CN112673132A - Method for redispersing dry solid matter of microfibrous cellulose and method for producing redispersion liquid of microfibrous cellulose - Google Patents
Method for redispersing dry solid matter of microfibrous cellulose and method for producing redispersion liquid of microfibrous cellulose Download PDFInfo
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- CN112673132A CN112673132A CN201980057281.5A CN201980057281A CN112673132A CN 112673132 A CN112673132 A CN 112673132A CN 201980057281 A CN201980057281 A CN 201980057281A CN 112673132 A CN112673132 A CN 112673132A
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- China
- Prior art keywords
- microfibrous cellulose
- cellulose
- mixture
- microfibrous
- dry solid
- Prior art date
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 173
- 239000001913 cellulose Substances 0.000 title claims abstract description 172
- 239000007787 solid Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000007788 liquid Substances 0.000 title description 15
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 235000010980 cellulose Nutrition 0.000 description 151
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000002994 raw material Substances 0.000 description 25
- 238000007254 oxidation reaction Methods 0.000 description 21
- 238000011282 treatment Methods 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 15
- 239000000835 fiber Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 239000002002 slurry Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 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 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- -1 medical supplies Substances 0.000 description 6
- 229920003043 Cellulose fiber Polymers 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920002201 Oxidized cellulose Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000021523 carboxylation Effects 0.000 description 4
- 238000006473 carboxylation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229940107304 oxidized cellulose Drugs 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 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
- 238000004090 dissolution Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005819 Potassium phosphonate Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 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
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 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
- 150000007942 carboxylates Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical class [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 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
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 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
- 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
- 238000007602 hot air drying Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 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
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 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
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 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
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
-
- 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
- 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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
A mixture of a dry solid containing microfibrous cellulose and an aqueous solvent is introduced into an inline mixer that mixes the contents by generating turbulent stirring at a flow rate that causes turbulent stirring, the mixture is stirred, and mechanical shear force is applied to the mixture.
Description
Technical Field
The present invention relates to a method for redispersing a dry solid content of microfibrous cellulose and a method for producing a redispersion solution of microfibrous cellulose.
Background
Microfibrous cellulose obtained by finely unraveling plant fibers includes microfibrillated cellulose (hereinafter referred to as "MFC") and cellulose nanofibers (hereinafter referred to as "CNF"). The microfibrous cellulose is a microfine fiber having a fiber diameter of about 1nm to about several 10 μm, and is expected to be applied to the fields of foods, cosmetics, medical supplies, paints and the like because of its excellent water-based dispersibility. Specifically, it is expected to be applied to viscosity maintenance of coating materials, strengthening of texture of food materials, maintenance of moisture, improvement of food stability, low calorie additives, emulsion stabilizing aids, or the like.
The microfibrous cellulose is usually obtained in a state of being dispersed in water, and has a very low solid content concentration of about 0.1% to about 5%. Therefore, when transporting an aqueous dispersion of microfibrous cellulose, a large amount of water must be transported, which results in a high transportation cost. In addition, in the case of an aqueous dispersion, there is a problem that a countermeasure against microorganisms, a preservative treatment, and the like are required. Therefore, it is preferable to prepare a dried product. However, once the microfibrous cellulose is dried, it is difficult to redisperse the microfibrous cellulose as it is without performing a dispersing treatment by stirring at a high rotation speed for a long time. Therefore, patent document 1 proposes a method in which a dry solid of microfibrous cellulose is treated with hot water and then redispersed in a solvent. However, this method requires a separate hot water treatment step, which complicates the steps.
In addition, in order to re-disperse the dried product of the microfibrous cellulose in an aqueous medium at the transportation destination, a batch process using a stirrer such as a rotary mixer is generally performed. However, when the batch treatment is performed using a rotary mixer, even if a small amount of the redispersion liquid is obtained, a preparation time of several tens of minutes to several hours is required, and therefore, the efficiency is poor. In addition, when the mass production of the redispersion liquid is attempted, the efficiency is also poor in the case of the batch treatment.
Therefore, even when the microfibrous cellulose is dried, a method is required which can redisperse the microfibrous cellulose in an aqueous solvent as it is without drying and which can redisperse efficiently regardless of the amount.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-2136
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a method by which, even when microfibrous cellulose is dried, microfibrous cellulose can be redispersed in an aqueous solvent as it is without being dried, and can be efficiently redispersed regardless of the amount.
Means for solving the problems
The present inventors have conducted extensive studies to achieve the above object, and as a result, have found that stirring under specific conditions is extremely efficient by using a specific mixing device, thereby completing the present invention.
The present invention provides the following.
(1) A method for redispersing a dry solid of microfibrous cellulose, comprising redispersing a dry solid of microfibrous cellulose obtained by drying a produced microfibrous cellulose dispersion in the form of microfibrous cellulose in an aqueous solvent, characterized in that a mixture comprising the dry solid of microfibrous cellulose and the aqueous solvent is introduced into an inline mixer, in which the contents are mixed by generating turbulent stirring, at a flow rate that causes turbulent stirring, the mixture is stirred, and a mechanical shearing force is applied to the mixture.
(2) The method for redispersing a dry solid content of microfibrous cellulose according to (1), wherein the microfibrous cellulose is chemically modified microfibrous cellulose.
(3) The method for redispersing a dry solid microfibrous cellulose according to (1) or (2), wherein the inline mixer has a pipe body, at least two plates intersecting each other for causing turbulent stirring are provided on an upstream side in the pipe body, and a plurality of protrusions are provided on an inner peripheral wall of the pipe body on a downstream side of the plates.
(4) A method for producing a redispersion of microfibrous cellulose, comprising: introducing a mixture containing a dry solid matter of microfibrous cellulose obtained by drying the produced microfibrous cellulose dispersion and an aqueous solvent into an inline mixer for mixing the contents by causing turbulent stirring at a flow rate that causes turbulent stirring; and a step of stirring the mixture in the inline mixer and applying a mechanical shearing force to the mixture to redisperse the dry solid matter of the microfibrous cellulose in the aqueous solvent to obtain a redispersed solution of the microfibrous cellulose.
(5) The process for producing a redispersed liquid of microfibrous cellulose according to (4), wherein the microfibrous cellulose is chemically modified microfibrous cellulose.
(6) The method for producing a redispersed liquid of microfibrous cellulose according to (4) or (5), wherein said inline mixer has a pipe body, at least two plates intersecting each other for causing turbulent stirring are provided on an upstream side in said pipe body, and a plurality of protrusions are provided on an inner peripheral wall of said pipe body on a downstream side of said plates.
Effects of the invention
According to the present invention, even when microfibrous cellulose is dried, it is possible to provide a method by which microfibrous cellulose can be redispersed in an aqueous solvent in the form of microfibrous cellulose as in the case of production without drying, and can be redispersed efficiently regardless of the amount.
Drawings
FIG. 1 is a schematic diagram showing a cross section of an in-line mixer used in the redispersion method of the present invention.
FIG. 2 is an image of the observation result by the optical microscope in example 1.
FIG. 3 is an image of the observation result by the optical microscope in comparative example 1.
FIG. 4 is an image of the observation result by the optical microscope in reference example 1.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. In the present invention, "to" includes end values. That is, "X to Y" includes values X and Y at both ends thereof.
The present invention is a method for redispersing a dry solid of microfibrous cellulose obtained by drying a produced microfibrous cellulose dispersion in the form of microfibrous cellulose in an aqueous solvent, wherein a mixture containing the dry solid of microfibrous cellulose and the aqueous solvent is introduced into an inline mixer, in which the contents are mixed by generating turbulent stirring, at a flow rate that causes turbulent stirring, the mixture is stirred, and a mechanical shearing force is applied to the mixture.
(microfibrous cellulose)
The microfibrous cellulose used in the present invention is microfine fibers made from cellulose. The average fiber diameter of the microfibrous cellulose is not particularly limited, but is about 1nm to about 10 μm. The average fiber diameter and average fiber length of the microfibrous cellulose can be obtained by observing each fiber using a Scanning Electron Microscope (SEM), an Atomic Force Microscope (AFM), or a Transmission Electron Microscope (TEM), and averaging the fiber diameter and fiber length obtained from the results of the observation. The microfibrous cellulose can be produced by defibrating cellulose.
The average aspect ratio of the microfibrous cellulose used in the present invention is usually 50 or more. The upper limit is not particularly limited, and is usually 1000 or less. The average aspect ratio can be calculated according to the following formula:
length to diameter ratio average fiber length/average fiber diameter
The cellulose material may contain cellulose, and is not particularly limited, and examples thereof include: examples of the cellulose raw material include a combination of two or more kinds of cellulose raw materials, preferably a cellulose raw material derived from a plant or a microorganism (e.g., a cellulose fiber), more preferably a cellulose raw material derived from a plant (e.g., a cellulose fiber), and still more preferably a cellulose raw material derived from a plant (e.g., cellulose fibers).
The number average fiber diameter of the cellulose raw material is not particularly limited, and is about 30 μm to about 60 μm in the case of softwood kraft pulp, which is a general pulp, and about 10 μm to about 30 μm in the case of hardwood kraft pulp. In the case of other pulps, the pulp after general refining is about 50 μm. For example, in the case of a material obtained by refining a raw material having a size of several cm such as wood chips, it is preferable to adjust the particle size to about 50 μm by mechanical treatment using a disintegrator such as a refiner or a beater.
Cellulose has 3 hydroxyl groups per glucose unit and can be chemically modified in various ways. In the present invention, from the viewpoint of promoting the progress of defibration, it is preferable to use chemically modified microfibrous cellulose produced by defibering a cellulose raw material (chemically modified cellulose) obtained by chemical modification.
Examples of the chemical modification include carboxymethylation, oxidation (carboxylation), cationization, and esterification. Among them, carboxymethylation and oxidation (carboxylation) are more preferable.
(chemical modification)
(carboxymethylation)
In the present invention, when carboxymethylated microfibrous cellulose obtained by defibrating carboxymethylated cellulose is used, carboxymethylated cellulose can be obtained by carboxymethylating the above-mentioned cellulose raw material by a known method, or a commercially available product can be used. In either case, the degree of substitution of carboxymethyl groups per anhydroglucose unit of cellulose is preferably 0.01 to 0.50. As an example of a method for producing such carboxymethylated cellulose, the following method can be mentioned. Cellulose is used as a starting material and as a solvent, 3 to 20 times by mass of water and/or a lower alcohol, specifically water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, and the like are used alone or as a mixed medium of 2 or more. When lower alcohols are mixed, the mixing ratio of the lower alcohols is 60 to 95% by mass. The mercerizing agent is an alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide, used in an amount of 0.5 to 20 times by mole per anhydroglucose residue of the starting material. The starting material is mixed with a solvent and a mercerizing agent, and mercerizing treatment is carried out at a reaction temperature of 0 ℃ to 70 ℃, preferably 10 ℃ to 60 ℃ and a reaction time of 15 minutes to 8 hours, preferably 30 minutes to 7 hours. Then, 0.05 to 10.0 times mole of carboxymethylating agent is added per glucose residue, and etherification reaction is carried out at a reaction temperature of 30 to 90 ℃, preferably 40 to 80 ℃, and a reaction time of 30 minutes to 10 hours, preferably 1 to 4 hours.
In the present specification, "carboxymethylated cellulose" which is one of chemically modified celluloses used for producing microfibrous cellulose means a cellulose which retains at least a part of a fibrous shape even when dispersed in water. Therefore, it is different from carboxymethyl cellulose, which is one of water-soluble polymers. When an aqueous dispersion of "carboxymethylated cellulose" was observed with an electron microscope, fibrous substances could be observed. On the other hand, even when an aqueous dispersion of carboxymethyl cellulose, which is one of water-soluble polymers, was observed, fibrous substances were not observed. In addition, the "carboxymethylated cellulose" can observe a peak of a cellulose I-type crystal when measured by X-ray diffraction, but a cellulose I-type crystal is not observed in a water-soluble high-molecular carboxymethyl cellulose.
(Oxidation)
In the present invention, when oxidized microfibrous cellulose obtained by defibrating oxidized (carboxylated) cellulose is used, oxidized cellulose (also referred to as carboxylated cellulose) can be obtained by oxidizing (carboxylating) the above-mentioned cellulose raw material by a known method. Although not particularly limited, the amount of the carboxyl group is preferably adjusted to 0.6 mmol/g to 2.0 mmol/g, and more preferably 1.0 mmol/g to 2.0 mmol/g, based on the absolute dry mass of the chemically modified microfibrous cellulose during oxidation.
As an example of the oxidation (carboxylation) method, a method of oxidizing a cellulose raw material 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 can be cited. By this oxidation reaction, the primary hydroxyl group at C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized, and an aldehyde group and a carboxyl group (-COOH) or an aldehyde group and a carboxylate group (-COO) on the surface can be obtained-) The cellulose fiber of (1). The concentration of cellulose during the reaction is not particularly limited, but is preferably 5% by mass or less.
An N-oxyl compound is understood to mean a compound which is capable of generating nitroxyl radicals. Any compound may be used as the N-oxyl compound as long as it promotes the desired oxidation reaction. Mention may be made, for example, of 2,2,6, 6-tetramethylpiperidin-1-oxyl radical (TEMPO) and its derivatives (for example 4-hydroxy TEMPO).
The amount of the N-oxyl compound to be used is not particularly limited as long as it is an amount of a catalyst capable of oxidizing the cellulose as a raw material. For example, it is preferably 0.01 to 10 mmol, more preferably 0.01 to 1 mmol, and still more preferably 0.05 to 0.5 mmol, based on 1g of the absolute cellulose. Further, it is preferably from about 0.1 mmol/L to about 4 mmol/L relative to the reaction system.
The bromide means a compound containing bromine, and examples thereof include alkali metal bromides capable of being ionized by dissociation in water. In addition, the iodide means a compound containing iodine, and examples thereof include alkali metal iodides. The amount of bromide or iodide used may be selected from a range capable of promoting the oxidation reaction. The total amount of bromide and iodide is, for example, preferably 0.1 mmol to 100 mmol, more preferably 0.1 mmol to 10 mmol, and still more preferably 0.5 mmol to 5 mmol, based on 1g of the absolutely dry cellulose.
As the oxidizing agent, known oxidizing agents such as halogen, hypohalous acid, perhalogenic acid or salts thereof, halogen oxides, peroxides, and the like can be used. Among them, sodium hypochlorite is preferred which is inexpensive and has a small environmental load. The amount of the oxidizing agent to be 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, based on 1g of the absolute dry cellulose. For example, the amount is preferably 1 to 40 moles based on 1 mole of the N-oxyl compound.
The oxidation of cellulose can be efficiently carried out even under relatively mild conditions. Therefore, the reaction temperature is preferably 4 to 40 ℃ and may be room temperature of about 15 to about 30 ℃. As the reaction proceeded, carboxyl groups were formed in the cellulose, and it was confirmed that the pH of the reaction solution decreased. In order to efficiently perform the oxidation reaction, it is preferable to add an alkaline solution such as an aqueous sodium hydroxide solution and to maintain the pH of the reaction solution at 8 to 12, preferably about 10 to about 11. The reaction medium is preferably water from the viewpoint of ease of handling, difficulty in causing side reactions, and the like.
The reaction time in the oxidation reaction may 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 about 4 hours.
In addition, 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 oxidation can be efficiently performed while avoiding reaction inhibition by common salt by-produced in the first-stage reaction.
As another example of the oxidation (carboxylation) method, a method of performing oxidation by bringing a gas containing ozone into contact with a cellulose raw material can be cited. By this oxidation reaction, hydroxyl groups at least at the 2-and 6-positions of the glucopyranose ring are oxidized, and decomposition of the cellulose chain is caused. The concentration of ozone in the ozone-containing gas is preferably 50g/m3～250g/m3More preferably 50g/m3～220g/m3. The amount of ozone added to the cellulose raw material is preferably 0.1 to 30 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the solid content of the cellulose raw material. The ozone treatment temperature is preferably 0 to 50 ℃, more preferably 20 to 50 ℃. The ozone treatment time is not particularly limited, and is about 1 minute to about 360 minutes, preferably about 30 minutes to about 360 minutes. When the conditions of the ozone treatment are within these ranges, excessive oxidation and decomposition of the cellulose can be prevented, and the yield of oxidized cellulose becomes good. After the ozone treatment, an 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 compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfuric acid, and peracetic acid. For example, the additional oxidation treatment can be performed by dissolving the oxidizing agent 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 carboxyl groups in the oxidized cellulose can be adjusted by controlling the reaction conditions such as the amount of the oxidizing agent added and the reaction time.
(cationization)
In the present invention, a cationized microfibrous cellulose obtained by defibrating a cellulose obtained by further cationizing the carboxylated cellulose can be used. The cationically modified cellulose can be obtained by reacting the carboxylated cellulose raw material with a cationizing agent such as glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrialkylammonium chloride or a halohydrin thereof and an alkali metal hydroxide (e.g., sodium hydroxide or potassium hydroxide) as a catalyst in the presence of water or an alcohol having 1 to 4 carbon atoms.
The degree of substitution of cations per glucose unit is preferably 0.02 to 0.50. By introducing cationic substituents into the cellulose, the cellulose is electrically repelled from each other. Therefore, cellulose having a cationic substituent introduced therein can be easily subjected to nano-defibration. At a cationic substitution degree per glucose unit of less than 0.02, the nano-defibration cannot be sufficiently performed. On the other hand, when the cationic substitution degree per glucose unit is more than 0.50, swelling or dissolution occurs, and thus a nanofiber form may not be obtained. In order to efficiently perform defibration, it is preferable to wash the cation-modified cellulose raw material obtained in the above. The degree of substitution of the cation can be adjusted by the amount of the cationizing agent added in the reaction and the composition ratio of water or alcohol having 1 to 4 carbon atoms.
(esterification)
In the present invention, esterified microfibrous cellulose obtained by defibrating esterified cellulose can be used. The esterified cellulose can be obtained by a method of mixing a powder or an aqueous solution of the phosphoric acid compound a with the cellulose raw material, or a method of adding an aqueous solution of the phosphoric acid compound a to a slurry of the cellulose raw material.
Examples of the phosphoric acid-based compound a include phosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, polyphosphonic acid, and esters thereof. They may also be in the form of salts. Among these, a compound having a phosphoric acid group is preferable for reasons of low cost, easy handling, and improvement in defibration efficiency by introducing a phosphoric acid group into cellulose of pulp fibers. As the compound having a phosphoric acid group, there can be mentioned: phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium phosphite, potassium phosphite, sodium hypophosphite, potassium hypophosphite, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate, and the like. These may be used alone or in combination of two or more. Among these, phosphoric acid, sodium salts of phosphoric acid, potassium salts of phosphoric acid, and ammonium salts of phosphoric acid are more preferable from the viewpoints of high efficiency of introduction of phosphoric acid groups, easy defibration in the below-described defibration step, and easy industrial application. Sodium dihydrogen phosphate and disodium hydrogen phosphate are particularly preferable. In addition, the phosphoric acid-based compound a is preferably used in the form of an aqueous solution in view of improvement in the uniformity of the reaction and improvement in the efficiency of introducing a phosphoric acid group. The pH of the aqueous solution of the phosphoric acid-based compound a is preferably 7 or less from the viewpoint of improving the efficiency of introducing the phosphoric acid group, and is preferably 3 to 7 from the viewpoint of suppressing hydrolysis of pulp fibers.
As an example of the method for producing the phosphorylated cellulose, the following method can be mentioned. A phosphoric acid compound A is added to a dispersion of a cellulose raw material having a solid content of 0.1 to 10 mass% while stirring, thereby introducing a phosphoric acid group into the cellulose. The amount of the phosphoric acid compound a added is preferably 0.2 to 500 parts by mass, more preferably 1 to 400 parts by mass, based on the amount of the phosphorus element, when the amount of the cellulose raw material is set to 100 parts by mass. If the ratio of the phosphoric acid-based compound A is not less than the lower limit, the yield of the microfibrous cellulose can be further improved. However, if the value exceeds the upper limit, the effect of improving the yield reaches the highest point, and therefore, this is not preferable from the viewpoint of cost.
In this case, in addition to the cellulose material and the phosphoric acid-based compound a, powders and aqueous solutions of the compound B other than these may be mixed. The compound B is not particularly limited, and is preferably a nitrogen-containing compound exhibiting basicity. "basic" is defined herein as the aqueous solution appearing peach-red to red in the presence of phenolphthalein indicator or the pH of the aqueous solution being greater than 7. The nitrogen-containing compound having a basic property used in the present invention is not particularly limited as long as the effect of the present invention is exerted, and a compound having an amino group is preferable. Examples thereof include urea, methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, and hexamethylenediamine, without any particular limitation. Among them, urea which is low in cost and easy to handle is preferable. The amount of the compound B to be added is preferably 2 to 1000 parts by mass, and 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 from 0 ℃ to 95 ℃, more preferably from 30 ℃ to 90 ℃. The reaction time is not particularly limited, and is about 1 minute to about 600 minutes, and more preferably 30 minutes to 480 minutes. When the conditions of the esterification reaction are within these ranges, the cellulose can be prevented from being excessively esterified and easily dissolved, and the yield of the phosphorylated cellulose becomes good. After the obtained suspension of the phosphorylated cellulose is dehydrated, it is preferable to perform a heat treatment at 100 to 170 ℃ from the viewpoint of suppressing hydrolysis of the cellulose. It is preferable that the heating treatment is performed at 130 ℃ or lower, preferably 110 ℃ or lower, during the period of water inclusion, and the heating treatment is performed at 100 to 170 ℃ after the water is removed.
The substitution degree of the phosphate group per glucose unit of the phosphorylated cellulose is preferably 0.001 to 0.40. By introducing phosphate group substituents into the cellulose, the cellulose is electrically repelled from each other. Therefore, the cellulose into which the phosphoric acid group is introduced can be easily subjected to nano-defibration. When the substitution degree of the phosphate group per glucose unit is less than 0.001, sufficient nano-fibrillation cannot be performed. On the other hand, when the substitution degree of the phosphoric acid group per glucose unit is more than 0.40, swelling or dissolution occurs, and thus a microfibrous cellulose form may not be obtained in some cases. In order to efficiently perform defibration, it is preferable that the phosphorylated cellulose raw material obtained in the above-described manner is boiled and then washed with cold water.
(defibering)
In the present invention, the apparatus for defibrating the chemically modified cellulose is not particularly limited, and it is preferable to apply a strong shearing force to the aqueous dispersion using an apparatus such as a high-speed rotary type, a colloid mill type, a high pressure type, a roll mill type, or an ultrasonic type. In particular, in order to efficiently perform defibration, a wet high-pressure or ultra-high-pressure homogenizer capable of applying a pressure of 50MPa or more and a strong shearing force to the aqueous dispersion is preferably used. The pressure is more preferably 100MPa or more, and still more preferably 140MPa or more. The microfibrous cellulose may be pretreated, as necessary, by using a known mixing, stirring, emulsifying, or dispersing apparatus such as a high-speed shear mixer before the defibration or dispersion treatment in the high-pressure homogenizer. The number of treatments (passes) in the defibering apparatus may be one or two or more, preferably two or more.
In the dispersion treatment, the chemically modified cellulose is generally dispersed in a solvent. The solvent is not particularly limited as long as it can disperse the chemically modified cellulose, and examples thereof include water, an organic solvent (e.g., 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 chemically modified cellulose in the dispersion is usually 0.1 mass% or more, preferably 0.2 mass% or more, and more preferably 0.3 mass% or more. This makes it possible to obtain an appropriate amount of liquid for the amount of the cellulose fiber material, which is highly efficient. The upper limit is usually 10% by mass or less, preferably 6% by mass or less. This can maintain fluidity.
Pretreatment may be performed as necessary before the defibration treatment or the dispersion treatment. The pretreatment may be carried out by using a mixing, stirring, emulsifying or dispersing apparatus such as a high-speed shear mixer.
When the chemically modified microfibrous cellulose obtained by the defibration step is in the form of a salt, it may be used as it is, or may be used in the form of an acid by acid treatment using an inorganic acid, a method using a cation exchange resin, or the like. Further, the cationic additive may be used by imparting hydrophobicity thereto.
(dried solid Material)
The dry solid content of the microfibrous cellulose used in the present invention can be obtained by drying the dispersion of microfibrous cellulose produced as described above and evaporating the solvent. As the dry solid content of the microfibrous cellulose, a commercially available product can be used.
In the present invention, the dry solid content means a state in which the amount of dry water is 20 mass% or less. The water content is preferably 0 to 20% by mass, and more preferably 0 to 12% by mass. In the case of drying, the water content may be dried to 0% (absolute dry). For example, it can be oven dried by drying at 105 ℃ for 3 hours.
The method of drying is not particularly limited, and may be appropriately selected depending on the object, and examples thereof include spray drying, squeezing, air drying, hot air drying, freeze drying, spray drying, and vacuum drying. The drying apparatus is not particularly limited, and a continuous tunnel drying apparatus, a belt drying apparatus, a vertical turbine drying apparatus, a multistage circular plate drying apparatus, an aeration drying apparatus, a rotary drying apparatus, an air flow drying apparatus, a spray drying apparatus, a cylinder drying apparatus, a drum drying apparatus, a belt drying apparatus, a screw conveyor drying apparatus, a rotary drying apparatus having a heating pipe, a vibration conveying drying apparatus, a batch-type box drying apparatus, a vacuum box drying apparatus, a stirring drying apparatus, and the like may be used alone or in combination of two or more.
(aqueous solvent)
In the present invention, the aqueous solvent includes water, a water-soluble organic solvent, or a mixed solvent thereof, and water is preferably used from the viewpoint that a good dispersion state is easily obtained at the time of dispersion because the cellulose material is hydrophilic.
The water-soluble organic solvent is an organic solvent dissolved in water. Examples thereof include methanol, ethanol, 2-propanol, butanol, glycerol, acetone, methyl ethyl ketone, and 1, 4-bis
Alkanes, N-methyl-2-pyrrolidone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetonitrile, and combinations thereof. Among them, lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol, and 2-propanol are preferable, and methanol and ethanol are more preferable, and ethanol is further more preferable, from the viewpoint of safety and easy availability.
When the mixed solvent is used, the amount of the water-soluble organic solvent in the mixed solvent is preferably 10% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more. The upper limit of the amount is not limited, but is preferably 95% by mass or less, and more preferably 90% by mass or less. The aqueous solvent may contain a water-insoluble organic solvent to the extent that the effects of the invention are not impaired.
(mixture)
From the viewpoint of preventing clogging of the pipe by the sample before introduction into the inline mixer, the mixture of the microfibrous cellulose and the aqueous solvent introduced into the inline mixer is preferably obtained by preliminary stirring the dry solid matter and the aqueous solvent. The preliminary stirring conditions are not particularly limited, and may be, for example, 500 to 1000rpm, about 30 to about 120 seconds. As the preliminary stirring device, for example, a homogenizing disperser, a homogenizing mixer, or the like can be used.
The solid content concentration of the microfibrous cellulose in the mixture is not particularly limited, but is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass.
(Online type mixer)
The inline mixer that can be used in the present invention is not particularly limited as long as it can turbulently stir the mixture and apply a mechanical shearing force to the mixture. An OHR mixer, which is one of the static mixers, is preferably used from the viewpoint of excellent redispersibility and being capable of being redispersed efficiently in a short time.
An example of an inline mixer will be described with reference to fig. 1. Fig. 1 is a schematic view showing a cross section of an in-line type mixer. It should be noted that the inline mixer that can be used in the present invention is not limited to the mixer shown in fig. 1.
In the inline mixer 2 shown in fig. 1, a pipe body 4 through which the mixture passes and two crossed plates 6 for causing turbulent stirring located on the upstream side of the pipe body 4 are provided, the plates 6 being fixed on the inner wall of the pipe body 4. Further, a plurality of protrusions 8 are provided on the inner peripheral wall of the pipe body 4 on the downstream side of the plate 6. In fig. 1, the direction of passage of the mixture is indicated by an arrow.
When the mixture is introduced into the inline mixer 2 at a flow rate or more, the mixture forms a spiral flow with strong twist by the action of the two sheets 6. At this point, the mixture develops mechanical shear forces due to the sharp splitting and flow alteration caused by the two plates 6. Then, turbulent stirring is generated to perform stirring. The mixture is further conveyed in the downstream direction in the tube, and collides with the protrusions 8 while being stirred, whereby the mixture is more vigorously mixed to promote dispersion, and a re-dispersion of the microfibrous cellulose is obtained. The number of times the mixture is passed through the in-line mixer is not particularly limited, and may be once or twice or more.
In the case of carrying out the redispersion process of the invention, the mixture is introduced into an in-line mixer at a flow rate which causes turbulent stirring. The flow rate at which the mixture is introduced is not particularly limited as long as it causes turbulent stirring, but from the viewpoint of efficient dispersion of the sample, it is preferably 1.0 m/sec to 10.0 m/sec, and more preferably 3.0 m/sec to 10.0 m/sec.
In order to introduce the mixture into the inline mixer 2 at a desired flow rate, it is preferable to use a pump having sufficient liquid-feeding capacity. By using a pump having sufficient liquid-feeding ability, intense turbulence is induced in the inline mixer 2, and dispersion of the dry solid matter of the microfibrous cellulose is promoted in the process of collision of the turbulence with the protruded objects 8. The pump is not particularly limited, and a vortex pump, a mohno pump, and the like can be cited. The liquid-feeding capacity of the pump is preferably 0.1 kW/hour to 0.8 kW/hour, and more preferably 0.3 kW/hour to 0.8 kW/hour.
The number and shape of the plates 6 provided on the upstream side of the pipe 4 are not limited as long as turbulent stirring can be caused, but the number of the plates is preferably 2 to 8, more preferably 2, from the viewpoint of increasing the number of times of shearing. In addition, from the viewpoint of stirring efficiency, the shape is preferably a semi-elliptical shape.
In addition, the shape of the protrusion 8 of the inner peripheral wall of the tube body 4 is not particularly limited, but a mushroom shape is preferable from the viewpoint of improving the mixing efficiency.
According to the redispersion method of the present invention, since the inline mixer is used, when a small amount of the redispersion liquid is produced, the preparation time of several tens of minutes to several hours required for redispersion using the batch mixer can be significantly shortened, and the efficiency is excellent. In addition, when a large amount of the redispersion liquid is produced, a redispersion liquid having stable quality can be efficiently obtained.
The redispersion obtained by the redispersion method of the present invention can be confirmed whether or not the microfibrous cellulose is redispersed in an aqueous solvent in the form of microfibrous cellulose by observing a nanosized cellulose having a width of 1nm to 10 μm, preferably about 2nm to about 5nm using a field emission scanning electron microscope (FE-SEM) or the like. For example, it can be confirmed by observing a redispersion liquid obtained by adding a coloring material such as ink to a redispersion liquid adjusted to have a solid content concentration of 1.0 mass% at a magnification of 100 times using an optical microscope, and comparing the size and number of white-appearing lumps in an image with an observed image of the dispersion liquid before drying.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples. In the case where the method of measuring and calculating the numerical values in the respective examples is not particularly described, the numerical values are measured and calculated by the method described in the specification.
(example 1)
Water was added to a dry solid content (moisture content: 10.1%) of carboxymethylated cellulose nanofibers, and preliminary stirring was performed (500rpm, 30 seconds) to prepare 10L of a slurry containing 1.0 mass% of a CNF solid component. The total amount of the slurry was transferred at 5.69 m/sec using a vortex pump (20 NED04Z-V, manufactured by Niconi corporation) and passed through a connected OHR mixer (MX-F8, manufactured by OHR engineering research, Ltd.; outlet cross-sectional area: 50.2 mm)2) Once, a CNF redispersion was obtained. Note that the outlet flow of the slurryThe amount was 17.1L/min, and the time required for the total amount of slurry to pass through the OHR mixer once was 35 seconds. Note that in example 1, in which the flow rate of the slurry was made 5.69 m/sec, strong turbulence was generated in the OHR mixer.
Further, 2 drops of ink droplets (10% solid content, manufactured by Wuzhu, K.K.) were dropped on 1g of the CNF redispersion liquid obtained in the above manner, and the mixture was stirred for 1 minute while setting the rotation speed scale of a vortex mixer (manufactured by IUCHI, equipment name: Automatic Lab-mixer HM-10H) at the maximum. Then, the cellulose nanofiber dispersion containing ink droplets was sandwiched between two glass plates so that the film thickness was 0.15mm, and observed at a magnification of 100 times using an optical microscope (digital microscope KH-8700 (manufactured by Hirox corporation)). The results are shown in FIG. 2.
Comparative example 1
A CNF redispersion was obtained in the same manner as in example 1 by passing through an OHR mixer once, except that the liquid was transferred at 2.01 m/sec using a Mohno Pump (Mohno Pump). Note that the outlet flow rate of the slurry was 6.1L/min, and the time required for the total amount of the slurry to pass through the OHR mixer once was 99 seconds. In comparative example 1 in which the flow rate of the slurry was set to 2.01 m/sec, although turbulence was generated in the OHR mixer, the turbulence was weak. In addition, the CNF redispersion obtained in this way was observed using an optical microscope as in example 1. The results are shown in FIG. 3.
(reference example 1)
Water was added to the dry solid content (moisture content 10.1%) of carboxymethylated cellulose nanofibers, and preliminary stirring was performed (500rpm, 30 seconds) to prepare 10L of a slurry containing 1.0 mass% of the CNF solid content. The slurry was stirred with a homogenizing disperser (3000rpm, 1 hour) to give a CNF redispersion. The CNF redispersion obtained in this way was observed using an optical microscope as in example 1. The results are shown in FIG. 4.
(evaluation method of Dispersion State)
The image obtained in example 1 (fig. 2) and the image obtained in comparative example 1 (fig. 3) were observed, and the dispersed state was judged by comparing whether or not the size and amount of white lumps (gel particles) seen in the images were close to the image obtained in reference example 1 (fig. 4). The dispersion state can be said to be good if it is close to the case of reference example 1.
(evaluation result of Dispersion State)
In example 1, the size and amount of the gel particles were close to those in reference example 1, and the dispersion state was good. On the other hand, in comparative example 1, a plurality of gel particles larger than in reference example 1 were observed, and it cannot be said that the dispersion state was poor as close to reference example 1.
Claims (6)
1. A method for redispersing a dry solid matter of microfibrous cellulose, which comprises drying a microfibrous cellulose dispersion produced to obtain a dry solid matter of microfibrous cellulose, and redispersing the same in the form of microfibrous cellulose in an aqueous solvent,
introducing a mixture of the dry solid containing the microfibrous cellulose and the aqueous solvent into an inline mixer that mixes the contents by generating turbulent stirring at a flow rate that causes turbulent stirring, stirring the mixture, and applying mechanical shear force to the mixture.
2. The method for redispersing dry solids of microfibrous cellulose according to claim 1, wherein the microfibrous cellulose is chemically modified microfibrous cellulose.
3. The method for redispersing dry solids of microfibrous cellulose according to claim 1 or 2, wherein the solid content of the microfibrous cellulose is at least one selected from the group consisting of,
the inline mixer has a pipe body, at least two plates intersecting each other for causing turbulent stirring are provided on an upstream side in the pipe body, and a plurality of protrusions are provided on an inner peripheral wall of the pipe body on a downstream side of the plates.
4. A method for producing a redispersion of microfibrous cellulose, comprising:
introducing a mixture containing a dry solid matter of microfibrous cellulose obtained by drying the produced microfibrous cellulose dispersion and an aqueous solvent into an inline mixer for mixing the contents by causing turbulent stirring at a flow rate that causes turbulent stirring; and
and a step of stirring the mixture in the inline mixer and applying a mechanical shearing force to the mixture to redisperse the dry solid matter of the microfibrous cellulose in the aqueous solvent to obtain a redispersed solution of the microfibrous cellulose.
5. The method for producing a redispersion of microfibrous cellulose according to claim 4, wherein the microfibrous cellulose is chemically modified microfibrous cellulose.
6. The method of producing a redispersion of microfibrous cellulose according to claim 4 or 5, wherein said inline mixer has a pipe body, at least two plates for causing intersection of turbulent stirring are provided on an upstream side in said pipe body, and a plurality of protrusions are provided on an inner peripheral wall of said pipe body on a downstream side of said plates.
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| JP2018197094 | 2018-10-19 | ||
| PCT/JP2019/039067 WO2020080119A1 (en) | 2018-10-19 | 2019-10-03 | Redispersion method of dry solid of microfibrous cellulose and method of producing redispersion liquid of microfibrous cellulose |
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| JP2000354749A (en) * | 1999-06-17 | 2000-12-26 | Ohr:Kk | Cavitation generating device, fluid mixing device using the same and mixing projection used in latter device |
| CN102356093A (en) * | 2009-03-31 | 2012-02-15 | 陶氏环球技术有限责任公司 | Carboxymethyl cellulose with improved properties |
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| JP2017002138A (en) * | 2015-06-05 | 2017-01-05 | 大王製紙株式会社 | Cellulose nanofiber-containing dried body, method for producing the same, and method for producing cellulose nanofiber-dispersed liquid |
| JP2018009134A (en) * | 2016-07-15 | 2018-01-18 | 大王製紙株式会社 | Cellulose nanofiber-containing dried body, method for producing the same, and method for producing cellulose nanofiber-containing dried body-dispersed liquid |
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| WO2017154568A1 (en) * | 2016-03-11 | 2017-09-14 | 日本製紙株式会社 | Method for re-dispersing cellulose nanofiber dispersion |
| BR112018069542B1 (en) * | 2016-04-22 | 2022-11-16 | Fiberlean Technologies Limited | RE-DISPERSE MICROFIBRILLATED CELLULOSE |
| WO2018038194A1 (en) * | 2016-08-26 | 2018-03-01 | 王子ホールディングス株式会社 | Fibrous cellulose-containing material and method for producing fibrous cellulose-containing material |
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|---|---|---|---|---|
| JP2000354749A (en) * | 1999-06-17 | 2000-12-26 | Ohr:Kk | Cavitation generating device, fluid mixing device using the same and mixing projection used in latter device |
| CN102356093A (en) * | 2009-03-31 | 2012-02-15 | 陶氏环球技术有限责任公司 | Carboxymethyl cellulose with improved properties |
| CN105377959A (en) * | 2013-04-22 | 2016-03-02 | 赫尔克里士公司 | Methods for dispersing water soluble polymer powder |
| JP2017002138A (en) * | 2015-06-05 | 2017-01-05 | 大王製紙株式会社 | Cellulose nanofiber-containing dried body, method for producing the same, and method for producing cellulose nanofiber-dispersed liquid |
| JP2018009134A (en) * | 2016-07-15 | 2018-01-18 | 大王製紙株式会社 | Cellulose nanofiber-containing dried body, method for producing the same, and method for producing cellulose nanofiber-containing dried body-dispersed liquid |
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| JP7323549B2 (en) | 2023-08-08 |
| JPWO2020080119A1 (en) | 2021-09-30 |
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