JP3106251B2 - Preparation method of composite porous body of plant fiber and chitosan - Google Patents
Preparation method of composite porous body of plant fiber and chitosanInfo
- Publication number
- JP3106251B2 JP3106251B2 JP03021433A JP2143391A JP3106251B2 JP 3106251 B2 JP3106251 B2 JP 3106251B2 JP 03021433 A JP03021433 A JP 03021433A JP 2143391 A JP2143391 A JP 2143391A JP 3106251 B2 JP3106251 B2 JP 3106251B2
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- porous body
- plant fiber
- water
- composite porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Paper (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、植物繊維とキトサンを
原料として複合多孔質体を調製する方法、及びこの方法
により得られた植物繊維とキトサンの複合多孔質体に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a composite porous body using plant fibers and chitosan as raw materials, and a composite porous body of plant fibers and chitosan obtained by the method.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】キトサン
は、カニ、エビなどの甲殻類、カブトムシなどの昆虫類
に含まれるキチンを脱アセチル化して誘導される高分子
物質である。キチンは生物界ではセルロースについで多
量に生産されており、これから誘導されるキトサンはキ
チン同様、種々の分野への応用が期待されている物質で
ある。例えば、分離膜、食品包装紙、医療材料等に使用
するキトサン系抄造体（特開昭63-59499号) 、キトサン
を付着させて抗菌性および抗カビ性を付与したフィルム
（特開昭62-83875号) などがある。またキトサンと植物
繊維の組み合わせでは、紙基材にキトサンを処理して食
肉製品を充填するケーシング用材料としての利用（特開
平1-174699号) 、天然パルプシートにキトサンを塗布し
た農業用シート（特開平2-2303号) 等が知られている。BACKGROUND OF THE INVENTION Chitosan is a high molecular substance derived by deacetylating chitin contained in crustaceans such as crabs and shrimps and insects such as beetles. Chitin is produced in the living world in abundance after cellulose, and chitosan derived therefrom is a substance expected to be applied to various fields like chitin. For example, a chitosan-based paper used for separation membranes, food wrapping paper, medical materials, etc. (JP-A-63-59499), a film to which chitosan is attached to impart antibacterial and antifungal properties (JP-A-62-59499) No. 83875). In the combination of chitosan and vegetable fiber, the paper base is treated with chitosan and used as a casing material for filling meat products (Japanese Unexamined Patent Publication No. 1-174699), and a natural pulp sheet coated with chitosan for agricultural sheets ( Japanese Patent Application Laid-Open No. 2-2303) is known.
【０００３】しかしながら、本発明のようにキトサンと
植物繊維を組み合わせて、多孔質体を製造する方法は未
だない。従って、本発明は、植物繊維とキトサンを原料
として複合多孔質体を調製する方法、及びこの方法によ
り得られた植物繊維とキトサンの複合多孔質体を提供す
ることを目的とする。[0003] However, there is no method for producing a porous body by combining chitosan and plant fiber as in the present invention. Accordingly, an object of the present invention is to provide a method of preparing a composite porous body using plant fibers and chitosan as raw materials, and a composite porous body of plant fibers and chitosan obtained by this method.
【０００４】[0004]
【課題を解決するための手段】本発明は、水、植物繊
維、キトサンおよび酢酸を混合し、混合溶液を凍結乾燥
し、次いで無水酢酸で処理することを特徴とする植物繊
維とキトサンの複合多孔質体の調製方法、およびこれに
より得られた多孔質体である。本発明に使用する植物繊
維は特に制限はないが、パルプ繊維など水不溶性の高分
子か、水溶性ならば負の電荷を持ち、キトサンとポリイ
オンコンプレックスを形成して凝集塊を生成するものが
好ましい。例えばカルボキシメチルセルロースや澱粉類
や大豆圧搾残渣（おから）等である。SUMMARY OF THE INVENTION The present invention relates to a composite fiber of vegetable fiber and chitosan, comprising mixing water, vegetable fiber, chitosan and acetic acid, freeze-drying the mixed solution, and then treating with acetic anhydride. It is a method for preparing a porous body, and a porous body obtained thereby. The plant fiber used in the present invention is not particularly limited, but is preferably a water-insoluble polymer such as pulp fiber, or a water-soluble polymer having a negative charge and forming an agglomerate by forming a polyion complex with chitosan. . For example, carboxymethylcellulose, starch, soybean pressed residue (okara) and the like.
【０００５】キトサンは、重合度100 以上で脱アセチル
化度70％以上のものが好ましい。重合度100 以下では製
品の強度が充分でなく、脱アセチル化度70％以下では酢
酸に充分に溶解しないからである。本発明によれば、使
用する植物繊維の長さと、キトサンの濃度を変えること
によって、多孔質体の孔の大きさを調節することができ
る。即ち、繊維長の短いものを使用し、キトサン濃度を
高くすると、孔径は小さくなり、キトサン濃度を低くす
ると孔径の大きいザラついた感触の製品が得られる。[0005] Chitosan preferably has a degree of polymerization of 100 or more and a degree of deacetylation of 70% or more. If the degree of polymerization is less than 100, the strength of the product is not sufficient, and if the degree of deacetylation is less than 70%, the product is not sufficiently dissolved in acetic acid. According to the present invention, the size of the pores of the porous body can be adjusted by changing the length of the plant fiber used and the concentration of chitosan. That is, when a fiber having a short fiber length is used and the concentration of chitosan is increased, the pore size becomes smaller.
【０００６】耐水性を調節するためには、キトサンのア
セチル化度を変えれば良く、全くアセチル化しないもの
では酸溶液で数分、蒸留水中でも１日程度でほぐれてく
る。また、アセチル化度を高めたものでは、微生物によ
る分解を受けなければ、半永久的にその構造を保持でき
る。アセチル化度を調節することによって、キトサンの
抗菌性を変えることができ、例えば、開放系で本物質を
水道水に膨潤させたまま放置しても、１ヶ月以上黴の発
生を見ない。In order to adjust the water resistance, the degree of acetylation of chitosan may be changed. In the case of non-acetylated chitosan, it can be loosened in an acid solution for several minutes and even in distilled water in about one day. In addition, those with a high degree of acetylation can retain their structure semi-permanently unless they are decomposed by microorganisms. By adjusting the degree of acetylation, the antibacterial properties of chitosan can be changed. For example, even if this substance is left swelled in tap water in an open system, no mold is observed for one month or more.
【０００７】さらに、本物質を水に浸漬し60℃で乾燥さ
せ、再び水に浸漬するという繰り返しの再生を試みたと
ころ、少なくても５回の再生でも、吸水性能が保持され
ていた。次に、本発明の多孔質体の調製方法を好適例に
より説明する。水に紙パルプ等の植物繊維とキトサンを
目的に応じて、各々0.1 〜10重量％混合する。次いで、
酢酸を加えてキトサンを溶解する。酢酸の添加量は、キ
トサンを溶解するに必要充分な分量、例えばキトサンと
等量を使用することができる。予めキトサンの酢酸溶液
を調製し、これに水と植物繊維を添加してもよい。均一
になるように攪拌し、得られた懸濁液を凍結乾燥する。
乾燥した試料に無水酢酸を用いてキトサンをアセチル化
する。これにより、キトサンはキチン質に変化し水不溶
性になる。アセチル化度は使用する無水酢酸の量と反応
液のpH、及び反応時間で調節する。最後にアルカリで中
和し、試料をよく水洗し乾燥させる。[0007] Furthermore, when repeated regeneration of the substance was immersed in water, dried at 60 ° C, and immersed in water again, water absorption performance was maintained even at least five times. Next, a method for preparing the porous body of the present invention will be described with reference to preferred examples. 0.1 to 10% by weight of vegetable fiber such as paper pulp and chitosan are mixed with water according to the purpose. Then
Acetic acid is added to dissolve the chitosan. The amount of acetic acid to be added may be an amount necessary and sufficient to dissolve chitosan, for example, an equivalent amount to chitosan. An acetic acid solution of chitosan may be prepared in advance, and water and plant fiber may be added thereto. Stir to homogeneity and freeze-dry the resulting suspension.
The dried sample is acetylated with chitosan using acetic anhydride. This converts chitosan to chitin and becomes water-insoluble. The degree of acetylation is adjusted by the amount of acetic anhydride used, the pH of the reaction solution, and the reaction time. Finally, the sample is neutralized with an alkali, and the sample is thoroughly washed with water and dried.
【０００８】本発明のキトサンと植物繊維の混合の割合
は使用目的に応じて自由に変えることができる。即ちキ
トサンの添加効果は植物繊維の約10重量％から現れ、使
用目的によっては90重量％以上キトサンを添加しても何
ら問題はない。また、アセチル化の際の溶媒としてエチ
ルアルコールの他に、メタノール、プロピルアルコール
などのアルコール類を好ましく使用することが出来る。The mixing ratio of chitosan and plant fiber of the present invention can be freely changed according to the purpose of use. That is, the effect of adding chitosan appears from about 10% by weight of the plant fiber, and there is no problem even if 90% by weight or more of chitosan is added depending on the purpose of use. In addition, as a solvent for acetylation, alcohols such as methanol and propyl alcohol can be preferably used in addition to ethyl alcohol.
【０００９】本発明による多孔質体は、次の特徴を有す
る。 1) 多孔質であり、吸水性と復元性がある。 2) アセチル化度を変えて水への溶解性を変えることが
できる。 3) 天然物を素材とすることができ、有害物質を含まな
いので焼却処分に際して公害の問題がない。The porous body according to the present invention has the following features. 1) It is porous and has water absorption and resilience. 2) The solubility in water can be changed by changing the degree of acetylation. 3) It can be made of natural products and contains no harmful substances, so there is no problem of pollution during incineration.
【００１０】4) キトサンの抗菌性が期待できる。 5) 土壌中に放置しても微生物による生分解性が期待で
きる。 従って本発明による多孔質体は、種々の分野で応用する
ことでき、例えばその吸水性、生体適合性、抗菌作用、
繊維がほぐれ難い等の性質を利用した創傷被覆材料、給
排水性、抗菌作用を利用した水耕栽培用苗床、給排水
性、生体適合性、多孔質性を利用した細胞固定化担体、
吸湿、排湿作用、保型性、軽量性を利用した調湿ケー
ス、多孔質性と熱伝導率、燃えても有害ガスが出ないこ
とを利用した断熱材、多孔質性とキトサンの吸着性を利
用した湿式及び乾式フィルター等に応用できる。4) The antibacterial properties of chitosan can be expected. 5) Even if left in the soil, biodegradability by microorganisms can be expected. Therefore, the porous body according to the present invention can be applied in various fields, for example, its water absorption, biocompatibility, antibacterial action,
Wound-covering material using properties such as difficulty in unraveling fibers, water supply / drainage, nursery beds for hydroponics using antibacterial action, cell-immobilization carrier using water supply / drainage, biocompatibility, porousness,
Humidity control case using moisture absorption, dehumidification, shape retention and light weight, porosity and thermal conductivity, heat insulation material using no harmful gas when burned, porosity and chitosan adsorption It can be applied to wet and dry filters and the like using
【００１１】[0011]
【発明の効果】このように本発明によれば、植物繊維と
キトサンの複合多孔質体を調製することができ、その多
孔質性を利用してバイオテクノロジー関連素材や医薬品
素材、農業用材料、包装材等として利用することが可能
であり、産業界にとって極めて有益である。As described above, according to the present invention, a composite porous body of plant fiber and chitosan can be prepared, and a biotechnology-related material, a pharmaceutical material, an agricultural material, It can be used as a packaging material and the like, and is extremely useful for the industry.
【００１２】[0012]
【実施例】以下、実施例に基づき本発明を具体的に説明
する。 実施例１ 水１リットルに裁断した紙パルプ（商品名、東洋濾紙N
O.2) 10ｇおよびキトサン10ｇを混入し、攪拌しながら
酢酸10ｇを加えてキトサンを溶解した。混合溶液を液の
厚みが１cmになるように、バットに流しこみ−20℃の冷
凍室に放置し凍結させた。このとき液体窒素などを用い
て急速凍結すると、氷晶が細かくなりキメの細かいもの
が得られる。次いで凍結物を45℃で１日間凍結乾燥し
た。乾燥試料を５cm四方に切出し、100ml の50％エチル
アルコール水溶液に10分間浸漬した。無水酢酸５mlを添
加して１時間放置し、キトサンをアセチル化した。つい
で１％水酸化ナトリウムに浸漬して中和した後、試料を
よく水洗して乾燥させた。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. Example 1 Paper pulp cut to 1 liter of water (trade name, Toyo Roshi N
O.2) 10 g and chitosan 10 g were mixed, and acetic acid 10 g was added with stirring to dissolve chitosan. The mixed solution was poured into a vat so that the thickness of the solution became 1 cm, and left in a freezer at -20 ° C to freeze. At this time, if the liquid crystal is rapidly frozen using liquid nitrogen or the like, the ice crystals become finer, and fine grains can be obtained. The frozen material was then lyophilized at 45 ° C. for 1 day. The dried sample was cut into a square of 5 cm and immersed in 100 ml of a 50% aqueous ethyl alcohol solution for 10 minutes. 5 ml of acetic anhydride was added and left for 1 hour to acetylate the chitosan. Then, the sample was neutralized by immersion in 1% sodium hydroxide, and the sample was thoroughly washed with water and dried.
【００１３】得られた試料の物性を測定した。対照試料
としては、キトサンを使用しないで紙パルプを使用して
同様に凍結乾燥した多孔質体（アセチル化せず）を使用
した。 試料形状：断面５mm×20mm、長さ50mm 測定機 ：レオナーＲＥ3305 (山電株式会社製) 引張強度：１mm／sec 測定試料 850g／cm2 対照試料 5g／cm2 見掛け比重：測定試料 0.02 g／cm3 対照試料 0.02 g／cm3 The physical properties of the obtained sample were measured. As a control sample, a porous material (not acetylated) which was similarly freeze-dried using paper pulp without using chitosan was used. Sample shape: cross section 5 mm × 20 mm, length 50 mm Measuring machine: Leona RE3305 (manufactured by Yamaden Corporation) Tensile strength: 1 mm / sec Measurement sample 850 g / cm 2 Control sample 5 g / cm 2 Apparent specific gravity: measurement sample 0.02 g / cm 3 Control sample 0.02 g / cm 3
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−76025（ＪＰ，Ａ) 特開 平２−261838（ＪＰ，Ａ) 特開 平２−2303（ＪＰ，Ａ) 特開 平１−174699（ＪＰ，Ａ) 特開 昭62−83875（ＪＰ，Ａ) 特開 昭63−59499（ＪＰ，Ａ) 特開 平４−126734（ＪＰ，Ａ) 特開 平３−109930（ＪＰ，Ａ) 特開 平２−225539（ＪＰ，Ａ) 特開 平２−208332（ＪＰ，Ａ) 特開 昭62−167331（ＪＰ，Ａ) 特開 平３−41131（ＪＰ，Ａ) 特開 平２−268766（ＪＰ，Ａ) 特開 平４−101000（ＪＰ，Ａ) 特開 平３−15475（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 9/00 - 9/42 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-76025 (JP, A) JP-A-2-26,838 (JP, A) JP-A-2-2303 (JP, A) JP-A-1- 174699 (JP, A) JP-A-62-83875 (JP, A) JP-A-63-59499 (JP, A) JP-A-4-126734 (JP, A) JP-A-3-109930 (JP, A) JP-A-2-22539 (JP, A) JP-A-2-208332 (JP, A) JP-A-62-167331 (JP, A) JP-A-3-41131 (JP, A) JP-A-2-268766 (JP, A) JP-A-4-101000 (JP, A) JP-A-3-15475 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08J 9/00-9 / 42
Claims (4)
合し、混合溶液を凍結乾燥し、次いで無水酢酸で処理す
ることを特徴とする植物繊維とキトサンの複合多孔質体
の調製方法。1. A method for preparing a composite porous body of plant fiber and chitosan, comprising mixing water, plant fiber, chitosan and acetic acid, freeze-drying the mixed solution, and treating with acetic anhydride.
の方法。2. The method according to claim 1, wherein the plant fiber is pulp.
ル化度70％以上である請求項１または２記載の方法。3. The method according to claim 1, wherein the chitosan has a degree of polymerization of 100 or more and a degree of deacetylation of 70% or more.
により得られた植物繊維とキトサンの複合多孔質体。4. A composite porous body of plant fiber and chitosan obtained by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03021433A JP3106251B2 (en) | 1991-01-23 | 1991-01-23 | Preparation method of composite porous body of plant fiber and chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03021433A JP3106251B2 (en) | 1991-01-23 | 1991-01-23 | Preparation method of composite porous body of plant fiber and chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07179649A JPH07179649A (en) | 1995-07-18 |
| JP3106251B2 true JP3106251B2 (en) | 2000-11-06 |
Family
ID=12054850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03021433A Expired - Fee Related JP3106251B2 (en) | 1991-01-23 | 1991-01-23 | Preparation method of composite porous body of plant fiber and chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3106251B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379462C (en) * | 1999-11-09 | 2008-04-09 | 电气化学工业株式会社 | Use of soluble cellulose derivative having been made hardly soluble in water and process for producing the same |
| CN109137133B (en) * | 2018-08-20 | 2020-08-18 | 安徽工程大学 | Preparation method of loofah sponge cellulose/chitosan composite fiber |
-
1991
- 1991-01-23 JP JP03021433A patent/JP3106251B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07179649A (en) | 1995-07-18 |
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