JPH0623201B2 - Method for producing chitosan granules - Google Patents
Method for producing chitosan granulesInfo
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- JPH0623201B2 JPH0623201B2 JP16093086A JP16093086A JPH0623201B2 JP H0623201 B2 JPH0623201 B2 JP H0623201B2 JP 16093086 A JP16093086 A JP 16093086A JP 16093086 A JP16093086 A JP 16093086A JP H0623201 B2 JPH0623201 B2 JP H0623201B2
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はキトサン粒体の製造方法に関し、更に詳しく
は、医療品担体、注射薬材料、クロマトグラフィー用吸
着材、バイオリアクタ担体等として有用な種々の粒径の
高純度キトサン粒体の提供を目的とする。Description: TECHNICAL FIELD The present invention relates to a method for producing chitosan granules, and more specifically, it is useful as a carrier for medical products, an injectable material, an adsorbent for chromatography, a bioreactor carrier, and the like. The object is to provide high-purity chitosan granules having various particle sizes.
（従来の技術） 従来、キチンを脱アセチル化して得られるキトサンは公
知であり、そのユニークな性質からして各種の吸着材、
医療品担体、医療材料としての研究が行なわれている。(Prior Art) Chitosan obtained by deacetylating chitin has heretofore been known, and due to its unique property, various adsorbents,
Research is being conducted as a carrier for medical products and a medical material.
例えば、各種担体として利用する場合には、キトサンを
粒状化する技術が重要であり、このような粒状化技術と
しては、キトサンが酸の水溶液に可溶であり、アルカリ
によって凝固するという性質を利用して、キトサンの水
溶液を調製し、これをアルカリにより中和して粒状化す
る技術が最も多く提案されている。For example, when used as various carriers, a technology for granulating chitosan is important. As such a granulating technology, the property that chitosan is soluble in an acid aqueous solution and coagulates with an alkali is used. The most proposed technique is to prepare an aqueous solution of chitosan and neutralize it with an alkali to granulate it.
これらの粒状化方法によれば、平均粒径が数ｍｍから数
１００μｍ程度の粒状キトサンが提供される。According to these granulation methods, granular chitosan having an average particle size of several mm to several hundreds of μm is provided.
（発明が解決しようとしている問題点） 上記の公知の方法は、いずれも水性媒体中において、キ
トサンの凝固を行うものであり、比較的平均粒径の大な
る粒状キトサンは得られるものの、例えば、数１０μｍ
程度のキトサン粒体を得るのは非常に困難であり、更に
数μｍ程度のキトサン粒体を得ることはできない。これ
は、キトサンの粒状化を水性媒体中で行う結果、キトサ
ン粒子が微小であるとそれらが水性媒体中で凝集を生じ
易いこと、および、このような微小な状態を凝集を生じ
ることなく乾燥するのは極めて困難なためである。(Problems to be solved by the invention) In any of the above-mentioned known methods, in an aqueous medium, chitosan is coagulated, and although granular chitosan having a relatively large average particle size is obtained, for example, Several tens of μm
It is very difficult to obtain chitosan granules of a certain degree, and it is not possible to obtain chitosan granules of a few μm. This is because, as a result of performing granulation of chitosan in an aqueous medium, if chitosan particles are minute, they are likely to aggregate in an aqueous medium, and such a minute state is dried without causing aggregation. Because it is extremely difficult.
また、従来方法の場合には、水性媒体中における凝固方
法を使用する結果、操作が煩雑で且つ条件設定が困難で
あるため、一定の粒度および品質の粒体を得るのが困難
であつた。更に、キトサンの粒状化に際しては、アルカ
リ等の凝固剤、界面活性剤等の懸濁剤等が必要であるた
め、これらの各種補助剤が、得られるキトサン粒体中に
混入し、不純物を含んだキトサン粒体となるという問題
がある。この問題は、キトサン粒体を医療分野で使用し
ようとする時には非常に重要であり、従来方法によるキ
トサン粒体は殆ど医療分野では利用することができなか
った。Further, in the case of the conventional method, as a result of using the coagulation method in an aqueous medium, it is difficult to obtain granules having a certain particle size and quality because the operation is complicated and the condition setting is difficult. Furthermore, when granulating chitosan, a coagulant such as an alkali and a suspending agent such as a surfactant are required, and thus various auxiliary agents are mixed in the obtained chitosan granules to contain impurities. There is a problem that it becomes a chitosan granule. This problem is very important when attempting to use chitosan granules in the medical field, and chitosan granules obtained by the conventional method could hardly be used in the medical field.
また、最近では、キトサンが免疫活性効果があること、
また生理活性物の徐放性担体としての利用可能性等が報
告されているが、このような用途においては、キトサン
の平均粒径はμｍオーダーであること、および不純物を
含有しないことが要求されるため、従来技術によるキト
サン粒体は殆ど利用可能性が見い出し得ないものであっ
た。Also, recently, chitosan has an immunoreactive effect,
Further, it has been reported that the bioactive substance can be used as a sustained-release carrier, but in such applications, it is required that the average particle size of chitosan be on the order of μm and that it contain no impurities. Therefore, the chitosan granules according to the prior art could hardly find applicability.
従って、その平均粒径が１０μｍ以下のものから任意の
平均粒径の球状のキトサン粒体を提供できる方法が強く
要望されている。Therefore, there is a strong demand for a method capable of providing spherical chitosan particles having an average particle diameter of 10 μm or less and having an arbitrary average particle diameter.
（問題点を解決するための手段） 本発明者は上記の如き従来技術の問題点を解決し、上記
の要望に応えるべく鋭意研究の結果、本発明を完成し
た。(Means for Solving Problems) The present inventor has completed the present invention as a result of earnest research to solve the above-mentioned problems of the prior art and meet the above-mentioned demand.
すなわち、本発明は、キトサンの酸水溶液をアンモニア
雰囲気中で噴霧乾燥することを特徴とするキトサン粒体
の製造方法である。That is, the present invention is a method for producing chitosan granules, which comprises spray-drying an aqueous acid solution of chitosan in an ammonia atmosphere.
次に本発明を更に詳細に説明する。本発明者は従来から
キトサンの粒状化について鋭意研究のところ、キトサン
を酸の水溶液に適当な濃度で溶解し、従来技術の如く、
凝固浴中に加えて凝固させるのではなく、得られたキト
サン水溶液を種々の条件で加熱アンモニア雰囲気中に噴
霧して乾燥する、すなわちスプレードライ方式で乾燥す
る時は、噴霧乾燥条件に従って種々の平均粒径のキトサ
ン粒体が極めて容易に得られることを知見したものであ
る。しかも、このようにして得られる種々の平均粒径の
キトサン粉体は、その形式が殆ど角のない球状であり、
しかも、乾燥時固体になるような凝固剤等を使用しない
ため、得られるキトサン粒体は非常に高純度であり、吸
着材等の一般的用途は勿論、平均粒径が１０μｍ以下の
ものは特に医療分野における担体材料等として非常に適
しているものであった。Next, the present invention will be described in more detail. The present inventor has been earnestly researching the granulation of chitosan, and the chitosan was dissolved in an aqueous solution of an acid at an appropriate concentration, as in the prior art.
Rather than adding to the coagulation bath to coagulate, the resulting chitosan aqueous solution is sprayed in a heated ammonia atmosphere under various conditions to dry, that is, when the spray drying method is used for drying, various averages are obtained according to the spray drying conditions. It was discovered that chitosan particles having a particle size can be obtained very easily. Moreover, the chitosan powders having various average particle diameters obtained in this manner are spherical with almost no corners,
Moreover, since a coagulant or the like which becomes a solid when dried is not used, the obtained chitosan granules have a very high purity. Of course, general applications such as adsorbents and those having an average particle diameter of 10 μm or less are particularly preferable. It was very suitable as a carrier material in the medical field.
以上の如き本発明方法は次の如くして行われ種々の平均
粒径のキトサン粒体が提供される。The method of the present invention as described above is performed as follows to provide chitosan granules having various average particle diameters.
本発明において使用するキトサンとは、カニやエビの甲
殻類の外皮中に存在するキチンを脱アセチル化して得ら
れるものであり、それ自体としては周知の材料であり、
種々の脱アセチル化度、種々の分子量ものが市場から入
手できるし、また容易に製造し得るものである。本発明
において使用するキトサンは、これらの公知のキトサン
中で、酸の水溶液に溶解できるものはいずれの脱アセチ
ル化度でもいずれの分子量のものでも使用できる。Chitosan used in the present invention is obtained by deacetylating chitin existing in the crustaceans and shrimp crustacean shells, and is a material known per se.
Various degrees of deacetylation and various molecular weights are commercially available and can be easily produced. The chitosan used in the present invention may be any one of these known chitosans that can be dissolved in an aqueous acid solution and have any degree of deacetylation and any molecular weight.
キトサンを溶解するための酸の水溶液は、酢酸、乳酸等
の有機酸および塩酸等の無機酸のいずれの水溶液でもよ
い。The aqueous solution of an acid for dissolving chitosan may be any of an aqueous solution of an organic acid such as acetic acid and lactic acid and an inorganic acid such as hydrochloric acid.
酸の水溶液の酸濃度は、溶解するキトサンの濃度にもよ
るが、一般的には０．１〜１０重量％程度の濃度が好ま
しく、またキトサンの濃度はいずれの濃度でもよいが、
一般的には０．０５〜２０重量％、好ましくは０．１〜
１０重量％程度である。濃度が上記範囲未満であると経
済性が劣り、また上記濃度を越えると、キトサン水溶液
の粘度が高くなり、取扱不便となる。このようなキトサ
ンの濃度を調製することによって、サブミクロンのもの
から１００μｍオーダーの種々のキトサン粒体を提供す
ることができる。The acid concentration of the aqueous acid solution depends on the concentration of dissolved chitosan, but is generally preferably about 0.1 to 10% by weight, and the concentration of chitosan may be any concentration.
Generally from 0.05 to 20% by weight, preferably from 0.1 to
It is about 10% by weight. If the concentration is less than the above range, the economy is poor, and if the concentration exceeds the above range, the viscosity of the chitosan aqueous solution becomes high, which is inconvenient to handle. By adjusting the concentration of such chitosan, various chitosan particles of submicron to 100 μm order can be provided.
上記のキトサンの水溶液はキトサンの溶解によってｐＨ
は７に近くなるが、更に無害な塩基性物質を加えてｐＨ
を更に７に近づけることによって、一層容易にキトサン
粒体を得ることができる。またキトサンが凝固しない程
度にアルコール等の有機溶剤を添加してもよい。更に、
キトサン水溶液中には予め有用な薬剤、例えば、酵素、
生理活性物質等を適当量添加させておくこともできる。The above-mentioned aqueous solution of chitosan has a pH due to the dissolution of chitosan.
Is close to 7, but the pH can be adjusted by adding harmless basic substances.
By further approaching to 7, chitosan granules can be obtained more easily. An organic solvent such as alcohol may be added to the extent that chitosan does not solidify. Furthermore,
A useful drug such as an enzyme in the chitosan aqueous solution is previously prepared.
It is also possible to add an appropriate amount of a physiologically active substance or the like.
本発明で使用する噴霧乾燥方法自体は、アンモニア雰囲
気中行うことを除き公知の方法であり、いずれの公知の
噴霧乾燥装置も有用である。The spray drying method itself used in the present invention is a known method except that it is carried out in an ammonia atmosphere, and any known spray drying apparatus is also useful.
このような噴霧乾燥機中で上記の如きキトサンの水溶液
を５０〜１５０℃程度のアンモニア雰囲気中に噴霧する
ことにより、溶液は微細な液滴が凝固するとともに水分
が蒸発し、本発明方法によるキトサン粒体が得られる。
使用するアンモニア雰囲気は、いずれの濃度でもよい
が、一般的には約１００〜１００００ｐｐｍの濃度であ
る。アンモニア濃度が低すぎると、キトサンの凝固が遅
れるため、乾燥温度を高めることが必要となり、その結
果、形成されるキトサン粒体が凝集したり、変質したり
する可能性が生じるので好ましくない。また上記範囲以
上のアンモニア濃度でも経済性を考慮しなければ何等問
題はない。このようにして得られた本発明のキトサン粒
体は、角の殆ど無い球状体であり、その平均粒経は噴霧
乾燥条件に従って１０μｍ以下のものから１００μｍオ
ーダーのものである。得られたキトサン粒体には若干酸
とアンモニアからなる塩が残っていることもあるので、
更に水洗して残っている酸を十分に除去してもよく、少
量の塩が残留しても問題のない用途ではそのままでもよ
い。By spraying an aqueous solution of chitosan as described above in an ammonia atmosphere at about 50 to 150 ° C. in such a spray dryer, fine droplets are coagulated in the solution and water is evaporated, and chitosan according to the method of the present invention is obtained. Granules are obtained.
The ammonia atmosphere to be used may have any concentration, but it is generally about 100 to 10,000 ppm. If the ammonia concentration is too low, coagulation of chitosan will be delayed, and it will be necessary to raise the drying temperature. As a result, the formed chitosan granules may aggregate or deteriorate, which is not preferable. Further, even if the ammonia concentration exceeds the above range, there is no problem unless the economical efficiency is taken into consideration. The thus-obtained chitosan granules of the present invention are spherical bodies having almost no corners, and the average particle diameter thereof is from 10 μm or less to 100 μm order according to the spray drying conditions. In the obtained chitosan granules, some salts of acid and ammonia may remain, so
Furthermore, the remaining acid may be sufficiently removed by washing with water, and it may be left as it is in the case where there is no problem even if a small amount of salt remains.
また得られたキトサン粒体は、用途によってはポリイソ
シアネート、ポリエポキシ化合物等の架橋剤によって架
橋処理を行い、その耐水性等を高めてもよい。The obtained chitosan granules may be subjected to a cross-linking treatment with a cross-linking agent such as a polyisocyanate or a polyepoxy compound to increase the water resistance thereof depending on the use.
（作用・結果） 以上の如き本発明方法によれば、従来方法では提供でき
なかった球状のキトサン粒体が提供でき、また噴霧乾燥
条件を変化させることによって平均粒経が１０μｍ以下
の微小のものから１００μｍオーダーの粒体が提供でき
る。従って、本発明方法によるキトサン粒体は、従来公
知の平均粒経の大なキトサン粒子と同様にゲルクロマト
グラフィー、イオン変換クロマトグラフィー等の交換
材、透析材、イオン交換体、バイオリアクタの担体等と
して有用であること勿論、従来技術において球状の形状
が要求される用途においても有用である。更に平均粒経
が１０μｍ以下のキトサン微小粒体の合には、高純度で
あることから、従来では使用できなかった医療分野での
用途、例えば、生理活性物質の担体や静脈注射剤の材料
等としての有用である。(Operation / Results) According to the method of the present invention as described above, spherical chitosan granules which cannot be provided by the conventional method can be provided, and fine particles having an average particle diameter of 10 μm or less by changing the spray drying conditions. It is possible to provide particles of the order of 100 μm. Therefore, the chitosan granules according to the method of the present invention include gel chromatography, ion exchange chromatography and other exchange materials, dialysis materials, ion exchangers, bioreactor carriers, etc., similar to conventionally known large chitosan particles having an average particle size. Of course, it is also useful in applications where a spherical shape is required in the prior art. Furthermore, when chitosan fine particles having an average particle size of 10 μm or less are used, they have a high purity, and thus have been used in the medical field that could not be used in the past, such as a carrier of a physiologically active substance or a material for intravenous injection. It is useful as
次に実施例を挙げて本発明を更に具体的に説明する。な
お、文中、部または％とあるのは特に断りのない限り重
量基準である。Next, the present invention will be described more specifically with reference to examples. In the text, parts or% are based on weight unless otherwise specified.
実施例１ １％の酢酸水溶液中に脱アセチル化６３％のキトサン
（分子量約２３万）を０．１％の濃度に溶解してキトサ
ンの水溶液を調製し、これを入口温度５０℃、噴霧空気
圧１kg／cm2、送液量１〜２ml／min.および１０００ｐ
ｐｍのアンモニア濃度の条件で噴霧乾燥した。得られた
キトサン粒体をエタノール中に分散させ、遠心分離器に
より分離し、乾燥して、本発明のキトサン粒体を得た。
このキトサン粒体の１００個を任意に取り出し、顕微鏡
下で観察したところ殆どが真球状であり、平均粒経は２
μｍであった。このキトサン粒体は各種吸着材や静脈注
射剤の材料として有用である。Example 1 An aqueous solution of chitosan was prepared by dissolving deacetylated 63% chitosan (molecular weight: about 230,000) in a 1% aqueous acetic acid solution at a concentration of 0.1%. 1 kg / cm 2 , liquid transfer rate 1-2 ml / min. And 1000p
Spray drying was performed under the condition of ammonia concentration of pm. The obtained chitosan granules were dispersed in ethanol, separated by a centrifuge, and dried to obtain a chitosan granule of the present invention.
When 100 pieces of this chitosan granules were arbitrarily taken out and observed under a microscope, most of them were spherical and the average grain diameter was 2
was μm. This chitosan granule is useful as a material for various adsorbents and intravenous injections.
実施例２〜６ 実施例１におけるキトサン、酸および噴霧乾燥条件を下
記第１表の如く変えたことを除いて、他は実施例１と同
様にして本発明のキトサン粒体を得た。これらのキトサ
ン粒体はいずれも各種吸着材や静脈注射剤の材料として
有用である。Examples 2 to 6 Chitosan granules of the present invention were obtained in the same manner as in Example 1 except that the chitosan, acid and spray drying conditions in Example 1 were changed as shown in Table 1 below. All of these chitosan granules are useful as materials for various adsorbents and intravenous injections.
第 １ 表 実施例２ キトサン；脱アセチル化度８５％ 分子量３万 溶液濃度１０％ 酸； ８％酢酸 噴霧乾燥；入口温度８０℃ 噴霧空気圧１kgf／cm2 送液速度１〜２ml／min. アンモニア濃度；１００００ｐｐｍ キトサン微小粒体の平均粒経；１００μｍ 実施例３ キトサン；脱アセチル化度７２％ 分子量５万 溶液濃度５％ 酸； ２％塩酸 噴霧乾燥；入口温度９０℃ 噴霧空気圧１kgf／cm2 送液速度１〜２ml／min. アンモニア濃度；１００ｐｐｍ キトサン微小粒体の平均粒経；５０μｍ 実施例４ キトサン；脱アセチル化度９９％ 分子量２３万 溶液濃度１％ 酸； １％酢酸 噴霧乾燥；入口温度７０℃ 噴霧空気圧１kgf／cm2 速液速度１〜２ml／min. アンモニア濃度；５００ｐｐｍ キトサン微小粒体の平均粒経；７μｍ 実施例５ キトサン；脱アセチル化度５０％ 分子量２０万 溶液濃度０．１％ 酸； ０．４％酢酸 噴霧乾燥；入口温度８０℃ 噴霧空気圧１kgf／cm2 送液速度２〜３ml/min. アンモニア濃度；１０００ｐｐｍ キトサン微小粒体の平均粒経；２μｍ 実施例６ キトサン；脱アセチル化度８５％ 分子量３万 溶液濃度０．５％ 酸； ０．５％酢酸 噴霧乾燥；入口温度１００℃ 噴霧空気圧１kgf/cm2 送液速度４〜５ml／min. アンモニア濃度；１０００ｐｐｍ キトサン微小粒体の平均粒経；６μｍTable 1 Example 2 Chitosan; Deacetylation degree 85%, Molecular weight 30,000 Solution concentration 10% Acid; 8% Acetic acid Spray drying; Inlet temperature 80 ° C Spray air pressure 1 kgf / cm 2 Liquid feed rate 1-2 ml / min. Ammonia concentration Average particle size of 10,000 ppm chitosan fine particles; 100 μm Example 3 chitosan; Deacetylation degree 72%, molecular weight 50,000, solution concentration 5% acid; 2% hydrochloric acid spray drying; inlet temperature 90 ° C., spray air pressure 1 kgf / cm 2 liquid transfer Speed 1-2 ml / min. Ammonia concentration; 100 ppm Average particle size of chitosan microparticles; 50 μm Example 4 Chitosan; Deacetylation degree 99% Molecular weight 230,000 Solution concentration 1% Acid; 1% Acetic acid Spray drying; Inlet temperature 70 ° C Spraying air pressure 1 kgf / cm 2 Rapid liquid velocity 1-2 ml / min. Ammonia concentration; 500 ppm Average particle size of chitosan fine particles; 7 μm Example 5 Chitosan; Deacetylation degree 50 % Molecular weight 200,000 Solution concentration 0.1% Acid; 0.4% Acetic acid Spray drying; Inlet temperature 80 ° C Spraying air pressure 1kgf / cm 2 Liquid feeding speed 2-3ml / min. Ammonia concentration; 1000ppm Average particle size of chitosan fine particles 2 μm Example 6 Chitosan; Deacetylation degree 85% Molecular weight 30,000 Solution concentration 0.5% Acid; 0.5% Acetic acid Spray drying; Inlet temperature 100 ° C. Spray air pressure 1 kgf / cm 2 Liquid transfer rate 4-5 ml / min. Ammonia concentration: 1000 ppm Average particle size of chitosan microparticles: 6 μm
Claims (4)
で噴霧乾燥することを特徴とするキトサン粒体の製造方
法。1. A method for producing chitosan granules, which comprises spray-drying an aqueous acid solution of chitosan in an ammonia atmosphere.
ｐｍであるである特許請求の範囲第(1)項に記載のキト
サン粒体の製造方法。2. Ammonia concentration is 100 to 10,000 p
The method for producing chitosan granules according to claim (1), which is pm.
％である特許請求の範囲第(1)項に記載のキトサン粒体
の製造方法。3. The method for producing chitosan granules according to claim (1), wherein the aqueous solution concentration of chitosan is 0.1 to 20% by weight.
るキトサン粒体の平均粒径を制御する特許請求の範囲第
(1)項に記載のキトサン粒体の製造方法。4. A method for controlling the average particle size of the obtained chitosan granules by controlling the concentration of an aqueous chitosan solution.
The method for producing a chitosan granule according to the item (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16093086A JPH0623201B2 (en) | 1986-07-10 | 1986-07-10 | Method for producing chitosan granules |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16093086A JPH0623201B2 (en) | 1986-07-10 | 1986-07-10 | Method for producing chitosan granules |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6317902A JPS6317902A (en) | 1988-01-25 |
| JPH0623201B2 true JPH0623201B2 (en) | 1994-03-30 |
Family
ID=15725326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16093086A Expired - Fee Related JPH0623201B2 (en) | 1986-07-10 | 1986-07-10 | Method for producing chitosan granules |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623201B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5010181A (en) * | 1988-03-28 | 1991-04-23 | Coughlin Robert W | Partially treated shellfish waste for removal of heavy metals from aqueous solution |
| KR100566336B1 (en) | 1998-06-04 | 2006-03-31 | 가오가부시끼가이샤 | Polymer emulsion and process for producing the same |
| KR100661125B1 (en) | 2005-05-06 | 2006-12-22 | 주식회사 바이오폴리텍 | Chitosan particle and process therefor |
-
1986
- 1986-07-10 JP JP16093086A patent/JPH0623201B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6317902A (en) | 1988-01-25 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |