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JP2814701B2 - Method for producing water-soluble partially deacetylated chitin - Google Patents
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JP2814701B2 - Method for producing water-soluble partially deacetylated chitin - Google Patents

Method for producing water-soluble partially deacetylated chitin

Info

Publication number
JP2814701B2
JP2814701B2 JP14600490A JP14600490A JP2814701B2 JP 2814701 B2 JP2814701 B2 JP 2814701B2 JP 14600490 A JP14600490 A JP 14600490A JP 14600490 A JP14600490 A JP 14600490A JP 2814701 B2 JP2814701 B2 JP 2814701B2
Authority
JP
Japan
Prior art keywords
chitin
partially deacetylated
water
dispersion
deacetylated chitin
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
Application number
JP14600490A
Other languages
Japanese (ja)
Other versions
JPH0439301A (en
Inventor
富男 小林
亨 小林
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.)
Ajinomoto Co Inc
Original Assignee
Ajinomoto Co Inc
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 Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Priority to JP14600490A priority Critical patent/JP2814701B2/en
Publication of JPH0439301A publication Critical patent/JPH0439301A/en
Application granted granted Critical
Publication of JP2814701B2 publication Critical patent/JP2814701B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related 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〕 本発明は化粧品、食品に用いられる浸潤剤である水溶
性部分脱アセチル化キチンの製造方法に関する。
Description: TECHNICAL FIELD The present invention relates to a method for producing a water-soluble partially deacetylated chitin, which is a wetting agent used in cosmetics and foods.

〔従来の技術〕[Conventional technology]

水溶性部分脱アセチル化キチンの製造方法は、特開昭
53−47479に開示されたごとく、天然産キチン粉末を高
濃度のアルカリ水溶液に分散させ、その分散液を希釈し
つつ溶解させている。溶解に際しては天然産キチンの加
水分解を制御しキトサンの生成を押えること、分散液を
完全に溶解させること、溶解後のアルカリキチン濃度を
一定範囲におさめることが必要である。このため分散液
温度をコントロールしつつ溶解させている。この際水を
用いると、発熱するためキチンが溶解しない。そこで溶
解方法としては該分散液に氷を加えるか、又は分散液を
凍結し、次に解凍する操作をくり返すことにより粘稠な
アルカリキチン水溶液を調製している。しかし、この方
法は氷を大量に使用するので、吸熱反応となり分散液
の温度が0℃以下になるため氷の溶解に長時間を要すこ
と。製氷及びその保管設備必要なこと。氷の投入装
置等付属設備が必要なこと。撹拌時の撹拌機への負荷
や溶解槽の損傷等、工業化に際しては工程が複雑にな
り、大量生産が難かしかった。
A method for producing water-soluble partially deacetylated chitin is disclosed in
As disclosed in JP-A-53-47479, natural chitin powder is dispersed in a high-concentration aqueous alkaline solution, and the dispersion is dissolved while being diluted. In dissolution, it is necessary to control the hydrolysis of naturally occurring chitin to suppress the production of chitosan, to completely dissolve the dispersion, and to keep the concentration of alkali chitin after dissolution within a certain range. For this reason, the dispersion is dissolved while controlling the temperature. At this time, if water is used, chitin does not dissolve due to heat generation. Therefore, as a dissolving method, a viscous alkaline chitin aqueous solution is prepared by adding ice to the dispersion or freezing and then thawing the dispersion. However, since this method uses a large amount of ice, an endothermic reaction occurs and the temperature of the dispersion becomes 0 ° C. or less, so that it takes a long time to melt the ice. Necessary ice making and its storage facilities. Auxiliary equipment such as ice loading equipment is required. During industrialization, the process becomes complicated, such as load on the stirrer during stirring and damage to the dissolution tank, and mass production was difficult.

〔発明が解決しようとする課題〕[Problems to be solved by the invention]

本発明は従来の欠点を改善し、水溶性部分脱アセチル
化キチンを製造するにあたって、天然産キチン粉末をア
ルカリ水溶液に分散させ、その分散液の溶解に際し、キ
トサンの生成を防ぎつつ温度コントロールするために加
える氷を使用せず又は凍結、解凍操作の代りに工業的に
有効な方法を見出すことにある。
The present invention is to improve the conventional disadvantages, to produce a water-soluble partially deacetylated chitin, to disperse naturally occurring chitin powder in an aqueous alkaline solution, and to dissolve the dispersion, to control the temperature while preventing the production of chitosan An object of the present invention is to find an industrially effective method without using ice or in place of freezing and thawing operations.

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

本発明者らは上記問題点を解決すべく鋭意研究した結
果、天然産キチン粉末をアルカリ水溶液に分散させ、そ
の分散液を溶解する際、溶解温度を0〜30℃以下に保つ
ことで目的で達成されることを見出し本発明を完成され
た。
The present inventors have conducted intensive studies to solve the above problems, and as a result, disperse naturally produced chitin powder in an aqueous alkali solution, and when dissolving the dispersion, aiming at maintaining the dissolution temperature at 0 to 30 ° C or lower. It has been found that the present invention has been accomplished and the present invention has been completed.

すなわち本発明は、N−アセチル−D−グルコサミン
とD−グルコサミンとを構成単位とし、N−アセチル−
D−グルコサミン単位の含量40〜60%、D−グルコサミ
ン単位の含量60〜40%であるところの非晶質の水溶性部
分脱アセチル化キチンの製造法に於て、天然産キチン粉
末を30〜50wt%濃度のアルカリ水溶液に分散させ、この
分散液に0〜10℃の冷水を該分散液の1.0倍以上、該分
散液の温度が30℃を越えないように徐々に添加し、撹拌
することにより粘稠なアルカリキチン水溶液を調製し、
50℃以下の温度で均一系でアルカリ加水分解する際にキ
チンの脱アセチル化率が40〜60%になるように部分脱ア
セチル化を行い、次いで酸で該部分脱アセチル化キチン
の等電点pHに調整する水溶性部分脱アセチル化キチンの
製造法である。
That is, the present invention comprises N-acetyl-D-glucosamine and D-glucosamine as constituent units,
In a method for producing an amorphous water-soluble partially deacetylated chitin having a D-glucosamine unit content of 40 to 60% and a D-glucosamine unit content of 60 to 40%, naturally occurring chitin powder is mixed with 30 to 60%. Disperse in a 50 wt% aqueous alkali solution, gradually add cold water at 0 to 10 ° C. to the dispersion 1.0 times or more of the dispersion so that the temperature of the dispersion does not exceed 30 ° C., and stir. To prepare a viscous aqueous alkali chitin solution,
When alkaline hydrolysis is performed in a homogeneous system at a temperature of 50 ° C. or less, partial deacetylation is performed so that the deacetylation rate of chitin is 40 to 60%, and then the isoelectric point of the partially deacetylated chitin is adjusted with an acid. This is a method for producing water-soluble partially deacetylated chitin adjusted to pH.

本発明に於て、天然産キチンとはかに、えびあるいは
おきあみ等の甲殻類の外皮より炭酸カルシュウム等の無
機物、および、蛋白質を除去して得られる天然高分子の
ことである。
In the present invention, naturally-occurring chitin is a natural polymer obtained by removing inorganic substances such as calcium carbonate and proteins from the shell of a crustacean such as crab, shrimp or oyster.

製造方法はまず この天然産キチンを30〜50%濃度のアルカリ水溶液に
添加する。この際、天然産キチン濃度は10%以下が望ま
しい。10%越えると分散状態が悪くなり、アルカリ水溶
液が該キチン中に浸漬しにくくなる。
The production method is to first add this naturally occurring chitin to a 30-50% concentration aqueous alkaline solution. At this time, the concentration of naturally produced chitin is desirably 10% or less. If it exceeds 10%, the dispersion state will be poor, and it will be difficult for the alkaline aqueous solution to be immersed in the chitin.

アルカリ濃度は30%未満だと水を添加して溶解する
際、溶解性が悪くなり該キチンを透明に溶解することが
できず好ましくない。
When the alkali concentration is less than 30%, the solubility becomes poor when adding and dissolving water, and the chitin cannot be transparently dissolved, which is not preferable.

アルカリ加水分解剤として、水酸化ナトリウム、水酸
化カリウム、水酸化リチウム等のアルカリ金属水酸化
物、水酸化バリウム、水酸化カルシウム等のアルカリ土
金属水酸化物、炭酸ナトリウム、炭酸カリウム等の炭酸
アルカリ金属塩等が用いられるが、特に、水酸化ナトリ
ウム、水酸化カリウムが好ましい。
Examples of the alkali hydrolyzing agent include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as barium hydroxide and calcium hydroxide, and alkali carbonates such as sodium carbonate and potassium carbonate. Although metal salts and the like are used, sodium hydroxide and potassium hydroxide are particularly preferable.

分散液の溶解方法として 分散液を0〜20℃に冷却し、水を加える際、溶解後の
アルカリキチン濃度が0.5%〜5%になるように、0〜2
0℃の冷水を徐々に滴下する。この際の冷水滴下速度は
分散液内温が30℃以下に保たれるよう滴下する。この操
作により粘稠な、アルカリキチン水溶液が得られる。
As a method for dissolving the dispersion, the dispersion is cooled to 0 to 20 ° C., and when water is added, 0 to 2% is added so that the alkali chitin concentration after dissolution becomes 0.5% to 5%.
Chilled water at 0 ° C. is slowly added dropwise. At this time, the cooling water is dropped so that the temperature inside the dispersion is kept at 30 ° C. or lower. By this operation, a viscous aqueous alkali chitin solution is obtained.

溶解内温は30℃付近だと、若干キチンの不溶物が残り
完全な透明液を得ることは難しい。又、溶解内温0℃以
下にすると、これ迄と同様氷が必要になる。又、氷を使
用しない場合は、大型の冷凍機が必要となる。本発明の
アルカリキチン濃度は0.5〜5%以下、溶解内温は0〜2
0℃が好ましい。
If the internal temperature of the solution is around 30 ° C., it is difficult to obtain a completely transparent liquid because some chitin insolubles remain. If the internal melting temperature is 0 ° C. or lower, ice is required as before. When ice is not used, a large refrigerator is required. The alkali chitin concentration of the present invention is 0.5 to 5% or less, and the internal dissolution temperature is 0 to 2%.
0 ° C. is preferred.

実施例−1 キチン粉末(北海道曹達(株)品、80メッシュ)3gを
75gの40%水酸化ナトリウム水溶液に分散し、40℃で3
時間放置する。この分散液を10℃に冷却し、これに225g
の冷水(5〜10℃)を内温10℃に保ちつつ、徐々に滴下
しながら撹拌するとポリマー濃度1%、アルカリ濃度10
%のアルカリキチンのアルカリ水溶液が得られる。この
水溶液をグラスフィルターで濾過し、濾液を25℃で50時
間放置した後、冷却する。次にこの濾液に酸を加えてpH
を約7とする。
Example 1 3 g of chitin powder (Hokkaido Soda Co., Ltd. product, 80 mesh)
Disperse in 75g of 40% sodium hydroxide aqueous solution,
Leave for a time. Cool the dispersion to 10 ° C and add 225 g
Of cold water (5 to 10 ° C.) while maintaining the internal temperature at 10 ° C. and stirring while gradually dropping, polymer concentration 1%, alkali concentration 10
% Aqueous alkali chitin is obtained. The aqueous solution is filtered through a glass filter, and the filtrate is left at 25 ° C. for 50 hours and then cooled. Then add acid to the filtrate and add pH
To about 7.

中和して得られた水溶性部分脱アセチル化キチンを、
単離後、アルコール水で繰り返し洗浄した後、約70℃で
一夜減圧乾燥して2.5gの部分脱アセチル化キチンを得
た。
Water-soluble partially deacetylated chitin obtained by neutralization,
After isolation, the mixture was repeatedly washed with alcohol water, and dried under reduced pressure at about 70 ° C. overnight to obtain 2.5 g of partially deacetylated chitin.

この水溶性部分脱アセチル化キチンは冷水、氷水、及
び水に溶解する。またこの部分脱アセチル化キチンを水
に溶解して1/400規定ポリビニル硫酸カリウム溶液(コ
ロイド滴定法)で滴定し定量した結果、脱アセチル化率
51%であった。
This water-soluble partially deacetylated chitin dissolves in cold water, ice water, and water. The partially deacetylated chitin was dissolved in water and titrated with 1 / 400N polyvinyl potassium sulfate solution (colloid titration method).
It was 51%.

実施例−2 キチン粉末(北海道曹達(株)品、80メッシュ)を4.
5gを75gの48%水酸化ナトリウム水溶液に分散し、40℃
で3時間放置する。この分散液を20℃に冷却し、これに
225gの冷水(5〜15℃)を内温20℃に保ちつつ、徐々に
滴下しながら撹拌するとポリマー濃度1%、アルカリ濃
度12%のアルカリキチン水溶液が得られる。この水溶液
をグラスフィルターで濾過し、濾液を30℃で40時間放置
した後、実施例−1と同様な操作を行い3.0gの水溶性部
分脱アセチル化キチンを得た。この水溶性部分脱アセチ
ル化キチンは脱アセチル化率45%であり、他の性状は実
施例−1と同様であった。
Example-2 Chitin powder (Hokkaido Soda Co., Ltd. product, 80 mesh) was added to 4.
Disperse 5 g in 75 g of 48% sodium hydroxide aqueous solution,
And leave for 3 hours. Cool the dispersion to 20 ° C and add
Stirring while slowly dropping 225 g of cold water (5 to 15 ° C.) at an internal temperature of 20 ° C. gives an aqueous solution of alkali chitin having a polymer concentration of 1% and an alkali concentration of 12%. This aqueous solution was filtered through a glass filter, and the filtrate was allowed to stand at 30 ° C. for 40 hours, and then the same operation as in Example 1 was performed to obtain 3.0 g of a water-soluble partially deacetylated chitin. This water-soluble partially deacetylated chitin had a deacetylation rate of 45%, and the other properties were the same as in Example-1.

実施例−3 キチン粉末(北海道曹達(株)品、80メッシュ)3gを
75gの38%水酸化ナトリウム水溶液に分散し、40℃で3
時間放置する。この分散液を5℃に冷却し、これに225g
の冷水(0〜5℃)を内温5℃に保ちつつ、徐々に滴下
しながら撹拌すると、ポリマー濃度1%、アルカリ濃度
9.5%のアルカリキチン水溶液が得られる。この水溶液
をグラスフィルターで濾過し、濾液を20℃で60時間放置
した後、実施例−1と同様な操作を行い2.2gの水溶性部
分脱アセチル化キチンを得た。この水溶性部分脱アセチ
ル化キチンは脱アセチル化率55%であり、他の性状は実
施例−1と同様であった。
Example 3 3 g of chitin powder (Hokkaido Soda Co., Ltd. product, 80 mesh)
Disperse in 75 g of 38% aqueous sodium hydroxide solution,
Leave for a time. Cool the dispersion to 5 ° C and add 225 g
Of cold water (0-5 ° C.) while maintaining the internal temperature at 5 ° C. and stirring gradually while dropping, polymer concentration 1%, alkali concentration
A 9.5% aqueous solution of alkaline chitin is obtained. This aqueous solution was filtered through a glass filter, and the filtrate was allowed to stand at 20 ° C. for 60 hours. Then, the same operation as in Example 1 was performed to obtain 2.2 g of a water-soluble partially deacetylated chitin. This water-soluble partially deacetylated chitin had a deacetylation rate of 55%, and the other properties were the same as in Example-1.

〔発明の効果〕 以上説明したように、本発明製造法によれば、工業化
スケールで製造することができ、従来方法の有する方法
は氷を大量に使用するので、製氷及びその保管、氷
の投入装置等付属設備が必要なこと、又、撹拌時の撹拌
機への負荷や、溶解槽の損傷等工業化に際しては工程が
複雑になり大量生産が難かしいといった、欠点を活称す
ることが出来る。
[Effects of the Invention] As described above, according to the manufacturing method of the present invention, it can be manufactured on an industrial scale, and the method of the conventional method uses a large amount of ice. The drawbacks include the necessity of ancillary equipment and the like, the load on the stirrer at the time of stirring, and damage to the dissolution tank, which make the process complicated and difficult to mass-produce in industrialization.

尚、本発明によって得られる、水溶性アルカリキチン
を使って、グリコールキチン、グリセロールキチン、カ
ルボキシメチルキチンなどを合成することが可能であ
る。
In addition, glycol chitin, glycerol chitin, carboxymethyl chitin and the like can be synthesized using the water-soluble alkali chitin obtained by the present invention.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】N−アセチル−D−グルコサミンとD−グ
ルコサミンとを構成単位としN−アセチル−D−グルコ
サミン単位の含量40〜60%、D−グルコサミン単位の含
量60〜40%であるところの水溶性部分脱アセチル化キチ
ンの製造法に於て、天然産キチン粉末を30〜50wt%濃度
のアルカリ水溶液に分散させ、この分散液に冷水を該分
散液の1.0倍以上、該分散液の温度が30℃を越えないよ
うに徐々に添加し、粘稠なアルカリキチン水溶液を調製
し、50℃以下の温度で均一系でアルカリ加水分解する際
にキチンの脱アセチル化率が40〜60%になるように部分
脱アセチル化を行い、次いで酸で該部分脱アセチル化キ
チンの等電点pHに調整することを特徴とする水溶性部分
脱アセチル化キチンの製造法。
(1) A composition comprising N-acetyl-D-glucosamine and D-glucosamine as constituent units, wherein the content of N-acetyl-D-glucosamine units is 40 to 60% and the content of D-glucosamine units is 60 to 40%. In the method for producing water-soluble partially deacetylated chitin, natural chitin powder is dispersed in an aqueous alkali solution having a concentration of 30 to 50% by weight, and cold water is added to the dispersion at least 1.0 times the temperature of the dispersion, and the temperature of the dispersion is increased. Is gradually added so as not to exceed 30 ° C to prepare a viscous alkaline chitin aqueous solution, and the deacetylation rate of chitin is increased to 40 to 60% when alkaline hydrolysis is performed in a homogeneous system at a temperature of 50 ° C or less. A method for producing a water-soluble partially deacetylated chitin, comprising performing partial deacetylation so as to obtain a partially deacetylated chitin, and then adjusting the isoelectric point pH of the partially deacetylated chitin with an acid.
JP14600490A 1990-06-04 1990-06-04 Method for producing water-soluble partially deacetylated chitin Expired - Fee Related JP2814701B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14600490A JP2814701B2 (en) 1990-06-04 1990-06-04 Method for producing water-soluble partially deacetylated chitin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14600490A JP2814701B2 (en) 1990-06-04 1990-06-04 Method for producing water-soluble partially deacetylated chitin

Publications (2)

Publication Number Publication Date
JPH0439301A JPH0439301A (en) 1992-02-10
JP2814701B2 true JP2814701B2 (en) 1998-10-27

Family

ID=15397926

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14600490A Expired - Fee Related JP2814701B2 (en) 1990-06-04 1990-06-04 Method for producing water-soluble partially deacetylated chitin

Country Status (1)

Country Link
JP (1) JP2814701B2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1917218B1 (en) * 2005-06-14 2017-05-17 Genís hf. Compositions of partially deacetylated chitin derivatives
CN110964129B (en) * 2018-09-30 2021-05-04 武汉大学 Method for preparing chitin and chitosan derivatives with different deacetylation degrees from chitin by one-pot homogeneous method

Also Published As

Publication number Publication date
JPH0439301A (en) 1992-02-10

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