JP7389660B2 - Cellulose fine fiber and its manufacturing method - Google Patents
Cellulose fine fiber and its manufacturing method Download PDFInfo
- Publication number
- JP7389660B2 JP7389660B2 JP2020009635A JP2020009635A JP7389660B2 JP 7389660 B2 JP7389660 B2 JP 7389660B2 JP 2020009635 A JP2020009635 A JP 2020009635A JP 2020009635 A JP2020009635 A JP 2020009635A JP 7389660 B2 JP7389660 B2 JP 7389660B2
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- Prior art keywords
- cellulose
- defibration
- fine fibers
- reaction
- fibrillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920002678 cellulose Polymers 0.000 title claims description 127
- 239000001913 cellulose Substances 0.000 title claims description 127
- 239000000835 fiber Substances 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000000654 additive Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 22
- 230000001737 promoting effect Effects 0.000 claims description 19
- 239000000010 aprotic solvent Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 229920001567 vinyl ester resin Polymers 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- 206010061592 cardiac fibrillation Diseases 0.000 description 47
- 230000002600 fibrillogenic effect Effects 0.000 description 44
- 239000002904 solvent Substances 0.000 description 39
- 239000003054 catalyst Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 28
- 210000001724 microfibril Anatomy 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 22
- -1 vinyl octylate Chemical compound 0.000 description 20
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000012986 modification Methods 0.000 description 14
- 230000004048 modification Effects 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000032050 esterification Effects 0.000 description 8
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 7
- 235000019743 Choline chloride Nutrition 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 229960003178 choline chloride Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 description 2
- JJCWKVUUIFLXNZ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCO JJCWKVUUIFLXNZ-UHFFFAOYSA-M 0.000 description 2
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- UATOFRZSCHRPBG-UHFFFAOYSA-N acetamide;hydrate Chemical compound O.CC(N)=O UATOFRZSCHRPBG-UHFFFAOYSA-N 0.000 description 2
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 2
- 229960004373 acetylcholine Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229940075419 choline hydroxide Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229940073579 ethanolamine hydrochloride Drugs 0.000 description 2
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LKAWQFHWVVSFTR-UHFFFAOYSA-N 2-(methylamino)ethanol;hydrochloride Chemical compound [Cl-].C[NH2+]CCO LKAWQFHWVVSFTR-UHFFFAOYSA-N 0.000 description 1
- NWYYWIJOWOLJNR-UHFFFAOYSA-N 2-Amino-3-methyl-1-butanol Chemical compound CC(C)C(N)CO NWYYWIJOWOLJNR-UHFFFAOYSA-N 0.000 description 1
- KSXJJXIDBVLDBZ-UHFFFAOYSA-N 2-amino-2-phenylethanol hydrochloride Chemical compound [Cl-].OCC([NH3+])C1=CC=CC=C1 KSXJJXIDBVLDBZ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YJHSJERLYWNLQL-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)CCO YJHSJERLYWNLQL-UHFFFAOYSA-N 0.000 description 1
- FNPBHXSBDADRBT-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CCO FNPBHXSBDADRBT-UHFFFAOYSA-M 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
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- BALXUFOVQVENIU-GNAZCLTHSA-N Ephedrine hydrochloride Chemical compound Cl.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 BALXUFOVQVENIU-GNAZCLTHSA-N 0.000 description 1
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- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
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- 239000012346 acetyl chloride Substances 0.000 description 1
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- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
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- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 description 1
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- VJLOFJZWUDZJBX-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;chloride Chemical compound [Cl-].OCC[NH2+]CCO VJLOFJZWUDZJBX-UHFFFAOYSA-N 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- QAWBXZYPFCFQLA-UHFFFAOYSA-N butanoyl bromide Chemical compound CCCC(Br)=O QAWBXZYPFCFQLA-UHFFFAOYSA-N 0.000 description 1
- ZEEDSWFDNIDARI-UHFFFAOYSA-N butanoyl iodide Chemical compound CCCC(I)=O ZEEDSWFDNIDARI-UHFFFAOYSA-N 0.000 description 1
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Description
本発明は、セルロース微細繊維及びその製造方法に関する。 The present invention relates to cellulose fine fibers and a method for producing the same.
セルロース繊維（細胞壁単位）は、セルロース微細繊維（ミクロフィブリル）の集合体である。微細繊維は鋼鉄に匹敵する機械特性を持ち、直径約２０ｎｍのナノ構造を持つため補強剤として社会的に熱く注目されている。しかし、微細繊維は繊維間が水素結合により結束されるため、その微細繊維を取り出すために、水素結合を解けてミクロフィブリルを分離すること（解繊という）が必要である。そのため、激しい物理力を加えた機械解繊法が開発された。 Cellulose fibers (cell wall units) are aggregates of cellulose fine fibers (microfibrils). Fine fibers have mechanical properties comparable to steel and have a nanostructure with a diameter of about 20 nm, so they are attracting hot social attention as reinforcing agents. However, since fine fibers are bound together by hydrogen bonds, in order to extract the fine fibers, it is necessary to break the hydrogen bonds and separate the microfibrils (referred to as fibrillation). For this reason, a mechanical defibration method that applies intense physical force was developed.
セルロースナノファイバーは水中機械解繊法により製造する方法に関しては、セルロースは水により膨潤され、柔らかい状態で高圧ホモジナイザー等の強力的な機械せん断によりナノ化する。天然のセルロースミクロフィブリルは結晶ゾーンと非結晶性ゾーンから構成され、非結晶ゾーンは水等の膨潤性溶媒を吸収、膨潤した状態になると、強力なせん断により変形するため、得られたセルロース微細繊維にはダメージが存在し、絡み合い引っかかりしやすい形状となる。 Regarding the method of producing cellulose nanofibers by an underwater mechanical defibration method, cellulose is swollen with water and in a soft state is transformed into nanofibers by strong mechanical shearing using a high-pressure homogenizer or the like. Natural cellulose microfibrils are composed of a crystalline zone and an amorphous zone, and the amorphous zone absorbs swelling solvents such as water, and when it becomes swollen, it is deformed by strong shearing, resulting in the resulting cellulose fine fibers. There is damage to the parts, and the shape makes them easy to get entangled with each other.
また、ボールミル等の強力的な機械粉砕法により固体状態特有のメカノケミカル反応が起こり、この作用によりセルロースの結晶構造が破壊されたり、溶解されたりすることが避けられなくなる。その結果、収率は低くなり、結晶化度が低くなる恐れがある。 In addition, a strong mechanical grinding method such as a ball mill causes a mechanochemical reaction peculiar to the solid state, and this action inevitably destroys or dissolves the crystal structure of cellulose. As a result, the yield may be low and the degree of crystallinity may be low.
水中解繊のもう一つ問題は、解繊の後、樹脂と複合化するため、脱水して表面疎水化修飾したりする必要がある。その脱水工程には高いエネルギーが要する。 Another problem with underwater fibrillation is that after fibrillation, it becomes composite with resin, so it is necessary to dehydrate and modify the surface to make it hydrophobic. The dehydration process requires high energy.
また、表面をエステル化したセルロース微細繊維の製造方法として、イオン液体と有機溶媒を含有する混合溶媒を用いてセルロース系物質を膨潤及び／または部分溶解させた後、エステル化する方法がある（特許文献１）。しかし、特許文献１のイオン液体と有機溶媒を含有する混合溶媒を用いた場合は、イオン液体の回収や再利用に関するコストが高くなる課題があった。 In addition, as a method for producing cellulose fine fibers with esterified surfaces, there is a method in which cellulose-based materials are swollen and/or partially dissolved using a mixed solvent containing an ionic liquid and an organic solvent, and then esterified (patented). Reference 1). However, when the mixed solvent containing an ionic liquid and an organic solvent of Patent Document 1 was used, there was a problem that the cost related to recovery and reuse of the ionic liquid was high.
また、表面をエステル化したセルロース微細繊維の製造方法に関して、セルロースと有機溶剤とを混合して、エステル化剤を加えた後に強力な機械的破砕とともにエステル化反応をすることにより、セルロース表面をエステル化し、解離する方法が、特許文献２に開示されている。しかし、特許文献２の方法では、その実施例に示すように用いたエステル化剤と有機溶媒を含む解繊用溶液はセルロースへの浸透性が低く、機械的粉砕処理の間に有機溶剤とエステル化剤をセルロース内部へ殆ど浸透できなかったため、化学解繊でなく、強力な機械力が必要となる機械解繊方法である。強力な機械的破砕はセルロースナノファイバーを損傷する可能性があるため前記と同様な問題がある。また、パルプ繊維の内部になるほど有機溶剤とエステル化剤は入りにくいためパルプ内部の方はエステル化修飾されにくくなり、パルプ繊維内部の微細繊維は機械解繊により解繊されても、表面修飾がほとんどできていないと推測できる。また、表面芳香置換基で修飾セルロース微細繊維の製造方法が特許文献３に開示されているが、しかし、化学修飾工程のみでは解繊できず強力な機械解繊工程が必要とされている。
また、特許文献４に記載したように、カルボン酸ビニルエステル、反応及び／又は解繊促進添加剤とドナー数２６以上の非プロトン性溶媒とを含む解繊溶液をセルロースに浸透させて、セルロースを解繊するとともにアシル化修飾する方法もあった。しかし、この方法は、解繊するのに２～３時間が必要であり、１時間程度の解繊時間では解繊不完全な粗大繊維が残留する問題がある。
In addition, regarding the method for producing cellulose fine fibers with an esterified surface, by mixing cellulose and an organic solvent, adding an esterifying agent, and performing an esterification reaction with strong mechanical crushing, the surface of the cellulose is esterified. A method of oxidation and dissociation is disclosed in Patent Document 2. However, in the method of Patent Document 2, as shown in the examples, the defibrating solution containing the esterifying agent and organic solvent has low permeability into cellulose, and the organic solvent and ester are mixed during the mechanical crushing process. Because the curing agent could hardly penetrate inside the cellulose, this method is not a chemical defibration method, but a mechanical defibration method that requires strong mechanical force. Strong mechanical crushing may damage the cellulose nanofibers, causing the same problem as above. In addition, organic solvents and esterifying agents are less likely to enter the inside of the pulp fibers, so the inside of the pulp is less likely to be modified by esterification, and even if the fine fibers inside the pulp fibers are defibrated by mechanical defibration, surface modification will not occur. It can be assumed that almost nothing has been done. Further, a method for producing cellulose fine fibers modified with surface aromatic substituents is disclosed in Patent Document 3, but the fibers cannot be defibrated only by a chemical modification step, and a powerful mechanical defibration step is required.
Furthermore, as described in Patent Document 4, a fibrillation solution containing a carboxylic acid vinyl ester, a reaction and/or fibrillation promoting additive, and an aprotic solvent having a donor number of 26 or more is infiltrated into cellulose. There was also a method of fibrillation and acylation modification. However, this method requires 2 to 3 hours for defibration, and when the defibration time is about 1 hour, there is a problem that incompletely defibrated coarse fibers remain.
本発明は、物理粉砕を必要としない省エネルギーな方法で、ナノサイズで結晶化度が高く、繊維形状の損傷が少ないセルロース微細繊維の製造法及びエステル化修飾セルロース微細繊維の製造法を提供する。 The present invention provides a method for producing nano-sized cellulose fine fibers with high crystallinity and less damage to the fiber shape, and a method for producing esterification-modified cellulose fine fibers by an energy-saving method that does not require physical pulverization.
本発明者らは、前記課題を達成するため鋭意検討した結果、機械的に破砕することなく、カルボン酸ビニルエステル、反応及び／又は解繊促進添加剤と反応及び／又は解繊錠剤を含む解繊溶液をセルロースに浸透させて、セルロースを解繊し、ナノサイズで結晶化度が高く、粗大繊維の残留が少ないセルロース微細繊維の製造方法を見出した。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have discovered that a tablet containing a carboxylic acid vinyl ester, a reaction and/or a defibration promoting additive, and a reacting and/or defibrating tablet can be prepared without mechanically crushing. We have found a method for producing cellulose fine fibers that are nano-sized, have a high degree of crystallinity, and have little residual coarse fibers by infiltrating cellulose with a fiber solution and defibrating the cellulose.
すなわち本発明は、以下の構成からなることを特徴とし、上記課題を解決するものである。
［１］ ドナー数２６以上の非プロトン性溶媒と、カルボン酸ビニルエステル、反応及び／又は解繊促進添加剤と、を含む解繊溶液をセルロースに浸透させて、セルロースを解繊することを含むセルロース微細繊維の製造方法であって、前記反応及び／又は解繊促進添加剤が、下記式（１）で示される４級アンモニウム塩である製造方法：
Ｘ－（Ｒ１）（Ｒ２）（Ｒ３）Ｎ＋－Ｒ４－Ｙ （１）
（式中、Ｘ－は、フッ素イオン、塩素イオン、臭素イオン、ヨウ素イオン、水酸化物イオン、硝酸イオン、テトラフルオロホウ素イオン及びヘキサフルオロホウ素イオンのいずれかを表し、Ｒ１、Ｒ２、Ｒ３はそれぞれ独立して炭素数が１～２４のアルキル基、シクロアルキル基またはアリール基を表し、Ｒ４は炭素数が１～６のアルキレン基、ＹはＯＨ、ＳＨ又はＮＨ２を表す）。
［２］ 前記ドナー数２６以上の非プロトン性溶媒が、スルホキシド類、ピリジン類、ピロリドン類およびアミド類からなる群より選択される少なくとも１種である、前記［１］に記載の製造方法。
［３］ 前記反応及び／又は解繊促進添加剤の含有割合が、解繊溶液全体に対して０．１重量％～２０重量％である前記［１］又は前記［２］に記載の製造方法。
That is, the present invention is characterized by having the following configuration, and is intended to solve the above problems.
[1] Involves defibrating the cellulose by permeating the cellulose with a defibrating solution containing an aprotic solvent having a donor number of 26 or more, a carboxylic acid vinyl ester, and a reaction and/or defibrating additive. A method for producing cellulose fine fibers, wherein the reaction and/or defibration promoting additive is a quaternary ammonium salt represented by the following formula (1):
X - (R1) (R2) (R3) N + -R4-Y (1)
( In the formula , each independently represents an alkyl group, cycloalkyl group, or aryl group having 1 to 24 carbon atoms, R4 represents an alkylene group having 1 to 6 carbon atoms, and Y represents OH, SH or NH 2 ).
[2] The production method according to [1] above, wherein the aprotic solvent having 26 or more donors is at least one selected from the group consisting of sulfoxides, pyridines, pyrrolidones, and amides.
[3] The production method according to [1] or [2] above, wherein the content of the reaction and/or defibration promoting additive is 0.1% to 20% by weight based on the entire defibrating solution. .
本発明では、機械的に破砕することなく、カルボン酸ビニルエステル、反応及び／又は解繊促進添加剤とドナー数２６以上の非プロトン性溶媒を含む解繊溶液をセルロースに浸透させて、セルロースを解繊するため、セルロースのミクロフィブリルに与える損傷が少なくてアスペクト比が大きいセルロース微細繊維を製造する方法に関する。反応及び／又は解繊促進添加剤を添加することにより解繊効率を向上すると共にカルボン酸ビニルとセルロースの水酸基とをエステル化交換反応させて表面修飾セルロース微細繊維を製造することができる。解繊溶液をセルロースに浸透させて繊維間、ラメラ間およびミクロフィブリル間の水素結合を切断しながらミクロフィブリルの表面を修飾するため、天然由来のセルロースの結晶構造やミクロフィブリル構造を破壊することなく、セルロースを解繊し、ミクロフィブリルの表面を効率よく修飾することができる。そのため、ナノサイズで結晶化度が高く、繊維形状の損傷が少なくてアスペクト比が大きく、且つ乾燥後溶媒や樹脂への再分散性が優れたセルロース微細繊維を、省エネルギーな方法で簡便かつ効率良く生産できる。さらに、他の修飾反応化剤を添加して共存させることにより修飾官能基の種類を多用化することができ、用途に応じて様々な修飾官能基を導入し、樹脂などの有機媒体との親和性をさらに向上できる。 In the present invention, a fibrillation solution containing a carboxylic acid vinyl ester, a reaction and/or fibrillation promoting additive, and an aprotic solvent having a donor number of 26 or more is infiltrated into cellulose without mechanically crushing it. The present invention relates to a method for producing cellulose fine fibers that cause less damage to cellulose microfibrils and have a large aspect ratio due to defibration. By adding a reaction and/or fibrillation promoting additive, the fibrillation efficiency can be improved, and surface-modified cellulose fine fibers can be produced by carrying out an esterification exchange reaction between vinyl carboxylate and the hydroxyl group of cellulose. The fibrillating solution permeates cellulose to modify the surface of microfibrils while breaking hydrogen bonds between fibers, lamellae, and microfibrils, without destroying the crystalline or microfibril structure of naturally derived cellulose. , cellulose can be defibrated and the surface of microfibrils can be efficiently modified. Therefore, cellulose fine fibers, which are nano-sized and have a high degree of crystallinity, have a large aspect ratio with little damage to the fiber shape, and have excellent redispersibility in solvents and resins after drying, can be produced simply and efficiently using an energy-saving method. Can be produced. Furthermore, by adding and coexisting other modification reaction agents, it is possible to increase the number of types of modification functional groups. You can further improve your sexuality.
さらに、本発明のエステル化修飾セルロース微細繊維の製造法は、反応及び／又は解繊促進添加剤を添加することにより、短時間の解繊時間でも解繊不完全の粗大繊維の残留率を大きく低減させることができ、解繊不完全な粗大繊維が混在することなくセルロース微細繊維を得ることができる。すなわち、反応及び／又は解繊促進添加剤を添加することにより、解繊時間を１／２～１／６、それ以下に短縮することができる。 Furthermore, in the method for producing esterified modified cellulose fine fibers of the present invention, by adding reaction and/or defibration accelerating additives, the residual rate of incompletely defibrated coarse fibers can be greatly increased even in a short defibration time. cellulose fine fibers can be obtained without the presence of incompletely defibrated coarse fibers. That is, by adding a reaction and/or defibration accelerating additive, the defibration time can be shortened to 1/2 to 1/6 or even less.
本発明のセルロース微細繊維の製造方法は、カルボン酸ビニルエステル、反応及び／又は解繊促進添加剤とドナー数２６以上の非プロトン性溶媒とを含む解繊溶液をセルロースに浸透させて、セルロースを解繊することを特徴とする。
詳細には、カルボン酸ビニル、反応及び／又は解繊促進添加剤とドナー数２６以上の非プロトン性溶媒とを含む解繊液をセルロースに浸透させてセルロースを膨潤しながらミクロフィブリルの間の水素結合を解除することによりミクロフィブリルが自ら解してセルロース微細繊維を得ることができる。
The method for producing cellulose fine fibers of the present invention involves infiltrating cellulose with a fibrillation solution containing a carboxylic acid vinyl ester, a reaction and/or fibrillation promoting additive, and an aprotic solvent having a donor number of 26 or more. Characterized by defibration.
In detail, a fibrillation solution containing vinyl carboxylate, a reaction and/or fibrillation promoting additive, and an aprotic solvent having a donor number of 26 or more is infiltrated into cellulose to swell the cellulose and generate hydrogen between microfibrils. By releasing the bonds, the microfibrils self-disintegrate and cellulose fine fibers can be obtained.
原料となるセルロースは、セルロース単独の形態であってもよく、リグニンやヘミセルロースなどの非セルロース成分を含む混合形態であってもよい。
好ましいセルロール物質としては、Ｉ結晶型セルロース構造を含むセルロース物質であり、例えば、木材由来パルプ、木材、竹、リンダーパルプ、綿、セルロースパウダーを含む物質等がある。
The cellulose used as a raw material may be in the form of cellulose alone, or may be in the form of a mixture containing non-cellulose components such as lignin and hemicellulose.
Preferred cellulose materials include cellulose materials having a type I crystalline cellulose structure, such as wood-derived pulp, wood, bamboo, linder pulp, cotton, and materials containing cellulose powder.
前記カルボン酸ビニルエステルは、下記式（２）で表されるカルボン酸ビニルエステルである。
Ｒ５－ＣＯＯ－Ｃ（Ｒ６）＝Ｃ（Ｒ７）（Ｒ８） （２）
（式中、Ｒ５は炭素数１～１６のアルキル基、アルキレン基シクロアルキル基及びアリール基のいずれかを表わし、Ｒ６，Ｒ７，Ｒ８は水素または炭素数１～１６のアルキル基、アルキレン基シクロアルキル基及びアリール基のいずれかを表わす。）
The carboxylic acid vinyl ester is a carboxylic acid vinyl ester represented by the following formula (2).
R5-COO-C(R6)=C(R7)(R8) (2)
(In the formula, R5 represents either an alkyl group having 1 to 16 carbon atoms, an alkylene cycloalkyl group, or an aryl group, and R6, R7, and R8 are hydrogen, an alkyl group having 1 to 16 carbon atoms, an alkylene cycloalkyl group, (Represents either a group or an aryl group.)
さらに、前記カルボン酸ビニルエステルが、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、シクロヘキサンカルボン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、ピバリン酸ビニル、オクチル酸ビニルアジピン酸ジビニル、メタクリル酸ビニル、クロトン酸ビニル、ピバリン酸ビニル、オクチル酸ビニル、安息香酸ビニル、桂皮酸ビニル、酢酸イソプロペニルの群より選択された少なくとも１種であることが好ましい。 Furthermore, the carboxylic acid vinyl ester is vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl cyclohexanecarboxylate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, stearic acid. At least one member selected from the group consisting of vinyl, vinyl pivalate, vinyl octylate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl pivalate, vinyl octylate, vinyl benzoate, vinyl cinnamate, and isopropenyl acetate. It is preferable that there be.
これらのカルボン酸ビニルは、単独で又は二種以上を組み合わせて使用できる。これらのカルボン酸ビニルのうち、解繊性と反応性の点から、酢酸ビニル、プロピオン酸ビニルと酪酸ビニル等の炭素数２～７（特に２～５）の低級脂肪族カルボン酸ビニルが好ましく、Ｃ１－４アルキルカルボン酸ビニルが特に好ましい。炭素数が大きすぎると、ミクロフィブリル間への浸透性とセルロース水酸基に対する反応性が低下するおそれがあるため、低級脂肪族カルボン酸ビニルと併用することが好ましい。 These vinyl carboxylates can be used alone or in combination of two or more. Among these vinyl carboxylates, lower aliphatic vinyl carboxylates having 2 to 7 carbon atoms (especially 2 to 5 carbon atoms) such as vinyl acetate, vinyl propionate and vinyl butyrate are preferred from the viewpoint of fibrillating properties and reactivity. Vinyl C1-4 alkylcarboxylate is particularly preferred. If the number of carbon atoms is too large, the permeability between microfibrils and the reactivity with cellulose hydroxyl groups may decrease, so it is preferable to use it in combination with lower aliphatic vinyl carboxylate.
前記反応及び／又は解繊促進添加剤は、前記式（１）で表される４級アンモニウム系化合物からなる群より選択された少なくとも１種であってもよい。
前記反応及び／又は解繊促進添加剤は、前記式（１）で示される４級アンモニウム塩であれば特に限定されないが、Ｘ
－ が塩素イオン、Ｒ１、Ｒ２、Ｒ３がメチル基、Ｒ４は炭素数が２のアルキレン基、ＹはＯＨの化合物が好ましい。
The reaction and/or defibration promoting additive may be at least one selected from the group consisting of quaternary ammonium compounds represented by the formula (1).
The reaction and/or fibrillation promoting additive is not particularly limited as long as it is a quaternary ammonium salt represented by the formula (1), but X - is a chlorine ion, R1, R2, R3 are methyl groups, and R4 is carbon A compound in which the number is 2 alkylene groups and Y is OH is preferred.
具体的に化合物名の例を示すと、（２－ヒドロキシエチル）トリメチルアンモニウムクロリド （塩化コリン）、（２－ヒドロキシエチル）トリメチルアンモニウムヒドロキシド （水酸化コリン）、ヨウ化（２－ヒドロキシエチル）トリメチルアンモニウム（ヨウ化コリン）、臭化（２－ヒドロキシエチル）トリメチルアンモニウム（臭化コリン）、アセチルコリン、（２－ヒドロキシエチル）トリエチルアンモニウムクロリド、（２－ヒドロキシエチル）ジエチルメチルアンモニウムクロリド、（２－ヒドロキシエチル）エチルジメチルアンモニウムクロリド、（２－ヒドロキシエチル）ジメチルアンモニウムクロリド、（２－ヒドロキシエチル）メチルアンモニウムクロリド、（２－ヒドロキシエチル）アンモニウムクロリド （エタノールアミン塩酸塩）、ジ（２－ヒドロキシエチル）アンモニウムクロリド、トリ（２－ヒドロキシエチル）アンモニウムクロリド、エフェドリン塩酸塩、バリノール塩酸塩、フェニルアラニオール塩酸塩、フェニルグリシノール塩酸塩、等である。
上記化合物の中でも（２－ヒドロキシエチル）トリメチルアンモニウムクロリド （塩化コリン）、（２－ヒドロキシエチル）トリメチルアンモニウムヒドロキシド （水酸化コリン）、アセチルコリン、（２－ヒドロキシエチル）アンモニウムクロリド （エタノールアミン塩酸塩）を最も好ましく用いることができる。
Specific examples of compound names include (2-hydroxyethyl)trimethylammonium chloride (choline chloride), (2-hydroxyethyl)trimethylammonium hydroxide (choline hydroxide), and (2-hydroxyethyl)trimethyl iodide. Ammonium (choline iodide), (2-hydroxyethyl)trimethylammonium bromide (choline bromide), acetylcholine, (2-hydroxyethyl)triethylammonium chloride, (2-hydroxyethyl)diethylmethylammonium chloride, (2-hydroxyethyl)trimethylammonium chloride, (2-hydroxyethyl)trimethylammonium chloride, (2-hydroxyethyl)trimethylammonium chloride, Ethyl)ethyldimethylammonium chloride, (2-hydroxyethyl)dimethylammonium chloride, (2-hydroxyethyl)methylammonium chloride, (2-hydroxyethyl)ammonium chloride (ethanolamine hydrochloride), di(2-hydroxyethyl)ammonium chloride, tri(2-hydroxyethyl)ammonium chloride, ephedrine hydrochloride, valinol hydrochloride, phenylalaniol hydrochloride, phenylglycinol hydrochloride, and the like.
Among the above compounds, (2-hydroxyethyl)trimethylammonium chloride (choline chloride), (2-hydroxyethyl)trimethylammonium hydroxide (choline hydroxide), acetylcholine, (2-hydroxyethyl)ammonium chloride (ethanolamine hydrochloride) can be used most preferably.
前記カルボン酸ビニルエステル、反応及び／又は解繊促進添加剤は、ドナー数２６以上の非プロトン性溶媒と混合して解繊溶液としてセルロースに浸透させる。 The carboxylic acid vinyl ester, reaction and/or fibrillation-promoting additive is mixed with an aprotic solvent having a donor number of 26 or more and permeated into cellulose as a fibrillation solution.
溶媒としては、カルボン酸ビニルの反応性及びセルロースへの浸透性を損なわないドナー数２６以上の非プロトン性溶媒であれば特に限定されない。 The solvent is not particularly limited as long as it is an aprotic solvent having 26 or more donors that does not impair the reactivity of vinyl carboxylate and permeability into cellulose.
前記ドナー数２６以上の非プロトン性溶媒の中でも、ドナー数２６～３５のものが好ましく、より好ましくは２６．５～３３、さらに好ましくは２７～３２程度である。ドナー数が低すぎると、カルボン酸ビニルを含む解繊溶液のミクロフィブリル間への浸透性を向上させる効果が発現しないおそれがある。なお、ドナー数については、文献「Ｎｅｔｓｕ Ｓｏｋｕｔｅｉ ２８（３）１３５－１４３」の記載による。 Among the aprotic solvents having 26 or more donors, those having 26 to 35 donors are preferable, more preferably 26.5 to 33, and even more preferably about 27 to 32. If the number of donors is too low, there is a risk that the effect of improving the permeability of the fibrillating solution containing vinyl carboxylate between microfibrils will not be expressed. Note that the number of donors is based on the description in the document "Netsu Sokutei 28(3) 135-143".
前記非プロトン性溶媒としては、例えば、スルホキシド類、ピリジン類、ピロリドン類及びアミド類などが挙げられる。これらの溶媒は、単独で又は二種以上組み合わせて使用できる。 Examples of the aprotic solvent include sulfoxides, pyridines, pyrrolidones, and amides. These solvents can be used alone or in combination.
さらに、前記ドナー数２６以上の非プロトン性溶媒のうち、カルボン酸ビニルのミクロフィブリル間への浸透性を高度に促進できる点から、ジメチルスルホキシド（ドナー数：２９．８）、ピリジン（ドナー数：３３．１）、Ｎ，Ｎ－ジメチルアセトアミド（ドナー数：２７．８）、Ｎ，Ｎ－ジメチルホルムアミド（ドナー数：２６．６）及びＮ－メチル－２－ピロリドン（ドナー数：２７．３）からなる群より選択された少なくとも１種であることがより好ましい。 Furthermore, among the aprotic solvents having a donor number of 26 or more, dimethyl sulfoxide (donor number: 29.8), pyridine (donor number: 33.1), N,N-dimethylacetamide (number of donors: 27.8), N,N-dimethylformamide (number of donors: 26.6) and N-methyl-2-pyrrolidone (number of donors: 27.3) More preferably, it is at least one selected from the group consisting of:
溶媒は、他の溶媒として、ドナー数２６未満の慣用の非プロトン性溶媒、例えば、アセトニトリル、ジオキサン、アセトン、テトラヒドフランなどを含んでいてもよいが、ジメチルスルホキシドを主溶媒として含むのが好ましい。ドナー数２６未満の溶媒が多すぎると、セルロースミクロフィブリル間への反応性解繊液の浸透性が低下するため、セルロースの解繊効果が低下するおそれがある。 The solvent may contain, as other solvents, conventional aprotic solvents with a donor number of less than 26, such as acetonitrile, dioxane, acetone, tetrahydrofuran, etc., but preferably contains dimethyl sulfoxide as the main solvent. . If there is too much of a solvent having a donor number of less than 26, the permeability of the reactive fibrillating liquid between cellulose microfibrils will decrease, so there is a risk that the fibrillating effect of cellulose will decrease.
解繊溶液中のカルボン酸ビニルの濃度（重量割合）は、解繊溶液全体に対して０．５～５０重量％であることが好ましい。０．５重量％以下になると解繊不十分又は修飾率が低いため好ましくない。また、５０重量％以上になると解繊溶液のセルロース内部への浸透性が低下する恐れがあるため好ましくない。
ミクロフィブリル間への浸透性とセルロース水酸基に対する反応性のバランスに優れる点からは、より好ましくは１～４０重量％、さらに好ましくは２～３０重量％である。
The concentration (weight percentage) of vinyl carboxylate in the defibrating solution is preferably 0.5 to 50% by weight based on the entire defibrating solution. If it is less than 0.5% by weight, it is not preferable because fibrillation is insufficient or the modification rate is low. Moreover, if it exceeds 50% by weight, the permeability of the defibrating solution into the cellulose may decrease, which is not preferable.
From the viewpoint of an excellent balance between permeability between microfibrils and reactivity with cellulose hydroxyl groups, the content is more preferably 1 to 40% by weight, and even more preferably 2 to 30% by weight.
解繊溶液中の反応及び／又は解繊促進添加剤の濃度は、解繊溶液全体に対して０．１～２０重量％であることが好ましい。０．１重量％以下になると解繊不十分又は修飾率が低いため好ましくない。また、２０重量％以上になると解繊溶液に溶けなくなる恐れがあるため好ましくない。
解繊と解繊促進効果のバランスに優れる点からは、より好ましくは０．５～１５重量％、さらに好ましくは１～１０重量％である。
The concentration of the reaction and/or defibration promoting additive in the defibration solution is preferably from 0.1 to 20% by weight based on the total defibration solution. If it is less than 0.1% by weight, it is not preferable because fibrillation is insufficient or the modification rate is low. Moreover, if it exceeds 20% by weight, it is not preferable because it may become insoluble in the fibrillation solution.
From the standpoint of achieving a good balance between defibration and defibration promoting effects, the content is more preferably 0.5 to 15% by weight, and even more preferably 1 to 10% by weight.
セルロースのエステル化を促進させるためには、解繊溶液中に触媒を共存させることによりエステル化は促進することができる。
触媒を共存させるとセルロースが解繊されると同時に、カルボン酸ビニルエステル、反応及び／又は解繊促進添加剤はセルロースの水酸基とエステル交換反応するため、エステル化された修飾セルロース微細繊維が得られる。触媒は酸触媒及び塩基触媒のいずれであっても良いが、塩基触媒を用いることが好ましい。塩、酸やアルカリ等の触媒は極性が高く、それらの添加により解繊溶媒の電気伝導度が大きくなり、解繊溶液のセルロースに対する親和性が増大し、浸透速度と膨潤率が向上する。さらにセルロース中に含まれる可溶性のヘミセルロースなどの非結晶性成分の溶解を促進し、ミクロフィブリルの解繊を加速する作用が考えられる。
In order to promote esterification of cellulose, esterification can be promoted by coexisting a catalyst in the fibrillation solution.
When a catalyst coexists, cellulose is fibrillated, and at the same time, carboxylic acid vinyl ester, reaction and/or fibrillation promoting additive undergoes a transesterification reaction with the hydroxyl groups of cellulose, resulting in esterified modified cellulose fine fibers. . The catalyst may be either an acid catalyst or a base catalyst, but it is preferable to use a base catalyst. Catalysts such as salts, acids, and alkalis have high polarity, and their addition increases the electrical conductivity of the fibrillating solvent, increasing the affinity of the fibrillating solution to cellulose, and improving the penetration rate and swelling rate. Furthermore, it is thought to have the effect of promoting the dissolution of amorphous components such as soluble hemicellulose contained in cellulose and accelerating the fibrillation of microfibrils.
塩基触媒のアルカリ性が高すぎると解繊溶媒は結晶内まで侵入し、セルロース微細繊維の結晶化度を低下させる恐れがある。塩基触媒は、セルロースの結晶構造を破壊させない限り、何れの塩基触媒を用いても良いが、強アルカリ性触媒はセルロースの安定性が低下するため、アルカリ金属又はアルカリ土類金属の炭酸塩、炭酸水素塩、酢酸塩等のカルボン酸塩、ホウ酸塩、リン酸塩又はリン酸水素塩、テトラアルキルアンモニウム酢酸塩、ピリジン類、イミダゾール類及びアミン類からなる群より選択された少なくとも１種であることが好ましい。これらの塩基触媒は単独で又は二種以上組み合わせて使用できる。これらの塩基を含有することにより、溶媒の極性（誘電率）が増大し、浸透速度を向上する効果もあるため好ましいである。 If the alkalinity of the base catalyst is too high, the fibrillation solvent may penetrate into the crystals and reduce the crystallinity of the cellulose fine fibers. Any base catalyst may be used as long as it does not destroy the crystal structure of cellulose, but strong alkaline catalysts reduce the stability of cellulose, so carbonates of alkali metals or alkaline earth metals, hydrogen carbonate, etc. At least one selected from the group consisting of salts, carboxylates such as acetates, borates, phosphates or hydrogen phosphates, tetraalkylammonium acetates, pyridines, imidazoles, and amines. is preferred. These base catalysts can be used alone or in combination of two or more. Containing these bases is preferable because it increases the polarity (dielectric constant) of the solvent and has the effect of improving the permeation rate.
さらに、塩基触媒の添加量が大きすぎると得られたセルロース微細繊維の結晶化度が低下する恐れがある。解繊溶液中の塩基触媒の濃度（重量割合）は、前記塩基触媒の割合が、解繊溶液全体に対して０．００１～２０重量％であることが好ましい。そして、塩基触媒がアルカリ金属又はアルカリ土類金属の炭酸塩、炭酸水素塩、酢酸塩等のカルボン酸塩、ホウ酸塩、リン酸塩又はリン酸水素塩の場合に０．００１～８重量％が好ましく、さらに０．０５～６重量％が特に好ましい。特に、炭酸塩を用いる場合は、０．００５～５重量％が好ましい。一方、塩基触媒がピリジン類（溶媒としてピリジン類としない場合）、アミン類、イミダゾール類の場合には３～２０重量％が好ましく、１０～２０重量％がより好ましいが、これらの触媒はアルカリ金属又はアルカリ土類金属に比べてエステル化反応が遅く、通常エステル化に８時間以上の反応時間が必要である。また、ピリジン類を溶媒とした場合は、ピリジン類は触媒としても作用するが、この場合もエステル化反応が遅く、通常エステル化に８時間以上の反応時間が必要である。 Furthermore, if the amount of the base catalyst added is too large, the degree of crystallinity of the obtained cellulose fine fibers may decrease. The concentration (weight percentage) of the base catalyst in the defibration solution is preferably 0.001 to 20% by weight based on the entire defibration solution. When the base catalyst is an alkali metal or alkaline earth metal carbonate, hydrogen carbonate, acetate, or other carboxylate, borate, phosphate, or hydrogen phosphate, 0.001 to 8% by weight. is preferred, and 0.05 to 6% by weight is particularly preferred. In particular, when carbonate is used, it is preferably 0.005 to 5% by weight. On the other hand, when the base catalyst is pyridine (when pyridine is not used as a solvent), amine, or imidazole, the amount is preferably 3 to 20% by weight, more preferably 10 to 20% by weight, but these catalysts are Alternatively, the esterification reaction is slower than that of alkaline earth metals, and usually a reaction time of 8 hours or more is required for esterification. Furthermore, when pyridine is used as a solvent, pyridine acts as a catalyst, but the esterification reaction is slow in this case as well, and the reaction time for esterification is usually 8 hours or more.
本発明の解繊溶液中に他の反応化剤、例えば、カルボン酸ハロゲン化物類、カルボン酸無水物類及びイソシアネート類の内のいずれか１種以上を加えると、エステル交換反応以外に多様の修飾反応により種々の官能基をセルロース微細繊維の表面に導入することが可能である。
すなわち、修飾解繊工程では、本発明の効果を損なわない範囲で、解繊溶液中に他の修飾化剤を加えてもよい。また、以下に例示する修飾化剤は、単独で又は二種以上組み合わせて使用できる。
When one or more of other reactants such as carboxylic acid halides, carboxylic acid anhydrides, and isocyanates are added to the fibrillation solution of the present invention, various modifications other than transesterification can occur. Various functional groups can be introduced onto the surface of cellulose fine fibers by reaction.
That is, in the modified defibration step, other modifying agents may be added to the defibration solution within a range that does not impair the effects of the present invention. Moreover, the modifying agents illustrated below can be used alone or in combination of two or more.
修飾化剤であるカルボン酸ハロゲン化物類は、下記式（３）で表されるカルボン酸ハロゲン化物からなる群より選択された少なくとも１種であってもよい。
Ｒ－Ｃ（＝Ｏ）－Ｘ （３）
（式中、Ｒは炭素数１～１６のアルキル基、アルキレン基、シクロアルキル基及びアリール基のいずれかを表わす。ＸはＣｌ、Ｂｒ又はＩである。）
The carboxylic acid halide that is the modifying agent may be at least one selected from the group consisting of carboxylic acid halides represented by the following formula (3).
RC(=O)-X (3)
(In the formula, R represents any one of an alkyl group, an alkylene group, a cycloalkyl group, and an aryl group having 1 to 16 carbon atoms. X is Cl, Br, or I.)
カルボン酸ハロゲン化物としては、カルボン酸塩化物、カルボン酸臭化物、カルボン酸ヨウ化物が挙げられる。カルボン酸ハロゲン化物の具体例としては、塩化アセチル、臭化アセチル、ヨウ化アセチル、塩化プロピオニル、臭化プロピオニル、ヨウ化プロピオニル、塩化ブチリル、臭化ブチリル、ヨウ化ブチリル、塩化ベンゾイル、臭化ベンゾイル、ヨウ化ベンゾイルなどが挙げられるが、これらに限定されない。なかでも、カルボン酸塩化物は反応性と取り扱い性の点から好適に採用できる。 Examples of carboxylic acid halides include carboxylic acid chlorides, carboxylic acid bromides, and carboxylic acid iodides. Specific examples of carboxylic acid halides include acetyl chloride, acetyl bromide, acetyl iodide, propionyl chloride, propionyl bromide, propionyl iodide, butyryl chloride, butyryl bromide, butyryl iodide, benzoyl chloride, benzoyl bromide, Examples include, but are not limited to, benzoyl iodide. Among them, carboxylic acid chlorides are preferably employed from the viewpoint of reactivity and ease of handling.
修飾化剤であるカルボン酸無水物類としては、カルボン酸無水物［たとえば、酢酸、プロピオン酸、（イソ）酪酸、吉草酸などの飽和脂肪族モノカルボン酸；（メタ）アクリル酸、オレイン酸などの不飽和脂肪族モノカルボン酸無水物；シクロヘキサンカルボン酸、テトラヒドロ安息香酸などの脂環族モノカルボン酸無水物；安息香酸、４－メチル安息香酸などの芳香族モノカルボン酸無水物］、二塩基カルボン酸無水物［例えば、無水コハク酸、アジピン酸などの無水飽和脂肪族ジカルボン酸；無水マレイン酸、無水イタコン酸などの無水不飽和脂肪族ジカルボン酸無水物；無水１－シクロヘキセン－１，２－ジカルボン酸、無水ヘキサヒドロフタル酸、無水メチルテトラヒドロフタル酸などの無水脂環族ジカルボン酸；無水フタル酸、無水ナフタル酸などの無水芳香族ジカルボン酸無水物など］、多塩基カルボン酸無水物類（例えば、無水トリメリット酸、無水ピロメリット酸などの（無水）ポリカルボン酸など）などが挙げられる。 Examples of carboxylic acid anhydrides that are modifying agents include carboxylic acid anhydrides [for example, saturated aliphatic monocarboxylic acids such as acetic acid, propionic acid, (iso)butyric acid, and valeric acid; (meth)acrylic acid, oleic acid, etc. unsaturated aliphatic monocarboxylic acid anhydrides; alicyclic monocarboxylic acid anhydrides such as cyclohexanecarboxylic acid and tetrahydrobenzoic acid; aromatic monocarboxylic acid anhydrides such as benzoic acid and 4-methylbenzoic acid], dibasic Carboxylic acid anhydrides [for example, saturated aliphatic dicarboxylic acid anhydrides such as succinic anhydride and adipic acid; unsaturated aliphatic dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; 1-cyclohexene-1,2-anhydride alicyclic dicarboxylic anhydrides such as dicarboxylic acid, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; aromatic dicarboxylic anhydrides such as phthalic anhydride and naphthalic anhydride], polybasic carboxylic acid anhydrides ( Examples include (anhydrous) polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride.
修飾化剤であるイソシアネート類としては、下記式（４）又は（５）で表されるイソシアネートからなる群より選択された少なくとも１種であってもよい。
Ｒ－Ｎ＝Ｃ＝Ｏ （４）
Ｏ＝Ｃ＝Ｎ－Ｒ－Ｎ＝Ｃ＝Ｏ （５）
式中、Ｒは炭素数１～１６のアルキル基、アルキレン基、シクロアルキル基及びアリール基のいずれかを表わす。
イソシアネートとしては、イソシアン酸メチル（ＭＩＣ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、トルエンジイソシアネート（ＴＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、２－イソシアナトエチルメタクリレート（ＭＯＩ）等のイソシアネート類が挙げられる。
The isocyanate that is the modifying agent may be at least one selected from the group consisting of isocyanates represented by the following formula (4) or (5).
RN=C=O (4)
O=C=NR-N=C=O (5)
In the formula, R represents any one of an alkyl group, an alkylene group, a cycloalkyl group, and an aryl group having 1 to 16 carbon atoms.
Examples of isocyanates include methyl isocyanate (MIC), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), and 2-isocyanatoethyl methacrylate (MOI). Can be mentioned.
他の修飾化剤の割合は、解繊溶液のセルロースへの浸透性を低下しない限り特に制限しないが、解繊溶液に対して３０重量％以下であり、例えば０．１～３０重量％、好ましくは０．１～２０重量％、さらに好ましくは０．５～１５重量％程度である。他の修飾化剤の割合が多すぎると、解繊度合が低下するおそれがある。
他の修飾化剤の添加タイミングは特に制限しないが、解繊溶液のセルロースへの浸透性を低下させないため、解繊がある程度進んでから加えることが好ましい。
The proportion of other modifiers is not particularly limited as long as it does not reduce the permeability of the fibrillation solution into cellulose, but it is 30% by weight or less, for example 0.1 to 30% by weight, preferably 0.1 to 30% by weight based on the fibrillation solution. is about 0.1 to 20% by weight, more preferably about 0.5 to 15% by weight. If the proportion of other modifying agents is too large, the degree of defibration may decrease.
The timing of addition of other modifiers is not particularly limited, but it is preferable to add them after the fibrillation has progressed to a certain extent so as not to reduce the permeability of the fibrillation solution into cellulose.
セルロースと解繊溶液との重量割合は、前者／後者＝０．５／９９．５～２５／７５程度の範囲から選択でき、例えば１／９９～２０／８０、好ましくは１．５／９８．５～１５／８５、さらに好ましくは２／９８～１２／８８程度である。セルロースの割合が少なすぎると、セルロース微細繊維の生産効率が低くなり、多すぎると、解繊溶媒はセルロース繊維間、ラメラ間およびミクロフィブリル間への浸透は不十分のため解繊度合いが低下する恐れがある。また、粘度が高いため反応時間が長くなる。いずれにしても生産性が低下するおそれがある。さらに、修飾セルロース微細繊維を得る場合には、セルロースの割合が多すぎると得られた微細繊維のサイズと修飾率の均一性が低下するおそれがある。 The weight ratio of cellulose and defibration solution can be selected from the range of former/latter = 0.5/99.5 to 25/75, for example 1/99 to 20/80, preferably 1.5/98. It is about 5 to 15/85, more preferably about 2/98 to 12/88. If the proportion of cellulose is too small, the production efficiency of cellulose fine fibers will be low, and if it is too large, the degree of fibrillation will decrease because the fibrillation solvent will not penetrate between cellulose fibers, lamellae, and microfibrils insufficiently. There is a fear. In addition, the reaction time is longer due to the higher viscosity. In either case, productivity may decrease. Furthermore, when obtaining modified cellulose fine fibers, if the proportion of cellulose is too high, the uniformity of the size and modification rate of the obtained fine fibers may decrease.
また、本発明の解繊溶液は、ミクロフィブリルの結晶ゾーン（ドメイン）に浸透しないため、得られたセルロース微細繊維は、ダメージが少なく、天然のミクロフィブリルに近い構造を有している。同時に、この工程では、剪断力の働きによる機械的解繊手段を用いることなく、セルロースを解繊できるため、物理的な作用によるダメージも少ない。そのため、得られた修飾セルロース微細繊維は、高い強度を保持していると推定できる。さらに、表面の荒さが少ないため一旦乾燥しても溶媒や樹脂への再分散が容易である。 Moreover, since the defibrating solution of the present invention does not penetrate into the crystalline zone (domain) of microfibrils, the obtained cellulose fine fibers have less damage and have a structure close to that of natural microfibrils. At the same time, in this step, cellulose can be defibrated without using mechanical defibration means using shearing force, so there is little damage caused by physical action. Therefore, it can be estimated that the obtained modified cellulose fine fibers maintain high strength. Furthermore, since the surface has less roughness, it is easy to redisperse it in a solvent or resin even if it is once dried.
本発明の製造方法では、前記触媒と前記促進剤と前記カルボン酸ビニルと前記反応及び／又は解繊促進添加剤と前記溶媒とを含む解繊溶液をセルロースに浸透させて、セルロース繊維間、ラメラ間およびミクロフィブリル同士間の水素結合を解除したり、表面にある水酸基を修飾したりすることができればよく、このような化学解繊方法は、特に限定されないが、通常、前記解繊溶液を調製し、調製した解繊溶液にセルロースを添加して混合する方法を利用できる。 In the production method of the present invention, cellulose is infiltrated with a fibrillation solution containing the catalyst, the promoter, the vinyl carboxylate, the reaction and/or the fibrillation-promoting additive, and the solvent. Any chemical defibration method can be used as long as it can break the hydrogen bonds between microfibrils and between microfibrils, or modify the hydroxyl groups on the surface.Such chemical defibration methods are not particularly limited, but usually involve preparing the defibration solution. A method can be used in which cellulose is added to the prepared defibration solution and mixed.
解繊溶液の調製方法は、カルボン酸ビニル、反応及び／又は解繊促進剤と前記溶媒とを攪拌などによって混合する。
また、解繊溶液に塩基触媒を含む場合は、カルボン酸ビニル、反応及び／又は解繊促進剤と塩基触媒と前記溶媒とを攪拌などによって混合し、均一に溶解又は懸濁させる。カルボン酸ビニル、反応及び／又は解繊促進剤と塩基触媒と前記溶媒の混合の順序は、いずれであっても良いが、通常は、前記溶媒に他の物質を加えていく方法が用いられる。
さらに、解繊溶液にカルボン酸ビニル以外の修飾化剤を含む場合は、カルボン酸ビニルと前記反応及び／又は解繊促進添加剤と前記修飾化剤と前記溶媒又はカルボン酸ビニルと前記反応及び／又は解繊促進添加剤と塩基触媒と前記修飾化剤と前記溶媒とを攪拌などによって混合し、均一に溶解させてもよいが、他の修飾化剤は極性が低い場合、解繊溶媒の浸透速度、膨潤速度、そして解繊速度を低下させないため、解繊がある程度進んでから他の修飾化剤を加えることが好ましい。これらの混合物の混合の順序は、いずれであっても良いが、通常は、前記溶媒に他の物質を加えていく方法が用いられる。
A method for preparing a fibrillation solution is to mix vinyl carboxylate, reaction and/or fibrillation accelerator, and the solvent by stirring or the like.
When the defibration solution contains a basic catalyst, the vinyl carboxylate, the reaction and/or defibration accelerator, the base catalyst, and the solvent are mixed by stirring or the like to uniformly dissolve or suspend them. The vinyl carboxylate, the reaction and/or defibration accelerator, the base catalyst, and the solvent may be mixed in any order, but usually a method is used in which another substance is added to the solvent.
Furthermore, when the defibrating solution contains a modifying agent other than vinyl carboxylate, the reaction with the vinyl carboxylate and/or the reaction between the defibration promoting additive and the modifying agent and the solvent or the vinyl carboxylate and/or Alternatively, the fibrillation-promoting additive, the base catalyst, the modifying agent, and the solvent may be mixed by stirring or the like and dissolved uniformly. However, if the other modifiers have low polarity, the penetration of the fibrillation solvent may In order not to reduce the speed, swelling rate, and defibration rate, it is preferable to add other modifying agents after defibration has progressed to a certain extent. These mixtures may be mixed in any order, but usually a method is used in which another substance is added to the solvent.
得られた解繊溶液は、セルロースに対する浸透性が高いため、セルロースを解繊溶液に添加して混合することにより、解繊溶液は、ミクロフィブリル間に浸入して、ミクロフィブリル同士間の水素結合を解除することにより、セルロースを解繊できる。更に触媒を共存することにより微細繊維の表面を修飾することができる。 The obtained fibrillation solution has high permeability to cellulose, so by adding cellulose to the fibrillation solution and mixing it, the fibrillation solution penetrates between the microfibrils and creates hydrogen bonds between the microfibrils. By releasing this, cellulose can be defibrated. Furthermore, the surface of the fine fibers can be modified by the coexistence of a catalyst.
解繊方法について詳しく説明すると、本発明の解繊方法は、解繊溶液にセルロースを混合して０．５～１時間以上放置してもよく、混合後、さらに溶液中でセルロースが均一な状態を維持できる程度の撹拌を行ってもよい。すなわち、解繊は解繊溶液にセルロースを混合して放置するだけでも進行するが、浸透又は均一性を促進するために、撹拌手段を用いて撹拌を行ってもよい。撹拌機は特に制限しないが、通常、撹拌又はブレンドや混練できる装置であればよい。例えば、通常、有機合成で汎用されている撹拌機による撹拌であればよい。また、ニーダーや押出機のような混練機でもよい。特にセルロースの濃度が高い場合、高粘度に対応できるニーダーや押出機が好ましい。
また、撹拌は、連続的に攪拌してもよいいし、断続的に攪拌してもよい。
To explain the defibration method in detail, in the defibration method of the present invention, cellulose may be mixed in a defibration solution and left for 0.5 to 1 hour or more, and after mixing, the cellulose is further homogenized in the solution. Stirring may be performed to the extent that the temperature can be maintained. That is, defibration can proceed by simply mixing cellulose in a defibration solution and leaving it to stand, but in order to promote penetration or uniformity, stirring may be performed using a stirring means. The stirrer is not particularly limited, but any device capable of stirring, blending, or kneading may be used. For example, stirring may be performed using a stirrer commonly used in organic synthesis. Alternatively, a kneader such as a kneader or an extruder may be used. Particularly when the concentration of cellulose is high, a kneader or extruder that can handle high viscosity is preferred.
Further, stirring may be performed continuously or intermittently.
本発明での解繊における反応温度は、加熱する必要はなく、室温で反応させればよく、０．５時間以上反応させることにより、剪断力の働きによる機械的解繊手段を用いることなく、セルロースを前記述べたような化学的に解繊できる。そのため、本発明では、余分なエネルギーを使用することなくセルロースを解繊できる。なお、反応を促進するために、加熱してもよく、加熱温度は、例えば９０℃以下（例えば４０～９０℃程度）、好ましくは８０℃以下、さらに好ましくは７０℃以下程度である。特に常圧の場合、５０℃以下程度である。 The reaction temperature for defibration in the present invention does not require heating, and the reaction may be carried out at room temperature. By reacting for 0.5 hours or more, the defibration process can be carried out without using mechanical defibration means using shearing force. Cellulose can be chemically defibrated as described above. Therefore, in the present invention, cellulose can be defibrated without using extra energy. In order to promote the reaction, heating may be performed, and the heating temperature is, for example, 90° C. or lower (eg, about 40 to 90° C.), preferably 80° C. or lower, and more preferably about 70° C. or lower. Particularly in the case of normal pressure, the temperature is about 50°C or less.
本発明での解繊処理時間は、前記溶媒のドナー数及びカルボン酸ビニルや反応及び／又は解繊促進添加剤や塩基触媒の種類によって選択でき、例えば０．５～５時間、好ましくは０．５～３時間、さらに好ましくは０．５～２時間程度である。酢酸ビニルなどの低級カルボン酸ビニルとドナー数の高いジメチルスルホキシド（ＤＭＳＯ）の非プロトン性極性溶媒を用いる場合、０．５～２時間程度の時間であってもよく、好ましくは０．５～１時間程度である。さらに、前述のように、処理温度（反応温度）を高めたり、攪拌速度を増加したりすることで反応時間を短くしてもよい。この時、カルボン酸ビニルの蒸発を避けるため密閉系統又は加圧系統が好ましい。反応時間が短すぎると、解繊溶液がミクロフィブリル間まで浸透するのが不十分となり、反応が不十分となり、解繊度合いも低下するおそれがある。一方、触媒が存在する場合、反応時間が長すぎたり、温度が高すぎたりすることによる過修飾によりセルロース微細繊維の収率が低下するおそれがある。他の修飾剤を途中から加える場合、修飾化剤を加えてからさらに０．５～５時間以上反応させることが好ましい。 The fibrillation treatment time in the present invention can be selected depending on the number of donors in the solvent, the vinyl carboxylate, the reaction and/or fibrillation promoting additive, and the type of base catalyst, and is, for example, 0.5 to 5 hours, preferably 0.5 hours. It is about 5 to 3 hours, more preferably about 0.5 to 2 hours. When using an aprotic polar solvent such as lower vinyl carboxylate such as vinyl acetate and dimethyl sulfoxide (DMSO) having a high number of donors, the time may be about 0.5 to 2 hours, preferably 0.5 to 1 hour. It takes about an hour. Furthermore, as described above, the reaction time may be shortened by raising the treatment temperature (reaction temperature) or increasing the stirring speed. At this time, a closed system or a pressurized system is preferred to avoid evaporation of vinyl carboxylate. If the reaction time is too short, the fibrillation solution may not sufficiently penetrate between the microfibrils, the reaction may become insufficient, and the degree of fibrillation may decrease. On the other hand, when a catalyst is present, the yield of cellulose fine fibers may decrease due to over-modification due to too long reaction time or too high temperature. When adding another modifier midway through, it is preferable to allow the reaction to continue for 0.5 to 5 hours or more after adding the modifier.
反応は、通常、密閉反応容器内又は還流系統内で行う場合が多い。このような反応条件であれば、カルボン酸ビニルなどの低沸点成分の蒸発を避けるため、加圧することが好ましい。 The reaction is usually carried out in a closed reaction vessel or in a reflux system. Under such reaction conditions, it is preferable to apply pressure to avoid evaporation of low-boiling components such as vinyl carboxylate.
解繊して得られたセルロース微細繊維は、慣用の方法（例えば、遠心分離、濾過、濃縮、沈殿など）により分離精製してもよい。例えば、解繊混合物を遠心分離又は濾過することにより微細繊維と解繊溶液を分離してもよい。または、触媒及び溶媒を溶解可能な溶媒（水、アルコール類、ケトン類など）を解繊混合物に添加し、前記遠心分離、濾過、沈殿などの分離法（慣用の方法）で分離精製（洗浄）してもよい。なお、分離操作は複数回（例えば、２～５回程度）行うことができる。反応終了後、水又はメタノールなどでカルボン酸ビニルを失活させてもよいが、再利用の観点から失活せずに蒸留により回収して再利用することができる。 The cellulose fine fibers obtained by defibration may be separated and purified by conventional methods (eg, centrifugation, filtration, concentration, precipitation, etc.). For example, the fine fibers and the defibrating solution may be separated by centrifuging or filtering the defibrating mixture. Alternatively, a solvent capable of dissolving the catalyst and solvent (water, alcohols, ketones, etc.) is added to the defibration mixture, and separation and purification (washing) is performed by the separation method (commonly used) such as centrifugation, filtration, and precipitation. You may. Note that the separation operation can be performed multiple times (for example, about 2 to 5 times). After the reaction is completed, vinyl carboxylate may be deactivated with water or methanol, but from the viewpoint of reuse, it can be recovered by distillation and reused without being deactivated.
得られたセルロース微細繊維は、ナノサイズ又はサブミクロンメーターに解繊されており、平均繊維径は、例えば１０～８００ｎｍ、好ましくは２０～６００ｎｍ、さらに好ましくは２５～５００ｎｍ（特に３０～３００ｎｍ）程度である。繊維径が大きすぎると、補強材としての効果が低下するおそれがあり、小さすぎると、微細繊維の取り扱い性や耐熱性も低下するおそれがある。 The obtained cellulose fine fibers are defibrated to nanosize or submicron size, and the average fiber diameter is, for example, about 10 to 800 nm, preferably 20 to 600 nm, more preferably 25 to 500 nm (especially 30 to 300 nm). It is. If the fiber diameter is too large, the effect as a reinforcing material may be reduced, and if it is too small, the handling properties and heat resistance of the fine fibers may also be reduced.
得られたセルロース微細繊維は、強力な機械力を加えないため、従来の機械解繊法で得られた微細繊維よりも長い繊維長を有しており、平均繊維長は０．５μｍ以上である。そして、０．５～２００μｍ程度の平均繊維長の範囲になっているが、その用途に応じて反応条件をコントロールして適当な平均繊維長のセルロース微細繊維を得ることができる。一般的には、１～１００μｍ、好ましくは２～６０μｍ、さらに好ましくは３～５０μｍ程度がよい。繊維長が短すぎると、補強効果や成膜機能が低下するおそれがある。また、長すぎると、繊維が絡み易くなるため溶媒や樹脂への分散性が低下するおそれがある。 Since the obtained cellulose fine fibers do not apply strong mechanical force, they have a longer fiber length than fine fibers obtained by conventional mechanical defibration methods, and the average fiber length is 0.5 μm or more. . Although the average fiber length is in the range of about 0.5 to 200 μm, cellulose fine fibers with a suitable average fiber length can be obtained by controlling the reaction conditions depending on the application. Generally, the thickness is about 1 to 100 μm, preferably about 2 to 60 μm, and more preferably about 3 to 50 μm. If the fiber length is too short, the reinforcing effect and film-forming function may be reduced. Furthermore, if the length is too long, the fibers tend to become entangled, which may reduce the dispersibility in solvents and resins.
微細繊維のアスペクト比は解繊溶液の組成と浸透時間により容易に制御できる。一般的には、４０～１０００が好ましい。分散性と補強効果の観点からより好ましくは５０～８００、さらに好ましくは８０～６００程度がよい。４０以下になると分散しやすいものの補強効果や自立膜の強度が低いため好ましくない。一方、１０００以上になると繊維の絡み合いにより分散性が低下するおそれがある。 The aspect ratio of the fine fibers can be easily controlled by the composition of the fibrillation solution and the penetration time. Generally, 40 to 1000 is preferred. From the viewpoint of dispersibility and reinforcing effect, it is more preferably about 50 to 800, and even more preferably about 80 to 600. If it is less than 40, it is not preferable because although it is easy to disperse, the reinforcing effect and the strength of the self-supporting film are low. On the other hand, if it exceeds 1000, the dispersibility may decrease due to fiber entanglement.
また、本発明の前記〔１〕～〔３〕の製造方法で製造されたエステル化等により修飾された微細繊維は、ＳＰ値１０以下の有機溶媒又は樹脂に分散が可能である。
分散可能なＳＰ値１０以下の溶媒としては、例えば、アセトン（９．９）、１，４－ジオキサン（１０）、１－ドデカノール（９．８）、テトラヒドロフラン（９．４）、メチルエチルケトン（ＭＥＫ）（９．３）、酢酸エチル（９．１）、トルエン（８．８）、酢酸－ブチル（８．７）、メチルイソブチルケトン（ＭＩＢＫ）（８．６）、が挙げられる。樹脂の場合では、例えば、ポリウレタン（１０．０）、エポキシ樹脂（９～１０）、ポリ塩化ビニル（９．５～９．７）、ポリカーボネート（９．７）、ポリ酢酸ビニル（９．４）、ポリメタクリル酸メチル樹脂（９．２）、ポリスチレン（８．６～９．７）、ＮＢＲゴム（８．８～９．５）、ポリプロピレン（８．０）及びポリエチレン（７．９）が挙げられる。
Furthermore, the fine fibers modified by esterification or the like produced by the production methods [1] to [3] of the present invention can be dispersed in an organic solvent or resin having an SP value of 10 or less.
Examples of dispersible solvents with an SP value of 10 or less include acetone (9.9), 1,4-dioxane (10), 1-dodecanol (9.8), tetrahydrofuran (9.4), and methyl ethyl ketone (MEK). (9.3), ethyl acetate (9.1), toluene (8.8), butyl acetate (8.7), and methyl isobutyl ketone (MIBK) (8.6). In the case of resins, for example, polyurethane (10.0), epoxy resin (9-10), polyvinyl chloride (9.5-9.7), polycarbonate (9.7), polyvinyl acetate (9.4) , polymethyl methacrylate resin (9.2), polystyrene (8.6-9.7), NBR rubber (8.8-9.5), polypropylene (8.0) and polyethylene (7.9). It will be done.
本発明により得られた微細繊維の表面は均一にエステル化修飾されているため、有機溶媒、反応化剤又は樹脂によく分散できる。特に従来技術で実現できないＳＰ値１０以下の溶媒や樹脂への分散が可能となる。その理由としては、本発明の微細繊維は伸びた状態で解繊溶液中に修飾されるため、表面の水酸基は斑なく修飾されるため、乾燥した後も伸びた状態を維持できることが考える。一方、一般先行技術では、表面修飾セルロース微細繊維を調製するため、まず水中にセルロースを強力的な機械粉砕又はせん断力により解繊された後、アセトンやトルエンなどの非プロトン性極性溶媒で水を置換して修飾反応する。未修飾セルロース微細繊維は溶媒置換の際、微細繊維同士が結合したり、寄り集まったり、又は微細繊維が自ら絡み合いしたりすることにより微細繊維が塊の凝集態になる。この状態で反応溶媒中に入れても凝集の塊として存在するため、塊の表面の水酸基しかが修飾されないため得られる修飾微細繊維は、溶媒や樹脂によく分散することができない。 Since the surfaces of the fine fibers obtained according to the present invention are uniformly modified by esterification, they can be well dispersed in organic solvents, reactants, or resins. In particular, dispersion into solvents and resins with an SP value of 10 or less, which cannot be achieved with conventional techniques, becomes possible. The reason for this is thought to be that since the fine fibers of the present invention are modified in the fibrillation solution in an elongated state, the hydroxyl groups on the surface are modified evenly, so that the elongated state can be maintained even after drying. On the other hand, in the general prior art, in order to prepare surface-modified cellulose fine fibers, cellulose is first defibrated in water by strong mechanical crushing or shearing force, and then water is diluted with an aprotic polar solvent such as acetone or toluene. Substitute and modify. When the unmodified cellulose fine fibers are replaced with a solvent, the fine fibers are bonded to each other, gathered together, or entangled themselves, so that the fine fibers become agglomerated. Even if it is placed in a reaction solvent in this state, it exists as an aggregated mass, and only the hydroxyl groups on the surface of the mass are modified, so the obtained modified fine fibers cannot be well dispersed in the solvent or resin.
本発明のセルロース微細繊維は、例えば、塗料、接着剤、複合化材などの分野への用途が想定できる。そして、樹脂に分散させた場合は、従来の修飾セルロース微細繊維に比べて分散効果の高い本発明の修飾セルロース微細繊維の樹脂への分散させた場合の補強効果が強力である。 The cellulose fine fibers of the present invention can be expected to be used in fields such as paints, adhesives, and composite materials. When dispersed in a resin, the modified cellulose fine fibers of the present invention, which have a higher dispersion effect than conventional modified cellulose fine fibers, have a strong reinforcing effect when dispersed in a resin.
セルロース微細繊維の平均繊維径に対する平均繊維長の割合（アスペクト比）は用途に応じて対応でき、例えば樹脂と複合化する場合、３０以上であってもよく、例えば４０～１０００、好ましくは５０～５００、さらに好ましくは６０～２００（特に８０～１５０）程度であってもよい。 The ratio (aspect ratio) of the average fiber length to the average fiber diameter of the cellulose fine fibers can be adjusted depending on the application. For example, when composited with a resin, it may be 30 or more, for example, 40 to 1000, preferably 50 to It may be about 500, more preferably about 60 to 200 (particularly about 80 to 150).
なお、本発明では、修飾セルロース微細繊維の平均繊維径、平均繊維長及びアスペクト比を求める方法の一例としては、走査型電子顕微鏡写真の画像からランダムに５０個の繊維を選択し、加算平均して算出する方法がある。 In the present invention, as an example of a method for determining the average fiber diameter, average fiber length, and aspect ratio of modified cellulose fine fibers, 50 fibers are randomly selected from scanning electron micrograph images, and the average is calculated. There is a method to calculate it.
また、カルボン酸ビニル、反応及び／又は解繊促進添加剤と塩基触媒で処理して得られた修飾セルロース微細繊維は、各繊維又は全ての繊維がむら無くエステル化修飾されているため、有機溶媒や樹脂などの有機媒体によく分散できる。
修飾セルロース微細繊維の特性（例えば、低線膨張特性、強度、耐熱性など）を樹脂に有効に発現させるためには、結晶性の高い修飾セルロース微細繊維が好ましい。
In addition, modified cellulose fine fibers obtained by treatment with vinyl carboxylate, reaction and/or defibration accelerating additives, and base catalysts are evenly esterified and modified with organic solvents. It can be well dispersed in organic media such as resins and resins.
In order to effectively exhibit the properties of modified cellulose fine fibers (for example, low linear expansion properties, strength, heat resistance, etc.) in the resin, highly crystalline modified cellulose fine fibers are preferred.
本発明のエステル化修飾セルロース微細繊維及び他の修飾剤での修飾セルロース微細繊維では、化学解繊され、原料セルロースの結晶性を維持できるため、修飾セルロース微細繊維の結晶化度は前記セルロースの数値をそのまま参照できる。修飾セルロース微細の結晶化度は５０％以上（特に６５％以上）であってもよく、例えば５０～９８％、好ましくは５５～９５％、さらに好ましくは６０～９２％（特に６５～９０％）程度であってもよい。結晶化度が小さすぎると、線膨張特性や強度などの特性を低下させるおそれがある。 The esterified modified cellulose fine fibers of the present invention and the cellulose fine fibers modified with other modifiers are chemically defibrated and can maintain the crystallinity of the raw material cellulose. You can refer to it as is. The degree of crystallinity of the modified cellulose fine particles may be 50% or more (especially 65% or more), for example 50 to 98%, preferably 55 to 95%, more preferably 60 to 92% (especially 65 to 90%). It may be a degree. If the degree of crystallinity is too low, there is a risk that properties such as linear expansion properties and strength will be deteriorated.
修飾セルロース微細繊維の平均置換度（セルロースの基本構成単位であるグルコース当たりの置換された水酸基の平均数）は、微細繊維径とカルボン酸ビニルの種類によるが、１．６以下（例えば０．０２～１．６）であり、例えば０．１～１．５（例えば０．０５～１．５）、好ましくは０．１５～１．２、さらに好ましくは０．２５～０．９（特に０．３～０．９）程度である。平均置換度が大きすぎると、微細繊維の結晶化度又は収率が低下するおそれがある。平均置換度（ＤＳ：ｄｅｇｒｅｅ ｏｆ ｓｕｂｓｔｉｔｕｔｉｏｎ）は、セルロースの基本構成単位であるグルコース当たりの置換された水酸基の平均数であり、Ｂｉｏｍａｃｒｏｍｏｌｅｃｕｌｅｓ ２００７，８，１９７３－１９７８やＷＯ２０１２／１２４６５２Ａ１又はＷＯ２０１４／１４２１６６Ａ１などを参照できる。 The average degree of substitution (the average number of substituted hydroxyl groups per glucose, which is the basic structural unit of cellulose) of the modified cellulose fine fibers depends on the fine fiber diameter and the type of vinyl carboxylate, but is 1.6 or less (for example, 0.02 1.6), for example 0.1 to 1.5 (for example 0.05 to 1.5), preferably 0.15 to 1.2, more preferably 0.25 to 0.9 (especially 0 .3 to 0.9). If the average degree of substitution is too large, the crystallinity or yield of the fine fibers may decrease. The average degree of substitution (DS) is the average number of substituted hydroxyl groups per glucose, which is the basic constituent unit of cellulose, and is described in Biomacromolecules 2007, 8, 1973-1978, WO2012/124652A1 or WO2014/142166A1, etc. The You can refer to it.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、用いた原料の詳細は以下の通りであり、得られた修飾セルロース微細繊維の特性は以下のようにして測定した。 The present invention will be explained in more detail below based on Examples, but the present invention is not limited by these Examples. The details of the raw materials used are as follows, and the properties of the obtained modified cellulose fine fibers were measured as follows.
（用いた原料、触媒及び溶媒）
セルロースパルプ：市販木材パルプ（Ｇｅｏｒｇｉａ Ｐａｃｉｆｉｃ社製、商品名：フラッフパルプＡＲＣ４８０００ＧＰ）をサンプル瓶に入れるサイズまで千切ったパルプ。
他の原料、触媒及び溶媒：ナカライテスク（株）製の試薬。
(Raw materials, catalyst and solvent used)
Cellulose pulp: Pulp obtained by shredding commercially available wood pulp (manufactured by Georgia Pacific, trade name: Fluff Pulp ARC48000GP) to a size that can be placed in a sample bottle.
Other raw materials, catalysts and solvents: Reagents manufactured by Nacalai Tesque Co., Ltd.
（修飾セルロース微細繊維の表面飾率又は平均置換度）
セルロース微細繊維のＩＲスペクトルはフーリエ変換赤外分光光度計（ＦＴ－ＩＲ）で測定した。なお、測定は、ＮＩＣＯＬＥＴ社製「ＮＩＣＯＬＥＴ ＭＡＧＮＡ－ＩＲ７６０ Ｓｐｅｃｔｒｏｍｅｔｅｒ」を用い、反射モードで分析した。修飾率をＩＲ ｉｎｄｅｘ（周波数１７３０ｃｍ－１と１３７０ｃｍ－１の吸収の強度比Ｉ１７３０／１３７０）で評価した。
(Surface decoration rate or average degree of substitution of modified cellulose fine fibers)
The IR spectrum of the cellulose fine fibers was measured using a Fourier transform infrared spectrophotometer (FT-IR). The measurement was conducted in reflection mode using "NICOLET MAGNA-IR760 Spectrometer" manufactured by NICOLET. The modification rate was evaluated using IR index (intensity ratio of absorption at frequencies 1730 cm −1 and 1370 cm −1 I1730/1370).
（溶剤分散性）
乾燥したセルロース微細繊維０．０５ｇと分散用溶媒（表に示す）１０ｇを２０ｍｌのサンプル瓶に入れ、スターラーでよく撹拌した後、均一な分散液になる場合は分散可能と判断した。一方、沈殿したり、乾燥状態（塊又はチップ状）のままで残る場合は分散不可と評価した。
(Solvent dispersibility)
0.05 g of dried cellulose fine fibers and 10 g of a dispersion solvent (shown in the table) were placed in a 20 ml sample bottle, and after stirring well with a stirrer, if a uniform dispersion was obtained, it was judged that dispersion was possible. On the other hand, if it precipitated or remained in a dry state (in the form of lumps or chips), it was evaluated that it could not be dispersed.
〔実施例１〕
酢酸ビニル１．０ｇ、塩化コリン０．２０ｇ、炭酸ナトリウム０．０１ｇとＤＭＳＯ９．０ｇとを２０ｍｌのサンプル瓶に入れ、磁性スターラーで混合液が均一に混ざるまで攪拌した。次に、セルロースパルプ０．３０ｇを加え、さらに１時間攪拌した後、蒸留水で洗浄することにより解繊溶液（酢酸ビニル、塩化コリン、炭酸ナトリウムとＤＭＳＯ）と副生物（アセトアルデヒド又は酢酸）を除いた。得られたセルロース微細繊維について、修飾有無をＦＴ－ＩＲ分析で確認し、光学顕微鏡で形状を観察し、解繊度合及び溶剤分散性を評価した。ＦＴ－ＩＲ分析の結果により修飾率ＩＲ ｉｎｄｅｘは１．５５であった。また、ＩＲスペクトルは周波数１０５０ｃｍ－１（ピーク）と１０８１ｃｍ－１（谷）、および３２００～３５００ｃｍ－１の吸収帯の分裂が明確に観測されることからセルロースＩ型の結晶性を保っている。光学顕微鏡写真を図１に示す。光学顕微鏡観察の結果、セルロース微細繊維は全体的に良く解繊されていることを確認した。溶媒への分散性を評価した結果、水又はジメチルアセトアミドによく分散できることを確認した。
[Example 1]
1.0 g of vinyl acetate, 0.20 g of choline chloride, 0.01 g of sodium carbonate, and 9.0 g of DMSO were placed in a 20 ml sample bottle, and stirred with a magnetic stirrer until the mixture was uniformly mixed. Next, 0.30 g of cellulose pulp was added, and after stirring for an additional hour, the defibration solution (vinyl acetate, choline chloride, sodium carbonate and DMSO) and by-products (acetaldehyde or acetic acid) were removed by washing with distilled water. Ta. The presence or absence of modification of the obtained cellulose fine fibers was confirmed by FT-IR analysis, the shape was observed with an optical microscope, and the degree of fibrillation and solvent dispersibility were evaluated. According to the results of FT-IR analysis, the modification rate IR index was 1.55. Further, in the IR spectrum, the crystallinity of type I cellulose is maintained, as the splitting of the absorption band between frequencies 1050 cm -1 (peak) and 1081 cm -1 (trough) and 3200 to 3500 cm -1 is clearly observed. An optical micrograph is shown in Figure 1. As a result of optical microscopic observation, it was confirmed that the cellulose fine fibers were generally well defibrated. As a result of evaluating the dispersibility in solvents, it was confirmed that it could be well dispersed in water or dimethylacetamide.
〔実施例２〕
反応時間を３０分とした以外は実施例１と同様にして解繊を行った。実施例１と同様に洗浄し固形分を回収した。ＦＴ－ＩＲ分析の結果により修飾率ＩＲ ｉｎｄｅｘは１．３８であった。また、ＩＲスペクトルは周波数１０５０ｃｍ－１（ピーク）と１０８１ｃｍ－１（谷）、および３２００～３５００ｃｍ－１の吸収帯の分裂が明確に観測されることからセルロースＩ型の結晶性を保っている。
[Example 2]
Defibration was carried out in the same manner as in Example 1 except that the reaction time was 30 minutes. It was washed in the same manner as in Example 1 and the solid content was collected. According to the results of FT-IR analysis, the modification rate IR index was 1.38. Further, in the IR spectrum, the crystallinity of type I cellulose is maintained, as the splitting of the absorption band between frequencies 1050 cm -1 (peak) and 1081 cm -1 (trough) and 3200 to 3500 cm -1 is clearly observed.
〔実施例３〕
塩化コリン添加量を１．０ｇとした以外は実施例１と同様にして解繊を行った。実施例１と同様に洗浄し固形分を回収した。ＦＴ－ＩＲ分析の結果により修飾率ＩＲ ｉｎｄｅｘは１．４２であった。また、ＩＲスペクトルは周波数１０５０ｃｍ－１（ピーク）と１０８１ｃｍ－１（谷）、および３２００～３５００ｃｍ－１の吸収帯の分裂が明確に観測されることからセルロースＩ型の結晶性を保っている。光学顕微鏡観察の結果、セルロース微細繊維は全体的に良く解繊されていることを確認した。溶媒への分散性を評価した結果、水又はジメチルアセトアミドによく分散できることを確認した。
[Example 3]
Defibration was carried out in the same manner as in Example 1 except that the amount of choline chloride added was 1.0 g. It was washed in the same manner as in Example 1 and the solid content was collected. According to the results of FT-IR analysis, the modification rate IR index was 1.42. Further, in the IR spectrum, the crystallinity of type I cellulose is maintained, as the splitting of the absorption band between frequencies 1050 cm -1 (peak) and 1081 cm -1 (trough) and 3200 to 3500 cm -1 is clearly observed. As a result of optical microscopic observation, it was confirmed that the cellulose fine fibers were generally well defibrated. As a result of evaluating the dispersibility in solvents, it was confirmed that it could be well dispersed in water or dimethylacetamide.
〔比較例１〕
塩化コリンを添加しない以外は実施例１と同様にして解繊を行った。実施例１と同様に洗浄し固形分を回収した。回収した固形分の光学顕微鏡写真を図２に示す。解繊不完全の粗大繊維が沢山残った。ＦＴ－ＩＲ分析の結果により修飾率ＩＲ ｉｎｄｅｘは１．２４であり、塩化コリンを加えた場合より劣る結果であった。
[Comparative example 1]
Defibration was performed in the same manner as in Example 1 except that choline chloride was not added. It was washed in the same manner as in Example 1 and the solid content was collected. FIG. 2 shows an optical micrograph of the recovered solids. Many coarse fibers that were incompletely defibrated remained. The results of FT-IR analysis showed that the modification rate IR index was 1.24, which was inferior to the result when choline chloride was added.
本発明の修飾セルロース微細繊維は、各種複合材料、コーティング剤に利用でき、シートやフィルムに成形して利用することもできる。
The modified cellulose fine fibers of the present invention can be used in various composite materials and coating agents, and can also be used by being formed into sheets and films.
Claims (3)
Ｘ－（Ｒ１）（Ｒ２）（Ｒ３）Ｎ＋－Ｒ４－Ｙ （１）
（式中、Ｘ－は、フッ素イオン、塩素イオン、臭素イオン、ヨウ素イオン、水酸化物イオン、硝酸イオン、テトラフルオロホウ素イオン及びヘキサフルオロホウ素イオンのいずれかを表し、Ｒ１、Ｒ２、Ｒ３はそれぞれ独立して炭素数が１～２４のアルキル基、シクロアルキル基またはアリール基を表し、Ｒ４は炭素数が１～６のアルキレン基、ＹはＯＨ、ＳＨ又はＮＨ２を表す）。 Cellulose fine fibers, which comprises defibrating cellulose by permeating cellulose with a defibrating solution containing an aprotic solvent having a donor number of 26 or more, a carboxylic acid vinyl ester, and a reaction and/or defibration promoting additive. A manufacturing method in which the reaction and/or defibration promoting additive is a quaternary ammonium salt represented by the following formula (1):
X - (R1) (R2) (R3) N + -R4-Y (1)
( In the formula , each independently represents an alkyl group, cycloalkyl group, or aryl group having 1 to 24 carbon atoms, R4 represents an alkylene group having 1 to 6 carbon atoms, and Y represents OH, SH or NH 2 ).
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| JP2010104768A (en) | 2008-10-02 | 2010-05-13 | Kri Inc | Polysaccharide nanofiber, method for manufacturing the same, and ionic liquid solution and composite material containing polysaccharide nanofiber |
| JP2013043984A (en) | 2011-08-26 | 2013-03-04 | Olympus Corp | Cellulose nanofiber, method of manufacturing the same, composite resin composition, and molded product |
| WO2016010016A1 (en) | 2014-07-14 | 2016-01-21 | 中越パルプ工業株式会社 | Derivatized cnf, method for producing same, and polyolefin resin composition |
| WO2017159823A1 (en) | 2016-03-16 | 2017-09-21 | 株式会社Kri | Fine cellulose fiber and production method for same |
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