JPH03234702A - Hydroxypropylated deacetylated chitin and its production - Google Patents
Hydroxypropylated deacetylated chitin and its productionInfo
- Publication number
- JPH03234702A JPH03234702A JP2920990A JP2920990A JPH03234702A JP H03234702 A JPH03234702 A JP H03234702A JP 2920990 A JP2920990 A JP 2920990A JP 2920990 A JP2920990 A JP 2920990A JP H03234702 A JPH03234702 A JP H03234702A
- Authority
- JP
- Japan
- Prior art keywords
- water
- hydroxypropylated
- chitin
- hydroxypropylation
- degree
- 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
- 229920002101 Chitin Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 229920001661 Chitosan Polymers 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 4
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229940079889 pyrrolidonecarboxylic acid Drugs 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 4
- 230000006196 deacetylation Effects 0.000 description 3
- 238000003381 deacetylation reaction Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003214 pyranose derivatives Chemical group 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical group C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はヒドロキシプロピル化脱アセチルキチンに関し
、更に詳しくは不純物混入率が非常に低い粒状ヒドロキ
シプロピル化脱アセチルキチンの提供を目的とする。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to hydroxypropylated deacetylated chitin, and more specifically aims to provide granular hydroxypropylated deacetylated chitin with a very low impurity rate.
（従来の技術及びその問題点）
従来、ヒドロキシプロピル化脱アセチルキチンの一種で
あるヒドロキシプロピル化キトサンは、例えば、特公昭
６４−００５６０１号公報に記載されており、又、該公
報にはヒドロキシプロピル化キトサンが水溶性高分子と
して各種用途に有用であることが記載されている。(Prior art and its problems) Hitherto, hydroxypropylated chitosan, which is a type of hydroxypropylated deacetyl chitin, has been described, for example, in Japanese Patent Publication No. 64-005601; It has been described that chitosan is useful as a water-soluble polymer for various purposes.
しかしながら、上記ヒドロキシプロピル化キトサンは多
くの不純物を含有しており、化粧品や食品等の如く高純
度が要求される用途では純度の問題が生じている。これ
らの不純物の問題はヒドロキシプロピル化キトサンが水
溶性である為、水中でキトサンをヒドロキシプロピル化
する際に多くの副生物が生成され、これらの副生物ち同
様に水溶性であることから、これらの水溶性副生物をヒ
ドロキシプロピル化キトサンから水洗によって除去する
ことが困難であることによる。However, the above-mentioned hydroxypropylated chitosan contains many impurities, and purity problems arise in applications that require high purity, such as cosmetics and foods. The problem with these impurities is that hydroxypropylated chitosan is water-soluble, so many by-products are produced when chitosan is hydroxypropylated in water, and these by-products are also water-soluble. This is because it is difficult to remove water-soluble by-products from hydroxypropylated chitosan by washing with water.
上記ヒドロキシプロピル化キトサンの純度の問題は、適
当な溶解性を有する有機溶剤を使用して多数回の分別沈
澱で精製したり、透析等の特別の装置を使用して精製す
ればある程度は解決されるが、これらの精製方法はいず
れにしてもコスト高であり、工業的には使用困難である
。The above-mentioned purity problem of hydroxypropylated chitosan can be solved to some extent by purifying it by multiple rounds of fractional precipitation using an organic solvent with appropriate solubility, or by using special equipment such as dialysis. However, these purification methods are expensive and difficult to use industrially.
従って本発明の目的は、高純度ヒドロキシプロピル化脱
アセチルキチンを工業的方法で容易に提供することであ
る。It is therefore an object of the present invention to easily provide highly purified hydroxypropylated deacetyl chitin in an industrial manner.
（問題点を解決する為に手段） 上記目的は以下の本発明によって達成される。(Means to solve the problem) The above objects are achieved by the present invention as described below.
即ち、本発明は、ヒドロキシプロピル化度が０．１〜１
．２であり、且つ不均一系でヒドロキシプロピル化した
状態では水不溶性であり、水に一旦溶解後は水溶性にな
る粒状ヒドロキシプロピル化脱アセチルキチン及びその
製造方法である。That is, in the present invention, the degree of hydroxypropylation is 0.1 to 1.
．． 2, which is water-insoluble in a heterogeneously hydroxypropylated state and becomes water-soluble once dissolved in water, and a method for producing the same.
（作 用）
粒状脱アセチルキチンを水性媒体に分散させ、ヒドロキ
シプロピル化度０．１〜１．２の範囲にヒドロキシプロ
ピル化することによって、ヒドロキシプロピル化した状
態では水不溶性である粒状ヒドロキシプロピル化脱アセ
チルキチンが得られる。(Function) By dispersing granular deacetylated chitin in an aqueous medium and hydroxypropylating it to a degree of hydroxypropylation in the range of 0.1 to 1.2, granular hydroxypropylation, which is water-insoluble in the hydroxypropylated state, is achieved. Deacetyl chitin is obtained.
従ってこの生成物は水洗（有機溶剤を含み得る。以下同
様）が容易であり、単なる水洗によって、水溶性の副生
物が容易に除去され、高純度の粒状ヒドロキシプロピル
化脱アセチルキチンが極めて容易に提供される。Therefore, this product is easy to wash with water (which may contain organic solvents, the same applies hereinafter), and water-soluble by-products are easily removed by simple water washing, and highly pure granular hydroxypropylated deacetyl chitin can be produced very easily. provided.
尚、この粒状ヒドロキシプロピル化脱アセチルキチンは
、例えば、有機酸の塩にして水に一旦溶解すると、その
後は水から分離しても再度水溶性であり、以後水溶性の
ヒドロキシプロピル化脱アセチルキチンとして使用する
ことが出来る。Note that once this granular hydroxypropylated deacetyl chitin is dissolved in water, for example, as a salt of an organic acid, it becomes water-soluble again even if it is separated from water. It can be used as
粒状の脱アセチルキチンは結晶性を有しており、これを
、例えば、水中に分散させた状態である程度までヒドロ
キシプロピル化しても、その結晶性が破壊されず、従っ
て、ヒドロキシプロピル化生成物は水不溶性の状態であ
る。しかしながら、この粒状ヒドロキシプロピル化脱ア
セチルキチンを酸を用いて水中に溶解すると、溶解によ
って結晶性が失われ、以後−量水から分離するも結晶性
が復元しない。Granular deacetylated chitin has crystallinity, and even if it is hydroxypropylated to a certain extent while dispersed in water, its crystallinity will not be destroyed, and therefore, the hydroxypropylated product will not be destroyed. It is in a water-insoluble state. However, when this granular hydroxypropylated deacetyl chitin is dissolved in water using an acid, the crystallinity is lost due to the dissolution, and the crystallinity is not restored even after it is separated from water.
従って一旦溶解後は自由に水溶液として使用可能となる
。Therefore, once dissolved, it can be freely used as an aqueous solution.
尚、上記の内容は単なる本発明者の推測であり、本発明
はかかる推測によって何ら限定されるものではない。It should be noted that the above content is merely speculation by the inventor, and the present invention is not limited by such speculation in any way.
（好ましい実施態様）
次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。(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.
本発明において使用する粒状脱アセチルキチンとは、カ
ニ、エビ、昆虫等の甲殻或いはキノコ等に含まれている
天然高分子物の１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。The granular deacetylated chitin used in the present invention is a deacetylated product of chitin, which is a type of natural polymer contained in the shells of crabs, shrimp, insects, etc., or mushrooms, etc. -Deoxy-D-glucose is a basic polysaccharide having one constituent unit.
この様な脱アセチルキチンそれ自体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市場から人手出来
、いずれも本発明で使用することが出来る。例えば、本
発明の最終生成物が増粘剤として使用される場合には、
比較的高重合度の脱アセチルキチンを使用すればよく、
一方、低粘度の生成物が要求される用途には、比較的低
重合度の脱アセチルキチンを使用すればよい。いずれに
しても本発明において特に好適な脱アセチル化度は約５
０〜１００％のものである。Such deacetylated chitin itself has already been produced industrially, and various grades of chitin can be obtained manually from the market, any of which can be used in the present invention. For example, when the final product of the invention is used as a thickener,
It is sufficient to use deacetyl chitin with a relatively high degree of polymerization.
On the other hand, for applications requiring a low viscosity product, deacetylated chitin with a relatively low degree of polymerization may be used. In any case, the particularly preferred degree of deacetylation in the present invention is about 5.
It is from 0 to 100%.
上記粒状脱アセチルキチンのヒドロキシプロピル化は分
散系で行うことが必要であり、反応媒体としては水又は
水とイソプロピルアルコール等の水溶性有機溶剤との混
合溶媒が適当である。溶媒に分散させる脱アセチルキチ
ンは、均一な生成物を得る為には、微細な状態、例えば
、５０〜１．０００μｍの粒径に分散させることが好ま
しく、分散濃度は特に限定されないが、媒体１００重量
部中で約５〜２０重量部程度が一般的である。Hydroxypropylation of the granular deacetylated chitin needs to be carried out in a dispersion system, and the reaction medium is preferably water or a mixed solvent of water and a water-soluble organic solvent such as isopropyl alcohol. In order to obtain a uniform product, deacetylated chitin to be dispersed in a solvent is preferably dispersed in a fine state, for example, in a particle size of 50 to 1.000 μm, and the dispersion concentration is not particularly limited, but It is generally about 5 to 20 parts by weight.
使用するプロピレンオキサイドは、脱アセチルキチン１
００重量部当たり約１００〜８００重量部が適当であり
、反応時間は、例えば、１０〜５０時間程度で、この間
に徐々に温度を上げ、水、イソプロピルアルコール等及
びプロピレンオキサイドの混合物の沸点値の温度で反応
を行う。The propylene oxide used is deacetyl chitin 1
Approximately 100 to 800 parts by weight per 00 parts by weight is suitable, and the reaction time is, for example, about 10 to 50 hours, during which time the temperature is gradually raised and the boiling point of the mixture of water, isopropyl alcohol, etc. The reaction is carried out at temperature.
上記プロピレンオキサイドの量は脱アセチルキチンのピ
ラノース環１個当たり約３〜２４モルに相当し、このま
ま反応を継続すると、生成物は完全に水溶性になる。本
発明では、反応状態をサンプリングにより監視しつつ、
ヒドロキシプロピル化がピラノース環１個当たり１．２
モル以下において反応を停止する必要がある。ヒドロキ
シプロピル化度が１．２以上になると生成物は水溶性に
なり、本発明の効果が得られなくなる。又、ヒドロキシ
プロピル化度が低過ぎると得られる生成物は一旦酸等に
より溶解しても水溶性にならないので、ヒドロキシプロ
ピル化度は０．１以上が好ましい。The above amount of propylene oxide corresponds to about 3 to 24 moles per pyranose ring of deacetylated chitin, and if the reaction is continued, the product becomes completely water-soluble. In the present invention, while monitoring the reaction state by sampling,
Hydroxypropylation is 1.2 per pyranose ring
It is necessary to stop the reaction when the amount is less than molar. When the degree of hydroxypropylation is 1.2 or more, the product becomes water-soluble and the effects of the present invention cannot be obtained. Furthermore, if the degree of hydroxypropylation is too low, the resulting product will not become water-soluble even if it is once dissolved in an acid or the like, so the degree of hydroxypropylation is preferably 0.1 or more.
反応が所定のヒドロキシプロピル化度に達した後は、反
応を停止し反応生成物を濾過し、この状態で水や水−ア
ルコール混合溶剤等の洗浄液によって洗浄することによ
って、水溶性の副生物は殆ど除去され、副生物含有量の
非常に低いヒドロキシプロピル化脱アセチルキチンが得
られる。After the reaction reaches a predetermined degree of hydroxypropylation, the reaction is stopped, the reaction product is filtered, and water-soluble by-products are removed by washing with a washing liquid such as water or a water-alcohol mixed solvent. hydroxypropylated deacetyl chitin is obtained with very low by-product content.
以上の如き本発明の粒状ヒドロキシプロピル化脱アセチ
ルキチンは、そのままでは水や水−アルコール混合溶剤
等の水系溶媒には不溶であるが、任意の有機酸又は無機
酸の水溶液を溶媒とすることにより容易に溶解する。The granular hydroxypropylated deacetyl chitin of the present invention as described above is insoluble as it is in aqueous solvents such as water and water-alcohol mixed solvents, but by using an aqueous solution of any organic acid or inorganic acid as a solvent. Dissolves easily.
使用する酸はいずれの酸でもよいが、溶液を化粧品や食
品等の如く高い安全性が要求される用途に使用する場合
には、ピロリドンカルボン酸や乳酸を使用することが好
ましい。この様な酸の水溶液はこれに苛性ソーダ等の適
当なアルカリを添加することによって中性又はアルカル
性の水溶液とすることが出来る。Although any acid may be used, it is preferable to use pyrrolidone carboxylic acid or lactic acid when the solution is used in applications that require high safety, such as cosmetics and foods. Such an acid aqueous solution can be made into a neutral or alkaline aqueous solution by adding a suitable alkali such as caustic soda.
更に上記のヒドロキシプロピル化脱アセチルキチンの水
溶液又は酸の溶液或いはその酸を中和した溶液から乾固
や析出により取り出したヒドロキシプロピル化脱アセチ
ルキチンは、そのままで充分に水溶性であり、繰り返し
水溶液とすることが可能である。Furthermore, the hydroxypropylated deacetylated chitin extracted from the aqueous solution, acid solution, or neutralized solution of the hydroxypropylated deacetylated chitin by drying or precipitation is sufficiently water-soluble as it is, and can be repeatedly dissolved in aqueous solution. It is possible to do so.
（実施例） 次に実施例を挙げて本発明を更に具体的に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１〜６
脱アセチル化度８０％の脱アセチルキチン１部を１０部
のイソプロピルアルコールに分散させ（分散粒子径１５
０〜２００μｍ）、この中にイオン交換水２部を添加し
充分に撹拌する。この混合物に下記第１表に記載の割合
でプロピレンオキサイドを添加し、常圧下２時間をかけ
てプロピレンオキサイドの沸点まで昇温させ、加熱還流
下に下記第１表の時間反応を継続した。Examples 1 to 6 1 part of deacetylated chitin with a degree of deacetylation of 80% was dispersed in 10 parts of isopropyl alcohol (dispersed particle size 15%).
0 to 200 μm), 2 parts of ion-exchanged water is added to this, and the mixture is thoroughly stirred. Propylene oxide was added to this mixture in the proportions shown in Table 1 below, the temperature was raised to the boiling point of propylene oxide under normal pressure over 2 hours, and the reaction was continued under heating under reflux for the time shown in Table 1 below.
反応終了後室温まで冷却し、懸濁物を濾過し、８０％の
イソプロピルアルコールを含む水及び１００％イソプロ
ピルアルコールで充分に洗浄及び乾燥し、本発明の粒状
ヒドロキシプロピル化脱アセチルキチンを得た。After the reaction was completed, the suspension was cooled to room temperature, filtered, thoroughly washed with water containing 80% isopropyl alcohol and 100% isopropyl alcohol, and dried to obtain granular hydroxypropylated deacetyl chitin of the present invention.
実施例１〜４のヒドロキシプロピル化脱アセチルキチン
はいずれも反応媒体に不溶であり、又、反応媒体から取
り出したものも水不溶性であり、充分に洗浄可能である
。The hydroxypropylated deacetyl chitins of Examples 1 to 4 are all insoluble in the reaction medium, and those removed from the reaction medium are also water-insoluble and can be thoroughly washed.
これらの物を水に分散させ、この中のヒドロキシプロピ
ル化脱アセチルキチンとほぼ同量のピロリドンカルボン
酸又は乳酸を添加して撹拌すると速やかに溶解し無色透
明な溶液となった。These materials were dispersed in water, and when pyrrolidone carboxylic acid or lactic acid in an amount approximately equal to the hydroxypropylated deacetyl chitin was added and stirred, they were rapidly dissolved to form a colorless and transparent solution.
又、この溶液を苛性ソーダでｐＨ１２まで徐々に中和し
た場合、どの状態のｐＨでも析出は生じなかった。又、
ｐＨ７，０に中和したものを蒸発乾固したものは、その
ままで水道水に容易に溶解し、再度無色透明の溶液とな
った。Further, when this solution was gradually neutralized with caustic soda to pH 12, no precipitation occurred under any pH condition. or,
The product neutralized to pH 7.0 and evaporated to dryness was easily dissolved in tap water as it was, and became a colorless and transparent solution again.
これに対して、実施例５の物は一部が水に溶解し、他は
反応媒体に著しく膨潤し、そのままでは濾過が不能であ
る為、反応液と同量の１００％イソプロピルアルコール
を添加して撹拌し、上澄をデカンテーションで分離し、
この操作を２回繰り返した後、吸引濾過し、乾燥した。On the other hand, in Example 5, part of the product dissolved in water and the other part swelled significantly in the reaction medium, making it impossible to filter as it was, so 100% isopropyl alcohol in the same amount as the reaction solution was added. The supernatant was separated by decantation, and the supernatant was separated by decantation.
This operation was repeated twice, followed by suction filtration and drying.
この乾燥物を水に添加すると、一部平溶分を残して粘性
の高い濁った水溶液となった。When this dried product was added to water, a highly viscous and turbid aqueous solution was obtained, leaving some plainly soluble components behind.
又、実施例６の生成物は反応終了時点で殆ど反応媒体に
溶解していたので、反応終了後そのまま凍結乾燥し、大
過剰のアセトンで洗浄後乾燥した。この乾燥物を水に添
加すると、粘性の高い水溶液となった。Moreover, since most of the product of Example 6 was dissolved in the reaction medium at the time of completion of the reaction, it was directly freeze-dried after the completion of the reaction, washed with a large excess of acetone, and then dried. When this dried product was added to water, it became a highly viscous aqueous solution.
実施例７
脱アセチル化度６０％の脱アセチル化キチン１部を実施
例４と同様の条件でヒドロキシプロピル化して、本発明
の粒状ヒドロキシプロピル化脱アセチルキチンを得た。Example 7 One part of deacetylated chitin with a degree of deacetylation of 60% was hydroxypropylated under the same conditions as in Example 4 to obtain granular hydroxypropylated deacetylated chitin of the present invention.
このものの水に対する溶解性は実施例３のものと類似し
ていた。Its solubility in water was similar to that of Example 3.
（効 果）
以上如き本発明によれば、不純物混入率が非常に低いヒ
ドロキシプロピル化脱アセチルキチンが工業的に容易に
提供される。(Effects) According to the present invention as described above, hydroxypropylated deacetyl chitin with a very low impurity contamination rate can be easily provided industrially.
（他１名）(1 other person)
Claims (6)
、且つ不均一系でヒドロキシプロピル化した状態では水
不溶性であり、酸を用いて水に一旦溶解後は水溶性にな
る粒状ヒドロキシプロピル化脱アセチルキチン。(1) Particulate hydroxyl having a degree of hydroxypropylation of 0.1 to 1.2, which is water-insoluble when hydroxypropylated in a heterogeneous system, and becomes water-soluble once dissolved in water using an acid. Propylated deacetyl chitin.
ルキチンの水溶液。(2) An aqueous solution of hydroxypropylated deacetyl chitin according to claim 1.
ルキチンと有機酸との塩の水溶液。(3) An aqueous solution of a salt of the hydroxypropylated deacetyl chitin according to claim 1 and an organic acid.
求項３に記載の水溶液(4) The aqueous solution according to claim 3, wherein the organic acid is pyrrolidonecarboxylic acid or lactic acid.
液。(5) The solution according to any one of claims 2 to 4, wherein the solution contains alcohol.
ドロキシプロピル化度０．１〜１．２の範囲にヒドロキ
シプロピル化することを特徴とする粒状ヒドロキシプロ
ピル化脱アセチルキチンの製造方法。(6) A method for producing granular hydroxypropylated deacetylated chitin, which comprises dispersing granular deacetylated chitin in an aqueous medium and hydroxypropylating it to a degree of hydroxypropylation in the range of 0.1 to 1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2029209A JP2537421B2 (en) | 1990-02-08 | 1990-02-08 | Hydroxypropylated deacetylated chitin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2029209A JP2537421B2 (en) | 1990-02-08 | 1990-02-08 | Hydroxypropylated deacetylated chitin and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03234702A true JPH03234702A (en) | 1991-10-18 |
| JP2537421B2 JP2537421B2 (en) | 1996-09-25 |
Family
ID=12269806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2029209A Expired - Fee Related JP2537421B2 (en) | 1990-02-08 | 1990-02-08 | Hydroxypropylated deacetylated chitin and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2537421B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0618233A2 (en) * | 1993-03-27 | 1994-10-05 | Hoechst Aktiengesellschaft | Process for the preparation and treatment of N-hydroxyalkylchitosane soluble in aqueous medium |
| WO1996026965A1 (en) * | 1995-03-02 | 1996-09-06 | Akzo Nobel N.V. | High yield preparation of dimeric to decameric chitin oligomers |
| EP1247819A1 (en) * | 2001-04-04 | 2002-10-09 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Purified chitins and production process thereof |
| KR100395654B1 (en) * | 2001-05-29 | 2003-08-21 | 주식회사 이제 | A manufacturing method of Hydroxypropyl isopropyl ether chitosan |
| KR100407790B1 (en) * | 2001-05-29 | 2003-12-03 | 주식회사 이제 | Manufacturing method chitosan derivatives |
| CN104130339A (en) * | 2014-07-31 | 2014-11-05 | 赵东育 | Chemical synthetic method for hydroxypropyl chitin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0224045A2 (en) * | 1985-11-22 | 1987-06-03 | Wella Aktiengesellschaft | Cosmetic preparations based on N-hydroxypropyl chitosans, N-hydroxypropyl chitosans, and process for preparing them |
-
1990
- 1990-02-08 JP JP2029209A patent/JP2537421B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0224045A2 (en) * | 1985-11-22 | 1987-06-03 | Wella Aktiengesellschaft | Cosmetic preparations based on N-hydroxypropyl chitosans, N-hydroxypropyl chitosans, and process for preparing them |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0618233A2 (en) * | 1993-03-27 | 1994-10-05 | Hoechst Aktiengesellschaft | Process for the preparation and treatment of N-hydroxyalkylchitosane soluble in aqueous medium |
| EP0618233B1 (en) * | 1993-03-27 | 1999-04-28 | Clariant GmbH | Process for the preparation and treatment of N-hydroxyalkylchitosane soluble in aqueous medium |
| WO1996026965A1 (en) * | 1995-03-02 | 1996-09-06 | Akzo Nobel N.V. | High yield preparation of dimeric to decameric chitin oligomers |
| US5705634A (en) * | 1995-03-02 | 1998-01-06 | Perimmune Holdings, Inc. | High yield preparation of dimeric to decameric chitin oligomers |
| EP1247819A1 (en) * | 2001-04-04 | 2002-10-09 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Purified chitins and production process thereof |
| KR100395654B1 (en) * | 2001-05-29 | 2003-08-21 | 주식회사 이제 | A manufacturing method of Hydroxypropyl isopropyl ether chitosan |
| KR100407790B1 (en) * | 2001-05-29 | 2003-12-03 | 주식회사 이제 | Manufacturing method chitosan derivatives |
| CN104130339A (en) * | 2014-07-31 | 2014-11-05 | 赵东育 | Chemical synthetic method for hydroxypropyl chitin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2537421B2 (en) | 1996-09-25 |
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