JPS6185957A - Porous hollow yarn filter membrane - Google Patents
Porous hollow yarn filter membraneInfo
- Publication number
- JPS6185957A JPS6185957A JP20854984A JP20854984A JPS6185957A JP S6185957 A JPS6185957 A JP S6185957A JP 20854984 A JP20854984 A JP 20854984A JP 20854984 A JP20854984 A JP 20854984A JP S6185957 A JPS6185957 A JP S6185957A
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- plasma
- porous hollow
- membrane
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- External Artificial Organs (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
[産業上の利用分野]
未発明は血’Jrt中のヒリルビン等の有害物質を逮択
的に除去する血液灯1化用膜に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a blood lamp conversion membrane that selectively removes harmful substances such as hirirubin from blood.
[従来の技術]
最近難治性疾、pの治療に血漿交換療法が臨床応用され
効果を挙げつつある。しかしこれは血漿成分をすべて除
去し、新鮮血漿、血漿製剤、アルブミ/等の補充液を補
充するもので、血漿中の有効成分を〔4i1収できない
ことのみならず、補充液としての血漿あるいは血漿製剤
の不足、血II−肝炎やアレルギーの発生等多くの問題
が指摘されている。[Prior Art] Plasma exchange therapy has recently been clinically applied to the treatment of the intractable disease p. However, this method removes all plasma components and replenishes them with replenishers such as fresh plasma, plasma preparations, and albumin. Many problems have been pointed out, including a shortage of preparations, occurrence of blood II-hepatitis, and allergies.
このため血球を分離した血漿からn2分離により病気原
因となる高分子物質(以下有害物質という)を防人しよ
うとする方法として二段分離法や低温癌過法が考案され
ている。しかしIIυI細孔の孔径によって有害物質の
みを選択的に除去することはそれぞれの病気によって有
害物質の分子量が異なること、孔1至を所定の大きさの
みのものにするようコントロールすることか非常に困難
なことから限界がある。For this reason, a two-stage separation method and a low-temperature cancer filtration method have been devised as methods for preventing disease-causing polymeric substances (hereinafter referred to as harmful substances) by separating N2 from plasma from which blood cells have been separated. However, it is very difficult to selectively remove only harmful substances depending on the pore size of the IIυI pores, since the molecular weight of harmful substances differs depending on each disease, and it is difficult to control the pores to only have a predetermined size. There are limits because it is difficult.
−・力、有害物質を吸着剤を用いて除去する方法も検、
;・Iされ、ヒリルヒン等のイj害物rtを吸7.Vr
、人するノ」法として特開昭57−64059号、特開
昭55−106165t′7”rに7ニオン交換樹脂や
ポリアミン系吸1、材等が提案されている。これは血」
;を中のビリルヒン簿を後右するとはいっても未だその
能力は充分とはいえず、実用化に至っていない現状にあ
る。−・We also investigated the method of removing harmful substances using adsorbents.
;・If you are exposed to harmful substances such as hiriruhin, etc.7. Vr
7-ion exchange resins, polyamine-based absorbents, materials, etc. have been proposed in JP-A No. 57-64059 and JP-A-55-106165t'7''r as a method to prevent people from using blood.
; Even though it is said that the biliruhin book in the system is controlled, its ability is still not sufficient, and it has not yet been put into practical use.
[づ’l IIかM決しようとする問題点)(発明は血
漿や血清を濾過せしめるだけでピリルヒフ等のrj害物
を選択的に除去することのできる多孔質中空糸i!!過
膜を提供することを目的とする。[Issues to be decided between II and M] (The invention is based on a porous hollow fiber membrane that can selectively remove rj harmful substances such as pyrilhif by simply filtering plasma and serum. The purpose is to provide.
[問題を解決するための手段]
■!Uち、未発IIの貿旨は微細孔表面にアミノ基又は
4級アンモニウム基が導入されてなり、IQ厚5μm乃
至300ルmで、比表面積が少なくとも10m″/gで
あり、内壁面より外壁面へ貫通した多数の微小空孔を有
し1人血枯アルブミンの透過率が80%以上である多孔
質中空糸l!!過膜にある。[Means to solve the problem] ■! Uchi, the characteristics of undeveloped II are that amino groups or quaternary ammonium groups are introduced on the surface of the micropores, the IQ thickness is 5 μm to 300 μm, the specific surface area is at least 10 m''/g, and the surface is smaller than the inner wall surface. The porous hollow fiber l!! membrane has a large number of micropores penetrating to the outer wall surface and has a permeability of 80% or more for blood-induced albumin.
、に発明の膜は膜厚が5用m未満の場合は吸看面積が小
さく、逆に300JLmを越えると血漿透過性か低下す
るのでIIり厚が5pm乃至300pmであることが必
要である。多孔質膜の材質は特に駆足されるものではな
いが、微細孔表面に7ミノ基又は4級アンモニウムノS
が導入されている必要がある。アミノ基としては1級、
2級、3級アミノ2t、(のいずれでもよい、この中で
は3級アミノ基と4級アンモニウム基が好ましい、アミ
ン基や4級ア/モニウムノ、(の・9人方法としては中
空糸微細孔表面に化学反応により・9人してもよく、中
空糸微細孔表面にアミツノ、(又は4級アンモニウム基
をイJする小合体を形成してもよい、囲体的には例えば
ポリエチレン多孔TIy中′乍糸にスチレン、アクリフ
レアミド、アクリロニトリル等をクラフト共重合し、こ
れに7ミノ基又は4級アンモニウム基を導入する方法、
ポリスチレン多孔質中空糸膜においてポリスチレンをク
ロルメチル化した後アミンを反応させてアミツノ1(を
導入する方法、ポリアクリロニトリル多孔質中空糸のン
アノ基を還元してアミツノ、(に転化させる方法等を例
示することができる、又、多孔質中空糸膜の表面に多価
アミンと多価エポキシ化合物からの付加重合体を形成さ
せてもよい。In the membrane of the present invention, if the membrane thickness is less than 5 JLm, the absorption area will be small, and if it exceeds 300 JLm, the plasma permeability will decrease, so the thickness should be between 5pm and 300pm. The material of the porous membrane is not particularly important, but it may contain 7-mino groups or quaternary ammonium S on the surface of the micropores.
must be introduced. The amino group is primary,
Any of secondary and tertiary amino 2t, (can be used, among which tertiary amino group and quaternary ammonium group are preferable, amine group and quaternary amino group, (9-person method is hollow fiber micropore) A chemical reaction may be carried out on the surface of the hollow fiber, or a small aggregation of quaternary ammonium groups may be formed on the surface of the hollow fiber micropores. 'A method of craft copolymerizing styrene, acrylamide, acrylonitrile, etc. to the yarn and introducing a 7-mino group or a quaternary ammonium group therein;
Examples include a method in which polystyrene is chloromethylated in a polystyrene porous hollow fiber membrane and then reacted with an amine to introduce Amituno 1(), and a method in which the N-ano group of a polyacrylonitrile porous hollow fiber is reduced and converted to Amituno, (). Alternatively, an addition polymer of a polyvalent amine and a polyvalent epoxy compound may be formed on the surface of the porous hollow fiber membrane.
多孔質中空糸lI+2の素材としてはポリビニルアルコ
ール、セルロースアセテート、ポリオレフィン等を例示
することかできるが、ポリオレフィン等からなる高配向
結晶性未延伸中空糸を比較的低温で延伸して督られる多
孔質中空糸11Qが微細孔内部表II′lj枯が大きい
ので好ましく用いられる。Examples of the material for the porous hollow fiber II+2 include polyvinyl alcohol, cellulose acetate, polyolefin, etc.; The yarn 11Q is preferably used because the inner surface of the micropores II'lj is large.
+、全発明用いる多孔質膜は比表面積が少なくともlo
m’/g以上である必要がある。比表面積がtorn’
/gより小さい場合は血液中の有害物質の除去効・(シ
が充分でない。この比表面積は窒素ガス吸、6法で測定
することができる。また、該多孔質jIQは人血清アル
ブミン透過率80%以上であることを要する。ここで大
血清アルブミン透過率は膜か中空糸の場合は有効長7c
mの中空糸を用い、112間差圧が50mmHHの条件
でO,1%の人血清アルブミン血清の生理食塩水溶液を
中空糸内部にfIにさせた時に、吐液中に含まれる人血
11−アルブミンC度を280nmの吸光度測定から求
め、この1111を用いて次式で計算できるものである
。+, the porous membrane used in all inventions has a specific surface area of at least lo
m'/g or more is required. The specific surface area is torn'
/g, the removal effect of harmful substances in the blood is not sufficient. This specific surface area can be measured by nitrogen gas absorption method. It is required to be 80% or more.Here, the large serum albumin permeability is determined by the effective length of 7c in the case of a membrane or hollow fiber.
When a physiological saline solution of O, 1% human serum albumin serum is brought into fI inside the hollow fiber under the condition that the differential pressure between 112 and 112 is 50 mmHH, human blood 11- The albumin C degree is determined from absorbance measurement at 280 nm, and can be calculated using the following formula using this 1111.
人血1+−アルブミン透過率が80%未満の場合は血液
を濾過した場合有害物質の除去は可能であっても有用な
血漿成分の透過が不充分となり好ましくない。If the human blood 1+-albumin permeability is less than 80%, it is not preferable that the permeation of useful plasma components becomes insufficient even if harmful substances can be removed when blood is filtered.
112の微細孔の寸法はバブルポイントで表示した場合
1乃至10 k g / c m’であることが血漿透
過性の点で好ましい、バブルポイントはテスト液として
エタノールを用い、ASTM F316−80にべ1
;じた力7ノ、で測定することができる。多孔質++X
はモ1模でも良いか、装置をコンパクトにできる点で中
゛全糸であることが好ましい、中空糸の場合は内径は1
50乃至500μmであることが好ましい、また、空孔
;41は30%以上であることが血漿又は血清II!過
の点で好ましく、40%以−Lであることがより好まし
い。From the viewpoint of plasma permeability, it is preferable that the size of the micropores of No. 112 is 1 to 10 kg/cm' when expressed as a bubble point. 1
It can be measured with a tensile force of 7 mm. porous ++
A hollow fiber may be used, but it is preferable to use a hollow fiber in order to make the device compact.In the case of a hollow fiber, the inner diameter is 1.
It is preferably 50 to 500 μm, and the pores; 41 are preferably 30% or more of plasma or serum II! It is preferable in terms of the L content, and more preferably 40% or more.
[実施例] 以下に実施例を用いて本発明をさらに詳しく説明する。[Example] The present invention will be explained in more detail below using Examples.
実施例1
内11?面より外IHf血へ貫通した多数の微小空孔を
一イ1する多孔質■りとして、内径270μm、膜厚6
0μm、空孔イ160vo1%、エタノール中でJ11
定したバブルポイント3.2kg/cm’、N2’4E
t。Example 1 11? A porous film with an inner diameter of 270 μm and a film thickness of 6
0μm, pore size 160vo1%, J11 in ethanol
Bubble point 3.2kg/cm', N2'4E
t.
71法で1llll定した内部表面積32m’/gのポ
リエチシン多孔質中す;= ;?+ l’2 E HF
(商品名、三菱レイヨン株製)を用い、空気中前照射
法によりスチレンを電子線グラフト共七合した。スチレ
ンの付加穴はポリエチレン中空糸に対して約38%であ
った。次いでこの中空糸11Qをクロロメチル化した後
ト11メチIレアミンを用いてアミノ化した。この中空
糸を用いて有効長7cm、膜面[200crrr’(中
′・と糸内径基準)の血漿濾過ミニモジュールを作成し
た。このミニモジュールの人血砧アルブミンの透過率を
測定したところ95%であった。このミニモジュールを
用い、ビリルビンを19.5 m g /dl含右金石
血漿を37℃で中空糸内部に4m文、’ m i nの
速度で流し、0.3m文/ m i nの割合で中空糸
膜面を通して60分間+!!めした。濾過されなかった
血漿は未濾過の血漿に戻す循環濾過方式を採用した。t
l!i過後の血漿中のビリルビン濃度は7.8mg/d
uであった。これに対し全蛋白質、アルブミン、免疫グ
ロブリンの損失は僅かであった・
比較例1
実施例1で用いたと同様のポリエチレン多孔質「lビ・
ニー系欣を用い、グラフト共張合を行なうことなく二二
モシュールヲ作成し、エチルアルコールで親水化処理を
Ijなった後実施例1と同様の条件で実施例1と同様の
血漿を濾過した。賭過後の血漿中のヒリルビ7 e +
f!Lは15.6mg/clQであった。Polyethicine porous medium with an internal surface area of 32 m'/g determined by the 71 method; = ;? + l'2 E HF
(trade name, manufactured by Mitsubishi Rayon Co., Ltd.), styrene was grafted with an electron beam by an air pre-irradiation method. The additional pores of styrene were approximately 38% of the polyethylene hollow fiber. Next, this hollow fiber 11Q was chloromethylated and then aminated using 11-methyl-I-reamine. Using this hollow fiber, a plasma filtration mini module with an effective length of 7 cm and a membrane surface of 200 crrr' (based on the inner diameter of the fiber) was prepared. The human blood albumin transmittance of this mini module was measured and was 95%. Using this mini module, chalcolithic plasma containing 19.5 mg/dl of bilirubin was flowed inside the hollow fiber at a rate of 4 m/min at 37°C, and at a rate of 0.3 m/min. 60 minutes + through the hollow fiber membrane surface! ! I tried it. A circulating filtration method was used in which unfiltered plasma was returned to unfiltered plasma. t
l! The bilirubin concentration in plasma after i was 7.8 mg/d.
It was u. In contrast, the loss of total protein, albumin, and immunoglobulin was slight. Comparative Example 1 Polyethylene porous material similar to that used in Example 1
Two mosules were prepared using a knee-type tube without performing graft co-adhesion, and after being hydrophilized with ethyl alcohol, the same plasma as in Example 1 was filtered under the same conditions as in Example 1. Hirirubi7e+ in plasma after gambling
f! L was 15.6 mg/clQ.
比較例2
3級アミン型の陰イオン交換樹脂Amberlyte
A−21(ローム アント ハースン1製)0.4gと
実施例1で用いたと同様の血漿18℃父とを37℃で2
時間インキュベートした− h/+7の血漿のビリルビ
ン濃度はl 6.8 m g / d lであった。又
。Comparative Example 2 Tertiary amine type anion exchange resin Amberlyte
0.4 g of A-21 (manufactured by Rohm Ant Haasen 1) and the same plasma used in Example 1 at 18°C were incubated at 37°C for 2 hours.
The bilirubin concentration in the plasma of −h/+7 incubated for hours was 6.8 mg/dl. or.
イオン交換樹脂のrI;を4gとして同様にインキユヘ
ートシたところ上清の血漿のビリルビン濃度は12、3
m g/ d文であった。When the ink was injected in the same manner using 4 g of rI of the ion exchange resin, the bilirubin concentration in the supernatant plasma was 12.3 g.
It was a mg/d sentence.
[発明の効果]
本発明の多孔質中空糸膜はその微細孔表面にアミノ基又
は4級アンモニウム基が導入されているため、活性表面
積が苫しく太きく、アミン型陰イオン交換樹脂のような
表面にアミツノ、(を有する粒状吸着剤に比べ血漿を処
理したときの処理効率がはるかに優れ、有用物質の損失
も少ないという特徴を有・する。[Effects of the Invention] The porous hollow fiber membrane of the present invention has an amino group or a quaternary ammonium group introduced into the surface of its micropores, so the active surface area is dull and large, and it is similar to amine-type anion exchange resins. Compared to particulate adsorbents that have sulfur on the surface, they have a much better processing efficiency when processing plasma, and have the characteristics of less loss of useful substances.
Claims (1)
入されてなり、膜厚5μm乃至300μmで、比表面積
が少なくとも10m^2/gであり、内壁面より外壁面
へ貫通した多数の微小空孔を有し、人血清アルブミンの
透過率が80%以上である多孔質中空糸濾過膜。1. Amino groups or quaternary ammonium groups are introduced into the surface of the micropores, the film thickness is 5 μm to 300 μm, the specific surface area is at least 10 m^2/g, and there are many micro cavities that penetrate from the inner wall surface to the outer wall surface. A porous hollow fiber filtration membrane having pores and having a permeability of human serum albumin of 80% or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59208549A JPH0611326B2 (en) | 1984-10-04 | 1984-10-04 | Porous hollow fiber filtration membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59208549A JPH0611326B2 (en) | 1984-10-04 | 1984-10-04 | Porous hollow fiber filtration membrane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6185957A true JPS6185957A (en) | 1986-05-01 |
JPH0611326B2 JPH0611326B2 (en) | 1994-02-16 |
Family
ID=16558020
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59208549A Expired - Lifetime JPH0611326B2 (en) | 1984-10-04 | 1984-10-04 | Porous hollow fiber filtration membrane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0611326B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108103662A (en) * | 2018-01-25 | 2018-06-01 | 天津工业大学 | For the amino acid engrafted nanometer fiber membrane preparation method of bilirubin adsorption |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57149509A (en) * | 1981-03-09 | 1982-09-16 | Toray Ind Inc | Preparation of hollow separating membrane |
-
1984
- 1984-10-04 JP JP59208549A patent/JPH0611326B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57149509A (en) * | 1981-03-09 | 1982-09-16 | Toray Ind Inc | Preparation of hollow separating membrane |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108103662A (en) * | 2018-01-25 | 2018-06-01 | 天津工业大学 | For the amino acid engrafted nanometer fiber membrane preparation method of bilirubin adsorption |
Also Published As
Publication number | Publication date |
---|---|
JPH0611326B2 (en) | 1994-02-16 |
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