JP2013220328A - Chitin sheet and method of producing the same - Google Patents
Chitin sheet and method of producing the same Download PDFInfo
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- JP2013220328A JP2013220328A JP2012095864A JP2012095864A JP2013220328A JP 2013220328 A JP2013220328 A JP 2013220328A JP 2012095864 A JP2012095864 A JP 2012095864A JP 2012095864 A JP2012095864 A JP 2012095864A JP 2013220328 A JP2013220328 A JP 2013220328A
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Abstract
Description
本発明は、タンパク質などに対する吸着材料としての利用、及び、キチンの生体吸収性と創傷治癒効果を利用した医療用材料としての利用が期待される、キチンシートとその製造方法に関する。 The present invention relates to a chitin sheet which is expected to be used as an adsorbing material for proteins and the like, and as a medical material utilizing the bioabsorbability and wound healing effect of chitin.
キチンをシート状に成形する技術はすでにいくつか知られている。 Several techniques for forming chitin into a sheet are already known.
例えば、有機溶媒（ハロゲン化炭化水素とトリクロル酢酸の混合物、Ｎ−メチルピロリドン又はＮ，Ｎ−ジメチルアセトアミドと塩化リチウムとの混合物、など）にキチンを溶解して紡糸し、不織布状に成形することが知られている（特許文献１）。また、エレクトロスピニング装置（特許文献２）や加圧噴射装置（特許文献３）を用いてキチンナノファイバーを作製してから、不織布状に成形する方法も知られている。しかし、これらの方法は、ファイバーへの加工を伴うため、工程数が多くなるという欠点があった。 For example, dissolving chitin in an organic solvent (a mixture of halogenated hydrocarbon and trichloroacetic acid, N-methylpyrrolidone, or a mixture of N, N-dimethylacetamide and lithium chloride, etc.) and spinning to form a nonwoven fabric Is known (Patent Document 1). Also known is a method of forming chitin nanofibers using an electrospinning device (Patent Document 2) or a pressure injection device (Patent Document 3) and then forming the nanofiber into a nonwoven fabric. However, these methods have a drawback in that the number of steps increases because they involve processing into fibers.
一方、ファイバーへの加工を伴わないでキチンをシート状に成形する方法においても、まず、塩化カルシウム・２水和物飽和メタノールにα−キチンを溶解してキチン溶液を調製し（特許文献４）、つづいて、このキチン溶液に大過剰の水を加えてゲルを調製し、透析によるカルシウムの除去後、蒸留水に懸濁して紙漉きにかけ、プレス乾燥によってシート状とする（非特許文献１）といった操作が必要である。なお、水の代わりにメタノールを用いてゲル粒子を作製する方法も提案されている（特許文献５）が、遠心脱水機でゲルを捕集し、その後も紙漉き操作やプレス乾燥を行うが必要がある。 On the other hand, also in the method of forming chitin into a sheet shape without processing into fibers, first, a chitin solution is prepared by dissolving α-chitin in calcium chloride dihydrate saturated methanol (Patent Document 4). Then, a gel is prepared by adding a large excess of water to the chitin solution, and after removing calcium by dialysis, suspended in distilled water, papered, and formed into a sheet by press drying (Non-patent Document 1) Operation is required. In addition, although the method of producing a gel particle using methanol instead of water is proposed (patent document 5), it is necessary to collect gel with a centrifugal dehydrator, and to perform papermaking operation and press drying after that. is there.
このように、従来の方法は、工程数が多いという欠点があった。 Thus, the conventional method has a drawback that the number of steps is large.
そこで本発明では上記問題点に鑑み、簡便に生分解性・生体吸収性材料であるキチンをシート状に成形する方法を提供することをその目的とする。 In view of the above problems, an object of the present invention is to provide a method for easily forming chitin, which is a biodegradable / bioabsorbable material, into a sheet shape.
上記課題を達成するため種々検討した結果、塩化カルシウム・２水和物飽和メタノールにα−キチンを溶解して調製したキチン溶液を型に流し込み、型とともにアルコールに浸漬し、その後、水で洗浄するという簡便な方法でキチンシートが得られることを見出し、本発明を完成させた。 As a result of various studies to achieve the above problems, a chitin solution prepared by dissolving α-chitin in calcium chloride dihydrate saturated methanol was poured into a mold, immersed in alcohol together with the mold, and then washed with water. The present inventors have found that a chitin sheet can be obtained by such a simple method.
すなわち、本発明のキチンシートの製造方法は、塩化カルシウム・２水和物飽和メタノールにα−キチンを溶解して調製したキチン溶液を型に塗布した後、このキチン溶液を前記型とともにアルコールに浸漬し、その後、生成したシート状のキチンゲルを水で洗浄することを特徴とする。 That is, in the method for producing a chitin sheet of the present invention, a chitin solution prepared by dissolving α-chitin in calcium chloride dihydrate saturated methanol is applied to a mold, and then the chitin solution is immersed in alcohol together with the mold. Then, the produced sheet-shaped chitin gel is washed with water.
本発明のキチンシートは、塩化カルシウム・２水和物飽和メタノールにα−キチンを溶解して調製したキチン溶液を型に塗布した後、このキチン溶液を前記型とともにアルコールに浸漬し、その後、生成したシート状のキチンゲルを水で洗浄することによって得られたことを特徴とする。 The chitin sheet of the present invention is produced by applying a chitin solution prepared by dissolving α-chitin in calcium chloride dihydrate saturated methanol to a mold, immersing the chitin solution in alcohol together with the mold, and then forming The obtained sheet-like chitin gel was obtained by washing with water.
本発明のキチンシートの製造方法によれば、加熱や冷却の操作は必要とせず、簡便に生分解性・生体吸収性材料であるキチンをシート状に成形することができる。 According to the method for producing a chitin sheet of the present invention, heating and cooling operations are not required, and chitin which is a biodegradable / bioabsorbable material can be easily formed into a sheet shape.
本発明のキチンシートは、柔軟性のある透明なシートであり、タンパク質の吸脱着特性を有する。
この簡便な方法により得られたキチンシートを提供することができる。
The chitin sheet of the present invention is a flexible transparent sheet and has protein adsorption / desorption characteristics.
A chitin sheet obtained by this simple method can be provided.
本発明のキチンシートの製造方法は、塩化カルシウム・２水和物飽和メタノールにα−キチンを溶解して調製したキチン溶液を型に塗布した後、このキチン溶液を前記型とともにアルコールに浸漬し、その後、生成したシート状のキチンゲルを水で洗浄するものである。なお，浸漬に用いるアルコールとしては、メタノール、エタノール、イソプロパノールなどが利用可能である。以下、本発明のキチンシートの製造方法について説明する。なお、以下の操作はすべて２５℃程度の室温で実施することができ、とくに加熱や冷却の操作は必要としない。 The method for producing a chitin sheet of the present invention comprises applying a chitin solution prepared by dissolving α-chitin in calcium chloride dihydrate saturated methanol to a mold, and then immersing the chitin solution in an alcohol together with the mold. Thereafter, the produced sheet-shaped chitin gel is washed with water. In addition, methanol, ethanol, isopropanol, etc. can be used as alcohol used for immersion. Hereinafter, the manufacturing method of the chitin sheet of this invention is demonstrated. The following operations can all be performed at a room temperature of about 25 ° C., and heating and cooling operations are not particularly required.
はじめに、塩化カルシウム・２水和物飽和メタノールに１〜３％程度になるようにキチン粉末を加えた後、しばらく撹拌してキチンを溶解する。なお、塩化カルシウム・２水和物およびキチンの溶解度を高めるためにメタノールに対して０〜２％程度の水を添加してもよい。 First, after adding chitin powder to calcium chloride dihydrate saturated methanol so that it may become about 1-3%, it stirs for a while and dissolves chitin. In order to increase the solubility of calcium chloride dihydrate and chitin, about 0 to 2% of water may be added to methanol.
つづいて、上記で得られたキチン溶液を型に塗布する。 Subsequently, the chitin solution obtained above is applied to the mold.
ここで用いられる型としては、例えば、平面のガラス板を用いることができ、或いは、連続型の製造装置を利用する場合には、曲面のロール型を用いてもよい。また、型の材質は、特定のものに限定されない。なお、適度な厚さと強度を有するキチンシートを得るために、キチン溶液を例えば０．５〜２ｍｍ程度の厚さの薄膜状になるように型に塗布するのが好ましい。 As a type | mold used here, a flat glass plate can be used, for example, When using a continuous type manufacturing apparatus, you may use a curved roll type | mold. Further, the material of the mold is not limited to a specific material. In order to obtain a chitin sheet having an appropriate thickness and strength, the chitin solution is preferably applied to a mold so as to form a thin film having a thickness of about 0.5 to 2 mm.
そして、キチン溶液を型とともにアルコールに浸漬する。その結果、型上にシート状のキチンゲルが生成する。その後、生成したキチンゲルを型から剥離し、水で洗浄することによって、キチンシートが得られる。 Then, the chitin solution is immersed in alcohol together with the mold. As a result, a sheet-like chitin gel is formed on the mold. Then, the produced chitin gel is peeled from the mold and washed with water to obtain a chitin sheet.
以上のように、本発明のキチンシートの製造方法によれば、加熱や冷却の操作は必要とせず、少ない工程数で簡便に生分解性・生体吸収性材料であるキチンをシート状に成形することができる。すなわち、塩化カルシウム・２水和物飽和メタノール溶媒を用いる従来の方法では、ゲル粒子を調製後に紙漉き操作によりシート状に成形し、その後、プレス乾燥により結合させる必要があったが、本発明によれば、これらの紙漉き操作とプレス乾燥が不要となる。 As described above, according to the method for producing a chitin sheet of the present invention, heating and cooling operations are not required, and the chitin which is a biodegradable / bioabsorbable material is easily formed into a sheet shape with a small number of steps. be able to. That is, in the conventional method using a calcium chloride dihydrate saturated methanol solvent, it was necessary to form the gel particles into a sheet by a paper-making operation after preparation, and then bind them by press drying. For example, these paper-making operations and press drying are unnecessary.
また、本発明のキチンシートは、柔軟性のある透明なシートであり、タンパク質の吸脱着特性を有する。 The chitin sheet of the present invention is a flexible transparent sheet and has protein adsorption / desorption characteristics.
なお、本発明は上記実施形態に限定されるものではなく、本発明の思想を逸脱しない範囲で種々の変形実施が可能である。 The present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.
キチンシートの作製は室温で実施した。キチン溶液は市販のα-キチン（Chitin from crab shells, practical grade, powder, C7170-100G, SIGMA社）を０．６％の水を含む塩化カルシウム・２水和物飽和メタノールに２％になるように溶解して調製した。調製したキチン溶液をガラス板上に１ｍｍになるようにキャスト後、エタノールに浸漬した。シート状に成形されたキチンゲルをゲル化したキチンをガラス板から剥離し、水で洗浄後、キチンシートとした。 The chitin sheet was produced at room temperature. The chitin solution should be 2% of calcium chloride dihydrate saturated methanol containing 0.6% water of commercially available α-chitin (Chitin from crab shells, practical grade, powder, C7170-100G, SIGMA). And dissolved. The prepared chitin solution was cast to 1 mm on a glass plate and then immersed in ethanol. The chitin gelled from the chitin gel formed into a sheet was peeled from the glass plate and washed with water to obtain a chitin sheet.
図１にキチンシートの写真を示す。水での洗浄時に縦横が型の寸法の２分の１程度に収縮した。この収縮率を考慮することにより、必要な型の大きさが決定できる。作製したキチンシートは柔軟性のある透明なシートであった。高い柔軟性はキチンシートで腕などの曲線部分の創傷を被覆に利用する場合に有効である。高い透明性は患部に貼り付ける際に有用である。 Fig. 1 shows a photograph of the chitin sheet. When washed with water, the length and breadth contracted to about one half of the size of the mold. By considering this shrinkage rate, the required mold size can be determined. The produced chitin sheet was a flexible transparent sheet. High flexibility is effective when a wound of a curved portion such as an arm is used for covering with a chitin sheet. High transparency is useful when affixing to the affected area.
図２には作製したキチンシートのタンパク質の吸脱着特性の例を示す。吸着実験用のタンパク質としては牛血清アルブミンを用い、１０ｍＭのクエン酸−リン酸ナトリウム緩衝液（ｐＨ３〜８）に２００ｍｇ／ｍＬになるように溶解した。作製したゲルを５×５ｍｍに切断したものを４枚、タンパク質溶液に浸漬し、２４時間後に上清のタンパク質濃度を市販のビシンコニン酸法タンパク質定量キットを用いて測定した。また、タンパク質の溶出（脱着）には上記緩衝液に塩化ナトリウムを４００ｍＭになるように加えた溶液を溶出液として用い、２４時間後に溶出したタンパク質の濃度をビシンコニン酸法により測定した。図２より、作製したキチンシートはｐＨ５〜７においてタンパク質を吸着し、塩濃度を高めることにより、タンパク質を溶出可能であることが示された。この吸脱着特性は作製したキチンシートを医薬品などの製造におけるタンパク質の回収・除去や薬物徐放材料として用いる場合に有用である。 FIG. 2 shows an example of protein adsorption / desorption characteristics of the produced chitin sheet. Bovine serum albumin was used as a protein for the adsorption experiment, and dissolved in 10 mM citrate-sodium phosphate buffer (pH 3 to 8) to 200 mg / mL. Four of the prepared gels cut to 5 × 5 mm were immersed in a protein solution, and after 24 hours, the protein concentration of the supernatant was measured using a commercially available bicinchoninic acid method protein quantification kit. For protein elution (desorption), a solution obtained by adding sodium chloride to the above buffer to 400 mM was used as an eluate, and the concentration of the protein eluted after 24 hours was measured by the bicinchoninic acid method. From FIG. 2, it was shown that the produced chitin sheet was able to elute proteins by adsorbing proteins at pH 5 to 7 and increasing the salt concentration. This adsorption / desorption property is useful when the produced chitin sheet is used as a material for protein recovery / removal or drug sustained release in the production of pharmaceuticals.
ガラス板上にキャストしたキチン溶液の浸漬に用いるアルコールを、エタノールの代わりにメタノールとしたほかは実施例１と同様に操作したところ、実施例１と同様にキチンシートが得られた。 A chitin sheet was obtained in the same manner as in Example 1 except that the alcohol used for dipping the chitin solution cast on the glass plate was changed to methanol instead of ethanol.
ガラス板上にキャストしたキチン溶液の浸漬に用いるアルコールを、エタノールの代わりにイソプロパノールとしたほかは実施例１と同様に操作したところ、実施例１と同様にキチンシートが得られた。 A chitin sheet was obtained in the same manner as in Example 1 except that the alcohol used for dipping the chitin solution cast on the glass plate was replaced with isopropanol instead of ethanol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07316202A (en) * | 1994-05-25 | 1995-12-05 | Fuji Spinning Co Ltd | Preparation of chitin sponge, chitin paper, and chitin film |
| JPH10101811A (en) * | 1996-09-30 | 1998-04-21 | Kyocera Corp | Production of molded product of chitin |
| JP2005035934A (en) * | 2003-07-15 | 2005-02-10 | Chitosan Kowa:Kk | Simple method for producing chitin gel from chitin powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07316202A (en) * | 1994-05-25 | 1995-12-05 | Fuji Spinning Co Ltd | Preparation of chitin sponge, chitin paper, and chitin film |
| JPH10101811A (en) * | 1996-09-30 | 1998-04-21 | Kyocera Corp | Production of molded product of chitin |
| JP2005035934A (en) * | 2003-07-15 | 2005-02-10 | Chitosan Kowa:Kk | Simple method for producing chitin gel from chitin powder |
Non-Patent Citations (1)
| Title |
|---|
| JPN6016020593; Ｃｅｌｌｕｌｏｓｅ， ２００６， Ｖｏｌ．１３， ｐ．３５７-３６４ * |
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