JPH08157501A - N-carboxyacylchitosan and its production - Google Patents
N-carboxyacylchitosan and its productionInfo
- Publication number
- JPH08157501A JPH08157501A JP30789294A JP30789294A JPH08157501A JP H08157501 A JPH08157501 A JP H08157501A JP 30789294 A JP30789294 A JP 30789294A JP 30789294 A JP30789294 A JP 30789294A JP H08157501 A JPH08157501 A JP H08157501A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- degree
- carboxyacyl
- water
- anhydride
- 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.)
- Granted
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ｎ−カルボキシアシル
化度が80％以上のＮ−カルボキシアシルキトサン、及び
Ｎ−カルボキシアシルキトサンの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to N-carboxyacyl chitosan having an N-carboxyacylation degree of 80% or more, and a method for producing N-carboxyacyl chitosan.
【０００２】[0002]
【従来の技術】キトサンは、カニやエビなどの甲殻類の
殻に含まれる多糖類であって、Ｎ−アセチル−Ｄ−グル
コサミンがβ-1,4結合した直鎖状の多糖類であるキチン
のＮ−アセチル基の全部又は一部を脱アセチル化するこ
とにより得られる多糖類である。Chitosan is a polysaccharide contained in the shells of crustaceans such as crabs and shrimps, and is a linear polysaccharide in which N-acetyl-D-glucosamine is β-1,4-bonded, chitin. Is a polysaccharide obtained by deacetylating all or part of the N-acetyl group of.
【０００３】キトサンは、希酢酸などの薄い酸溶液には
溶解するが、水には溶解しない。一方、キトサンとカル
ボン酸無水物とを反応させることにより得られる、キト
サンのアミノ基（−NH2）の１個の水素原子がカルボキ
シアシル基で置換されたＮ−カルボキシアシルキトサン
の中で、例えば、キトサンと無水コハク酸、無水マレイ
ン酸、無水フタル酸等とをそれぞれ反応させることによ
り得られるＮ−サクシニルキトサン、Ｎ−マレオイルキ
トサン、Ｎ−フタロイルキトサンなどは、そのアルカリ
金属塩が水に溶解する。したがって、それらのＮ−カル
ボキシアシルキトサンは、化粧品、医薬部外品、医用材
料等への利用が期待されている。Chitosan is soluble in dilute acetic acid and other dilute acid solutions, but not in water. On the other hand, among N-carboxyacyl chitosans obtained by reacting chitosan with carboxylic acid anhydride, in which one hydrogen atom of the amino group (—NH 2 ) of chitosan is substituted with a carboxyacyl group, for example, , N-succinyl chitosan, N-maleoyl chitosan, N-phthaloyl chitosan and the like obtained by reacting chitosan with succinic anhydride, maleic anhydride, phthalic anhydride, etc., respectively, the alkali metal salt of which is dissolved in water. Dissolve. Therefore, those N-carboxyacyl chitosans are expected to be used in cosmetics, quasi drugs, medical materials and the like.
【０００４】ところで、Ｎ−カルボキシアシル化度が低
いＮ−カルボキシアシルキトサンは両性電解質の性質を
示すことから、中性付近から弱酸性の間の実際に利用す
るpH領域の水と混合した場合、沈殿を生じるという不都
合がある。従って、沈殿生成を低減するために、Ｎ−カ
ルボキシアシルキトサンには、高いＮ−カルボキシアシ
ル化度が要求される。By the way, since N-carboxyacyl chitosan having a low degree of N-carboxyacylation exhibits the property of an ampholyte, when it is mixed with water in the pH range from neutral to weakly acidic, which is actually used, The disadvantage is that precipitation occurs. Therefore, a high degree of N-carboxyacylation is required for N-carboxyacyl chitosan in order to reduce precipitation formation.
【０００５】従来、Ｎ−カルボキシアシルキトサンの製
造方法としては、例えば、キトサンを酢酸水溶液に溶解
後、メタノールで希釈し、カルボン酸無水物を添加して
キトサンをＮ−カルボキシアシル化する方法が知られて
いる（Preparation of partially N-succinylated chit
osans and their cross-linked gels. R.Yamaguchi,Y.A
rai and T.Itoh, Carbohydrate Research, 88, 172 (19
81) ) 。しかし、この方法によれば、Ｎ−カルボキシア
シル化度が80％以上のＮ−カルボキシアシルキトサンは
得られていない。また、この方法によれば、Ｎ−カルボ
キシアシル化度の高いＮ−カルボキシアシルキトサンを
得るためには、キトサンのアミノ基量（mol）に対して
大過剰のカルボン酸無水物を使用しなければならず、キ
トサンのアミノ基量（mol）の14.6倍量（mol）という大
過剰の無水コハク酸を使用してもＮ−カルボキシアシル
化度（Ｎ−サクシニル化度）がせいぜい79％のＮ−サク
シニルキトサンしか得られていない。また、上記方法に
よれば、粘性のあるキトサンを酢酸水溶液に溶解させた
状態で反応を行うため、キトサンの酢酸水溶液への仕込
み濃度を１重量％程度にしかできないので、多量のＮ−
カルボキシアシルキトサンを製造するにはきわめて効率
が悪く、工業的に利用できる方法ではない。Conventionally, as a method of producing N-carboxyacyl chitosan, for example, a method of dissolving chitosan in an aqueous acetic acid solution, diluting it with methanol, and adding a carboxylic acid anhydride to N-carboxyacylate chitosan is known. Preparation of partially N-succinylated chit
osans and their cross-linked gels. R. Yamaguchi, YA
rai and T. Itoh, Carbohydrate Research, 88, 172 (19
81)). However, according to this method, N-carboxyacyl chitosan having an N-carboxyacylation degree of 80% or more has not been obtained. Further, according to this method, in order to obtain N-carboxyacyl chitosan having a high degree of N-carboxyacylation, a large excess of carboxylic acid anhydride with respect to the amount of amino groups (mol) of chitosan must be used. However, even if a large excess of succinic anhydride (14.6 times the amount (mol) of the amino group amount (mol) of chitosan) was used, the degree of N-carboxyacylation (degree of N-succinylation) was 79% at most. Only succinyl chitosan is available. Further, according to the above method, since the reaction is carried out in a state in which viscous chitosan is dissolved in the acetic acid aqueous solution, the concentration of the chitosan charged into the acetic acid aqueous solution can only be about 1% by weight, so a large amount of N-
The production of carboxyacyl chitosan is extremely inefficient and is not an industrially applicable method.
【０００６】[0006]
【発明が解決しようとする課題】したがって、本発明の
課題は、Ｎ−カルボキシアシル化度が80％以上のＮ−カ
ルボキシアシルキトサン、及びＮ−カルボキシアシルキ
トサンの効率的な製造方法を提供することにある。Therefore, an object of the present invention is to provide N-carboxyacyl chitosan having an N-carboxyacylation degree of 80% or more, and an efficient method for producing N-carboxyacyl chitosan. It is in.
【０００７】[0007]
【課題を解決するための手段】本発明は、Ｎ−カルボキ
シアシル化度が80％以上のＮ−カルボキシアシルキトサ
ンにある。また、本発明は、キトサンと分子内カルボン
酸無水物とを、水と有機溶媒との混合溶媒中で懸濁状態
で反応させることを特徴とする、Ｎ−カルボキシアシル
キトサンの製造方法にある。The present invention resides in N-carboxyacyl chitosan having an N-carboxyacylation degree of 80% or more. The present invention also provides a method for producing N-carboxyacyl chitosan, which comprises reacting chitosan with an intramolecular carboxylic acid anhydride in a mixed state of water and an organic solvent in a suspended state.
【０００８】本発明のＮ−カルボキシアシルキトサン
は、キチンのＮ−アセチル基の全部又は一部を脱アセチ
ル化することにより得られるキトサン（脱アセチル化度
は、通常、50〜100％、好ましくは75〜100％。重合度
は、通常、100〜10000）のアミノ基（−NH2）がＮ−カ
ルボキシアシル化されたものであって、Ｎ−カルボキシ
アシル化度が80％以上である。ここで、Ｎ−カルボキシ
アシル化度とは、Ｎ−カルボキシアシル置換前のキトサ
ンのアミノ基（−NH2）量（mol）に対するＮ−カルボキ
シアシル置換後のキトサンのＮ−カルボキシアシル基量
（mol）の割合（％）をいう。本発明のＮ−カルボキシ
アシルキトサンは、Ｎ−カルボキシアシル化度が80％以
上と高いことから、アルカリ金属塩とした場合に弱酸性
から中性付近のpH領域、具体的にはpH５〜９付近の水と
混合した場合に沈殿がほとんど生じないので、食品、化
粧品、医薬部外品、医用材料、医薬品、農業用資材等の
幅広い用途に利用することができる。The N-carboxyacyl chitosan of the present invention is a chitosan obtained by deacetylating all or part of the N-acetyl group of chitin (deacetylation degree is usually 50 to 100%, preferably 75% to 100%. the polymerization degree is typically 100 to 10000) be one amino group (-NH 2) is N- carboxyacyl of, N- carboxymethyl degree of acylation of 80% or more. Here, the degree of N-carboxyacylation means the amount of N-carboxyacyl groups of chitosan after N-carboxyacyl substitution (mol) relative to the amount of amino groups (-NH 2 ) of chitosan before N-carboxyacyl substitution (mol). ) Is the ratio (%). Since the N-carboxyacyl chitosan of the present invention has a high N-carboxyacylation degree of 80% or more, when it is used as an alkali metal salt, it has a weakly acidic to neutral pH range, specifically around pH 5 to 9. Since it hardly precipitates when mixed with water, it can be used in a wide range of applications such as foods, cosmetics, quasi-drugs, medical materials, pharmaceuticals, agricultural materials and the like.
【０００９】本発明のＮ−カルボキシアシルキトサンの
カルボキシアシル基としては、具体的には、−COCH 2 C
H 2 COOH、−COCH=CH COOH、−COC(=CH 2 ) CH2 COOH、The carboxyacyl group of the N-carboxyacyl chitosan of the present invention is specifically --COCH 2 C.
H 2 COOH, -COCH = CH COOH, -COC (= CH 2 ) CH 2 COOH,
【００１０】[0010]
【化１】 Embedded image
【００１１】等が挙げられる。本発明のＮ−カルボキシ
アシルキトサンの製造方法は、キトサンと分子内カルボ
ン酸無水物とを、水と有機溶媒との混合溶媒中で懸濁状
態で反応させることを特徴とする。本発明の方法は、反
応終了まで懸濁状態で反応を行うものであり、キトサン
を溶解させる必要がないことから、キトサンの仕込み濃
度を高くすることができ、効率がよい。キトサンの仕込
み濃度は、前記混合溶媒に対して、通常、１〜30w/v％
であり、好ましくは５〜20w/v％である。And the like. The method for producing N-carboxyacyl chitosan of the present invention is characterized by reacting chitosan and an intramolecular carboxylic acid anhydride in a mixed state of water and an organic solvent in a suspended state. In the method of the present invention, the reaction is carried out in a suspended state until the end of the reaction, and since it is not necessary to dissolve chitosan, it is possible to increase the charging concentration of chitosan and it is efficient. The charge concentration of chitosan is usually 1 to 30 w / v% with respect to the mixed solvent.
And preferably 5 to 20 w / v%.
【００１２】キトサンとしては、通常、脱アセチル化度
50〜100％のものを使用し、好ましくは、75〜100％のも
のを使用する。また、使用するキトサンの粒径は、特に
制約はないが、反応効率を向上させために、５mm以下が
好ましく、さらに0.03〜１mmが好ましい。また、分子内
カルボン酸無水物としては、例えば、無水コハク酸、無
水マレイン酸、無水イタコン酸、無水フタル酸、無水ト
リメリト酸等が挙げられる。本発明の製造方法は、分子
内カルボン酸無水物が、特に無水コハク酸及び無水フタ
ル酸である場合、即ち、Ｎ−サクシニルキトサン及びＮ
−フタロイルキトサンの製造に好適である。分子内カル
ボン酸無水物の添加量は、特に制約はないが、経済性等
の向上の観点から、キトサンのアミノ基量（mol）の１
〜９倍量（mol）が好ましく、さらに３〜７倍量（mol）
が好ましい。Chitosan usually has a degree of deacetylation.
50 to 100%, preferably 75 to 100% is used. The particle size of chitosan used is not particularly limited, but is preferably 5 mm or less, and more preferably 0.03 to 1 mm in order to improve the reaction efficiency. Examples of the intramolecular carboxylic acid anhydride include succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, trimellitic anhydride, and the like. The production method of the present invention is carried out when the intramolecular carboxylic acid anhydride is succinic anhydride and phthalic anhydride, that is, N-succinyl chitosan and N-succinyl chitosan.
-Suitable for the production of phthaloyl chitosan. The addition amount of the intramolecular carboxylic acid anhydride is not particularly limited, but from the viewpoint of improving the economical efficiency, the amount of amino group (mol) of chitosan is 1
~ 9 times amount (mol) is preferable, and further 3 to 7 times amount (mol)
Is preferred.
【００１３】また、溶媒としては、水と有機溶媒との混
合溶媒を使用するが、該混合溶媒中の水の含有量は、５
〜70容量％が好ましく、特に20〜50容量％が好ましい。
水の含有量が少なすぎるとキトサンが膨潤せずＮ−カル
ボキシアシル化反応が進行しない。有機溶媒としては、
水と混和性を有し、かつ使用する分子内カルボン酸無水
物が溶解するものであればいかなる有機溶媒であっても
使用することができるが、反応効率及び経済性の向上の
観点からアルコール類及びケトン類を使用するのが好ま
しい。アルコール類としては、具体的には、メタノー
ル、エタノール、イソプロパノール、n-プロパノール等
が例示され、ケトン類としては、具体的には、アセト
ン、メチルエチルケトン等が例示される。これらの中で
最も好ましいものは、アセトンである。A mixed solvent of water and an organic solvent is used as the solvent, and the content of water in the mixed solvent is 5
It is preferably 70 to 70% by volume, and particularly preferably 20 to 50% by volume.
If the water content is too low, chitosan does not swell and the N-carboxyacylation reaction does not proceed. As an organic solvent,
Any organic solvent can be used as long as it is miscible with water and can dissolve the intramolecular carboxylic acid anhydride used, but alcohols are used from the viewpoint of improving reaction efficiency and economic efficiency. And ketones are preferably used. Specific examples of alcohols include methanol, ethanol, isopropanol, n-propanol and the like, and specific examples of ketones include acetone, methyl ethyl ketone and the like. Most preferred of these is acetone.
【００１４】また、反応温度は、10〜50℃の範囲が好ま
しく、反応時間は、１〜17時間が好ましい。本発明の製
造方法においては、触媒として酢酸、プロピオン酸等の
有機酸を添加することも可能である。本発明の方法によ
れば、使用するキトサンの粒径、分子内カルボン酸無水
物の量、反応温度、反応時間等を調節することにより種
々のＮ−カルボキシアシル化度のＮ−カルボキシアシル
キトサンを効率よく製造することができ、特に、Ｎ−カ
ルボキシアシル化度が80％以上のＮ−カルボキシアシル
キトサンをも製造することができる。The reaction temperature is preferably in the range of 10 to 50 ° C., and the reaction time is preferably 1 to 17 hours. In the production method of the present invention, it is possible to add an organic acid such as acetic acid or propionic acid as a catalyst. According to the method of the present invention, N-carboxyacyl chitosan having various degrees of N-carboxyacylation can be obtained by adjusting the particle size of chitosan to be used, the amount of intramolecular carboxylic acid anhydride, the reaction temperature, the reaction time and the like. It can be efficiently produced, and in particular, N-carboxyacyl chitosan having an N-carboxyacylation degree of 80% or more can also be produced.
【００１５】[0015]
【実施例】以下、本発明の実施例により、効果について
説明する。尚、本実施例によって本発明が限定されるも
のではない。実施例１ 脱アセチル化度94％のキトサン粉末（粒径１mm） 5.0ｇ
（アミノ基：0.029 モル）と、水−アセトン混合溶媒
（アセトン濃度：70容量％）50mlとを混合した後、さら
に、無水コハク酸 9.0ｇ（0.090モル）を添加し、懸濁
状態で40℃で一晩反応させた。反応終了後、ガラスフィ
ルターを用いて析出物を濾別して水−アセトン混合溶媒
（アセトン濃度：70容量％）及び水−メタノール混合溶
媒（メタノール濃度：80容量％）を用いて洗浄した。洗
浄後、該析出物に、水−メタノール混合溶媒（メタノー
ル濃度：80容量％）に水酸化ナトリウムを８重量％濃度
で溶解した溶液50mlを添加して室温で３時間放置した。
次いで、沈殿を濾別し、水−メタノール混合溶媒（メタ
ノール濃度：80容量％）及びアセトンを用いて洗浄後、
風乾した。このようにしてＮ−サクシニルキトサンのナ
トリウム塩 8.3ｇが得られた。得られたＮ−サクシニル
キトサンのナトリウム塩のＮ−サクシニル化度は83％で
あった。また、得られたＮ−サクシニルキトサンのナト
リウム塩を水に0.5重量％濃度となるように混合したと
ころ、不溶解分は3.8重量％であった。実施例２ 本実施例において、無水コハク酸を15.5ｇ（0.155モ
ル）使用した以外は実施例１と同様の方法でＮ−サクシ
ニルキトサンのナトリウム塩を製造した。得られたＮ−
サクシニルキトサンのナトリウム塩は 8.4ｇであり、Ｎ
−サクシニル化度は88％であった。また、実施例１と同
様の方法で不溶解分の割合を測定したところ、1.4重量
％であった。実施例３ 本実施例において、無水コハク酸を21.0ｇ(0.210モル)
使用した以外は実施例１と同様の方法でＮ−サクシニル
キトサンのナトリウム塩を製造した。得られたＮ−サク
シニルキトサンのナトリウム塩は8.4ｇであり、Ｎ−サ
クシニル化度は91％であった。また、実施例１と同様の
方法で不溶解分の割合を測定したところ、0.1重量％で
あった。実施例４ 本実施例において、キトサンと混合する溶媒として水−
アセトン混合溶媒（アセトン濃度：70容量％）の代わり
に水−イソプロピルアルコール混合溶媒（イソプロピル
アルコール濃度：70容量％）を使用した以外は実施例１
と同様の方法でＮ−サクシニルキトサンのナトリウム塩
を製造した。得られたＮ−サクシニルキトサンのナトリ
ウム塩は8.1ｇであり、Ｎ−サクシニル化度は81％であ
った。また、実施例１と同様の方法で不溶解分の割合を
測定したところ、4.0重量％であった。実施例５ 脱アセチル化度99％のキトサン粉末（粒径0.04mm）5.0
ｇ（アミノ基：0.031モル）と、水−アセトン混合溶媒
（アセトン濃度：50容量％）50mlとを混合した後、さら
に無水コハク酸 3.0ｇ（0.030モル）を添加し、懸濁状
態で40℃で３時間反応させた。反応終了後、ガラスフィ
ルターを用いて析出物を濾別して水−メタノール混合溶
媒（メタノール濃度：80容量％）を用いて洗浄した。洗
浄後、該析出物に、水−メタノール混合溶媒（メタノー
ル濃度：80容量％）に水酸化ナトリウムを８重量％濃度
で溶解した溶液50mlを添加して室温で３時間放置した。
次いで、沈殿を濾別し、水−メタノール混合溶媒（メタ
ノール濃度：80容量％）及びアセトンを用いて洗浄後、
風乾した。このようにしてＮ−サクシニルキトサンのナ
トリウム塩8.1ｇが得られた。得られたＮ−サクシニル
キトサンのナトリウム塩のＮ−サクシニル化度は95％で
あった。また、実施例１と同様の方法で不溶解分の割合
を測定したところ、0.1重量％であった。実施例６ 本実施例において、無水コハク酸の代わりに無水フタル
酸23.0ｇ(0.155モル)を使用した以外は実施例５と同様
の方法でＮ−フタロイルキトサンのナトリウム塩を製造
した。得られたＮ−フタロイルキトサンのナトリウム塩
は8.6ｇであり、Ｎ−フタロイル化度は95％であった。
また、実施例１と同様の方法で不溶解分の割合を測定し
たところ、0.1重量％であった。実施例７ 脱アセチル化度99％のキトサン粉末（粒径0.05mm）5.0
ｇ（アミノ基：0.031モル）に、水30mlを加えて膨潤さ
せた。さらに、アセトン70ml及び酢酸５mlを添加した
後、無水コハク酸15.5ｇ（0.155モル) を混合し、懸濁
状態で40℃で一晩反応させた。反応終了後、ガラスフィ
ルターを用いて析出物を濾別して水−メタノール混合溶
媒（メタノール濃度：80容量％）を用いて洗浄した。洗
浄後、該析出物に、水−メタノール混合溶媒（メタノー
ル濃度：80容量％）に水酸化ナトリウムを８重量％濃度
で溶解した溶液 400mlを添加して室温で３時間放置し
た。次いで、沈殿を濾別し、水−メタノール混合溶媒
（メタノール濃度：80容量％）及びアセトンを用いて洗
浄後、風乾した。このようにしてＮ−サクシニルキトサ
ンのナトリウム塩8.2ｇが得られた。得られたＮ−サク
シニルキトサンのＮ−サクシニル化度は97％であった。
また、実施例１と同様の方法で不溶解分の割合を測定し
たところ、0.1重量％であった。EXAMPLES The effects of the present invention will be described below. The present invention is not limited to the embodiments. Example 1 5.0 g of chitosan powder having a deacetylation degree of 94% (particle size 1 mm)
(Amino group: 0.029 mol) and 50 ml of water-acetone mixed solvent (acetone concentration: 70% by volume) were mixed, and then 9.0 g (0.090 mol) of succinic anhydride was added, and the mixture was suspended at 40 ° C. And reacted overnight at. After completion of the reaction, the precipitate was filtered off using a glass filter and washed with a water-acetone mixed solvent (acetone concentration: 70% by volume) and a water-methanol mixed solvent (methanol concentration: 80% by volume). After washing, 50 ml of a solution prepared by dissolving 8% by weight of sodium hydroxide in a water-methanol mixed solvent (methanol concentration: 80% by volume) was added to the precipitate, and the mixture was allowed to stand at room temperature for 3 hours.
Then, the precipitate was filtered off, washed with a water-methanol mixed solvent (methanol concentration: 80% by volume) and acetone,
Air dried. In this way 8.3 g of the sodium salt of N-succinyl chitosan was obtained. The degree of N-succinylation of the obtained sodium salt of N-succinyl chitosan was 83%. Further, when the obtained sodium salt of N-succinyl chitosan was mixed with water to a concentration of 0.5% by weight, the insoluble content was 3.8% by weight. Example 2 A sodium salt of N-succinyl chitosan was prepared in the same manner as in Example 1, except that 15.5 g (0.155 mol) of succinic anhydride was used. Obtained N-
The sodium salt of succinyl chitosan is 8.4g, N
The degree of succinylation was 88%. The proportion of insoluble matter was measured by the same method as in Example 1, and it was 1.4% by weight. Example 3 In this example, 21.0 g (0.210 mol) of succinic anhydride was used.
A sodium salt of N-succinyl chitosan was produced in the same manner as in Example 1 except that it was used. The sodium salt of N-succinyl chitosan obtained was 8.4 g, and the N-succinylation degree was 91%. Further, the proportion of insoluble matter was measured by the same method as in Example 1, and it was 0.1% by weight. Example 4 In this example, water as a solvent mixed with chitosan
Example 1 except that a water-isopropyl alcohol mixed solvent (isopropyl alcohol concentration: 70% by volume) was used in place of the acetone mixed solvent (acetone concentration: 70% by volume).
A sodium salt of N-succinyl chitosan was prepared in the same manner as in. The obtained sodium salt of N-succinyl chitosan was 8.1 g, and the N-succinylation degree was 81%. The proportion of insoluble matter was measured by the same method as in Example 1 and found to be 4.0% by weight. Example 5 Chitosan powder with a deacetylation degree of 99% (particle size 0.04 mm) 5.0
After mixing g (amino group: 0.031 mol) with 50 ml of water-acetone mixed solvent (acetone concentration: 50% by volume), 3.0 g (0.030 mol) of succinic anhydride was added, and the mixture was suspended at 40 ° C. And reacted for 3 hours. After completion of the reaction, the precipitate was filtered off using a glass filter and washed with a water-methanol mixed solvent (methanol concentration: 80% by volume). After washing, 50 ml of a solution prepared by dissolving 8% by weight of sodium hydroxide in a water-methanol mixed solvent (methanol concentration: 80% by volume) was added to the precipitate, and the mixture was allowed to stand at room temperature for 3 hours.
Then, the precipitate was filtered off, washed with a water-methanol mixed solvent (methanol concentration: 80% by volume) and acetone,
Air dried. In this way 8.1 g of the sodium salt of N-succinyl chitosan was obtained. The degree of N-succinylation of the obtained sodium salt of N-succinyl chitosan was 95%. Further, the proportion of insoluble matter was measured by the same method as in Example 1, and it was 0.1% by weight. Example 6 A sodium salt of N-phthaloyl chitosan was prepared in the same manner as in Example 5, except that 23.0 g (0.155 mol) of phthalic anhydride was used instead of succinic anhydride. The sodium salt of N-phthaloyl chitosan obtained was 8.6 g, and the degree of N-phthaloylation was 95%.
Further, the proportion of insoluble matter was measured by the same method as in Example 1, and it was 0.1% by weight. Example 7 5.0 Detoxylated 99% chitosan powder (particle size 0.05 mm) 5.0
30 g of water was added to g (amino group: 0.031 mol) to swell. Further, after adding 70 ml of acetone and 5 ml of acetic acid, 15.5 g (0.155 mol) of succinic anhydride was mixed, and the mixture was reacted overnight at 40 ° C. in a suspended state. After completion of the reaction, the precipitate was filtered off using a glass filter and washed with a water-methanol mixed solvent (methanol concentration: 80% by volume). After washing, 400 ml of a solution prepared by dissolving 8% by weight of sodium hydroxide in a water-methanol mixed solvent (methanol concentration: 80% by volume) was added to the precipitate, and the mixture was allowed to stand at room temperature for 3 hours. Next, the precipitate was filtered off, washed with a water-methanol mixed solvent (methanol concentration: 80% by volume) and acetone, and then air-dried. In this way 8.2 g of the sodium salt of N-succinyl chitosan was obtained. The N-succinylation degree of the obtained N-succinyl chitosan was 97%.
Further, the proportion of insoluble matter was measured by the same method as in Example 1, and it was 0.1% by weight.
【００１６】[0016]
【発明の効果】本発明のＮ−カルボキシアシルキトサン
は、Ｎ−カルボキシアシル化度が80％以上と高いことか
ら、アルカリ金属塩とした場合に弱酸性から中性付近の
pH領域の水と混合してもほとんど沈殿を生じることがな
いので、食品、化粧品、医薬部外品、医用材料、医薬
品、農業用資材等の幅広い用途に利用することができ、
きわめて有用である。INDUSTRIAL APPLICABILITY The N-carboxyacyl chitosan of the present invention has a high N-carboxyacylation degree of 80% or more.
Since it hardly causes precipitation even when mixed with water in the pH range, it can be used for a wide range of applications such as foods, cosmetics, quasi drugs, medical materials, pharmaceuticals, agricultural materials, etc.
Extremely useful.
【００１７】また、本発明の製造方法によれば、Ｎ−カ
ルボキシアシルキトサンを効率よく製造することがで
き、しかもＮ−カルボキシアシル化度が80％以上の有用
性の高いＮ−カルボキシアシルキトサンをも製造するこ
とができる。したがって、工業的生産に利用することが
できる。また、本発明の方法は、従来の方法と比較して
分子内カルボン酸無水物の使用量を減らすことができる
ので経済性にも優れる。According to the production method of the present invention, it is possible to efficiently produce N-carboxyacyl chitosan and to obtain highly useful N-carboxyacyl chitosan having an N-carboxyacylation degree of 80% or more. Can also be manufactured. Therefore, it can be used for industrial production. In addition, the method of the present invention can reduce the amount of the intramolecular carboxylic acid anhydride used as compared with the conventional method, and thus is excellent in economic efficiency.
Claims (5)
Ｎ−カルボキシアシルキトサン。1. An N-carboxyacyl chitosan having an N-carboxyacylation degree of 80% or more.
を、水と有機溶媒との混合溶媒中で懸濁状態で反応させ
ることを特徴とする、Ｎ−カルボキシアシルキトサンの
製造方法。2. A method for producing N-carboxyacyl chitosan, which comprises reacting chitosan and an intramolecular carboxylic acid anhydride in a mixed solvent of water and an organic solvent in a suspended state.
又は無水フタル酸である、請求項２記載の製造方法。3. The method according to claim 2, wherein the intramolecular carboxylic acid anhydride is succinic anhydride or phthalic anhydride.
ある請求項２又は３記載の製造方法。4. The production method according to claim 2, wherein the organic solvent is a ketone or an alcohol.
の製造方法。5. The method according to claim 4, wherein the organic solvent is acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30789294A JP3731007B2 (en) | 1994-12-12 | 1994-12-12 | N-carboxyacyl chitosan and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30789294A JP3731007B2 (en) | 1994-12-12 | 1994-12-12 | N-carboxyacyl chitosan and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08157501A true JPH08157501A (en) | 1996-06-18 |
| JP3731007B2 JP3731007B2 (en) | 2006-01-05 |
Family
ID=17974428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30789294A Expired - Lifetime JP3731007B2 (en) | 1994-12-12 | 1994-12-12 | N-carboxyacyl chitosan and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3731007B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001270828A (en) * | 2000-03-23 | 2001-10-02 | Pias Arise Kk | External preparation for prevention and therapy of vulgaris acne and cosmetic prepared by formulating the same |
| CN1294152C (en) * | 2005-03-02 | 2007-01-10 | 济南大学 | Hydrophobically modified succinylated chitosan derivative and its prepn process |
| WO2011004398A3 (en) * | 2009-07-07 | 2011-04-28 | Camlin Fine Chemicals Limited | Preservatives from chitin derivatives |
| CN114044834A (en) * | 2021-11-02 | 2022-02-15 | 千芝雅(湖北)卫生用品有限公司 | Polylactic acid fiber and application thereof in adult incontinence nursing pad |
-
1994
- 1994-12-12 JP JP30789294A patent/JP3731007B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001270828A (en) * | 2000-03-23 | 2001-10-02 | Pias Arise Kk | External preparation for prevention and therapy of vulgaris acne and cosmetic prepared by formulating the same |
| JP4669595B2 (en) * | 2000-03-23 | 2011-04-13 | ピアス株式会社 | External agent for preventing and treating acne vulgaris and cosmetics containing the external agent |
| CN1294152C (en) * | 2005-03-02 | 2007-01-10 | 济南大学 | Hydrophobically modified succinylated chitosan derivative and its prepn process |
| WO2011004398A3 (en) * | 2009-07-07 | 2011-04-28 | Camlin Fine Chemicals Limited | Preservatives from chitin derivatives |
| US20120108540A1 (en) * | 2009-07-07 | 2012-05-03 | Camlin Fine Sciences Limited | Preservatives from Chitin Derivatives |
| EP2451845A2 (en) * | 2009-07-07 | 2012-05-16 | Camlin Fine Sciences Limited | Preservatives from chitin derivatives |
| EP2451845A4 (en) * | 2009-07-07 | 2013-06-19 | Camlin Fine Sciences Ltd | Preservatives from chitin derivatives |
| CN114044834A (en) * | 2021-11-02 | 2022-02-15 | 千芝雅(湖北)卫生用品有限公司 | Polylactic acid fiber and application thereof in adult incontinence nursing pad |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3731007B2 (en) | 2006-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4301067A (en) | Chitin containing poly-ion complex | |
| JP2007153944A (en) | Cationized hyaluronic acid | |
| JP3034352B2 (en) | Intramolecular cross-linking (1 → 3) -β-D-glucans having stable single helix structure and method for producing the same | |
| JP5043364B2 (en) | Method for producing polysaccharide derivative | |
| JPS6219897B2 (en) | ||
| JP3731007B2 (en) | N-carboxyacyl chitosan and method for producing the same | |
| JP2003523459A (en) | Chitosan condensation products, their production and use | |
| JPH0649725B2 (en) | Method for producing cationic chitosan derivative | |
| Dunn et al. | Synthesis of N‐(aminoalkyl) chitosan for microcapsules | |
| JP2004002586A (en) | Polysaccharide complex and method for producing the same | |
| JPS6134004A (en) | Novel cationized chitin and its production | |
| JP4395573B2 (en) | Oxidized chitosan compound | |
| JP4254120B2 (en) | Method for producing oxidized chitosan | |
| JP4411847B2 (en) | Method for producing polyuronic acid | |
| JPS61118401A (en) | Production of anionic chitosan | |
| KR100381387B1 (en) | Manufacturing method of chitosan derivative | |
| JP2003026702A (en) | Water-soluble n-saturated aliphatic acid acyl chitosan derivative and preparation method thereof | |
| JP4215308B2 (en) | Composite chitosan compound and use thereof | |
| WO2009090950A1 (en) | Chitosan-containing compositions and process for production thereof | |
| JP2529729B2 (en) | Method for producing chitosan derivative | |
| JP3803123B2 (en) | Water-soluble partially deacetylated chitin and process for producing the same | |
| JP2758475B2 (en) | Chitosan oligomer and method for producing the same | |
| JP2619304B2 (en) | Method for producing hydroxypropylated deacetylated chitin | |
| JP3002867B2 (en) | Method for producing alkyl etherified cellulose derivative | |
| JP2573544B2 (en) | Chitin solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050315 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050512 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050830 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20050908 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050908 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20050908 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091021 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101021 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111021 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111021 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121021 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121021 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131021 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |