JP6888274B2 - Molding composition and molded article - Google Patents
Molding composition and molded article Download PDFInfo
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- JP6888274B2 JP6888274B2 JP2016218718A JP2016218718A JP6888274B2 JP 6888274 B2 JP6888274 B2 JP 6888274B2 JP 2016218718 A JP2016218718 A JP 2016218718A JP 2016218718 A JP2016218718 A JP 2016218718A JP 6888274 B2 JP6888274 B2 JP 6888274B2
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- fine cellulose
- molded product
- film
- cellulose fibers
- cellulose
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- 239000000203 mixture Substances 0.000 title claims description 56
- 238000000465 moulding Methods 0.000 title claims description 31
- 229920003043 Cellulose fiber Polymers 0.000 claims description 85
- 239000011347 resin Substances 0.000 claims description 46
- 229920005989 resin Polymers 0.000 claims description 46
- 239000002585 base Substances 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 9
- 238000002834 transmittance Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 description 46
- 235000010980 cellulose Nutrition 0.000 description 46
- 239000001913 cellulose Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 44
- 239000006185 dispersion Substances 0.000 description 41
- 239000000047 product Substances 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- 229920002201 Oxidized cellulose Polymers 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229940107304 oxidized cellulose Drugs 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- 241000003910 Baronia <angiosperm> Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Chemical group 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical compound CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 238000007068 beta-elimination reaction Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 108010040093 cellulose synthase Proteins 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical class O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical class O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- LPSWFOCTMJQJIS-UHFFFAOYSA-N sulfanium;hydroxide Chemical class [OH-].[SH3+] LPSWFOCTMJQJIS-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
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Description
本発明は、機能性積層材料として使用可能な、微細セルロース繊維を含有する成形用組成物、および当該成形用組成物を用いて形成された成形体に関する。 The present invention relates to a molding composition containing fine cellulose fibers that can be used as a functional laminated material, and a molded product formed by using the molding composition.
近年、環境問題への関心が高まる中、従来の石油系樹脂に対し、天然由来の澱粉やセルロース、キチン・キトサンなどの各種天然多糖類とその誘導体が、バイオマス材料として注目されている。 In recent years, with increasing interest in environmental issues, various natural polysaccharides such as naturally-derived starch, cellulose, chitin and chitosan and their derivatives have been attracting attention as biomass materials, as opposed to conventional petroleum-based resins.
これらの中でも、地球上で最も多量に生産されているセルロースは、繊維状で高い結晶性を有し、高強度、低線膨張率であり、化学的安定性や生体への安全性に優れることから注目されている。特に、微細セルロース繊維は、近年、樹脂の強化材料や包装材料をはじめ各種機能性材料としての利用が期待され、盛んに開発が進められている。 Among these, cellulose, which is produced in the largest amount on the earth, is fibrous, has high crystallinity, has high strength and low coefficient of linear expansion, and is excellent in chemical stability and safety to the living body. Is attracting attention from. In particular, fine cellulose fibers are expected to be used as various functional materials such as resin reinforcing materials and packaging materials in recent years, and are being actively developed.
微細セルロース繊維の製造方法として、例えば特許文献１には、ＴＥＭＰＯ（２，２，６，６−テトラメチルピペリジノオキシラジカル）触媒を用い水酸基の一部をカルボキシル基に酸化させたセルロースを媒体中に分散させ微細セルロース繊維を得る方法が記載されている。この方法によれば、負の電荷を有するカルボキシル基の電気的反発作用を利用し、セルロースＩ型の結晶構造を有する微細セルロース繊維を比較的容易に得ることが可能である。 As a method for producing fine cellulose fibers, for example, in Patent Document 1, cellulose obtained by oxidizing a part of hydroxyl groups to carboxyl groups using a TEMPO (2,2,6,6-tetramethylpiperidinooxy radical) catalyst is used as a medium. A method for obtaining fine cellulose fibers by dispersing them therein is described. According to this method, it is possible to relatively easily obtain fine cellulose fibers having a cellulose I-type crystal structure by utilizing the electric repulsion action of a carboxyl group having a negative charge.
また、特許文献２には、ＴＥＭＰＯ酸化処理により得た微細セルロース繊維を水中に分散させていたものとＰＶＡの水溶液とを混合し、これを加熱乾燥させることで、形状保持性が改善し、寸法安定性の高いＰＶＡフィルムを得る方法が記載されている。 Further, in Patent Document 2, the shape retention is improved and the dimensions are improved by mixing a fine cellulose fiber obtained by TEMPO oxidation treatment in water and an aqueous solution of PVA and heating and drying the mixture. A method for obtaining a highly stable PVA film is described.
しかし、上記のような微細セルロース繊維の水系分散液を添加して形成された膜は、微細セルロース繊維の強い親水性のため、ＰＶＡやポリアクリル酸などの親水性の高い水溶性樹脂との複合化はしやすいものの、親水性の低い樹脂との親和性に問題がある。樹脂と微細セルロース繊維との親和性が低いと、製膜後の膜の中での微細セルロース繊維の分散が不均一になる等の問題が生じ、十分な効果が得られない。 However, the film formed by adding the aqueous dispersion of fine cellulose fibers as described above is a composite with a highly hydrophilic water-soluble resin such as PVA or polyacrylic acid due to the strong hydrophilicity of the fine cellulose fibers. Although it is easy to convert, there is a problem in compatibility with resins with low hydrophilicity. If the affinity between the resin and the fine cellulose fibers is low, problems such as non-uniform dispersion of the fine cellulose fibers in the film after film formation occur, and a sufficient effect cannot be obtained.
例えば、ＰＶＡとポリエチレンの共重合体であるエチレン−ビニルアルコール共重合体（ＥＶＯＨ）は、水に一定量のアルコールを添加した混合液に溶解する。一方、特許文献２に記載の微細セルロース繊維は水中で安定であるが、この水にアルコールを添加していくと分散性が不安定になり、凝集物が発生してしまう。このような特性のため、ＥＶＯＨと微細セルロース繊維との均一な混合物を成型することは容易ではない。 For example, ethylene-vinyl alcohol copolymer (EVOH), which is a copolymer of PVA and polyethylene, is dissolved in a mixed solution in which a certain amount of alcohol is added to water. On the other hand, the fine cellulose fibers described in Patent Document 2 are stable in water, but when alcohol is added to the water, the dispersibility becomes unstable and aggregates are generated. Due to these properties, it is not easy to mold a uniform mixture of EVOH and fine cellulose fibers.
上記事情を踏まえ、本発明は、樹脂の種類によらず微細セルロース繊維が均一に混合された、成形用組成物および成形体を提供することを目的とする。 Based on the above circumstances, it is an object of the present invention to provide a molding composition and a molded product in which fine cellulose fibers are uniformly mixed regardless of the type of resin.
本発明の第一の態様は、ベース樹脂であるエチレン−ビニルアルコール共重合体と、前記ベース樹脂１００質量部に対して０．５質量部以上４０質量部以下混合され、数平均繊維径が２−２００ｎｍである微細セルロース繊維と、アンモニアまたは有機アルカリとを含む微細セルロース繊維複合成形用組成物である。
前記微細セルロース繊維は、酸化反応によりカルボキシル基が導入されており、前記カルボキシル基の含有量が０．１ｍｍｏｌ／ｇ以上３ｍｍｏｌ／ｇ以下である。
In the first aspect of the present invention, an ethylene-vinyl alcohol copolymer as a base resin is mixed with 0.5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the base resin, and the number average fiber diameter is 2. A composition for composite molding of fine cellulose fibers containing fine cellulose fibers having a mass of −200 nm and ammonia or an organic alkali.
A carboxyl group is introduced into the fine cellulose fiber by an oxidation reaction, and the content of the carboxyl group is 0.1 mmol / g or more and 3 mmol / g or less.
本発明の第二の態様は、本発明の成形用組成物を用いて形成された成形体であって、３０℃−１００℃における線熱膨張率が５０ｐｐｍ/℃以下の成形体である。 A second aspect of the present invention is a molded product formed by using the molding composition of the present invention, which has a linear thermal expansion coefficient of 50 ppm / ° C. or less at 30 ° C. to 100 ° C.
本発明の成形体の厚さは、１μｍ〜５００μｍであってもよい。
また、厚さが３０μｍ以下であり、厚さ方向における波長６６０ｎｍの光線透過率が７０％以上であってもよい。
The thickness of the molded product of the present invention may be 1 μm to 500 μm.
Further, the thickness may be 30 μm or less, and the light transmittance at a wavelength of 660 nm in the thickness direction may be 70% or more.
本発明の成形用組成物によれば、樹脂の種類によらず微細セルロース繊維が均一に混合された成形体を作製することができる。 According to the molding composition of the present invention, a molded product in which fine cellulose fibers are uniformly mixed can be produced regardless of the type of resin.
本発明の一実施形態について説明する。
本実施形態の成形用組成物（以下、「本組成物」と称することがある。）は、例えば、厚さがμｍ単位のフィルム状（膜状）の成形体を作製する際に好適に使用可能な微細セルロース繊維含有複合組成物である。
An embodiment of the present invention will be described.
The molding composition of the present embodiment (hereinafter, may be referred to as "the present composition") is suitably used, for example, when producing a film-like (film-like) molded body having a thickness of μm. A possible fine cellulose fiber-containing composite composition.
以下では、まず本組成物に用いられる微細セルロースについて説明する。
微細セルロース繊維の原料となるセルロース材料は、特に限定されるものではなく、各種木材、非木材パルプ、微生物産生セルロース、バロニアセルロース、ホヤセルロース、レーヨン等の再生セルロース等を用いることができ、パルプ化の方法や、精製方法、漂白方法などについて特に限定されるべきものではない。しかし、より反応を制御し、純度や再現性を高くするためには、漂白済みのパルプや溶解パルプなど精製度の高いセルロース材料を用いることが好ましい。また、高圧ホモジナイザーや凍結粉砕、ミル、石臼等で粉砕した粉末状のものや加水分解などの化学的処理により精製した微細セルロース、市販されている各種セルロース粉末や、微結晶セルロース粉末も使用できる。
In the following, first, the fine cellulose used in the present composition will be described.
The cellulose material used as a raw material for the fine cellulose fibers is not particularly limited, and various types of wood, non-wood pulp, microbially produced cellulose, baronia cellulose, squirrel cellulose, regenerated cellulose such as rayon and the like can be used for pulping. The method, purification method, bleaching method, etc. should not be particularly limited. However, in order to control the reaction more and improve the purity and reproducibility, it is preferable to use a highly purified cellulose material such as bleached pulp or dissolving pulp. Further, a high-pressure homogenizer, a powdery substance crushed by freeze pulverization, a mill, a stone mill or the like, fine cellulose purified by chemical treatment such as hydrolysis, various commercially available cellulose powders, and microcrystalline cellulose powder can also be used.
天然のセルロースは、セルロース合成酵素による合成と、広い意味での自己組織化により、高い結晶構造を有する数ｎｍから数百ｎｍのセルロースナノファイバー（ＣＮＦ）を形成する。このＣＮＦが様々な方向に配向・集合することで、セルロース繊維を形成している。従って、天然のセルロースは元々７０％以上の結晶化度を有している。パルプやコットン、バクテリアセルロースなどの天然のセルロース素材を用い、結晶構造を壊すことなく、できるだけＣＮＦに近い構造単位にまでほぐすことで、高い結晶構造を有する微細セルロース繊維を得ることができる。具体的な方法例としては、後述のように、パルプの結晶表面に効率的にカルボキシル基を導入する酸化処理を施した後、含水状態での物理的解繊処理を施す処理や、特段の化学的処理なく、高圧ホモジナイザーやジェットミルなどにより解繊する方法を用いることができる。 Natural cellulose forms cellulose nanofibers (CNFs) with a high crystal structure of several nm to several hundred nm by synthesis by cellulose synthase and self-assembly in a broad sense. Cellulose fibers are formed by orienting and assembling these CNFs in various directions. Therefore, natural cellulose originally has a crystallinity of 70% or more. Fine cellulose fibers having a high crystal structure can be obtained by using a natural cellulose material such as pulp, cotton, or bacterial cellulose and loosening the structural unit as close as possible to CNF without destroying the crystal structure. Specific examples of the method include, as described later, a treatment of efficiently introducing a carboxyl group into the crystal surface of pulp and then a physical defibration treatment in a water-containing state, and a special chemistry. A method of defibrating with a high-pressure homogenizer, a jet mill, or the like can be used without specific treatment.
セルロース繊維にカルボキシル基を導入する方法としては、セルロース繊維の結晶構造を残したまま反応が進行し、カルボキシル基を導入できる方法が好ましい。現在では様々な方法が開発されているが、木材パルプを水系で処理する一例を挙げて説明する。 As a method for introducing a carboxyl group into the cellulose fiber, a method in which the reaction proceeds while leaving the crystal structure of the cellulose fiber and the carboxyl group can be introduced is preferable. Currently, various methods have been developed, but an example of treating wood pulp in an aqueous system will be described.
水系で処理でき、セルロース繊維表面に効率的にカルボキシル基を導入できる酸化方法としては、Ｎ−オキシル化合物（オキソアンモニウム塩）の存在下、共酸化剤を用いて、セルロースを酸化する方法を挙げることができる。Ｎ−オキシル化合物には、２，２，６，６−テトラメチル−１−ピペリジン−Ｎ−オキシル（以下ＴＥＭＰＯと称する）やその誘導体などが含まれる。この酸化方法では、酸化の程度に応じて、カルボキシル基を均一かつ効率よく導入できる。本酸化反応は、前記Ｎ−オキシル化合物と、臭化物又はヨウ化物との共存下で行うのが有利である。臭化物又はヨウ化物としては、水中で解離してイオン化可能な化合物、例えば、臭化アルカリ金属やヨウ化アルカリ金属などが使用できる。酸化剤としては、ハロゲン、次亜ハロゲン酸，亜ハロゲン酸や過ハロゲン酸又はそれらの塩、ハロゲン酸化物、窒素酸化物、過酸化物など、目的の酸化反応を推進し得る酸化剤であれば、いずれの酸化剤も使用できる。 As an oxidation method that can be treated with an aqueous system and can efficiently introduce a carboxyl group onto the surface of the cellulose fiber, a method of oxidizing cellulose using an copolymer in the presence of an N-oxyl compound (oxoammonium salt) can be mentioned. Can be done. The N-oxyl compound includes 2,2,6,6-tetramethyl-1-piperidin-N-oxyl (hereinafter referred to as TEMPO) and its derivatives. In this oxidation method, a carboxyl group can be introduced uniformly and efficiently depending on the degree of oxidation. It is advantageous that this oxidation reaction is carried out in the coexistence of the N-oxyl compound with bromide or iodide. As the bromide or iodide, a compound that can be dissociated and ionized in water, for example, an alkali metal bromide or an alkali metal iodide can be used. As the oxidizing agent, any oxidizing agent capable of promoting the desired oxidation reaction, such as halogen, hypohalogenic acid, hypohalogenic acid, perhalogenic acid or a salt thereof, halogen oxide, nitrogen oxide, or peroxide, can be used. , Any oxidizing agent can be used.
この酸化方法では、セルロース繊維の結晶あるいは繊維表面かつ、セルロース骨格中の６位の水酸基を選択的に酸化することができ、骨格中のグルコースをグルクロン酸に変換するものである。Ｎ−オキシル化合物は触媒量で済み、例えば、セルロース繊維に対して重量比で２％−１０ｐｐｍあれば充分である。 In this oxidation method, the crystal or fiber surface of the cellulose fiber and the hydroxyl group at the 6-position in the cellulose skeleton can be selectively oxidized, and glucose in the skeleton is converted into glucuronic acid. The amount of the N-oxyl compound is sufficient, for example, 2% -10 ppm by weight with respect to the cellulose fiber is sufficient.
酸化反応条件などは特に限定されず、セルロース繊維の性状、使用する設備などによって最適化されるべきであるが、臭化物やヨウ化物との共存下で酸化反応を行うと、温和な条件下でも酸化反応を円滑に進行させることができ、カルボキシル基の導入効率を大きく改善できる。 Oxidation reaction conditions are not particularly limited and should be optimized according to the properties of cellulose fibers, equipment used, etc. However, if the oxidation reaction is carried out in the coexistence with bromide and iodide, oxidation will occur even under mild conditions. The reaction can proceed smoothly, and the efficiency of introducing the carboxyl group can be greatly improved.
臭化物及び／又はヨウ化物は、必要であれば添加することができ、その使用量は、酸化反応を促進できる範囲で選択でき、例えば、セルロース繊維に対し２０％−１００ｐｐｍである。 Bromide and / or iodide can be added if necessary, and the amount used can be selected within the range in which the oxidation reaction can be promoted, for example, 20% -100 ppm with respect to the cellulose fiber.
本発明におけるセルロース繊維の酸化反応系は、Ｎ−オキシル化合物にはＴＥＭＰＯを用い、臭化ナトリウムの存在下、酸化剤として次亜塩素酸ナトリウムを用いるのが好ましい。 In the oxidation reaction system of cellulose fibers in the present invention, it is preferable to use TEMPO as the N-oxyl compound and sodium hypochlorite as the oxidizing agent in the presence of sodium bromide.
このセルロース繊維の酸化反応では、セルロース繊維の結晶表面への酸化の選択性を上げ、副反応を抑える目的で、反応温度は室温以下で、系が凍らない範囲で、できるだけ低温で反応させることが望ましい。０−３０℃より好ましくは５−２０℃の範囲であると、セルロース繊維の結晶内部の酸化などの副反応が抑えられる。 In this oxidation reaction of cellulose fibers, for the purpose of increasing the selectivity of oxidation of the cellulose fibers to the crystal surface and suppressing side reactions, the reaction temperature should be below room temperature and the reaction should be as low as possible within the range where the system does not freeze. desirable. When the temperature is preferably in the range of 5-20 ° C. than 0-30 ° C., side reactions such as oxidation inside the crystals of the cellulose fibers are suppressed.
また、上記セルロースの酸化反応における反応系のｐＨは、反応の効率の面から、ｐＨ９−１１の間で反応を行うことが望ましい。 Further, it is desirable that the pH of the reaction system in the above-mentioned oxidation reaction of cellulose is between pH 9-11 from the viewpoint of reaction efficiency.
ここで得られた酸化セルロースを用いて伝導度測定を行うことにより、酸化セルロースのカルボキシル基量を求める事ができる。
得られる酸化セルロースに適度にカルボキシル基が導入されている場合、安定した微細な繊維として存在し得る。例えば木材パルプや綿パルプの場合、セルロース繊維に存在するカルボキシル基の量がセルロース繊維の重量に対し、０．１ｍｍｏｌ/ｇ〜３ｍｍｏｌ/ｇ、好ましくは０.６ｍｍｏｌ/ｇ〜２ｍｍｏｌ/ｇであれば、安定したＣＮＦとして提供できる。
By measuring the conductivity using the cellulose oxide obtained here, the amount of carboxyl groups of the cellulose oxide can be determined.
When a carboxyl group is appropriately introduced into the obtained cellulose oxide, it can exist as a stable fine fiber. For example, in the case of wood pulp or cotton pulp, if the amount of carboxyl groups present in the cellulose fibers is 0.1 mmol / g to 3 mmol / g, preferably 0.6 mmol / g to 2 mmol / g, based on the weight of the cellulose fibers. , Can be provided as a stable CNF.
酸化反応は、他のアルコールを過剰量添加し系内の共酸化剤を完全に消費させることにより停止する。添加するアルコールとしては、反応をすばやく終了させるため、メタノール、エタノール、プロパノールなどの低分子量アルコールを用いるのが望ましい。この中でも、安全性や酸化により生成する副生成物を考慮すると、エタノールが好ましい。 The oxidation reaction is stopped by adding an excessive amount of other alcohol to completely consume the copolymer in the system. As the alcohol to be added, it is desirable to use a low molecular weight alcohol such as methanol, ethanol or propanol in order to terminate the reaction quickly. Of these, ethanol is preferable in consideration of safety and by-products produced by oxidation.
酸化反応停止後、生成した酸化セルロースは、ろ過により反応液中から回収することができる。反応停止後の酸化セルロースにおいて、カルボキシル基は共酸化剤やｐＨ調整用の無機アルカリに由来する金属イオンを対イオンとした塩を形成している。回収の方法としては、カルボキシル基が塩を形成したまま濾別する方法、反応液に酸を添加しｐＨ３以下に調整しカルボン酸としてから濾別する方法、有機溶剤を添加し凝集させた後に濾別する方法がある。その中でも、ハンドリング性や収率、廃液処理の点からカルボン酸に変換し回収する方法が好適である。また、後述する微細セルロース繊維組成物調製の際にも、対イオンとして金属イオンを含有しないほうが溶剤との混和性に優れるため、カルボン酸に変換し回収する方法が好適である。 After the oxidation reaction is stopped, the produced cellulose oxide can be recovered from the reaction solution by filtration. In the oxidized cellulose after the reaction is stopped, the carboxyl group forms a salt with a metal ion derived from an copolymer or an inorganic alkali for pH adjustment as a counter ion. As a recovery method, a method of filtering while the carboxyl group forms a salt, a method of adding an acid to the reaction solution to adjust the pH to 3 or less to obtain a carboxylic acid and then filtering, and a method of adding an organic solvent to aggregate and then filtering. There is another way. Among them, a method of converting to a carboxylic acid and recovering it is preferable from the viewpoint of handleability, yield, and waste liquid treatment. Further, also in the preparation of the fine cellulose fiber composition described later, the method of converting to a carboxylic acid and recovering the fine cellulose fiber composition is preferable because the miscibility with the solvent is better if the metal ion is not contained as a counter ion.
酸化セルロース中に含まれる金属イオン含有量は、様々な分析方法で調べることができるが、例えば、電子線マイクロアナライザーを用いたＥＰＭＡ法、蛍光Ｘ線分析法の元素分析等によって簡易的に調べることができる。塩を形成したまま濾別する方法により回収した場合、金属イオンの含有率は５ｗｔ％以上であるのに対し、カルボン酸としてから濾別する方法により回収した場合、金属イオン含有量は１ｗｔ％以下となる。特に、下記のような方法により酸化セルロースを洗浄した場合には、金属イオン含有量は検出限界以下となる。 The metal ion content contained in cellulose oxide can be examined by various analytical methods. For example, it can be simply examined by elemental analysis such as EPMA method using an electron probe microanalyzer or fluorescent X-ray analysis method. Can be done. The metal ion content is 5 wt% or more when recovered by the method of filtering with the salt formed, whereas the metal ion content is 1 wt% or less when recovered by the method of filtering after converting into carboxylic acid. It becomes. In particular, when the oxidized cellulose is washed by the following method, the metal ion content is below the detection limit.
回収した酸化セルロースは、洗浄を繰り返すことにより精製でき、触媒や副生成物である塩化ナトリウム、イオンなどの残渣を取り除くことができる。このとき、洗浄液としては水が好ましく、さらに塩酸などを用いｐＨ３以下、より好ましくはｐＨ１．８以下の酸性条件に調整し洗浄を行った後、水による洗浄を行うと、金属イオンを上記分析方法における検出限界量以下とすることができる。または、残存する金属イオン量をより低減させるため、酸性条件での洗浄を複数回行ってもよい。また、セルロース中に塩等が残留していると、後述の分散工程にて分散しにくくなるため、水洗浄は複数回洗浄を行うことが好ましい。 The recovered cellulose oxide can be purified by repeating washing, and residues such as catalysts and by-products such as sodium chloride and ions can be removed. At this time, water is preferable as the cleaning liquid, and if the cleaning is performed by adjusting the acidic conditions to pH 3 or less, more preferably pH 1.8 or less using hydrochloric acid or the like, and then cleaning with water, the metal ions are analyzed by the above analysis method. It can be less than or equal to the detection limit in. Alternatively, in order to further reduce the amount of residual metal ions, washing under acidic conditions may be performed a plurality of times. Further, if salt or the like remains in the cellulose, it becomes difficult to disperse in the dispersion step described later, so it is preferable to perform water washing a plurality of times.
次に、セルロース繊維を分散処理し微細セルロース繊維分散液を調製する工程を説明する。
洗浄した酸化セルロースを微細化する工程としては、まず、酸化セルロースを分散媒である水系媒体に浸漬する。この時、浸漬した液のｐＨは例えば４以下となる。酸化セルロースは水系媒体に不溶であり、浸漬した時点では不均一な懸濁液となっている。
Next, a step of dispersing the cellulose fibers to prepare a fine cellulose fiber dispersion liquid will be described.
As a step of refining the washed cellulose oxide, first, the cellulose oxide is immersed in an aqueous medium as a dispersion medium. At this time, the pH of the immersed liquid is, for example, 4 or less. Cellulose oxide is insoluble in aqueous media and becomes a non-uniform suspension at the time of immersion.
微細セルロース繊維懸濁液中、微細セルロース繊維の固形分濃度は、１０質量％以下が好ましく、５質量％以下がより好ましい。固形分濃度が５質量％以下、特に３質量％以下であると、分散性、透明性が良好である。固形分濃度が１０質量％を超えると、分散液の粘度が著しく上昇し、分散処理が困難になる。固形分濃度の下限は特に限定されず、０質量％超であればよい。 The solid content concentration of the fine cellulose fibers in the fine cellulose fiber suspension is preferably 10% by mass or less, more preferably 5% by mass or less. When the solid content concentration is 5% by mass or less, particularly 3% by mass or less, the dispersibility and transparency are good. If the solid content concentration exceeds 10% by mass, the viscosity of the dispersion liquid increases remarkably, and the dispersion treatment becomes difficult. The lower limit of the solid content concentration is not particularly limited, and may be more than 0% by mass.
次に、アルカリを用いて懸濁液のｐＨをｐＨ４以上ｐＨ１２以下の範囲に調整する。特に、ｐＨをｐＨ７以上ｐＨ１２以下のアルカリ性とし、カルボン酸塩を形成する。これにより、カルボキシル基同士の電気的反発が起こりやすくなるため、分散性が向上し微細セルロース繊維を得やすくなる。ここで、ｐＨ４未満でも機械的分散処理によりセルロースを微細繊維化することは可能であるが、分散処理により長時間・高エネルギーを要し、得られる繊維の繊維径も本発明のものより大きくなり、分散液の透明性が劣る。一方、ｐＨ１２を超えると分散処理中に酸化セルロースのβ脱離反応による低分子量化や分散液の黄変が促進されるため、製膜後の膜強度や透明性が劣る。 Next, the pH of the suspension is adjusted to a range of pH 4 or more and pH 12 or less using alkali. In particular, the pH is set to be alkaline with a pH of 7 or more and a pH of 12 or less to form a carboxylate. As a result, electrical repulsion between the carboxyl groups is likely to occur, so that the dispersibility is improved and fine cellulose fibers can be easily obtained. Here, it is possible to make cellulose into fine fibers by mechanical dispersion treatment even if the pH is less than 4, but the dispersion treatment requires a long time and high energy, and the fiber diameter of the obtained fiber is also larger than that of the present invention. , The transparency of the dispersion is inferior. On the other hand, if the pH exceeds 12, the molecular weight reduction due to the β-elimination reaction of cellulose oxide and the yellowing of the dispersion are promoted during the dispersion treatment, so that the film strength and transparency after film formation are inferior.
アルカリとしては、アンモニア水または有機アルカリを用いてｐＨを調整することとする。有機アルカリとしては、各種脂肪族アミン、芳香族アミン、ジアミンなどのアミン類や水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラｎ−ブチルアンモニウム、水酸化ベンジルトリメチルアンモニウム、水酸化２−ヒドロキシエチルトリメチルアンモニウム、などＮＲ４ＯＨ（Ｒはアルキル基、またはベンジル基、またはフェニル基、またはヒドロキシアルキル基で、４つのＲが同一でも異なっていてもよい）で表される水酸化物イオンを対イオンとする第４級アンモニウム化合物、水酸化テトラエチルホスホニウムなどの水酸化ホスホニウム化合物、水酸化オキソニウム化合物、水酸化スルホニウム化合物、などの水酸化物イオンを対イオンとする有機オニウム化合物が挙げられる。有機アルカリを用いた場合も、アルカリの種類によらず、無機アルカリを用いた場合と同様の分散処理により繊維を微細化することが可能である。 As the alkali, the pH is adjusted using aqueous ammonia or an organic alkali. Organic alkalis include various aliphatic amines, aromatic amines, diamines and other amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetran-butylammonium hydroxide, benzyltrimethylammonium hydroxide, and 2-hydroxy hydroxide. Ethyltrimethylammonium, etc. Hydroxide ions represented by NR4OH (R is an alkyl group, a benzyl group, a phenyl group, or a hydroxyalkyl group, and the four Rs may be the same or different) are referred to as counterions. Examples thereof include organic onium compounds having hydroxide ions as counterions such as quaternary ammonium compounds, phosphonium hydroxide compounds such as tetraethylphosphonium hydroxide, oxonium hydroxide compounds, and sulfonium hydroxide compounds. Even when an organic alkali is used, the fibers can be made finer by the same dispersion treatment as when an inorganic alkali is used, regardless of the type of alkali.
特に、アルカリとして有機アルカリを用いると、金属イオンを対イオンとする無機アルカリを用いた場合よりも低エネルギー、短時間で分散処理を行うことができ、かつ最終的到達する分散液の透明性も高い。これは、有機アルカリを用いた方が対イオンのイオン径が大きいため分散媒中で微細セルロース繊維同士をより引き離す効果が大きいためと考えられる。 In particular, when an organic alkali is used as the alkali, the dispersion treatment can be performed with lower energy and in a shorter time than when an inorganic alkali having a metal ion as a counter ion is used, and the transparency of the dispersion liquid finally reached is also improved. high. It is considered that this is because the use of organic alkali has a larger ionic radius of the counterion and therefore has a greater effect of separating the fine cellulose fibers from each other in the dispersion medium.
さらに、有機アルカリを用いると、有機溶剤に対する親和性が高いため、媒体としてアルコールなどの有機溶剤を用いた際にも、微細セルロース繊維分散液を調製することができる。さらに、水系媒体中で分散処理した微細セルロース繊維分散液に、分散処理後に有機溶剤を添加することも可能である。水系媒体としては、水、または水と有機溶剤との混合溶剤が挙げられる。有機溶剤としては、例えばメタノール、エタノール、２−プロパノール（ＩＰＡ）などのアルコール類、アセトン、メチルエチルケトン（ＭＥＫ）などのケトン類、１,４−ジオキサン、テトラヒドロフラン（ＴＨＦ）などのエーテル類、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、ジメチルスルホキシド（ＤＭＳＯ）、アセトニトリル、酢酸エチルなどが挙げられる。これらのいずれか１種単独でも、２種以上の混合溶媒でもよい。 Furthermore, since an organic alkali has a high affinity for an organic solvent, a fine cellulose fiber dispersion can be prepared even when an organic solvent such as alcohol is used as a medium. Further, it is also possible to add an organic solvent to the fine cellulose fiber dispersion liquid dispersed in the aqueous medium after the dispersion treatment. Examples of the aqueous medium include water or a mixed solvent of water and an organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol and 2-propanol (IPA), ketones such as acetone and methyl ethyl ketone (MEK), ethers such as 1,4-dioxane and tetrahydrofuran (THF), N and N. -Dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetonitrile, ethyl acetate and the like can be mentioned. Any one of these may be used alone, or a mixed solvent of two or more thereof may be used.
水酸化ナトリウム等の無機アルカリを用いると、溶剤中での分散処理や分散処理後の溶剤との混合は困難である。無機アルカリによる金属イオンを含んだ微細セルロース繊維分散液では、有機溶剤を添加すると分散させた微細セルロース繊維が凝集し、分散液の凝集白濁、不均一化を起してしまう。 When an inorganic alkali such as sodium hydroxide is used, it is difficult to disperse it in a solvent or mix it with the solvent after the dispersion treatment. In a fine cellulose fiber dispersion containing metal ions due to an inorganic alkali, when an organic solvent is added, the dispersed fine cellulose fibers agglomerate, causing agglomeration white turbidity and non-uniformity of the dispersion.
媒体への分散処理の方法としては、既に知られている各種分散処理が可能である。例えば、ホモミキサー処理、回転刃つきミキサー処理、高圧ホモジナイザー処理、超高圧ホモジナイザー処理、超音波ホモジナイザー処理、ナノジナイザー処理、ディスク型レファイナー処理、コニカル型レファイナー処理、ダブルディスク型レファイナー処理、グラインダー処理、ボールミル処理、ニ軸混練機による混練処理、水中対向処理などがある。この中でも、微細化効率の面から回転刃つきミキサー処理、高圧ホモジナイザー処理、超高圧ホモジナイザー処理、超音波ホモジナイザー処理が好適である。なお、これらの処理のうち二つ以上の処理方法を組み合わせて分散を行うことも可能である。 As a method of distributed processing on a medium, various already known distributed processing can be used. For example, homomixer processing, mixer processing with rotary blade, high pressure homogenizer processing, ultrahigh pressure homogenizer processing, ultrasonic homogenizer processing, nanogenizer processing, disc type refiner processing, conical type refiner processing, double disc type refiner processing, grinding processing, ball mill processing. , Kneading process with a twin-screw kneader, underwater facing process, etc. Among these, a mixer treatment with a rotary blade, a high-pressure homogenizer treatment, an ultra-high pressure homogenizer treatment, and an ultrasonic homogenizer treatment are preferable from the viewpoint of miniaturization efficiency. It is also possible to perform dispersion by combining two or more of these processes.
分散処理を行うと、懸濁液は目視上均一な透明分散液となる。分散処理により酸化セルロースは微細化し、微細セルロース繊維となる。
分散処理後の微細セルロース繊維は、好ましくは数平均繊維径（繊維の短軸方向の幅）が２ｎｍ以上２００ｎｍ以下であり、より好ましくは５ｎｍ以上５０ｎｍ以下である。微細セルロース繊維の繊維径は、走査型電子顕微鏡（ＳＥＭ）や原子間力顕微鏡（ＡＦＭ）により確認できる。分散が不十分・不均一で、一部に繊維径の大きいものが含まれていると、微細セルロース繊維を含む塗液を製膜した際、膜の透明性や平滑性が著しく低下してしまう問題がある。
When the dispersion treatment is performed, the suspension becomes a visually uniform transparent dispersion liquid. By the dispersion treatment, the oxidized cellulose becomes finer and becomes fine cellulose fibers.
The fine cellulose fibers after the dispersion treatment preferably have a number average fiber diameter (width in the minor axis direction of the fibers) of 2 nm or more and 200 nm or less, and more preferably 5 nm or more and 50 nm or less. The fiber diameter of the fine cellulose fibers can be confirmed by a scanning electron microscope (SEM) or an atomic force microscope (AFM). If the dispersion is insufficient or non-uniform and some of the fibers have a large fiber diameter, the transparency and smoothness of the film will be significantly reduced when a coating liquid containing fine cellulose fibers is formed. There's a problem.
続いて、本組成物について説明する。
本組成物は、微細セルロース繊維とベース樹脂とを混合し、微細セルロース繊維を均一に樹脂中に分散させることにより作製される。本組成物は、微細セルロース繊維を含有することにより、ベース樹脂を単体で使用する場合に比べて形状保持性が著しく向上される。その結果、ベース樹脂単体で成形体を作製するよりも、寸法安定性および剛性（強度）に優れる成形体を作製することができる。
Subsequently, the present composition will be described.
The present composition is produced by mixing fine cellulose fibers and a base resin and uniformly dispersing the fine cellulose fibers in the resin. By containing the fine cellulose fibers in this composition, the shape retention is remarkably improved as compared with the case where the base resin is used alone. As a result, it is possible to produce a molded product having excellent dimensional stability and rigidity (strength) as compared with producing a molded product using the base resin alone.
寸法安定性は、例えば、線熱膨張率で示すことができる。本組成物を用いて作製された成形体は、３０℃−１００℃の温度範囲における線熱膨張率が５０ｐｐｍ/℃以下であり、概ねベース樹脂単体の線熱膨張率の約１／２以下となる。 Dimensional stability can be indicated, for example, by the coefficient of linear thermal expansion. The molded product produced using this composition has a linear thermal expansion coefficient of 50 ppm / ° C. or less in the temperature range of 30 ° C.-100 ° C., which is approximately 1/2 or less of the linear thermal expansion coefficient of the base resin alone. Become.
また、本組成物は、微細セルロース繊維が均一に分散されているため、ベース樹脂が透明性を有していれば、作製された成形体も透明性に優れる。例えば、本組成物を厚さ３０μｍの膜状に成形した場合、成形体の厚さ方向における波長６６０ｎｍの光線の透過率は７０％以上となる。 Further, in this composition, since the fine cellulose fibers are uniformly dispersed, if the base resin has transparency, the produced molded product also has excellent transparency. For example, when the present composition is molded into a film having a thickness of 30 μm, the transmittance of light rays having a wavelength of 660 nm in the thickness direction of the molded product is 70% or more.
微細セルロース繊維とベース樹脂との混合方法に特に制限はないが、例えば微細セルロース繊維の懸濁液とベース樹脂の溶液とを混合する方法が挙げられる。
他の方法として、微細セルロース繊維の懸濁液を加熱乾燥し、溶媒を除去した後にベース樹脂のペレットと混合（混練）する方法によっても本組成物を得ることができる。この場合、得られた本組成物を、二軸押出し成型などの手法でフィルム等の膜状成形体に加工することができる。この際、溶融温度は使用する樹脂の融点以上２００℃以下であることが好ましい。２００℃を超えるとセルロースの分解などにより本来の強度を保つことができない場合がある。
The method for mixing the fine cellulose fibers and the base resin is not particularly limited, and examples thereof include a method of mixing a suspension of the fine cellulose fibers and a solution of the base resin.
As another method, the present composition can also be obtained by heating and drying a suspension of fine cellulose fibers, removing the solvent, and then mixing (kneading) with the pellets of the base resin. In this case, the obtained composition can be processed into a film-like molded product such as a film by a method such as biaxial extrusion molding. At this time, the melting temperature is preferably not less than the melting point of the resin used and not more than 200 ° C. If the temperature exceeds 200 ° C., the original strength may not be maintained due to decomposition of cellulose or the like.
微細セルロース繊維は、ベース樹脂１００質量部に対して０．５質量部以上４０質量部以下混合される。この範囲であれば、寸法安定性および剛性（強度）に優れる成形体を作製することができるが、微細セルロースの含有率が高まるにつれて、成形体が脆くなる傾向があるため、より優れた成形体を作製する観点からは、微細セルロース繊維の含有率を、ベース樹脂１００質量部に対して１質量部以上１５質量部以下とするのが好ましい。 The fine cellulose fibers are mixed in an amount of 0.5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the base resin. Within this range, a molded product having excellent dimensional stability and rigidity (strength) can be produced, but as the content of fine cellulose increases, the molded product tends to become brittle, so that the molded product is more excellent. From the viewpoint of producing the above, the content of the fine cellulose fibers is preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the base resin.
ベース樹脂としては、酢酸ビニル系、ウレタン系、アクリル系、スチレン系、フェノール系、アミノ系、アミド系、ポリエステル系、エチレン系、ポリビニルアルコール（ＰＶＡ）系等の各種樹脂を用いることができる。ベース樹脂は単独でもよく、共重合したものや二種類以上併せて用いることができる。 As the base resin, various resins such as vinyl acetate-based, urethane-based, acrylic-based, styrene-based, phenol-based, amino-based, amide-based, polyester-based, ethylene-based, and polyvinyl alcohol (PVA) -based resins can be used. The base resin may be used alone, or may be copolymerized or used in combination of two or more.
ベース樹脂として親水性の低い樹脂を用いる場合は、アルコール等の有機溶媒を含む溶媒中で酸化セルロース繊維に有機アルカリを添加してｐＨ調整した後に分散処理を施すことで、微細セルロース繊維の凝集が抑制される。また、分散処理を施した後にも適宜有機溶媒を添加することができる。このようにして本組成物を製造した場合、本組成物は、アンモニア又は有機アルカリを含有する。
親水性の低い樹脂の中では、ＥＶＯＨがベース樹脂として特に好ましい。ＥＶＯＨは、有機溶媒を含む溶媒に分散した微細セルロース繊維との相溶性が高く成形用組成物としての効果が発現しやすい。
When a resin with low hydrophilicity is used as the base resin, the fine cellulose fibers are aggregated by adding an organic alkali to the oxidized cellulose fibers in a solvent containing an organic solvent such as alcohol to adjust the pH and then performing a dispersion treatment. It is suppressed. Further, an organic solvent can be appropriately added even after the dispersion treatment is performed. When the present composition is produced in this way, the present composition contains ammonia or an organic alkali.
Among the resins having low hydrophilicity, EVOH is particularly preferable as the base resin. EVOH has high compatibility with fine cellulose fibers dispersed in a solvent containing an organic solvent, and the effect as a molding composition is likely to be exhibited.
なお、微細セルロースは、緻密な膜状に形成することにより、水蒸気や酸素等のガスバリア性を発揮する。しかし、本組成物がアンモニア又は有機アルカリを含有する場合、微細セルロース間に分子量の大きいアンモニア又は有機アルカリが存在することになるため、本組成物を用いて作製された成形体に関しては、微細セルロースの含有率やアンモニア又は有機アルカリの含有率に関わらず、微細セルロースがガスバリア性を向上させることはない。 By forming the fine cellulose into a dense film, it exhibits gas barrier properties such as water vapor and oxygen. However, when the present composition contains ammonia or an organic alkali, ammonia or an organic alkali having a large molecular weight is present between the fine celluloses. Therefore, for the molded product produced by using the present composition, the fine celluloses are used. Fine cellulose does not improve the gas barrier property regardless of the content of ammonia or organic alkali.
ベース樹脂として親水性の高い樹脂を用いる場合は、水中で酸化セルロース繊維に有機アルカリを添加してｐＨ調整した後に分散処理を施してもよい。ただし、上述したように有機アルカリ等の添加によりアルコール等の有機溶媒を含む溶媒中に分散させた微細セルロース繊維を用いると、成形時に溶媒が揮発しやすくなり、効率よく溶媒を除去して成形体を作製することができる。 When a highly hydrophilic resin is used as the base resin, an organic alkali may be added to the oxidized cellulose fibers in water to adjust the pH, and then the dispersion treatment may be performed. However, as described above, if fine cellulose fibers dispersed in a solvent containing an organic solvent such as alcohol by adding an organic alkali or the like are used, the solvent is likely to volatilize during molding, and the solvent is efficiently removed to form a molded product. Can be produced.
本組成物は、ベース樹脂および微細セルロースの他に、添加剤としてアミノ基、エポキシ基、水酸基、メルカプト基、カルボジイミド基、ポリエチレンイミン、イソシアネート基、アルコキシ基などの反応性官能基を有する化合物を含んでいてもよい。これらの添加剤は、酸化セルロース中の水酸基、カルボキシル基、アルデヒド基と反応し被膜の各性能、特に膜強度、耐水性、耐湿性、隣接層との密着性向上に効果がある。 In addition to the base resin and fine cellulose, this composition contains compounds having reactive functional groups such as amino groups, epoxy groups, hydroxyl groups, mercapto groups, carbodiimide groups, polyethyleneimines, isocyanate groups and alkoxy groups as additives. You may be. These additives react with hydroxyl groups, carboxyl groups, and aldehyde groups in cellulose oxide and are effective in improving each performance of the film, particularly film strength, water resistance, moisture resistance, and adhesion to adjacent layers.
さらに、必要に応じて、上述した効果を著しく損なわない範囲で、上記以外の他の成分が含有されてもよい。他の成分としては、特に限定されず、本発明の微細セルロース繊維組成物により形成する膜状成形体の用途等に応じて、公知の添加剤のなかから適宜選択できる。具体的には、たとえばレベリング剤、消泡剤、安定剤、無機系粒子、有機系粒子、潤滑剤、帯電防止剤、紫外線吸収剤、染料、顔料、シランカップリング剤等が挙げられる。 Further, if necessary, other components other than the above may be contained as long as the above-mentioned effects are not significantly impaired. The other components are not particularly limited, and can be appropriately selected from known additives according to the use of the film-shaped molded product formed by the fine cellulose fiber composition of the present invention. Specific examples thereof include leveling agents, defoaming agents, stabilizers, inorganic particles, organic particles, lubricants, antistatic agents, ultraviolet absorbers, dyes, pigments, silane coupling agents and the like.
本組成物を用いて膜状の成形体を作製する際の成膜方法については、特に制限はなく、一般にキャストフィルムを製造する際に採用されている製膜方法を採用することができる。製膜されたフィルムには、必要に応じて熱処理を施すことができる。熱処理の温度は、７０〜２００℃の範囲内であることが好ましく、１００〜１５０℃の範囲内であることがより好ましい。熱処理の時間としては、例えば、３０秒〜１時間の範囲内が挙げられる。なお、熱処理をはじめとする複合組成物を製造する工程中で、高すぎる温度に晒されると得られる膜状成形体の寸法安定性が低下する場合があることから、製膜原液としての本組成物を用いて膜状成形体を製造するまでの間、本組成物の温度を２００℃以下に保つことが好ましい。２００℃を超えるとセルロースが脱水縮合や分解をしてしまい、本来の強度を保つことができない場合がある。 The film forming method for producing a film-shaped molded product using the present composition is not particularly limited, and a film forming method generally used for producing a cast film can be adopted. The formed film can be heat-treated if necessary. The heat treatment temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 100 to 150 ° C. The heat treatment time includes, for example, the range of 30 seconds to 1 hour. In the process of producing a composite composition such as heat treatment, the dimensional stability of the obtained film-shaped molded product may decrease if it is exposed to an excessively high temperature. Therefore, this composition as a film-forming stock solution. It is preferable to keep the temperature of the present composition at 200 ° C. or lower until a film-shaped molded product is produced using the product. If the temperature exceeds 200 ° C., cellulose may be dehydrated and condensed or decomposed, and the original strength may not be maintained.
製膜時は、必要に応じて、乾燥前、乾燥中または乾燥後のうちのいずれか１つまたは２つ以上の段階で一軸または二軸の延伸を行うこともできる。延伸の際の温度としては、２０〜１２０℃の範囲内であることが好ましい。また、延伸倍率は、延伸前の長さに基づいて１．０５〜５．０倍の範囲内であることが好ましく、１．１〜３．０倍の範囲内であることがより好ましい。さらに必要であれば、延伸後にフィルムを熱固定して残存応力を低下させることもできる。 At the time of film formation, uniaxial or biaxial stretching may be performed at any one or more steps of before, during or after drying, if necessary. The temperature at the time of stretching is preferably in the range of 20 to 120 ° C. The stretching ratio is preferably in the range of 1.05 to 5.0 times, more preferably in the range of 1.1 to 3.0 times, based on the length before stretching. Further, if necessary, the film can be thermally fixed after stretching to reduce the residual stress.
本組成物について、実施例および比較例を用いてさらに説明する。ただし、本発明の技術的範囲は、これら実施例の具体的内容により何ら限定されるものではない。 The present composition will be further described with reference to Examples and Comparative Examples. However, the technical scope of the present invention is not limited to the specific contents of these examples.
まず、微細セルロース繊維を得るためのセルロースの調整について示す。
（酸化セルロースの調製方法）
セルロースとして、汎用的に入手可能な針葉樹漂白パルプを用いた。セルロース６０ｇ（絶乾質量換算）を蒸留水１０００ｇに加え撹拌し、膨潤させた後ミキサーにより解繊した。ここに蒸留水２２００ｇと、予め蒸留水４００ｇに溶解させたＴＥＭＰＯを０．６ｇ、臭化ナトリウム６ｇの溶液を加え、２ｍｏｌ／Ｌ濃度の次亜塩素酸ナトリウム水溶液１７２ｇを滴下により添加し、酸化反応を開始した。反応温度は常に２０℃以下に維持した。反応中は系内のｐＨが低下するが、０．５ＮのＮａＯＨ水溶液を逐次添加し、ｐＨ１０に調整した。そして、４時間反応させた時点で、エタノール６０ｇを添加し、反応を停止した。続いて反応液に０．５ＮのＨＣｌを滴下しｐＨを２まで低下させた。ナイロンメッシュを用いてこの反応液をろ過し、固形分をさらに水で数回洗浄し、反応試薬や副生成物を除去し、固形分濃度７％の水を含有した酸化セルロースを得た。
First, the preparation of cellulose for obtaining fine cellulose fibers will be described.
(Preparation method of oxidized cellulose)
As the cellulose, commonly available softwood bleached pulp was used. 60 g of cellulose (in terms of absolute dry mass) was added to 1000 g of distilled water, stirred, swollen, and then defibrated by a mixer. A solution of 2200 g of distilled water, 0.6 g of TEMPO previously dissolved in 400 g of distilled water, and 6 g of sodium bromide is added thereto, and 172 g of a 2 mol / L sodium hypochlorite aqueous solution is added dropwise to carry out an oxidation reaction. Started. The reaction temperature was always maintained below 20 ° C. Although the pH in the system decreased during the reaction, a 0.5 N NaOH aqueous solution was sequentially added to adjust the pH to 10. Then, when the reaction was carried out for 4 hours, 60 g of ethanol was added to stop the reaction. Subsequently, 0.5 N HCl was added dropwise to the reaction solution to lower the pH to 2. The reaction solution was filtered using a nylon mesh, and the solid content was further washed with water several times to remove reaction reagents and by-products to obtain water-containing oxidized cellulose having a solid content concentration of 7%.
（官能基の導入量の測定）
絶乾質量換算で０．２ｇの湿潤酸化セルロースをビーカーに量りとり、蒸留水を加えて６０ｇとした。０．１ＭのＮａＣｌ水溶液を０．５ｍＬ加え、０．５Ｍの塩酸でｐＨを３とした後、０．５ＭのＮａＯＨ水溶液を滴下して伝導度測定を行った。測定はｐＨが１１程度になるまで続けた。弱酸の中和段階に相当する部分がカルボキシル基量となるので、得られた伝導度曲線からＮａＯＨの添加量を読み取ると、カルボキシル基量は１．６ｍｍｏｌ／ｇであった。
(Measurement of introduction amount of functional group)
Weighed 0.2 g of wet cellulose oxide in terms of absolute dry mass in a beaker, and added distilled water to make 60 g. 0.5 mL of a 0.1 M NaCl aqueous solution was added, the pH was adjusted to 3 with 0.5 M hydrochloric acid, and then a 0.5 M NaOH aqueous solution was added dropwise to measure the conductivity. The measurement was continued until the pH reached about 11. Since the portion corresponding to the neutralization step of the weak acid is the carboxyl group amount, the amount of NaOH added was read from the obtained conductivity curve, and the carboxyl group amount was 1.6 mmol / g.
（微細セルロース繊維分散液の調製）
上記により調製した固形分濃度７％の酸化セルロース５７．１４ｇ（固形分４ｇ）に、蒸留水と、１０ｗｔ％水酸化テトラブチルアンモニウム（ＴＢＡＨ）とを加え、ｐＨ１０の酸化セルロース懸濁液２００ｇとした。続いてイソプロピルアルコール２００ｇを混合して総量を４００ｇとした。調製した懸濁液を回転刃つきミキサーにて６０分間処理し、固形分濃度１％の微細セルロース繊維分散液を得た。微細セルロース繊維の数平均繊維径は、５ｎｍであった。
(Preparation of fine cellulose fiber dispersion)
Distilled water and 10 wt% tetrabutylammonium hydroxide (TBAH) were added to 57.14 g (4 g of solid content) of cellulose oxide having a solid content concentration of 7% prepared as described above to obtain 200 g of a cellulose oxide suspension having a pH of 10. .. Subsequently, 200 g of isopropyl alcohol was mixed to bring the total amount to 400 g. The prepared suspension was treated with a mixer with a rotary blade for 60 minutes to obtain a fine cellulose fiber dispersion having a solid content concentration of 1%. The number average fiber diameter of the fine cellulose fibers was 5 nm.
（ベース樹脂溶液の調整）
市販品のＥＶＯＨ（ソアノールＤ２９０８Ｂ、日本合成化学工業（株）製）５０ｇをビーカーに量りとり、純水４７５ｇ、イソプロピルアルコール４７５ｇを加えた。これを１００℃に加熱し、溶解させ５％溶液を得た。この５％溶液を水：イソプロピルアルコール＝１：１の溶液を用いて希釈し、濃度１％のベース樹脂溶液を得た。
(Adjustment of base resin solution)
50 g of commercially available EVOH (Soanol D2908B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was weighed in a beaker, and 475 g of pure water and 475 g of isopropyl alcohol were added. This was heated to 100 ° C. and dissolved to obtain a 5% solution. This 5% solution was diluted with a water: isopropyl alcohol = 1: 1 solution to obtain a base resin solution having a concentration of 1%.
（実施例１）
ベース樹脂溶液中に微細セルロース繊維分散液を攪拌しながら添加して混合した。微細セルロース繊維分散液の混合量は、ベース樹脂１００重量部に対して微細セルロース繊維が１０重量部となるように設定した。
以上により、実施例１の成形用組成物を得た。
(Example 1)
The fine cellulose fiber dispersion was added to the base resin solution with stirring and mixed. The mixing amount of the fine cellulose fiber dispersion liquid was set so that the amount of the fine cellulose fiber was 10 parts by weight with respect to 100 parts by weight of the base resin.
From the above, the molding composition of Example 1 was obtained.
（実施例２）
微細セルロース繊維分散液の調製の際に、イソプロピルアルコールに代えてアセトン（２００ｇ）を使用した点を除き、実施例１と同様の手順で実施例２の成形用組成物を得た。
(Example 2)
A molding composition of Example 2 was obtained in the same procedure as in Example 1 except that acetone (200 g) was used instead of isopropyl alcohol in the preparation of the fine cellulose fiber dispersion.
（実施例３）
微細セルロース繊維分散液の調製の際に、ＴＢＡＨに代えて１０ｗｔ％水酸化テトラエチルアンモニウム（ＴＥＡＨ）を使用した点を除き、実施例１と同様の手順で実施例３の成形用組成物を得た。
(Example 3)
The molding composition of Example 3 was obtained in the same procedure as in Example 1 except that 10 wt% tetraethylammonium hydroxide (TEAH) was used instead of TBAH in the preparation of the fine cellulose fiber dispersion liquid. ..
（実施例４）
微細セルロース繊維分散液の調製の際に、ＴＢＡＨに代えて１０ｗｔ％水酸化ベンジルトリエチルアンモニウム（ＢＴＥＡＨ）を使用した点を除き、実施例１と同様の手順で実施例４の成形用組成物を得た。
(Example 4)
The molding composition of Example 4 was obtained in the same procedure as in Example 1 except that 10 wt% benzyltriethylammonium hydroxide (BTEAH) was used in place of TBAH in the preparation of the fine cellulose fiber dispersion. It was.
（膜状成形体の作製）
各実施例の成形用組成物をシャーレに移し、１２０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの膜状成形体を各実施例について得た。
(Preparation of film-shaped molded product)
The molding composition of each example was transferred to a petri dish and heated at 120 ° C. for 10 minutes to remove the solvent, whereby a film-like molded product having a film thickness of 30 μm was obtained for each example in a dry state.
（実施例５）
実施例１の成形用組成物を用い、１５０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの実施例５の膜状成形体を得た。
(Example 5)
By using the molding composition of Example 1 and heating at 150 ° C. for 10 minutes to remove the solvent, a film-like molded product of Example 5 having a film thickness of 30 μm was obtained in a dry state.
（実施例６）
微細セルロース繊維分散液の混合量を、ベース樹脂１００重量部に対して微細セルロース繊維が０．５重量部となるように設定した点を除き、実施例１と同様の手順で実施例６の成形用組成物を得た。
実施例６の成形用組成物を用い、１２０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの実施例６の膜状成形体を得た。
(Example 6)
Molding of Example 6 in the same procedure as in Example 1 except that the mixing amount of the fine cellulose fiber dispersion was set so that the amount of the fine cellulose fibers was 0.5 parts by weight with respect to 100 parts by weight of the base resin. The composition for use was obtained.
By using the molding composition of Example 6 and heating at 120 ° C. for 10 minutes to remove the solvent, a film-like molded product of Example 6 having a film thickness of 30 μm was obtained in a dry state.
（実施例７）
微細セルロース繊維分散液の混合量を、ベース樹脂１００重量部に対して微細セルロース繊維が４０重量部となるように設定した点を除き、実施例１と同様の手順で実施例７の成形用組成物を得た。
実施例７の成形用組成物を用い、１２０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの実施例７の膜状成形体を得た。
(Example 7)
The molding composition of Example 7 was carried out in the same procedure as in Example 1 except that the mixing amount of the fine cellulose fiber dispersion was set so that the amount of the fine cellulose fibers was 40 parts by weight with respect to 100 parts by weight of the base resin. I got something.
By using the molding composition of Example 7 and heating at 120 ° C. for 10 minutes to remove the solvent, a film-like molded product of Example 7 having a film thickness of 30 μm was obtained in a dry state.
（実施例８）
微細セルロース繊維分散液の調製の際に、ＴＢＡＨに代えて１０ｗｔ％アンモニアを使用した点を除き、実施例１と同様の手順で実施例８の成形用組成物を得た。
実施例８の成形用組成物を用い、１２０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの実施例８の膜状成形体を得た。
(Example 8)
A molding composition of Example 8 was obtained in the same procedure as in Example 1 except that 10 wt% ammonia was used instead of TBAH in the preparation of the fine cellulose fiber dispersion liquid.
By using the molding composition of Example 8 and heating at 120 ° C. for 10 minutes to remove the solvent, a film-like molded product of Example 8 having a film thickness of 30 μm was obtained in a dry state.
（比較例１）
ベース樹脂溶液のみを用い、１２０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの比較例１の膜状成形体を得た。
(Comparative Example 1)
By using only the base resin solution and heating at 120 ° C. for 10 minutes to remove the solvent, a film-like molded product of Comparative Example 1 having a film thickness of 30 μm was obtained in a dry state.
（比較例２）
微細セルロース繊維分散液の調製の際に、水酸化テトラブチルアンモニウムに代えて１０ｗｔ％水酸化ナトリウムを使用した点を除き、実施例１と同様の手順で比較例２の成形用組成物を得た。
比較例２の成形用組成物を用い、１２０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの比較例２の膜状成形体を得た。
(Comparative Example 2)
A molding composition of Comparative Example 2 was obtained in the same procedure as in Example 1 except that 10 wt% sodium hydroxide was used instead of tetrabutylammonium hydroxide in the preparation of the fine cellulose fiber dispersion. ..
By using the molding composition of Comparative Example 2 and heating at 120 ° C. for 10 minutes to remove the solvent, a film-shaped molded product of Comparative Example 2 having a film thickness of 30 μm was obtained in a dry state.
（比較例３）
微細セルロース繊維分散液の混合量を、ベース樹脂１００重量部に対して微細セルロース繊維が１００重量部となるように設定した点を除き、実施例１と同様の手順で比較例３の成形用組成物を得た。
比較例３の成形用組成物を用い、１２０℃で１０分加熱して溶媒を除去することにより、乾燥状態で膜厚３０μｍの比較例３の膜状成形体を得た。
(Comparative Example 3)
The molding composition of Comparative Example 3 was carried out in the same procedure as in Example 1 except that the mixing amount of the fine cellulose fiber dispersion was set so that the amount of the fine cellulose fibers was 100 parts by weight with respect to 100 parts by weight of the base resin. I got something.
By using the molding composition of Comparative Example 3 and heating at 120 ° C. for 10 minutes to remove the solvent, a film-shaped molded product of Comparative Example 3 having a film thickness of 30 μm was obtained in a dry state.
各実施例および比較例の膜状成形体に対し、以下の評価を行った。
（線熱膨張率）
窒素雰囲気下における３０℃〜１００℃の範囲内における線膨張率を、エスアイアイ・ナノテクノロジー社製ＥＸＳＴＡＲ ＴＭＡ／ＳＳ６１００を用いて測定した。測定値を安定させるために、二度目の加熱（２ｎｄ ｈｅａｔ）における値を測定値として採用した。
The following evaluations were performed on the film-shaped molded products of each Example and Comparative Example.
(Coefficient of linear thermal expansion)
The coefficient of linear expansion in the range of 30 ° C. to 100 ° C. under a nitrogen atmosphere was measured using EXSTAR TMA / SS6100 manufactured by SII Nanotechnology. In order to stabilize the measured value, the value in the second heating (2nd heat) was adopted as the measured value.
（光線透過率）
分光光度計を用い、波長６６０ｎｍの光の、厚さ方向における透過率を測定した。
(Light transmittance)
Using a spectrophotometer, the transmittance of light having a wavelength of 660 nm in the thickness direction was measured.
（引っ張り強度測定）
膜状成形体を、１５ｍｍ幅、７０ｍｍ長さの短冊状に切り出し、試験片とした。恒温恒湿槽付き引張試験機（テスター産業社製、ＴＥ−７００１）を用いて、チャック間隔５０ｍｍ、試験速度５ｍｍ／ｍｉｎにて温度４０℃、相対湿度３０％の環境下で引張り強度（ｋｇ／ｃｍ２）を測定した。なお、測定前に予め２日間測定環境にて調湿した。
(Tensile strength measurement)
The film-shaped molded product was cut into strips having a width of 15 mm and a length of 70 mm to prepare test pieces. Using a tensile tester with a constant temperature and humidity chamber (TE-7001 manufactured by Tester Sangyo Co., Ltd.), the tensile strength (kg / kg /) under an environment with a chuck interval of 50 mm, a test speed of 5 mm / min, a temperature of 40 ° C., and a relative humidity of 30%. cm 2 ) was measured. Before the measurement, the humidity was adjusted in the measurement environment for 2 days in advance.
結果を表１に示す。 The results are shown in Table 1.
表１に示すように、各実施例の膜状成形体は、ベース樹脂のみで形成した比較例１の膜状成形体に比べて線熱膨張率が低く、寸法安全性が向上されていた。また、比較例１に比べて引っ張り強度も高く、剛性も向上していることが示された。 As shown in Table 1, the film-shaped molded product of each example had a lower coefficient of linear thermal expansion than the film-shaped molded product of Comparative Example 1 formed only of the base resin, and the dimensional safety was improved. It was also shown that the tensile strength was higher and the rigidity was improved as compared with Comparative Example 1.
有機アルカリを含有しない比較例２の成形用組成物では、ベース樹脂であるＥＶＯＨの親水性が低いために、微細セルロース繊維の凝集が発生した。その結果、比較例２の膜状成形体は白く曇った外観を呈し、光線透過率も低かった。これに対し、各実施例の膜状成形体はいずれも８５％以上の光線透過率を示し、透明性が良好であった。
なお、有機アルカリを含有しない構成の成形用組成物であっても、ベース樹脂がＰＶＡ等の親水性の高い樹脂である場合は、線熱膨張率および光線透過率のいずれも良好な膜状成形体を形成できることを確認している。
In the molding composition of Comparative Example 2 containing no organic alkali, agglomeration of fine cellulose fibers occurred because EVOH, which is a base resin, had low hydrophilicity. As a result, the film-shaped molded product of Comparative Example 2 exhibited a white and cloudy appearance, and the light transmittance was also low. On the other hand, the film-shaped molded products of each example showed a light transmittance of 85% or more, and the transparency was good.
Even if the molding composition does not contain an organic alkali, if the base resin is a highly hydrophilic resin such as PVA, both the linear thermal expansion coefficient and the light transmittance are good film-like molding. We have confirmed that we can form a body.
微細セルロース繊維の含有率が高すぎる比較例３の膜状成形体は、脆くなった結果、引っ張り強度が低下し、線熱膨張率も測定不能であった。 The film-shaped molded product of Comparative Example 3 in which the content of the fine cellulose fibers was too high became brittle, and as a result, the tensile strength decreased and the linear thermal expansion coefficient could not be measured.
以上、本発明の一実施形態および実施例について説明したが、本発明の技術範囲は上記実施形態等の内容に限定されるものではなく、本発明の趣旨を逸脱しない範囲において各構成要素に種々の変更を加えたり、削除したりすることが可能である。 Although one embodiment and examples of the present invention have been described above, the technical scope of the present invention is not limited to the contents of the above-described embodiments and the like, and various components are included within a range that does not deviate from the gist of the present invention. It is possible to make or delete changes to.
Claims (4)
前記ベース樹脂１００質量部に対して０．５質量部以上４０質量部以下混合され、数平均繊維径が２−２００ｎｍである微細セルロース繊維と、
アンモニアまたは有機アルカリと、
を含み、
前記微細セルロース繊維は、酸化反応によりカルボキシル基が導入されており、前記カルボキシル基の含有量が０．１ｍｍｏｌ／ｇ以上３ｍｍｏｌ／ｇ以下である、
成形用組成物。 Ethylene-vinyl alcohol copolymer, which is the base resin, and
Fine cellulose fibers having a number average fiber diameter of 2-200 nm mixed with 0.5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the base resin.
With ammonia or organic alkali,
Including
A carboxyl group is introduced into the fine cellulose fiber by an oxidation reaction, and the content of the carboxyl group is 0.1 mmol / g or more and 3 mmol / g or less.
Composition for molding.
成形体。 A molded product formed by using the molding composition according to claim 1, wherein the linear thermal expansion coefficient at 30 ° C. to 100 ° C. is 50 ppm / ° C. or less.
Molded body.
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