JP2905093B2 - Dilute sulfuric acid aqueous solution of chitosan and method for producing the same - Google Patents
Dilute sulfuric acid aqueous solution of chitosan and method for producing the sameInfo
- Publication number
- JP2905093B2 JP2905093B2 JP14408894A JP14408894A JP2905093B2 JP 2905093 B2 JP2905093 B2 JP 2905093B2 JP 14408894 A JP14408894 A JP 14408894A JP 14408894 A JP14408894 A JP 14408894A JP 2905093 B2 JP2905093 B2 JP 2905093B2
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- sulfuric acid
- dilute sulfuric
- aqueous solution
- producing
- 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 - Lifetime
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はキトサンの希硫酸水溶液
及びその製造方法に関する。The present invention relates to a dilute aqueous solution of chitosan in sulfuric acid and a method for producing the same.
【０００２】[0002]
【従来の技術】キチンを脱アセチル化して得られるキト
サンは、そのユニークな性質を利用して種々の分野への
応用が試みられている。例えば、医療分野では創傷被覆
剤として、化粧品分野では粉体特性の改良剤として、塗
料分野では増粘剤、分散剤あるいは被膜形成剤として等
の利用が試みられている。2. Description of the Related Art Chitosan obtained by deacetylating chitin has been attempted to be applied to various fields by utilizing its unique properties. For example, attempts have been made to use it as a wound dressing in the medical field, as a powder property improver in the cosmetic field, and as a thickener, dispersant or film-forming agent in the coating field.
【０００３】特に化粧品の分野では、パウダー化粧品の
粉体特性改良剤として微粒子状のキトサンに対する要望
が強い。キトサンは、希酸水溶液に常温で溶解すること
はよく知られている。また、サリチル酸、リン酸等の水
溶液には難溶性であるが、加熱すると溶解するが、冷却
してもキトサンは析出せずに安定な水溶液のままで存在
することもよく知られている。これらの水溶液から固体
粒子状のキトサンを単離するには、凍結乾燥や噴霧乾燥
等の費用のかかる方法が必要であり、粒子状のキトサン
を得ることは容易ではない。[0003] In the field of cosmetics in particular, there is a strong demand for fine chitosan as a powder property improving agent for powder cosmetics. It is well known that chitosan dissolves in a dilute acid aqueous solution at room temperature. It is also well known that although it is hardly soluble in aqueous solutions of salicylic acid, phosphoric acid, etc., it dissolves when heated, but does not precipitate chitosan even when cooled, and remains as a stable aqueous solution. In order to isolate solid particulate chitosan from these aqueous solutions, expensive methods such as freeze drying and spray drying are required, and it is not easy to obtain particulate chitosan.
【０００４】特公昭５１−６７２０号公報には、キトサ
ンは濃硫酸に溶解するが、キトサンは硫酸化キトサンに
変化しキトサンそのものは回収することができないこ
と、また、０〜３０℃の温度で溶解することも必要であ
り、３０℃を越えるとキトサンは炭化分解乃至キトサン
の構成糖そのものが分解することが記載されている。Japanese Patent Publication No. Sho 51-6720 discloses that chitosan is dissolved in concentrated sulfuric acid, but chitosan is converted into sulfated chitosan and cannot be recovered. It is also described that when the temperature exceeds 30 ° C., the chitosan is decomposed by carbonization or the constituent sugar itself of chitosan is decomposed.
【０００５】[0005]
【本発明が解決しようとする課題】本発明者等は、溶液
からキトサン微粒子を容易に析出させ、単離できるキト
サンの溶液を得るべく種々検討した結果、希酸の中では
キトサンを溶解しない数少ない代表である希硫酸に特定
の条件下ではキトサンが溶解し、この溶液からキトサン
微粒子を容易に析出させ、単離できることを知見し、本
発明を完成するに至った。SUMMARY OF THE INVENTION The present inventors have made various studies to easily precipitate chitosan fine particles from a solution and obtain a solution of chitosan that can be isolated. Under specific conditions, chitosan was dissolved in dilute sulfuric acid as a representative, and it was found that chitosan fine particles could be easily precipitated and isolated from this solution, and the present invention was completed.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、キトサ
ンが０．５〜３０重量％濃度の希硫酸に溶解してなるこ
とを特徴とするキトサンの希硫酸水溶液が提供される。
また、本発明によれば、キトサンと少なくとも５０℃の
希硫酸とを接触させることを特徴とするキトサンの希硫
酸水溶液の製造方法が提供される。According to the present invention, there is provided a dilute sulfuric acid aqueous solution of chitosan, wherein chitosan is dissolved in dilute sulfuric acid having a concentration of 0.5 to 30% by weight.
Further, according to the present invention, there is provided a method for producing a diluted sulfuric acid aqueous solution of chitosan, which comprises contacting chitosan with dilute sulfuric acid at least at 50 ° C.
【０００７】[0007]
【作用】少なくとも５０℃の特定濃度の希硫酸とキトサ
ンを接触させることにより、キトサンが希硫酸に溶解し
た溶液が得られる。また、この溶液を冷却することによ
って微粒子状のキトサンが析出する。By contacting chitosan with dilute sulfuric acid at a specific concentration of at least 50 ° C., a solution in which chitosan is dissolved in dilute sulfuric acid is obtained. When the solution is cooled, fine chitosan precipitates.
【０００８】[0008]
【好ましい実施態様】以下に好ましい実施態様を挙げて
本発明を更に詳しく説明する。本発明において使用する
キトサンは、カニ、エビ、昆虫等の甲殻あるいはキノコ
等に含まれている天然高分子物の一種であるキチンの脱
アセチル化物であり、２−アミノ−２−デオキシ−Ｄ−
グルコースを１構成単位とする塩基性多糖類である。こ
のような脱アセチル化キチンであるキトサンは、既に工
業的に生産されており、種々のグレードのものが入手で
きるが、脱アセチル化度は約７０〜８０％程度である。
本発明においては脱アセチル化度は特に制約はない。ま
た、キトサンの分子量も特に制約はない。用途に応じて
キトサン微粒子に要求される特性を満足するように、最
適な脱アセチル化度や分子量を適宜選択すればよい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The chitosan used in the present invention is a deacetylated product of chitin, which is a kind of natural polymer contained in crustaceans, shrimps, insects and other shells or mushrooms, and is 2-amino-2-deoxy-D-.
It is a basic polysaccharide having glucose as a constituent unit. Such deacetylated chitin, chitosan, has already been industrially produced and various grades are available, but the degree of deacetylation is about 70-80%.
In the present invention, the degree of deacetylation is not particularly limited. The molecular weight of chitosan is not particularly limited. The optimum degree of deacetylation and molecular weight may be appropriately selected so as to satisfy the characteristics required for chitosan fine particles according to the application.
【０００９】本発明において使用する希硫酸は、キトサ
ンを変質させずに溶解させるには、濃度が０．５〜３０
重量％の範囲で、硫酸の使用量はキトサンのアミノ基に
対して０．２〜１０倍モルであるのが好ましい。０．２
倍モル未満ではキトサンは溶解し難く、１０倍モルを越
える加水分解による低分子量化が激しくなり好ましくな
い。好ましくは０．８〜４倍モルである。The dilute sulfuric acid used in the present invention has a concentration of 0.5 to 30 to dissolve chitosan without deteriorating chitosan.
In the range of weight%, the amount of sulfuric acid used is preferably 0.2 to 10 moles per mole of the amino group of chitosan. 0.2
If the molar ratio is less than twice, the chitosan is difficult to dissolve, and the molecular weight of the chitosan is more than 10 times the molar ratio due to hydrolysis. Preferably it is 0.8 to 4 times mol.
【００１０】本発明においてキトサンを希硫酸に溶解さ
せるには、少なくとも５０℃の希硫酸を使用することが
必要である。５０℃未満ではキトサンは溶解し難い。９
０℃以上となると褐色に着色してくるので好ましくな
い。好ましくは６０〜８０℃である。キトサンを希硫酸
に溶解させるには、キトサンと５０℃以上に加熱した希
硫酸とを混合しても、キトサンと希硫酸を混合してから
混合物を５０℃以上に加熱してもよい。キトサンの濃度
は特に制約されないが、通常、希硫酸溶液中０．５〜１
５重量％である。In order to dissolve chitosan in dilute sulfuric acid in the present invention, it is necessary to use dilute sulfuric acid at least at 50 ° C. Below 50 ° C., chitosan is difficult to dissolve. 9
If the temperature is 0 ° C. or higher, it is undesirably colored brown. Preferably it is 60-80 degreeC. In order to dissolve chitosan in diluted sulfuric acid, chitosan and diluted sulfuric acid heated to 50 ° C. or higher may be mixed, or chitosan and diluted sulfuric acid may be mixed, and then the mixture may be heated to 50 ° C. or higher. The concentration of chitosan is not particularly limited, but is usually 0.5 to 1 in dilute sulfuric acid solution.
5% by weight.
【００１１】このようしてキトサンの希硫酸水溶液が得
られる。この溶液を５０℃未満に冷却することにより、
微粒子状のキトサンが析出する。本発明では、希硫酸に
溶解したキトサンは、使用する硫酸の量（濃度）によっ
てキトサンもしくはキトサンの硫酸塩またはこれらの混
合物である。従って、キトサン微粒子を硫酸塩の形で使
用することが不都合な場合には、単離した微粒子を公知
のアルカリ水溶液で中和すれば本来のキトサンとするこ
とができる。Thus, a dilute sulfuric acid aqueous solution of chitosan is obtained. By cooling this solution below 50 ° C.,
Fine particulate chitosan precipitates. In the present invention, chitosan dissolved in dilute sulfuric acid is chitosan or a sulfate salt of chitosan or a mixture thereof depending on the amount (concentration) of sulfuric acid used. Therefore, when it is inconvenient to use the chitosan fine particles in the form of a sulfate, the isolated fine particles can be neutralized with a known aqueous alkali solution to obtain the original chitosan.
【００１２】[0012]
【実施例】以下に実施例を挙げて本発明をさらに詳細に
説明する。特に断らない限り実施例中の％は重量基準で
ある。 実施例１ ５リットルのセパラブルフラスコに、キトサン（０．５
％濃度、粘度１５００ｃｐｓ、脱アセチル化度７５％）
２４０ｇとイオン交換水３６００ｇを入れ、攪拌しなが
ら９５％濃硫酸２９０ｇを添加した。添加終了後、フラ
スコの内容物を加熱して８０℃に昇温するとキトサンは
溶解し、本発明のキトサンの硫酸水溶液が得られた。そ
のまま１時間保持した後、グラスフィルターで熱時濾過
して不溶解分を除去し、濾過液を室温まで冷却するとキ
トサンが微粒子状に析出した。The present invention will be described in more detail with reference to the following examples. Unless otherwise specified, the percentages in the examples are on a weight basis. Example 1 A 5-liter separable flask was charged with chitosan (0.5
% Concentration, viscosity 1500 cps, degree of deacetylation 75%)
240 g and 3600 g of ion-exchanged water were added, and 290 g of 95% concentrated sulfuric acid was added with stirring. After the addition was completed, the contents of the flask were heated to a temperature of 80 ° C., and the chitosan was dissolved, and the aqueous solution of chitosan in sulfuric acid of the present invention was obtained. After holding for 1 hour as it was, the solution was filtered while hot with a glass filter to remove insoluble components, and when the filtrate was cooled to room temperature, chitosan was precipitated in fine particles.
【００１３】実施例２ ５リットルのセパラブルフラスコに、キトサン（１％濃
度、粘度１０ｃｐｓ、脱アセチル化度９８％）２４０ｇ
とイオン交換水３６００ｇを入れ、攪拌下に９５％濃硫
酸１５０ｇを添加した。添加後、内容物を加熱して６０
℃に昇温するとキトサンは溶解し、本発明のキトサンの
硫酸水溶液が得られた。実施例１と同様にして濾液を室
温に冷却するとキトサンが微粒子状に析出した。Example 2 240 g of chitosan (1% concentration, viscosity 10 cps, degree of deacetylation 98%) was placed in a 5-liter separable flask.
And 3600 g of ion-exchanged water, and 150 g of 95% concentrated sulfuric acid was added with stirring. After the addition, heat the contents to 60
When the temperature was raised to ° C., the chitosan was dissolved, and a sulfuric acid aqueous solution of chitosan of the present invention was obtained. When the filtrate was cooled to room temperature in the same manner as in Example 1, chitosan was precipitated in fine particles.
【００１４】実施例３ ５リットルのセパラブルフラスコに、キトサン（０．５
％濃度、粘度１０００ｃｐｓ、脱アセチル化度８５％）
２４０ｇとイオン交換水３６００ｇを入れ、攪拌下に９
５％濃硫酸２２０ｇを添加した。添加終了後、フラスコ
の内容物を加熱して８０℃に昇温するとキトサンは溶解
し、本発明のキトサンの硫酸水溶液が得られた。実施例
１と同様にして濾液を室温に冷却するとキトサンが微粒
子状に析出した。Example 3 A 5 liter separable flask was charged with chitosan (0.5
% Concentration, viscosity 1000 cps, degree of deacetylation 85%)
240 g and 3600 g of ion-exchanged water are added, and 9
220 g of 5% concentrated sulfuric acid was added. After the addition was completed, the contents of the flask were heated to a temperature of 80 ° C., and the chitosan was dissolved, and the aqueous solution of chitosan in sulfuric acid of the present invention was obtained. When the filtrate was cooled to room temperature in the same manner as in Example 1, chitosan was precipitated in fine particles.
【００１５】[0015]
【発明の効果】本発明方法を実施することによりキトサ
ンの硫酸水溶液が得られ、この溶液を冷却することによ
りキトサンを微粒子状に析出させることができる。微粒
子状のキトサンは、パウダー化粧品等の粉体改良剤や農
業用保水ゲル等の用途に用いることができる。By carrying out the method of the present invention, an aqueous solution of chitosan in sulfuric acid is obtained. By cooling this solution, chitosan can be precipitated in fine particles. Fine-particle chitosan can be used for applications such as powder improvers such as powder cosmetics and water retention gels for agricultural use.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 土田 真也 東京都中央区日本橋馬喰町１丁目７番６ 号 大日精化工業株式会社内 (72)発明者 山南 隆徳 東京都中央区日本橋馬喰町１丁目７番６ 号 大日精化工業株式会社内 (72)発明者 堀口 正二郎 東京都中央区日本橋馬喰町１丁目７番６ 号 大日精化工業株式会社内 (58)調査した分野(Int.Cl.6，ＤＢ名) C08B 37/08 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinya Tsuchida 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Takanori Yamanan 1-7 Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 6 Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Shojiro Horiguchi 1-7-6 Bakurocho, Nihonbashi, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (58) Field surveyed (Int. Cl. 6 , DB name) ) C08B 37/08
Claims (6)
硫酸に溶解してなることを特徴とするキトサンの希硫酸
水溶液。1. A dilute sulfuric acid aqueous solution of chitosan, wherein chitosan is dissolved in dilute sulfuric acid having a concentration of 0.5 to 30% by weight.
接触させることを特徴とするキトサンの希硫酸水溶液の
製造方法。2. A method for producing a diluted aqueous solution of chitosan in sulfuric acid, comprising contacting chitosan with dilute sulfuric acid at least at 50 ° C.
酸とを混合する請求項２に記載のキトサンの希硫酸水溶
液の製造方法。3. The method according to claim 2, wherein chitosan is mixed with dilute sulfuric acid at a temperature of at least 50 ° C.
５０℃に加熱する請求項２に記載のキトサンの希硫酸水
溶液の製造方法。4. The method according to claim 2, wherein a mixture of chitosan and dilute sulfuric acid is heated to at least 50 ° C.
る請求項２に記載のキトサンの希硫酸水溶液の製造方
法。5. The method according to claim 2, wherein the concentration of the dilute sulfuric acid is 0.5 to 30% by weight.
２〜１０倍モルである請求項２に記載のキトサンの希硫
酸水溶液の製造方法。6. The amount of sulfuric acid is 0.1% of the amount of amino group of chitosan.
The method for producing a chitosan dilute aqueous sulfuric acid solution according to claim 2, wherein the molar amount is 2 to 10 times the molar amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14408894A JP2905093B2 (en) | 1994-06-03 | 1994-06-03 | Dilute sulfuric acid aqueous solution of chitosan and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14408894A JP2905093B2 (en) | 1994-06-03 | 1994-06-03 | Dilute sulfuric acid aqueous solution of chitosan and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07330808A JPH07330808A (en) | 1995-12-19 |
| JP2905093B2 true JP2905093B2 (en) | 1999-06-14 |
Family
ID=15353956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14408894A Expired - Lifetime JP2905093B2 (en) | 1994-06-03 | 1994-06-03 | Dilute sulfuric acid aqueous solution of chitosan and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2905093B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2313836C (en) | 2000-03-15 | 2009-06-09 | Cargill, Incorporated | Chitosan and method of preparing chitosan |
| CN1104504C (en) * | 2000-05-23 | 2003-04-02 | 厦门大学 | Process for preparing amylovorin of sea bacteria and its application |
| US7816514B2 (en) | 2001-02-16 | 2010-10-19 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
| US7923437B2 (en) | 2001-02-16 | 2011-04-12 | Cargill, Incorporated | Water soluble β-glucan, glucosamine, and N-acetylglucosamine compositions and methods for making the same |
| US8222232B2 (en) | 2001-02-16 | 2012-07-17 | Cargill, Incorporated | Glucosamine and N-acetylglucosamine compositions and methods of making the same fungal biomass |
| US6693188B2 (en) | 2001-08-08 | 2004-02-17 | Cargill Incorporated | N-acetyl-D-glucosamine and process for producing N-acetyl-D-glucosamine |
| BR0303666A (en) | 2002-04-02 | 2004-07-27 | Cargill Inc | Chitosan Production |
-
1994
- 1994-06-03 JP JP14408894A patent/JP2905093B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07330808A (en) | 1995-12-19 |
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