JP5544747B2 - Method for producing fine fibrous cellulose - Google Patents
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- JP5544747B2 JP5544747B2 JP2009102630A JP2009102630A JP5544747B2 JP 5544747 B2 JP5544747 B2 JP 5544747B2 JP 2009102630 A JP2009102630 A JP 2009102630A JP 2009102630 A JP2009102630 A JP 2009102630A JP 5544747 B2 JP5544747 B2 JP 5544747B2
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- 229920002678 cellulose Polymers 0.000 title claims description 70
- 239000001913 cellulose Substances 0.000 title claims description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 50
- 238000011282 treatment Methods 0.000 claims description 40
- 229920003043 Cellulose fiber Polymers 0.000 claims description 39
- 239000000835 fiber Substances 0.000 claims description 39
- 238000010298 pulverizing process Methods 0.000 claims description 21
- 239000007900 aqueous suspension Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004575 stone Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 4
- 235000010980 cellulose Nutrition 0.000 description 63
- 238000000034 method Methods 0.000 description 32
- 239000000725 suspension Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 11
- 239000000123 paper Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 241000186514 Warburgia ugandensis Species 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 241001474374 Blennius Species 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
- 108010059892 Cellulase Proteins 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Description
本発明は、微細繊維状セルロースを効率よく製造する方法であり、最大繊維幅１０００ｎｍ以下の微細繊維状セルロースを簡便な方法により効率的に製造する方法を提供することを目的とする。 The present invention is a method for efficiently producing fine fibrous cellulose, and an object thereof is to provide a method for efficiently producing fine fibrous cellulose having a maximum fiber width of 1000 nm or less by a simple method.
近年、物質をナノメートルサイズの大きさにすることによりバルクや分子レベルとは異なる物性を得ることを目的としたナノテクノロジーが注目されている。一方で、石油資源の代替および環境意識の高まりから再生産可能な天然繊維の応用にも注目が集まっている。
天然繊維の中でもセルロース繊維、とりわけ木材由来のセルロース繊維（パルプ）は主に紙製品として幅広く使用されている。紙に使用されるセルロース繊維の幅は１０〜５０μｍのものがほとんどである。このようなセルロース繊維から得られる紙（シート）は不透明であり、不透明であるが故に印刷用紙として幅広く利用されている。一方、セルロース繊維をレファイナーやニーダー、サンドグラインダーなどで処理（叩解、粉砕）し、セルロース繊維を微細化（ミクロフィブリル化）すると透明紙（グラシン紙等）が得られる。しかし、この透明紙の透明性は半透明レベルであり、光の透過性は高分子フィルムに比べると低く、曇り度合い（ヘーズ値）も大きい。
In recent years, nanotechnology aimed at obtaining physical properties different from the bulk and molecular levels by making a material a nanometer size has attracted attention. On the other hand, attention is also focused on the application of natural fibers that can be regenerated due to the substitution of petroleum resources and the growing environmental awareness.
Among natural fibers, cellulose fibers, particularly wood-derived cellulose fibers (pulp) are widely used mainly as paper products. Most cellulose fibers used for paper have a width of 10 to 50 μm. Paper (sheet) obtained from such cellulose fibers is opaque and is widely used as printing paper because it is opaque. On the other hand, when the cellulose fiber is treated (beating, pulverizing) with a refiner, kneader, sand grinder or the like, and the cellulose fiber is refined (microfibril), a transparent paper (glassine paper or the like) is obtained. However, the transparency of the transparent paper is at a semi-transparent level, the light transmittance is lower than that of the polymer film, and the haze level (haze value) is large.
また、セルロース繊維は弾性率が高く、熱膨張率の低いセルロース結晶の集合体であり、セルロース繊維を樹脂と複合化することによって耐熱寸法安定性が高まるため、積層板などに利用されている。ただし、通常のセルロース繊維は結晶の集合体であり、筒状の空隙のある繊維のため寸法安定性には限界がある。
さらに、セルロース繊維を機械的に粉砕し、その繊維幅を５０ｎｍ以下とした微細繊維状セルロースの水分散液は透明である。他方、微細繊維状セルロースシートは空隙を含むため白く乱反射し、不透明性が高くなるが、微細繊維状セルロースシートに樹脂を含浸すると空隙が埋まるため、透明なシートが得られる。微細繊維状セルロースシートの繊維はセルロース結晶の集合体であり、非常に剛直で、また、繊維幅が小さいため、通常のセルロースシート（紙）に比べると同質量において繊維の本数が飛躍的に多くなり、樹脂と複合化すると樹脂中で細い繊維がより均一かつ緻密に分散し、耐熱寸法安定性が飛躍的に高まる。さらに、繊維が細いため透明性も高い。このような特性を有する微細繊維状セルロースの複合体は、有機ＥＬや液晶ディスプレイ用のフレキシブル透明基板（曲げたり折ったりすることのできる透明基板）として非常に大きな期待が寄せられている。
Cellulose fibers are aggregates of cellulose crystals having a high elastic modulus and a low coefficient of thermal expansion, and heat resistant dimensional stability is increased by combining the cellulose fibers with a resin, so that they are used for laminates and the like. However, ordinary cellulose fibers are aggregates of crystals and have a limit in dimensional stability due to fibers having a cylindrical void.
Furthermore, the aqueous dispersion of fine fibrous cellulose having mechanically pulverized cellulose fibers and having a fiber width of 50 nm or less is transparent. On the other hand, since the fine fibrous cellulose sheet contains voids, it is diffusely reflected white and becomes highly opaque. However, when the fine fibrous cellulose sheet is impregnated with a resin, the voids are filled, so that a transparent sheet is obtained. The fibers of the fine fibrous cellulose sheet are aggregates of cellulose crystals, very stiff, and have a small fiber width, so that the number of fibers is dramatically greater at the same mass than ordinary cellulose sheets (paper). Thus, when combined with a resin, fine fibers are more uniformly and densely dispersed in the resin, and the heat-resistant dimensional stability is dramatically increased. Furthermore, since the fibers are thin, the transparency is high. The composite of fine fibrous cellulose having such characteristics is expected to be very large as a flexible transparent substrate (a transparent substrate that can be bent or folded) for organic EL or liquid crystal displays.
ところで、セルロース繊維を機械的に粉砕して微細なセルロース繊維を製造する方法として、回転型ミルやジェットミルのような高速衝撃粉砕法、ロールクラッシャー法などが主に使用されている。しかしながら、セルロースは有機物であり、柔らかいため機械的な粉砕処理のみでは微細なセルロース繊維を得ることが難しく、本発明の最大繊維幅１０００ｎｍ以下の微細繊維状セルロースを得るためには、化学的処理と機械的粉砕処理とを組合せた方法が一般的に使用されている。 By the way, as a method for mechanically pulverizing cellulose fibers to produce fine cellulose fibers, a high-speed impact pulverization method such as a rotary mill and a jet mill, a roll crusher method, and the like are mainly used. However, since cellulose is an organic substance and is soft, it is difficult to obtain fine cellulose fibers only by mechanical pulverization treatment. In order to obtain fine fibrous cellulose having a maximum fiber width of 1000 nm or less according to the present invention, chemical treatment and A method combined with mechanical grinding is generally used.
具体的に、化学的処理と機械的粉砕処理とを組合せた方法としては、パルプを軽度に加水分解し、濾過水洗後、乾燥、粉砕して一部非晶領域を含むセルロース微粒子の製造方法や精製パルプを塩酸または硫酸で加水分解して結晶領域のみを残して微粉化する技術が開示されているが、微細化のレベルとしては充分ではなく、得られた微細繊維状セルロースの水系懸濁液の透明性も不充分である（非特許文献１）。 Specifically, as a method of combining the chemical treatment and the mechanical pulverization treatment, the pulp is slightly hydrolyzed, washed with filtered water, dried and pulverized, and a method for producing cellulose fine particles partially containing amorphous regions, Although a technology for hydrolyzing a refined pulp with hydrochloric acid or sulfuric acid to make a fine powder leaving only a crystalline region is disclosed, it is not sufficient as a level of fineness, and the obtained aqueous suspension of fine fibrous cellulose Is also insufficient in transparency (Non-patent Document 1).
微小な繊維幅の繊維状セルロースの製造方法として、繊維状セルロースの水懸濁液を少なくとも３０００ｐｓｉの圧力差で小径オリフィスを高速度で通過させる方法、すなわち高圧均質化装置（高圧ホモジナイザー）により繊維状セルロース懸濁液を処理する方法が開示されている（特許文献１、２）が、繊維状セルロース懸濁液に高圧をかけて細いオリフィスを通す必要があるため、処理効率が非常に低いという問題がある。 As a method for producing fibrous cellulose having a small fiber width, a fibrous cellulose aqueous suspension is passed through a small-diameter orifice at a high speed with a pressure difference of at least 3000 psi, that is, fibrous by a high-pressure homogenizer (high-pressure homogenizer). Although a method for treating a cellulose suspension has been disclosed (Patent Documents 1 and 2), it is necessary to apply a high pressure to the fibrous cellulose suspension and pass through a narrow orifice, so that the treatment efficiency is very low. There is.
紙の紙力を増加させたり、透気度を高めることができる微細繊維化セルロースの製造方法として、予め叩解処理したパルプを粒度が１６〜１２０番の砥粒からなる砥粒板を複数枚擦り合わせ配置した砥粒板擦り合わせ装置を用いて微細化する技術が開示されている（特許文献３）が、微細化に供するパルプスラリーの固形分濃度を高くすると急激に処理効率が低下するという問題が依然として残されている。 As a method for producing fine fiberized cellulose that can increase the paper strength of paper or increase the air permeability, a plurality of abrasive plates made of abrasive grains having a particle size of No. 16 to 120 are rubbed in advance. Although the technique which refines | miniaturizes using the abrasive-plate rubbing apparatus arrange | positioned together is disclosed (patent document 3), if the solid content concentration of the pulp slurry used for refinement | miniaturization is made high, the problem that processing efficiency will fall rapidly. Is still left.
Ｎ−オキシル化合物によるセルロースの表面酸化反応を利用し、最大繊維径１０００ｎｍ以下かつ数平均繊維径が２〜１５０ｎｍであり、セルロースの水酸基の一部がカルボキシル基およびアルデヒド基からなる群から選ばれる少なくとも１つの官能基に酸化されており、且つセルロースＩ型結晶構造を有する微細セルロースを提供する技術（特許文献４）が開示されているが、工程が複雑で実用性に乏しい。 Utilizing the surface oxidation reaction of cellulose by an N-oxyl compound, the maximum fiber diameter is 1000 nm or less and the number average fiber diameter is 2 to 150 nm, and at least a part of the hydroxyl group of cellulose is selected from the group consisting of a carboxyl group and an aldehyde group A technique (Patent Document 4) that provides fine cellulose that has been oxidized to one functional group and has a cellulose I-type crystal structure is disclosed, but the process is complicated and the practicality is poor.
また、酵素または薬品により前処理した繊維状セルロースを振動ミル粉砕機にて湿式粉砕する技術が開示されている（特許文献５）が、酵素反応や化学反応の効率が依然として低く、生産性の高い微細繊維状セルロースの製造方法とはいえない。 Further, a technique for wet-grinding fibrous cellulose pretreated with an enzyme or a chemical by a vibration mill grinder is disclosed (Patent Document 5), but the efficiency of the enzyme reaction and chemical reaction is still low and the productivity is high. It cannot be said that it is a manufacturing method of a fine fibrous cellulose.
上記のように、繊維状セルロースを微細化する技術が種々開示されているが、工業的なレベルの生産性を確保するまでには至っておらず、繊維状セルロースを微細化する簡便な方法の提供が望まれている。 As described above, various techniques for refining fibrous cellulose have been disclosed, but the industrial level of productivity has not been ensured, and a simple method for refining fibrous cellulose has been provided. Is desired.
本発明は、微細繊維状セルロースを効率よく製造する方法であり、最大繊維幅１０００ｎｍ以下の微細繊維状セルロースを簡便な方法により効率的に製造する方法を提供するものである。 The present invention is a method for efficiently producing fine fibrous cellulose, and provides a method for efficiently producing fine fibrous cellulose having a maximum fiber width of 1000 nm or less by a simple method.
本発明は、以下の各発明を包含する。
（１）最大繊維幅１０００ｎｍ以下の微細繊維状セルロースの製造方法において、セルロース繊維をオゾン処理した後、水に分散し、得られたセルロース繊維の水系懸濁液を粉砕処理する微細繊維状セルロースの製造方法。
The present invention includes the following inventions.
(1) In the method for producing fine fibrous cellulose having a maximum fiber width of 1000 nm or less, after the cellulose fiber is treated with ozone, it is dispersed in water, and the aqueous suspension of the obtained cellulose fiber is pulverized and treated. Production method.
（２）オゾン処理におけるオゾン添加率が絶乾セルロース繊維質量当たり０．１〜３０質量％である（１）に記載の微細繊維状セルロースの製造方法。 (2) The manufacturing method of the fine fibrous cellulose as described in (1) whose ozone addition rate in ozone treatment is 0.1-30 mass% per the absolute dry cellulose fiber mass.
（３）粉砕処理が石臼粉砕、高圧ホモジナイザー、ボールミルから選択される少なくとも１種である（１）または（２）に記載の微細繊維状セルロースの製造方法。 (3) The method for producing fine fibrous cellulose according to (1) or (2), wherein the pulverization treatment is at least one selected from stone milling, high-pressure homogenizer, and ball mill.
（４）粉砕処理における水系懸濁液の濃度が０．１〜３質量％である（１）〜（３）のいずれか１項に記載の微細繊維状セルロースの製造方法。 (4) The manufacturing method of the fine fibrous cellulose of any one of (1)-(3) whose density | concentration of the aqueous suspension in a grinding | pulverization process is 0.1-3 mass%.
（５）オゾン処理の後に洗浄処理、粉砕処理を順次行う（１）〜（４）のいずれか１項に記載の微細繊維状セルロースの製造方法。 (5) The method for producing fine fibrous cellulose according to any one of (1) to (4), wherein washing treatment and pulverization treatment are sequentially performed after the ozone treatment.
本発明者らは、セルロース繊維を膨潤させ得る方法を種々検討し、セルロース繊維に前処理としてオゾン処理を施すことによりセルロース繊維を膨潤し、微細なフィブリル間、さらには結晶領域を構成するミクロフィブリル間の結合力を弱め、後続する粉砕処理により原料の繊維状セルロースを効率よく微細化できることを見出した。 The present inventors have studied various methods that can swell cellulose fibers, and by subjecting cellulose fibers to ozone treatment as a pretreatment, cellulose fibers are swollen to form microfibrils between fine fibrils and further to form crystal regions. It was found that the fibrous cellulose as a raw material can be efficiently refined by the subsequent pulverization treatment by weakening the bonding force between them.
従来から、セルロース繊維を膨潤させる方法として、酵素（キシラナーゼ、セルラーゼ）処理や薬品（アルカリ、塩化亜鉛、エチレンジアミン、チオ尿素、ベンゼンスルホン酸）処理が知られているが、本発明ではオゾン処理を採用したことに特徴を有するものである。本発明によって、微細繊維状セルロースを非常に効率よく生産できる製造方法を提供することができる。 Conventionally, enzyme (xylanase, cellulase) treatment and chemical (alkali, zinc chloride, ethylenediamine, thiourea, benzenesulfonic acid) treatment are known as methods for swelling cellulose fibers, but ozone treatment is adopted in the present invention. It has the feature in having done. By this invention, the manufacturing method which can produce a fine fibrous cellulose very efficiently can be provided.
以下、本発明について詳細に説明する。
本発明においては、セルロース繊維を微細化するに当たり、前処理としてオゾン処理を採用するものである。オゾン処理は他の酵素処理や薬品処理と比べて、反応時間が短い、洗浄負荷が低いといった優れた特性がある。但し、オゾン処理を過度に進めるとセルロース繊維の分解・切断が進行し過ぎ、粉砕処理により繊維状セルロースの微細化と同時に微小化も早く進行するため、要求される微細繊維状セルロースの物性ごとに処理条件を適正に調節する必要がある。
Hereinafter, the present invention will be described in detail.
In the present invention, ozone treatment is adopted as a pretreatment for refining cellulose fibers. Ozone treatment has excellent characteristics such as shorter reaction time and lower washing load than other enzyme treatments and chemical treatments. However, if the ozone treatment is advanced excessively, the decomposition and cutting of the cellulose fibers will proceed excessively, and the pulverization process will make the fibrous cellulose finer and at the same time make it finer, so each required physical property of the fine fibrous cellulose. It is necessary to adjust the processing conditions appropriately.
オゾン処理は、セルロース繊維をオゾン分子と接触させて、酸化反応とともにセルロース繊維を膨潤させることを目的とする。該オゾン処理は、セルロース繊維を暴露することによって行われる。暴露方法は、オゾンが存在する雰囲気に所定時間保持する方法、オゾン気流中に所定時間暴露する方法等適宜の方法で行うことができる。 The purpose of the ozone treatment is to bring the cellulose fiber into contact with ozone molecules and swell the cellulose fiber together with the oxidation reaction. The ozone treatment is performed by exposing cellulose fibers. The exposure method can be performed by an appropriate method such as a method of holding in an atmosphere in which ozone exists for a predetermined time, a method of exposing in an ozone stream for a predetermined time.
オゾンは、空気、酸素ガス、または酸素添加空気等の酸素含有気体を公知のオゾン発生装置に供給することによって発生させることができる。得られたオゾン含有気体を、上記材料を保持してある容器、槽等に導入してオゾン処理を行う。オゾン含有気体中のオゾン濃度、セルロース繊維に対するオゾン添加率、処理温度、処理時間等の諸条件は、セルロース繊維を膨潤させるという目的に応じて適宜定めることができる。 Ozone can be generated by supplying an oxygen-containing gas such as air, oxygen gas, or oxygen-added air to a known ozone generator. The obtained ozone-containing gas is introduced into a container, tank, or the like holding the above materials to perform ozone treatment. Various conditions such as the ozone concentration in the ozone-containing gas, the ozone addition rate with respect to the cellulose fiber, the treatment temperature, and the treatment time can be appropriately determined according to the purpose of swelling the cellulose fiber.
ここで、オゾン含有気体中のオゾン濃度としては、５０〜１０００ｇ／ｍ３であることが好ましく、１００〜５００ｇ／ｍ３であることがより好ましい。オゾン濃度が５０ｇ／ｍ３未満であると酸化反応とともにセルロース繊維を分解・切断する効果に乏しくなるおそれがある。オゾン濃度が１０００ｇ／ｍ３を超えると後続する粉砕処理においてセルロース繊維の切断が過度に進行してしまう、あるいは過度に分解した低分子物質・酸化物質、ラジカルが発生し、加熱による変色などを引き起こすおそれがある。 Here, the ozone concentration in the ozone-containing gas is preferably 50 to 1000 g / m 3, more preferably 100 to 500 g / m 3. If the ozone concentration is less than 50 g / m 3 , the effect of decomposing / cutting the cellulose fibers may be reduced along with the oxidation reaction. When the ozone concentration exceeds 1000 g / m 3 , the cellulose fibers are excessively cut in the subsequent pulverization process, or excessively decomposed low molecular substances / oxidized substances and radicals are generated, causing discoloration due to heating. There is a fear.
セルロース繊維に対するオゾン添加率としては、０．１〜３０質量％であることが好ましく、１〜１０質量％であることがより好ましい。オゾン添加率が０．１質量％未満であると酸化反応とともにセルロース繊維を分解・切断する効果に乏しくなるおそれがある。オゾン添加率が３０質量％を超えると後続する粉砕処理においてセルロース繊維の切断が過度に進行してしまう、あるいは過度に分解した低分子物質・酸化物質、ラジカルが発生し、加熱による変色などを引き起こすおそれがある。 As an ozone addition rate with respect to a cellulose fiber, it is preferable that it is 0.1-30 mass%, and it is more preferable that it is 1-10 mass%. If the ozone addition rate is less than 0.1% by mass, the effect of decomposing / cutting the cellulose fibers may be reduced along with the oxidation reaction. When the ozone addition rate exceeds 30% by mass, cutting of cellulose fibers proceeds excessively in the subsequent pulverization process, or excessively decomposed low molecular substances / oxidized substances and radicals are generated, causing discoloration due to heating. There is a fear.
処理温度としては、０〜１００℃であることが好ましく、２０〜５０℃であることがより好ましい。処理温度が０℃未満であると試料の取り扱いが難しく、装置も大型化し、コスト的に不利になるおそれがある。処理温度が１００℃を超えるとオゾンが容易に分解し、酸化反応とともにセルロース繊維を分解・切断する効果に乏しくなるおそれがある。 As processing temperature, it is preferable that it is 0-100 degreeC, and it is more preferable that it is 20-50 degreeC. When the processing temperature is less than 0 ° C., it is difficult to handle the sample, the apparatus becomes large, and there is a risk that the cost may be disadvantageous. When the treatment temperature exceeds 100 ° C., ozone is easily decomposed, and there is a possibility that the effect of decomposing / cutting cellulose fibers together with the oxidation reaction may be poor.
処理時間としては、１〜６０分であることが好ましく、５〜３０分であることがより好ましい。処理時間が１分未満であると酸化反応とともにセルロース繊維を分解・切断する効果に乏しくなるおそれがある。処理時間が６０分を超えるとオゾンによる酸化反応はレベルオフし、それ以上はほとんど進行しない。 As processing time, it is preferable that it is 1 to 60 minutes, and it is more preferable that it is 5 to 30 minutes. If the treatment time is less than 1 minute, the effect of decomposing / cutting cellulose fibers may be reduced along with the oxidation reaction. When the treatment time exceeds 60 minutes, the oxidation reaction by ozone is leveled off, and the reaction time hardly proceeds beyond that.
本発明はリファイナー、シュレッダーといった繊維破砕・切断のような物理的処理、ＮａＯＨ水溶液、アンモニア、エチレンジアミンその他のアルカリ系薬品処理といった化学処理を反応前に施したパルプに対して行うと更に効果が高い。 The present invention is more effective when it is applied to pulp that has been subjected to physical treatment such as refiner and shredder such as fiber crushing and cutting, and chemical treatment such as aqueous NaOH solution, ammonia, ethylenediamine, and other alkaline chemicals before the reaction.
本発明においては、オゾン処理の後に水、アルカリ性水溶液（ＮａＯＨ等）、酸性水溶液（塩酸等）等により洗浄してから粉砕処理を施すことが好ましい実施態様である。 In the present invention, it is a preferred embodiment that the ozone treatment is followed by washing with water, an alkaline aqueous solution (NaOH, etc.), an acidic aqueous solution (hydrochloric acid, etc.) and the like, followed by a pulverization treatment.
上記オゾン処理を施したセルロース繊維は水に分散され、水性懸濁液として粉砕処理に供される。該水性懸濁液の濃度としては０．１〜３質量％であることが好ましく、０．３〜１質量％であることがより好ましい。因みに、濃度が０．１質量％未満であると後工程のセルロース解繊負荷低減効果がほとんどなくなるおそれがある。濃度が３質量%を超えると粉砕処理中に粘度が上昇し過ぎ、取扱いが非常に困難となるおそれがある。 The cellulose fiber that has been subjected to the ozone treatment is dispersed in water and subjected to a pulverization treatment as an aqueous suspension. The concentration of the aqueous suspension is preferably 0.1 to 3% by mass, and more preferably 0.3 to 1% by mass. Incidentally, if the concentration is less than 0.1% by mass, the effect of reducing the cellulose fibrillation load in the subsequent step may be almost lost. If the concentration exceeds 3% by mass, the viscosity may increase excessively during the pulverization process, and handling may become very difficult.
本発明において、繊維状セルロースの粉砕方法には特に制限はないが、グラインダー（石臼型粉砕機）、高圧ホモジナイザーや超高圧ホモジナイザー、高圧衝突型粉砕機、ボールミル、ディスク型リファイナー、コニカルリファイナー、二軸混錬機（二軸押出機）、振動ミル、高速回転下でのホモミキサー、超音波分散機、ビーターなどの機械的作用を利用する湿式粉砕でセルロース系繊維を細くする方法が好ましい。なかでも、石臼粉砕、高圧ホモジナイザー、ボールミル処理が微細な繊維が効率的に得られるため、特に好ましい。微細化するセルロース系繊維としては、植物由来のセルロース、動物由来のセルロース、バクテリア由来のセルロースなどが挙げられる。より具体的には、針葉樹パルプや広葉樹パルプ等の木材系製紙用パルプ、コットンリンターやコットンリントなどの綿系パルプ、麻や麦わら、バガスなどの非木材系パルプ、ホヤや海草などから単離されるセルロースなどが挙げられる。これらの中でも木材系製紙用パルプや非木材系パルプが入手のし易さという点で好ましい。 In the present invention, the method for pulverizing fibrous cellulose is not particularly limited, but a grinder (stone mill type pulverizer), a high-pressure homogenizer or an ultra-high pressure homogenizer, a high-pressure collision type pulverizer, a ball mill, a disk type refiner, a conical refiner, biaxial A method of thinning the cellulosic fibers by wet pulverization utilizing mechanical action such as a kneader (double screw extruder), vibration mill, homomixer under high-speed rotation, ultrasonic disperser, beater, etc. is preferred. Among these, a fine fiber can be efficiently obtained by grinding with a mortar, high-pressure homogenizer, or ball mill, which is particularly preferable. Examples of cellulosic fibers to be refined include plant-derived cellulose, animal-derived cellulose, and bacterial-derived cellulose. More specifically, it is isolated from wood-based paper pulp such as conifer pulp and hardwood pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw and bagasse, sea squirt and seaweed. A cellulose etc. are mentioned. Among these, wood-based paper pulp and non-wood pulp are preferable in terms of easy availability.
本発明により得られる微細繊維状セルロースは通常製紙用途で用いるパルプ繊維よりもはるかに細いセルロース繊維あるいは棒状粒子である。微細繊維状セルロースは結晶状態のセルロース分子の集合体であり、その結晶構造はＩ型（平行鎖）である。微細繊維状セルロースの幅は電子顕微鏡で観察して１ｎｍ〜１０００ｎｍが好ましく、より好ましくは２ｎｍ〜５００ｎｍ、さらに好ましくは４ｎｍ〜１００ｎｍである。繊維の幅が１ｎｍ未満であると、セルロース分子として水に溶解しているため、微細繊維としての物性（強度や剛性、寸法安定性）が発現しなくなる。１０００ｎｍを超えると微細繊維とは言えず、通常のパルプに含まれる繊維にすぎないため、微細繊維としての物性（強度や剛性、寸法安定性）が得られない。微細繊維状セルロースに透明性が求められる用途であると、微細繊維の幅は５０ｎｍ以下が好ましい。これらの微細繊維状セルロースから得られる複合材料は密度が高く、緻密な構造体となるために強度が高く、セルロース結晶に由来した高い弾性率が得られることに加え、可視光の散乱が少ないため高い透明性も得られる。 The fine fibrous cellulose obtained according to the present invention is a cellulose fiber or rod-like particles that are much thinner than pulp fibers usually used in papermaking applications. Fine fibrous cellulose is an aggregate of crystalline cellulose molecules, and its crystal structure is type I (parallel chain). The width of the fine fibrous cellulose is preferably 1 nm to 1000 nm as observed with an electron microscope, more preferably 2 nm to 500 nm, and still more preferably 4 nm to 100 nm. When the width of the fiber is less than 1 nm, since the cellulose molecule is dissolved in water, the physical properties (strength, rigidity, dimensional stability) as the fine fiber are not expressed. If it exceeds 1000 nm, it cannot be said that it is a fine fiber, and is merely a fiber contained in ordinary pulp, and physical properties (strength, rigidity, dimensional stability) as a fine fiber cannot be obtained. If the fine fibrous cellulose is used for transparency, the fine fiber width is preferably 50 nm or less. Composite materials obtained from these fine fibrous celluloses have high density and high density because they become dense structures, and in addition to obtaining high elastic modulus derived from cellulose crystals, there is little scattering of visible light High transparency is also obtained.
以下、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。また、例中の部及び％は特に断らない限り、それぞれ質量部及び質量％を示す。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these Examples. Moreover, unless otherwise indicated, the part and% in an example show a mass part and mass%, respectively.
＜実施例１＞
容器にＬＢＫＰ（セニブラ社製：水分５０％、フリーネス６００ｍＬｃｓｆ）４０ｇおよび空気２Ｌを加えた後、オゾン濃度２００ｇ／ｍ３のオゾン／酸素混合気体を１Ｌ加え、２５℃で２分間振とうした後、３０分静置した。この時のオゾン添加率はパルプ乾燥質量に対して１質量％である。オゾン処理後のパルプをイオン交換水で十分に洗浄した後に、パルプ濃度が１％になるように水を加えてディスインテグレーターで解繊した。
得られたパルプ懸濁液を０．５％に希釈し、このパルプ懸濁液を石臼型分散機（増幸産業社製「スーパーマスコロイダー」）を用いて４回処理を行った後、高圧衝突型分散機（スギノマシン社製「アルティマイザー」）で１０回処理し、最後に２０ＫＨｚの超音波処理を１分間行い、微細繊維状セルロース水系懸濁液を得た。
得られた微細繊維状セルロース懸濁液について遠心分離機（コクサン社製「Ｈ−２００ＮＲ」）を用いて約５０００Ｇで５分間処理し、上澄濃度を測定したところ、０．３４％であった。ここで得られた上澄液を孔径０．４５μｍのメンブレンフィルター上で吸引ろ過し、シート化したところ歩留りはほぼ１００％であった。また、上澄み液中の繊維を電子顕微鏡で観察したところ、繊維径は２００ｎｍ以下であった。
<Example 1>
After 40 g of LBKP (manufactured by CENIBRA: moisture 50%, freeness 600 mLcsf) and 2 L of air were added to the container, 1 L of an ozone / oxygen mixed gas having an ozone concentration of 200 g / m 3 was added and shaken at 25 ° C. for 2 minutes. Let stand for 30 minutes. The ozone addition rate at this time is 1 mass% with respect to the pulp dry mass. After the ozone-treated pulp was sufficiently washed with ion-exchanged water, water was added so that the pulp concentration was 1%, and defibration was performed with a disintegrator.
The obtained pulp suspension was diluted to 0.5%, and this pulp suspension was treated four times using a stone mill type disperser (“Supermass colloider” manufactured by Masuko Sangyo Co., Ltd.), and then subjected to high-pressure collision. 10 times with a type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.), and finally, ultrasonic treatment at 20 KHz was performed for 1 minute to obtain a fine fibrous cellulose aqueous suspension.
The obtained fine fibrous cellulose suspension was treated at about 5000 G for 5 minutes using a centrifuge (“H-200NR” manufactured by Kokusan Co., Ltd.), and the supernatant concentration was measured and found to be 0.34%. . The supernatant obtained here was suction filtered on a membrane filter having a pore diameter of 0.45 μm and formed into a sheet. The yield was almost 100%. Moreover, when the fiber in a supernatant liquid was observed with the electron microscope, the fiber diameter was 200 nm or less.
＜実施例２＞
容器にＬＢＫＰ（セニブラ社製：水分５０％、フリーネス６００ｍＬｃｓｆ）４０ｇおよび空気２Ｌを加えた後、オゾン濃度２００ｇ／ｍ３のオゾン／酸素混合気体を３Ｌ加え、２５℃で２分間振とうした後、３０分静置した。この時のオゾン添加率はパルプ乾燥質量に対して３質量％である。処理後のパルプをイオン交換水で十分に洗浄した後に、パルプ濃度が１％になるように水を加えてディスインテグレーターで解繊した。
得られたパルプ懸濁液を０．５％に希釈し、このパルプ懸濁液を石臼型分散機（増幸産業社製「スーパーマスコロイダー」）を用いて４回処理を行った後、高圧衝突型分散機（スギノマシン社製「アルティマイザー」）で１０回処理し、最後に２０ＫＨｚの超音波処理を１分間行い、微細繊維状セルロース水系懸濁液を得た。
微細繊維状セルロース水系懸濁液について遠心分離機（コクサン社製「Ｈ−２００ＮＲ」）を用いて約５０００Ｇで５分間処理し、上澄濃度を測定したところ、０．３５％であった。また、上澄み液中の繊維を電子顕微鏡で観察したところ、繊維径は２００ｎｍ以下であった。
<Example 2>
After 40 g of LBKP (manufactured by CENIBRA: moisture 50%, freeness 600 mLcsf) and 2 L of air were added to the container, 3 L of an ozone / oxygen mixed gas having an ozone concentration of 200 g / m 3 was added and shaken at 25 ° C. for 2 minutes. Let stand for 30 minutes. The ozone addition rate at this time is 3 mass% with respect to the pulp dry mass. After the treated pulp was sufficiently washed with ion-exchanged water, water was added so that the pulp concentration was 1%, and defibration was performed with a disintegrator.
The obtained pulp suspension was diluted to 0.5%, and this pulp suspension was treated four times using a stone mill type disperser (“Supermass colloider” manufactured by Masuko Sangyo Co., Ltd.), and then subjected to high-pressure collision. 10 times with a type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.), and finally, ultrasonic treatment at 20 KHz was performed for 1 minute to obtain a fine fibrous cellulose aqueous suspension.
The fine fibrous cellulose aqueous suspension was treated at about 5000 G for 5 minutes using a centrifuge (“H-200NR” manufactured by Kokusan Co., Ltd.), and the supernatant concentration was measured and found to be 0.35%. Moreover, when the fiber in a supernatant liquid was observed with the electron microscope, the fiber diameter was 200 nm or less.
＜実施例３＞
容器にＬＢＫＰ（セニブラ社製：水分５０％、フリーネス６００ｍＬｃｓｆ）４０ｇおよび空気２Ｌを加えた後、オゾン濃度２００ｇ／ｍ３のオゾン／酸素混合気体を５Ｌ加え、２５℃で２分間振とうした後、３０分静置した。この時のオゾン添加率はパルプ乾燥質量に対して５質量％である。処理後のパルプをイオン交換水で十分に洗浄した後に、パルプ濃度が１％になるように水を加えてディスインテグレーターで解繊した。
得られたパルプ懸濁液を０．５％に希釈し、このパルプ懸濁液を石臼型分散機（増幸産業社製「スーパーマスコロイダー」）を用いて４回処理を行った後、高圧衝突型分散機（スギノマシン社製「アルティマイザー」）で１０回処理し、最後に２０ＫＨｚの超音波処理を１分間行い、微細繊維状セルロース水系懸濁液を得た。
得られた微細繊維状セルロースの水系懸濁液について遠心分離機（コクサン社製「Ｈ−２００ＮＲ」）を用いて約５０００Ｇで５分間処理し、上澄濃度を測定したところ、０．３７％であった。また、上澄み液中の繊維を電子顕微鏡で観察したところ、繊維径は２００ｎｍ以下であった。
<Example 3>
After 40 g of LBKP (manufactured by CENIBRA: moisture 50%, freeness 600 mLcsf) and 2 L of air were added to the container, 5 L of an ozone / oxygen mixed gas having an ozone concentration of 200 g / m 3 was added and shaken at 25 ° C. for 2 minutes. Let stand for 30 minutes. The ozone addition rate at this time is 5 mass% with respect to the pulp dry mass. After the treated pulp was sufficiently washed with ion-exchanged water, water was added so that the pulp concentration was 1%, and defibration was performed with a disintegrator.
The obtained pulp suspension was diluted to 0.5%, and this pulp suspension was treated four times using a stone mill type disperser (“Supermass colloider” manufactured by Masuko Sangyo Co., Ltd.), and then subjected to high-pressure collision. 10 times with a type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.), and finally, ultrasonic treatment at 20 KHz was performed for 1 minute to obtain a fine fibrous cellulose aqueous suspension.
The obtained aqueous suspension of fine fibrous cellulose was treated at about 5000 G for 5 minutes using a centrifuge (“H-200NR” manufactured by Kokusan Co., Ltd.), and the supernatant concentration was measured to be 0.37%. there were. Moreover, when the fiber in a supernatant liquid was observed with the electron microscope, the fiber diameter was 200 nm or less.
＜実施例４＞
容器にＬＢＫＰ（セニブラ社製：水分５３．０％、フリーネス６００ｍＬｃｓｆ）４０ｇおよび空気２Ｌを加えた後、オゾン濃度２００ｇ／ｍ３のオゾン／酸素混合気体を２０Ｌ加え、２５℃で２分間振とうした後、３０分静置した。この時のオゾン添加率はパルプ乾燥質量に対して２０質量％である。処理後のパルプをイオン交換水で十分に洗浄した後に、パルプ濃度が１％になるように水を加えてディスインテグレーターで解繊した。
得られたパルプ懸濁液を０．５％に希釈し、このパルプ懸濁液を石臼型分散機（増幸産業社製「スーパーマスコロイダー」）を用いて４回処理を行った後、高圧衝突型分散機（スギノマシン社製「アルティマイザー」）で１０回処理し、最後に２０ＫＨｚの超音波処理を１分間行い、微細繊維状セルロース水系懸濁液を得た。
得られた微細繊維状セルロースの水系懸濁液について遠心分離機（コクサン社製「Ｈ−２００ＮＲ」）を用いて約５０００Ｇで５分間処理し、上澄濃度を測定したところ、０．３９％であった。また、上澄み液中の繊維を電子顕微鏡で観察したところ、繊維径は２００ｎｍ以下であった。
<Example 4>
After 40 g of LBKP (manufactured by CENIBRA: moisture 53.0%, freeness 600 mLcsf) and 2 L of air were added to the container, 20 L of an ozone / oxygen mixed gas having an ozone concentration of 200 g / m 3 was added and shaken at 25 ° C. for 2 minutes. Then, it was left still for 30 minutes. The ozone addition rate at this time is 20 mass% with respect to the pulp dry mass. After the treated pulp was sufficiently washed with ion-exchanged water, water was added so that the pulp concentration was 1%, and defibration was performed with a disintegrator.
The obtained pulp suspension was diluted to 0.5%, and this pulp suspension was treated four times using a stone mill type disperser (“Supermass colloider” manufactured by Masuko Sangyo Co., Ltd.), and then subjected to high-pressure collision. 10 times with a type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.), and finally, ultrasonic treatment at 20 KHz was performed for 1 minute to obtain a fine fibrous cellulose aqueous suspension.
The obtained aqueous suspension of fine fibrous cellulose was treated at about 5000 G for 5 minutes using a centrifuge (“H-200NR” manufactured by Kokusan Co., Ltd.), and the supernatant concentration was measured. there were. Moreover, when the fiber in a supernatant liquid was observed with the electron microscope, the fiber diameter was 200 nm or less.
＜比較例１＞
ＬＢＫＰ（セニブラ社製：水分５０％、フリーネス６００ｍＬｃｓｆ）４０ｇをパルプ濃度が１％になるように水を加えてディスインテグレーターで解繊した。
得られたパルプ懸濁液を０．５％に希釈し、このパルプ懸濁液を石臼型分散機（増幸産業社製「スーパーマスコロイダー」）を用いて４回処理を行った後、高圧衝突型分散機（スギノマシン社製「アルティマイザー」）で１０回処理し、最後に２０ＫＨｚの超音波処理を１分間行い、微細繊維状セルロース水系懸濁液を得た。
遠心分離機（コクサン社製「Ｈ−２００ＮＲ」）を用いて約５０００Ｇで５分間処理し、上澄濃度を測定したところ、０．１７％であった。また、上澄み液中の繊維を電子顕微鏡で観察したところ、繊維径は２００ｎｍ以下であった。
<Comparative Example 1>
40 g of LBKP (manufactured by CENIBRA: moisture 50%, freeness 600 mLcsf) was added with water so that the pulp concentration was 1%, and defibrated with a disintegrator.
The obtained pulp suspension was diluted to 0.5%, and this pulp suspension was treated four times using a stone mill type disperser (“Supermass colloider” manufactured by Masuko Sangyo Co., Ltd.), and then subjected to high-pressure collision. 10 times with a type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.), and finally, ultrasonic treatment at 20 KHz was performed for 1 minute to obtain a fine fibrous cellulose aqueous suspension.
Using a centrifuge (“H-200NR” manufactured by Kokusan Co., Ltd.), it was treated at about 5000 G for 5 minutes, and the supernatant concentration was measured and found to be 0.17%. Moreover, when the fiber in a supernatant liquid was observed with the electron microscope, the fiber diameter was 200 nm or less.
本発明により、最大繊維幅１０００ｎｍ以下の微細繊維状セルロースを簡便な方法により効率的に製造することが可能となる。 According to the present invention, it becomes possible to efficiently produce fine fibrous cellulose having a maximum fiber width of 1000 nm or less by a simple method.
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| JP5862345B2 (en) * | 2012-02-13 | 2016-02-16 | 王子ホールディングス株式会社 | Method for producing fine fibrous cellulose |
| JP5783253B2 (en) * | 2012-05-21 | 2015-09-24 | 王子ホールディングス株式会社 | Method for producing fine fiber and fine fiber-containing sheet |
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| WO2013176102A1 (en) * | 2012-05-24 | 2013-11-28 | 王子ホールディングス株式会社 | Fine fibrous cellulose, method for producing same, fine fibrous cellulose dispersion, and non-woven fabric |
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