JP6293780B2 - セルロースの触媒酸化方法、およびセルロース製品の製造方法 - Google Patents
セルロースの触媒酸化方法、およびセルロース製品の製造方法 Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims description 110
- 230000003647 oxidation Effects 0.000 title claims description 106
- 229920002678 cellulose Polymers 0.000 title claims description 79
- 239000001913 cellulose Substances 0.000 title claims description 79
- 238000000034 method Methods 0.000 title claims description 60
- 230000003197 catalytic effect Effects 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000012429 reaction media Substances 0.000 claims description 43
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 28
- 239000007800 oxidant agent Substances 0.000 claims description 28
- 230000001590 oxidative effect Effects 0.000 claims description 26
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 239000004155 Chlorine dioxide Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 14
- 239000012190 activator Substances 0.000 claims description 12
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical compound [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002201 Oxidized cellulose Polymers 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 229940107304 oxidized cellulose Drugs 0.000 claims description 10
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 9
- -1 bromine compound Chemical class 0.000 claims description 8
- 150000007942 carboxylates Chemical class 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910001919 chlorite Inorganic materials 0.000 claims description 6
- 229910052619 chlorite group Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000002657 fibrous material Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 3
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- 238000006243 chemical reaction Methods 0.000 description 65
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 36
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 25
- 239000002609 medium Substances 0.000 description 21
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 14
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 13
- 238000007086 side reaction Methods 0.000 description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
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- 229920003043 Cellulose fiber Polymers 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
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- 238000010979 pH adjustment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical group OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
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- 229940077239 chlorous acid Drugs 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- UXBLSWOMIHTQPH-UHFFFAOYSA-N 4-acetamido-TEMPO Chemical compound CC(=O)NC1CC(C)(C)N([O])C(C)(C)C1 UXBLSWOMIHTQPH-UHFFFAOYSA-N 0.000 description 1
- SFXHWRCRQNGVLJ-UHFFFAOYSA-N 4-methoxy-TEMPO Chemical compound COC1CC(C)(C)N([O])C(C)(C)C1 SFXHWRCRQNGVLJ-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- 238000007068 beta-elimination reaction Methods 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
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- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
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- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Wood Science & Technology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
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Description
いくらかの酸化剤は10%の濃度においてMCミキサによって、いくらかはMCパルパーによって、11%の濃度まで実施された。高濃度における酸化は、理論上より選択的である。なぜなら、所望の反応は繊維内において生じ、望まない副反応は液相において生じるからである。実際のところ、TEMPO触媒および二酸化塩素の量を、濃度増加によって投入された繊維量に関して減少させることが可能である。我々の試験において、我々は中濃度までの濃度上昇にて、TEMPOを用いる酸化の実施において問題を見出すことはなかった。従来技術において示された典型的な反応は、4%未満の1%濃度で実施される。図3は、濃度が1〜4%の低濃度範囲において増加するとき、酸化の選択性(消費される次亜塩素酸あたりに形成されるカルボン酸)が向上することを示す。
酸化パルプ(0.82mmol COOH/g パルプ)試料は、パルプを高頻度で反対方向からの衝撃にさらす装置であって、間隔を空けた衝撃羽根によって形成される流路を備える同心円筒状ロータを構成する装置である「Atrex」分散器を用いてフィブリル化された。
濁度は、光学濁度測定装置を用いて定量的に測定されてもよい。濁度を定量的に測定するために利用可能な市販の濁度計がいくつか存在する。本実施例において、比濁法に基づく方法が使用される。目盛付き比濁計からの濁度の単位は、比濁計濁度単位(NTU)と称される。測定装置(濁度計)は、調整され、標準調整試料を用いて制御され、希釈されたNFC試料の粘度の測定に続く。
NFCは脱イオン水で0.5の濃度まで希釈され、200gの混合物は3×10秒間にわたってビュッヒミキサ(B−400、最大2100W、ビュッヒレイバテクニク アーゲー、スイス)を用いて均一化された。
Claims (20)
- 触媒として複素環ニトロキシルラジカルと、酸素源として作用する主酸化剤と、複素環ニトロキシルラジカルの活性化剤とを用いるセルロースの触媒酸化方法であって、
前記酸化は、8〜12%の濃度のセルロースパルプである反応媒体中において、反応器内の前記反応媒体を、前記反応器に戻る循環ループを通す前記反応媒体の循環を通して混合することによって実施され、
臭素化合物を用いないことを特徴とする方法。 - 前記反応媒体は、9〜11%の濃度のセルロースパルプであることを特徴とする請求項1に記載の方法。
- 前記反応媒体は、10〜11%の濃度のセルロースパルプであることを特徴とする請求項1に記載の方法。
- 主酸化剤および/またはpH調整剤の少なくとも一部が、前記反応媒体の循環に添加されることを特徴とする請求項1〜3のいずれか1項に記載の方法。
- 二酸化塩素または3級アミンが、複素環ニトロキシルラジカルの活性化剤として使用されることを特徴とする請求項1〜4のいずれか1項に記載の方法。
- 次亜塩素酸塩が、主酸化剤として使用されることを特徴とする請求項1〜5のいずれか1項に記載の方法。
- セルロースは、1段階または2段階で所望のレベルまで酸化され、
2段階の酸化において、第1触媒工程中で、二酸化塩素が活性化剤として使用され、次亜塩素酸塩が主酸化剤として使用され、亜塩素酸塩が第2工程の酸化を完了する酸化剤として使用され、第2工程のpHが第1工程に比べて低いことを特徴とする請求項1〜6のいずれか1項に記載の方法。 - 第1工程間のpHは6〜10であり、第2工程間のpHは1.5〜4であることを特徴とする請求項7に記載の方法。
- 前記触媒酸化は、pH7〜9、20〜50℃で実施されることを特徴とする請求項6に記載の方法。
- 前記酸化は、0.5〜1.4mmol COOH/g パルプのレベルまで実施されることを特徴とする請求項1〜9のいずれか1項に記載の方法。
- 前記酸化後、酸化セルロースはさらに処理され、酸化セルロースが含まれる繊維性原料がナノフィブリル化セルロースに分解されることを特徴とする請求項1〜10のいずれか1項に記載の方法。
- 酸化に曝されるセルロースは、繊維性原料、特に植物材料から得られる繊維におけるセルロースであることを特徴とする請求項1〜11のいずれか1項に記載の方法。
- セルロース製品を作製するための方法であって、
−繊維性出発材料、特に植物材料から得られる繊維を、請求項1〜10のいずれか1項に記載の方法による酸化に曝し、酸化繊維性材料を得ることと、
−酸化繊維性原料を分解することとを含むことを特徴とする方法。 - 酸化繊維性原料は、ナノフィブリル化セルロース(NFC)まで分解されることを特徴とする請求項13に記載の方法。
- ナノフィブリル化セルロースの小繊維は、2〜20nmの平均直径と、0.3〜5μmの平均長さとを有することを特徴とする請求項14に記載の方法。
- ナノフィブリル化セルロースは、水中における0.1%濃度で測定されたとき、70未満NTU(比濁計濁度単位)の濁度を有することを特徴とする請求項14または15に記載の方法。
- ナノフィブリル化セルロースは、水中における0.1%濃度で測定されたとき、20〜60NTU(比濁計濁度単位)の濁度を有することを特徴とする請求項14または15に記載の方法。
- ナノフィブリル化セルロースは、水中における0.5%濃度で測定されたとき、10000〜50000Pa・sゼロせん断粘度と、8〜40Paの降伏応力とを有することを特徴とする請求項14〜16のいずれか1項に記載の方法。
- 酸化セルロースのカルボン酸塩含有量は、少なくとも0.6mmol COOH/g パルプであることを特徴とする請求項14〜18のいずれか1項に記載の方法。
- 酸化セルロースのカルボン酸塩含有量は、0.7〜1.4mmol COOH/g パルプであることを特徴とする請求項14〜18のいずれか1項に記載の方法。
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