JPH0852331A - Plasma collecting membrane and production thereof - Google Patents

Plasma collecting membrane and production thereof

Info

Publication number
JPH0852331A
JPH0852331A JP7159452A JP15945295A JPH0852331A JP H0852331 A JPH0852331 A JP H0852331A JP 7159452 A JP7159452 A JP 7159452A JP 15945295 A JP15945295 A JP 15945295A JP H0852331 A JPH0852331 A JP H0852331A
Authority
JP
Japan
Prior art keywords
membrane
hydrophobic
hydrophilic component
water
plasma collecting
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.)
Pending
Application number
JP7159452A
Other languages
Japanese (ja)
Inventor
Yoshitada Sakai
良忠 酒井
Masaaki Shimagaki
昌明 島垣
Kazusane Tanaka
和実 田中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP7159452A priority Critical patent/JPH0852331A/en
Publication of JPH0852331A publication Critical patent/JPH0852331A/en
Pending legal-status Critical Current

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  • External Artificial Organs (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

PURPOSE:To instantly enable the use of a hydrophobic membrane as a plasma collecting membrane by introducing a hydrophilic component made water- insoluble by radiation during a process for producing a membrane based on a hydrophobic polymer. CONSTITUTION:A hydrophobic membrane is produced by using a hydrophobic polymer such as polyethylene or polypropylene as a main material. In this membrane manufacturing process, a hydrophilic component such as vinyl pyrrolidone or vinyl alcohol is introduced into a membrane forming raw soln. This hydrophilic component is insolubilized by radiation such as gamma-rays and/or heat. By this constitution, a plasma collecting membrane using an instantly usable hydrophobia membrane is obtained without being accompanied by an elution component.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、新規な採血漿膜および
その製造法に関する。
TECHNICAL FIELD The present invention relates to a novel plasma collection membrane and a method for producing the same.

【0002】[0002]

【従来の技術】従来、濾過処理や透析処理で用いられる
水処理用膜は、グリセリンなどの水溶性膜透過能維持
剤を用いた状態、膜素材として親水性高分子を用いた
状態、水を共存させた状態、などで供給されてきた。
しかし、では使用に先立って膜透過能維持剤を洗浄除
去する必要があり、即時使用ができないこと、では一
般にポアサイズが小さくなり、分子量数万以上の成分の
分離に使える膜ができにくいこと、では被処理液体が
血液である場合など、共存している水を予め被処理液体
に変質を与えない液体に置換する必要がある用途があ
り、即時使用できないことなど、それぞれに問題があ
る。
2. Description of the Related Art Conventionally, water treatment membranes used in filtration and dialysis treatments use a water-soluble membrane permeability maintaining agent such as glycerin, a hydrophilic polymer as a membrane material, and water. It has been supplied in a coexisting state.
However, with, it is necessary to wash and remove the membrane permeability maintaining agent before use, and it is not possible to use immediately, and with that, the pore size is generally small, and it is difficult to form a membrane that can be used for separating components having a molecular weight of tens of thousands or more. For example, when the liquid to be treated is blood, there are applications in which coexisting water needs to be replaced in advance with a liquid that does not deteriorate the liquid to be treated, and there are problems in that it cannot be used immediately.

【0003】一方、膜素材として、ポリエチレン、ポリ
プロピレン、ポリカーボネート、ポリアクリロニトリ
ル、ポリスルホン、ポリエステル、ポリ2弗化ビニリデ
ン、ポリ4弗化エチレン、ポリメチルメタクリレート、
セルローストリアセテートなどの疎水性高分子を主たる
素材とした膜が濾過膜や透析膜として提供されている
が、これらの疎水性膜ではやの状態にしておかない
と直ちには本来の透過能を発揮できず、したがって前記
のように即時使用できない問題は疎水性膜の宿命とされ
てきた。また、疎水性膜に対して親水性成分を導入し、
固着させることで即時使用を可能にするいう例(例え
ば、特開昭61−120602、特開昭61−1254
05、特開昭61−125408、特開昭61−125
409、特開昭61−133102、特開昭61−13
3105など)もみられるが、これらでは親水性高分子
の固着が不充分で、使用中に膜から親水性成分が溶出し
てくるなどの問題がある。
On the other hand, as film materials, polyethylene, polypropylene, polycarbonate, polyacrylonitrile, polysulfone, polyester, poly (vinylidene difluoride), poly (tetrafluoroethylene), polymethylmethacrylate,
Membranes mainly composed of hydrophobic polymers such as cellulose triacetate are provided as filtration membranes and dialysis membranes, but these hydrophobic membranes can immediately exhibit their original permeability unless they are left in a bald state. Therefore, the problem that the hydrophobic membrane cannot be used immediately has been destined for the hydrophobic membrane. Also, by introducing a hydrophilic component into the hydrophobic membrane,
Examples of enabling immediate use by fixing (for example, JP-A-61-120602 and JP-A-61-1254)
05, JP-A-61-125408, JP-A-61-125
409, JP-A-61-133102, JP-A-61-13
3105), but these have a problem that the hydrophilic polymer is not firmly fixed and the hydrophilic component is eluted from the membrane during use.

【0004】[0004]

【発明が解決しようとする課題】本発明者らは、かかる
状況に鑑み、溶出性成分を伴わずに疎水性膜を即時使え
るようにするには如何にすべきかにつき鋭意検討を重ね
たところ本発明に到達した。
In view of the above situation, the inventors of the present invention have made extensive studies as to how to immediately use the hydrophobic membrane without the eluting component. The invention was reached.

【0005】[0005]

【課題を解決するための手段】即ち、疎水性高分子を主
たる素材とした疎水性膜へ、該膜の製造工程中で放射線
または/および熱により水不溶化する親水性成分を導入
することにより、溶出性成分を伴わずに疎水性膜を即時
採血漿膜として使えるようにしうることを見出した。
[Means for Solving the Problems] That is, by introducing a hydrophilic component, which is water-insoluble by radiation or / and heat in the manufacturing process of the membrane, into a hydrophobic membrane mainly made of a hydrophobic polymer, It has been found that a hydrophobic membrane can be used as an immediate blood plasma membrane without elutable components.

【0006】本手段を適用できる疎水性膜素材としては
特に限定するものではないが、ポリエチレン、ポリプロ
ピレン、ポリカーボネート、ポリアクリロニトリル、ポ
リスルホン、ポリエステル、ポリ2弗化ビニリデン、ポ
リ4弗化エチレン、ポリメチルメタクリレート、セルロ
ーストリアセテート、ポリスチレン、ポリエチルアクリ
レート、ポリ酢酸ビニル、ポリ塩化ビニルなど、および
これらの誘導体、あるいはこれら重合体の構成単量体間
の共重合体、さらにはこれらを主体とするが共重合成分
として親水性成分を少量含む重合体などが挙げられ、本
手段は平衡吸水率(20℃、相対湿度65%の雰囲気下
に1週間置いて測定した吸水率で、水重量/ポリマー重
量を%で表示した値)が5%以下、さらに望ましくは2
%以下の素材に適用できる。
The hydrophobic membrane material to which the present means can be applied is not particularly limited, but polyethylene, polypropylene, polycarbonate, polyacrylonitrile, polysulfone, polyester, poly (vinylidene difluoride), poly (tetrafluoroethylene), polymethylmethacrylate. , Cellulose triacetate, polystyrene, polyethyl acrylate, polyvinyl acetate, polyvinyl chloride, etc., and derivatives thereof, or copolymers between the constituent monomers of these polymers, and further mainly these copolymerization components. Examples of the polymer include a polymer containing a small amount of a hydrophilic component, and this means is a water absorption rate measured by leaving it at equilibrium water absorption rate (20 ° C., relative humidity 65% for 1 week, water weight / polymer weight%). The displayed value) is 5% or less, more preferably 2
Applicable to less than% material.

【0007】親水性高分子の水不溶化手段として放射線
を照射する方法と加熱する方法とがあるが、前者ではポ
リエチレン、ポリスルホン、ポリスチレン、ポリエステ
ル、ポリエチルアクリレート、ポリ酢酸ビニルなどを主
成分とする耐放射線性に優れた素材に対して、後者では
ポリカーボネート、ポリスルホン、ポリ2弗化ビニリデ
ン、ポリ4弗化エチレン、ポリエステルなどを主成分と
する耐熱性に優れた素材に対して好適に用いられる。ま
たさらに、ポリスルホン、ポリエステルなどのように耐
放射線性および耐熱性に共に優れた素材に対しては、両
手段を併用することも可能である。
There are a method of irradiating with radiation and a method of heating as a means for insolubilizing a hydrophilic polymer in water. In the former, the resistance mainly composed of polyethylene, polysulfone, polystyrene, polyester, polyethyl acrylate, polyvinyl acetate, etc. The latter is preferably used for materials having excellent radiation resistance, and the latter is preferably used for materials having excellent heat resistance mainly composed of polycarbonate, polysulfone, poly (vinylidene difluoride), poly (tetrafluoroethylene), polyester and the like. Furthermore, for materials having both excellent radiation resistance and heat resistance such as polysulfone and polyester, it is possible to use both means in combination.

【0008】放射線により水不溶化する親水性成分とし
ては、ビニルピロリドン、ヒドロキシエチルメタクリレ
ート、ビニルアルコール、エチレングリコール、メトキ
シポリエチレングリコールメタクリレートなど、および
これらの誘導体のモノマー、オリゴマー、ポリマーおよ
びこれらの間のコポリマー、あるいはペプタイド、アル
ブミン、コラーゲンなどの蛋白などが挙げられる。熱に
より水不溶化する親水性成分としては、ビニルピロリド
ン、ε−カプロラクタム、ビニルアルコール、エチレン
オキサイド、ヒドロキシエチルメタクリレートなど、お
よびこれらの誘導体のモノマー、オリゴマー、ポリマ
ー、およびこれらの間のコポリマー、あるいはペプタイ
ド、アルブミン、コラーゲンなどの蛋白などが挙げられ
る。
As the hydrophilic component which becomes insoluble in water by radiation, vinylpyrrolidone, hydroxyethyl methacrylate, vinyl alcohol, ethylene glycol, methoxy polyethylene glycol methacrylate and the like, and monomers, oligomers, polymers and copolymers of these derivatives, Alternatively, proteins such as peptide, albumin and collagen may be used. As the hydrophilic component which is insoluble in water by heat, vinylpyrrolidone, ε-caprolactam, vinyl alcohol, ethylene oxide, hydroxyethyl methacrylate and the like, and monomers, oligomers, polymers of these derivatives, and copolymers between them, or peptides, Examples thereof include proteins such as albumin and collagen.

【0009】水不溶化手段としての放射線としては、ガ
ンマー線、紫外線、電子線などが用いられるが、特にガ
ンマー線では浸透性が高いので単一膜だけでなく、膜集
合体や膜を組込んだモジュール状態でも親水性成分の水
不溶化処理が行なえるので好適に用いられる。水不溶化
手段としての加熱手段としては、乾熱、湿熱、温浴加熱
のいずれも用いることができる。加熱温度としては、疎
水性素材の軟化点や融点、親水性成分の熱分解温度など
を考慮する必要があるが、50℃から200℃が好まし
い。また、加熱処理を親水性成分を水不溶化する手段と
してだけでなく、ポアサイズの調整手段も兼ね合せた手
段として用いることも可能である。
Gamma rays, ultraviolet rays, electron beams, etc. are used as the radiation as the water insolubilizing means. Especially, since the gamma rays have high penetrability, not only a single membrane but also a membrane aggregate or a membrane is incorporated. It is preferably used because the hydrophilic component can be treated to insolubilize water even in a module state. As the heating means as the water insolubilizing means, any of dry heat, wet heat and hot bath heating can be used. As the heating temperature, it is necessary to consider the softening point and melting point of the hydrophobic material, the thermal decomposition temperature of the hydrophilic component, etc., but 50 ° C. to 200 ° C. is preferable. Further, the heat treatment can be used not only as a means for making the hydrophilic component insoluble in water, but also as a means that also serves as a means for adjusting the pore size.

【0010】親水性成分を導入する製膜段階としては、
膜素材へのブロック共重合体化、製膜原液への混入、疎
水性膜製膜後の後処理など、いずれの段階でも良いが、
製膜原液への混入や後処理による導入が大きな孔を確保
しやすいという点、親水性成分の使用量を削減できると
いう点などで有利である。また、放射線照射や加熱処理
を膜や膜を組込んだモジュールの殺菌手段を兼ねたもの
とすることも可能である。
The film-forming step of introducing the hydrophilic component is as follows:
At any stage, such as block copolymerization into the membrane material, incorporation into the membrane forming stock solution, post-treatment after formation of the hydrophobic membrane,
It is advantageous in that it is easy to secure large pores when it is mixed into the membrane forming solution or introduced by post-treatment, and the amount of hydrophilic component used can be reduced. Further, the irradiation of radiation and the heat treatment may also serve as a sterilizing means for the membrane or the module incorporating the membrane.

【0011】本発明でいう膜の形態は特に限定するもの
ではなく、例えばシート状、中空糸状、マイクロカプセ
ル状の膜などが挙げられる。
The form of the membrane in the present invention is not particularly limited, and examples thereof include a sheet-shaped, hollow fiber-shaped, and microcapsule-shaped membrane.

【0012】以下、本発明の有効性を実施例をもって説
明する。そこで用いた測定法は次の通りである。
The effectiveness of the present invention will be described below with reference to examples. The measuring method used there is as follows.

【0013】(1) 透水性 中空糸膜の場合は、両端に環流液用の孔を備えたガラス
製のケースに該中空糸膜を挿入し、市販のポッティング
剤を用いて小型モジュールを作製し、37℃に保って中
空糸内側に水圧をかけ膜を通して外側へ透過する一定時
間の水の量と有効膜面積および膜間圧力差から算出する
方法で透水性能を測定した。
(1) Water-permeable In the case of a hollow fiber membrane, the hollow fiber membrane is inserted into a glass case having holes for reflux liquid at both ends, and a small module is prepared using a commercially available potting agent. The water permeability was measured by a method in which the water pressure was applied to the inside of the hollow fiber while maintaining the temperature at 37 ° C., and the amount of water permeating to the outside through the membrane for a certain period of time, the effective membrane area, and the transmembrane pressure difference were used to calculate.

【0014】平膜の場合は、攪拌円筒セルを用いて同様
にして測定した。
In the case of a flat membrane, the same measurement was carried out using a stirring cylindrical cell.

【0015】(2) 溶出物 膜0.5gを70℃温水50ccで1時間加熱して試験液
を調製する。試験液の波長220〜350μmにおける
吸光度を測定する。なお、透析型人工腎臓装置承認基準
では、本条件での規格を0.1以下としている。
(2) Eluate A test solution is prepared by heating 0.5 g of the membrane with 50 cc of hot water at 70 ° C. for 1 hour. The absorbance of the test solution at a wavelength of 220 to 350 μm is measured. The dialysis-type artificial kidney device approval standard sets the standard under this condition to 0.1 or less.

【0016】[0016]

【実施例】【Example】

実施例1 ポリスルホン(ユーデルポリサルホンP-3500)15部、
ポリビニルビロリドン(K-90)8部、ジメチルアセトア
ミド75部、水2部からなる原液から製膜した中空糸膜
を170℃、5時間乾燥処理し、親水化膜を作った。本
中空糸膜を膜面積0.15m2 になるよう束ね、モジュ
ール化後、2.5Mradγ線照射処理後乾燥し、ドライ膜
として牛血(ヘマトクリット値40%、総タンパク濃度
65g/dl)での血漿分離性能を測定したところ、温度3
7℃、膜間圧力差47mmHg、血液流量50ml/minで血漿
濾過流量16ml/minの性能を得た。水がついていないた
め、初期からタンパク透過率(濾液中濃度/血液中濃
度)が95%を越える優れたドライ採血漿膜としての性
能を認めた。
Example 1 15 parts of polysulfone (Udel Polysulfone P-3500),
A hollow fiber membrane formed from an undiluted solution containing 8 parts of polyvinylpyrrolidone (K-90), 75 parts of dimethylacetamide and 2 parts of water was dried at 170 ° C. for 5 hours to form a hydrophilic film. The hollow fiber membranes were bundled to have a membrane area of 0.15 m 2 , modularized, dried with 2.5 Mrad γ-ray irradiation, and dried to obtain a dry membrane with bovine blood (hematocrit value 40%, total protein concentration 65 g / dl). When the plasma separation performance was measured, the temperature was 3
Performance of plasma filtration flow rate of 16 ml / min was obtained at 7 ° C., transmembrane pressure difference of 47 mmHg, and blood flow rate of 50 ml / min. Since there is no water, the performance as an excellent dry plasma membrane with protein permeability (concentration in filtrate / concentration in blood) exceeding 95% was recognized from the initial stage.

【0017】実施例2 実施例1の中空糸膜の溶出物試験をしたところ、すべて
220nm〜350nmでの吸光度は0.1以下であった。
Example 2 When the hollow fiber membrane of Example 1 was subjected to an eluate test, the absorbances at 220 nm to 350 nm were all 0.1 or less.

【0018】[0018]

【発明の効果】本発明により、溶出性成分を伴わずに、
疎水性膜を用いた採血漿膜を提供することができる。
EFFECTS OF THE INVENTION According to the present invention, without any elutable component,
A plasma collection membrane using a hydrophobic membrane can be provided.

───────────────────────────────────────────────────── 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 C08J 7/04 CEZ T // C08L 81:06 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display area C08J 7/04 CEZ T // C08L 81:06

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】疎水性成分と物理的に不溶化した親水性成
分からなることを特徴とする採血漿膜。
1. A plasma collection membrane comprising a hydrophobic component and a physically insolubilized hydrophilic component.
【請求項2】疎水性高分子を主たる素材とした膜の製造
工程中で親水性成分を導入し該親水性成分を放射線また
は/および熱により水不溶化することを特徴とする採血
漿膜の製造法。
2. A method for producing a plasma-collecting membrane, which comprises introducing a hydrophilic component in a process for producing a membrane containing a hydrophobic polymer as a main material and insolubilizing the hydrophilic component with radiation or / and heat. .
JP7159452A 1995-06-26 1995-06-26 Plasma collecting membrane and production thereof Pending JPH0852331A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7159452A JPH0852331A (en) 1995-06-26 1995-06-26 Plasma collecting membrane and production thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7159452A JPH0852331A (en) 1995-06-26 1995-06-26 Plasma collecting membrane and production thereof

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP61243372A Division JPH089668B2 (en) 1986-10-14 1986-10-14 Hydrophilized film and method for producing the same

Publications (1)

Publication Number Publication Date
JPH0852331A true JPH0852331A (en) 1996-02-27

Family

ID=15694075

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7159452A Pending JPH0852331A (en) 1995-06-26 1995-06-26 Plasma collecting membrane and production thereof

Country Status (1)

Country Link
JP (1) JPH0852331A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001205057A (en) * 2000-01-27 2001-07-31 Toyobo Co Ltd Hollow fiber membrane
JP2007260592A (en) * 2006-03-29 2007-10-11 Toray Ind Inc Method of manufacturing separation membrane, and method of manufacturing separation membrane module using the separation membrane
JP2008543546A (en) * 2005-06-20 2008-12-04 シーメンス・ウォーター・テクノロジーズ・コーポレーション Cross-linking treatment of polymer film
JP2011092928A (en) * 2009-09-30 2011-05-12 Toray Ind Inc Separation membrane and separation membrane module
US9868834B2 (en) 2012-09-14 2018-01-16 Evoqua Water Technologies Llc Polymer blend for membranes
US10322375B2 (en) 2015-07-14 2019-06-18 Evoqua Water Technologies Llc Aeration device for filtration system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001205057A (en) * 2000-01-27 2001-07-31 Toyobo Co Ltd Hollow fiber membrane
JP2008543546A (en) * 2005-06-20 2008-12-04 シーメンス・ウォーター・テクノロジーズ・コーポレーション Cross-linking treatment of polymer film
JP2007260592A (en) * 2006-03-29 2007-10-11 Toray Ind Inc Method of manufacturing separation membrane, and method of manufacturing separation membrane module using the separation membrane
JP2011092928A (en) * 2009-09-30 2011-05-12 Toray Ind Inc Separation membrane and separation membrane module
US9868834B2 (en) 2012-09-14 2018-01-16 Evoqua Water Technologies Llc Polymer blend for membranes
US10322375B2 (en) 2015-07-14 2019-06-18 Evoqua Water Technologies Llc Aeration device for filtration system

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