JP2587892B2 - Cellulose porous particles - Google Patents
Cellulose porous particlesInfo
- Publication number
- JP2587892B2 JP2587892B2 JP4338014A JP33801492A JP2587892B2 JP 2587892 B2 JP2587892 B2 JP 2587892B2 JP 4338014 A JP4338014 A JP 4338014A JP 33801492 A JP33801492 A JP 33801492A JP 2587892 B2 JP2587892 B2 JP 2587892B2
- Authority
- JP
- Japan
- Prior art keywords
- diameter
- cellulose
- particles
- partition wall
- pores
- 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
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Description
【０００１】[0001]
【産業上の利用分野】この発明は、セルロースの隔壁を
介して多数の空孔が集合するセルロース多孔質粒子に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous cellulose particle in which a large number of pores are gathered through a partition wall of cellulose.
【０００２】[0002]
【従来の技術】従来、この種のセルロース多孔質粒子と
して、特開平１−４３５３０号公報に示すものがある。2. Description of the Related Art Conventionally, as this kind of cellulose porous particles, there is one disclosed in JP-A-1-43530.
【０００３】このものは、セルロースの隔壁に、多数の
貫通小孔が形成されており、隔壁が平坦なものに比べ、
大きな比表面積を有する。In this case, a large number of small through holes are formed in a partition wall of cellulose.
It has a large specific surface area.
【０００４】したがって、隔壁に多数の貫通小孔を有す
るセルロース多孔質粒子は、抗菌剤・吸着剤・機能性セ
ラミックなどの担体、香料・農薬・医薬品などの担体、
菌体・酵母等の固定化担体、イオン交換体・消臭剤・化
粧品などの原料等として使用した場合、担持量が多く、
有用なものとなる。[0004] Therefore, the porous cellulose particles having a large number of through-holes in the partition can be used as carriers for antibacterial agents, adsorbents, functional ceramics, etc., carriers for fragrances, agricultural chemicals, pharmaceuticals, etc.
When used as a carrier for immobilizing bacteria, yeast, etc., as a raw material for ion exchangers, deodorants, cosmetics, etc., the loading amount is large,
It will be useful.
【０００５】[0005]
【発明が解決しようとする課題】ところが、上記構造の
セルロース多孔質粒子では、大きな比表面積を得ようと
すれば、それだけ隔壁に貫通小孔を多数あけなければな
らないので、隔壁強度が弱く、セルロース多孔質粒子を
カラムに充填して通液を行った場合、粒子が通液の圧力
によりつぶれて圧密化し、通液性が阻害されたり、液が
粒子内部にまで侵入しないので処理の効率が悪くなると
いう問題がある。However, in order to obtain a large specific surface area, a large number of small through-holes must be formed in the partition walls of the cellulose porous particles having the above structure. When porous particles are packed in a column and liquid is passed through, the particles are crushed by the pressure of the liquid flow and consolidate, impeding liquid permeability, or the liquid does not penetrate into the particles , resulting in poor treatment efficiency. the there is a problem that <br/>.
【０００６】また、セルロース多孔質粒子を水で膨潤さ
せた状態で攪拌したり、あるいはエアーによって搬送し
たりすると、隔壁の貫通小孔の部分から隔壁が細かく破
れてしまうという問題もある。[0006] Further, when the cellulose porous particles are agitated in a state of being swollen with water or conveyed by air, there is also a problem that the partition walls are torn finely from the small through holes of the partition walls.
【０００７】上記隔壁の強度は、隔壁の厚みを厚くすれ
ば大きくなるが、隔壁の厚みは、粒径や空孔の形状、あ
るいは多孔性の度合等と共に、用途に応じて決める必要
があるので、強度の点だけで隔壁の厚みを厚くすること
はできない。The strength of the partition wall increases as the thickness of the partition wall increases, but the thickness of the partition wall needs to be determined according to the use together with the particle size, the shape of pores, the degree of porosity, and the like. However, it is impossible to increase the thickness of the partition walls only in terms of strength.
【０００８】そこで、この発明は、大きな比表面積を有
し、しかも隔壁強度が大きい、多孔質セルロースを得よ
うとするものである。Accordingly, the present invention aims to obtain porous cellulose having a large specific surface area and a large partition wall strength.
【０００９】[0009]
【課題を解決するための手段】上記の課題を解決するた
めに、この発明は、多数の空孔を仕切るセルロースの隔
壁表面に、隔壁を貫通しない多数の凹部を形成したので
あり、粒子の径と空孔の径と凹部の径の関係は次の通り
である。 粒子の径が０．５ｍ／ｍ以上１０ｍ／ｍ未満の
場合には、空孔の径を粒子の径の１／１００〜１／２、
凹部の径を空孔の径の１／３０〜１／４とし、粒子の径
が０．０２ｍ／ｍ以上０．０５ｍ／ｍ未満の場合には、
空孔の径を粒子の径の１／２０〜１／２、凹部の径を空
孔の径の１／１００〜１／４とする。 In order to solve the above problems, according to the present invention, a large number of concave portions which do not penetrate the partition wall are formed on the surface of the partition wall of cellulose partitioning a large number of pores. The relationship between the diameter of the particles, the diameter of the pores and the diameter of the recess is as follows.
It is. Particle diameter of 0.5 m / m or more and less than 10 m / m
In this case, the diameter of the pores is 1/100 to 1/2 of the particle diameter,
The diameter of the recess is 1/30 to 1/4 of the diameter of the pore,
Is 0.02 m / m or more and less than 0.05 m / m,
The diameter of the pores should be 1/20 to 1/2 of the diameter of the particles,
1/100 to 1/4 of the hole diameter.
【００１０】[0010]
【作用】隔壁表面に多数の凹部を形成することにより、
大きな比表面積が得られる。By forming a large number of recesses on the partition wall surface,
A large specific surface area can be obtained.
【００１１】そして、上記凹部は、隔壁を貫通しないの
で、隔壁の機械的強度が大きい。Since the recess does not penetrate the partition, the partition has high mechanical strength.
【００１２】[0012]
【実施例】この発明に係るセルロース多孔質粒子は、セ
ルロースの隔壁を介して多数の空孔が集合し、隔壁の表
面に多数の凹部が形成されている。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the porous cellulose particles according to the present invention, a large number of pores are gathered via a partition wall of cellulose, and a large number of concave portions are formed on the surface of the partition wall.
【００１３】かかる構造のセルロース多孔質粒子は、種
々の用途に使用できるが、比表面積が大きく、しかも隔
壁強度が高いので、特に、水処理等、カラム等に充填し
て通液するような用途に好適である。The cellulose porous particles having such a structure can be used for various purposes. However, since the specific surface area is large and the partition wall strength is high, it is particularly used for water treatment or the like which is packed in a column or the like and passed through. It is suitable for.
【００１４】このような用途に使用する場合、粒子の径
としては、０．０２〜１０ｍ／ｍの範囲が望ましい。な
ぜなら、粒子の径が、０．０２ｍ／ｍ未満のものは、カ
ラム等に充填して通液した場合に、圧力損失が大きくな
りすぎるという問題が生じ、また、１０ｍ／ｍを超える
と、かさ比重が小さすぎて所定の効果を出すには容積が
大きくなりすぎ、実用的でないからである。したがっ
て、特に好ましい粒径としては、０．０５〜５ｍ／ｍの
範囲である。When used in such applications, the diameter of the particles is preferably in the range of 0.02 to 10 m / m. If the particle diameter is less than 0.02 m / m, there is a problem that the pressure loss becomes excessively large when the liquid is packed in a column or the like and passed therethrough. This is because the specific gravity is too small and the volume is too large to obtain a predetermined effect, which is not practical. Therefore, a particularly preferred particle size is in the range of 0.05 to 5 m / m.
【００１５】また、隔壁によって仕切られた空孔と、隔
壁に形成した凹部の寸法は、粒径によりその好ましい範
囲が異なる。The preferred range of the size of the pores partitioned by the partition and the size of the recess formed in the partition differs depending on the particle size.
【００１６】粒径が０．５ｍ／ｍ以上の場合、空孔の径
は、粒径の１／１００〜１／２となる。１／１００未満
だと内部通液性が悪くなり、１／２を超えると、薬剤や
菌体等の固定化量が少なくなるからであり、好ましくは
１／５０〜１／４である。また、隔壁に形成した凹部の
径は、空孔の径の１／３０〜１／４である。１／３０未
満だと、薬剤等が浸透しにくく、１／４を超えると、固
定化量が少ないという問題を生じやすくなる。When the particle diameter is 0.5 m / m or more, the diameter of the pores is 1/100 to 1/2 of the particle diameter. If it is less than 1/100, the internal liquid permeability will be poor, and if it exceeds １ ／, the amount of immobilized drug or bacterial cells will be small, preferably 1/50 to ４. The diameter of the recess formed in the partition is 1/30 to 1/4 of the diameter of the hole. If it is less than 1/30, it is difficult for the drug or the like to penetrate, and if it is more than 1/4, the problem that the amount of immobilization is small tends to occur.
【００１７】一方粒径が０．５ｍ／ｍ未満の場合には、
空孔の径は、粒径の１／２０〜１／２となる。１／２０
未満だと処理液が浸透しにくく、固定化物質の放出もし
にくく、また、１／２を超えると、含浸量が少なく、固
定化物質の放出が直ちに生じて徐放性が得られなくな
る。また、隔壁に形成した凹部の径は、空孔の径の１／
１００〜１／４である。On the other hand, when the particle size is less than 0.5 m / m,
The diameter of the pores is 1/20 to 1/2 of the particle diameter. 1/20
When the amount is less than the above, the treatment liquid hardly permeates and the immobilizing substance is hardly released. When the amount exceeds １ ／, the amount of impregnation is small , the immobilizing substance is immediately released, and the sustained release property cannot be obtained. Also, the diameter of the recess formed in the partition is 1 / the diameter of the hole.
100 to 1/4.
【００１８】なお、粒径、空孔の径、凹部の径について
は、それが真円、あるいは真球でない場合、最も短い部
分の径をいうものとする。When the particle diameter, the diameter of the pores, and the diameter of the concave portion are not a perfect circle or a perfect sphere, they refer to the diameter of the shortest part.
【００１９】上記粒子の内部の空孔の形状は、断面で見
たときに、空孔がランダムに並んでいても、中心部から
規則的に放射状に並んでいても、いくつかの方向に並ん
でいても、またこれらを組合せたようになっていてもよ
く、これらの形状は主に用途に応じて選択される。The shape of the pores inside the above-mentioned particles can be arranged in several directions, when viewed in cross section, whether the pores are arranged randomly or regularly radially from the center. Or a combination thereof, and these shapes are selected mainly depending on the application.
【００２０】また、粒子の表面の構造は、表面に多数の
孔や亀裂があって、内部への通液が十分であればどのよ
うな構造であってもよい。The structure of the surface of the particles may be any structure as long as the surface has a large number of holes and cracks and the liquid flow into the inside is sufficient.
【００２１】この発明に係るセルロース多孔質粒子、即
ち、多数の空孔を仕切る粒子の隔壁表面に、隔壁を貫通
しない多数の凹部を形成した粒子は、次のようにして製
造することができる。The cellulose porous particles according to the present invention, that is, particles having a large number of concave portions which do not penetrate the partition walls on the surface of the partition walls of the particles which partition a large number of pores, can be produced as follows.
【００２２】その製法は、原則的にはビスコースと炭酸
カルシウムを混合し、該混合液を加圧し、ノズルより液
滴状に押し出し、凝固・再生浴上に落下させ、液滴状の
ままセルロースの凝固・再生と炭酸カルシウムの酸分解
を同時に行い、また必要に応じてその後脱硫、漂白、水
洗、乾燥を行う方法である。The manufacturing method is basically to mix viscose and calcium carbonate, pressurize the mixed solution, extrude the mixture from a nozzle in the form of droplets, drop it onto a coagulation / regeneration bath, and leave cellulose in the form of droplets. Coagulation / regeneration and acid decomposition of calcium carbonate at the same time, and if necessary, desulfurization, bleaching, washing and drying.
【００２３】この方法においては、まずビスコースと炭
酸カルシウムを混合し炭酸カルシウムを含有するビスコ
ース液を作成する。該溶液を加圧し、ノズルを通して液
滴状に押し出し、該液滴を凝固・再生浴上に落下させ
る。その後所定時間攪拌することによって、各ビスコー
ス条件及び凝固・再生条件などに応じた内部空孔構造を
持ったセルロース多孔質粒子を製造することができる。In this method, first, viscose and calcium carbonate are mixed to prepare a viscose liquid containing calcium carbonate. The solution is pressurized, extruded through a nozzle into droplets, and the droplets are dropped onto a coagulation / regeneration bath. Thereafter, by stirring for a predetermined time, it is possible to produce cellulose porous particles having an internal pore structure corresponding to each viscose condition, coagulation / regeneration condition, and the like.
【００２４】使用するビスコースは例えば次のような性
質を持つ。セルロース濃度が３〜１５重量％（以下ｗｔ
％で表す）、好ましくは４ｗｔ％〜１０ｗｔ％である。
塩化アンモニウム価は３〜１２、好ましくは４〜９であ
る。アルカリ濃度は苛性ソーダとして２〜１５ｗｔ％、
好ましくは５〜１３ｗｔ％である。The viscose used has, for example, the following properties. Cellulose concentration is 3 to 15% by weight (hereinafter referred to as wt.
%), Preferably 4 wt% to 10 wt%.
The ammonium chloride value is from 3 to 12, preferably from 4 to 9. The alkali concentration is 2 to 15 wt% as caustic soda,
Preferably it is 5 to 13 wt%.
【００２５】ビスコースの粘度は２０℃に於いて５０セ
ンチポイズ〜１０，０００センチポイズ、好ましくは１
００センチポイズ〜７，０００センチポイズである。Viscose has a viscosity of 50 to 10,000 centipoise at 20 ° C., preferably 1 centipoise.
It is from 00 centipoise to 7,000 centipoise.
【００２６】使用する炭酸カルシウムは特に制限はな
く、軽質炭酸カルシウムでも重質炭酸カルシウムでも構
わない。通常混合のしやすさやノズル詰まりなどの作業
性の観点より平均粒径が０．５μｍ〜１５μｍのものが
使用される。この炭酸カルシウムの平均粒子径によって
セルロース多孔質粒子の内部空孔構造が大きく影響され
ることはない。炭酸カルシウムはビスコース中セルロー
ス１重量部当たり０．１〜１０重量部好ましくは０．４
〜７重量部用いられる。The calcium carbonate used is not particularly limited, and may be light calcium carbonate or heavy calcium carbonate. Usually, those having an average particle size of 0.5 μm to 15 μm are used from the viewpoint of ease of mixing and workability such as nozzle clogging. The average pore size of the calcium carbonate does not significantly affect the internal pore structure of the porous cellulose particles. Calcium carbonate is used in an amount of 0.1 to 10 parts by weight, preferably 0.4 to 1 part by weight of cellulose in viscose.
To 7 parts by weight.
【００２７】セルロースの凝固・再生と発泡剤である炭
酸カルシウムの酸分解を行う凝固・再生剤としては塩
酸、リン酸、炭酸、硫酸等の無機酸が使われるが塩酸が
好ましい。凝固・再生浴は１個ではなく複数個設置して
直列に又は並列に使用する方が生産性の観点から有利で
あるばかりでなく、各凝固・再生浴の条件を変化させて
おけば、１個の浴で作成したものとは異なる内部空孔構
造を持った粒子を製造可能である点からも有利である。
凝固・再生浴中酸の濃度は塩酸の場合で通常１０ｇ／ｌ
〜９０ｇ／ｌより好ましくは１５ｇ／ｌ〜７０ｇ／ｌ浴
中の塩の濃度は塩化カルシウムと塩化ナトリウムの場合
で、２つの合計が０〜４００ｇ／ｌであり、より好まし
くは１００〜２００ｇ／ｌである。凝固・再生浴温は通
常１０〜５０℃であり、より好ましくは２０〜４０℃で
ある。Inorganic acids such as hydrochloric acid, phosphoric acid, carbonic acid and sulfuric acid are used as a coagulating / regenerating agent for coagulating / regenerating cellulose and acid-decomposing calcium carbonate as a foaming agent, but hydrochloric acid is preferred. It is not only advantageous from the viewpoint of productivity that installing a plurality of coagulation / regeneration baths but using a plurality of coagulation / regeneration baths in series or in parallel is advantageous from the viewpoint of productivity. This is also advantageous in that particles having an internal pore structure different from those prepared in individual baths can be produced.
The concentration of acid in the coagulation / regeneration bath is usually 10 g / l for hydrochloric acid.
The concentration of the salt in the bath is preferably calcium chloride and sodium chloride, the sum of the two being 0-400 g / l, more preferably 100-200 g / l. It is. The coagulation / regeneration bath temperature is usually from 10 to 50 ° C, and more preferably from 20 to 40 ° C.
【００２８】ところで、空孔の大きさ、数、配置の仕
方、隔壁の厚み、隔壁の表面に形成される凹部の径、深
さ、数等は、ビスコースの塩化アンモニウム価、凝固・
再生浴の酸の濃度と浴の温度、塩の濃度などの組合せに
よって決まるが、実際の製造においては、ビスコースの
塩化アンモニウム価と凝固・再生浴の温度と塩の濃度を
一定にし、炭酸カルシウムの量と塩酸の濃度を次の範囲
で組合せると、隔壁の表面に多数の凹部が形成され、そ
の凹部の深さは隔壁を貫通しない。その範囲は、セルロ
ース１重量部当たり炭酸カルシウム０．１〜２重量部の
場合、塩酸濃度が６０〜８０ｇ／ｌであり、セルロース
１重量部当たり炭酸カルシウム２〜１０重量部の場合、
塩酸濃度が３０〜５０ｇ／ｌである。By the way, the size, number and arrangement of the pores, the thickness of the partition walls, the diameter, depth and number of the concave portions formed on the surface of the partition walls are determined by the ammonium chloride value of viscose,
It is determined by the combination of the concentration of acid in the regenerating bath, the temperature of the bath, the concentration of salt, etc.In actual production, the ammonium chloride value of viscose, the temperature of the coagulation / regenerating bath and the concentration of salt are kept constant, and calcium carbonate is When the amount and the concentration of hydrochloric acid are combined in the following range, a large number of concave portions are formed on the surface of the partition wall, and the depth of the concave portion does not penetrate the partition wall. The range is as follows: in the case of 0.1 to 2 parts by weight of calcium carbonate per 1 part by weight of cellulose, the hydrochloric acid concentration is 60 to 80 g / l, and in the case of 2 to 10 parts by weight of calcium carbonate per 1 part by weight of cellulose,
The hydrochloric acid concentration is 30 to 50 g / l.
【００２９】（実験例１）セルロース濃度９．０％、粘
度４５００ｃｐ（２０℃）、塩化アンモニウム価８．
７、アルカリ濃度６．３％のセロハン製造用のビスコー
ス４００ｇと炭酸カルシウム（日東粉化工業（株）製Ｓ
Ｓ＃３０ 平均粒径７．４μｍ）、７２ｇを１ｌビーカ
ーに入れて攪拌機にて７００ｒｐｍで２０分間攪拌を行
い、炭酸カルシウムを含有するビスコース液を作成し
た。Experimental Example 1 Cellulose concentration: 9.0%, viscosity: 4500 cp (20 ° C.), ammonium chloride value: 8.
7. 400 g of viscose for manufacturing cellophane having an alkali concentration of 6.3% and calcium carbonate (S by Nitto Powder Chemical Co., Ltd.)
S # 30 (average particle size: 7.4 μm), 72 g, was placed in a 1-liter beaker and stirred with a stirrer at 700 rpm for 20 minutes to prepare a viscose liquid containing calcium carbonate.
【００３０】チューブポンプでビスコース液をビーカー
より吸引、加圧し、口径１．２ｍｍのノズルより３ｃｃ
／ｍｉｎの速度で液滴状に押出し凝固・再生浴とした５
ｌビーカー中に落とした。凝固・再生浴の塩酸濃度は３
６ｇ／ｌ、温度は２５℃、塩濃度は塩化ナトリウムと塩
化カルシウムの合計で２５０ｇ／ｌであった。滴下開始
から凝固・再生、炭酸カルシウムの酸分解までの時間を
２時間３０分とした。A viscose liquid is sucked from a beaker by a tube pump and pressurized, and 3 cc is supplied from a nozzle having a diameter of 1.2 mm.
/ Min and extruded into droplets at a speed of 5 min.
Dropped into 1 beaker. Hydrochloric acid concentration of coagulation / regeneration bath is 3
6 g / l, the temperature was 25 ° C., and the salt concentration was 250 g / l in total of sodium chloride and calcium chloride. The time from the start of dropping to coagulation / regeneration and acid decomposition of calcium carbonate was 2 hours and 30 minutes.
【００３１】次いで、大過剰の水で洗浄し、２ｇ／ｌの
苛性ソーダと２ｇ／ｌの硫化ソーダの入った脱硫浴にて
７０℃で１時間脱硫を行った。その後大過剰の水で洗浄
し次いで２ｇ／ｌの次亜塩素酸ソーダの入った漂白浴に
て２０℃、２０分間漂白を行った。再び大過剰の水で洗
浄してセルロース多孔質粒子を得た。Then, it was washed with a large excess of water, and desulfurized in a desulfurization bath containing 2 g / l of sodium hydroxide and 2 g / l of sodium sulfide at 70 ° C. for 1 hour. Thereafter, it was washed with a large excess of water and then bleached in a bleach bath containing 2 g / l of sodium hypochlorite at 20 ° C. for 20 minutes. After washing again with a large excess of water, cellulose porous particles were obtained.
【００３２】得られた粒子は、水膨潤状態で平均粒子径
３．１ｍｍ、空孔径５０〜６００μｍ、凹部径６〜１０
μｍ、平均比表面積１０．５ｍ 2 ／ｇであった。空孔の
径、凹部の径は、得られたセルロース粒子を、溶媒置換
乾燥法により、湿潤状態とほぼ同じ形状のまま乾燥さ
せ、それを走査型電子顕微鏡で観察して実測した。湿潤
状態でも走査型電子顕微鏡での観察は不可能ではない
が、より鮮明な画像を得るため、粒子を乾燥させて観察
した。この走査型電子顕微鏡の観察結果は、図１〜図３
に示すとおりであり、内部に、隔壁によって仕切られた
空孔がランダムに平均して形成され、その隔壁表面に
は、小さな凹部が密に形成されていた。 なお、上記溶媒
置換乾燥法の操作手順は次の通りである。 まず、湿潤状
態のセルロース粒子をエタノールと水の割合が５０：５
０の溶液中で３０分間攪拌した後、セルロース粒子を分
取し、この分取したセルロース粒子を、順次、エタノー
ルと水の割合が７０：３０、エタノール（１００％）中
で各１回ずつ、ｔ−ブタノール（１００％）中で３回、
各３０分間攪拌して分取することにより、セルロース粒
子中の水分をｔ−ブタノールに置換し、その後、このセ
ルロース粒子を冷媒（例えば、メタノール−２０℃）中
で凍結し、そのまま真空乾燥するという方法である。 The obtained particles have an average particle size in a water-swelled state.
3.1 mm, hole diameter 50 to 600 μm, concave diameter 6 to 10
μm, and the average specific surface area was 10.5 m 2 / g. Vacant
The diameter and the diameter of the recess are determined by replacing the obtained cellulose particles with a solvent.
By the drying method, it is dried with almost the same shape as the wet state
It was observed with a scanning electron microscope and measured. wet
Observation with a scanning electron microscope is not impossible even in the state
However, to obtain clearer images, dry the particles and observe
did. The results of observation by this scanning electron microscope are shown in FIGS.
As shown in the figure, internally partitioned by a partition
Voids are formed randomly and averaged, and
Had small recesses formed densely. The above solvent
The operation procedure of the displacement drying method is as follows. First, wet
Cellulose particles are in a 50: 5 ratio of ethanol to water.
After stirring for 30 minutes in the solution of
And the separated cellulose particles are successively added to ethanol
Ratio of water to water is 70:30, in ethanol (100%)
Once in each, three times in t-butanol (100%),
By stirring for 30 minutes each and sorting, cellulose granules
The water in the pellets is replaced with t-butanol, and then
In the refrigerant (for example, methanol -20 ° C)
And then vacuum-dry as it is.
【００３３】（実験例２）塩化アンモニウム価を８．
０、凝固・再生浴の塩酸濃度を１８ｇ／ｌ、塩濃度を３
５０ｇ／ｌとした以外は、実験例１と同様に行い、セル
ロース多孔質粒子を得た。(Experimental Example 2) The ammonium chloride value was set at 8.
0, the hydrochloric acid concentration of the coagulation / regeneration bath is 18 g / l, and the salt concentration is 3
Except that the amount was changed to 50 g / l, the same procedure as in Experimental Example 1 was carried out to obtain cellulose porous particles.
【００３４】得られた粒子は、水膨潤状態で平均粒子径
３．５ｍｍ、空孔径１００〜６５０μｍ、凹部径７〜２
５μｍ、平均比表面積７．２ｍ2 ／ｇであった。この粒
子を、走査型電子顕微鏡で観察したところ、図４〜６に
示すとおり、実験例１のものよりも、１粒子中に占める
１つの空孔の径が大きく、即ち、空孔の数が少なく、ま
た、隔壁表面の凹部の径も比較的大きく形成されてい
た。The obtained particles have an average particle diameter of 3.5 mm, a pore diameter of 100 to 650 μm, and a concave diameter of 7 to 2 in a water-swelled state.
5 μm and an average specific surface area of 7.2 m 2 / g. When these particles were observed with a scanning electron microscope, as shown in FIGS. 4 to 6, the diameter of one hole in one particle was larger than that in Experimental Example 1, that is, the number of holes was smaller. In addition, the diameter of the concave portion on the partition wall surface was relatively large.
【００３５】（実験例３） 炭酸カルシウムを日東粉化工業（株）製、ＮＳ＃２５０
０、平均粒径０．８μｍとして、滴下を口径２ｍ／ｍの
空気噴霧式の２流体ノズルを使用し、５０ｃｃ／ｍｉｎ
の速度で２００ｌ容量のパン中に噴霧した以外は、実験
例１と同様に行い、セルロース多孔質粒子を得た。(Experimental Example 3) Calcium carbonate was NS # 250 manufactured by Nitto Powder Chemical Industry Co., Ltd.
0, an average particle diameter of 0.8 μm, and using an air spray type two-fluid nozzle with a diameter of 2 m / m for dropping, 50 cc / min.
The procedure was the same as in Experimental Example 1 except that the mixture was sprayed into a 200-liter capacity pan at the speed described above to obtain cellulose porous particles.
【００３６】得られた粒子は、水膨潤状態で平均粒子径
１５０μｍ、空孔径２５〜４０μｍ、凹部径１〜６μ
ｍ、平均比表面積１２．１ｍ2 ／ｇであった。The obtained particles had an average particle diameter of 150 μm, a pore diameter of 25 to 40 μm, and a concave diameter of 1 to 6 μm in a water-swelled state.
m, and the average specific surface area was 12.1 m 2 / g.
【００３７】（比較例１）炭酸カルシウムの量を９ｇと
した以外は、実験例１と同様にして、セルロース多孔質
粒子を製造したところ、その粒子の空孔及び隔壁の構造
は実験例１とほぼ同じであったが、隔壁にはほとんど凹
部が形成されていなかった。この粒子の平均粒子径は、
水膨潤状態で３．２ｍ／ｍ、平均比表面積は２．４ｍ2
／ｇであった。(Comparative Example 1) Cellulose porous particles were produced in the same manner as in Experimental Example 1 except that the amount of calcium carbonate was changed to 9 g. Although almost the same, almost no recess was formed in the partition. The average particle size of these particles is
3.2 m / m in water swelling state, average specific surface area is 2.4 m 2
/ G.
【００３８】（比較例２）炭酸カルシウムの量を１４４
ｇとした以外は、実験例１と同様にして、セルロース多
孔質粒子を製造したところ、その粒子の空孔及び隔壁の
構造は実験例１とほぼ同じであったが、隔壁には多数の
貫通小孔が形成されていた。この粒子の平均粒子径は、
水膨潤状態で２．９ｍ／ｍ、平均比表面積は１１．３ｍ
2 ／ｇであった。Comparative Example 2 The amount of calcium carbonate was 144
g of cellulose porous particles were produced in the same manner as in Experimental Example 1, except that the structure of the pores and the partition walls of the particles was almost the same as in Experimental Example 1. Small holes were formed. The average particle size of these particles is
2.9 m / m in water swelling state, average specific surface area 11.3 m
2 / g.
【００３９】上記のようにして製造した実験例１〜３と
比較例１、２の多孔質セルロースについて、攪拌強度、
通水量、リモネン保持量を比較した結果を表１に示す。For the porous celluloses of Experimental Examples 1 to 3 and Comparative Examples 1 and 2 produced as described above, the stirring strength,
Table 1 shows the results of comparing the amount of water passed and the amount of limonene retained.
【００４０】なお、攪拌強度とは、乾燥粒子２ｇを１ｌ
のビーカー内に入れ、２Ｎ−ＮａＯＨ水溶液５００ｍｌ
を投入した後、２５℃の温度に保持して７ｃｍの回転羽
根をもった攪拌機で５００ｒｐｍの回転数で２時間攪拌
し、次いで４０メッシュのステンレスの金網にて濾別
し、大量の水で水洗し、乾燥させた後、重量を測定して
重量減少率（％）を算出し、この重量減少率（％）によ
って攪拌作業時における機械的強度の指標としたもので
ある。The stirring intensity is defined as 2 g of dry particles per liter.
Into a beaker, 500 ml of 2N-NaOH aqueous solution
After stirring at 25 ° C., the mixture was stirred for 2 hours at a rotation speed of 500 rpm with a stirrer having rotating blades of 7 cm and then filtered off with a 40-mesh stainless steel wire mesh, and washed with a large amount of water. After drying, the weight is measured to calculate the weight loss rate (%), and the weight loss rate (%) is used as an index of the mechanical strength during the stirring operation.
【００４１】また、通水量とは、６０ｍｍφのガラス製
カラムに１５０ｃｃの試験粒子を充填し、このカラムに
約２ｋｇ／ｃｍ2 の圧力で水を通した場合の１分間の通
水量を表わしたものである。圧力をかけ通水している
と、充填した粒子の強度が弱い場合は、次第につぶれ、
圧密化を起こしたり、また一部がはがれてリン片状とな
り、詰まっていく、結果として通水抵抗が大きくなり、
通水量が減っていく。The water flow rate is the one-minute flow rate when a glass column of 60 mmφ is filled with 150 cc test particles and water is passed through the column at a pressure of about 2 kg / cm 2. It is. If water is applied under pressure and the strength of the filled particles is weak, it gradually collapses,
Or cause compaction, also become scaly peeling part, will clogged, water flow resistance increases as a result,
Water flow decreases.
【００４２】また、リモネン保持量というのは、セルロ
ース多孔質粒子１ｇ当たりに保持されるリモネンの量
（ｇ）であり、各種薬品の浸み込みやすさ、あるいは保
持のしやすさの指標となる。The amount of limonene retained is the amount (g) of limonene retained per gram of the porous cellulose particles, and is an index of the ease of infiltration or retention of various chemicals. .
【００４３】[0043]
【表１】 上記表１の結果から、この発明に係るセルロース多孔質
粒子である実験例１〜３のものは、攪拌等の作業に対し
て強い強度を示し、また、カラムにつめた時の適性も良
好であり、かつ薬液の保持性も良好であることがわか
る。これに対し、隔壁に多数の貫通小孔を有する比較例
２のものは、薬液の保持性は良好であるが、機械的強度
に問題があることがわかる。また、隔壁表面が平坦で凹
部を有しない比較例１のものは、強度的には問題はない
が、薬液の保持性に問題があることがわかる。[Table 1] From the results in Table 1 above, those of Experimental Examples 1 to 3, which are the cellulose porous particles according to the present invention, show strong strength against operations such as stirring, and have good suitability when packed in a column. It can be seen that there is also a good retention of the chemical solution. On the other hand, Comparative Example 2 having a large number of small through holes in the partition wall has good mechanical solution retention, but has a problem in mechanical strength. In Comparative Example 1 in which the partition wall surface was flat and had no concave portion, there was no problem in strength, but it was found that there was a problem in the retention of the chemical solution.
【００４４】次に、この発明に係るセルロース多孔質粒
子に機能材を封入した場合の特性について検討する。機
能材として活性炭を封入した多孔質セルロース粒子を作
製し、これをカラムにつめて水処理適性を見た。その結
果は、表２に示す。この水処理適性は、前記通水量と塩
素除去率によって判定した。この場合の塩素除去率は、
６０ｍｍφのガラス製カラムに１５０ｃｃの試験粒子を
充填し、このカラムに約２ｋｇ／ｃｍ2 の圧力で遊離塩
素濃度約２ｐｐｍの試料水を約３．５ｌ／ｍｉｎの速度
で通水し、その際にカラムの前後の試料水をサンプリン
グし、それぞれの遊離塩素濃度を測定し、カラムを通し
たことによる塩素濃度の変化から算出したものであり、
次式で表わされる。Next, the characteristics when the functional material is encapsulated in the cellulose porous particles according to the present invention will be examined. Porous cellulose particles encapsulating activated carbon as a functional material were prepared, packed in a column, and examined for suitability for water treatment. Table 2 shows the results. The suitability for water treatment was determined based on the water flow rate and the chlorine removal rate. The chlorine removal rate in this case is
A glass column of 60 mmφ is filled with 150 cc of test particles, and sample water having a free chlorine concentration of about 2 ppm is passed through the column at a pressure of about 2 kg / cm 2 at a rate of about 3.5 l / min. Sampling the sample water before and after the column, measured the free chlorine concentration of each, calculated from the change in chlorine concentration due to passing through the column,
It is expressed by the following equation.
【００４５】塩素除去率（％）＝〔（カラムを通る前の
試料水の遊離塩素濃度）−（カラムを通った後の試料水
の遊離塩素濃度）〕÷（カラムを通る前の試料水の遊離
塩素濃度） （実験例４） 実験例１と同じビスコース４００ｇと炭酸カルシウム７
２ｇに粉体活性炭３６ｇ（武田薬品製 白サギＡＭ１５
４）を２ｌビーカーに入れて攪拌機にて１時間攪拌を行
って混合液を作成する。この混合液をポンプで加圧して
口径０．５ｍｍのノズルより３ｃｃ／ｍｉｎの速度で液
滴状に押出した。他は実験例１と同様に行ったところ、
活性炭を封入した実験例１とほぼ同じ孔構造をもった多
孔質セルロース粒子を得た。粒径は２．１ｍｍ、空孔径
３０〜３００μｍ、凹部径３〜７μｍであった。Chlorine removal rate (%) = [(concentration of free chlorine in sample water before passing through the column) − (concentration of free chlorine in sample water after passing through the column)] ÷ (sample water before passing through the column) (Experimental Example 4) 400 g of viscose and calcium carbonate 7 as in Experimental Example 1
2g of powdered activated carbon 36g (white heron AM15 manufactured by Takeda Pharmaceutical Co., Ltd.)
4) is placed in a 2 l beaker and stirred for 1 hour with a stirrer to prepare a mixed solution. The mixture was pressurized by a pump and extruded into droplets at a speed of 3 cc / min from a nozzle having a diameter of 0.5 mm. Others were performed in the same manner as in Experimental Example 1.
Porous cellulose particles having substantially the same pore structure as in Experimental Example 1 in which activated carbon was sealed were obtained. Particle size is 2.1 mm, pore diameter
The diameter was 30 to 300 μm, and the diameter of the concave portion was 3 to 7 μm .
【００４６】（比較例３）炭酸カルシウムの量を９ｇと
した以外は、実験例４と同じ方法により、比較例１とほ
ぼ同じ孔構造をもった、即ち、隔壁表面が平坦でほとん
ど凹部を有しない構造の活性炭を封入した多孔質セルロ
ース粒子を得た。粒径は２．２ｍ／ｍであった。Comparative Example 3 The same pore structure as in Comparative Example 1 was obtained in the same manner as in Experimental Example 4 except that the amount of calcium carbonate was changed to 9 g, that is, the partition wall surface was flat and almost had concave portions. Porous cellulose particles encapsulating activated carbon with no structure were obtained. The particle size was 2.2 m / m.
【００４７】（比較例４）炭酸カルシウムの量を１４４
ｇとした以外は、実験例４と同じ方法により、比較例２
とほぼ同じ孔構造をもった、即ち、隔壁表面に多数の貫
通小孔を有する構造の活性炭を封入した多孔質セルロー
ス粒子を得た。粒径は２．１ｍ／ｍであった。Comparative Example 4 The amount of calcium carbonate was 144
Comparative Example 2 by the same method as in Experimental Example 4 except that
Thus, porous cellulose particles having substantially the same pore structure as that of the above, that is, encapsulating activated carbon having a structure having a large number of small through holes on the surface of the partition wall were obtained. The particle size was 2.1 m / m.
【００４８】[0048]
【表２】 このように、この発明に係るセルロース多孔質粒子は、
通液性も良く、かつ隔壁表面の凹部により機能材が効果
を発揮しやすいようになっていることがわかる。また、
隔壁に多数の貫通小孔が形成された比較例４の場合に
は、機能材は効果を発揮するが、機械的強度が弱くてカ
ラム充填などの使用は困難である。また、隔壁表面が平
坦で凹部を有しない比較例３のものでは、機械的強度は
充分であっても、機能材は効果を発揮しにくいことがわ
かる。[Table 2] Thus, the cellulose porous particles according to the present invention,
It can be seen that the liquid permeability is good, and the functional material is easily exerted the effect by the concave portion on the partition wall surface. Also,
In the case of Comparative Example 4 in which a large number of small through-holes were formed in the partition walls, the functional material exhibited an effect, but the mechanical strength was weak and it was difficult to use such as column packing. In addition, in the case of Comparative Example 3 in which the partition wall surface is flat and has no concave portion, it can be seen that the functional material is hardly effective even if the mechanical strength is sufficient.
【００４９】[0049]
【発明の効果】この発明に係るセルロース多孔質粒子
は、以上のように、カラムに充填して使用しても粒子が
つぶれにくく、また、薬剤の保持性能も良好であるか
ら、各種の薬剤や機能材の担体として極めて有用であ
る。As described above, the cellulose porous particles according to the present invention are hard to be crushed even when used by filling them in a column, and also have a good drug holding performance. It is extremely useful as a carrier for functional materials.
【図１】この発明に係るセルロース多孔質粒子の構造を
示す走査型電子顕微鏡写真FIG. 1 is a scanning electron micrograph showing the structure of a cellulose porous particle according to the present invention.
【図２】この発明に係るセルロース多孔質粒子の構造を
示す走査型電子顕微鏡写真FIG. 2 is a scanning electron micrograph showing the structure of the cellulose porous particles according to the present invention.
【図３】この発明に係るセルロース多孔質粒子の構造を
示す走査型電子顕微鏡写真FIG. 3 is a scanning electron micrograph showing the structure of the cellulose porous particles according to the present invention.
【図４】この発明に係るセルロース多孔質粒子の構造を
示す走査型電子顕微鏡写真FIG. 4 is a scanning electron micrograph showing the structure of the cellulose porous particles according to the present invention.
【図５】この発明に係るセルロース多孔質粒子の構造を
示す走査型電子顕微鏡写真FIG. 5 is a scanning electron micrograph showing the structure of the cellulose porous particles according to the present invention.
【図６】この発明に係るセルロース多孔質粒子の構造を
示す走査型電子顕微鏡写真FIG. 6 is a scanning electron micrograph showing the structure of the cellulose porous particles according to the present invention.
Claims (2)
集合し、上記隔壁表面に、隔壁を貫通しない多数の凹部
を有し、かつ粒子の径が０．５ｍ／ｍ以上１０ｍ／ｍ未
満であって、空孔の径が粒子の径の１／１００〜１／２
であり、凹部の径が空孔の径の１／３０〜１／４である
ことを特徴とするセルロース多孔質粒子。1. A large number of pores through the cellulose partition walls is set in the partition surface, it has a plurality of depressions that do not extend through the partition wall, and the diameter is 0.5 m / m or more 10 m / m Not particles
Full, and the pore diameter is 1/100 to 1/2 of the particle diameter
And the diameter of the recess is 1/30 to 1/4 of the diameter of the hole.
Cellulose porous particles characterized by the above-mentioned .
集合し、上記隔壁表面に、隔壁を貫通しない多数の凹部
を有し、かつ粒子の径が０．０２ｍ／ｍ以上０．５ｍ／
ｍ未満であって、空孔の径が粒子の径の１／２０〜１／
２であり、凹部の径が空孔の径の１／１００〜１／４で
あることを特徴とするセルロース多孔質粒子。 2. A large number of pores are formed through a partition wall of cellulose.
A large number of recesses that gather and do not penetrate the partition wall surface
Having a particle diameter of 0.02 m / m or more and 0.5 m / m
m, and the diameter of the pores is 1/20 to 1 /
2 and the diameter of the recess is 1/100 to 1/4 of the diameter of the hole.
Cellulose porous particles, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4338014A JP2587892B2 (en) | 1992-11-24 | 1992-11-24 | Cellulose porous particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4338014A JP2587892B2 (en) | 1992-11-24 | 1992-11-24 | Cellulose porous particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157772A JPH06157772A (en) | 1994-06-07 |
| JP2587892B2 true JP2587892B2 (en) | 1997-03-05 |
Family
ID=18314140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4338014A Expired - Lifetime JP2587892B2 (en) | 1992-11-24 | 1992-11-24 | Cellulose porous particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2587892B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998030620A1 (en) * | 1997-01-07 | 1998-07-16 | Kaneka Corporation | Cellulosic particles, spherical object comprising cross-linked polymer particles, and adsorbent for body fluid purification |
| EP4292447A1 (en) | 2021-02-12 | 2023-12-20 | Japan Tobacco Inc. | Flavor filler and flavor inhaler |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2564201B2 (en) * | 1989-11-01 | 1996-12-18 | レンゴー株式会社 | Method for producing cellulose porous particles |
-
1992
- 1992-11-24 JP JP4338014A patent/JP2587892B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06157772A (en) | 1994-06-07 |
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