JPH0790154B2 - Method for producing aromatic polysulfone composite semipermeable membrane - Google Patents
Method for producing aromatic polysulfone composite semipermeable membraneInfo
- Publication number
- JPH0790154B2 JPH0790154B2 JP61004005A JP400586A JPH0790154B2 JP H0790154 B2 JPH0790154 B2 JP H0790154B2 JP 61004005 A JP61004005 A JP 61004005A JP 400586 A JP400586 A JP 400586A JP H0790154 B2 JPH0790154 B2 JP H0790154B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polysulfone
- membrane
- water
- composite semipermeable
- semipermeable membrane
- 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.)
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、芳香族ポリスルホン複合半透膜の製造方法に
関し、詳しくは、透過性能の安定性と耐圧強度にすぐれ
た芳香族ポリスルホン複合半透膜の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an aromatic polysulfone composite semipermeable membrane, and more specifically, to an aromatic polysulfone composite semipermeable membrane excellent in stability of permeation performance and pressure resistance. The present invention relates to a method for manufacturing a membrane.
（従来の技術） 近年、半透膜は、海水の淡水化、超純水の製造、医薬や
食品工業における精製、濃縮、除菌処理、工業排水及び
生活排水の処理、人工臓器における膜材料等、極めて多
様な分野において広く使用されており、また、これら用
途に応じて種々の特性を有する半透膜が製造されてい
る。しかし、従来、知られている半透膜は、尚、その用
途によつては、透過性能やその他の特性において満足す
べきものではない。例えば、セルロースエステルからな
る半透膜は、従来、逆浸透膜や人工臓器材料として用い
られているが、耐微生物や耐薬品性、耐熱性、耐溶剤性
等が劣る。(Prior art) In recent years, semipermeable membranes are desalination of seawater, production of ultrapure water, purification and concentration in pharmaceutical and food industries, disinfection treatment, treatment of industrial wastewater and domestic wastewater, membrane material for artificial organs, etc. It is widely used in a very wide variety of fields, and semipermeable membranes having various properties are manufactured according to these applications. However, conventionally known semipermeable membranes are still unsatisfactory in permeation performance and other properties depending on their applications. For example, a semipermeable membrane made of cellulose ester has been conventionally used as a reverse osmosis membrane or a material for artificial organs, but it is inferior in microorganism resistance, chemical resistance, heat resistance, solvent resistance and the like.
このために、特に、耐微生物性、耐熱性及び耐薬品性に
すぐれる半透膜として、例えば、特開昭49−23183号公
報や特開昭54−1637号公報に記載されているように、芳
香族ポリスルホンからなる半透膜が提案され、また、一
部で既に実用化されている。しかし、一般に芳香族ポリ
スルホンは、上記のようなすぐれた特性を有する反面、
比較的疎水性であって、水との親和性が小さいために、
水性溶体の処理において、本来、水の透過性が低いうえ
に、溶質が膜面に吸着されて汚染されやすいので、処理
すべき水性液体の性状によつては、透過性能が経時的に
急激に低下することがある。Therefore, in particular, as a semipermeable membrane excellent in microbial resistance, heat resistance and chemical resistance, for example, as described in JP-A-49-23183 and JP-A-54-1637. , A semipermeable membrane made of aromatic polysulfone has been proposed and has already been put to practical use in some areas. However, in general, the aromatic polysulfone has excellent properties as described above,
Because it is relatively hydrophobic and has a low affinity for water,
In the treatment of an aqueous solution, the permeability of water is originally low, and the solute is likely to be adsorbed on the membrane surface to be contaminated. It may decrease.
更に、芳香族ポリスルホンからなる中空糸膜は、芳香族
ポリスルホンが特に脆い性質を有するために、肉圧強度
が低く、用途や使用条件が制限されざるを得ないという
重要な問題を有している。Further, the hollow fiber membrane made of aromatic polysulfone has an important problem that the meat pressure strength is low because the aromatic polysulfone has a particularly brittle property, and the application and use conditions are limited. .
また、例えば、管状複合半透膜は、通常、不織布のよう
な補強材上に芳香族ポリスルホン半透膜を製膜して、補
強膜とし、これを管状に加工することによつて製造され
るが、この補強膜は、一般に可撓性に乏しく、製管に際
して、補強膜に割れが発生することもあり、従来より、
可撓性にすぐれる芳香族ポリスルホン補強膜が要望され
ている。Further, for example, a tubular composite semipermeable membrane is usually produced by forming an aromatic polysulfone semipermeable membrane on a reinforcing material such as a non-woven fabric to form a reinforcing membrane, and processing this into a tubular shape. However, this reinforcing film is generally poor in flexibility, and cracks may occur in the reinforcing film during pipe manufacturing.
There is a need for aromatic polysulfone reinforced membranes with excellent flexibility.
（発明の目的） 本発明は、芳香族ポリスルホン半透膜における上記した
問題を解決するためになされたものであつて、特に、透
過安定性、耐圧性や、可撓性が改善された芳香族ポリス
ルホン複合半透膜の製造方法を提供することを目的とす
る。(Object of the Invention) The present invention has been made in order to solve the above-mentioned problems in an aromatic polysulfone semipermeable membrane, and in particular, aromatic aromatic compounds having improved permeation stability, pressure resistance and flexibility. An object is to provide a method for producing a polysulfone composite semipermeable membrane.
（発明の構成） 本発明による芳香族ポリスルホン複合半透膜の製造方法
は、芳香族ポリスルホンからなる多孔質膜に水溶性ポリ
ビニルアルコール系重合体水溶液を塗布又は含浸した
後、多価アルデヒドと酸触媒を含む溶液に浸漬し、アセ
タール化処理を行なつて、上記水溶性ポリビニルアルコ
ール系重合体を水不溶化すると共に、上記多孔質膜の表
面及び上記多孔質膜が有する微孔の内表面に水不溶化処
理された上記ポリビニルアルコール系重合体を概ね均一
に付着させることを特徴とする。(Structure of the Invention) The method for producing an aromatic polysulfone composite semipermeable membrane according to the present invention is a method in which a porous membrane made of aromatic polysulfone is coated with or impregnated with a water-soluble polyvinyl alcohol-based polymer aqueous solution, and then a polyvalent aldehyde and an acid catalyst are used. And insolubilize the water-soluble polyvinyl alcohol-based polymer with water by performing an acetalization treatment, and also water-insolubilize the surface of the porous membrane and the inner surface of the micropores of the porous membrane. It is characterized in that the treated polyvinyl alcohol-based polymer is attached substantially uniformly.
本発明において用いる芳香族ポリスルホンは、好ましく
は、次の一般式（Ｉ）又は（II）で表わされる繰返し単
位を有する重合体である。The aromatic polysulfone used in the present invention is preferably a polymer having a repeating unit represented by the following general formula (I) or (II).
−Ａ−SO2−Ａ−Ｏ−（Ａ−Rm−Ａ−Ｘ）ｎ− （Ｉ） −Ａ−SO2−Ａ−SO2−Ａ−Ｏ− （II） 但し、Ａはそれぞれ同一又は異なる芳香族基を示し、Ｒ
は２価の有機基を示し、ＸはＯ又はSO2を示し、ｍ及び
ｎはそれぞれ０又は１を示す）。 -A-SO 2 -A-O- ( A-R m -A-X) n - (I) -A-SO 2 -A-SO 2 -A-O- (II) where, A respectively are the same or R is a different aromatic group,
Represents a divalent organic group, X represents O or SO 2 , and m and n each represent 0 or 1.).
例えば、次のいずれかの繰返し単位 を有する芳香族ポリスルホンは、入手も容易であり、本
発明において好適に用いることができる。For example, one of the following repeating units The aromatic polysulfone having a is easily available and can be preferably used in the present invention.
本発明による芳香族ポリスルホン複合半透膜が実用的な
透過性能及び強度を有するためには、上記したような芳
香族ポリスルホンは、1.0g/100mlのジメチルホルムアミ
ド溶液として、25℃において0.2〜1.0、好ましくは0.25
〜0.80の還元粘度ηSP/C（以下、還元粘度の測定条件は
同じである。）を有するのがよい。In order for the aromatic polysulfone composite semipermeable membrane according to the present invention to have practical permeability and strength, the aromatic polysulfone as described above is a 1.0 g / 100 ml dimethylformamide solution at 0.2 to 1.0 at 25 ° C., Preferably 0.25
It is preferable to have a reduced viscosity η SP / C of ˜0.80 (hereinafter, the reduced viscosity measurement conditions are the same).
本発明において、基材としての芳香族ポリスルホンから
なる多孔質膜としては、例えば、膜表面に厚さ20μｍ以
下の緻密な所謂スキン層と、このスキン層を一体的に支
持する比較的粗な多孔質構造を有すると共に、粒径0.01
μｍ以上の粒子の透過を実質的に阻止する性能を有する
多孔質膜や、膜の厚さ方向にほぼ均質であつて、且つ、
微孔孔径が実質的に0.01〜２μｍの範囲にある多孔質膜
が好適に用いられる。一般にこのような多孔質膜は20
/m2・時・気圧以上の高い純水透水速度を有する。この
ような多孔質膜も、通常、半透膜と称されている。In the present invention, the porous membrane made of aromatic polysulfone as the substrate is, for example, a dense so-called skin layer having a thickness of 20 μm or less on the membrane surface and a relatively coarse porous layer integrally supporting this skin layer. It has a quality structure and a grain size of 0.01
a porous membrane having a property of substantially preventing the permeation of particles of μm or more, and being substantially homogeneous in the thickness direction of the membrane, and
A porous membrane having a micropore diameter substantially in the range of 0.01 to 2 μm is preferably used. Generally, such a porous membrane has 20
/ m 2 · hour · High pure water permeation rate of over atmospheric pressure. Such a porous membrane is also usually called a semipermeable membrane.
また、本発明においては、基材としての上記芳香族ポリ
スルホンからなる多孔質膜は、不織布のような補強材上
に製膜されていてもよい。Further, in the present invention, the porous membrane made of the aromatic polysulfone as a substrate may be formed on a reinforcing material such as a nonwoven fabric.
基材としてのこのような芳香族ポリスルホン多孔質膜の
形状は、本発明においては、特に制限されるものではな
いが、本発明によれば、中空糸状多孔質膜を用いると
き、特に、耐内圧性が改善された芳香族ポリスルホン中
空糸状半透膜を得ることができる。基材としての中空系
状多孔質膜としては、外径500〜4000μｍ、内径200〜30
00μｍのものがよい。また、不織布上に製膜されたシー
ト状の芳香族ポリスルホン多孔質膜を用いるとき、可撓
性にすぐれた複合半透膜を得ることができる。The shape of such an aromatic polysulfone porous membrane as a substrate is not particularly limited in the present invention, but according to the present invention, when a hollow fiber-like porous membrane is used, in particular, internal pressure resistance is high. An aromatic polysulfone hollow fiber-like semipermeable membrane having improved properties can be obtained. As a hollow porous film as a substrate, an outer diameter of 500 to 4000 μm, an inner diameter of 200 to 30
00 μm is preferable. Further, when a sheet-like aromatic polysulfone porous film formed on a nonwoven fabric is used, a composite semipermeable membrane having excellent flexibility can be obtained.
本発明によれば、このような芳香族ポリスルホン多孔質
膜に水溶性ポリビニルアルコール系重合体水溶液を塗布
し、又は含浸した後、多価アルデヒドと酸触媒を含む水
溶液に浸漬し、アセタール化処理を行なつて、上記水溶
液ポリビニルアルコール系重合体を水不溶化すると共
に、上記多孔質膜の表面及び上記多孔質膜が有する微孔
の内表面に水不溶化処理された上記ポリビニルアルコー
ル系重合体を概ね均一に付着させる。According to the present invention, such an aromatic polysulfone porous membrane is coated or impregnated with a water-soluble polyvinyl alcohol-based polymer aqueous solution, and then immersed in an aqueous solution containing a polyhydric aldehyde and an acid catalyst for acetalization treatment. The water-insoluble polyvinyl alcohol-based polymer is water-insolubilized, and the water-insolubilized polyvinyl alcohol-based polymer is substantially uniform on the surface of the porous film and the inner surfaces of the micropores of the porous film. To adhere to.
本発明において用いるポリビニルアルコール系重合体
は、平均重合度200〜3500、ケン化度85〜100モル％のポ
リビニルアルコール、及び単量体組成の20モル％以下の
ビニル単量体単位を有する共重合体を含むものとする。
このようなビニル単量体としては、例えば、エチレン、
ビニルピロリドン、アクリロニトリル、塩化ビニル等を
挙げることができる。The polyvinyl alcohol-based polymer used in the present invention has an average degree of polymerization of 200 to 3500, a saponification degree of 85 to 100 mol% of polyvinyl alcohol, and a copolymer having a vinyl monomer unit of 20 mol% or less of the monomer composition. It shall include coalescence.
Examples of such vinyl monomers include ethylene,
Examples thereof include vinylpyrrolidone, acrylonitrile and vinyl chloride.
このような本発明の方法によれば、水溶性ポリビニルア
ルコール系重合体を高い密度にて架橋させることがで
き、従つて、例えば、芳香族ポリスルホンからなる中空
糸膜の透過性能を安定化させることができるのみなら
ず、内圧強度を著しく高めることができる。ここに、多
価アルデヒドとしては、例えば、ポリビニルアルコール
ジアルデヒド、グルタルアルデヒド、グリオキザール、
テレフタルアルデヒド等を挙げることができるが、これ
らに限定されるものではない。According to such a method of the present invention, the water-soluble polyvinyl alcohol-based polymer can be crosslinked at a high density, and thus stabilizes the permeation performance of the hollow fiber membrane made of aromatic polysulfone, for example. In addition to the above, the internal pressure strength can be remarkably increased. Here, as the polyvalent aldehyde, for example, polyvinyl alcohol dialdehyde, glutaraldehyde, glyoxal,
Examples thereof include terephthalaldehyde, but are not limited thereto.
上記多価アルデヒドを用いるアセタール化反応によつ
て、ポリビニルアルコール系重合体を架橋し、水不溶化
処理するには、例えば、基材としての芳香族ポリスルホ
ン多孔質膜を0.05〜10重量％濃度のポリビニルアルコー
ル系重合体の水溶液に浸漬して、上記重合体を多孔質膜
に含浸させ、乾燥させた後、又は乾燥させずに、この多
孔質膜を前記したような多価アルデヒドと少量の酸触
媒、例えば、塩酸や硫酸を含む溶液中に浸漬すればよ
く、このようにして、本発明による複合半透膜を得るこ
とができる。By the acetalization reaction using the polyhydric aldehyde, to cross-link the polyvinyl alcohol-based polymer, in order to insolubilize water, for example, the aromatic polysulfone porous membrane as a base material 0.05 to 10 wt% polyvinyl The porous membrane is immersed in an aqueous solution of an alcoholic polymer to impregnate the above polymer into the porous membrane, and after drying or without drying, the porous membrane is treated with the polyvalent aldehyde as described above and a small amount of an acid catalyst. For example, the composite semipermeable membrane according to the present invention can be obtained by immersing it in a solution containing hydrochloric acid or sulfuric acid.
好ましくは、上記のようにしてポリビニルアルコール系
重合体溶液にて処理した芳香族ポリスルホン多孔質膜を
多価アルデヒド濃度0.0001〜５重量％、酸触媒0.0001〜
30重量％の多価アルデヒド溶液中に浸漬し、０〜80℃の
温度で１分乃至数十時間浸漬する。このようにして、芳
香族ポリスルホン多孔質膜の表面及び微孔内表面に水不
溶化処理されたポリビニルアルコール系重合体を概ね均
一に付着させることができる。この後、必要に応じて、
この複合半透膜を熱水に浸漬する等の方法によつて、膜
を熱処理して、得られる複合半透膜の微孔孔径を調整す
ることもできる。上記の処理においては、好ましい温度
条件は60℃以上、特に80℃以上であり、５分以上、好ま
しくは30分以上浸漬する。Preferably, the aromatic polysulfone porous membrane treated with the polyvinyl alcohol polymer solution as described above has a polyvalent aldehyde concentration of 0.0001 to 5% by weight and an acid catalyst of 0.0001 to
It is dipped in a 30 wt% polyhydric aldehyde solution and dipped at a temperature of 0 to 80 ° C. for 1 minute to several tens of hours. In this way, the water-insolubilized polyvinyl alcohol-based polymer can be substantially uniformly attached to the surface of the aromatic polysulfone porous membrane and the surfaces of the micropores. After this, if necessary,
The micropore diameter of the resulting composite semipermeable membrane can also be adjusted by heat treating the composite semipermeable membrane by a method such as immersing the composite semipermeable membrane in hot water. In the above treatment, the preferred temperature condition is 60 ° C. or higher, particularly 80 ° C. or higher, and the immersion is performed for 5 minutes or longer, preferably 30 minutes or longer.
このようにして得られる本発明による芳香族ポリスルホ
ン複合半透膜において、基材である多孔質膜の表面及び
微孔の内表面に付着している水不溶化処理されたポリビ
ニルアルコール系重合体は、その付着量が膜表面と微孔
内表面とで同じである必要はないが、基材である多孔質
膜構造を保持して、透過性能、特に、溶質に対する除去
率が高まる程度であることが好ましい。具体的には、水
不溶化処理されたポリビニルアルコール系重合体の付着
量は、膜厚にもよるが、ポリスルホン多孔質膜に対し
て、通常、0.1〜20重量％の範囲が好ましい。水不溶化
ポリビニルアルコール系重合体の付着量が余りに少ない
ときは、透過性能及び耐圧性等が当初の基材としてのポ
リスルホン多孔質膜と殆ど変わらず、他方、20重量％よ
りも多いときは、通常、半透膜としての透過性質が劣る
ようになるからである。In the thus obtained aromatic polysulfone composite semipermeable membrane according to the present invention, the water-insolubilized polyvinyl alcohol-based polymer attached to the surface of the porous membrane which is the substrate and the inner surface of the micropores, The amount of adhesion does not have to be the same on the membrane surface and the inner surface of the micropores, but it may be such that the permeation performance, in particular, the removal rate for solute is increased by maintaining the porous membrane structure which is the base material. preferable. Specifically, the amount of the water-insolubilized polyvinyl alcohol-based polymer, which depends on the film thickness, is usually preferably 0.1 to 20% by weight with respect to the polysulfone porous film. When the amount of the water-insolubilized polyvinyl alcohol-based polymer attached is too small, the permeation performance and pressure resistance are almost the same as those of the polysulfone porous membrane as the original substrate, while when it is more than 20% by weight, it is usually The reason is that the permeation property as a semipermeable membrane becomes inferior.
以上のように、多価アルデヒドによつて水不溶化処理さ
れてなるポリビニルアルコール系重合体が表面に概ね均
一に付着されてなる複合半透膜は、ポリビニルアルコー
ル系重合体によつて表面が親水化されているために、膜
面への溶質の吸着が少なく、その結果、透過安定性が著
しく改善されると共に、膜が補強されているので、機械
的強度にすぐれ、特に、中空糸状複合半透膜の場合に、
その耐内圧性が著しく改善される。As described above, the composite semipermeable membrane in which the polyvinyl alcohol-based polymer, which has been water-insolubilized with the polyhydric aldehyde, is substantially uniformly attached to the surface, the surface is made hydrophilic by the polyvinyl alcohol-based polymer. Therefore, the adsorption of solute on the membrane surface is small, and as a result, the permeation stability is remarkably improved and the membrane is reinforced so that it has excellent mechanical strength. In the case of a membrane,
Its internal pressure resistance is significantly improved.
（発明の効果） 本発明の芳香族ポリスルホン複合半透膜によれば、以上
のように、基材としての芳香族ポリスルホン多孔質膜が
その当初の多孔質膜構造を保持しつつ、その表面乃微孔
内表面に水不溶化処理されたポリビニルアルコール系重
合体が概ね均一に付着してなるので、複合半透膜は孔径
0.01〜２μｍ程度の微孔を有すると共に、膜表面がポリ
ビニルアルコール系重合体によつて親水化されているた
めに、膜面への溶質の吸着が少なく、その結果、透過安
定性が著しく改善されると共に、微孔の内表面に水不溶
化処理されたポリビニルアルコール系重合体が付着し
て、膜を補強しているので、膜は機械的強度にすぐれ、
特に、中空糸状複合半透膜の場合に、その耐内圧性が著
しく改善される。(Effect of the Invention) According to the aromatic polysulfone composite semipermeable membrane of the present invention, as described above, the aromatic polysulfone porous membrane as the base material retains its original porous membrane structure while maintaining its surface area. Since the water-insolubilized polyvinyl alcohol-based polymer adheres almost uniformly to the inner surface of the micropores, the composite semipermeable membrane has a pore size
Since it has micropores of about 0.01 to 2 μm and the membrane surface is hydrophilized with a polyvinyl alcohol polymer, solute adsorption to the membrane surface is small, and as a result, permeation stability is significantly improved. At the same time, the water-insolubilized polyvinyl alcohol polymer adheres to the inner surface of the micropores to reinforce the membrane, so the membrane has excellent mechanical strength,
In particular, in the case of a hollow fiber composite semipermeable membrane, its internal pressure resistance is remarkably improved.
（実施例） 以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例によつて限定されるものではない。また、以
下において部は重量部を意味するものとする。(Examples) The present invention is described below with reference to examples, but the present invention is not limited to these examples. Further, in the following, parts mean parts by weight.
実施例１ 前記繰返し単位（III）を有する芳香族ポリスルホン
（ユニオン・カーバイド社製「ポリサルホンＰ−1700」
15部と平均分子量600のポリエチレングリコール５部を
Ｎ−メチル−２−ピロリドン80部に溶解した。この溶液
を環状ノズルから中空状に押出し、水を凝固液として内
側及び外側表面から凝固させ、内径0.5mm、外径1.0mmの
中空糸状多孔質膜を得た。Example 1 Aromatic polysulfone having the repeating unit (III) (“Polysulfone P-1700” manufactured by Union Carbide Co., Ltd.)
15 parts and 5 parts of polyethylene glycol having an average molecular weight of 600 were dissolved in 80 parts of N-methyl-2-pyrrolidone. This solution was extruded into a hollow shape from an annular nozzle, and water was used as a coagulating liquid to coagulate from the inner and outer surfaces to obtain a hollow fiber-like porous membrane having an inner diameter of 0.5 mm and an outer diameter of 1.0 mm.
この中空糸状多孔質膜は、断面を走査型電子顕微鏡で観
察した結果、表面にスキン層を有し、内部に向かうに従
つて粗な多孔質構造を有し、部分的に所謂指状構造と称
される重合体の欠落部分を有する異方性膜であつた。ま
た、この多孔質膜の純水透水速度は600/m2・時・気圧
であり、平均分子量20000のポリエチレングリコールに
対する除去率は65％であつた。As a result of observing the cross section with a scanning electron microscope, this hollow fiber-like porous membrane has a skin layer on the surface, has a rough porous structure as it goes inward, and partially has a so-called finger-like structure. It was an anisotropic film having a so-called polymer lacking portion. The pure water permeation rate of this porous membrane was 600 / m 2 · hour · atmospheric pressure, and the removal rate for polyethylene glycol having an average molecular weight of 20,000 was 65%.
次に、第１表に示すように、平均重合度1700、ケン化度
98.5モル％のポリビニルアルコール（PVA）の所定濃度
の水溶液に上記中空糸状多孔質膜を24時間浸漬した。こ
の後、中空糸状膜が合着しないように室温にて乾燥した
後、水96部、硫酸１部及びグルタルアルデヒド３部から
なる水溶液に30℃の温度で１時間浸漬し、ポリビニルア
ルコールを水不溶化処理した。Next, as shown in Table 1, average degree of polymerization 1700, degree of saponification
The hollow fiber-shaped porous membrane was immersed in an aqueous solution of 98.5 mol% polyvinyl alcohol (PVA) at a predetermined concentration for 24 hours. After that, the hollow fiber membrane was dried at room temperature so as not to adhere to it, and then immersed in an aqueous solution containing 96 parts of water, 1 part of sulfuric acid and 3 parts of glutaraldehyde at a temperature of 30 ° C. for 1 hour to insolubilize the polyvinyl alcohol in water. Processed.
このようにして得られた中空糸状複合半透膜は、電子顕
微鏡で観察した結果、当初の多孔質膜構造はそのまま保
持されていると共に、水不溶性ポリビニルアルコールが
膜表面及び微孔内表面にほぼ均一に付着していることが
確認された。The hollow fiber composite semipermeable membrane thus obtained was observed by an electron microscope, and the initial porous membrane structure was retained as it was, and the water-insoluble polyvinyl alcohol was almost formed on the membrane surface and the surface of the micropores. It was confirmed that they adhered uniformly.
これらの複合半透膜における水不溶化処理されたポリビ
ニルアルコールの付着量、平均分子量20000のポリエチ
レングリコールに対する除去率及び破裂強度を第１表に
示す。Table 1 shows the adhesion amount of water-insolubilized polyvinyl alcohol, the removal rate to polyethylene glycol having an average molecular weight of 20,000, and the burst strength in these composite semipermeable membranes.
比較例１及び２ 実施例１における芳香族ポリスルホン中空糸状多孔質膜
自体（比較例１）、及びこの多孔質膜を15重量％のポリ
ビニルアルコール水溶液に浸漬し、グルタルアルデヒド
による水不溶化処理を施して、水不溶化ポリビニルアル
コールの付着量を30重量％とした複合半透膜（比較例
２）について、平均分子量20000のポリエチレングリコ
ールに対する除去率及び破裂強度を第１表に示す。Comparative Examples 1 and 2 The aromatic polysulfone hollow fiber-like porous membrane itself in Example 1 (Comparative Example 1) and this porous membrane were immersed in a 15% by weight aqueous polyvinyl alcohol solution and subjected to water insolubilization treatment with glutaraldehyde. Table 1 shows the removal rate and burst strength of the composite semipermeable membrane (Comparative Example 2) in which the amount of water-insoluble polyvinyl alcohol attached was 30% by weight (Comparative Example 2).
実施例２ 実施例１で得られた芳香族ポリスルホン中空糸状多孔質
膜を、第２表に示すように、種々の条件下にポリビニル
アルコール水溶液に浸漬し、ポリビニルアルコールを水
不溶化した。尚、酸触媒を含む多価アルデヒド水溶液へ
の多孔質膜の浸漬条 件は、すべて60℃、30分の一定とした。Example 2 As shown in Table 2, the aromatic polysulfone hollow fiber-shaped porous membrane obtained in Example 1 was immersed in an aqueous polyvinyl alcohol solution under various conditions to insolubilize the polyvinyl alcohol in water. It should be noted that the porous membrane is immersed in a polyvalent aldehyde aqueous solution containing an acid catalyst. All cases were fixed at 60 ° C for 30 minutes.
処理条件及び得られた複合半透膜の特性を第２表に示
す。Table 2 shows the treatment conditions and the properties of the obtained composite semipermeable membrane.
実施例３ 前記繰返し単位（IV）を有する芳香族ポリスルホン（ポ
リエーテルスルホン、ICI社製）17部と塩化リチウム５
部をジメチルアセトアミド78部に溶解した。この溶液を
内径12mmのポリエステル不織布管の内面に250μｍの厚
さに塗布した後、水中に浸漬して、凝固させた。Example 3 17 parts of aromatic polysulfone (polyether sulfone, manufactured by ICI) having the repeating unit (IV) and 5 parts of lithium chloride
Parts were dissolved in 78 parts dimethylacetamide. This solution was applied to the inner surface of a polyester nonwoven fabric tube having an inner diameter of 12 mm to a thickness of 250 μm, and then immersed in water to coagulate.
このようにして、不織布を補強材とする管状多孔質膜
は、断面を走査型電子顕微鏡で観察した結果、表面にス
キン層を有し、内部に向かうに従つて粗な多孔質構造を
有する異方性多孔質膜であつた。また、この半透膜の純
水速度は300/m2・時・気圧であり、平均分子量20000
のポリエリレングリコールに対する除去率は75％であつ
た。In this way, the tubular porous membrane using the nonwoven fabric as a reinforcing material has a skin layer on the surface as a result of observing the cross section with a scanning electron microscope, and has a different porous structure having a coarse porous structure toward the inside. It was a porous porous membrane. Further, the pure water velocity of this semipermeable membrane is 300 / m 2 · hour · atmospheric pressure, and the average molecular weight is 20,000.
The removal rate of polyerylene glycol was 75%.
平均重合度500、ケン化度98.5モル％の2.0重量％ポリビ
ニルアルコール水溶液に上記管状多孔質膜を室温で24時
間浸漬した後、表面を軽く水洗し、室温にて１日放置乾
燥し、次いで、100℃で２時間乾燥した。この後、この
管状多孔質膜を水97部、硫酸１部及びグルタルアルデヒ
ド２部からなる水溶液に30℃の温度で２時間浸漬し、ポ
リビニルアルコールを水不溶化処理した。The tubular porous membrane was immersed in an aqueous 2.0% by weight polyvinyl alcohol solution having an average degree of polymerization of 500 and a degree of saponification of 98.5 mol% at room temperature for 24 hours, then lightly washed on the surface, left to dry at room temperature for 1 day, and then dried. It was dried at 100 ° C. for 2 hours. Then, this tubular porous membrane was immersed in an aqueous solution consisting of 97 parts of water, 1 part of sulfuric acid and 2 parts of glutaraldehyde at a temperature of 30 ° C. for 2 hours to insolubilize the polyvinyl alcohol with water.
このようにして得られた本発明による管状複合半透膜
は、電子顕微鏡で観察した結果、当初の多孔質構造はそ
のまま保存されていると共に、水不溶性ポリビニルアル
コールが膜表面及び微孔内表面にほぼ均一に付着してい
ることが確認された。付着量は、当初の芳香族ポリスル
ホン多孔質膜に対して3.2重量％であつた。また、この
膜の純水透水速度は260/m2・時・気圧、平均分子量20
000のポリエチレングリコールに対する除去率は88％で
あつた。The tubular composite semipermeable membrane according to the present invention thus obtained was observed by an electron microscope, and the initial porous structure was preserved as it was, and water-insoluble polyvinyl alcohol was formed on the membrane surface and the inner surface of the micropores. It was confirmed that they adhered almost uniformly. The adhered amount was 3.2% by weight with respect to the initial aromatic polysulfone membrane. The pure water permeation rate of this membrane is 260 / m 2 · hr · atmosphere, average molecular weight 20
The removal rate for polyethylene glycol of 000 was 88%.
この本発明による複合半透膜及び基材としての当初の芳
香族ポリスルホン多孔質膜を用いて、不揮発分15％のカ
オチン系電着塗料を連続的に2kg/cm2の圧力にて処理し
た。Using this composite semipermeable membrane according to the present invention and the original aromatic polysulfone porous membrane as a substrate, a KAOTIN-based electrodeposition coating composition having a nonvolatile content of 15% was continuously treated at a pressure of 2 kg / cm 2 .
その結果、第１図に示すように、本発明による複合半透
膜を用いるとき、透水速度は経時的に高く保持され、膜
の透過安定性が高いことが確認された。他方、当初の多
孔質膜によれは、透水速度が処理開始後、急激に低下し
た。As a result, as shown in FIG. 1, it was confirmed that when the composite semipermeable membrane according to the present invention was used, the water permeation rate was kept high with time, and the permeation stability of the membrane was high. On the other hand, depending on the initial porous membrane, the water permeation rate dropped sharply after the treatment started.
第１図は、本発明による芳香族ポリスルホン複合半透膜
（実施例３）及び比較例としての膜基材としての芳香族
ポリスルホン多孔質膜をそれぞれ用いて、カオチン系電
着塗料を連続処理したときの透水速度の経時変化を示す
グラフである。FIG. 1 shows a continuous treatment of a KAOTIN-based electrodeposition coating composition using an aromatic polysulfone composite semipermeable membrane according to the present invention (Example 3) and an aromatic polysulfone porous membrane as a membrane substrate as a comparative example, respectively. It is a graph which shows the time-dependent change of the water permeation rate at this time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 島津 彰 大阪府茨木市下穂積１丁目１番２号 日東 電気工業株式会社内 (56)参考文献 特開 昭54−95982（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Shimazu 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denki Kogyo Co., Ltd. (56) Reference JP-A-54-95982 (JP, A)
Claims (4)
溶性ポリビニルアルコール系重合体水溶液を塗布又は含
浸した後、多価アルデヒドと酸触媒を含む溶液に浸漬
し、アセタール化処理を行なつて、上記水溶性ポリビニ
ルアルコール系重合体を水不溶化すると共に、上記多孔
質膜の表面及び上記多孔質膜が有する微孔の内表面に水
不溶化処理された上記ポリビニルアルコール系重合体を
概ね均一に付着させることを特徴とする芳香族ポリスル
ホン複合半透膜の製造方法。1. A porous membrane made of aromatic polysulfone is coated with or impregnated with a water-soluble polyvinyl alcohol-based polymer aqueous solution, and then immersed in a solution containing a polyhydric aldehyde and an acid catalyst for acetalization treatment. The water-soluble polyvinyl alcohol-based polymer is water-insolubilized, and the water-insolubilized polyvinyl alcohol-based polymer is substantially uniformly attached to the surface of the porous film and the inner surfaces of the micropores of the porous film. A method for producing an aromatic polysulfone composite semipermeable membrane, comprising:
系重合体の付着量が芳香族ポリスルホンからなる多孔質
膜に対して20重量％以下であることを特徴とする特許請
求の範囲第１項記載の芳香族ポリスルホン複合半透膜の
製造方法。2. The water-insolubilized polyvinyl alcohol-based polymer is deposited in an amount of 20% by weight or less with respect to the porous membrane made of aromatic polysulfone. Method for producing aromatic polysulfone composite semipermeable membrane.
とを特徴とする特許請求の範囲第１項記載の芳香族ポリ
スルホン複合半透膜の製造方法。3. The method for producing an aromatic polysulfone composite semipermeable membrane according to claim 1, wherein the composite semipermeable membrane is a hollow fiber composite semipermeable membrane.
織布上に形成されていることを特徴とする特許請求の範
囲第１項記載の芳香族ポリスルホン複合半透膜の製造方
法。4. The method for producing an aromatic polysulfone composite semipermeable membrane according to claim 1, wherein a porous membrane made of aromatic polysulfone is formed on the nonwoven fabric.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-3883 | 1985-01-11 | ||
| JP388385 | 1985-01-11 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6449095A Division JP2572015B2 (en) | 1985-01-11 | 1995-03-23 | Method for producing aromatic polysulfone composite semipermeable membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61268302A JPS61268302A (en) | 1986-11-27 |
| JPH0790154B2 true JPH0790154B2 (en) | 1995-10-04 |
Family
ID=11569579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61004005A Expired - Fee Related JPH0790154B2 (en) | 1985-01-11 | 1986-01-10 | Method for producing aromatic polysulfone composite semipermeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0790154B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8794451B2 (en) | 2008-02-21 | 2014-08-05 | Toyo Boseki Kabushiki Kaisha | Hollow-fiber ultrafiltration membrane with excellent fouling resistance |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4834886A (en) * | 1987-01-08 | 1989-05-30 | Filmtec Corporation | Process for making alkali resistant hyperfiltration membrane and resulting product |
| US4802988A (en) * | 1987-09-17 | 1989-02-07 | Texaco Inc. | Dehydration of glycols |
| JPH02115028A (en) * | 1988-10-25 | 1990-04-27 | Daicel Chem Ind Ltd | Filtration membrane and its manufacturing method |
| DE4217335C2 (en) * | 1992-05-26 | 1996-01-18 | Seitz Filter Werke | Hydrophilic membrane and process for its manufacture |
| KR100744763B1 (en) | 2005-11-04 | 2007-08-01 | 김지현 | Manufacturing method of release paper with insoluble polyvinyl alcohol (PWA) film formed |
| JP2011094110A (en) * | 2009-09-29 | 2011-05-12 | Sumitomo Chemical Co Ltd | Aromatic polysulfone resin porous film |
| JP6931490B2 (en) * | 2016-07-01 | 2021-09-08 | 東洋紡株式会社 | Hollow fiber composite membrane module and its manufacturing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5850122B2 (en) * | 1978-01-11 | 1983-11-09 | 日東電工株式会社 | Manufacturing method of composite semipermeable membrane |
-
1986
- 1986-01-10 JP JP61004005A patent/JPH0790154B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8794451B2 (en) | 2008-02-21 | 2014-08-05 | Toyo Boseki Kabushiki Kaisha | Hollow-fiber ultrafiltration membrane with excellent fouling resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61268302A (en) | 1986-11-27 |
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