株式会社井元製作所製、1983型)を用いて100℃で4回圧延した。得られた膜を試料裁断機(ダンベル社製「SDL200」)で裁断して、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))、並びにポリウレタン樹脂を含むダンベル型の複合体を作製した。
実施例1と同様にして調製したCNF及びCNCの分散液4.68mLと、ポリビニルアルコール微粒子(クラレ製「クラレポバール」)1.5gと、蒸留水100mLとを、ビーカー中で24時間撹拌して、分散液を得た。得られた分散液を用いて、実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))、並びにポリビニルアルコールを含むダンベル型の複合体を作製した。
150mLの試料A及び150mLの試料Nを用いたこと以外は実施例1と同様にして、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))が水中で分散した分散液300mLを得た。この分散液と、固形分濃度50質量%の天然ゴムラテックス(ケニス株式会社製)194gとを、常温で混合した。ここにラジカル発生剤(日油株式会社製「パーヘキサ25B-40」)3gを加え、混合物をテフロン(登録商標)のトレイに入れて80℃で3日間乾燥させた。結果物を、三本ロール圧延装置(株式会社井元製作所製、1983型)を用いて100℃で4回圧延した。得られた膜を試料裁断機(ダンベル社製「SDL200」)で裁断して、硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))、並びに天然ゴムを含むダンベル型の複合体を作製した。
実施例1と同様にして調製したCNF及びCNCの分散液4.68mLと、ポリビニルアルコール微粒子(クラレ製「クラレポバール」)1.5gと、蒸留水100mLとを、ビーカー中で24時間撹拌して、分散液を得た。得られた分散液に、1Nの塩酸0.01g及び37質量%のホルムアルデヒド水溶液0.3gを加えた。それにより、アセタール結合を介した架橋構造が形成された。架橋反応後の分散液を用いて、実施例1と同様にして、ダンベル型の複合体を作製した。
実施例9と同様にして調製したCNF及びCNCの分散液150gに、ジフェニルメタンジイソシアネート41gを加え、50℃で3時間撹拌した。それにより、CNF、CNC、及びエチレングリコールのOH基がジフェニルメタンジイソシアネートのNCO基と反応して、ウレタン結合が形成された。その結果、CNF、CNC、及びウレタン樹脂がウレタン結合を介して架橋されている架橋体が得られた。反応後の分散液を、三本ロール圧延装置(株式会社井元製作所製、1983型)を用いて100℃で4回圧延した。得られた膜を試料裁断機(ダンベル社製「SDL200」)で裁断して、ダンベル型の複合体を作製した。
実施例1と同様にして調製したCNF及びCNCの分散液4.68mLと、ポリビニルアルコール微粒子(クラレ製「クラレポバール」)1.5gと、蒸留水100mLと、ジフェニルメタンジイソシアネート0.05gとを、50℃で24時間撹拌した。それにより、ウレタン結合を介した架橋構造が形成された。架橋反応後の分散液を用いて、実施例1と同様にして、ダンベル型の複合体を作製した。
実施例16と同様にして調製したCNF及びCNCの分散液150gに、ジフェニルメタンジイソシアネート20.5gを加え、50℃で3時間撹拌した。それにより、CNF、CNC、及びエチレングリコールのOH基がジフェニルメタンジイソシアネートのNCO基と反応して、ウレタン結合が形成された。その結果、CNF、CNC、及びウレタン樹脂がウレタン結合を介して架橋されている架橋体が得られた。反応後の分散液を、三本ロール圧延装置(株式会社井元製作所製、1983型)を用いて100℃で4回圧延した。得られた膜を試料裁断機(ダンベル社製「SDL200」)で裁断して、ダンベル型の複合体を作製した。
75mLの試料Aを、内寸20cm×20cm×5cmの角型PTFE容器に流し込み、含液率が20質量%になるまで自然乾燥した。含液率は質量変化によりモニタリングした。このPTFE容器に75mLの試料Nをさらに流し込み、2週間自然乾燥した。PTFE容器中に形成された膜を取り出し、実施例1と同様にしてダンベル型の複合体を作製した。
50mLの試料Aを、内寸20cm×20cm×5cmの角型PTFE容器に流し込み、含液率が20質量%になるまで自然乾燥した。含液率は質量変化によりモニタリングした。このPTFE容器に50mLの試料Nをさらに流し込み、含液率が20質量%になるまで自然乾燥した。このPTFE容器に50mLの試料Aをさらに流し込み、2週間自然乾燥した。PTFE容器中に形成された膜を取り出し、実施例1と同様にしてダンベル型の複合体を作製した。
50mLの試料Nを、内寸20cm×20cm×5cmの角型PTFE容器に流し込み、含液率が20質量%になるまで自然乾燥した。含液率は質量変化によりモニタリングした。このPTFE容器に50mLの試料Aをさらに流し込み、含液率が20質量%になるまで自然乾燥した。このPTFE容器に50mLの試料Nをさらに流し込み、2週間自然乾燥した。PTFE容器中に形成された膜を取り出し、実施例1と同様にしてダンベル型の複合体を作製した。
500mLの試料A及び0.0025gのシリカ微粒子(日鉄ケミカル&マテリアル株式会社製「HS-208」)をPrimix製のホモディスパー2.5型で5分間混合して、CNF及びシリカ微粒子が水中で分散した分散液を得た。また、500mLの試料N及び0.0025gのシリカ微粒子(日鉄ケミカル&マテリアル株式会社製「HS-208」)をPrimix製のホモディスパー2.5型で5分間混合して、CNC及びシリカ微粒子が水中で分散した分散液を得た。
試料A及び試料Nに混合するシリカ微粒子の量をそれぞれ0.005gとしたこと以外は実施例35と同様にして、ダンベル型の複合体を作製した。
試料A及び試料Nに混合するシリカ微粒子の量をそれぞれ0.125gとしたこと以外は実施例35と同様にして、ダンベル型の複合体を作製した。
試料A及び試料Nに混合するシリカ微粒子の量をそれぞれ0.25gとしたこと以外は実施例35と同様にして、ダンベル型の複合体を作製した。
試料A及び試料Nに混合するシリカ微粒子の量をそれぞれ0.30gとしたこと以外は実施例35と同様にして、ダンベル型の複合体を作製した。
試料Aに混合するシリカ微粒子の量を0.005gとし、試料Nにはシリカ微粒子を混合しなかったこと以外は実施例35と同様にして、ダンベル型の複合体を作製した。
試料Aにはシリカ微粒子を混合せず、試料Nに混合するシリカ微粒子の量を0.005gとしなかったこと以外は実施例35と同様にして、ダンベル型の複合体を作製した。
2.34mLの試料Aと、ポリビニルアルコール微粒子(クラレ製「クラレポバール」)0.75gと、蒸留水100mLとを、ビーカー中で24時間撹拌して、CNFとポリビニルアルコールを含む分散液を得た。
2.34mLの試料Nと、ポリビニルアルコール微粒子(クラレ製「クラレポバール」)0.75gと、蒸留水100mLとを、ビーカー中で24時間撹拌して、CNCとポリビニルアルコールを含む分散液を得た。
実施例42と同様にして、CNFとポリビニルアルコールを含む分散液を調製した。また、実施例43と同様にして、CNCとポリビニルアルコールを含む分散液を調製した。
2.34mLの試料Aと、ポリビニルアルコール微粒子(クラレ製「クラレポバール」)0.75gと、蒸留水100mLとを、ビーカー中で24時間撹拌して、CNFとポリビニルアルコールを含む分散液を得た。得られた分散液に、1Nの塩酸0.01g及び37質量%のホルムアルデヒド水溶液0.3gを加えた。それにより、アセタール結合を介した架橋構造が形成された。
2.34mLの試料Aと、ポリビニルアルコール微粒子(クラレ製「クラレポバール」)0.75gと、蒸留水100mLと、ジフェニルメタンジイソシアネート0.025gとを、50℃で3時間撹拌した。それにより、ウレタン結合を介した架橋構造が形成された。
試料Aを含液率が20質量%になるまで自然乾燥する代わりに、含液率が5質量%になるまで自然乾燥したこと以外は実施例32と同様にして、ダンベル型の複合体を作製した。
試料Aを含液率が20質量%になるまで自然乾燥する代わりに、105℃で3時間乾燥して含液率を0質量%としたこと以外は実施例32と同様にして、ダンベル型の複合体を作製した。
紙基材(定性ろ紙No.1、株式会社アドバンテック製)を19.5cm×19.5cmのサイズの正方形に切り、内寸20cm×20cm×5cmの角型PTFE容器内に置いた。このPTFE容器に、実施例1と同様にして調製したCNF及びCNCの分散液の全量を流し込み、室温下で2週間自然乾燥させて、膜を形成した。PTFE容器から紙基材及び膜を取り出し、試料裁断機(ダンベル社製「SDL200」)で裁断した。それにより、紙基材、及び硫酸エステル化CNF及び硫酸エステル化CNC(CNF:CNC=50:50(質量比))を含む膜からなるダンベル型の複合体を得た。
紙基材として段ボール原紙(レンゴー株式会社製「LCC120」)を用いたこと以外は実施例49と同様にしてダンベル型の複合体を作製した。
紙基材(定性ろ紙No.1、株式会社アドバンテック製)を19.5cm×19.5cmのサイズの正方形に切り、内寸20cm×20cm×5cmの角型PTFE容器内に置いた。このPTFE容器に75mLの試料Aを流し込み、含液率が20質量%になるまで自然乾燥した。含液率は質量変化によりモニタリングした。PTFE容器に75mLの試料Nをさらに流し込み、2週間自然乾燥した。PTFE容器から紙基材及び膜を取り出し、試料裁断機(ダンベル社製「SDL200」)で裁断した。それにより、紙基材、CNF層、及びCNC層からなるダンベル型の複合体を得た。
紙基材として段ボール原紙(レンゴー株式会社製「LCC120」)を用いたこと以外は実施例51と同様にしてダンベル型の複合体を作製した。
実施例1~24及び比較例1、2の分散液の初期粘度を、B型粘度計(東機産業製「TVB10」)で3回測定して、平均を求めた。
〇:乾燥再分散後の粘度変化率が10%未満
△:乾燥再分散後の粘度変化率が10%以上、且つ30%未満
×:乾燥再分散後の粘度変化率が30%以上
実施例1~24及び比較例1、2の分散液の初期粘度を、B型粘度計(東機産業製「TVB10」)で3回測定して、平均を求めた。各分散液を室温で保管し、1か月毎に分散液の粘度をB型粘度計(東機産業製「TVB10」)で3回測定して、平均を求めた。
〇:3か月後の粘度変化率が10%未満
△:2か月後の粘度変化率が10%未満、且つ3か月後の粘度変化率が10%超
×:2か月後の粘度変化率が10%超
実施例1~52及び比較例1、2のダンベル型の複合体の破断強度を、テンシロン万能材料試験機(株式会社エー・アンド・デイ製「RTF-2410」)を用いて、JIS C2151、ASTM D882に準じて3回測定し、平均を求めた。破断強度測定において、グリップ間隔は50mm、引張速度は200mm/分とした。
◎:破断強度が140MPa以上
〇:破断強度が120MPa以上、且つ140MPa未満
△:破断強度が100MPa以上、且つ120MPa未満
×:破断強度が100MPa未満
実施例1~52及び比較例1、2の複合体の酸素ガス透過率を、酸素ガス透過率計(MOCON製「OX-TRAN 2/22」)を用いて、JIS K7126-2(温湿度条件:23℃、50%)に準じて、温度23℃、湿度50%の条件下で3回測定し、平均を求めた。
◎:酸素ガス透過率が0.5ml/m2/day/atm未満
〇:酸素ガス透過率が0.5ml/m2/day/atm以上、且つ2.5ml/m2/day/atm未満
△:酸素ガス透過率が2.5ml/m2/day/atm以上、且つ4.5ml/m2/day/atm未満
×:酸素ガス透過率が4.5ml/m2/day/atm以上
実施例32~52の複合体を5cm×5cmに切断し、両面テープ(ニチバン製「ナイスタック」)で平滑なアクリル板に貼り付け1時間養生した。続いてJIS K5600-5-6に従いクロスカット試験を行った。具体的には、カッターナイフで複合体に2mm間隔で切込みを形成し、10×10のグリッドを形成した。複合体にセロハンテープを貼り、次いで、セロハンテープの端をつかんで45°の方向に迅速に引いて、セロハンテープを剥がした。複合体の表面を目視で観察し、下層又は基材からの膜剥がれの有無を確認した。
◎:膜剥がれが観察されたマスの数が3個未満
〇:膜剥がれが観察されたマスの数が3個以上、7個未満
△:膜剥がれが観察されたマスの数が7個以上、11個未満
×:膜剥がれが観察されたマスの数が11個以上
Claims (18)
- 硫酸エステル基を有するセルロースナノファイバー、及び硫酸エステル基を有するセルロースナノクリスタルを含む、分散液。
- 前記分散液の分散媒が、比誘電率が38以上である液体を、前記分散媒の総体積を基準として75~100体積%の量で含有する、請求項1に記載の分散液。
- 硫酸エステル基を有するセルロースナノファイバー、及び硫酸エステル基を有するセルロースナノクリスタルを含む、複合体。
- 前記セルロースナノファイバー及び前記セルロースナノクリスタルが混合されている、請求項3に記載の複合体。
- 前記複合体が、前記複合体の総質量を基準として0.09~5質量%の量で無機微粒子をさらに含む、請求項4に記載の複合体。
- 前記セルロースナノファイバー又は前記セルロースナノクリスタルの少なくとも1つと、前記セルロースナノファイバー又は前記セルロースナノクリスタルの少なくとも1つとの間に、架橋が形成されている、請求項4又は5に記載の複合体。
- 樹脂及びゴムからなる群から選択される少なくとも1種の物質をさらに含む、請求項4~6のいずれか一項に記載の複合体。
- 前記セルロースナノファイバー又は前記セルロースナノクリスタルの少なくとも1つと、前記樹脂及びゴムからなる群から選択される少なくとも1種の物質との間に、架橋が形成されている、請求項7に記載の複合体。
- 前記架橋が、ウレタン結合を含む、請求項6又は8に記載の複合体。
- 前記セルロースナノファイバーを含有する、少なくとも1層のセルロースナノファイバー層と、
前記セルロースナノクリスタルを含有する、少なくとも1層のセルロースナノクリスタル層と、
を含み、前記少なくとも1層のセルロースナノファイバー層と前記少なくとも1層のセルロースナノクリスタル層とが互いに隣接している、請求項3に記載の複合体。 - 前記少なくとも1層のセルロースナノファイバー層又は前記少なくとも1層のセルロースナノクリスタル層の少なくとも1層が、該層の総質量を基準として0.09~5質量%の量で無機微粒子をさらに含む、請求項10に記載の複合体。
- 前記少なくとも1層のセルロースナノファイバー層又は前記少なくとも1層のセルロースナノクリスタル層の少なくとも1層が、樹脂及びゴムからなる群から選択される少なくとも1種の物質をさらに含む、請求項10又は11に記載の複合体。
- 前記少なくとも1層のセルロースナノファイバー層又は前記少なくとも1層のセルロースナノクリスタル層の少なくとも1層が、架橋構造を有する、請求項10~12のいずれか一項に記載の複合体。
- 前記架橋構造が、ウレタン結合を含む、請求項13に記載の複合体。
- 前記セルロースナノファイバー、及び前記セルロースナノクリスタルを支持する紙基材をさらに含む、請求項3~14のいずれか一項に記載の複合体。
- 請求項1又は2に記載の分散液の調製方法であって、硫酸エステル基を有するセルロースナノファイバーの分散液と硫酸エステル基を有するセルロースナノクリスタルの分散液とを、せん断力を加えながら混合することを含む、方法。
- 請求項10~14のいずれか一項に記載の複合体の製造方法であって、
(a)硫酸エステル基を有するセルロースナノファイバー又は硫酸エステル基を有するセルロースナノクリスタルの一方、及び液体を含む第1層を形成することと、
(b)第1層上に、硫酸エステル基を有するセルロースナノファイバー又は硫酸エステル基を有するセルロースナノクリスタルの他方を含む分散液を供給して、第1層上に第2層を形成することと、
(c)第1層及び第2層から液体を除去することと、
を含む、方法。 - 第1層の含液率が0質量%超、30質量%以下であるときにステップ(b)を行う、請求項17に記載の方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/284,306 US20240183107A1 (en) | 2021-03-31 | 2022-03-23 | Dispersion, composite, and producing methods therefor |
JP2023511046A JP7444332B2 (ja) | 2021-03-31 | 2022-03-23 | 分散液及び複合体、並びにこれらの製造方法 |
CN202280026827.2A CN117157330A (zh) | 2021-03-31 | 2022-03-23 | 分散液和复合体、以及它们的制造方法 |
EP22780356.6A EP4317192A1 (en) | 2021-03-31 | 2022-03-23 | Dispersion, composite, and production methods therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021059274 | 2021-03-31 | ||
JP2021-059274 | 2021-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022210141A1 true WO2022210141A1 (ja) | 2022-10-06 |
Family
ID=83455345
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/013379 WO2022210141A1 (ja) | 2021-03-31 | 2022-03-23 | 分散液及び複合体、並びにこれらの製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20240183107A1 (ja) |
EP (1) | EP4317192A1 (ja) |
JP (1) | JP7444332B2 (ja) |
CN (1) | CN117157330A (ja) |
WO (1) | WO2022210141A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117903490A (zh) * | 2024-03-19 | 2024-04-19 | 北京大学 | 一种空心球增强纤维素气凝胶绝热材料及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018012629A1 (ja) * | 2016-07-14 | 2018-01-18 | 東洋製罐グループホールディングス株式会社 | セルロースナノファイバー含有セルロース繊維及び製造方法 |
WO2018131721A1 (ja) * | 2017-01-16 | 2018-07-19 | 株式会社Kri | 硫酸エステル化修飾セルロースナノファイバーおよびセルロースナノファイバーの製造方法 |
KR20190092876A (ko) * | 2018-01-31 | 2019-08-08 | 율촌화학 주식회사 | 가스배리어성을 갖는 셀룰로오스 나노파이버를 포함하는 코팅액 조성물 |
WO2020059525A1 (ja) * | 2018-09-21 | 2020-03-26 | 東洋製罐グループホールディングス株式会社 | ナノセルロース及びその製造方法 |
WO2020196175A1 (ja) * | 2019-03-22 | 2020-10-01 | 東洋製罐グループホールディングス株式会社 | ナノセルロース分散液及びその製造方法 |
JP2021059274A (ja) | 2019-10-09 | 2021-04-15 | 日産自動車株式会社 | ヘッドアップディスプレイ装置の車両搭載構造 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110281487A1 (en) | 2008-12-26 | 2011-11-17 | Kao Corporation | Gas barrier molded article and method for producing the same |
EP3872127A4 (en) | 2018-10-22 | 2022-08-10 | Toyo Seikan Group Holdings, Ltd. | GAS BARRIER COMPOSITION |
-
2022
- 2022-03-23 EP EP22780356.6A patent/EP4317192A1/en active Pending
- 2022-03-23 US US18/284,306 patent/US20240183107A1/en active Pending
- 2022-03-23 WO PCT/JP2022/013379 patent/WO2022210141A1/ja active Application Filing
- 2022-03-23 JP JP2023511046A patent/JP7444332B2/ja active Active
- 2022-03-23 CN CN202280026827.2A patent/CN117157330A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018012629A1 (ja) * | 2016-07-14 | 2018-01-18 | 東洋製罐グループホールディングス株式会社 | セルロースナノファイバー含有セルロース繊維及び製造方法 |
WO2018131721A1 (ja) * | 2017-01-16 | 2018-07-19 | 株式会社Kri | 硫酸エステル化修飾セルロースナノファイバーおよびセルロースナノファイバーの製造方法 |
JP2020041255A (ja) | 2017-01-16 | 2020-03-19 | 株式会社Kri | 硫酸エステル化修飾セルロースナノファイバーの製造方法 |
KR20190092876A (ko) * | 2018-01-31 | 2019-08-08 | 율촌화학 주식회사 | 가스배리어성을 갖는 셀룰로오스 나노파이버를 포함하는 코팅액 조성물 |
WO2020059525A1 (ja) * | 2018-09-21 | 2020-03-26 | 東洋製罐グループホールディングス株式会社 | ナノセルロース及びその製造方法 |
WO2020196175A1 (ja) * | 2019-03-22 | 2020-10-01 | 東洋製罐グループホールディングス株式会社 | ナノセルロース分散液及びその製造方法 |
JP2021059274A (ja) | 2019-10-09 | 2021-04-15 | 日産自動車株式会社 | ヘッドアップディスプレイ装置の車両搭載構造 |
Non-Patent Citations (4)
Title |
---|
PEDRO CLARO ET AL.: "Curaua and eucalyptus nanofiber films by continuous casting: mixture of cellulose nanocrystals and nanofibrils", CELLULOSE, vol. 26, 2019, pages 2453 - 2470, XP036728915, DOI: 10.1007/s10570-019-02280-9 |
RAPHAEL BARDET ET AL.: "Substitution of nanoclay in high gas barrier films of cellulose nanofibrils with cellulose nanocrystals and thermal treatment", CELLULOSE, vol. 22, 2015, pages 1227 - 1241, XP035462720, DOI: 10.1007/s10570-015-0547-9 |
TYAGI PREETI; LUCIA LUCIAN A.; HUBBE MARTIN A.; PAL LOKENDRA: "Nanocellulose-based multilayer barrier coatings for gas, oil, and grease resistance", CARBOHYDRATE POLYMERS, APPLIED SCIENCE PUBLISHERS , LTD BARKING, GB, vol. 206, 31 October 2018 (2018-10-31), GB , pages 281 - 288, XP085556411, ISSN: 0144-8617, DOI: 10.1016/j.carbpol.2018.10.114 * |
XIUXUAN SUN ET AL.: "Nanocellulose films with combined cellulose nanofibers and nanocrystals: tailored thermal, optical and mechanical properties", CELLULOSE, vol. 25, 2018, pages 1103 - 1115, XP036430337, DOI: 10.1007/s10570-017-1627-9 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117903490A (zh) * | 2024-03-19 | 2024-04-19 | 北京大学 | 一种空心球增强纤维素气凝胶绝热材料及其制备方法 |
CN117903490B (zh) * | 2024-03-19 | 2024-06-07 | 北京大学 | 一种空心球增强纤维素气凝胶绝热材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2022210141A1 (ja) | 2022-10-06 |
JP7444332B2 (ja) | 2024-03-06 |
EP4317192A1 (en) | 2024-02-07 |
US20240183107A1 (en) | 2024-06-06 |
CN117157330A (zh) | 2023-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Alves et al. | Composites of nanofibrillated cellulose with clay minerals: A review | |
Yao et al. | Bioinspired interface engineering for moisture resistance in nacre-mimetic cellulose nanofibrils/clay nanocomposites | |
JP5319806B2 (ja) | ガスバリア用材料の製造方法 | |
EP2897810B1 (en) | Coating composition of nano cellulose, its uses and a method for its manufacture | |
EP2395027B1 (en) | Suspension of cellulose fibers and method for producing same | |
JP5162438B2 (ja) | ガスバリア用材料 | |
WO2011065371A1 (ja) | 膜状体及びその製造方法並びに該膜状体の形成用水性分散液 | |
CA2923675C (en) | Water, grease and heat resistant bio-based products and method of making same | |
JP5350825B2 (ja) | ガスバリア性積層体とその製造方法 | |
JP2018531298A (ja) | Ncc膜およびこれをベースにした製品 | |
WO2022210141A1 (ja) | 分散液及び複合体、並びにこれらの製造方法 | |
JP5665487B2 (ja) | 膜状体及びその製造方法 | |
JP5350776B2 (ja) | ガスバリア性積層体 | |
Chi et al. | Electrostatically complexed natural polysaccharides as aqueous barrier coatings for sustainable and recyclable fiber-based packaging | |
CN110670408B (zh) | 一种疏水浆料及其制备方法与应用 | |
Maria Santos Chiromito et al. | Water-based processing of fiberboard of acrylic resin composites reinforced with cellulose wood pulp and cellulose nanofibrils | |
JP2012097236A (ja) | ガスバリア性膜状体の形成用水性分散液 | |
JP6604448B1 (ja) | 繊維状セルロース含有組成物、液状組成物及び成形体 | |
JP6429978B2 (ja) | 樹脂組成物及びその製造方法 | |
KR20210040430A (ko) | 섬유상 셀룰로오스 함유 조성물, 액상 조성물 및 성형체 | |
Sultana et al. | Preparation and characterization of nanocellulose from Albizia lebbeck sawdust and their application in nanocomposites using poly (vinyl chloride)(PVC) | |
JP7215554B1 (ja) | 微細セルロース繊維粉末、及び微細セルロース繊維粉末の製造方法 | |
JP2020050736A (ja) | 樹脂組成物 | |
Raynaud | Development of new barrier materials using microfibrillated cellulose | |
Luginina et al. | High lignin content cellulose nanofibrils obtained from thermomechanical pulp |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22780356 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2023511046 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022780356 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18284306 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2022780356 Country of ref document: EP Effective date: 20231031 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |