JPH0780921B2 - Microcrystalline chitosan and method for producing the same - Google Patents
Microcrystalline chitosan and method for producing the sameInfo
- Publication number
- JPH0780921B2 JPH0780921B2 JP62013834A JP1383487A JPH0780921B2 JP H0780921 B2 JPH0780921 B2 JP H0780921B2 JP 62013834 A JP62013834 A JP 62013834A JP 1383487 A JP1383487 A JP 1383487A JP H0780921 B2 JPH0780921 B2 JP H0780921B2
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- acid
- microcrystalline chitosan
- water
- organic solvent
- 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
Links
- 229920001661 Chitosan Polymers 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000003021 water soluble solvent Substances 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229920002101 Chitin Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000238424 Crustacea Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000850 deacetylating effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000546 pharmaceutical excipient Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は微結晶キトサンおよびその製造法に関する。詳
しくは天然物から分離して得たキトサンの非晶部分を酸
加水分解により除去して得られる微結晶キトサンならび
にその製造法に関する。TECHNICAL FIELD The present invention relates to microcrystalline chitosan and a method for producing the same. More particularly, it relates to microcrystalline chitosan obtained by removing an amorphous portion of chitosan obtained by separating from a natural product by acid hydrolysis, and a method for producing the same.
〈従来技術〉 セルロース，アミロース，キチン，コラーゲン等の結晶
性天然高分子物質さらにポリアミド，ポリエステル，ポ
リオレフィン等の結晶性合成高分子であって、結晶性部
分と非結晶部分を有する物質から酸加水分解により非晶
部分を除去して結晶部分を取りだして得た各種の微結晶
ポリマーの性質と製造方法がO.A.Battista著“Microcry
stal Polymer Science"Mc Graw Hill（1975年）に詳し
く述べられている。<Prior Art> Crystalline natural polymer substances such as cellulose, amylose, chitin, collagen and the like, and crystalline synthetic polymers such as polyamide, polyester, polyolefin and the like, which are acid-hydrolyzed from substances having a crystalline portion and an amorphous portion. OABattista's "Microcry" describes the properties and manufacturing method of various microcrystalline polymers obtained by removing the amorphous part by removing the crystalline part by
stal Polymer Science "Mc Graw Hill (1975).
これら微結晶ポリマーのうち、親水性ポリマーの性質に
共通するものとしては圧縮成型できること、及び微結晶
ポリマーの水分散物を剪断下高速攪拌すると容易にゲル
状となることなどである。Among these microcrystalline polymers, what is common to the properties of hydrophilic polymers is that they can be molded by compression, and that an aqueous dispersion of a microcrystalline polymer can easily become a gel when stirred at high speed under shear.
一方、甲殻類、昆虫類の組織支持体として自然界に広く
分布するキチンならびにキチンを脱アセチル化すること
により得られるキトサンは医療材料をはじめとして多く
の分野での機能性材料として近年注目されており活発な
研究がなされている。キトサンは遊離のアミン基を有す
ることから、カチオン性ポリマーとして種々の機能発現
が期待されるが、酸と接触すると酸塩を形成し水に溶解
するようになるため、先述の微結晶ポリマー製造技術を
適用することができず、キトサンを微結晶として得る先
行技術は発表されていない。On the other hand, chitin, which is widely distributed in nature as a tissue support for crustaceans and insects, and chitosan obtained by deacetylating chitin have been attracting attention in recent years as functional materials in many fields including medical materials. Active research is being done. Since chitosan has a free amine group, it is expected to exhibit various functions as a cationic polymer, but when it comes into contact with an acid, it forms an acid salt and dissolves in water. Is not applicable, and no prior art for obtaining chitosan as fine crystals has been published.
〈発明が解決しようとする問題点〉 従来の技術に準じキトサンを不均一系で酸加水分解しよ
うとしてもキトサンが溶解して均一系となり、分解が進
行して結晶部分，非結晶部分を問わず、モノマー単位で
ある２−アミノ−２−デオキシ−Ｄ−グリコースまで分
解されてしまい、微結晶キトサンを得ることはできな
い。<Problems to be solved by the invention> According to the conventional technique, even if an attempt is made to acid-hydrolyze chitosan in a heterogeneous system, chitosan is dissolved and becomes a homogeneous system, and the decomposition proceeds, regardless of whether it is a crystalline part or an amorphous part. However, 2-amino-2-deoxy-D-glycose, which is a monomer unit, is decomposed and microcrystalline chitosan cannot be obtained.
本発明は、上記したような従来の技術の問題点を解決し
て、すぐれた使途をもった微結晶キトサンとその製造方
法を提供しようとするものである。The present invention is intended to solve the above-mentioned problems of the conventional techniques and provide a microcrystalline chitosan and a method for producing the same, which have excellent uses.
〈問題点を解決するための手段〉 本発明者は、キトサンを適当な有機溶媒〜水〜鉱酸の系
で処理すれば、キトサンの不均一系での酸加水分解が可
能となり、これにより結晶部分を微結晶キトサンとして
回収することが可能になる、という事実を見いだし本発
明に到達した。<Means for Solving Problems> The present inventor can treat acid in a heterogeneous system of chitosan by treating chitosan with a system of a suitable organic solvent, water and a mineral acid. The present inventors have reached the present invention by discovering the fact that it is possible to recover a portion as microcrystalline chitosan.
キトサンを有機溶媒〜水〜鉱酸の系で処理し、非晶部分
を除去して得られる微結晶キトサンは微粉末である、原
料キトサンと物性を比較すると重合度は低く且つ均一化
され結晶化度は高くなっていることがみとめられる。Chitosan is a fine powder obtained by treating chitosan with a system of organic solvent-water-mineral acid, and removing the amorphous part, and it is a fine powder when compared with the raw material chitosan It can be seen that the degree is high.
〈発明の構成〉 本発明は１％酢酸水溶液を溶媒として測定する極限粘度
数が1.5％〜2.0dl/gの範囲にあり、Ｘ線法結晶化度が80
〜90％の範囲にあることを特徴とする微結晶キトサンに
関するものである。<Structure of the Invention> The present invention has an intrinsic viscosity in the range of 1.5% to 2.0 dl / g measured using a 1% acetic acid aqueous solution as a solvent, and an X-ray crystallinity of 80.
It relates to microcrystalline chitosan, which is characterized by being in the range of up to 90%.
本発明はまた、キトサンを有機溶媒〜水〜鉱酸よりなる
系で部分加水分解することを特徴とする微結晶キトサン
の製造方法に関するものである。The present invention also relates to a method for producing microcrystalline chitosan, which comprises partially hydrolyzing chitosan with a system consisting of an organic solvent, water and a mineral acid.
本発明の微結晶キトサンの原料であるキトサンは、エビ
やカニの甲殻類の殻を精製して得られるキチンをアルカ
リ処理により脱アセチル化して得られるがこの方法で製
造したフレーク状キトサンが市販されている。Chitosan, which is the raw material for the microcrystalline chitosan of the present invention, is obtained by deacetylating chitin obtained by purifying crustacean shells of shrimp and crab by alkali treatment, but flaky chitosan produced by this method is commercially available. ing.
本発明の製法において、原料キトサンの酸加水分解時に
用いる有機溶媒としては水と相溶性のあるものが好まし
く、アルコール類、ケトン類などが好ましい。特にｎ−
プロパノール,iso−プロパノール,n−ブタノール,sec−
ブタノール,iso−ブタノール,tert−ブタノール等が特
に好ましい。これらの溶媒は水と相溶性がよく、また比
較的沸点が高いので反応温度を高く設定し、短時間の反
応を可能にする。In the production method of the present invention, the organic solvent used during the acid hydrolysis of the raw material chitosan is preferably one that is compatible with water, and alcohols, ketones and the like are preferable. Especially n-
Propanol, iso-propanol, n-butanol, sec-
Butanol, iso-butanol, tert-butanol and the like are particularly preferable. Since these solvents have good compatibility with water and also have a relatively high boiling point, the reaction temperature is set high to enable a short reaction time.
本発明の製法に用いる鉱酸としては例えば塩酸，硫酸，
硝酸，燐酸などである。Examples of the mineral acid used in the production method of the present invention include hydrochloric acid, sulfuric acid,
Examples include nitric acid and phosphoric acid.
本発明の製法は、その好ましい態様に従えば、次のよう
にして実施することができる。According to the preferred embodiment, the production method of the present invention can be carried out as follows.
キトサンと下記の物質を記載の量（いずれもキトサン10
0重量部に対して）： 有機溶媒 300〜1,000重量部 水 300〜1,000重量部 鉱酸 100〜 200重量部 で混合して一緒に加水分解容器に仕込み、還流温度（85
〜90℃）で0.5〜２時間にわたって攪拌する。以上の処
理によってキトサンの酸加水分解が完了する。次いで、
該系を室温まで冷却別し、得られた粗微結晶キトサン
を加水分解に使用したのと同じ種類の有機溶媒1,000重
量部に投入し、室温で15〜30分攪拌した後別すると、
微粉末の製品が湿潤状態で得られる。これは付着鉱酸の
大部分が除去された微結晶キトサンであるが、このもの
をカセイソーダ30重量部、水1,500重量部、有機溶媒
（加水分解に使用したのと同じ種類のものが好ましい）
1,500重量部からなる溶液に投入し常温で15〜30分攪拌
し、付着酸とアミノ基へ付加している酸を中和する。こ
の後、微結晶キトサンを洗液が中性になるまで水で洗滌
する。水洗後、微結晶キトサンを乾燥するが、この乾燥
方法により微結晶キトサンの機能発現が左右される。The amounts of chitosan and the substances listed below (both chitosan 10
Organic solvent: 300-1,000 parts by weight Water: 300-1,000 parts by weight Mineral acid: 100-200 parts by weight Mix in a hydrolysis vessel at the reflux temperature (85
Stir at ~ 90 ° C) for 0.5-2 hours. The above-mentioned treatment completes the acid hydrolysis of chitosan. Then
The system was cooled to room temperature, and the obtained crude fine crystalline chitosan was added to 1,000 parts by weight of the same type of organic solvent used for the hydrolysis, and the mixture was stirred at room temperature for 15 to 30 minutes and then separated.
A finely divided product is obtained in the wet state. This is a microcrystalline chitosan from which most of the deposited mineral acid has been removed. This is 30 parts by weight caustic soda, 1,500 parts by weight of water, organic solvent (preferably the same type used for hydrolysis).
It is added to a solution consisting of 1,500 parts by weight and stirred at room temperature for 15 to 30 minutes to neutralize the attached acid and the acid added to the amino group. After that, the microcrystalline chitosan is washed with water until the washing liquid becomes neutral. After washing with water, the microcrystalline chitosan is dried. The function of microcrystalline chitosan is affected by this drying method.
好ましい乾燥の実施態様としては、（１）凍結乾燥、
（２）有機溶媒で水を置換した後50〜60℃の温度で乾燥
し、（３）噴霧乾燥が挙げられる。（１）または（２）
の方法で乾燥した場合は微粉末が２次凝集して塊とな
る。塊状の乾燥物を粉砕することで所望の微結晶キトサ
ンが得られる。通常90％以上が60μｍ以下の粒径を有す
る微粉末としてえられる。Preferred embodiments of drying include (1) freeze-drying,
(2) After substituting water with an organic solvent, it is dried at a temperature of 50 to 60 ° C., and (3) spray drying is mentioned. (1) or (2)
When dried by the above method, the fine powder is secondarily aggregated to form a lump. The desired microcrystalline chitosan is obtained by crushing the lumpy dried product. Usually, 90% or more is obtained as a fine powder having a particle size of 60 μm or less.
〈発明の効果〉 本発明の方法によって得ることのできる微結晶キトサン
は圧縮成型性があり打錠成型できるので錠剤の賦形剤兼
崩壊剤として使用可能である。医薬の打錠に用いた場合
の崩壊性は微結晶セルロースに比し優れている。また微
結晶キトサンを水に懸濁させ高剪断下攪拌すると該懸濁
液系は粘稠なゲル状になるため、食品に添加して賦形剤
としても利用できる。さらに上述のゲル状物をガラス板
上にアプリケーターを用い展延し、乾燥すると薄膜クロ
マトグラフィー用担体として使用することができる。<Effects of the Invention> The microcrystalline chitosan obtainable by the method of the present invention has compression moldability and can be formed into tablets, and therefore can be used as an excipient / disintegrant for tablets. The disintegration property when used for tableting a medicine is superior to that of microcrystalline cellulose. Further, when microcrystalline chitosan is suspended in water and stirred under high shear, the suspension system becomes a viscous gel, and therefore it can be added to foods and used as an excipient. Further, the above gel-like material is spread on a glass plate with an applicator and dried to be used as a carrier for thin film chromatography.
〈実施例〉 以下に本発明を実施例により、更に詳細に説明する。<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例１ 市販のキトサンフレーク（共和油脂（株）製、〔η〕1%
酢酸＝141,結晶化度60％）100gを、イソプロパノール
（IPA）524g、水60g、36％塩酸478gの混合液中に投入
し、還流温度（87℃）に加温し、攪拌しながら、30分間
保持した。その後冷却し、過し得られた粗微結晶キト
サンを1,000gのIPAに投入、室温で30分間攪拌した。こ
れを過した後、固形分を、カセイソーダ30g,水1,500
g,IPA1,500gの混合液中に入れ、室温で30分間処理し
た。処理後、水洗、アセトン置換、乾燥、粉砕を行な
い、微結晶キトサン粉末（〔η〕1% 酢酸＝1.9,結晶化度
85％，粒度95％以上が60μｍ以下）70gを得た。Example 1 Commercially available chitosan flakes (manufactured by Kyowa Yushi Co., Ltd., [η] 1%
100 g of acetic acid = 141, crystallinity of 60%) was added to a mixed solution of 524 g of isopropanol (IPA), 60 g of water, and 478 g of 36% hydrochloric acid, and the mixture was heated to a reflux temperature (87 ° C) and stirred to 30 Hold for minutes. Then, the mixture was cooled, and the crude fine crystal chitosan obtained was put into 1,000 g of IPA and stirred at room temperature for 30 minutes. After passing this, the solid content is 30 g of caustic soda, 1,500 of water.
It was put in a mixed solution of 1,500 g of IPA and treated for 30 minutes at room temperature. After the treatment, it was washed with water, replaced with acetone, dried, and pulverized to obtain fine crystalline chitosan powder ([η] 1% acetic acid = 1.9, crystallinity).
70% (85%, particle size 95% or more 60 μm or less) was obtained.
実施例２ 実施例１で用いたと同じキトサンフレークを実施例１と
同じ処方で、加水分解時間だけを１時間30分に変えて他
は全く同じ条件で処理した。後処理、乾燥、粉砕も全く
実施例１と同様に行ない、微結晶キトサン粉末（〔η〕
1% 酢酸＝1.9,結晶化度87％，粒度:95％以上が60μｍ以
下）60gを得た。Example 2 The same chitosan flakes as used in Example 1 were treated with the same formulation as in Example 1 except that the hydrolysis time was changed to 1 hour and 30 minutes, and the other conditions were exactly the same. Post-treatment, drying, and pulverization were carried out in the same manner as in Example 1, and microcrystalline chitosan powder ([η]
60% of 1% acetic acid = 1.9, crystallinity 87%, particle size: 95% or more and 60 μm or less) were obtained.
実施例３ 実施例１で用いたと同じキトサンフレーク100gを、イソ
プロパノール524g、水219g、36％塩酸319gの混合液中に
投入し、還流温度（88℃）に加温し、攪拌しながら１時
間保持した。その後の後処理は全く実施例１と同様に行
ない、微結晶キトサン粉末（〔η〕1% 酢酸＝2.0,結晶化
度80％，粒度90％以上が60μｍ以下）73gを得た。Example 3 100 g of the same chitosan flakes as used in Example 1 was put into a mixed solution of 524 g of isopropanol, 219 g of water and 319 g of 36% hydrochloric acid, heated to a reflux temperature (88 ° C.) and kept for 1 hour while stirring. did. Subsequent post-treatment was carried out in the same manner as in Example 1 to obtain 73 g of microcrystalline chitosan powder ([η] 1% acetic acid = 2.0, crystallinity 80%, particle size 90% or more 60 μm or less).
実施例４および５ 実施例１で得られた微結晶キトサンを用い水懸濁液とな
し、それをホモミキサーで10,000rpmで攪拌し、粘稠な
ゲル状物を得た。得られたゲル状物の粘度をＢ型粘度計
（ローターNo.4,60rpm,25℃）で測定した。結果を次表
に示す。Examples 4 and 5 The microcrystalline chitosan obtained in Example 1 was used to prepare an aqueous suspension, which was stirred with a homomixer at 10,000 rpm to obtain a viscous gel. The viscosity of the obtained gel-like material was measured with a B-type viscometer (rotor No. 4, 60 rpm, 25 ° C). The results are shown in the table below.
Claims (6)
粘度数が1.5〜2.0dl/gの範囲にあり、Ｘ線法結晶化度が
80〜90％の範囲にあることを特徴とする微結晶キトサ
ン。1. The intrinsic viscosity number measured with a 1% acetic acid aqueous solution as a solvent is in the range of 1.5 to 2.0 dl / g, and the X-ray crystallinity is
Microcrystalline chitosan characterized by being in the range of 80-90%.
で部分加水分解することを特徴とする微結晶キトサンの
製造方法。2. A method for producing microcrystalline chitosan, which comprises partially hydrolyzing chitosan with a system consisting of an organic solvent, water and a mineral acid.
徴とする特許請求の範囲第２項記載の微結晶キトサンの
製造方法。3. The method for producing microcrystalline chitosan according to claim 2, wherein the organic solvent is a water-soluble solvent.
徴とする特許請求の範囲第３項記載の微結晶キトサンの
製造方法。4. The method for producing microcrystalline chitosan according to claim 3, wherein the organic solvent is alcohol.
あることを特徴とする特許請求の範囲第２項記載の微結
晶キトサンの製造方法。5. The method for producing microcrystalline chitosan according to claim 2, wherein the mineral acid is any one of hydrochloric acid, sulfuric acid and nitric acid.
サンの使用量100重量部に対し、前記有機溶媒300〜1,00
0重量部、水300〜1,000重量部、鉱酸100〜200重量部を
それぞれの使用量とする特許請求の範囲第２項，第３
項，第４項および第５項のいずれかに記載の微結晶キト
サンの製造方法。6. The organic solvent 300 to 1,00 per 100 parts by weight of chitosan used in the production by the partial hydrolysis.
Claims 2 and 3 in which the amount of use is 0 parts by weight, 300 to 1,000 parts by weight of water, and 100 to 200 parts by weight of mineral acid.
Item 6. A method for producing microcrystalline chitosan according to any one of Items 4, 4 and 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62013834A JPH0780921B2 (en) | 1987-01-23 | 1987-01-23 | Microcrystalline chitosan and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62013834A JPH0780921B2 (en) | 1987-01-23 | 1987-01-23 | Microcrystalline chitosan and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63182304A JPS63182304A (en) | 1988-07-27 |
| JPH0780921B2 true JPH0780921B2 (en) | 1995-08-30 |
Family
ID=11844302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62013834A Expired - Lifetime JPH0780921B2 (en) | 1987-01-23 | 1987-01-23 | Microcrystalline chitosan and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780921B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI83426C (en) * | 1989-06-30 | 1991-07-10 | Firextra Oy | FOERFARANDE FOER KONTINUERLIG FRAMSTAELLNING AV MICROCRYSTALLINE KITOSAN. |
| CN1248679C (en) * | 2000-07-18 | 2006-04-05 | 株式会社艾贝克斯 | Water-soluble void-containing microflakes and preparation method thereof |
| JP4759151B2 (en) * | 2001-02-16 | 2011-08-31 | 日本水産株式会社 | Production method of low molecular weight chitosan by heterogeneous system |
| WO2003057736A1 (en) * | 2002-01-09 | 2003-07-17 | Abbott Laboratories De Costa Rica Ltd | Methods of producing modified microcrystalline chitosan and uses therefor |
| KR100553667B1 (en) * | 2002-05-08 | 2006-02-24 | 메디칸(주) | Manufacturing method of solid chitosan powder that can be injected into human body by injection |
| CN1223610C (en) * | 2003-07-16 | 2005-10-19 | 中国科学院海洋研究所 | Microware degradative crust oligose compound and its preparing method |
-
1987
- 1987-01-23 JP JP62013834A patent/JPH0780921B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63182304A (en) | 1988-07-27 |
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