JPH0232281B2 - - Google Patents

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Publication number
JPH0232281B2
JPH0232281B2 JP62218312A JP21831287A JPH0232281B2 JP H0232281 B2 JPH0232281 B2 JP H0232281B2 JP 62218312 A JP62218312 A JP 62218312A JP 21831287 A JP21831287 A JP 21831287A JP H0232281 B2 JPH0232281 B2 JP H0232281B2
Authority
JP
Japan
Prior art keywords
chitosan
aqueous solution
water
carbonate
acid
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
Application number
JP62218312A
Other languages
Japanese (ja)
Other versions
JPS6462302A (en
Inventor
Yoshuki Chiba
Takao Fujita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissui Corp
Original Assignee
Nippon Suisan Kaisha Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Suisan Kaisha Ltd filed Critical Nippon Suisan Kaisha Ltd
Priority to JP21831287A priority Critical patent/JPS6462302A/en
Publication of JPS6462302A publication Critical patent/JPS6462302A/en
Publication of JPH0232281B2 publication Critical patent/JPH0232281B2/ja
Granted legal-status Critical Current

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  • Polysaccharides And Polysaccharide Derivatives (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は中性域において水溶性であるキトサン
塩の製造法に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a chitosan salt that is water-soluble in the neutral range.

〔従来の技術〕[Conventional technology]

キトサンは、甲殻類、昆虫、菌類等自然界に広
く分布するキチンをアルカリ加水分解して得られ
る、D―グルコサミンがβ―1,4結合してなる
塩基性多糖類である。そしてその特有の化学構造
および性質から、凝集剤として余剰汚泥の脱水や
水溶液の除濁などに広く使用され、さらに食品、
化粧料、紙等の分野においても利用が期待されて
いる。
Chitosan is a basic polysaccharide consisting of β-1,4-linked D-glucosamine obtained by alkaline hydrolysis of chitin, which is widely distributed in nature such as crustaceans, insects, and fungi. Due to its unique chemical structure and properties, it is widely used as a coagulant for dehydrating excess sludge and removing turbidity from aqueous solutions.
It is also expected to be used in fields such as cosmetics and paper.

ところで、キトサンは中性域では水不溶性であ
ることから、これを水溶液とするには通常、ギ
酸、酢酸、乳酸、スルフアミン酸等の有機酸もし
くは塩酸、硝酸等の無機酸の塩としたのち水に溶
解させるか、またはこれらの酸の希薄水溶液に溶
解させる方法がとられている。従つて、キトサン
はPH2〜5の酸性水溶液として種々の用途に用い
られている。
By the way, chitosan is water-insoluble in the neutral range, so to make it into an aqueous solution, it is usually made into a salt of an organic acid such as formic acid, acetic acid, lactic acid, or sulfamic acid, or an inorganic acid such as hydrochloric acid or nitric acid, and then mixed with water. A method of dissolving these acids in a dilute aqueous solution or a dilute aqueous solution of these acids has been adopted. Therefore, chitosan is used for various purposes as an acidic aqueous solution with a pH of 2 to 5.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

しかしながら、キトサンの水溶液が酸性である
ことは、多くの問題を生じ、キトサン自身の有用
性が充分に発揮されず、自ずとその応用範囲は限
定されていた。例えば食品、化粧料、紙等の分野
においては、キトサンの水溶液が酸性であること
から品質低下、製造技術上の問題が生じ使用が制
限されていた。またキトサンの酸性水溶液は、長
時間放置すると、徐々に加水分解をうけ、分子量
の低下、粘度の低下が生じるという問題があつ
た。
However, the fact that the aqueous solution of chitosan is acidic causes many problems, and the usefulness of chitosan itself is not fully demonstrated, which naturally limits its range of application. For example, in the fields of foods, cosmetics, paper, etc., aqueous solutions of chitosan are acidic, which causes quality deterioration and production technology problems, which limits their use. Furthermore, when an acidic aqueous solution of chitosan is left for a long time, it gradually undergoes hydrolysis, resulting in a decrease in molecular weight and viscosity.

従つて、キトサンの応用範囲を拡大し、安定性
増大のために中性域において水溶性であるキトサ
ン塩の開発が熱望されていた。
Therefore, it has been eagerly desired to develop chitosan salts that are water-soluble in the neutral range in order to expand the range of applications of chitosan and increase stability.

〔問題点を解決するための手段〕[Means for solving problems]

斯かる実状に鑑み、本発明者は上記問題点を解
決すべく種々検討したところ、キトサンの酸性水
溶液に水酸化ナトリウム、水酸化アンモニウム等
のアルカリを添加しても白濁もしくはゲル化を起
こし中和することはできないが、炭酸塩を用いれ
ば中和することが可能であり、キトサンの中性水
溶液が得られることを見い出し、本発明を完成し
た。
In view of this situation, the present inventor conducted various studies to solve the above problems, and found that even if an alkali such as sodium hydroxide or ammonium hydroxide was added to an acidic aqueous solution of chitosan, it would become cloudy or gelatinous and would not be neutralized. However, the present invention was completed based on the discovery that it is possible to neutralize chitosan by using a carbonate, and a neutral aqueous solution of chitosan can be obtained.

すなわち、本発明は、キトサンの酸性水溶液
を、無機炭酸塩でPH6〜7の微酸性まで中和し
て、透明ないしコロイド状溶液を得ることを特徴
とする水溶性キトサン塩の製造法を提供するもの
である。
That is, the present invention provides a method for producing a water-soluble chitosan salt, which is characterized by neutralizing an acidic aqueous solution of chitosan with an inorganic carbonate to a slightly acidic pH of 6 to 7 to obtain a transparent or colloidal solution. It is something.

本発明の水溶性キトサン塩は、キトサンの酸性
水溶液を炭酸塩で中和することにより製造され
る。
The water-soluble chitosan salt of the present invention is produced by neutralizing an acidic aqueous solution of chitosan with a carbonate.

キトサンの酸性水溶液としては、例えばキトサ
ンにギ酸、酢酸、乳酸、スルフアミン酸等の有機
酸もしくは塩酸、硝酸等の無機酸を添加して溶解
せしめた水溶液が使用される。
As the acidic aqueous solution of chitosan, for example, an aqueous solution prepared by adding and dissolving chitosan with an organic acid such as formic acid, acetic acid, lactic acid, or sulfamic acid or an inorganic acid such as hydrochloric acid or nitric acid is used.

中和に用いる炭酸塩としては、例えば炭酸アン
モニウム、炭酸水素アンモニウム;炭酸ナトリウ
ム、炭酸水素ナトリウム、炭酸カリウム、炭酸水
素カリウム等のアルカリ金属炭酸塩;炭酸カルシ
ウム等のアルカリ土類金属炭酸塩等があげられ
る。これらの炭酸塩は単独で、もしくは二種以上
を組み合せて用いることができる。
Carbonates used for neutralization include, for example, ammonium carbonate, ammonium hydrogen carbonate; alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate; It will be done. These carbonates can be used alone or in combination of two or more.

中和反応は、キトサンの酸性水溶液に炭酸塩の
水溶液を徐々に添加すればよい。
The neutralization reaction may be carried out by gradually adding an aqueous carbonate solution to an acidic aqueous solution of chitosan.

炭酸塩水溶液添加終了時において、得られた本
発明のキトサン塩の水溶液のPH6〜7である。
At the end of the addition of the carbonate aqueous solution, the obtained aqueous solution of the chitosan salt of the present invention has a pH of 6 to 7.

斯くして得られる本発明の水溶性キトサン塩
は、上記の中性水溶液をそのまま食品、化粧料等
の分野において利用してもよいが、水溶液を凍結
乾燥して粉末とし、用時水溶液として使用するの
が好ましい。
The water-soluble chitosan salt of the present invention thus obtained may be used as it is in the fields of foods, cosmetics, etc. in the above-mentioned neutral aqueous solution; It is preferable to do so.

〔発明の効果〕〔Effect of the invention〕

本発明のキトサン塩は、中性域において水溶性
であるため、従来使用が制限されていた食品、化
粧料、紙の分野においても何ら品質低下、製造技
術上の問題点を生ずることなく利用できるもので
ある。例えば食品の分野では、従来キトサンの酸
性水溶液をフライ類のバツターに添加すること
は、蛋白の凝固が起こることから不可能であつた
が、本発明のキトサン塩はかかる問題がなく、増
粘剤、静菌剤としてバツターに使用できる。ま
た、化粧料の分野ではパツク剤に増粘剤、保湿剤
として使用できる。さらに紙の表面の光沢剤、紙
力増強剤としても使用できる。
Since the chitosan salt of the present invention is water-soluble in the neutral range, it can be used in the fields of food, cosmetics, and paper, where its use was previously restricted, without any quality deterioration or production technology problems. It is something. For example, in the food field, conventionally it has been impossible to add an acidic aqueous solution of chitosan to the batter of fried foods because it causes protein coagulation, but the chitosan salt of the present invention does not have this problem and has no thickening agent. , can be used in butter as a bacteriostatic agent. In addition, in the field of cosmetics, it can be used as a thickener and moisturizer in pack agents. It can also be used as a paper surface brightener and paper strength enhancer.

〔実施例〕〔Example〕

次に実施例を挙げて本発明を詳細に説明する。 Next, the present invention will be explained in detail with reference to Examples.

実施例 1 フローナツクc(化粧品用キトサン,共和油脂
工業製)6.0gを水300mlに分散させ、50%乳酸
10.8gを添加して溶解させ、キトサン酸性水溶液
(PH3.5)を得た。これに5%炭酸水素ナトリウム
水溶液215mlを加え、PH7.0の白色コロイド状溶液
を得た。
Example 1 Disperse 6.0 g of Flownac c (chitosan for cosmetics, manufactured by Kyowa Yushi Kogyo Co., Ltd.) in 300 ml of water, and add 50% lactic acid.
10.8g was added and dissolved to obtain an acidic chitosan aqueous solution (PH3.5). 215 ml of a 5% aqueous sodium hydrogen carbonate solution was added to this to obtain a white colloidal solution with a pH of 7.0.

得られた白色コロイド状溶液を、凍結乾燥して
白色粉末を得た。この粉末は0.5〜4%濃度とな
るように水に溶かしたところ、透明な水溶液とな
つた。
The resulting white colloidal solution was freeze-dried to obtain a white powder. When this powder was dissolved in water to a concentration of 0.5 to 4%, it became a transparent aqueous solution.

実施例 2 フローナツクN(凝集剤用キトサン,共和油脂
工業製)0.5gを水100mlに分散させ、これに90%
酢酸0.33gを添加してキトサンの酸性水溶液(PH
4.4)を得た。これに5%炭酸アンモニウム水溶
液33gを滴下し、PH7.0の透明な溶液を得た。
Example 2 0.5 g of Flownac N (chitosan for flocculant, manufactured by Kyowa Yushi Kogyo) was dispersed in 100 ml of water, and 90%
Add 0.33g of acetic acid to make an acidic aqueous solution of chitosan (PH
4.4) was obtained. 33 g of a 5% ammonium carbonate aqueous solution was added dropwise to this to obtain a clear solution with a pH of 7.0.

濃度5000ppmの活性汚泥500mlに、この溶液5
mlを添加した所、良好なフロツクを生じ凝集剤と
して有効であつた。
Add 500ml of this solution to 500ml of activated sludge with a concentration of 5000ppm.
When ml was added, a good floc was produced and it was effective as a flocculant.

実施例 3 フローナツクN1.5gを水300mlに分散させ、こ
れに90%乳酸1.3gを加えてキトサンの酸性水溶液
を得た。これに5%NaHCO3水溶液を加えてPH
7.0の半透明のコロイド状溶液を得た。
Example 3 1.5 g of Flownac N was dispersed in 300 ml of water, and 1.3 g of 90% lactic acid was added thereto to obtain an acidic aqueous solution of chitosan. Add 5% NaHCO 3 aqueous solution to this and adjust the pH
A translucent colloidal solution of 7.0 was obtained.

比較例 フローナツクC6.0gを水200mlに分散させ、50%
乳酸10.8gを加えてキトサンの酸性水溶液を得た。
これに5%NaHCO350mlを加えた後、更に2%
NaOH47mlを加えてPH7.5にしたが白色の不溶沈
澱が生じ、均一なコロイド溶液は得られなかつ
た。
Comparative example Disperse 6.0g of Flownatsu C in 200ml of water, 50%
10.8 g of lactic acid was added to obtain an acidic aqueous solution of chitosan.
After adding 50ml of 5% NaHCO 3 to this, an additional 2%
Although 47 ml of NaOH was added to adjust the pH to 7.5, a white insoluble precipitate was formed and a homogeneous colloidal solution could not be obtained.

Claims (1)

【特許請求の範囲】[Claims] 1 キトサンの酸性水溶液を、無機炭酸塩でPH6
〜7の微酸性まで中和して、透明ないしコロイド
状溶液を得ることを特徴とする水溶性キトサン塩
の製造法。
1. Adjust the acidic aqueous solution of chitosan to PH6 with inorganic carbonate.
A method for producing a water-soluble chitosan salt, characterized by neutralizing it to a slightly acidic level of ~7 to obtain a transparent or colloidal solution.
JP21831287A 1987-09-01 1987-09-01 Water-soluble chitosan salt and production thereof Granted JPS6462302A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21831287A JPS6462302A (en) 1987-09-01 1987-09-01 Water-soluble chitosan salt and production thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21831287A JPS6462302A (en) 1987-09-01 1987-09-01 Water-soluble chitosan salt and production thereof

Publications (2)

Publication Number Publication Date
JPS6462302A JPS6462302A (en) 1989-03-08
JPH0232281B2 true JPH0232281B2 (en) 1990-07-19

Family

ID=16717873

Family Applications (1)

Application Number Title Priority Date Filing Date
JP21831287A Granted JPS6462302A (en) 1987-09-01 1987-09-01 Water-soluble chitosan salt and production thereof

Country Status (1)

Country Link
JP (1) JPS6462302A (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5308663A (en) * 1989-06-20 1994-05-03 Kanai Juyo Kogyo Company Limited Biodegradable nonwoven fabric and its molding vessel
FR2695804B1 (en) * 1992-09-18 1994-11-25 Rhone Poulenc Nutrition Animal Nutritional or medicinal compositions for administration to ruminants based on chitosan.
JPH0790245A (en) * 1993-09-24 1995-04-04 Daiichi Seimo Kk Composition gelable on heating
US5599916A (en) * 1994-12-22 1997-02-04 Kimberly-Clark Corporation Chitosan salts having improved absorbent properties and process for the preparation thereof
DE19932076A1 (en) * 1999-07-12 2001-01-18 Cognis Deutschland Gmbh Crosslinker-free preparations
DE19932075A1 (en) * 1999-07-12 2001-01-18 Cognis Deutschland Gmbh Crosslinker-free preparations
KR20010105888A (en) * 2000-05-19 2001-11-29 정충근 Maunfacturing method of high purity chitosan oligosaccarid
JP4173305B2 (en) * 2000-11-30 2008-10-29 康雄 酒井 Method for dissolving chitosan or DAC in water, aqueous solution thereof, method for forming film with chitosan or DAC aqueous solution, method for coating solid surface, and method for forming yarn
JP2003171469A (en) * 2001-12-03 2003-06-20 Fujimori Kogyo Co Ltd Method for producing aqueous solution of chitosan, antibacterial coating agent and antibacterial film or sheet
JP4333966B1 (en) * 2008-08-29 2009-09-16 株式会社データアクション Bath salt and bath water
KR101657492B1 (en) * 2014-08-22 2016-09-19 황보용 System and method for cloud mobile certification
WO2016066195A1 (en) * 2014-10-29 2016-05-06 Laboratoire Medidom Sa Heat-sterilized formulation comprising chitosan and process of preparation thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56106901A (en) * 1980-01-30 1981-08-25 Mitsubishi Rayon Co Ltd Production of formed product of chitosan
JPS5829801A (en) * 1981-08-13 1983-02-22 Agency Of Ind Science & Technol Production of n-acylated chitosan

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56106901A (en) * 1980-01-30 1981-08-25 Mitsubishi Rayon Co Ltd Production of formed product of chitosan
JPS5829801A (en) * 1981-08-13 1983-02-22 Agency Of Ind Science & Technol Production of n-acylated chitosan

Also Published As

Publication number Publication date
JPS6462302A (en) 1989-03-08

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