JPH0730203B2 - Method for producing cellulose particles - Google Patents
Method for producing cellulose particlesInfo
- Publication number
- JPH0730203B2 JPH0730203B2 JP61229291A JP22929186A JPH0730203B2 JP H0730203 B2 JPH0730203 B2 JP H0730203B2 JP 61229291 A JP61229291 A JP 61229291A JP 22929186 A JP22929186 A JP 22929186A JP H0730203 B2 JPH0730203 B2 JP H0730203B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- particles
- water
- fatty acid
- acid ester
- 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
Landscapes
- Colloid Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 この発明は、セルロース粒状粒子の製造方法に関するも
のであり、詳しくは粒度が均一で真球度が高く、多孔性
にすぐれたセルロース球状粒子の製造方法に関するもの
である。TECHNICAL FIELD The present invention relates to a method for producing granular cellulose particles, and more specifically, to spherical cellulose particles having a uniform particle size, high sphericity, and excellent porosity. The present invention relates to a manufacturing method of.
（ロ）従来の技術 高分子物質の微小粒子は、プラスチック添加剤、薬剤賦
形剤、ブロッキング防止剤、化粧品添加物等に用いられ
ているが特に、セルロースの多孔質微小球体は、近年、
蛋白質や微生物の精製・分離用のゲルクロマトグラフィ
ー担体として用いられたり化学修飾することによりイオ
ン交換クロマトグラフィーやアフィニィティクロマトグ
ラフィー用担体として利用されている。さらに生体親和
性がよいので薬剤の徐放剤としてまた生体に害の少ない
化粧品添加物としての利用が検討されている。高分子物
質の微小粒子を得る最も一般的な方法は溶液からの沈澱
による方法である。セルロースにこの方法を適応したも
のに特公昭57−45254号、特開昭57−159801号、特開昭5
5−44312号、特公昭56−21761号などの発明がある。セ
ルロースは汎用の溶媒に溶解性がたく、その溶液は特殊
な溶媒を使用して製造される。この場合でもその濃度は
低い濃度に留まり、この溶液からの沈澱は実用上充分な
硬度を有する粒子を形成しがたく、100μｍの微小な粒
子を製造しにくい欠点がある。また、一般に溶媒等の単
価、回収の困難性などにも問題がある。これに対しセル
ロースの脂肪酸エステルを先ず球状粒子とし、これを加
水分解してセルロース粒子とする方法がいくつか提案さ
れている。(B) Conventional Technology Microparticles of polymeric substances are used in plastic additives, drug excipients, antiblocking agents, cosmetic additives, etc. In particular, porous microspheres of cellulose have recently been used.
It is used as a carrier for gel chromatography for purification / separation of proteins and microorganisms, or by being chemically modified, it is used as a carrier for ion exchange chromatography and affinity chromatography. Furthermore, since it has a good biocompatibility, its use as a sustained-release agent for drugs and as a cosmetic additive that is less harmful to the living body is being investigated. The most common method of obtaining microparticles of polymeric material is by precipitation from solution. Adapted to cellulose for this method, JP-B-57-45254, JP-A-57-159801, JP-A-5-159801
There are inventions such as 5-44312 and Japanese Patent Publication No. 56-21761. Cellulose is poorly soluble in general-purpose solvents, and its solution is produced using a special solvent. Even in this case, its concentration remains low, and precipitation from this solution makes it difficult to form particles having practically sufficient hardness, and it is difficult to produce fine particles of 100 μm. In addition, there are generally problems such as the unit price of the solvent and the like and the difficulty of recovery. On the other hand, several methods have been proposed in which a fatty acid ester of cellulose is first formed into spherical particles and then the particles are hydrolyzed to form cellulose particles.
特公昭55−39565号および特公昭55−40618号には、球状
粒子の製法として、セルロース脂肪酸エステルを乾式紡
糸し、得たフィラメントを切断してチップとし、高沸点
溶媒中で加熱して球状粒子とする方法、ならびにセルロ
ース脂肪酸エステルを低沸点溶媒に溶解し、高沸点貧溶
媒中に懸濁させた後そのまま加熱して懸濁粒子中の低沸
点溶媒を蒸発させ、球状粒子を得、このセルロース脂肪
酸エステル粒子を加水分解してセルロース球状粒子を得
ている。これらは工程が長く、エネルギー消費も大きい
製法である。また、得られるセルロース脂肪酸エステル
粒子が比較的緻密であるため、これから得られるセルロ
ース粒子も比較的緻密に過ぎ、クロマトグラフィー担体
用としては、空隙率の小さすぎるものしか得られない。JP-B-55-39565 and JP-B-55-40618 describe a method for producing spherical particles by dry-spinning a cellulose fatty acid ester, cutting the obtained filament into chips, and heating them in a high-boiling solvent to form spherical particles. And a method in which the cellulose fatty acid ester is dissolved in a low boiling point solvent, suspended in a high boiling point poor solvent and then heated as it is to evaporate the low boiling point solvent in the suspended particles to obtain spherical particles. The fatty acid ester particles are hydrolyzed to obtain spherical cellulose particles. These are manufacturing processes that require a long process and consume a large amount of energy. Further, since the obtained cellulose fatty acid ester particles are relatively dense, the cellulose particles obtained therefrom are also relatively dense, and as a chromatography carrier, only those having too small a porosity can be obtained.
空隙率の大きい粒子を得る方法として、特開昭54−5505
5号公報や特開昭56−24429号公報にみられるようにセル
ロース脂肪酸エステルを低沸点溶媒に溶解する際に高沸
点溶媒やセルロースエステルとは溶剤溶解性の異なる高
分子化合物、例えば水溶性高分子化合物を添加し、その
混合溶液を水性溶液中に分散懸濁させて液滴化した後、
加熱して低沸点溶媒を蒸発させ液滴を凝固せしめて、高
分子化合物もしくは高沸点溶剤を含有するセルロース脂
肪酸エステルの微小球体を得、これをケン化する前かケ
ン化後に高分子化合物又は高沸点溶媒を洗浄によって除
去し空隙率の大きいセルロース粒子を得る方法が提案さ
れている。As a method for obtaining particles having a large porosity, JP-A-54-5505
As disclosed in JP-A-56-24429 and JP-A-56-24429, when a cellulose fatty acid ester is dissolved in a low boiling point solvent, a polymer compound having a different solvent solubility from the high boiling point solvent or the cellulose ester, such as high water solubility, is used. After adding a molecular compound and dispersing and suspending the mixed solution in an aqueous solution to form droplets,
By heating to evaporate the low boiling point solvent and solidify the droplets, a polymer compound or a cellulose fatty acid ester microsphere containing a high boiling point solvent is obtained, which is before or after saponification. A method has been proposed in which the boiling point solvent is removed by washing to obtain cellulose particles having a high porosity.
（ハ）発明が解決しようとする問題点 上記従来の技術において、空隙率の大きい粒子を得るた
めになされた後者の方法には次のような問題点がある。(C) Problems to be Solved by the Invention In the above conventional technique, the latter method for obtaining particles having a large porosity has the following problems.
液滴あるいは液滴からの凝固粒子を加熱して低沸点溶媒
を除去する場合に、セルロース脂肪酸エステルの熱可塑
性のために、空孔の大きさ、粒子径、密度などの物性が
変動しやすく、再現性のある物性値を得るための工程管
理が面倒である。When the low boiling point solvent is removed by heating the droplets or the coagulated particles from the droplets, the physical properties such as pore size, particle size, and density easily change due to the thermoplasticity of the cellulose fatty acid ester, The process control to obtain reproducible physical property values is troublesome.
（ニ）問題点を解決するための手段と作用 この発明の発明者はセルロース脂肪酸エステルを球状粒
子としそれをケン化して多孔性度の大きいセルロース粒
子を得る方法について研究し、セルロース脂肪酸エステ
ルを溶かした溶液中に少量の水が微分散された状態、即
ちW/Oエマルジョンとしたものを水性媒体中に液滴と
し、該エマルジョン液滴からセルロース脂肪酸エステル
を凝固させると、液滴中の微細な水滴が粒子中の空孔を
生成し、それらがケン化によりセルロース粒子となる過
程で一部が連結された空孔となることを見出し、多孔性
度の大きいセルロース粒子を得る方法であるこの発明に
到達した。(D) Means and Actions for Solving Problems The inventor of the present invention researches a method of preparing spherical particles of cellulose fatty acid ester and saponifying the spherical particles to obtain cellulose particles having high porosity, and dissolving the cellulose fatty acid ester. When a small amount of water is finely dispersed in the solution, that is, a W / O emulsion is formed into droplets in an aqueous medium, and the cellulose fatty acid ester is coagulated from the emulsion droplets, fine particles in the droplets are formed. The present invention is a method for obtaining cellulose particles having a high degree of porosity, by finding that water droplets generate pores in the particles, and that they become pores that are partially linked in the process of becoming saponified cellulose particles. Reached
この発明は、セルロース脂肪酸エステルを水と自由に混
和しない有機溶媒に溶解した溶液に対して、少量の水を
攪拌下に添加してW/Oエマルジョンを形成し、該エマル
ジョン液を水性媒体中に加えてW/Oエマルジョンの水中
液滴を形成させ、該エマルジョン液滴から有機溶媒を除
去してセルロース脂肪酸エステルを多孔粒子として凝固
させ、この多孔性粒子をケン化して、セルロース粒子を
得ることを特徴とするセルロース粒子の製造方法に関す
るものである。This invention is a solution of cellulose fatty acid ester dissolved in an organic solvent that is not freely miscible with water, and a small amount of water is added with stirring to form a W / O emulsion, and the emulsion solution is added to an aqueous medium. In addition, water droplets of W / O emulsion are formed, the organic solvent is removed from the emulsion droplets to coagulate the cellulose fatty acid ester as porous particles, and the porous particles are saponified to obtain cellulose particles. The present invention relates to a method for producing characteristic cellulose particles.
この発明に使用するセルロース脂肪酸エステルは水に不
溶で且つ後述する有機溶媒に可溶のセルロース誘導体で
ケン可によってセルロースを再生しうるものであればよ
い。従って脂肪酸エステル基の置換度としては１以上が
好ましく実用的に有利なのはセルストリアセテート及び
セルロースジアセテートである。The cellulose fatty acid ester used in the present invention may be any cellulose derivative that is insoluble in water and soluble in the organic solvent described below, and can regenerate the cellulose by saponification. Therefore, the substitution degree of the fatty acid ester group is preferably 1 or more, and practically advantageous are sers triacetate and cellulose diacetate.
セルロース脂肪酸エステルを溶解する、水と自由に混和
しない有機溶媒としては、常圧で沸点が120℃以下程度
の溶媒が好ましく、特に塩化メチレン、クロロホルム、
テトラクロロエチレンなどのハロゲン化炭化水素に５〜
20容量％程度の、メタノール、エタノール、プラパノー
ル、イソプロパノールのような脂肪族アルコールを含有
させて混合溶媒としたものは、セルロース脂肪酸エステ
ルに対する溶解性が高くこの発明の目的に有用である。
これらの有機溶媒に対するセルロース脂肪酸エステルの
量は特に限定はないが、溶液中の濃度が３〜15％となる
程度の範囲が好適である。As the organic solvent that dissolves the cellulose fatty acid ester and is not freely miscible with water, a solvent having a boiling point of 120 ° C. or less at normal pressure is preferable, and particularly methylene chloride, chloroform,
5 to halogenated hydrocarbons such as tetrachloroethylene
A mixed solvent containing about 20% by volume of an aliphatic alcohol such as methanol, ethanol, prapanol, or isopropanol has high solubility in cellulose fatty acid ester and is useful for the purpose of the present invention.
The amount of the cellulose fatty acid ester with respect to these organic solvents is not particularly limited, but is preferably within a range such that the concentration in the solution is 3 to 15%.
セルロース脂肪酸エステルの有機溶媒溶液中に導入して
W/Oエマルジョンを生成させるための水の量は溶液に対
し５〜30％（W/W）程度がよい。水の導入に際しては高
速攪拌を与えて水の粒子を比較的小さく保つのがよい。
上述のセルローストリアセテート又はセルロースジアセ
テートとハロゲン化炭化水素からなる溶液はこのような
W/Oエマルジョンの形成能力がある。W/Oエマルジョンを
さらに水性媒体中に添加してエマルジョン液滴を形成さ
れるには、水性媒体としては、少量のゼラチン、CMC、P
VAなどの水溶性高分子又は界面活性剤及び消泡剤などを
溶解した水溶液が好ましい。これら水溶性高分子や界面
活性剤は一日生成した液滴の再会合を防ぎ粒径分布のせ
まい液滴の形成を助ける効果がある。Introduced into the organic solvent solution of cellulose fatty acid ester
The amount of water for forming the W / O emulsion is preferably about 5 to 30% (W / W) with respect to the solution. When introducing water, it is preferable to provide high-speed stirring to keep the water particles relatively small.
The above-mentioned solution of cellulose triacetate or cellulose diacetate and halogenated hydrocarbon is
Capable of forming W / O emulsion. To add the W / O emulsion to the aqueous medium to form emulsion droplets, the aqueous medium should be a small amount of gelatin, CMC, P
An aqueous solution in which a water-soluble polymer such as VA or a surfactant and an antifoaming agent is dissolved is preferable. These water-soluble polymers and surfactants have the effect of preventing re-association of droplets generated every day and helping to form droplets with a narrow particle size distribution.
このようにして生成したエマルジョン液滴／水性媒体の
系にアルカリ水溶液を添加して、液滴中のセルロース脂
肪酸エステルをケン化すればセルロース粒子が生成す
る。その際、液滴中に乳化懸濁の状態で含有されていた
水の小粒子はセルロース粒子内の空孔を形成するので、
多孔性のセルロース粒子が得られる。An aqueous alkaline solution is added to the emulsion droplet / aqueous medium system thus produced to saponify the cellulose fatty acid ester in the droplets, whereby cellulose particles are produced. At that time, since the small particles of water contained in the droplets in an emulsified suspension form pores in the cellulose particles,
Porous cellulose particles are obtained.
なおこの方法で作製したセルロース粒子は、ケン化過程
で固体化が液滴の表面から起り、液滴の容質濃度が漸次
低下してゆく機構をとるためと思われるが、生成粒子に
密度勾配があり粒子表面が密に粒子内部が疎になる傾向
があり表面が硬い粒子が得られる。It is considered that the cellulose particles produced by this method have a mechanism in which solidification occurs from the surface of the droplets during the saponification process and the concentration of the droplets in the droplets gradually decreases. There is a tendency that the particle surface becomes dense and the inside of the particle becomes sparse, and particles having a hard surface are obtained.
エマルジョン液滴／水性媒体の系を有機溶媒の沸点以上
にゆるやかに加熱して有機溶媒を溜去しセルロース脂肪
酸エステルの固体粒子を生成させてかつこの粒子をケン
化しセルロースを再生させる方法をとってもよい。この
方法を用いた場合の方が粒子内での密度勾配がく均質な
多孔性粒子が得られる。なおこの方法では有機溶媒は加
熱のみで完全に除去することはむずかしいのでケン化の
前又は／および後に低級アルコールで洗浄して抽出によ
り有機溶媒を完全に除去する方法がとられる。A method may be employed in which the system of emulsion droplets / aqueous medium is gently heated to a temperature higher than the boiling point of the organic solvent to distill off the organic solvent to produce solid particles of cellulose fatty acid ester and saponify the particles to regenerate the cellulose. . When this method is used, a homogeneous porous particle having a density gradient within the particle can be obtained. In this method, since it is difficult to completely remove the organic solvent only by heating, a method of completely removing the organic solvent by washing with a lower alcohol before and / or after saponification and extraction is employed.
（ホ）実施例 この発明を実施例によって説明するがこの発明を限定す
るものではない。(E) Embodiments The present invention will be described with reference to embodiments, but the present invention is not limited thereto.
実施例１ セルローストリアセテート〔ダイセル化学工業（株）製
酢化度61％〕50gを塩化メチレン350ml/メタノール10m
lの混合溶媒に溶解した溶液に、10000rpmの撹拌下水50m
lを加えてW/Oエマルジョンを作製した。Example 1 Cellulose triacetate [manufactured by Daicel Chemical Industries, Ltd., acetylation degree 61%] was added to 50 g of methylene chloride 350 ml / methanol 10 m.
50 ml of water under stirring at 10000 rpm
l was added to make a W / O emulsion.
上記懸濁液を水1000mlにゼラチン10gを溶解した水性媒
体中に800rpmの撹拌下に添加し、合計30分撹拌してW/O/
W懸濁液を作製した。上記W/O/W懸濁液を500rpmの撹拌を
続けながら40℃に加温し、塩化メチレンを溜去した。３
〜４時間で約100mlの塩化メチレンを留去した時点で液
滴中のセルロースアセテートが固化し、安定な球状粒子
となり、分散液となるのが観察された。分散液にイソプ
ロパノール200mlを加え、次いで25％水酸化ナトリウム
水溶液500mlを加え、引きつづき、約40℃で４時間撹拌
した。この間に溜出する塩化メチレンは還流させた。こ
の操作により球状粒子はセルロースにケン化された。酢
酸100mlを加えて中和し、セルロース球状粒子を濾別
し、水洗浄、メタノール洗浄、水洗浄の順に充分洗浄し
た。The above suspension was added under stirring at 800 rpm to an aqueous medium in which 10 g of gelatin was dissolved in 1000 ml of water, and stirred for a total of 30 minutes to obtain W / O /
A W suspension was prepared. The above W / O / W suspension was heated to 40 ° C. while continuing stirring at 500 rpm, and methylene chloride was distilled off. Three
It was observed that when about 100 ml of methylene chloride was distilled off in about 4 hours, the cellulose acetate in the liquid droplets solidified into stable spherical particles and became a dispersion liquid. 200 ml of isopropanol was added to the dispersion, and then 500 ml of a 25% aqueous sodium hydroxide solution was added, followed by stirring at about 40 ° C. for 4 hours. The methylene chloride distilled during this time was refluxed. By this operation, the spherical particles were saponified into cellulose. 100 ml of acetic acid was added for neutralization, and the spherical cellulose particles were separated by filtration and thoroughly washed with water, methanol, and water in this order.
得られたセルロース球状粒子を湿潤状態のまま分級し径
70〜150μｍのもの180mlを得て製品とした。The spherical cellulose particles obtained are classified in a wet state and
180 ml of 70 to 150 μm was obtained as a product.
得られたセルロース粒子は、光学顕微鏡観察によれば真
球度の高い球状粒子であり、また、乾燥した後赤外吸収
スペクトルを測定したところアセチル基の残存はみとめ
られなかった。The obtained cellulose particles were spherical particles having a high sphericity according to an optical microscope observation, and the infrared absorption spectrum was measured after drying. No residual acetyl group was found.
得られた含水状態のセルロース粒子のセルロース密度
（CD）を次の方法で測定した。The cellulose density (CD) of the obtained water-containing cellulose particles was measured by the following method.
膨潤状態のセルロース粒子を内径8mmのカラムに約10cm
のhcmの高さまで充填しその容積V0（ml）算出する。Approximately 10 cm of swollen cellulose particles in a column with an inner diameter of 8 mm
Fill up to a height of hcm and calculate the volume V 0 (ml).
V0＝（0.4）２πｈ 次に分子量200万のブルーテキストランの0.5％水溶液を
溶出させその溶出量（Vt ml）を求める。充填したセル
ロース粒子をカラムから取り出し濾別し充分に洗浄後乾
燥してその重量を求める〔Ｗ（ｇ）〕。これらのデータ
より次式によってセルロース密度〔CD（％）〕を算出し
た。V 0 = (0.4) 2 πh Next, elute a 0.5% aqueous solution of blue text run having a molecular weight of 2 million and obtain the elution amount (Vt ml). The packed cellulose particles are taken out from the column, separated by filtration, thoroughly washed and dried to determine the weight [W (g)]. From these data, the cellulose density [CD (%)] was calculated by the following formula.
実施例１で得られたセルロース粒子のCDは15％であっ
た。 The CD of the cellulose particles obtained in Example 1 was 15%.
実施例２ セルロースジアセテート〔ダイセル化学工業（株）製
酢化度55％〕50gを塩化メチレン350ml/メタノール10mg
の混合溶媒に溶解した溶液に10000rpmの撹拌下水50mlを
加えてW/Oエマルジョンを作製した。Example 2 Cellulose diacetate [manufactured by Daicel Chemical Industries, Ltd.
Acetylation degree 55%] 50g methylene chloride 350ml / methanol 10mg
50 ml of water with stirring at 10,000 rpm was added to the solution dissolved in the mixed solvent of to prepare a W / O emulsion.
上記エマルジョンを、水1200mlにゼラチン5gを溶解しイ
ソプロパノール200mlを加えた水性媒体中に800rpmの撹
拌下に添加し、さらに30分間撹拌をつづけW/O/W懸濁液
を作成した。The above emulsion was added to an aqueous medium prepared by dissolving 5 g of gelatin in 1200 ml of water and 200 ml of isopropanol under stirring at 800 rpm, and stirring was continued for 30 minutes to prepare a W / O / W suspension.
上記懸濁液にアルカリを加えて液滴中のセルロースジア
セテートをケン化した。即ち室温400rpmの撹拌下25％の
水酸化ナトリウム水溶液500mlを加え、撹拌を続行し
た。約１時間後に液滴中のセルロースジアセテートがケ
ン化すると共に固化し、セルロース球状粒子が得られ
た。引きつづき同条件で12時間処理しケン化を完了させ
た。実施例１と同様に中和及び洗浄を行い湿潤状態でセ
ルロース球状粒子を分級した。粒径30〜75μｍの粒子40
ml、75〜150μｍの粒子150ml、150〜250μｍの粒子90ml
を得た。径75〜150μｍのCDは７％であった。Alkali was added to the above suspension to saponify the cellulose diacetate in the droplets. That is, 500 ml of 25% aqueous sodium hydroxide solution was added with stirring at room temperature of 400 rpm, and stirring was continued. After about 1 hour, the cellulose diacetate in the droplets was saponified and solidified to obtain spherical cellulose particles. Subsequently, the saponification was completed by treating under the same conditions for 12 hours. Neutralization and washing were carried out in the same manner as in Example 1 to classify the spherical cellulose particles in a wet state. Particles 40 with a particle size of 30-75 μm
ml, 75-150μm particles 150ml, 150-250μm particles 90ml
Got The CD having a diameter of 75 to 150 μm was 7%.
実施例３ 実施例１に用いたと同じセルローストリアセテート50g
を塩化メチレン350ml/メタノール10ml/n−オクタノール
100mlの混合溶媒に溶解した溶液に10000rpmの撹拌下水5
0mlを加えてW/Oエマルジョンを作製した。Example 3 50 g of the same cellulose triacetate as used in Example 1
Methylene chloride 350 ml / methanol 10 ml / n-octanol
5 ml of water under stirring at 10000 rpm in a solution dissolved in 100 ml of mixed solvent
0 ml was added to make a W / O emulsion.
上記懸濁液を水1500mlにゼラチン15gを溶解した水溶液
に800rpmの撹拌下添加し、さらに30分間撹拌をつづけW/
O/W懸濁液を作製した上記W/O/W懸濁液を実施例１の方法
に準じて処理し塩化メチレンを一部溜去して液滴中のセ
ルローストリアセテートを固化させた。得られたセルロ
ーストリアセテート球状粒子を濾別し充分に洗浄した湿
潤状態で分級し、粒径30〜75μｍの粒子80ml、75〜150
μｍの粒子100ml、150〜250mlの粒子120mlを得た。The above suspension was added to an aqueous solution in which 15 g of gelatin was dissolved in 1500 ml of water while stirring at 800 rpm, and stirring was continued for further 30 minutes W /
The W / O / W suspension prepared as an O / W suspension was treated according to the method of Example 1 to partially distill off methylene chloride to solidify the cellulose triacetate in the droplets. The obtained cellulose triacetate spherical particles were separated by filtration, thoroughly washed, and classified in a wet state to obtain 80 ml of particles having a particle size of 30 to 75 μm, 75 to 150
100 ml of micron particles and 120 ml of 150-250 ml particles were obtained.
粒径75〜150μｍの粒子を1N水酸化カリウム水溶液／エ
タノール＝75/25混合液に室温下１昼夜浸漬してケン化
もセルロース球状粒子を得た。得られた粒子のCDは12％
であった。また湿潤したままの粒子をカラムにつめ、分
子量200万のブルーデキストラン及び分子量既知の種々
のテキストランを用いて濾過試験を行い排除体積分子量
50万の値を得た。Particles having a particle size of 75 to 150 μm were immersed in a 1N aqueous solution of potassium hydroxide / ethanol = 75/25 at room temperature for one day to saponify to obtain cellulose spherical particles. The resulting particles have a CD of 12%
Met. In addition, the as-wet particles were packed in a column, and a filtration test was performed using blue dextran with a molecular weight of 2,000,000 and various text runs with a known molecular weight, and the excluded volume molecular weight was measured.
Got a value of 500,000.
比較例 実施例３に用いたのと同じセルローストリアセテート50
gを用い、塩化メチレン350ml/メタノール10ml/n−オク
タノール100mlの混合溶媒に溶解し、以下該溶液に50ml
の水を導入しW/O懸濁液とする工程のみを省略して実施
例３と同様に処理し、粒径75〜150μｍのセルロースト
リアセテート粒径同様にケン化してセルロース粒子を得
た。得られた粒子のCDは35％であった。Comparative Example Cellulose triacetate 50 same as used in Example 3
g, and dissolved in a mixed solvent of 350 ml of methylene chloride / 10 ml of methanol / 100 ml of n-octanol, and then 50 ml of the solution.
The same procedure as in Example 3 was carried out by omitting only the step of introducing water to prepare a W / O suspension, and saponification was performed in the same manner as the cellulose triacetate particle diameter of 75 to 150 μm to obtain cellulose particles. The CD of the obtained particles was 35%.
（ヘ）発明の効果 この発明によれば、加熱処理が不要であり、使用する溶
媒も比較的安価な汎用溶媒から選択できるので、安価に
セルロース粒子を製造できる。しかも、空隙率の大きい
多孔性のセルロース粒子が得られるので、化粧品、ゲル
濾過クロマトグラフィ担体、徐放性薬剤担体などに好適
である。さらにセルロース粒子に化学修飾を施し、イオ
ン交換クロマトグラフ担体、アフィニティクロマトグラ
フ担体などに応用できる。(F) Effect of the Invention According to the present invention, since heat treatment is not necessary and the solvent to be used can be selected from relatively inexpensive general-purpose solvents, cellulose particles can be produced at low cost. Moreover, since porous cellulose particles having a large porosity can be obtained, it is suitable for cosmetics, gel filtration chromatography carriers, sustained release drug carriers and the like. Further, the cellulose particles can be chemically modified and applied to an ion exchange chromatographic carrier, an affinity chromatographic carrier and the like.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｂ 3/06 7433−4Ｃ Ｇ０１Ｎ 30/48 Ｔ 8310−2Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08B 3/06 7433-4C G01N 30/48 T 8310-2J
Claims (2)
和しない有機溶媒に溶解した溶液に対して、少量の水を
攪拌下に添加してW/Oエマルジョンを形成し、該エマル
ジョンを水性媒体中に加えてW/Oエマルジョンの水中液
滴を形成させ、該エマルジョン液滴から有機溶媒を除去
してセルロース脂肪酸エステルを多孔粒子として凝固さ
せ、該セルロース脂肪酸エステル多孔粒子をケン化して
セルロース粒子を得ることを特徴とするセルロース粒子
の製造方法。1. A W / O emulsion is formed by adding a small amount of water to a solution prepared by dissolving a cellulose fatty acid ester in an organic solvent which is not freely miscible with water to form a W / O emulsion. In addition, water droplets of W / O emulsion are formed, the organic solvent is removed from the emulsion droplets to coagulate the cellulose fatty acid ester as porous particles, and the cellulose fatty acid ester porous particles are saponified to obtain cellulose particles. A method for producing cellulose particles, comprising:
機溶媒の５〜25％（W/W）である特許請求の範囲第１項
記載の製造方法。2. The production method according to claim 1, wherein the amount of water added to the organic solvent solution is 5 to 25% (W / W) of the organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61229291A JPH0730203B2 (en) | 1986-09-27 | 1986-09-27 | Method for producing cellulose particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61229291A JPH0730203B2 (en) | 1986-09-27 | 1986-09-27 | Method for producing cellulose particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6383144A JPS6383144A (en) | 1988-04-13 |
| JPH0730203B2 true JPH0730203B2 (en) | 1995-04-05 |
Family
ID=16889824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61229291A Expired - Lifetime JPH0730203B2 (en) | 1986-09-27 | 1986-09-27 | Method for producing cellulose particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730203B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5328603A (en) * | 1990-03-20 | 1994-07-12 | The Center For Innovative Technology | Lignocellulosic and cellulosic beads for use in affinity and immunoaffinity chromatography of high molecular weight proteins |
| CN102911379B (en) * | 2011-08-04 | 2014-04-23 | 南通醋酸纤维有限公司 | Method for preparing cellulose acetate microspheres and product prepared by method |
| FI126122B (en) * | 2011-12-22 | 2016-06-30 | Upm Kymmene Corp | Use of a stationary phase comprising fibril pulp in a separation process |
| JP6369467B2 (en) * | 2013-09-02 | 2018-08-08 | Jnc株式会社 | Method for producing porous cellulose particles and porous cellulose particles |
| CN114555678B (en) * | 2019-12-05 | 2023-08-25 | 根上工业株式会社 | Cellulose particles and method for producing cellulose particles |
| WO2021230284A1 (en) * | 2020-05-12 | 2021-11-18 | 根上工業株式会社 | Inorganic-substance-including cellulose particles and method for producing same |
| JP2023037724A (en) * | 2021-09-06 | 2023-03-16 | Jnc株式会社 | Porous particle and production method of the same, and filler for chromatography using the same |
| CN116063726B (en) * | 2022-12-31 | 2023-09-19 | 杭州纽龙生物科技有限公司 | Cellulose porous gel microsphere with uniform particle size, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5539565A (en) * | 1978-09-14 | 1980-03-19 | Toyo Slate Kk | Corrugated slate roof |
-
1986
- 1986-09-27 JP JP61229291A patent/JPH0730203B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5539565A (en) * | 1978-09-14 | 1980-03-19 | Toyo Slate Kk | Corrugated slate roof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6383144A (en) | 1988-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6231032B2 (en) | Method for producing cellulose porous particles and cellulose porous particles | |
| US4118336A (en) | Novel cellulose microcapsules and preparation thereof | |
| JP2001504452A (en) | Process for the preparation of microcapsules coated with an active substance with a polymer and in particular novel microcapsules obtained by this process | |
| JPWO2008084854A1 (en) | Cellulose microparticles and dispersions and dispersions thereof | |
| Banerjee et al. | Investigation on crosslinking density for development of novel interpenetrating polymer network (IPN) based formulation | |
| WO2013016982A1 (en) | Cellulose acetate microsphere preparation method and product prepared thereby | |
| JPH0420938B2 (en) | ||
| JP3287798B2 (en) | Method for producing spherical cellulose fine particles | |
| US4888420A (en) | Water soluble cellulose acetate microspheres | |
| JPS6117851B2 (en) | ||
| JPH0730203B2 (en) | Method for producing cellulose particles | |
| JP2506682B2 (en) | Manufacturing method of spherical particles | |
| JPH082992B2 (en) | Manufacturing method of porous spherical particles | |
| US4937081A (en) | Process for producing porous, spherical particles | |
| JPH0730202B2 (en) | Manufacturing method of spherical particles | |
| US4948814A (en) | Ion exchanger based on cross-linked glucomannan | |
| JPH0556761B2 (en) | ||
| JPH0762042B2 (en) | Manufacturing method of cellulose microspheres | |
| JPH0576496B2 (en) | ||
| US4997599A (en) | Preparation of water soluble cellulose acetate microspheres | |
| JPS62267339A (en) | Production of bead of organic acid ester of cellulose | |
| JPS62253601A (en) | Production of spherical particle of cellulose | |
| US5670636A (en) | Fractionated agaroid compositions, their preparation and use | |
| Pimenov et al. | Ultra-low-density microcellular aerogels based on cellulose acetate | |
| JP2525308B2 (en) | Method for producing spherical particles of porous cellulose |