WO2021002194A1 - 混合液 - Google Patents
混合液 Download PDFInfo
- Publication number
- WO2021002194A1 WO2021002194A1 PCT/JP2020/023667 JP2020023667W WO2021002194A1 WO 2021002194 A1 WO2021002194 A1 WO 2021002194A1 JP 2020023667 W JP2020023667 W JP 2020023667W WO 2021002194 A1 WO2021002194 A1 WO 2021002194A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cellulose
- mixed solution
- filler
- nanofibers
- reaction
- Prior art date
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- 239000011259 mixed solution Substances 0.000 title claims abstract description 54
- 229920002678 cellulose Polymers 0.000 claims abstract description 160
- 239000001913 cellulose Substances 0.000 claims abstract description 158
- 239000002121 nanofiber Substances 0.000 claims abstract description 72
- 239000000945 filler Substances 0.000 claims abstract description 45
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 37
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 16
- 229920002201 Oxidized cellulose Polymers 0.000 claims description 10
- 229940107304 oxidized cellulose Drugs 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920006318 anionic polymer Polymers 0.000 claims description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 5
- 235000010980 cellulose Nutrition 0.000 description 153
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 48
- 239000002245 particle Substances 0.000 description 42
- 239000006185 dispersion Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000835 fiber Substances 0.000 description 28
- 239000002994 raw material Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000007254 oxidation reaction Methods 0.000 description 21
- 238000011282 treatment Methods 0.000 description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- -1 polyoxyethylene Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 239000002655 kraft paper Substances 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
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- 239000010452 phosphate Substances 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 150000001768 cations Chemical group 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 239000010445 mica Substances 0.000 description 6
- 229910052618 mica group Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 241000218631 Coniferophyta Species 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000021523 carboxylation Effects 0.000 description 4
- 238000006473 carboxylation reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical group OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 240000000797 Hibiscus cannabinus Species 0.000 description 2
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical group OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
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- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 229920006321 anionic cellulose Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000003508 chemical denaturation Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052811 halogen oxide Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005517 mercerization Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013586 microbial product Substances 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane 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
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229940099402 potassium metaphosphate Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 229910001575 sodium mineral Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
Definitions
- the present invention relates to a mixed solution containing cellulose nanofibers and a filler.
- Patent Document 1 fine cellulose fibers having a number average fiber diameter of 2 to 150 nm in which a carboxy group is introduced into a part of the hydroxyl groups of cellulose ( Cellulose nanofibers) are disclosed.
- This cellulose nanofiber has functions such as strength imparting and shape stability, and also has high viscosity at low shear rate and low viscosity at high shear rate. Therefore, foods, pharmaceuticals / cosmetics, daily necessities, civil engineering / building materials It is used as a highly functional thickener in various fields such as papermaking, paints / inks, and other industrial materials. In these fields, a mixed solution containing a filler may be used, and it has been found that the dispersion stability of the filler is improved by adding cellulose nanofibers as a thickener.
- an object of the present invention is to provide a mixed solution containing cellulose nanofibers having excellent dispersion stability of the filler.
- the present invention provides the following [1] to [8].
- [1] A mixed solution containing the following (1) to (3).
- the anionic polymer compound is a polymer compound having a carboxy group or a polymer compound having a phosphate group.
- [5] The mixture according to [4], wherein the anion-modified cellulose nanofibers are oxidized cellulose nanofibers.
- the mixed solution of the present invention is characterized by containing (1) a dispersant, (2) cellulose nanofibers, and (3) a filler.
- Dispersant can be used without particular limitation as long as the effects of the present invention are exhibited.
- any of carboxylic acid type, urethane type, acrylic resin type, polyether type, polyester type, fatty acid type and the like can be used.
- Low molecular weight and high molecular weight compounds can also be used. It is preferable to select a compound capable of obtaining good dispersibility in consideration of the properties of the filler and the cellulose nanofibers to be blended in the mixed solution of the present invention. Since cellulose nanofibers contain a large amount of hydroxyl groups, dispersibility may be impaired if the dispersant contains a large amount of hydrophobic groups.
- any of the anionic, cationic and nonionic types can be used. As the dispersant, one type may be used alone, or two or more types may be mixed and used. The dispersant used in the present invention does not contain the cellulose nanofibers described in (2).
- an anionic polymer compound When an anionic polymer compound is used as the dispersant, a polymer compound having a functional group such as a carboxy group, a sulfonic acid group, a phosphoric acid group, or a sulfate ester group can be used, and pKa of each functional group can be used. When used at a pH higher than (acid dissociation constant), it becomes an anionic group, and the mixed solution can be prepared without aggregating the anionic cellulose nanofiber dispersion.
- the functional group may be appropriately selected according to the pH of the mixed solution to be adjusted and the required basicity.
- Examples of the polymer compound having a carboxy group include polycarboxylic acid, carboxymethyl cellulose, alginic acid and the like.
- Examples of the polycarboxylic acid include polyacrylic acid, sodium polyacrylate, styrene / maleic anhydride copolymer, olefin / maleic anhydride copolymer, and the like.
- the carboxy group may be a metal salt type or an ammonium salt type.
- an ammonium salt type can be appropriately selected.
- polymer compound having a phosphoric acid group examples include polyoxyethylene alkyl ether phosphate, polyoxyethylene phenyl ether phosphoric acid, and alkyl phosphate ester.
- polyether compound examples include pluronic polyether, polyether dialkyl ester, polyether dialkyl ether, polyether epoxy modified product, polyether amine and the like. For example, by changing the ratio of polyoxyethylene or polyoxypropylene. , The balance between hydrophilicity and hydrophobicity can be adjusted.
- urethane-based compounds include urethane-associated compounds. For example, by using a polyester chain or a polyether chain as a side chain in polyurethane of the main skeleton, compatibility and steric hindrance stability can be adjusted. it can.
- fatty acid compounds include aliphatic alcohol sulfates, aliphatic amines, and aliphatic esters.
- the amount of the dispersant added to the mixed solution of the present invention may be an amount capable of sufficiently dispersing the filler, preferably 0.01 to 25 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the filler. More preferred.
- cellulose nanofibers are fine fibers having a fiber diameter of about 3 to 500 nm, which is obtained by refining pulp or the like, which is a raw material for cellulose, to the nanometer level.
- the average fiber diameter and average fiber length of cellulose nanofibers shall be the average of the fiber diameter and fiber length obtained from the results of observing each fiber using an atomic force microscope (AFM) or a transmission electron microscope (TEM).
- FAM atomic force microscope
- TEM transmission electron microscope
- Can be obtained by Cellulose nanofibers can be obtained by applying mechanical force to pulp to make it finer, or anion-modified cellulose (carboxylated cellulose (also called oxidized cellulose), carboxymethylated cellulose, or phosphate ester group.
- the average fiber length and average fiber diameter of the fine fibers can be adjusted by oxidation treatment and defibration treatment.
- the average aspect ratio of the cellulose nanofibers used in the present invention is usually 50 or more.
- the upper limit is not particularly limited, but is usually 1000 or less, more preferably 700 or less, still more preferably 500 or less.
- the origin of the cellulose raw material which is the raw material of the cellulose nanofibers, is not particularly limited, but for example, plants (for example, wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp (conifer unbleached kraft pulp (NUKP)).
- plants for example, wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp (conifer unbleached kraft pulp (NUKP)).
- NNKP Conifer bleached kraft pulp
- LKP broadleaf unbleached kraft pulp
- LKP broadleaf bleached kraft pulp
- BKP bleached kraft pulp
- NUSP conifer unbleached sulphite pulp
- NBSP conifer bleached sulphite pulp
- TMP Thermomechanical pulp
- recycled pulp used paper, etc.
- animals for example, squirrels
- algae for example, microorganisms (for example, acetic acid bacteria (acetobacter)), microbial products, etc.
- acetobacter acetic acid bacteria
- It may be either one or a combination of two or more kinds, but it is preferably a pulp raw material derived from a plant or a microorganism (for example, cellulose fiber), and more preferably a cellulose raw material derived from a plant (for example, cellulose). Fiber).
- a pulp raw material derived from a plant or a microorganism for example, cellulose fiber
- a cellulose raw material derived from a plant for example, cellulose). Fiber
- the number average fiber diameter of the cellulose raw material is not particularly limited, but it is about 30 to 60 ⁇ m in the case of softwood kraft pulp, which is a general pulp, and about 10 to 30 ⁇ m in the case of hardwood kraft pulp. In the case of other pulp, the one that has undergone general purification is about 50 ⁇ m.
- a dissociator such as a refiner or a beater to adjust the size to about 50 ⁇ m.
- the modified cellulose may be anion-modified or cation-modified, and may be used as the type of filler or dispersant to be blended in the mixed solution of the present invention.
- an anionic polymer compound is used as the dispersant, it is preferable to select anion-modified cellulose nanofibers from the viewpoint that a synergistic effect for suppressing the aggregation of the filler can be easily obtained.
- Examples of the functional group introduced by anion modification include a carboxy group, a carboxymethyl group, a sulfone group, a phosphoric acid ester group, and a nitro group. Of these, a carboxy group, a carboxymethyl group, and a phosphate ester group are preferable, and a carboxy group is more preferable.
- carboxylated (oxidized) cellulose when carboxylated (oxidized) cellulose is used as the modified cellulose, carboxylated cellulose (also referred to as oxidized cellulose) can be obtained by carboxylating (oxidizing) the above-mentioned cellulose raw material by a known method. .. At the time of carboxylation, it is preferable to adjust the amount of carboxy groups to 0.2 to 1.55 mmol / g with respect to the absolute dry mass of the anion-modified cellulose nanofibers, and 0.4 to 1. It is more preferable to adjust it to 0 mmol / g.
- the amount of carboxy groups is too small, a large amount of energy is required for defibration in order to obtain a highly transparent and uniform nanofiber dispersion.
- the highly transparent nanofiber dispersion liquid does not spoil the appearance of the mixed liquid because there is little residual coarse matter such as undefibrated fibers.
- the amount of the carboxy group is too large, there is a concern that the viscosity of the nanofiber dispersion liquid may be lowered due to the deterioration of the fibers due to the reaction by adding an excessive amount of an oxidizing chemical, or the viscosity retention rate may be lowered due to the stirring treatment.
- a cellulose raw material is oxidized in water using an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromide, iodide or a mixture thereof.
- the method can be mentioned.
- This oxidation reaction C6-position primary hydroxyl groups of the glucopyranose ring of the cellulose surface is selectively oxidized, and an aldehyde group on the surface, a carboxy group (-COOH) or carboxylate groups (-COO -) and cellulosic fibers having a Can be obtained.
- the concentration of cellulose during the reaction is not particularly limited, but is preferably 5% by mass or less.
- the N-oxyl compound is a compound capable of generating a nitroxy radical.
- any compound can be used as long as it is a compound that promotes the desired oxidation reaction.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxy radical
- its derivative for example, 4-hydroxy TEMPO
- the amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount capable of oxidizing cellulose as a raw material.
- 0.01 to 10 mmol is preferable, 0.01 to 1 mmol is more preferable, and 0.05 to 0.5 mmol is further preferable with respect to 1 g of cellulose that has been completely dried. Further, it is preferably about 0.1 to 4 mmol / L with respect to the reaction system.
- Bromide is a compound containing bromine, and examples thereof include alkali metals bromide that can be dissociated and ionized in water.
- the iodide is a compound containing iodine, and an example thereof includes an alkali metal iodide.
- the amount of bromide or iodide used can be selected within a range in which the oxidation reaction can be promoted.
- the total amount of bromide and iodide is, for example, preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, still more preferably 0.5 to 5 mmol, based on 1 g of dry cellulose.
- oxidizing agent known ones can be used, and for example, halogen, hypochlorous acid, hypochlorous acid, perhalogen acid or salts thereof, halogen oxide, peroxide and the like can be used.
- sodium hypochlorite which is inexpensive and has a low environmental impact, is preferable.
- the amount of the oxidizing agent used is, for example, preferably 0.5 to 500 mmol, more preferably 0.5 to 50 mmol, still more preferably 1 to 25 mmol, and most preferably 3 to 10 mmol with respect to 1 g of cellulose that has been dried completely. Further, for example, 1 to 40 mol is preferable with respect to 1 mol of the N-oxyl compound.
- the reaction temperature is preferably 4 to 40 ° C, and may be room temperature of about 15 to 30 ° C. Since a carboxy group is generated in cellulose as the reaction progresses, a decrease in pH of the reaction solution is observed.
- an alkaline solution such as an aqueous sodium hydroxide solution to maintain the pH of the reaction solution at about 8 to 12, preferably about 10 to 11. Water is preferable as the reaction medium because it is easy to handle and side reactions are unlikely to occur.
- the reaction time in the oxidation reaction can be appropriately set according to the degree of progress of oxidation, and is usually 0.5 to 6 hours, for example, about 0.5 to 4 hours.
- the oxidation reaction may be carried out in two stages. For example, by oxidizing the oxidized cellulose obtained by filtration after the completion of the first-stage reaction again under the same or different reaction conditions, the efficiency is not affected by the reaction inhibition by the salt produced as a by-product in the first-stage reaction. It can be oxidized well.
- the carboxylation (oxidation) method there is a method of oxidizing by contacting a gas containing ozone with a cellulose raw material.
- a gas containing ozone By this oxidation reaction, the hydroxyl groups at at least the 2nd and 6th positions of the glucopyranose ring are oxidized, and the cellulose chain is decomposed.
- the ozone concentration in the gas containing ozone is preferably 50 to 250 g / m 3 , and more preferably 50 to 220 g / m 3 .
- the amount of ozone added to the cellulose raw material is preferably 0.1 to 30 parts by mass, and more preferably 5 to 30 parts by mass, when the solid content of the cellulose raw material is 100 parts by mass.
- the ozone treatment temperature is preferably 0 to 50 ° C, more preferably 20 to 50 ° C.
- the ozone treatment time is not particularly limited, but is about 1 to 360 minutes, preferably about 30 to 360 minutes. When the ozone treatment conditions are within these ranges, it is possible to prevent the cellulose from being excessively oxidized and decomposed, and the yield of the oxidized cellulose becomes good.
- the additional oxidation treatment may be performed using an oxidizing agent.
- the oxidizing agent used for the additional oxidation treatment is not particularly limited, and examples thereof include chlorine-based compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfate, and peracetic acid.
- the additional oxidation treatment can be performed by dissolving these oxidizing agents in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution, and immersing the cellulose raw material in the solution.
- the amount of the carboxy group of cellulose oxide can be adjusted by controlling the reaction conditions such as the amount of the oxidizing agent added and the reaction time described above.
- carboxymethylated cellulose when carboxymethylated cellulose is used as the modified cellulose, the carboxymethylated cellulose may be obtained by carboxymethylating the above-mentioned cellulose raw material by a known method, or a commercially available product may be used. May be good. In either case, the degree of carboxymethyl group substitution per anhydrous glucose unit of cellulose is preferably 0.01 to 0.50. The following method can be mentioned as an example of a method for producing such carboxymethylated cellulose.
- cellulose As a base material, 3 to 20 times by mass of water and / or lower alcohol as a solvent, specifically water, methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, tertiary Use a single medium such as butanol or a mixed medium of two or more kinds.
- the mixing ratio of the lower alcohol is 60 to 95% by mass.
- the mercerizing agent 0.5 to 20 times mol of alkali metal hydroxide per anhydrous glucose residue of the bottoming material, specifically sodium hydroxide and potassium hydroxide is used.
- the bottoming material, the solvent, and the mercerizing agent are mixed, and the mercerization treatment is carried out at a reaction temperature of 0 to 70 ° C., preferably 10 to 60 ° C., and a reaction time of 15 minutes to 8 hours, preferably 30 minutes to 7 hours. Then, 0.05 to 10.0 times the molar amount of the carboxymethylating agent is added per glucose residue, the reaction temperature is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is 30 minutes to 10 hours, preferably 1 hour.
- the etherification reaction is carried out for about 4 hours.
- carboxymethyl cellulose which is a kind of water-soluble polymer exemplified as a dispersant in the present specification.
- carboxymethyl cellulose which is a kind of water-soluble polymer exemplified as a dispersant in the present specification.
- Phosphate esterification Phosphate-esterified cellulose can be used as the chemically modified cellulose.
- the cellulose can be obtained by a method of mixing a powder or an aqueous solution of a phosphoric acid compound A with the above-mentioned cellulose raw material, or a method of adding an aqueous solution of a phosphoric acid compound A to a slurry of a cellulose raw material.
- Examples of the phosphoric acid-based compound A include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, and esters thereof. These may be in the form of salts.
- a compound having a phosphoric acid group is preferable because it is low in cost, easy to handle, and a phosphoric acid group can be introduced into the cellulose of the pulp fiber to improve the defibration efficiency.
- Compounds having a phosphoric acid group include phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and phosphorus.
- Examples thereof include tripotassium acid, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate and the like. These can be used alone or in combination of two or more.
- phosphoric acid, sodium phosphate of phosphoric acid, potassium salt of phosphoric acid, and phosphoric acid from the viewpoints of high efficiency of introducing phosphoric acid groups, easy defibration in the following defibration steps, and easy industrial application.
- Ammonium salt is more preferred.
- sodium dihydrogen phosphate and disodium hydrogen phosphate are preferable.
- the phosphoric acid-based compound A is preferably used as an aqueous solution because the uniformity of the reaction is enhanced and the efficiency of introducing a phosphoric acid group is increased.
- the pH of the aqueous solution of the phosphoric acid-based compound A is preferably 7 or less because the efficiency of introducing the phosphoric acid group is high, but is preferably 3 to 7 from the viewpoint of suppressing the hydrolysis of pulp fibers.
- a phosphoric acid-based compound A is added to a dispersion of a cellulose raw material having a solid content concentration of 0.1 to 10% by mass with stirring to introduce a phosphoric acid group into the cellulose.
- the amount of the phosphoric acid-based compound A added is preferably 0.2 to 500 parts by mass and more preferably 1 to 400 parts by mass as the amount of phosphorus element.
- the ratio of the phosphoric acid compound A is at least the above lower limit value, the yield of the fine fibrous cellulose can be further improved. However, if the upper limit is exceeded, the effect of improving the yield will reach a plateau, which is not preferable from the viewpoint of cost.
- Compound B is not particularly limited, but a nitrogen-containing compound exhibiting basicity is preferable.
- “Basic” here is defined as the aqueous solution exhibiting a pink to red color in the presence of a phenolphthalein indicator, or the pH of the aqueous solution being greater than 7.
- the basic nitrogen-containing compound used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but a compound having an amino group is preferable.
- urea methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine and the like can be mentioned, but are not particularly limited. Of these, urea, which is low in cost and easy to handle, is preferable.
- the amount of compound B added is preferably 2 to 1000 parts by mass, more preferably 100 to 700 parts by mass, based on 100 parts by mass of the solid content of the cellulose raw material.
- the reaction temperature is preferably 0 to 95 ° C, more preferably 30 to 90 ° C.
- the reaction time is not particularly limited, but is about 1 to 600 minutes, more preferably 30 to 480 minutes.
- the conditions of the esterification reaction are within these ranges, it is possible to prevent the cellulose from being excessively esterified and easily dissolved, and the yield of the phosphate esterified cellulose becomes good.
- After dehydrating the obtained phosphoric acid esterified cellulose suspension it is preferable to heat-treat it at 100 to 170 ° C. from the viewpoint of suppressing hydrolysis of cellulose. Further, it is preferable to heat at 130 ° C. or lower, preferably 110 ° C. or lower while water is contained in the heat treatment, remove water, and then heat-treat at 100 to 170 ° C.
- the degree of phosphoric acid group substitution per glucose unit of the phosphoric acid esterified cellulose is preferably 0.001 to 0.40.
- the celluloses electrically repel each other. Therefore, the cellulose into which a phosphate group has been introduced can be easily nano-defibrated. If the degree of phosphate substitution per glucose unit is less than 0.001, nano-defibration cannot be sufficiently performed. On the other hand, if the degree of phosphate substitution per glucose unit is greater than 0.40, it swells or dissolves and may not be obtained as nanofibers. In order to efficiently perform defibration, it is preferable that the phosphoric acid esterified cellulose raw material obtained above is boiled and then washed with cold water.
- cellulose obtained by further cationizing the carboxylated cellulose can be used.
- the cation-modified cellulose is obtained by adding a cationizing agent such as glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrialkylammonium halide or a halohydrin type thereof to the carboxylated cellulose raw material, and an alkali metal hydroxide as a catalyst. It can be obtained by reacting (sodium hydroxide, potassium hydroxide, etc.) in the presence of water or an alcohol having 1 to 4 carbon atoms.
- the degree of cation substitution per glucose unit is preferably 0.02 to 0.50.
- the degree of cation substitution per glucose unit is less than 0.02, nano-defibration cannot be sufficiently performed.
- the degree of cation substitution per glucose unit is larger than 0.50, it may not be obtained as nanofibers because it swells or dissolves.
- the degree of cation substitution can be adjusted by the amount of the cationizing agent to be reacted and the composition ratio of water or alcohol having 1 to 4 carbon atoms.
- the anion-modified cellulose obtained by anion-modifying a cellulose raw material is a salt type
- a salt having good defibration and dispersibility such as sodium and ammonium can be used regardless of the type of salt type. It is preferable to select.
- the device for defibrating is not particularly limited, but a strong shearing force is applied to the aqueous dispersion using a device such as a high-speed rotary type, a colloid mill type, a high-pressure type, a roll mill type, or an ultrasonic type. Is preferable.
- a wet high-pressure or ultra-high pressure homogenizer capable of applying a pressure of 50 MPa or more to the aqueous dispersion and applying a strong shearing force.
- the pressure is more preferably 100 MPa or more, still more preferably 140 MPa or more.
- the defibration / dispersion treatment with a high-pressure homogenizer it is also possible to pre-treat the above CNF using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer, if necessary.
- the number of treatments (passes) in the defibrator may be once, twice or more, and preferably twice or more.
- the modified cellulose is usually dispersed in a solvent.
- the solvent is not particularly limited as long as it can disperse the modified cellulose, and examples thereof include water, an organic solvent (for example, a hydrophilic organic solvent such as methanol), and a mixed solvent thereof. Since the cellulose raw material is hydrophilic, the solvent is preferably water.
- the solid content concentration of the modified cellulose in the dispersion is usually 0.1% by mass or more, preferably 0.2% by mass or more, and more preferably 0.3% by mass or more. As a result, the amount of liquid becomes appropriate with respect to the amount of the cellulose fiber raw material, which is efficient.
- the upper limit is usually 10% by mass or less, preferably 6% by mass or less. This makes it possible to maintain liquidity.
- Pretreatment may be performed if necessary prior to the defibration treatment or dispersion treatment.
- the pretreatment may be performed using a mixing, stirring, emulsifying, or dispersing device such as a high-speed shear mixer.
- the modified cellulose nanofiber obtained through the defibration step is a salt type, it may be used as it is, or it may be used as an acid type by acid treatment using a mineral acid or a method using a cation exchange resin. Is also good. Further, the hydrophobicity may be imparted by a method using a cationic additive.
- a modifier may be added to the cellulose nanofibers used in the present invention.
- nitrogen-containing compounds, phosphorus-containing compounds, onium ions, etc. are bonded to anionic groups on the surface of the cellulose nanofibers to change properties such as polarity, thereby increasing the affinity for solvents. , The dispersibility of the filler can be adjusted.
- the dispersibility of the filler may deteriorate. Therefore, sodium hydroxide or ammonium hydroxide is appropriately used.
- a basic compound such as the above may be added to form a salt type.
- the mixed solution of the present invention is used for a paint or the like and water resistance is required for the coating film obtained after application and drying of the mixed solution, for example, as an anion-modified cellulose nanofiber, an ammonium salt type It is preferable to use one because ammonia volatilizes during drying, becomes an acid type, and the coating film becomes water resistant.
- the amount of cellulose nanofibers added to the mixed solution of the present invention has the advantage that the greater the amount added, the higher the effect of preventing the filler from settling. If the amount is too large, the mixed solution becomes thick and difficult to handle. From this viewpoint, the solid content concentration of CNF in the mixed solution is preferably 0.01 to 5% by mass, more preferably 0.1 to 0.5% by mass.
- the filler used in the present invention may be either an inorganic filler or an organic filler.
- the shape may be particulate, flat, fibrous, etc.
- inorganic fillers calcium carbonate (light calcium carbonate, heavy calcium carbonate), magnesium carbonate, barium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, clay (kaolin, calcined kaolin, deramikaolin) , Tarku, mica, zinc oxide, zinc stearate, titanium dioxide, silica made from sodium silicate and mineral acid (white carbon, silica / calcium carbonate complex, silica / titanium dioxide complex), white clay, bentonite, diatomaceous soil , Calcium carbonate, inorganic compounds such as zeolite, metals or alloys such as aluminum, aluminum oxide, copper, zinc, iron, nickel, tin, inorganic fillers that regenerate and utilize ash obtained from the deinking process, and the process of regeneration Inorganic fillers that form a complex with silica or calcium carbonate can be mentioned.
- amorphous silica such as white carbon may be used in combination with the calcium carbonate and
- Organic fillers include urea-formalin resin, polystyrene resin, phenolic resin, microhollow particles, acrylamide composites, wood-derived substances (fine fibers, microfibril fibers, powdered kenaf), modified insolubilized starch, and ungelatinized starch. And so on.
- the above filler may be used alone or in combination of two or more.
- a surfactant such as a preservative or a surface conditioner, a binder resin, a water resistant agent, a thickener, or the like may be added to the mixed solution of the present invention.
- the effect of preventing the sedimentation of the filler by the cellulose nanofibers is improved.
- the larger the particle size and the higher the aspect ratio of the filler the coarser the agglomerates when agglomerated and the higher the sedimentation property, so that the effect of adding the dispersant is likely to appear.
- the uniformity of the particle size distribution was measured using the same device and the same sample as the particle size measurement.
- the uniformity of the particle size distribution is expressed by the following equation.
- di is the particle size of each fraction
- d50 is the median particle size distribution
- Vi is the volume of each fraction.
- Homogeneity is a measure of the absolute deviation of the particle size distribution from the median and is preferably 1 or less. The results of the particle size and the uniformity of the particle size distribution obtained are shown in Table 1.
- transparency refers to the transmittance of light having a wavelength of 660 nm when CNF oxide is an aqueous dispersion having a solid content of 1% (w / v).
- a CNF dispersion solid content 1% (w / v), dispersion medium: water
- UV-VIS spectrophotometer UV-1800 manufactured by Shimadzu Corporation
- the cellulose oxide nano has a transparency of 75.2%.
- a fiber aqueous dispersion was obtained.
- the average fiber diameter was 4 nm and the aspect ratio was 380.
- a stability test was carried out on this oxidized CNF aqueous dispersion to obtain values of B-type viscosity before and after stirring. The viscosity retention rate at this time was 88%.
- Example 1 The aqueous dispersion of cellulose oxide nanofibers of Production Example 1 obtained above was prepared in an amount equivalent to CNF solid content in an amount of 0.2% by mass, and while stirring at 3000 rpm with a homomixer, a polycarboxylic acid (trade name:) was used as a dispersant.
- Aron T-50 manufactured by Toa Synthetic Co., Ltd.
- kaolin trade name: Varisurf HX, manufactured by Imeris
- water 100 mL of the mixed solution was prepared. The water separation rate, particle size, and particle size uniformity of the obtained mixed solution were measured.
- Example 2-6, Example 8-9, Example 12-16> The mixed solution was prepared in the same manner as in Example 1 by changing the carboxy group amount and addition concentration, the type and addition concentration of the dispersant, and the type of filler of the used cellulose oxide nanofiber aqueous dispersion as shown in Table 1. did. The water separation rate, particle size, and particle size uniformity of the obtained mixed solution were measured.
- Example 7 The oxidized pulp obtained in Production Example 1 was adjusted to pH 2.4 with hydrochloric acid, and then washed twice with ion-exchanged water. Then, 3.2 g of polyether amine (JEFFAMINE (registered trademark) M1000) was added to 4 g of the solid content of the oxidized pulp, adjusted to 400 g with ion-exchanged water, and the pressure was increased as in Production Example 1. The defibration treatment was carried out with a homogenizer to obtain an aqueous dispersion of cellulose oxide nanofibers having a transparency of 90%. The average fiber diameter was 4 nm and the aspect ratio was 275.
- JEFFAMINE registered trademark
- a stability test was carried out on this oxidized CNF aqueous dispersion to obtain values of B-type viscosity before and after stirring.
- the viscosity retention rate at this time was 52%.
- 10% by mass of kaolin (trade name: Varisurf HX, manufactured by Imeris) and water were added as fillers in the same manner as in Example 1, and 100 mL of a mixed solution was prepared. The water separation rate, particle size, and particle size uniformity of the obtained mixed solution were measured.
- Example 10 100 mL of the mixed solution was prepared in the same manner as in Example 1 except that the aqueous dispersion of cellulose oxide nanofibers obtained in Production Example 2 was used. The water separation rate, particle size, and particle size uniformity of the obtained mixed solution were measured.
- Example 11 100 mL of the mixed solution was prepared in the same manner as in Example 1 except that the aqueous dispersion of cellulose oxide nanofibers obtained in Production Example 3 was used. The water separation rate, particle size, and particle size uniformity of the obtained mixed solution were measured.
- Example 1-Comparative Example 5> A mixed solution was prepared in the same manner as in Example 1 by changing the addition concentration of the oxidized cellulose nanofibers and the type and addition concentration of the filler as shown in Table 1 without adding the dispersant. The water separation rate, particle size, and particle size uniformity of the obtained mixed solution were measured.
- Example 6-Comparative Example 11 A mixed solution was prepared in the same manner as in Example 1 by changing the type and concentration of the dispersant and the type and concentration of the filler as shown in Table 1 without adding the cellulose nanofibers. The water separation rate, particle size, and particle size uniformity of the obtained mixed solution were measured.
- polycarboxylic acid A solid content 36.0%
- the polycarboxylic acid A was produced by the following method. 148 parts of water in a glass reaction vessel equipped with a thermometer, agitator, reflux device, nitrogen introduction tube and dropping device, and polyethylene glycol polypropylene glycol monoallyl ether (average number of moles of ethylene oxide added 37, average of propylene oxide) 94 parts (5 mol%) of ethylene oxide and propylene oxide (random addition of ethylene oxide and propylene oxide) with 3 additional moles were charged, the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere.
- the fine cellulose nanofibers inhibit the sedimentation of the filler by entering the filler.
- anion-modified cellulose nanofibers it is considered that they function not only as an anti-sedimentation effect but also as an anionic dispersant.
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Abstract
Description
〔1〕以下の(1)~(3)を含有する混合液。
(1)分散剤
(2)セルロースナノファイバー
(3)フィラー
〔2〕前記分散剤が、アニオン性高分子化合物である〔1〕記載の混合液。
〔3〕前記アニオン性高分子化合物が、カルボキシ基を有する高分子化合物またはリン酸基を有する高分子化合物である〔2〕記載の混合液。
〔4〕前記セルロースナノファイバーが、アニオン変性セルロースナノファイバーである〔1〕~〔3〕に記載の混合液。
〔5〕前記アニオン変性セルロースナノファイバーが、酸化セルロースナノファイバーである〔4〕記載の混合液。
〔6〕前記酸化セルロースナノファイバーのカルボキシ基量が、0.4~1.0 mmol/gである〔5〕記載の混合液。
〔7〕前記セルロースナノファイバーの添加量が、濃度0.1質量%以上である〔1〕~〔6〕に記載の混合液。
〔8〕72時間静置した後の離水率が、1%未満である〔1〕~〔7〕に記載の混合液。
分散剤としては、本発明の効果を奏する限り特に制限なく用いることができ、例えば、カルボン酸系、ウレタン系、アクリル樹脂系、ポリエーテル系、ポリエステル系、脂肪酸系など、いずれの低分子・高分子化合物も用いることができる。本発明の混合液に配合するフィラーとセルロースナノファイバーの性質を考慮して、良好な分散性を得られる化合物を選択することが好ましい。なお、セルロースナノファイバーは水酸基を多く含有するため、分散剤に疎水基が多く含まれると分散性を阻害するおそれがある。また、アニオン性、カチオン性、ノニオン性の種類についても、いずれの種類でも用いることができる。分散剤としては、1種類を単独で用いても良いし、2種類以上を混合して用いても良い。
なお、本発明に用いる分散剤としては、(2)で説明するセルロースナノファイバーを含まない。
本発明において、セルロースナノファイバー(CNF)は、セルロース原料であるパルプなどがナノメートルレベルまで微細化されたもので、繊維径が3~500nm程度の微細繊維である。セルロースナノファイバーの平均繊維径および平均繊維長は、原子間力顕微鏡(AFM)または透過型電子顕微鏡(TEM)を用いて、各繊維を観察した結果から得られる繊維径および繊維長を平均することによって得ることができる。セルロースナノファイバーは、パルプに機械的な力を加えて微細化することで得られ、あるいは、アニオン変性したセルロース(カルボキシル化したセルロース(酸化セルロースとも呼ぶ)、カルボキシメチル化したセルロース、リン酸エステル基を導入したセルロース等)、カチオン変性したセルロースなどの化学変性により得られた変性セルロースを解繊することによって得ることができる。微細繊維の平均繊維長と平均繊維径は、酸化処理、解繊処理により調整することができる。
アスペクト比=平均繊維長/平均繊維径
セルロースナノファイバーの原料であるセルロース原料の由来は、特に限定されないが、例えば、植物(例えば、木材、竹、麻、ジュート、ケナフ、農地残廃物、布、パルプ(針葉樹未漂白クラフトパルプ(NUKP)、針葉樹漂白クラフトパルプ(NBKP)、広葉樹未漂白クラフトパルプ(LUKP)、広葉樹漂白クラフトパルプ(LBKP)、晒クラフトパルプ(BKP)、針葉樹未漂白サルファイトパルプ(NUSP)、針葉樹漂白サルファイトパルプ(NBSP)サーモメカニカルパルプ(TMP)、再生パルプ、古紙等)、動物(例えばホヤ類)、藻類、微生物(例えば酢酸菌(アセトバクター))、微生物産生物等が挙げられる。セルロース原料としては、これらのいずれかであってもよいし2種類以上の組み合わせであってもよいが、好ましくは植物又は微生物由来のセルロース原料(例えば、セルロース繊維)であり、より好ましくは植物由来のセルロース原料(例えば、セルロース繊維)である。
本発明においては、変性セルロースとして、アニオン変性されたものを用いてもよいし、カチオン変性して得られたものを用いてもよく、本発明の混合液に配合するフィラーや分散剤の種類に併せて、フィラーの分散が良好となるような変性セルロースとすることが好ましい。例えば、分散剤としてアニオン性高分子化合物を用いる場合は、フィラーの凝集を抑制するための相乗効果が得られやすい観点から、アニオン変性セルロースナノファイバーを選択することが好ましい。
本発明において、変性セルロースとしてカルボキシル化(酸化)したセルロースを用いる場合、カルボキシル化セルロース(酸化セルロースとも呼ぶ)は、上記のセルロース原料を公知の方法でカルボキシル化(酸化)することにより得ることができる。カルボキシル化の際には、アニオン変性セルロースナノファイバーの絶乾質量に対して、カルボキシ基の量が0.2~1.55mmol/gとなるように調整することが好ましく、0.4~1.0mmol/gになるように調整することがより好ましい。カルボキシ基の量が少なすぎると、高透明で均一なナノファイバー分散液を得るために解繊に多大なエネルギーが必要となる。高透明なナノファイバー分散液は、未解繊繊維等の粗大物の残存が少ないため、混合液の外観を損ねることが無い。また、カルボキシ基の量が多すぎると、酸化薬品を過剰に添加して反応することによる繊維の劣化で生じるナノファイバー分散液の粘度低下や、撹拌処理による粘度保持率の低下が懸念される。カルボキシ基量と粘度保持率の関係は必ずしも定かではないが、低い変性度の変性パルプを十分に解繊した方が、化学的に表面処理されていない水酸基を持つ箇所が露出し、酸化CNFの表面電荷の減少に加えて酸化CNF同士が相互的に水素結合を形成しやすくなり低せん断での粘度が保持されると推定される。
カルボキシ基量〔mmol/g酸化セルロース〕=a〔mL〕×0.05/酸化セルロース質量〔g〕
本発明において、変性セルロースとして、カルボキシメチル化したセルロースを用いる場合、カルボキシメチル化したセルロースは、上記のセルロース原料を公知の方法でカルボキシメチル化することにより得てもよいし、市販品を用いてもよい。いずれの場合も、セルロースの無水グルコース単位当たりのカルボキシメチル基置換度が0.01~0.50となるものが好ましい。そのようなカルボキシメチル化したセルロースを製造する方法の一例として次のような方法を挙げることができる。セルロースを発底原料にし、溶媒として3~20質量倍の水及び/又は低級アルコール、具体的には水、メタノール、エタノール、N-プロピルアルコール、イソプロピルアルコール、N-ブタノール、イソブタノール、第3級ブタノール等の単独、又は2種以上の混合媒体を使用する。なお、低級アルコールを混合する場合の低級アルコールの混合割合は、60~95質量%である。マーセル化剤としては、発底原料の無水グルコース残基当たり0.5~20倍モルの水酸化アルカリ金属、具体的には水酸化ナトリウム、水酸化カリウムを使用する。発底原料と溶媒、マーセル化剤を混合し、反応温度0~70℃、好ましくは10~60℃、かつ反応時間15分~8時間、好ましくは30分~7時間、マーセル化処理を行う。その後、カルボキシメチル化剤をグルコース残基当たり0.05~10.0倍モル添加し、反応温度30~90℃、好ましくは40~80℃、かつ反応時間30分~10時間、好ましくは1時間~4時間、エーテル化反応を行う。
化学変性セルロースとして、リン酸エステル化したセルロースを使用できる。当該セルロースは、前述のセルロース原料にリン酸系化合物Aの粉末や水溶液を混合する方法、セルロース原料のスラリーにリン酸系化合物Aの水溶液を添加する方法により得られる。
化学変性セルロースとして、前記カルボキシル化セルロースをさらにカチオン化したセルロースを使用することができる。当該カチオン変性されたセルロースは、前記カルボキシル化セルロース原料に、グリシジルトリメチルアンモニウムクロリド、3-クロロ-2-ヒドロキシプロピルトリアルキルアンモニウムハライドまたはそのハロヒドリン型などのカチオン化剤と、触媒である水酸化アルカリ金属(水酸化ナトリウム、水酸化カリウムなど)を、水または炭素数1~4のアルコールの存在下で反応させることによって得ることができる。
本発明において、解繊する装置は特に限定されないが、高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式などの装置を用いて前記水分散体に強力なせん断力を印加することが好ましい。特に、効率よく解繊するには、前記水分散体に50MPa以上の圧力を印加し、かつ強力なせん断力を印加できる湿式の高圧または超高圧ホモジナイザーを用いることが好ましい。前記圧力は、より好ましくは100MPa以上であり、さらに好ましくは140MPa以上である。また、高圧ホモジナイザーでの解繊・分散処理に先立って、必要に応じて、高速せん断ミキサーなどの公知の混合、撹拌、乳化、分散装置を用いて、上記のCNFに予備処理を施すことも可能である。解繊装置での処理(パス)回数は、1回でもよいし2回以上でもよく、2回以上が好ましい。
本発明に用いるフィラーとしては、無機系フィラー、有機系フィラーのいずれでもよい。粒子状、扁平状、繊維状などの形状も問わない。
実施例及び比較例で得られた混合液の内、50mLをJIS R 3505に準拠した容量50mLのメスシリンダーに注ぎ、72時間静置した後、目視にてメスシリンダー中の混合液の上部の透明な部分の液体の量を読み取った。その後、下式により離水率を算出した。結果は表1に示した。
離水率(%):(透明な部分の液体の量(mL)/混合液の全量(mL))×100
実施例及び比較例で得られた混合液の内、残りの50mLを3日間静置した後、容器の底の方からサンプルを採取した。得られたサンプルは、レーザー回折式粒度分布測定装置(マスターサイザー3000、マルバーン社製)を用いて、体積平均粒子径(D10、D50、D90)を測定した。D10は、体積平均粒子径による粒子径分布において、最小値から積算して10%が含まれる粒子径であり、D50は、最小値から積算して50%が含まれる粒子径であり、D90は、最小値から積算して90%が含まれる粒子径である。なお、この測定においては、分散溶媒としてイオン交換水を使用し、超音波は使用せず、ポンプによる循環を行った。
ここで、diは、各分画の粒子径であり、d50は、粒子径分布の中央値であり、Viは、各分画の体積である。均一性は、粒子径分布の中央値からの絶対偏差の尺度であり、1以下であることが好ましい。
得られた粒子径及び粒子径分布の均一性の結果は、表1に示した。
本明細書において、透明度は、酸化CNFを固形分1%(w/v)の水分散体とした際の、波長660nmの光の透過率をいうものとする。製造例で得られた酸化CNFの透明度は、CNF分散体(固形分1%(w/v)、分散媒:水)を調製し、UV-VIS分光光度計UV-1800(島津製作所製)を用い、光路長10mmの角型セルを用いて、660nm光の透過率を測定することにより求めた。
製造例で得られた1.0質量%の酸化セルロースナノファイバー水分散液210gを600mLのプラスチック容器に測りとった後、濃度が0.7%になるように脱イオン水を添加して撹拌(1000rpm、5分間)することで、0.7質量%の酸化CNF水分散液300gを得た。また、濃度を調整した直後に、B型粘度計を用いて6rpm、1分間の条件で、B型粘度を測定した(撹拌前の粘度)。
粘度保持率(%)=(撹拌後の粘度/撹拌前の粘度)×100
針葉樹由来の漂白済み未叩解クラフトパルプ(白色度85%)5.00g(絶乾)をTEMPO(Sigma Aldrich社)20mg(絶乾1gのセルロースに対し0.025mmol)と臭化ナトリウム514mg(絶乾1gのセルロースに対し1.0mmol)を溶解した水溶液500mLに加え、パルプが均一に分散するまで撹拌した。反応系に次亜塩素酸ナトリウム水溶液を、次亜塩素酸ナトリウムが2.2mmol/gになるように添加し、酸化反応を開始した。反応中は系内のpHが低下するが、3M水酸化ナトリウム水溶液を逐次添加し、pH10に調整した。次亜塩素酸ナトリウムを消費し、系内のpHが変化しなくなった時点で反応を終了した。反応後の混合物をガラスフィルターで濾過してパルプ分離し、パルプを十分に水で洗浄することで酸化されたパルプ(カルボキシル化セルロース)を得た。この時のパルプ収率は93%であり、酸化反応に要した時間は60分、カルボキシ基量(以下、「変性度」ということがある)は0.75mmol/gであった。これを水で1.0%(w/v)に調整し、高圧ホモジナイザーを用いて、透明度が十分に高くなるまで解繊処理を実施して、透明度が88%である酸化セルロースナノファイバー水分散液を得た。平均繊維径は4nm、アスペクト比は280であった。この酸化CNF水分散液に対し安定性試験を実施し、撹拌前と撹拌後のB型粘度の値を得た。このときの粘度保持率は50%であった。
針葉樹由来の漂白済み未叩解クラフトパルプ(白色度85%)5.00g(絶乾)をTEMPO(Sigma Aldrich社)39mg(絶乾1gのセルロースに対し0.05mmol)と臭化ナトリウム514mg(絶乾1gのセルロースに対し1.0mmol)を溶解した水溶液500mLに加え、パルプが均一に分散するまで撹拌した。反応系に次亜塩素酸ナトリウム水溶液を、次亜塩素酸ナトリウムが6.0mmol/gになるように添加し、酸化反応を開始した。反応中は系内のpHが低下するが、3M水酸化ナトリウム水溶液を逐次添加し、pH10に調整した。次亜塩素酸ナトリウムを消費し、系内のpHが変化しなくなった時点で反応を終了した。反応後の混合物をガラスフィルターで濾過してパルプ分離し、パルプを十分に水で洗浄することで酸化されたパルプ(カルボキシル化セルロース)を得た。この時のパルプ収率は90%であり、酸化反応に要した時間は90分、カルボキシ基量は1.51mmol/gであった。これを水で1.0%(w/v)に調整し、高圧ホモジナイザーを用いて解繊処理を実施することで、透明度が95.0%である酸化セルロースナノファイバー水分散液を得た。平均繊維径は3nm、アスペクト比は250であった。この酸化CNF水分散液に対し安定性試験を実施し、撹拌前と撹拌後のB型粘度の値を得た。このときの粘度保持率は39%であった。
針葉樹由来の漂白済み未叩解クラフトパルプ(白色度85%)5.00g(絶乾)をTEMPO(Sigma Aldrich社)20mg(絶乾1gのセルロースに対し0.025mmol)と臭化ナトリウム514mg(絶乾1gのセルロースに対し1.0mmol)を溶解した水溶液500mLに加え、パルプが均一に分散するまで撹拌した。反応系に次亜塩素酸ナトリウム水溶液を、次亜塩素酸ナトリウムが1.3mmol/gになるように添加し、酸化反応を開始した。反応中は系内のpHが低下するが、3M水酸化ナトリウム水溶液を逐次添加し、pH10に調整した。次亜塩素酸ナトリウムを消費し、系内のpHが変化しなくなった時点で反応を終了した。反応後の混合物をガラスフィルターで濾過してパルプ分離し、パルプを十分に水で洗浄することで酸化されたパルプ(カルボキシル化セルロース)を得た。この時のパルプ収率は99%であり、酸化反応に要した時間は50分、カルボキシ基量は0.42mmol/gであった。これを水で1.0%(w/v)に調整し、高圧ホモジナイザーを用いて、透明度が十分に高くなるまで解繊処理を実施することで、透明度が75.2%である酸化セルロースナノファイバー水分散液を得た。平均繊維径は4nm、アスペクト比は380であった。この酸化CNF水分散液に対し安定性試験を実施し、撹拌前と撹拌後のB型粘度の値を得た。このときの粘度保持率は88%であった。
上記で得られた製造例1の酸化セルロースナノファイバー水分散液をCNF固形分相当で0.2質量%用意し、ホモミキサーで3000rpmで撹拌を行いながら、分散剤としてポリカルボン酸(商品名:アロンT-50、東亜合成株式会社製)を固形分で0.1質量%含有するように添加し、続いてフィラーとしてカオリン(商品名:バリサーフHX、イメリス社製)10質量%と水を加え、混合液を100mL調製した。得られた混合液について、離水率、粒子径、及び粒子径の均一性を測定した。
用いた酸化セルロースナノファイバー水分散液のカルボキシ基量及び添加濃度、分散剤の種類及び添加濃度、及びフィラーの種類を表1に示す通り変更して、実施例1と同様にして混合液を調製した。得られた混合液について、離水率、粒子径、及び粒子径の均一性を測定した。
製造例1で得られた酸化されたパルプを塩酸でpH2.4に調整後、イオン交換水で2回洗浄した。その後、酸化されたパルプの固形分4gに対して、ポリエーテルアミン(JEFFAMINE(登録商標) M1000)を3.2g添加し、400gになるようイオン交換水で調整し、製造例1と同様に高圧ホモジナイザーで解繊処理を行い、透明度が90%である酸化セルロースナノファイバー水分散液を得た。平均繊維径は4nm、アスペクト比は275であった。この酸化CNF水分散液に対し安定性試験を実施し、撹拌前と撹拌後のB型粘度の値を得た。このときの粘度保持率は52%であった。この酸化セルロースナノファイバー分散液に、実施例1と同様にフィラーとしてカオリン(商品名:バリサーフHX、イメリス社製)10質量%と水を加え、混合液を100mL調製した。得られた混合液について、離水率、粒子径、及び粒子径の均一性を測定した。
製造例2で得られた酸化セルロースナノファイバー水分散液を用いたこと以外は、実施例1と同様にして混合液を100mL調製した。得られた混合液について、離水率、粒子径、及び粒子径の均一性を測定した。
製造例3で得られた酸化セルロースナノファイバー水分散液を用いたこと以外は、実施例1と同様にして混合液を100mL調製した。得られた混合液について、離水率、粒子径、及び粒子径の均一性を測定した。
分散剤を添加せず、酸化セルロースナノファイバーの添加濃度、並びに、フィラーの種類及び添加濃度を表1に示す通り変更して、実施例1と同様にして混合液を調製した。得られた混合液について、離水率、粒子径、及び粒子径の均一性を測定した。
セルロースナノファイバーを添加せず、分散剤の種類及び添加濃度、並びに、フィラーの種類及び添加濃度を表1に示す通り変更して、実施例1と同様にして混合液を調製した。得られた混合液について、離水率、粒子径、及び粒子径の均一性を測定した。
(分散剤)
・製品名:アロンT-50、ポリアクリル酸ナトリウム、固形分43%、東亜合成株式会社製
ここで、ポリカルボン酸Aは、下記の方法で製造した。
温度計、撹拌装置、還流装置、窒素導入管および滴下装置を備えたガラス反応容器に水148部、および、ポリエチレングリコールポリプロピレングリコールモノアリルエーテル(エチレンオキサイドの平均付加モル数37個、プロピレンオキサイドの平均付加モル数3個、エチレンオキサイドとプロピレンオキサイドのランダム付加)94部(5モル%)を仕込み、撹拌下で反応容器を窒素置換し、窒素雰囲気下で80℃に昇温した。その後、メタクリル酸35部(40モル%)、アクリル酸5部(7モル%)、メトキシポリエチレングリコールメタアクリレート(エチレンオキサイドの平均付加モル数25個)63部(5モル%)、ヒドロキシプロピルアクリレート60部(43モル%)、3-メルカプトプロピオン酸8部、水165部を混合したモノマー水溶液と、過硫酸アンモニウム3部および水47部の混合液とを、各々2時間で、80℃に保持した反応容器に連続滴下した。さらに、温度を100℃に保持した状態で1時間反応させることにより共重合体(ポリカルボン酸A)の水溶液を得た。
・製品名:アロンA-6114、カルボン酸系共重合体(アンモニウム塩)、固形分40%、東亜合成株式会社製
・製品名:FS600LC、カルボキシメチルセルロース、粉末状、日本製紙株式会社製
・製品名:JEFFAMINE(登録商標) M1000、ポリエーテルアミン、ハンツマン社製
・製品名:ディスパロンAQ-330、ポリエーテルリン酸エステル、有効成分100%、楠本化成株式会社製
・製品名:デモールEP、高分子ポリカルボン酸、固形分25%、花王株式会社製
・製品名:バリサーフHX、カオリン、粒径%:64(<2μm)、株式会社イメリス ミネラルズ・ジャパン製
・製品名:カルライトKT、炭酸カルシウム、一次粒子径:300nm(電子顕微鏡観察値)、白石工業株式会社製
・製品名:A-21S、マイカ、体積平均粒子径:23μm、アスペクト比:70、株式会社ヤマグチマイカ製
・製品名:A-11、マイカ、体積平均粒子径:3μm、株式会社ヤマグチマイカ製
・製品名:B-82、マイカ、体積平均粒子径:180μm、アスペクト比:100、株式会社ヤマグチマイカ製
Claims (8)
- 以下の(1)~(3)を含有する混合液。
(1)分散剤
(2)セルロースナノファイバー
(3)フィラー - 前記分散剤が、アニオン性高分子化合物である請求項1記載の混合液。
- 前記アニオン性高分子化合物が、カルボキシ基を有する高分子化合物またはリン酸基を有する高分子化合物である請求項2記載の混合液。
- 前記セルロースナノファイバーが、アニオン変性セルロースナノファイバーである請求項1~3の何れか一項に記載の混合液。
- 前記アニオン変性セルロースナノファイバーが、酸化セルロースナノファイバーである請求項4記載の混合液。
- 前記酸化セルロースナノファイバーのカルボキシ基量が、0.4~1.0 mmol/gである請求項5記載の混合液。
- 前記セルロースナノファイバーの添加量が、濃度0.1質量%以上である請求項1~6の何れか一項に記載の混合液。
- 72時間静置した後の離水率が、1%未満である請求項1~7の何れか一項に記載の混合液。
Priority Applications (5)
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JP2020566010A JP6887067B1 (ja) | 2019-07-03 | 2020-06-17 | 混合液 |
CA3143494A CA3143494A1 (en) | 2019-07-03 | 2020-06-17 | Mixed suspension comprising cellulose nanofibers |
CN202080031155.5A CN113728045A (zh) | 2019-07-03 | 2020-06-17 | 混合液 |
US17/608,586 US20220227998A1 (en) | 2019-07-03 | 2020-06-17 | Mixed suspension |
EP20834469.7A EP3995543A4 (en) | 2019-07-03 | 2020-06-17 | LIQUID MIXTURE |
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JP2019-124096 | 2019-07-03 | ||
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JP2020-010469 | 2020-01-27 | ||
JP2020010469 | 2020-01-27 |
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WO2021002194A1 true WO2021002194A1 (ja) | 2021-01-07 |
Family
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PCT/JP2020/023667 WO2021002194A1 (ja) | 2019-07-03 | 2020-06-17 | 混合液 |
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US (1) | US20220227998A1 (ja) |
EP (1) | EP3995543A4 (ja) |
JP (1) | JP6887067B1 (ja) |
CN (1) | CN113728045A (ja) |
CA (1) | CA3143494A1 (ja) |
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JP2023004974A (ja) * | 2021-06-25 | 2023-01-17 | 王子ホールディングス株式会社 | セメント組成物用添加剤、セメントスラリー、セメント組成物及びセメント硬化体 |
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CN113728045A (zh) | 2021-11-30 |
JPWO2021002194A1 (ja) | 2021-09-13 |
TWI817248B (zh) | 2023-10-01 |
TWI803758B (zh) | 2023-06-01 |
EP3995543A1 (en) | 2022-05-11 |
TW202214708A (zh) | 2022-04-16 |
JP6887067B1 (ja) | 2021-06-16 |
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