JP6727531B2 - Method for producing dry solid of cellulose nanofiber - Google Patents
Method for producing dry solid of cellulose nanofiber Download PDFInfo
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- JP6727531B2 JP6727531B2 JP2015123837A JP2015123837A JP6727531B2 JP 6727531 B2 JP6727531 B2 JP 6727531B2 JP 2015123837 A JP2015123837 A JP 2015123837A JP 2015123837 A JP2015123837 A JP 2015123837A JP 6727531 B2 JP6727531 B2 JP 6727531B2
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- 229920002678 cellulose Polymers 0.000 title claims description 21
- 239000001913 cellulose Substances 0.000 title claims description 21
- 239000002121 nanofiber Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000007787 solid Substances 0.000 title description 14
- 238000001035 drying Methods 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 16
- 239000007900 aqueous suspension Substances 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229920003043 Cellulose fiber Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 5
- 239000011122 softwood Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241000589220 Acetobacter Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 241000251557 Ascidiacea Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000013586 microbial product Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Artificial Filaments (AREA)
Description
本発明は、セルロースナノファイバーの乾燥固形物の製造方法に関する。 The present invention relates to a method for producing a dry solid product of cellulose nanofibers.
セルロースナノファイバー（ＣＮＦ）は、水系分散性に優れている約４〜数百ｎｍ程度の大きさの微細繊維であり、食品、化粧品、医療品又は塗料等の粘度の保持、食品原料生地の強化、水分の保持、食品安定性向上、低カロリー添加物又は乳化安定化助剤として利用されていることが期待されている。 Cellulose nanofiber (CNF) is a fine fiber having a size of about 4 to several hundreds nm, which is excellent in water-based dispersibility, and retains the viscosity of foods, cosmetics, medical products or paints, and strengthens food material dough. It is expected to be used as a water retention, food stability improvement, low calorie additive or emulsion stabilization aid.
水に分散している状態（湿潤状態）のＣＮＦを乾燥させた固形物は、微細なセルロース繊維間に水素結合が形成されるため、この乾燥固形物に水を加えても、乾燥前（湿潤状態）の溶解性、分散性、沈降度、及び粘度などの諸特性が復元しない。このため、ＣＮＦは水に分散している状態（湿潤状態）で製造され、乾燥させずに湿潤状態のままで各種用途に使用されることが通常行われている。 The solid matter obtained by drying CNF in a state of being dispersed in water (wet state) has hydrogen bonds formed between fine cellulose fibers. Various properties such as solubility, dispersibility, sedimentation degree, and viscosity of state) are not restored. Therefore, CNF is usually produced in a state of being dispersed in water (wet state), and is usually used for various purposes in a wet state without being dried.
しかしながら、この湿潤状態のＣＮＦを安定させるためには、ＣＮＦに対して数倍〜数百倍の重量の水が必要であり、保存スペースの確保、保存及び輸送コストの増大等、種々の問題点がある。 However, in order to stabilize this CNF in a wet state, several to several hundred times the weight of water is required to the CNF, which causes various problems such as securing storage space, increasing storage and transportation costs. There is.
この問題を解決する手段として、凍結乾燥法や臨界点乾燥法などの他に、有機溶剤で置換処理した後に乾燥する方法（特許文献１）などが提案されている。 As means for solving this problem, in addition to the freeze-drying method, the critical point drying method, and the like, a method of performing substitution treatment with an organic solvent and then drying (Patent Document 1) and the like have been proposed.
しかしながら、ＣＮＦを凍結乾燥した場合、膨大なエネルギーが必要になるとともに、条件によってはＣＮＦの微細繊維間の水が凍結される際に、微細なセルロース繊維間の空隙よりも大きな氷晶の成長がおこり、ＣＮＦの微細繊維同士の会合が発生するなどの問題が発生する。 However, when CNF is freeze-dried, a huge amount of energy is required, and depending on the conditions, when water between the fine fibers of CNF is frozen, the growth of ice crystals larger than the voids between the fine cellulose fibers is caused. Then, problems such as occurrence of association between fine fibers of CNF occur.
また、ＣＮＦの微細繊維の間の空隙は非常に小さい上に、微細なセルロース繊維の表面には多量の水が水和しているため、溶剤置換によって乾燥させるには、多量の溶剤と時間が必要となる。さらに、溶剤に置換することができない水分が内在してしまうために、溶剤の乾燥過程でＣＮＦの微細なセルロース繊維の表面同士が水素結合によって強固に結合してしまう。このため、もとのＣＮＦの状態に復元することは困難である。 Further, since the voids between the fine fibers of CNF are very small and a large amount of water is hydrated on the surface of the fine cellulose fibers, it is necessary to use a large amount of solvent and time for drying by solvent replacement. Will be needed. Furthermore, since water that cannot be replaced with the solvent is present internally, the surfaces of the fine CNF cellulose fibers are firmly bonded to each other by hydrogen bonds during the drying process of the solvent. Therefore, it is difficult to restore the original CNF state.
そこで、本発明は、安定に分散されているＣＮＦ分散液を乾燥させたＣＮＦ乾燥固形物を水に再分散したＣＮＦ分散液の粘度、透明性などの物性が、乾燥前のＣＮＦ分散液と比較して変化が少ない特性（再分散性）を有するＣＮＦの乾燥固形物の製造方法を提供することを目的とする。
Therefore, in the present invention, physical properties such as viscosity and transparency of a CNF dispersion obtained by redispersing a CNF dry solid obtained by drying a stably dispersed CNF dispersion in water are compared with those of a CNF dispersion before drying. It is an object of the present invention to provide a method for producing a dry solid of CNF, which has characteristics (redispersibility) with little change.
本発明は、下記の[１]〜[２]を提供する。
[１] セルロースナノファイバーの水性懸濁液のｐＨを９〜１１に調整した後に、脱水・乾燥させることを特徴とするセルロースナノファイバーの乾燥固形物の製造方法。
[２] [１]に記載の方法により製造されるセルロースナノファイバーの乾燥固形物。
The present invention provides the following [1] to [2].
[1] A method for producing a dry solid of cellulose nanofibers, which comprises dehydrating and drying after adjusting the pH of an aqueous suspension of cellulose nanofibers to 9 to 11.
[2] A dried solid product of cellulose nanofibers produced by the method according to [1].
本発明によれば、安定に分散されているＣＮＦ分散液を乾燥させたＣＮＦ乾燥固形物を水に再分散したＣＮＦ分散液の粘度、透明性などの物性が、乾燥前のＣＮＦ分散液と比較して変化が少ない特性（再分散性）を有するＣＮＦの乾燥固形物の製造方法を提供することができる。 According to the present invention, physical properties such as viscosity and transparency of a CNF dispersion obtained by redispersing a CNF dry solid obtained by drying a stably dispersed CNF dispersion in water are compared with those of a CNF dispersion before drying. Thus, it is possible to provide a method for producing a dry solid product of CNF which has a characteristic of little change (redispersibility).
本発明は、セルロースナノファイバーの水性懸濁液のｐＨを９〜１１に調整した後に、脱水・乾燥させることで得られるセルロースナノファイバーの乾燥固形物は、その固形物を水に分散させた湿潤状態のＣＮＦが、乾燥前の湿潤状態のＣＮＦの溶解性、分散性、沈降度、及び粘度などの諸特性の変化が少ない特性（再分散性）のを有する。 According to the present invention, the dry solid matter of cellulose nanofibers obtained by dehydrating and drying after adjusting the pH of the aqueous suspension of cellulose nanofibers to 9 to 11 is a wet solid obtained by dispersing the solid matter in water. The CNF in the state has a characteristic (redispersibility) in which changes in various properties such as solubility, dispersibility, sedimentation degree and viscosity of the CNF in a wet state before drying are small.
本発明のＣＮＦの乾燥固形物が優れた再分散性を発現する理由は明らかではないが、乾燥前のＣＮＦの水分散液のアルカリ領域（ｐＨ９〜１１）に調整することで、乾燥時による酸劣化、ＣＮＦの凝集を抑制されていると推測される。ただし、ｐＨが高すぎると、アルカリによる劣化、ＣＮＦの結晶構造の変化の恐れがある。 It is not clear why the dried solid product of CNF of the present invention exhibits excellent redispersibility, but by adjusting to the alkaline region (pH 9 to 11) of the aqueous dispersion of CNF before drying, acid by It is presumed that deterioration and aggregation of CNF are suppressed. However, if the pH is too high, there is a risk of deterioration due to alkali and a change in the crystal structure of CNF.
なお、本発明において、セルロースナノファイバーの乾燥固形物とは、水分量が１２重量％以下になるように脱水・乾燥したセルロースナノファイバーを意味する。 In the present invention, the dry solid matter of cellulose nanofibers means the cellulose nanofibers dehydrated and dried so that the water content is 12% by weight or less.
（ｐＨ調整剤）
本発明において、セルロースナノファイバーの水性懸濁液のｐＨを９〜１１に調整するために用いる薬品は特に限定されるものではなく、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化バリウム、水酸化マグネシウム、アンモニア、水酸化銅、水酸化アルミニウム、水酸化鉄、水酸化アンモニウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウムから選ばれた塩基性無機化合物、あるいはアルギニン、リジン、ヒスチジン及びオルニチンから選ばれた塩基性有機化合物などを例示することができる。
(PH adjuster)
In the present invention, the chemicals used to adjust the pH of the aqueous suspension of cellulose nanofibers to 9 to 11 are not particularly limited, and include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, A basic inorganic compound selected from magnesium hydroxide, ammonia, copper hydroxide, aluminum hydroxide, iron hydroxide, ammonium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate and magnesium oxide, Alternatively, a basic organic compound selected from arginine, lysine, histidine and ornithine can be exemplified.
（セルロースナノファイバー）
本発明において、セルロースナノファイバー（ＣＮＦ）は、繊維幅が４〜５００ｎｍ程度、アスペクト比が１００以上の微細繊維であり、パルプなどのセルロース原料を解繊することによって得ることができる。
(Cellulose nanofiber)
In the present invention, the cellulose nanofiber (CNF) is a fine fiber having a fiber width of about 4 to 500 nm and an aspect ratio of 100 or more, and can be obtained by defibrating a cellulose raw material such as pulp.
（セルロース原料）
本発明において、セルロース原料としては、植物（例えば、木材、竹、麻、ジュート、ケナフ、農地残廃物、布、パルプ（針葉樹未漂白クラフトパルプ（ＮＵＫＰ）、針葉樹漂
白クラフトパルプ（ＮＢＫＰ）、広葉樹未漂白クラフトパルプ（ＬＵＫＰ）、広葉樹漂白クラフトパルプ（ＬＢＫＰ）、針葉樹未漂白サルファイトパルプ（ＮＵＳＰ）、針葉樹漂白サルファイトパルプ（ＮＢＳＰ）サーモメカニカルパルプ（ＴＭＰ）、再生パルプ、古紙等）、動物（例えばホヤ類）、藻類、微生物（例えば酢酸菌（アセトバクター））、微生物産生物等を起源とするものが知られており、本発明ではそのいずれも使用できる。好ましくは植物又は微生物由来のセルロース繊維であり、より好ましくは植物由来のセルロース繊維である。
(Cellulose raw material)
In the present invention, as the cellulose raw material, plants (for example, wood, bamboo, hemp, jute, kenaf, agricultural land waste, cloth, pulp (softwood unbleached kraft pulp (NUKP), softwood bleached kraft pulp (NBKP), broadleaf wood) Bleached kraft pulp (LUKP), hardwood bleached kraft pulp (LBKP), softwood unbleached sulfite pulp (NUSP), softwood bleached sulfite pulp (NBSP) thermomechanical pulp (TMP), recycled pulp, waste paper, etc., animals (eg Those originating from ascidians), algae, microorganisms (eg acetic acid bacteria (acetobacter)), microbial products, etc. are known, and any of them can be used in the present invention. And more preferably plant-derived cellulose fibers.
（解繊）
本発明において、解繊する装置は特に限定されないが、高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式などの装置を用いて前記水分散体に強力なせん断力を印加することが好ましい。特に、効率よく解繊するには、前記水分散体に５０ＭＰａ以上の圧力を印加し、かつ強力なせん断力を印加できる湿式の高圧または超高圧ホモジナイザを用いることが好ましい。前記圧力は、より好ましくは１００ＭＰａ以上であり、さらに好ましくは１４０ＭＰａ以上である。また、高圧ホモジナイザでの解繊・分散処理に先立って、必要に応じて、高速せん断ミキサーなどの公知の混合、攪拌、乳化、分散装置を用いて、上記のＣＮＦに予備処理を施すことも可能である。
(Defibration)
In the present invention, the device for defibration is not particularly limited, but a strong shearing force is applied to the water dispersion using a device such as a high-speed rotation type, colloid mill type, high pressure type, roll mill type, or ultrasonic type. Is preferred. In particular, for efficient defibration, it is preferable to use a wet high-pressure or ultra-high-pressure homogenizer that can apply a pressure of 50 MPa or more and a strong shearing force to the water dispersion. The pressure is more preferably 100 MPa or more, further preferably 140 MPa or more. If necessary, prior to the defibration/dispersion treatment with a high-pressure homogenizer, the above CNF can be pretreated by using a known mixing, stirring, emulsifying, or dispersing device such as a high-speed shear mixer. Is.
（乾燥方法）
本発明方法において、脱水・乾燥方法としては、従来公知のものであれば良く、例えば、スプレイドライ、圧搾、風乾、熱風乾燥、及び真空乾燥を挙げることができる。本発明方法で具体的に用いる乾燥装置の例としては、以下のようなものである。すなわち、連続式のトンネル乾燥装置、バンド乾燥装置、縦型乾燥装置、垂直ターボ乾燥装置、多重段円板乾燥装置、通気乾燥装置、回転乾燥装置、気流乾燥装置、スプレードライヤ乾燥装置、噴霧乾燥装置、円筒乾燥装置、ドラム乾燥装置、スクリューコンベア乾燥装置、加熱管付回転乾燥装置、振動輸送乾燥装置等、回分式の箱型乾燥装置、通気乾燥装置、真空箱型乾燥装置、及び撹拌乾燥装置等の乾燥装置を単独で又は２つ以上組み合わせて用いることができる。
(Drying method)
In the method of the present invention, the dehydration/drying method may be any conventionally known method, and examples thereof include spray drying, pressing, air drying, hot air drying, and vacuum drying. Examples of the drying device specifically used in the method of the present invention are as follows. That is, a continuous tunnel dryer, a band dryer, a vertical dryer, a vertical turbo dryer, a multi-stage disc dryer, an aeration dryer, a rotary dryer, an air flow dryer, a spray dryer dryer, a spray dryer. , Cylindrical dryer, drum dryer, screw conveyor dryer, rotary dryer with heating tube, vibration transport dryer, batch-type box dryer, aeration dryer, vacuum box dryer, stirring dryer, etc. These drying devices can be used alone or in combination of two or more.
これらの中でも、ドラム乾燥装置を用いることが、均一に被乾燥物に熱エネルギーを直接供給するためエネルギー効率の点から好ましい。また、乾燥前の水を含んだセルロースナノファイバーに於いて、乾燥処理効率を上げるために、水分をできるだけ少なくする前濃縮処理を行うことが通常行われるが、この際液粘度の上昇が乾燥処理の障害となる。これに対して、ドラムにブレードやダイ等により薄膜を形成させて乾燥させる事により、乾燥処理をより効率的に、均一に短時間で行うことができる。更に、ドラム乾燥装置は必要以上に熱を加えずに、直ちに乾燥物を回収できる点からも好ましい。 Among these, it is preferable to use the drum dryer from the viewpoint of energy efficiency because the heat energy is directly supplied directly to the material to be dried. In addition, in the case of water-containing cellulose nanofibers before drying, in order to improve the efficiency of the drying process, a pre-concentration process is usually performed to reduce the water content as much as possible. Becomes an obstacle. On the other hand, by forming a thin film on the drum with a blade, a die or the like and drying the film, the drying process can be performed more efficiently and uniformly in a short time. Furthermore, the drum dryer is preferable in that the dried product can be immediately recovered without applying excessive heat.
以下、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定される
ものではない。
＜ＣＮＦの製造＞
針葉樹由来の漂白済み未叩解クラフトパルプ（白色度８５％）を水で１．０％（ｗ／ｖ）に調整し、超高圧ホモジナイザー（２０℃、１５０Ｍｐａ）で５０回処理して、セルロースナノファイバー分散液を得た。得られた繊維は、平均繊維径が６０ｎｍ、アスペクト比が１１０であった。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
<Manufacture of CNF>
Bleached unbeaten kraft pulp from softwood (85% whiteness) is adjusted to 1.0% (w/v) with water and treated with an ultra-high pressure homogenizer (20°C, 150Mpa) 50 times to give cellulose nanofibers. A dispersion was obtained. The obtained fiber had an average fiber diameter of 60 nm and an aspect ratio of 110.
（平均繊維径、アスペクト比の測定方法）
セルロース繊維の平均繊維径および平均繊維長は、電界放出型走査電子顕微鏡（ＦＥ−ＳＥＭ）を用いて、ランダムに選んだ２００本の繊維について解析した。なおアスペクト比は下記の式により算出した：
アスペクト比＝平均繊維長／平均繊維径
(Measuring method of average fiber diameter and aspect ratio)
The average fiber diameter and the average fiber length of the cellulose fibers were analyzed for 200 randomly selected fibers by using a field emission scanning electron microscope (FE-SEM). The aspect ratio was calculated by the following formula:
Aspect ratio = average fiber length / average fiber diameter
＜実施例１＞
上記ＣＮＦ（平均繊維径：６０ｎｍ、アスペクト比：１１０）の０．７質量％水性懸濁液をＴＫホモミキサー（１２，０００ｒｐｍ）で６０分間攪拌した。この水性懸濁液に、水酸化ナトリウム水溶液０．５％を加え、ｐＨを９に調整した後、蒸気圧力０．５ＭＰａ．Ｇ、ドラム回転数２ｒｐｍのドラム乾燥機Ｄ０３０３（カツラギ工業）で乾燥し、水分量５重量％のＣＮＦの乾燥固形物を得た。
<Example 1>
A 0.7 mass% aqueous suspension of the above CNF (average fiber diameter: 60 nm, aspect ratio: 110) was stirred for 60 minutes with a TK homomixer (12,000 rpm). To this aqueous suspension, 0.5% aqueous sodium hydroxide solution was added to adjust the pH to 9, and then the vapor pressure was 0.5 MPa. G was dried with a drum dryer D0303 (Katsuragi Industry Co., Ltd.) having a drum rotation speed of 2 rpm to obtain a dry solid of CNF having a water content of 5% by weight.
次に、上記で得られた乾燥固形物に０．７質量％水性懸濁液になるように水を添加し、ＴＫホモミキサー（１２，０００ｒｐｍ）を用いて６０分間攪拌し、ＣＮＦを再分散した水性懸濁液を得た。 Next, water was added to the dry solid obtained above so as to form a 0.7 mass% aqueous suspension, and the mixture was stirred for 60 minutes using a TK homomixer (12,000 rpm) to redisperse CNF. An aqueous suspension was obtained.
（Ｂ型粘度の測定）
ＣＮＦ（固形分０．７％、２５℃）のＢ型粘度を測定した。なおＢ型粘度の測定条件は、回転数３０ｒｐｍ、３分とした。
（透明度の測定）
ＣＮＦ分散液（固形分０．１％）の透明度（６６０ｎｍ 光の透過率）をＵＶ分光光度計 Ｕ−３０００（日立ハイテク）を用いて測定した。
(B-type viscosity measurement)
The B type viscosity of CNF (solid content 0.7%, 25° C.) was measured. The measurement conditions for the B-type viscosity were a rotation speed of 30 rpm and 3 minutes.
(Measurement of transparency)
The transparency (transmittance of 660 nm light) of the CNF dispersion liquid (solid content 0.1%) was measured using a UV spectrophotometer U-3000 (Hitachi High-Tech).
（復元率の評価）
Ｂ型粘度、透明度の復元率は以下の式で算出した。
復元率（％）＝（乾燥前の粘度あるいは透明度）／（再分散後の粘度あるいは透明度）×１００
(Evaluation of restoration rate)
The B-type viscosity and the restoration rate of transparency were calculated by the following formulas.
Recovery rate (%)=(viscosity or transparency before drying)/(viscosity or transparency after redispersion)×100
＜実施例２＞
ｐＨを１１に調整以外は実施例１と同様にして行った。
<Example 2>
The same procedure as in Example 1 was carried out except that the pH was adjusted to 11.
＜比較例１＞
ｐＨ調整を行わなかった以外は実施例１と同様にして行ったが、水性懸濁液にＣＮＦの凝集物の沈降物が著しく発生したため、評価することができなかった。
<Comparative Example 1>
The procedure was performed in the same manner as in Example 1 except that the pH was not adjusted, but it was not possible to evaluate because the precipitation of CNF aggregates remarkably occurred in the aqueous suspension.
＜比較例２＞
ｐＨを８に調整以外は実施例１と同様にして行ったが、水性懸濁液にＣＮＦの凝集物の沈降物が著しく発生したため、評価することができなかった。
<Comparative example 2>
The procedure was performed in the same manner as in Example 1 except that the pH was adjusted to 8. However, it was not possible to evaluate because the precipitation of aggregates of CNFs significantly occurred in the aqueous suspension.
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