JP2008001728A - Fine cellulose fiber - Google Patents
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Abstract
【課題】最大繊維径１０００ｎｍ以下かつ数平均繊維径が２〜１５０ｎｍの分散安定性に優れるセルロース系のナノファイバー材料の提供。
【解決手段】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繊維。
【選択図】なしA cellulose-based nanofiber material having a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm and excellent dispersion stability is provided.
[MEANS FOR SOLVING PROBLEMS] A group using a surface oxidation reaction of cellulose by an N-oxyl compound, having a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm, and a part of hydroxyl groups of cellulose is composed of a carboxyl group and an aldehyde group. A fine cellulose fiber that is oxidized to at least one functional group selected from the group consisting of cellulose I-type crystal structure.
[Selection figure] None
Description
本発明は、各種機能性添加剤や構造材として使用できる微細なセルロース繊維に関する。 The present invention relates to fine cellulose fibers that can be used as various functional additives and structural materials.
ナノサイズの材料として、シリカ微粒子や金属微粒子等の球状の微粒子やカーボンナノロッドに代表される棒状（ウィスカー）タイプの材料の開発は盛んに進められている。これに対し、繊維状のナノ材料については上述した２種類の材料に比べ、まだまだ報告が少なく、アプリケーションの開発も含めこれからの技術領域と言える。実際に、現時点でナノサイズの繊維径をもった繊維（単にナノファイバーと呼ぶ）を人工的に作製する技術として、湿式成形をベースとしたエレクトロスピニング法や種々の溶融成形によるナノファイバー作製方法が知られている（例えば、非特許文献１参照）。しかし、これらの方法で供給される微細繊維は、真のナノサイズと呼ぶにはまだ大き過ぎ、サブミクロンサイズ（１００ｎｍ−１０００ｎｍの繊維径）に止まりサブミクロンファイバーというべきものである。 As nano-sized materials, spherical fine particles such as silica fine particles and metal fine particles, and rod-shaped (whisker) type materials represented by carbon nanorods are being actively developed. In contrast, fibrous nanomaterials are still less reported than the two types of materials described above, and can be said to be a future technical area including application development. In fact, as a technology for artificially producing fibers with nano-sized fiber diameters (simply called nanofibers) at present, there are electrospinning methods based on wet molding and nanofiber production methods by various melt moldings. It is known (for example, refer nonpatent literature 1). However, the fine fibers supplied by these methods are still too large to be called true nano-size, and should only be sub-micron fibers (sub-micron size) (fiber diameter of 100 nm-1000 nm).
これに対し、天然に多量に存在するバイオマスであるセルロースは、生合成によって繊維が生成される時点では例外なくミクロフィブリルと呼ばれるナノファイバーであり、これがやがて繊維方向に集束化してより大きな単位の繊維を成長していくという特徴を有する。こうしてできた繊維の束が乾燥状態となり、主に植物の強靭な構造材として機能している。このようなマクロなセルロース構造材中では、ナノファイバー表面間での主に水素結合を介した結合力によって強く集束しているため、容易には元のナノファイバーの状態には分散させることができない。 On the other hand, cellulose, which is a biomass that exists in large quantities in nature, is a nanofiber called microfibril without exception at the time when the fiber is produced by biosynthesis, which eventually converges in the fiber direction and becomes a larger unit of fiber. It has the feature of growing. The bundle of fibers thus formed is in a dry state and functions mainly as a strong structural material for plants. In such a macroscopic cellulose structure material, the nanofiber surface is strongly focused mainly by a bonding force via hydrogen bonds, and thus cannot be easily dispersed in the original nanofiber state. .
特許文献１に記載されているように、唯一バクテリアセルロース（以下、ＢＣと呼ぶ）と呼ばれる原始的な菌の生成するセルロースは、比較的低次元に集積した集合体をネバードライの状態で抽出できるため、ナノファイバーとして扱うことができる。特許文献２および特許文献３には、典型的なセルロースナノファイバーであるＢＣを樹脂材料とハイブリッド化させることにより、透明であり、しかも力学強度にも優れ、熱膨張率の低いフィルム材料として提供できることが開示されている。しかしながら、ＢＣに関しては、通常１重量％以下のセルロース濃度のゲルの状態で生産され、生産速度も極めて遅いため、工業的な生産性という観点では必ずしも有利ではない。 As described in Patent Document 1, cellulose produced by only primitive bacteria called bacterial cellulose (hereinafter referred to as BC) can extract aggregates collected in a relatively low dimension in a never dry state. Therefore, it can be handled as nanofiber. Patent Documents 2 and 3 describe that BC, which is a typical cellulose nanofiber, is hybridized with a resin material so that it can be provided as a film material that is transparent, excellent in mechanical strength, and has a low coefficient of thermal expansion. Is disclosed. However, BC is usually not advantageous from the viewpoint of industrial productivity because it is produced in a gel state having a cellulose concentration of 1% by weight or less and the production rate is extremely slow.
汎用的に入手可能な植物系の精製セルロース（木材パルプやリンターパルプ等）を元のミクロフィブリルまでダウンサイジングする技術として、特許文献４には、高圧ホモジナイザーと呼ばれる、極めて高い圧力でフィブリル状物質を高度に微細化できる装置を用いることによりセルロースのナノファイバーが得られることが開示されている。しかしながら、該方法では、高圧ホモジナイザーによる処理時に多大なエネルギーを要し、コスト的に不利であると同時に、得られる微細化繊維の繊維径にも分布が存在し、一般的な処理条件下では微細化の程度も不完全であり、１μｍ以上の太い繊維も若干残ることが多い。 As a technology for downsizing plant-based refined cellulose (wood pulp, linter pulp, etc.) that can be used for general purposes to the original microfibrils, Patent Document 4 discloses a fibrillar substance at an extremely high pressure, called a high-pressure homogenizer. It is disclosed that cellulose nanofibers can be obtained by using a device that can be highly miniaturized. However, this method requires a great deal of energy when processing with a high-pressure homogenizer, and is disadvantageous in terms of cost. At the same time, there is also a distribution in the fiber diameter of the resulting refined fiber, and fine processing under general processing conditions. The degree of conversion is incomplete and thick fibers of 1 μm or more often remain a little.
一方、化学的な処理条件によりセルロースの微細化を行う方法として、特許文献５や非特許文献２にて開示されている酸加水分解法による微細化技術が知られている。しかし、該方法では、セルロース繊維の繊維方向に垂直な方向に断裂が起こることが知られており、一般に繊維の形状を保ったまま微細化することが困難である。
すなわち、汎用的に入手可能なセルロースがその構造中に内包しているナノファイバー性を活用して、産業的に利用可能な極めて微小な繊維径をもつナノファイバーを効率的に
得る方法は存在しなかった。
On the other hand, as a method for refining cellulose under chemical treatment conditions, a refining technique by an acid hydrolysis method disclosed in Patent Document 5 and Non-Patent Document 2 is known. However, in this method, it is known that tearing occurs in a direction perpendicular to the fiber direction of the cellulose fiber, and it is generally difficult to make the fiber fine while maintaining the shape of the fiber.
In other words, there is a method for efficiently obtaining nanofibers with extremely small fiber diameters that can be used industrially, by utilizing the nanofiber properties that are contained in the structure of commonly available cellulose. There wasn't.
本発明は、数平均繊維径が１５０ｎｍ以下の微細セルロース繊維を提供することを目的とする。また、該セルロース繊維及びその分散体をミクロフィブリルのナノファイバー性を利用して効率的に製造する方法を提供することを目的とする。 An object of this invention is to provide the fine cellulose fiber whose number average fiber diameter is 150 nm or less. It is another object of the present invention to provide a method for efficiently producing the cellulose fiber and the dispersion using the nanofiber property of microfibril.
本発明者の一部は、植物資源からリグニン等の不純物を除去、精製して得る天然セルロースをいったん溶媒に溶解させて得られる再生セルロースを原料とし、２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル（以下、ＴＥＭＰＯと表記する）の存在下、次亜塩素酸のような酸化剤を作用させて酸化反応を進行させることにより、再生セルロースを形成するセルロース鎖が分子鎖レベルで、しかもセルロース鎖の構成モノマー単位であるグルコピラノーズ環中のＣ６位の一級水酸基のみが選択的に酸化され、アルデヒドを経由してカルボキシル基にまで酸化されるという報告（「Ｃｅｌｌｕｌｏｓｅ」Ｖｏｌ．５、１９９８年、第１５３〜１６４ページにおけるＡ． Ｉｓｏｇａｉ及びＹ． Ｋａｔｏによる「ＴＥＭＰＯ触媒酸化によるセルロースからのポリウロン酸の調製」と題する記事）を以前に検討した。該反応により、β−１，４結合したポリグルクロン酸と呼ばれる新規な水溶性の多糖を得ることができる。一方、上述の報告において、再生セルロースの原料である天然セルロースに対して同様の反応を施してもポリグルクロン酸を得ることはできず、反応生成物は非水溶性のままであることが記載されている。 Some of the present inventors use 2,2,6,6-tetramethylpiperidine as a raw material, using as a raw material a regenerated cellulose obtained by dissolving natural cellulose obtained by removing impurities such as lignin from a plant resource and purifying them. In the presence of -N-oxyl (hereinafter referred to as TEMPO), an oxidant such as hypochlorous acid is allowed to act to advance the oxidation reaction, whereby the cellulose chain forming the regenerated cellulose is at the molecular chain level. In addition, only the primary hydroxyl group at the C6 position in the glucopyranose ring, which is a constituent monomer unit of the cellulose chain, is selectively oxidized and is oxidized to a carboxyl group via an aldehyde (“Cellulose” Vol. 5, In 1998, pages 153 to 164 “by TEMPO catalyzed oxidation” by A. Isogai and Y. Kato. An article entitled “Preparation of Polyuronic Acid from Cellulose” was previously investigated. By this reaction, a novel water-soluble polysaccharide called β-1,4-linked polyglucuronic acid can be obtained. On the other hand, in the above-mentioned report, it is described that polyglucuronic acid cannot be obtained even if the same reaction is applied to natural cellulose which is a raw material of regenerated cellulose, and the reaction product remains insoluble in water. ing.
ところが、本発明者らは天然セルロース原料から得られる非水溶性の上記反応性生物を精製後、水分散体とし、該分散体中へ比較的弱い分散力を加えたところ、該反応性生物は極めて容易に水中に分散することを見出した。得られた分散体を解析したところ、該分散体は数ｎｍから数１０ｎｍの繊維径のナノファイバーの分散体であることが判明した。
さらに本発明者らは、その機構や反応条件と得られるナノファイバーの化学構造との因果関係を考察し、上記反応において、高度に膨潤したミクロフィブリルの表面にまでＴＥＭＰＯ触媒による酸化が到達するものの、再生セルロースに比べ結晶性の高い天然セルロースを構成するミクロフィブリルの内部にまでは反応が到らず、ほぼミクロフィブリルの表面酸化にとどまること、通常のセルロースのミクロフィブリルと異なり、該反応により得られるミクロフィブリル表面には負の電荷を有するカルボキシル基が定量的に導入されているため、ミクロフィブリル間の反発力を誘引し分散体中での安定な分散の原因となっていることを突き止め、本発明を完成させた。
However, the present inventors purified the water-insoluble reactive organism obtained from a natural cellulose raw material and then used it as an aqueous dispersion. When a relatively weak dispersion force was applied to the dispersion, the reactive organism was It was found to disperse in water very easily. Analysis of the obtained dispersion revealed that the dispersion was a dispersion of nanofibers having a fiber diameter of several nanometers to several tens of nanometers.
Furthermore, the present inventors considered the causal relationship between the mechanism and reaction conditions and the chemical structure of the resulting nanofiber, and in the above reaction, although the oxidation by the TEMPO catalyst reaches the surface of the highly swollen microfibril. The reaction does not reach the inside of the microfibrils constituting the natural cellulose, which has higher crystallinity than the regenerated cellulose, and the surface oxidation of the microfibrils remains almost the same. Since the negatively charged carboxyl group is quantitatively introduced on the surface of the microfibril, the repulsive force between the microfibrils is attracted and it is found that it causes stable dispersion in the dispersion. The present invention has been completed.
本発明の一は、最大繊維径が１０００ｎｍ以下かつ数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、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ことを特徴とする微細セルロース繊維である。
カルボキシル基とアルデヒド基の量の総和が、セルロース繊維の重量に対し０．１〜２．２ｍｍｏｌ／ｇであることが好ましい。また、最大繊維径が５００ｎｍ以下かつ数平均繊維径が２〜１００ｎｍであることがより好ましい。また、最大繊維径が３０ｎｍ以下かつ数平均繊維径が２〜１０ｎｍであることが更に好ましい。また、カルボキシル基の量が、セルロース繊維の重量に対し０．１〜２．２ｍｍｏｌ／ｇであることが好ましい。
One aspect of the present invention is a cellulose fiber having a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm, wherein at least one functional group selected from the group consisting of a carboxyl group and an aldehyde group. It is a fine cellulose fiber characterized by being oxidized to a base and having a cellulose I-type crystal structure.
The total amount of carboxyl groups and aldehyde groups is preferably 0.1 to 2.2 mmol / g based on the weight of the cellulose fiber. More preferably, the maximum fiber diameter is 500 nm or less and the number average fiber diameter is 2 to 100 nm. More preferably, the maximum fiber diameter is 30 nm or less and the number average fiber diameter is 2 to 10 nm. Moreover, it is preferable that the quantity of a carboxyl group is 0.1-2.2 mmol / g with respect to the weight of a cellulose fiber.
本発明の二は、本発明の一の微細セルロース繊維が媒体中に分散していることを特徴とする微細セルロース繊維の分散体である。
本発明の三は、本発明の二の微細セルロース繊維の分散体の製造方法であって、天然セルロースを原料とし、水中においてＮ−オキシル化合物を酸化触媒とし、共酸化剤を作用させることにより該天然セルロースを酸化して反応物繊維を得る酸化反応工程、不純物を除去して水を含浸させた反応物繊維を得る精製工程、および水を含浸させた反応物繊維を溶媒に分散させる分散工程を有することを特徴とする微細セルロース繊維の分散体の製造方法である。
A second aspect of the present invention is a dispersion of fine cellulose fibers, wherein the fine cellulose fibers according to the present invention are dispersed in a medium.
A third aspect of the present invention is a method for producing a dispersion of fine cellulose fibers according to the second aspect of the present invention, wherein natural cellulose is used as a raw material, an N-oxyl compound is used as an oxidation catalyst in water, and a co-oxidant is allowed to act. An oxidation reaction step of oxidizing natural cellulose to obtain a reactant fiber, a purification step of obtaining a reactant fiber impregnated with water by removing impurities, and a dispersion step of dispersing the reactant fiber impregnated with water in a solvent It is a manufacturing method of the dispersion of the fine cellulose fiber characterized by having.
Ｎ−オキシル化合物が２，２，６，６−テトラメチル−１−ピペリジン−Ｎ−オキシルであることが好ましい。共酸化剤が次亜ハロゲン酸またはその塩、亜ハロゲン酸またはその塩、過ハロゲン酸またはその塩、過酸化水素、及び過有機酸からなる群から選ばれた少なくとも一つであることが好ましい。分散工程が、高速回転下でのホモミキサー処理、高圧ホモジナイザー処理、超高圧ホモジナイザー処理、超音波分散処理、ビーター処理、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、およびグラインダー処理のうち少なくとも一つを含むことが好ましい。
本発明の四は、本発明の一の微細セルロース繊維の製造方法であって、本発明の三の微細セルロース繊維の分散体の製造方法に加え、該分散体から溶媒を乾燥する工程を含むことを特徴とする微細セルロース繊維の製造方法である。
The N-oxyl compound is preferably 2,2,6,6-tetramethyl-1-piperidine-N-oxyl. The co-oxidant is preferably at least one selected from the group consisting of hypohalous acid or a salt thereof, hypohalous acid or a salt thereof, perhalogenic acid or a salt thereof, hydrogen peroxide, and a perorganic acid. The dispersion process includes homomixer processing under high-speed rotation, high-pressure homogenizer processing, ultra-high-pressure homogenizer processing, ultrasonic dispersion processing, beater processing, disc type refiner processing, conical type refiner processing, double disc type refiner processing, and grinder processing. It is preferable that at least one of them is included.
Four of the present invention is a method for producing a fine cellulose fiber according to one aspect of the present invention, and includes a step of drying a solvent from the dispersion in addition to the method for producing a dispersion of three fine cellulose fibers according to the present invention. It is the manufacturing method of the fine cellulose fiber characterized by these.
本発明により、数平均繊維径が１５０ｎｍ以下の微細セルロース繊維、及びその分散体をミクロフィブリルのナノファイバー性を利用して効率的に製造する方法を提供することが可能となる。 According to the present invention, it is possible to provide a method for efficiently producing fine cellulose fibers having a number average fiber diameter of 150 nm or less and a dispersion thereof using the nanofiber property of microfibrils.
次に、本発明について詳細に説明する。
本発明の微細セルロース繊維は、最大繊維径が１０００ｎｍ以下かつ数平均繊維径が２〜１５０ｎｍであり、好ましくは最大繊維径が５００ｎｍ以下かつ数平均繊維径が２〜１００ｎｍ、さらに好ましくは最大繊維径が３０ｎｍ以下かつ数平均繊維径が２〜１０ｎｍのセルロース繊維である。
Next, the present invention will be described in detail.
The fine cellulose fiber of the present invention has a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm, preferably a maximum fiber diameter of 500 nm or less and a number average fiber diameter of 2 to 100 nm, more preferably a maximum fiber diameter. Is a cellulose fiber having a number average fiber diameter of 2 to 10 nm.
ここで最大繊維径および数平均繊維径の解析は次のようにして行う。固形分率で０．０５重量〜０．１重量％の微細セルロースの水分散体を調製し、該分散体を、親水化処理済みのカーボン膜被覆グリッド上にキャストしてＴＥＭ観察用試料とする。また、大きな繊維径の繊維を含む場合には、ガラス上へキャストした表面のＳＥＭ像を観察してもよい。構成する繊維の大きさに応じて５０００倍、１００００倍あるいは５００００倍のいずれかの倍率で電子顕微鏡画像による観察を行う。この際に、得られた画像内に縦横任意の画像幅の軸を想定した場合に少なくとも軸に対し、２０本以上の繊維が軸と交差するような試料および観察条件（倍率等）とする。この条件を満足する観察画像に対し、１枚の画像当たり縦横２本ずつの無作為な軸を引き、軸に交錯する繊維の繊維径を目視で読み取っていく。こうして最低３枚の重なっていない表面部分の画像を電子顕微鏡で撮影し、各々２つの軸に交錯する繊維の繊維径の値を読み取る（したがって、最低２０本×２×３＝１２０本の繊維径の情報が得られる）。こうして得られた繊維径のデータにより最大繊維径お
よび数平均繊維径を算出する。
Here, the analysis of the maximum fiber diameter and the number average fiber diameter is performed as follows. An aqueous dispersion of fine cellulose having a solid content of 0.05 to 0.1% by weight is prepared, and the dispersion is cast on a hydrophilized carbon film-coated grid to obtain a sample for TEM observation. . Moreover, when the fiber of a big fiber diameter is included, you may observe the SEM image of the surface cast on glass. Observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times, or 50000 times depending on the size of the constituent fibers. At this time, when an axis having an arbitrary vertical and horizontal image width is assumed in the obtained image, a sample and observation conditions (magnification, etc.) are set so that at least 20 fibers intersect the axis at least with respect to the axis. With respect to an observation image satisfying this condition, two random axes are drawn vertically and horizontally per image, and the fiber diameter of the fiber intersecting with the axis is visually read. Thus, images of at least three non-overlapping surface portions are taken with an electron microscope, and the value of the fiber diameter of the fibers intersecting with each of the two axes is read (thus, at least 20 × 2 × 3 = 120 fiber diameters). Information). The maximum fiber diameter and the number average fiber diameter are calculated from the fiber diameter data thus obtained.
本発明において、最大繊維径が１０００ｎｍより大きくかつ数平均繊維径が１５０ｎｍより大きな場合には、本発明で目的とするナノファイバーとしての特性が現れ難く、従来の微細化繊維との差別性が低くなるため好ましくない。
さらに本発明の微細セルロース繊維はセルロースの水酸基の一部がカルボキシル基またはアルデヒド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。これは、本発明の微細セルロース繊維が、Ｉ型結晶構造を有する天然由来のセルロース固体原料を表面酸化し微細化した繊維であることを意味する。すなわち、天然セルロースの生合成の過程においてはほぼ例外なくミクロフィブリルと呼ばれるナノファイバーがまず形成され、これらが多束化して高次な固体構造を構築していることを原理的に利用し、ここにおいてミクロフィブリル間の強い凝集力の原動となっている表面間の水素結合を弱めるために、その一部が酸化され、アルデヒド基やあるいはカルボキシル基に変換されているものである。
In the present invention, when the maximum fiber diameter is larger than 1000 nm and the number average fiber diameter is larger than 150 nm, the characteristics as the nanofiber intended in the present invention hardly appear, and the differentiation from the conventional fine fiber is low. Therefore, it is not preferable.
Furthermore, the fine cellulose fiber of the present invention has a cellulose I type crystal structure in which a part of the hydroxyl group of cellulose is oxidized to a carboxyl group or an aldehyde group. This means that the fine cellulose fiber of the present invention is a fiber obtained by surface-oxidizing a naturally-derived cellulose solid raw material having an I-type crystal structure. That is, in the process of biosynthesis of natural cellulose, nanofibers called microfibrils are first formed almost without exception, and it is used in principle to build a higher-order solid structure by bunching them. In order to weaken the hydrogen bond between the surfaces, which is the driving force of strong cohesive force between microfibrils, a part thereof is oxidized and converted into an aldehyde group or a carboxyl group.
ここで、本発明の微細セルロース繊維がＩ型結晶構造であることは、その広角Ｘ線回折像測定により得られる回折プロファイルにおいて、２シータ＝１４〜１７°付近と２シータ＝２２〜２３°付近の二つの位置に典型的なピークをもつことから同定することができる。さらに、本発明の微細セルロース繊維のセルロースにアルデヒド基あるいはカルボキシル基が導入されていることは、水分を完全に除去したサンプルにおいて全反射式赤外分光スペクトル（ＡＴＲ）においてカルボニル基に起因する吸収（１６０８ｃｍ−１付近）が存在することにより確認することができる。特に、酸型のカルボキシル基（ＣＯＯＨ）の場合には、上記の測定において１７３０ｃｍ−１に吸収が存在する。 Here, the fine cellulose fiber of the present invention has an I-type crystal structure in the diffraction profile obtained by the wide-angle X-ray diffraction image measurement, in the vicinity of 2 theta = 14 to 17 ° and 2 theta = 22 to 23 °. It can be identified from having typical peaks at the two positions. Furthermore, the introduction of an aldehyde group or a carboxyl group into the cellulose of the fine cellulose fiber of the present invention means that absorption caused by a carbonyl group in a total reflection infrared spectroscopic spectrum (ATR) in a sample from which moisture has been completely removed (ATR) It can be confirmed by the presence of the vicinity of 1608 cm −1 . In particular, in the case of an acid-type carboxyl group (COOH), absorption exists at 1730 cm −1 in the above measurement.
本発明の微細なセルロース繊維は、上述した理由により、セルロースに存在するカルボキシル基とアルデヒド基の量の総和が多いほうがより微小な繊維径として安定に存在し得る。たとえば木材パルプや綿パルプの場合、本発明の微細なセルロース繊維に存在するカルボキシル基とアルデヒド基の量の総和がセルロース繊維の重量に対し、０．２〜２．２ｍｍｏｌ／ｇ、好ましくは０．５〜２．２ｍｍｏｌ／ｇ、さらに好ましくは０．８〜２．２ｍｍｏｌ／ｇであるとナノファイバーとしての安定性に優れた繊維として提供することができる。また、ＢＣやホヤからの抽出セルロースのような比較的ミクロフィブリルの繊維径が太いセルロースの場合（平均径が数１０ｎｍのオーダー）には、該総和量は０．１〜０．８ｍｍｏｌ／ｇ、好ましくは０．２〜０．８ｍｍｏｌ／ｇであるとナノファイバーとしての安定性に優れた繊維として提供できる。該総和量が０．１ｍｍｏｌ／ｇよりも小さい場合には、従来知られている微細化されたセルロース繊維との物性上の差異（例えば、分散体における分散安定化効果）も小さくなると同時に、微小な繊維径の繊維として得られ難くなるため、好ましくない。 For the reasons described above, the fine cellulose fiber of the present invention can be stably present as a finer fiber diameter when the total amount of carboxyl groups and aldehyde groups present in cellulose is larger. For example, in the case of wood pulp or cotton pulp, the total amount of carboxyl groups and aldehyde groups present in the fine cellulose fibers of the present invention is 0.2 to 2.2 mmol / g, preferably 0.8. When it is 5 to 2.2 mmol / g, more preferably 0.8 to 2.2 mmol / g, it can be provided as a fiber having excellent stability as a nanofiber. Further, in the case of cellulose having a relatively large fiber diameter of microfibrils such as cellulose extracted from BC or sea squirt (average diameter is on the order of several tens of nm), the total amount is 0.1 to 0.8 mmol / g, It can provide as a fiber excellent in stability as a nanofiber as it is preferably 0.2-0.8 mmol / g. When the total amount is less than 0.1 mmol / g, the difference in physical properties from the conventionally known refined cellulose fibers (for example, the dispersion stabilizing effect in the dispersion) is also reduced and at the same time This is not preferable because it is difficult to obtain a fiber having a large fiber diameter.
さらに、ノニオン性の置換基であるアルデヒド基に対し、カルボキシル基が導入されることにより、電気的な反発力が生まれ、ミクロフィブリルが凝集を維持せずにばらばらになろうとする傾向が増大するため、ナノファイバーとしての安定性はより増大する。たとえば木材パルプや綿パルプの場合、本発明の微細な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、０．２〜２．２ｍｍｏｌ／ｇ、好ましくは０．４〜２．２ｍｍｏｌ／ｇ、さらに好ましくは０．６〜２．２ｍｍｏｌ／ｇであるとナノファイバーとしての極めて安定性に優れた繊維として提供することができる。また、ＢＣやホヤからの抽出セルロースのような比較的ミクロフィブリルの繊維径が太いセルロースの場合には、カルボキシル基の量は０．１〜０．８ｍｍｏｌ／ｇ、好ましくは０．２〜０．８ｍｍｏｌ／ｇであるとナノファイバーとしての安定性に優れた繊維として提供できる。 Furthermore, the introduction of a carboxyl group with respect to an aldehyde group that is a nonionic substituent creates an electric repulsive force, which increases the tendency of microfibrils to break apart without maintaining aggregation. In addition, the stability as a nanofiber is further increased. For example, in the case of wood pulp or cotton pulp, the amount of carboxyl groups present in the fine cellulose fiber of the present invention is 0.2 to 2.2 mmol / g, preferably 0.4 to 2.2 mmol, based on the weight of the cellulose fiber. / G, more preferably 0.6 to 2.2 mmol / g, it can be provided as a fiber having extremely excellent stability as a nanofiber. In the case of cellulose having a relatively large fiber diameter of microfibrils, such as cellulose extracted from BC or sea squirt, the amount of carboxyl groups is 0.1 to 0.8 mmol / g, preferably 0.2 to 0.00. It can provide as a fiber excellent in stability as nanofiber as it is 8 mmol / g.
ここで、セルロース繊維の重量に対するセルロースのアルデヒド基およびカルボキシル
基の量（ｍｍｏｌ／ｇ）は、以下の手法により評価する。
乾燥重量を精秤したセルロース試料から０．５〜１重量％スラリーを６０ｍｌ調製し、０．１Ｍの塩酸水溶液によってｐＨを約２．５とした後、０．０５Ｍの水酸化ナトリウム水溶液を滴下して電気伝導度測定を行う。測定はｐＨが約１１になるまで続ける。電気伝導度の変化が緩やかな弱酸の中和段階において消費された水酸化ナトリウム量（Ｖ）から、下式を用いて官能基量１を決定する。該官能基量１がカルボキシル基の量を示す。
官能基量（ｍｍｏｌ／ｇ）＝Ｖ（ｍｌ）×０．０５／セルロースの質量（ｇ）
次に、セルロース試料を、酢酸でｐＨを４〜５に調製した２％亜塩素酸ナトリウム水溶液中でさらに４８時間常温で酸化し、上記手法によって再び官能基量２を測定する。この酸化によって追加された官能基量（＝官能基量２−官能基量１）を算出し、アルデヒド基量とする。
Here, the amount (mmol / g) of aldehyde group and carboxyl group of cellulose relative to the weight of cellulose fiber is evaluated by the following method.
60 ml of a 0.5 to 1 wt% slurry was prepared from a dry-weighted cellulose sample, and the pH was adjusted to about 2.5 with a 0.1 M aqueous hydrochloric acid solution, and then a 0.05 M aqueous sodium hydroxide solution was added dropwise. To measure the electrical conductivity. The measurement is continued until the pH is about 11. The amount of functional group 1 is determined from the amount (V) of sodium hydroxide consumed in the neutralization step of the weak acid whose electrical conductivity changes slowly. The functional group amount 1 indicates the amount of carboxyl groups.
Functional group amount (mmol / g) = V (ml) × 0.05 / mass of cellulose (g)
Next, the cellulose sample is further oxidized at room temperature for 48 hours in a 2% aqueous sodium chlorite solution adjusted to pH 4 to 5 with acetic acid, and the functional group amount 2 is measured again by the above method. The amount of functional groups added by this oxidation (= functional group amount 2 -functional group amount 1) is calculated and used as the aldehyde group amount.
以上の条件を満たす本発明の微細セルロース繊維は、他材料との混合性に優れ、水などの親水性媒体中で極めて高い分散安定効果を示すばかりでなく、例えば、水や親水性の有機溶媒中に分散させることにより高いチキソトロピー性を発現し、条件によってはゲル状となるため、ゲル化剤としても有効である。また、本発明が例えば最大繊維径が３０ｎｍ以下かつ数平均繊維径が３〜１０ｎｍのような極めて微小な繊維として提供される場合には、水や親水性の有機溶媒中への分散体は透明となる場合もある。また、本発明の微細なセルロース繊維は、抄紙法やキャスト法により製膜することにより、高強度で耐熱性にも優れ、かつ極めて低い熱膨張性を有する材料となる。製膜の際の原液として使用する本発明の微細なセルロース繊維の分散体が透明である場合には、得られる膜も透明なものとなる。該膜は親水性付与を目的としたコーティング層としても有効に機能する。 The fine cellulose fiber of the present invention that satisfies the above conditions is excellent in mixing with other materials and exhibits not only a very high dispersion stability effect in a hydrophilic medium such as water, but also, for example, water or a hydrophilic organic solvent. When dispersed in the gel, it exhibits high thixotropic properties and, depending on the conditions, becomes a gel, it is also effective as a gelling agent. In addition, when the present invention is provided as extremely fine fibers having a maximum fiber diameter of 30 nm or less and a number average fiber diameter of 3 to 10 nm, for example, the dispersion in water or a hydrophilic organic solvent is transparent. It may become. Further, the fine cellulose fiber of the present invention becomes a material having high strength, excellent heat resistance and extremely low thermal expansion by forming a film by a papermaking method or a casting method. When the fine cellulose fiber dispersion of the present invention used as a stock solution for film formation is transparent, the resulting film is also transparent. The film functions effectively as a coating layer for the purpose of imparting hydrophilicity.
さらに、本発明の微細なセルロース繊維を例えば樹脂材料などの他材料と複合化する際には、他材料中での分散性に優れるため、好適な場合には透明性に優れた複合体を提供することができる。該複合体においては、本発明の微細なセルロース繊維は補強フィラーとしても機能し、複合体中で繊維が高度にネットワークを形成するような場合には、使用した樹脂単体に比べ、著しく高強度を示すようになると同時に著しい熱膨張率の低下を誘引することもできる。この他にも本発明の微細なセルロース繊維は、セルロースのもつ両親媒的性質も併せ持つため、例えば乳化剤や分散安定剤としても機能する。特に繊維中にカルボキシル基を有することで、表面電位の絶対値が大きくなるため、等電点（イオン濃度が増大した際に凝集が起こり始める濃度）が低ｐＨ側にシフトすることが期待される。これによって、より広範なイオン濃度条件で分散安定化効果が期待できる。さらに、カルボキシル基は金属イオンと対イオンを形成するため、金属イオンの捕集剤等としても有効である。 Furthermore, when the fine cellulose fiber of the present invention is compounded with other materials such as resin materials, it is excellent in dispersibility in other materials, and therefore, a composite with excellent transparency is provided when suitable. can do. In the composite, the fine cellulose fiber of the present invention also functions as a reinforcing filler, and when the fiber forms a high network in the composite, the strength is significantly higher than that of the single resin used. At the same time, a significant decrease in the coefficient of thermal expansion can be induced. In addition, since the fine cellulose fiber of the present invention also has the amphipathic properties of cellulose, it functions as, for example, an emulsifier or a dispersion stabilizer. In particular, the presence of a carboxyl group in the fiber increases the absolute value of the surface potential, so the isoelectric point (the concentration at which aggregation begins to occur when the ion concentration increases) is expected to shift to the lower pH side. . As a result, a dispersion stabilizing effect can be expected under a wider range of ion concentration conditions. Furthermore, since the carboxyl group forms a counter ion with the metal ion, it is also effective as a metal ion scavenger or the like.
次に、本発明の微細セルロース繊維が媒体中に分散している分散体、および該分散体の製造方法について説明する。
本発明の微細セルロース繊維の分散体は、前述した微細セルロース繊維が後述する溶媒中に分散しているものをいう。該分散体は、例えば、天然セルロースを原料とし、水中においてＮ−オキシル化合物を酸化触媒とし、共酸化剤を作用させることにより該天然セルロースを酸化して反応物繊維を得る酸化反応工程、不純物を除去して水を含浸させた反応物繊維を得る精製工程、および水を含浸させた反応物繊維を溶媒に分散させる分散工程の３つの工程により得ることができる。以下に各工程について詳細に説明する。
Next, a dispersion in which the fine cellulose fibers of the present invention are dispersed in a medium and a method for producing the dispersion will be described.
The dispersion of fine cellulose fibers of the present invention refers to a dispersion in which the fine cellulose fibers described above are dispersed in a solvent described later. The dispersion includes, for example, an oxidation reaction step in which natural cellulose is used as a raw material, an N-oxyl compound is used as an oxidation catalyst in water, and a natural fiber is oxidized by acting a cooxidant to obtain a reaction product fiber. It can be obtained by three steps: a purification step for obtaining a reactant fiber impregnated with water by removal and a dispersion step for dispersing the reactant fiber impregnated with water in a solvent. Each step will be described in detail below.
まず、酸化反応工程では、水中に天然セルロースを分散させた分散液を調製する。ここで、天然セルロースは、植物，動物，バクテリア産生ゲル等のセルロースの生合成系から単離した精製セルロースを意味する。より具体的には、針葉樹系パルプ、広葉樹系パルプ、コットンリンターやコットンリントのような綿系パルプ、麦わらパルプやバガスパルプ等の非木材系パルプ、ＢＣ、ホヤから単離されるセルロース、海草から単離されるセルロ
ースなどを挙げることができるが、これに限定されるものではない。天然セルロースは好ましくは、叩解等の表面積を高める処理を施すと、反応効率を高めることができ、生産性を高めることができる。さらに、天然セルロースとして、単離、精製の後、ネバードライで保存していたものを使用するとミクロフィブリルの集束体が膨潤し易い状態であるため、やはり反応効率を高め、微細化処理後の数平均繊維径を小さくすることができ、好ましい。
反応における天然セルロースの分散媒は水であり、反応水溶液中の天然セルロース濃度は、試薬の十分な拡散が可能な濃度であれば任意であるが、通常、反応水溶液の重量に対して約５％以下である。
First, in the oxidation reaction step, a dispersion in which natural cellulose is dispersed in water is prepared. Here, natural cellulose means purified cellulose isolated from cellulose biosynthetic systems such as plants, animals, and bacteria-producing gels. More specifically, softwood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, BC, cellulose isolated from sea squirt, and seaweed The cellulose can be exemplified, but is not limited thereto. Natural cellulose is preferably subjected to a treatment for increasing the surface area such as beating, whereby the reaction efficiency can be increased and the productivity can be increased. Furthermore, when natural cellulose that has been isolated and purified and stored in Never Dry is used, the microfibril bundles are likely to swell. The average fiber diameter can be reduced, which is preferable.
The dispersion medium of natural cellulose in the reaction is water, and the concentration of natural cellulose in the reaction aqueous solution is arbitrary as long as the reagent can sufficiently diffuse, but usually about 5% with respect to the weight of the reaction aqueous solution. It is as follows.
また、セルロースの酸化触媒として使用可能なＮ−オキシル化合物は数多く報告されている（「Ｃｅｌｌｕｌｏｓｅ」Ｖｏｌ．１０、２００３年、第３３５〜３４１ページにおけるＩ． Ｓｈｉｂａｔａ及びＡ． Ｉｓｏｇａｉによる「ＴＥＭＰＯ誘導体を用いたセルロースの触媒酸化：酸化生成物のＨＰＳＥＣ及びＮＭＲ分析」と題する記事）が、特にＴＥＭＰＯ、４−アセトアミド−ＴＥＭＰＯ、４−カルボキシ−ＴＥＭＰＯ、及び４−フォスフォノオキシ−ＴＥＭＰＯは水中常温での反応速度において好ましい。これらＮ−オキシル化合物の添加は触媒量で十分であり、好ましくは０．１〜４ｍｍｏｌ／ｌ、さらに好ましくは０．２〜２ｍｍｏｌ／ｌの範囲で反応水溶液に添加する。 Many N-oxyl compounds that can be used as an oxidation catalyst for cellulose have been reported ("Cellulose" Vol. 10, 2003, pages 335 to 341, using "TEMPO derivatives by I. Shibata and A. Isogai"). Articles entitled “Catalyzed Oxidation of Cellulose: HPSEC and NMR Analysis of Oxidation Products”), in particular, TEMPO, 4-acetamido-TEMPO, 4-carboxy-TEMPO, and 4-phosphonooxy-TEMPO react at room temperature in water. Preferred in speed. A catalytic amount is sufficient for the addition of these N-oxyl compounds, preferably 0.1 to 4 mmol / l, more preferably 0.2 to 2 mmol / l.
共酸化剤として、次亜ハロゲン酸またはその塩、亜ハロゲン酸またはその塩、過ハロゲン酸またはその塩、過酸化水素、および過有機酸などが本発明において使用可能であるが、好ましくはアルカリ金属次亜ハロゲン酸塩、たとえば、次亜塩素酸ナトリウムや次亜臭素酸ナトリウムである。次亜塩素酸ナトリウムを使用する場合、臭化アルカリ金属、たとえば臭化ナトリウムの存在下で反応を進めることが反応速度において好ましい。この臭化アルカリ金属の添加量は、Ｎ−オキシル化合物に対して約１〜４０倍モル量、好ましくは約１０〜２０倍モル量である。
反応水溶液のｐＨは約８〜１１の範囲で維持されることが好ましい。水溶液の温度は約４〜４０度において任意であるが、反応は室温で行うことが可能であり、特に温度の制御は必要としない。
As the co-oxidant, hypohalous acid or a salt thereof, hypohalous acid or a salt thereof, perhalogen acid or a salt thereof, hydrogen peroxide, a perorganic acid, and the like can be used in the present invention. Hypohalites such as sodium hypochlorite and sodium hypobromite. When sodium hypochlorite is used, it is preferable in terms of the reaction rate to advance the reaction in the presence of an alkali metal bromide such as sodium bromide. The addition amount of the alkali metal bromide is about 1 to 40 times mol, preferably about 10 to 20 times mol for the N-oxyl compound.
The pH of the aqueous reaction solution is preferably maintained in the range of about 8-11. The temperature of the aqueous solution is arbitrary at about 4 to 40 degrees, but the reaction can be performed at room temperature, and the temperature is not particularly required to be controlled.
本発明の微細セルロース繊維を得るために必要なカルボキシル基量は天然セルロース種により異なり、カルボキシル基量が多いほど、微細化処理後の最大繊維径、及び数平均繊維径は小さくなる。たとえば、木材系パルプおよび綿系パルプでは０．２〜２．２ｍｍｏｌ／ｇ、ＢＣやホヤからの抽出セルロースでは０．１〜０．８ｍｍｏｌ／ｇの範囲でカルボキシル基が導入されて微細化は進む。従って、酸化の程度を共酸化剤の添加量と反応時間により制御し、天然セルロース種に応じた酸化条件を最適化することで、目的とするカルボキシル基量を得ることが好ましい。一般に共酸化剤の添加量は、天然セルロース１ｇに対して約０．５〜８ｍｍｏｌの範囲で選択することが好ましく、反応は約５〜１２０分、長くとも２４０分以内に完了する。 The amount of carboxyl groups required to obtain the fine cellulose fibers of the present invention varies depending on the natural cellulose species. The greater the amount of carboxyl groups, the smaller the maximum fiber diameter and the number average fiber diameter after refinement. For example, in the case of wood-based pulp and cotton-based pulp, the carboxyl group is introduced in the range of 0.2 to 2.2 mmol / g, and in the case of cellulose extracted from BC and sea squirt, the carboxyl group is introduced in the range of 0.1 to 0.8 mmol / g, and the refinement proceeds. . Therefore, it is preferable to obtain the target amount of carboxyl groups by controlling the degree of oxidation by the addition amount of the co-oxidant and the reaction time and optimizing the oxidation conditions according to the natural cellulose species. In general, the amount of co-oxidant added is preferably in the range of about 0.5 to 8 mmol with respect to 1 g of natural cellulose, and the reaction is completed within about 5 to 120 minutes and at most 240 minutes.
精製工程に於いては、未反応の次亜塩素酸や各種副生成物等の反応スラリー中に含まれる反応物繊維と水以外の化合物を系外へ除去するが、反応物繊維は通常、この段階ではナノファイバー単位までばらばらに分散しているわけではないため、通常の精製法、すなわち水洗とろ過を繰り返すことで高純度（９９重量％以上）の反応物繊維と水の分散体とする。該精製工程における精製方法は遠心脱水を利用する方法（例えば、連続式デカンダー）のように、上述した目的を達成できる装置であればどんな装置を利用しても構わない。こうして得られる反応物繊維の水分散体は絞った状態で固形分（セルロース）濃度としておよそ１０重量％〜５０重量％の範囲にある。この後の工程で、ナノファイバーへ分散させることを考慮すると、５０重量％よりも高い固形分濃度とすると、分散に極めて高いエネルギーが必要となることから好ましくない。 In the refining process, the reactant fibers and compounds other than water contained in the reaction slurry such as unreacted hypochlorous acid and various by-products are removed from the system. At the stage, the nanofiber unit is not dispersed in a dispersed manner, so that the usual purification method, that is, washing with water and filtration are repeated to obtain a high purity (99% by weight or more) reactant fiber and water dispersion. As the purification method in the purification step, any apparatus can be used as long as it can achieve the above-described object, such as a method using centrifugal dehydration (for example, a continuous decanter). The aqueous dispersion of the reactant fibers thus obtained is in the range of approximately 10 wt% to 50 wt% as the solid content (cellulose) concentration in the squeezed state. In consideration of the dispersion in the nanofiber in the subsequent step, if the solid content concentration is higher than 50% by weight, it is not preferable because extremely high energy is required for the dispersion.
さらに、本発明では、上述した精製工程にて得られる水を含浸した反応物繊維（水分散体）を溶媒中に分散させ分散処理を施すことにより、本発明の微細セルロース繊維の分散体として提供することができる。
ここで、分散媒としての溶媒は通常は水が好ましいが、水以外にも目的に応じて水に可溶するアルコール類（メタノール、エタノール、イソプロパノール、イソブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、メチルセロソルブ、エチルセロソルブ、エチレングリコール、グリセリン等）、エーテル類（エチレングリコールジメチルエーテル、１，４−ジオキサン、テトラヒドロフラン等）、ケトン類（アセトン、メチルエチルケトン）やＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキサイド等を使用してもよい。また、これらの混合物も好適に使用できる。さらに、上述した反応物繊維の分散体を溶媒によって希釈、分散する際には、少しづつ溶媒を加えて分散していく、段階的な分散を試みると効率的にナノファイバーレベルの繊維の分散体を得ることができることがある。操作上の問題から、分散工程後の状態は粘性のある分散液あるいはゲル状の状態となるように分散条件を選ぶとよい。
Furthermore, in the present invention, the reaction fiber (water dispersion) impregnated with water obtained in the purification step described above is dispersed in a solvent and subjected to dispersion treatment, thereby providing a dispersion of fine cellulose fibers of the present invention. can do.
Here, the solvent as the dispersion medium is usually preferably water, but in addition to water, alcohols that are soluble in water depending on the purpose (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methyl) Cellosolve, ethyl cellosolve, ethylene glycol, glycerin, etc.), ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone), N, N-dimethylformamide, N, N-dimethylacetamide Dimethyl sulfoxide or the like may be used. Moreover, these mixtures can also be used conveniently. Furthermore, when the dispersion of the above-described reactant fibers is diluted and dispersed with a solvent, the solvent is gradually added to disperse, and when a stepwise dispersion is attempted, a nanofiber-level fiber dispersion is efficiently obtained. You may be able to get Due to operational problems, the dispersion conditions may be selected so that the state after the dispersion step is a viscous dispersion or gel.
次に、分散工程で使用する分散機としては、種々なものを使用することができる。具体例を示せば、反応物繊維における反応の進行度（アルデヒド基やカルボキシル基への変換量）にも依存するが、好適に反応が進行する条件下では、スクリュー型ミキサー、パドルミキサー、ディスパー型ミキサー、タービン型ミキサー等の工業生産機としての汎用の分散機で十分に本発明の微細セルロース繊維の分散体を得ることができる。
しかし、高速回転下でのホモミキサー、高圧ホモジナイザー、超高圧ホモジナイザー、超音波分散処理、ビーター、ディスク型レファイナー、コニカル型レファイナー、ダブルディスク型レファイナー、およびグラインダーのようなより強力で叩解能力のある装置を使用することにより、より効率的かつ高度なダウンサイジングが可能となる。さらに、これらの装置を使用することにより、アルデヒド基やカルボキシル基の量が比較的小さい場合（例えば、アルデヒド基やカルボキシル基のセルロースに対する総和量として、０．１〜０．５ｍｍｏｌ／ｇ）にも高度に微細化された本発明の微細セルロース繊維の分散体を提供できる。
Next, various devices can be used as the disperser used in the dispersion step. For example, depending on the progress of the reaction in the reaction product fiber (the amount of conversion to aldehyde groups and carboxyl groups), a screw-type mixer, paddle mixer, and disper type are suitable under conditions where the reaction proceeds appropriately. The dispersion of fine cellulose fibers of the present invention can be sufficiently obtained with a general-purpose disperser as an industrial production machine such as a mixer or a turbine mixer.
However, more powerful and defeating devices such as homomixers, high pressure homogenizers, ultra high pressure homogenizers, ultrasonic dispersion processing, beaters, disc refiners, conical refiners, double disc refiners, and grinders under high speed rotation By using, more efficient and advanced downsizing becomes possible. Furthermore, by using these devices, even when the amount of aldehyde group or carboxyl group is relatively small (for example, 0.1 to 0.5 mmol / g as the total amount of aldehyde group or carboxyl group to cellulose). A highly refined dispersion of fine cellulose fibers of the present invention can be provided.
次に、本発明の微細セルロース繊維を媒体中に分散させた分散体から、本発明の微細セルロース繊維を製造する方法について説明する。
上述した本発明の微細セルロース繊維の分散体を乾燥させることによって本発明の微細セルロース繊維を製造することができる。
ここで乾燥には、例えば、分散体の溶媒が水である場合には凍結乾燥法、分散体の溶媒が水と有機溶媒の混合溶液である場合には、ドラムドライヤーによる乾燥や場合によってはスプレイドライヤーによる噴霧乾燥を好適に使用することができる。また、上述した微細セルロースの分散体の中にバインダーとして水溶性高分子（ポリエチレンオキサイド、ポリビニルアルコール、ポリアクリルアミド、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、デンプン、天然ガム類等）や糖類（グルコース、フルクトース、マンノース、ガラクトース、トレハロース等）のような極めて沸点が高くしかもセルロースに対して親和性を有する化合物を混入させておくことにより、ドラムドライヤーやスプレイドライヤーのような汎用の乾燥法でも再度溶媒中にナノファイバーとして分散できる本発明の微細セルロース繊維を得ることができる。この場合には、分散体中に添加するバインダーの量は、反応物繊維に対して１０重量％〜８０重量％の範囲にあることが望ましい。
該微細セルロース繊維は再び、溶媒（水や有機溶媒あるいはその混合溶液）中へ混入し、適当な分散力（例えば、上述した本発明の微細セルロース繊維の分散体の製造における分散工程で使用する各種分散機を用いた分散）を加えることにより微細セルロース繊維の分散体とすることができる。
Next, a method for producing the fine cellulose fiber of the present invention from a dispersion in which the fine cellulose fiber of the present invention is dispersed in a medium will be described.
The fine cellulose fiber of this invention can be manufactured by drying the dispersion of the fine cellulose fiber of this invention mentioned above.
Here, the drying may be performed by, for example, a freeze-drying method when the solvent of the dispersion is water, or by a drum dryer or a spray depending on the case when the solvent of the dispersion is a mixed solution of water and an organic solvent. Spray drying with a dryer can be suitably used. In addition, a water-soluble polymer (polyethylene oxide, polyvinyl alcohol, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, starch, natural gums, etc.) and saccharides (such as natural gums) as a binder in the fine cellulose dispersion described above. By mixing a compound having an extremely high boiling point such as glucose, fructose, mannose, galactose, trehalose, etc. and having an affinity for cellulose, a general drying method such as a drum dryer or a spray dryer can be used again. The fine cellulose fiber of this invention which can be disperse | distributed as a nanofiber in a solvent can be obtained. In this case, the amount of the binder added to the dispersion is desirably in the range of 10% by weight to 80% by weight with respect to the reactant fiber.
The fine cellulose fibers are mixed again in a solvent (water, an organic solvent or a mixed solution thereof), and have an appropriate dispersion force (for example, various types used in the dispersion step in the production of the fine cellulose fiber dispersion of the present invention described above). A dispersion of fine cellulose fibers can be obtained by adding dispersion using a disperser.
本発明を実施例に基づいて説明する。
［実施例１および比較例１］
実施例１として、乾燥重量で２ｇ相当分の未乾燥の亜硫酸漂白針葉樹パルプ（主に１０００ｎｍを超える繊維径の繊維から成る）、０．０２５ｇのＴＥＭＰＯおよび０．２５ｇの臭化ナトリウムを水１５０ｍｌに分散させた後、１３重量％次亜塩素酸ナトリウム水溶液を、１ｇのパルプに対して次亜塩素酸ナトリウムの量が２．５ｍｍｏｌとなるように次亜塩素酸ナトリウムを加えて反応を開始した。反応中は０．５Ｍの水酸化ナトリウム水溶液を滴下してｐＨを１０．５に保った。ｐＨに変化が見られなくなった時点で反応終了と見なし、反応物をガラスフィルターにてろ過した後、十分な量の水による水洗、ろ過を５回繰り返し、固形分量２５重量％の水を含浸させた反応物繊維を得た。
The present invention will be described based on examples.
[Example 1 and Comparative Example 1]
As Example 1, 2 g of dry sulfite bleached softwood pulp (mainly consisting of fibers with a fiber diameter of more than 1000 nm), 0.025 g of TEMPO and 0.25 g of sodium bromide in 150 ml of water was used. After the dispersion, 13% by weight sodium hypochlorite aqueous solution was added with sodium hypochlorite so that the amount of sodium hypochlorite was 2.5 mmol with respect to 1 g of pulp to initiate the reaction. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10.5. When the pH no longer changes, the reaction is considered to be complete, the reaction product is filtered through a glass filter, washed with a sufficient amount of water and filtered five times to impregnate with a solid content of 25% by weight of water. Reactant fibers were obtained.
次に、該反応物繊維に水を加え、２重量％スラリーとし、回転刃式ミキサーで約５分間の処理を行った。処理に伴って著しくスラリーの粘度が上昇したため、少しづつ水を加えていき固形分濃度が０．１５重量％となるまでミキサーによる分散処理を続けた。こうして得られたセルロース濃度が０．１５重量％の微細セルロース繊維の分散体に対して、遠心分離により浮遊物の除去を行った後、水による濃度調製を行ってセルロース濃度が０．１重量％の透明かつやや粘調な微細セルロース繊維の分散体Ｓ１を得た。Ｓ１を乾燥させて得られた透明な膜状のセルロースの広角Ｘ線回折像から、Ｓ１がセルロースＩ型結晶構造を有するセルロースから成ることが示され、また同じ膜状セルロースのＡＴＲスペクトルのパターンからカルボニル基の存在が確認された。 Next, water was added to the reactant fiber to make a 2 wt% slurry, which was then treated for about 5 minutes with a rotary blade mixer. Since the viscosity of the slurry increased significantly with the treatment, water was gradually added, and the dispersion treatment with the mixer was continued until the solid content concentration became 0.15% by weight. The dispersion of fine cellulose fibers having a cellulose concentration of 0.15% by weight thus obtained was subjected to removal of suspended matter by centrifugation, and then the concentration was adjusted with water to give a cellulose concentration of 0.1% by weight. A transparent and slightly viscous fine cellulose fiber dispersion S1 was obtained. A wide-angle X-ray diffraction image of a transparent membranous cellulose obtained by drying S1 shows that S1 is composed of cellulose having a cellulose I-type crystal structure, and from the ATR spectrum pattern of the same membranous cellulose. The presence of a carbonyl group was confirmed.
これに対し、比較例１として、実施例１の原料として用いた亜硫酸漂白針葉樹パルプ（主に１０００ｎｍを超える繊維径の繊維から成る）に水を加え、Ｓ１と同等のミキサー処理により０．１重量％とした分散体（Ｈ１）を調製した。
図１のａおよびｂに、Ｈ１（非コロイド）およびＳ１（コロイド）の写真をそれぞれ示した。酸化反応工程を経ていない比較例１の分散体Ｈ１は機械処理のみでは懸濁せず、沈降が起こるのに対し、Ｓ１は透明な分散液であり、沈降が全く起こらず、極めて微細な繊維から成る分散体（コロイド）であることが分かる。微細繊維の分散体においては光の透過方向に対する繊維片の持続長さ（最も短い場合には繊維径）が可視波長よりも小さくなると分散液中での界面散乱が著しく抑えられるため、透明性が大きく向上したと解釈される。
On the other hand, as Comparative Example 1, water was added to the sulfite bleached softwood pulp (mainly composed of fibers having a fiber diameter exceeding 1000 nm) used as the raw material of Example 1, and 0.1 wt. % Dispersion (H1) was prepared.
FIGS. 1a and 1b show photographs of H1 (non-colloid) and S1 (colloid), respectively. Dispersion H1 of Comparative Example 1 that has not undergone the oxidation reaction step does not suspend only by mechanical treatment and sedimentation occurs, whereas S1 is a transparent dispersion and does not undergo sedimentation at all. It can be seen that this is a dispersion (colloid). In the dispersion of fine fibers, if the continuous length of the fiber piece in the light transmission direction (fiber diameter in the shortest case) becomes smaller than the visible wavelength, interface scattering in the dispersion liquid is remarkably suppressed, so that transparency is reduced. It is interpreted as a great improvement.
さらに、Ｓ１は０．１重量％でも粘度が極めて高く、直交偏光板の間に置くと、静止した状態でも複屈折が確認でき、分散液中に含まれる微細な繊維が高い結晶配向性を有しており、かつ分散液中で部分的に秩序構造を有している可能性も示唆された。図２には、Ｓ１の微細セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャスト後、２％ウラニルアセテートでネガティブ染色したＴＥＭ像を示した。Ｓ１は繊維状のセルロースから構成されており、最大繊維径が１０ｎｍかつ数平均繊維径が６ｎｍであった。
また、上述した方法により評価したＳ１を乾燥させて得られる透明膜状のセルロース中のアルデヒド基の量およびカルボキシル基の量は、それぞれ０．３３ｍｍｏｌ／ｇおよび０．９９ｍｍｏｌ／ｇであった。
以上により実施例１により得られた微細セルロース繊維の分散体は本発明の微細セルロース繊維を含有していることが確認された。
Furthermore, S1 has a very high viscosity even at 0.1% by weight, and when placed between crossed polarizing plates, birefringence can be confirmed even in a stationary state, and fine fibers contained in the dispersion have high crystal orientation. In addition, the possibility of having an ordered structure partially in the dispersion was also suggested. FIG. 2 shows a TEM image in which S1 fine cellulose fibers were cast on a hydrophilized carbon film-coated grid and then negatively stained with 2% uranyl acetate. S1 is composed of fibrous cellulose, and has a maximum fiber diameter of 10 nm and a number average fiber diameter of 6 nm.
Moreover, the amount of aldehyde groups and the amount of carboxyl groups in the transparent film-like cellulose obtained by drying S1 evaluated by the method described above were 0.33 mmol / g and 0.99 mmol / g, respectively.
From the above, it was confirmed that the fine cellulose fiber dispersion obtained in Example 1 contained the fine cellulose fiber of the present invention.
［実施例２，３，４］
実施例１において、原料を、精製後未乾燥のコットンリント（実施例２）、精製後未乾燥の酢酸菌生産のバクテリアセルロース（ＢＣ）（実施例３）、ホヤから単離した精製後未乾燥のセルロース（実施例４）とし、原料セルロースに対する次亜塩素酸ナトリウムの
添加量を、実施例２では実施例１と同様、２．５ｍｍｏｌ／ｇ、実施例３および実施例４では共に１．８ｍｍｏｌ／ｇとし、他の条件はすべて実施例１と同じとしていずれも０．１重量％の透明な微細セルロース繊維の分散体を得た。実施例２，３，４の各々において得られた０．１重量％のセルロース濃度の微細セルロース繊維の分散体を各々、Ｓ２、Ｓ３、Ｓ４とする。
[Examples 2, 3, and 4]
In Example 1, the raw material was purified from undried cotton lint (Example 2), purified from undried acetic acid bacteria produced bacterial cellulose (BC) (Example 3), and purified from squirt The amount of sodium hypochlorite added to the raw material cellulose was 2.5 mmol / g in the same manner as in Example 1 and 1.8 mmol in both Examples 3 and 4. / G, and all other conditions were the same as in Example 1, and a 0.1% by weight transparent fine cellulose fiber dispersion was obtained. The dispersions of fine cellulose fibers having a cellulose concentration of 0.1% by weight obtained in each of Examples 2, 3, and 4 are designated as S2, S3, and S4, respectively.
Ｓ２−Ｓ４のいずれからも乾燥により、透明な膜状のセルロースが得られ、セルロースＩ型結晶構造を有することとカルボニル基の吸収バンドを有することが実施例１と同様の手法により確認された。
実施例１と同様にしてＴＥＭ観察により評価した、Ｓ２−Ｓ４の最大繊維径および数平均繊維径は、それぞれ、最大繊維径，１５ｎｍ，数平均繊維径，８ｎｍ（Ｓ２）、最大繊維径，９０ｎｍ，数平均繊維径，３７ｎｍ（Ｓ３）、最大繊維径，６２ｎｍ，数平均繊維径，２２ｎｍ（Ｓ４）であった。
さらにＳ２−Ｓ４の各々を乾燥させて得られる透明膜状のセルロース中のアルデヒド基の量およびカルボキシル基の量は、それぞれ０．２１ｍｍｏｌ／ｇおよび０．６７ｍｍｏｌ／ｇ（Ｓ２）、０．０１ｍｍｏｌ／ｇおよび０．５０ｍｍｏｌ／ｇ（Ｓ３）、０．０３ｍｍｏｌ／ｇおよび０．３１ｍｍｏｌ／ｇであり、実施例２〜４により得られた微細セルロース繊維の分散体Ｓ２−Ｓ４が本発明の微細セルロース繊維を含有していることが証明された。
By drying from any of S2-S4, transparent film-like cellulose was obtained, and it was confirmed by the same method as in Example 1 that it had a cellulose I-type crystal structure and had a carbonyl group absorption band.
The maximum fiber diameter and the number average fiber diameter of S2-S4 evaluated by TEM observation in the same manner as in Example 1 were the maximum fiber diameter, 15 nm, the number average fiber diameter, 8 nm (S2), the maximum fiber diameter, and 90 nm, respectively. , Number average fiber diameter, 37 nm (S3), maximum fiber diameter, 62 nm, number average fiber diameter, 22 nm (S4).
Furthermore, the amount of aldehyde groups and the amount of carboxyl groups in the transparent film-like cellulose obtained by drying each of S2-S4 were 0.21 mmol / g, 0.67 mmol / g (S2), 0.01 mmol / g and 0.50 mmol / g (S3), 0.03 mmol / g and 0.31 mmol / g, and the fine cellulose fiber dispersion S2-S4 obtained in Examples 2 to 4 is the fine cellulose fiber of the present invention. It was proved to contain.
以上Ｓ１−Ｓ４に含まれる微細セルロース繊維がコーティング材として有効に機能することを示すために以下の実験を実施した。すなわち、Ｓ１−Ｓ４の各々をガラス上にキャストしたところ、いずれも平滑性に優れ透明な表面を形成した。また、各サンプルの端をピンセットで摘み上げるといずれも自立した膜を形成していることが明らかになった。すなわち、本発明の微細セルロース繊維の分散液は優れたコーティング材としての性能を有する可能性が示唆された。 In order to show that the fine cellulose fibers contained in S1-S4 function effectively as a coating material, the following experiment was performed. That is, when each of S1-S4 was cast on glass, all formed a transparent surface with excellent smoothness. In addition, it was revealed that when the ends of each sample were picked up with tweezers, a self-supporting film was formed. That is, it was suggested that the dispersion of fine cellulose fibers of the present invention may have excellent performance as a coating material.
［比較例２］
木材パルプの高圧ホモジナイザー処理により得られる微細化繊維状セルロースとして知られるセリッシュ（ダイセル化学社製、セリッシュＫＹ−１００Ｇ、セルロース濃度１０重量％の水分散体）の０．１重量％の水分散体（Ｈ２）を、実施例１と同様のミキサー処理により調製した。得られた白色の分散液から構成する繊維のＳＥＭ観察を行ったところ、最大繊維径は、１．９μｍ、数平均繊維径は１４０ｎｍであった。
得られた水分散体（Ｈ２）は、ミキサー分散後静置しておくと数分程度で沈降が起こった。同時に、Ｈ２をガラス上にキャストしたところ、自立膜は形成するものの白色でざらざらした表面平滑性に劣る表面であり、コーティング材としては不適であることが判明した。
[Comparative Example 2]
0.1% by weight aqueous dispersion of serish (manufactured by Daicel Chemical Industries, serish KY-100G, aqueous dispersion having a cellulose concentration of 10% by weight) known as refined fibrous cellulose obtained by high-pressure homogenizer treatment of wood pulp ( H2) was prepared by the same mixer treatment as in Example 1. When the SEM observation of the fiber comprised from the obtained white dispersion liquid was performed, the maximum fiber diameter was 1.9 μm and the number average fiber diameter was 140 nm.
When the obtained water dispersion (H2) was allowed to stand after dispersing the mixer, sedimentation occurred in about several minutes. At the same time, when H2 was cast on glass, it was found that a self-supporting film was formed, but it was a white and rough surface with poor surface smoothness, and was unsuitable as a coating material.
本発明の微細セルロース繊維は、新規なナノファイバー膜の原料や複合化材料用のナノフィラーとして適用し得るだけでなく、コーティング基材、各種機能性添加剤（ゲル化剤、乳化剤等）としても好適に利用できる。 The fine cellulose fiber of the present invention can be applied not only as a raw material for novel nanofiber membranes and nanofillers for composite materials, but also as a coating substrate and various functional additives (gelling agent, emulsifier, etc.) It can be suitably used.
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