JP2001157823A - Ion exchange membrane and method of manufacturing the same - Google Patents
Ion exchange membrane and method of manufacturing the sameInfo
- Publication number
- JP2001157823A JP2001157823A JP34552599A JP34552599A JP2001157823A JP 2001157823 A JP2001157823 A JP 2001157823A JP 34552599 A JP34552599 A JP 34552599A JP 34552599 A JP34552599 A JP 34552599A JP 2001157823 A JP2001157823 A JP 2001157823A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- ion
- ion exchange
- exchange resin
- microporous 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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Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、微多孔性膜を母材
とする新規なイオン交換膜に関する。詳しくは、優れた
耐有機汚染性を有し、また膜の電気抵抗（以下、膜抵抗
という。）が極めて低いイオン交換膜である。[0001] The present invention relates to a novel ion exchange membrane using a microporous membrane as a base material. Specifically, it is an ion-exchange membrane having excellent resistance to organic contamination and extremely low electric resistance (hereinafter referred to as membrane resistance) of the membrane.
【０００２】[0002]
【従来の技術】一般に、食品、医薬品、農薬などの分野
における有機物の合成工程では、塩類などを副生する場
合が多い。かかる有機物に含まれる塩類を分離するため
に、イオン交換膜法電気透析によって被処理液を脱塩す
る場合、被処理液中の有機汚染物質、特に荷電を有する
巨大分子（以下、巨大有機イオンという。）がイオン交
換膜に付着して膜の性能を低下させる、所謂、膜の有機
汚染という問題が生じる。2. Description of the Related Art Generally, in the process of synthesizing organic substances in the fields of foods, pharmaceuticals, agricultural chemicals and the like, salts and the like are often produced as by-products. When the liquid to be treated is desalted by ion exchange membrane electrodialysis in order to separate salts contained in such organic substances, organic contaminants in the liquid to be treated, particularly macromolecules having a charge (hereinafter, referred to as giant organic ions). ) Adheres to the ion-exchange membrane to lower the performance of the membrane, that is, there is a problem of so-called organic contamination of the membrane.
【０００３】従来、有機汚染を抑制するイオン交換膜と
して、膜内への巨大有機イオンの侵入を膜表層部で阻止
するようにしたイオン交換膜と、巨大有機イオンが容易
に膜透過するようにしたイオン交換膜が提案されてい
る。Conventionally, as ion exchange membranes for suppressing organic contamination, ion exchange membranes in which intrusion of giant organic ions into the membrane is prevented at the surface layer of the membrane, and ion exchange membranes in which giant organic ions easily permeate the membrane. Ion exchange membranes have been proposed.
【０００４】上記巨大有機イオンの膜内への浸入を防止
するようにしたイオン交換膜は、膜表面に中性、両性あ
るいはイオン交換基とは反対荷電の薄層を形成したもの
である。このイオン交換膜は、膜構造が緻密なもの程、
また、巨大有機イオンの分子量が大きい程、その効果は
顕著である。上記イオン交換膜の代表的なものとして、
陰イオン交換基を有する樹脂膜の表層部に反対荷電のス
ルホン酸基を導入し有機陰イオンの膜内への浸入を抑制
した陰イオン交換膜（特公昭５１−４０５５６号）等が
ある。[0004] The ion-exchange membrane in which the giant organic ions are prevented from penetrating into the membrane has a thin layer having a neutral, amphoteric or ion-exchange group oppositely charged on the membrane surface. This ion exchange membrane has a denser membrane structure,
The effect is more remarkable as the molecular weight of the giant organic ion is larger. As a typical ion exchange membrane,
There is an anion exchange membrane (Japanese Patent Publication No. 51-40556) in which a sulfonic acid group of an opposite charge is introduced into the surface layer of a resin membrane having an anion exchange group to suppress the penetration of organic anions into the membrane.
【０００５】他方、巨大有機イオンの膜透過を容易にす
る方法は、膜構造をルーズにすることによって容易に達
成される。On the other hand, a method for facilitating permeation of giant organic ions through a membrane is easily achieved by making the membrane structure loose.
【０００６】[0006]
【発明が解決しようとする課題】しかし、上記巨大有機
イオンの膜内への浸入を防止するようにしたイオン交換
膜は、ある程度の耐有機汚染性を発揮することができる
が、前記樹脂膜の表層部に設ける反対荷電層の形成によ
り膜抵抗が著しく増大するという欠点を有していた。However, the ion exchange membrane which prevents the huge organic ions from penetrating into the membrane can exhibit a certain degree of organic contamination resistance. There was a drawback that the formation of the oppositely charged layer provided on the surface portion significantly increased the film resistance.
【０００７】また、巨大有機イオンの膜透過を容易にす
る方法は、必然的にイオン選択性が低下し、その結果、
電気透析等における効率が低下するという問題があっ
た。Further, the method for facilitating permeation of giant organic ions through a membrane necessarily reduces ion selectivity, and as a result,
There is a problem that efficiency in electrodialysis and the like is reduced.
【０００８】従って、本発明の目的は、有機汚染を抑制
し、かつ、膜抵抗やイオン選択性などの基礎特性に優れ
たイオン交換膜を提供することにある。Accordingly, it is an object of the present invention to provide an ion exchange membrane which suppresses organic contamination and has excellent basic characteristics such as membrane resistance and ion selectivity.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意研究を重ねた。その結果、微多孔性膜
の空隙内にイオン交換樹脂が充填されたイオン交換膜に
おいて、その表層部の微細孔内に存在するイオン交換樹
脂を除去して、該微細孔において、充填されたイオン交
換樹脂が陥没した位置で露出するように構成することに
より、膜抵抗やイオン選択性などの基礎特性を低下させ
ることなく、優れた耐有機汚染性を発揮するイオン交換
膜が得られることを見い出し、本発明を完成するに至っ
た。Means for Solving the Problems The present inventors have intensively studied to achieve the above object. As a result, in the ion exchange membrane filled with the ion exchange resin in the voids of the microporous membrane, the ion exchange resin present in the fine pores in the surface layer is removed, and the ion By exposing the exchange resin at the depressed position, it has been found that an ion exchange membrane exhibiting excellent organic contamination resistance can be obtained without lowering basic characteristics such as membrane resistance and ion selectivity. Thus, the present invention has been completed.
【００１０】即ち、本発明は、微多孔性膜の空隙内にイ
オン交換樹脂が充填されて成り、該微多孔性膜の少なく
とも片面に存在する微細孔において、上記イオン交換樹
脂が微多孔性膜表面より陥没した位置で露出したことを
特徴とするイオン交換膜である。That is, the present invention is characterized in that the ion exchange resin is filled in the voids of the microporous membrane, and the ion exchange resin is filled in the micropores on at least one surface of the microporous membrane. An ion exchange membrane exposed at a position depressed from the surface.
【００１１】[0011]
【発明の実施の形態】図１は、本発明のイオン交換膜の
代表的な態様を概念的に示す断面図である。FIG. 1 is a sectional view conceptually showing a typical embodiment of the ion exchange membrane of the present invention.
【００１２】本発明のイオン交換膜における最大の特徴
は、上記図１にも示すように、微多孔性膜１の少なくと
も片面に存在する微細孔２において、該微多孔性膜に充
填されたイオン交換樹脂３が微多孔性膜表面４より陥没
した位置において露出していることにある。The most significant feature of the ion exchange membrane of the present invention is that, as shown in FIG. 1, the fine pores 2 existing on at least one side of the microporous membrane 1 are filled with ions filled in the microporous membrane. That is, the exchange resin 3 is exposed at a position depressed from the microporous membrane surface 4.
【００１３】尚、上記微多孔性膜表面の微細孔２は膜内
部に形成された空隙を介して裏面と連通する。The micropores 2 on the surface of the microporous film communicate with the back surface through voids formed inside the film.
【００１４】従来、微多孔性膜にイオン交換樹脂を充填
したイオン交換膜は、図２に示すように、イオン交換樹
脂３が、微多孔性膜１表層の微細孔２を含む空隙内の全
域に充填され、更には、微多孔性膜の全表面を覆うまで
に存在していた。このように、イオン交換樹脂が微多孔
性膜表面に露出している従来のイオン交換膜において
は、該イオン交換基と反対荷電を有する巨大有機イオン
との間で静電的引力に起因する強い相互作用が発生し、
膜表面に巨大有機イオンが吸着し易くなり、その結果、
いわゆる有機汚染が起こって膜抵抗が急激に上昇する。Conventionally, in an ion exchange membrane in which an ion exchange resin is filled in a microporous membrane, as shown in FIG. 2, the ion exchange resin 3 has the entire area in the void including the micropores 2 in the surface layer of the microporous membrane 1. And further existed until the entire surface of the microporous membrane was covered. As described above, in the conventional ion exchange membrane in which the ion exchange resin is exposed on the surface of the microporous membrane, the strong force caused by electrostatic attraction between the ion exchange group and the giant organic ion having the opposite charge. Interaction occurs,
Giant organic ions are easily adsorbed on the membrane surface, and as a result,
So-called organic contamination occurs and the film resistance rises sharply.
【００１５】これに対し、本発明のイオン交換膜は、微
多孔性膜の空隙内に充填されたイオン交換樹脂が、微多
孔性膜表面より陥没した位置において露出する構造を有
することにより、耐有機汚染性に対して優れた効果を発
揮する。On the other hand, the ion-exchange membrane of the present invention has a structure in which the ion-exchange resin filled in the voids of the microporous membrane is exposed at a position depressed from the surface of the microporous membrane. Excellent effect on organic pollution.
【００１６】上記効果の発現機構は明らかでないが、該
イオン交換樹脂と微多孔性膜表面の間にある、微細孔の
空間部が巨大有機イオンの膜内への侵入を抑制する効果
を持ち、イオン交換基と巨大有機イオン間の相互作用が
弱まり巨大有機イオンが膜表面に吸着しにくくなるもの
と推定される。Although the mechanism of the above effects is not clear, the space of the micropores between the ion exchange resin and the surface of the microporous membrane has the effect of suppressing the penetration of giant organic ions into the membrane, It is presumed that the interaction between the ion exchange group and the giant organic ion is weakened and the giant organic ion is less likely to be adsorbed on the membrane surface.
【００１７】また、一般に、微多孔性膜は、表層にのみ
緻密な微細孔を有しているものが多く、この場合、上記
微多孔性膜の表層部における微細孔の空間部は、通常、
内部の空隙より細い空間となっている。そして、これに
イオン交換樹脂が充填されている従来のイオン交換樹脂
の場合は、巨大有機イオンの侵入による上記空間の部分
における膜抵抗の上昇が著しいが、本発明のイオン交換
膜は、かかる部分に存在するイオン交換樹脂が少ない
か、或いは実質的に存在しないため、上記膜抵抗の急激
な上昇も防止できるものとも推定している。In general, many microporous membranes have dense micropores only in the surface layer. In this case, the microporous space in the surface layer of the microporous membrane is usually
The space is smaller than the internal space. In the case of the conventional ion-exchange resin in which the ion-exchange resin is filled, the membrane resistance in the space is significantly increased due to the intrusion of the huge organic ions. It is presumed that the above-mentioned rapid increase in membrane resistance can be prevented because the amount of ion-exchange resin present in the resin is small or substantially absent.
【００１８】また、前記特徴的構造を有する本発明のイ
オン交換膜は、耐汚染性を発現するために、イオン交換
膜表面に反対荷電の層を設ける必要が無く、かかるイオ
ン交換膜に対して、極めて低抵抗のイオン交換膜とな
る。Further, the ion exchange membrane of the present invention having the above-mentioned characteristic structure does not need to provide an oppositely charged layer on the surface of the ion exchange membrane in order to exhibit contamination resistance. , Resulting in an ion exchange membrane with extremely low resistance.
【００１９】しかも、上記微細孔の空間部は、塩類など
の小さなイオンに対しては移動の阻害層としては働か
ず、低抵抗である。そのため、該部分にイオン交換樹脂
が存在する、従来の微多孔性膜を母材としたイオン交換
膜に対しても低い膜抵抗を示す。In addition, the space of the micropores does not act as a migration inhibiting layer for small ions such as salts, and has a low resistance. Therefore, it exhibits a low membrane resistance even with respect to a conventional microporous membrane having a base material of an ion exchange resin in which an ion exchange resin is present in the portion.
【００２０】更に、本発明のイオン交換膜は、巨大有機
イオンの侵入を防止することで有機汚染を防いでいるた
め、前記したイオン交換樹脂部をルーズにする必要も無
く、その結果、良好なイオン選択性を示す。Furthermore, since the ion exchange membrane of the present invention prevents organic contamination by preventing intrusion of giant organic ions, it is not necessary to make the above-mentioned ion exchange resin part loose. Shows ion selectivity.
【００２１】以上のように、本発明のイオン交換膜は、
従来の手段とは全く異なる構成により、耐汚染性を達成
したものであり、膜抵抗が低く、イオン選択性にも優れ
た、理想的な特性を発揮する。As described above, the ion exchange membrane of the present invention
Stain resistance is achieved by a configuration completely different from that of the conventional means, and ideal characteristics with low membrane resistance and excellent ion selectivity are exhibited.
【００２２】本発明において、微多孔性膜表面４からイ
オン交換樹脂の露出面までの陥没深度Ａは特に制限され
ない。しかし、効果的な耐有機汚染性と低い膜抵抗をイ
オン交換膜に付与する上で、かかる陥没深度は、その平
均値（以下、単に陥没深度ともいう。）が０．０１μｍ
〜１０μｍ、好ましくは０．０３μｍ〜５μｍのものが
好ましい。即ち、上記陥没深度が０．０１μｍより浅い
場合、有機汚染物質の吸着抑制効果が低下し、十分な耐
有機汚染性が得られない。また、陥没深度が１０μｍよ
り深い場合、耐汚染防止効果が頭打ちとなる。また、イ
オン交換樹脂充填層が結果的に薄くなりイオン選択性の
低下を招く場合がある。In the present invention, the depression depth A from the microporous membrane surface 4 to the exposed surface of the ion exchange resin is not particularly limited. However, in order to impart effective organic contamination resistance and low membrane resistance to the ion exchange membrane, the average value of the depression depth (hereinafter, simply referred to as the depression depth) is 0.01 μm.
The thickness is preferably from 10 to 10 μm, more preferably from 0.03 to 5 μm. That is, when the depression depth is less than 0.01 μm, the effect of suppressing the adsorption of organic pollutants is reduced, and sufficient organic contamination resistance cannot be obtained. Further, when the depression depth is deeper than 10 μm, the effect of preventing contamination is leveled off. In addition, the ion-exchange resin packed layer may be thinned as a result, resulting in a decrease in ion selectivity.
【００２３】本発明のイオン交換膜において、表面に存
在する上記微細孔の孔径、その占める面積等は特に制限
されるものではない。しかし、耐汚染性等の特性を十分
発揮するには、その表面に存在する微細孔の最大孔径が
５μｍ以下、好ましくは１μｍ以下であることが好まし
い。また、該微細孔の平均孔径は、０．００５〜４μｍ
が好ましく、特に、０．０１〜０．８μｍが好ましい。
即ち、対象となる有機汚染物質の種類にも依存するが、
イオン交換膜表面に存在する微細孔の最大径が５μmよ
り大きい場合、更には、微細孔の平均孔径が４μｍを超
える場合、有機汚染物質が容易にイオン交換樹脂部に到
達し易くなり、耐有機汚染性が低下する傾向がある。一
方、該微細孔の平均孔径が０．００５μｍより小さい場
合、膜抵抗が高くなり好ましくない。In the ion-exchange membrane of the present invention, the pore size, the area occupied by the micropores, and the like occupied on the surface are not particularly limited. However, in order to sufficiently exhibit properties such as stain resistance, the maximum pore diameter of the fine pores existing on the surface is preferably 5 μm or less, more preferably 1 μm or less. The average pore diameter of the micropores is 0.005 to 4 μm.
Is preferred, and particularly preferably 0.01 to 0.8 μm.
In other words, although it depends on the type of the organic pollutant of interest,
When the maximum diameter of the micropores present on the surface of the ion exchange membrane is larger than 5 μm, and further, when the average pore diameter of the micropores exceeds 4 μm, the organic contaminants easily reach the ion exchange resin part, and The contamination tends to decrease. On the other hand, when the average pore size of the micropores is smaller than 0.005 μm, the film resistance is undesirably high.
【００２４】また、イオン交換膜表面における上記微細
孔の面積占有率は、３〜６０％、特に、２０〜５０％で
あることが好ましい。即ち、該面積占有率が６０％を超
える場合には、膜の機械的強度が低下する傾向にあり、
逆に３％より小さい場合には、膜抵抗の上昇を招くおそ
れがある。Further, the area occupancy of the micropores on the surface of the ion exchange membrane is preferably 3 to 60%, particularly preferably 20 to 50%. That is, when the area occupancy exceeds 60%, the mechanical strength of the film tends to decrease,
Conversely, if it is less than 3%, the film resistance may increase.
【００２５】尚、上記微細孔の面積占有率は、孔径０．
００３μｍ以上の孔を提唱として測定した値である。Incidentally, the area occupancy of the above-mentioned micropores is determined as follows.
It is a value measured with a hole of 003 μm or more proposed.
【００２６】更に、上記微細孔の形状は、特に制限され
るものではなく、任意の形状を採り得る。通常、該形状
は母材である微多孔性膜の製造方法によって決定され、
円状、楕円状、正方状、菱形状、その他不定形状の形状
を採る。Further, the shape of the fine holes is not particularly limited, and may be any shape. Usually, the shape is determined by the manufacturing method of the base material microporous membrane,
Circular, elliptical, square, rhombic, and other irregular shapes.
【００２７】尚、本発明において、円状以外の前記微細
孔の径は、相当径として示したものである。In the present invention, the diameter of the fine holes other than the circular shape is shown as an equivalent diameter.
【００２８】また、本発明のイオン交換膜の膜抵抗は、
３モル／ｌ濃度の硫酸中、２５℃において測定される膜
抵抗を膜厚１０μｍ当たりに換算した値で、０．０１〜
０．４Ω・ｃｍ2の範囲にあることが好ましい。The membrane resistance of the ion exchange membrane of the present invention is as follows:
The value obtained by converting the film resistance measured at 25 ° C. in sulfuric acid having a concentration of 3 mol / l into a value per 10 μm film thickness is 0.01 to 0.01 μm.
It is preferably in the range of 0.4 Ω · cm 2 .
【００２９】上記イオン交換膜の膜抵抗は、母材である
微多孔性膜に充填されるイオン交換樹脂の種類によって
多少異なるが、主として、後記の微多孔性膜の空隙率、
微細孔の孔径、微細孔の占める面積等によって殆ど決定
されるため、これらの条件を適宜調節して任意の膜抵抗
に調節することができる。The membrane resistance of the above-mentioned ion-exchange membrane varies somewhat depending on the type of ion-exchange resin filled in the microporous membrane as a base material.
Since it is almost determined by the pore diameter of the micropores, the area occupied by the micropores, and the like, these conditions can be appropriately adjusted to adjust the film resistance to an arbitrary value.
【００３０】また、本発明のイオン交換膜の厚みは、全
厚みにおける膜抵抗を低下させると共に必要な機械的強
度を付与するという観点から、通常、１０〜１５０μｍ
の厚みを有するものが好ましく、より好ましくは１５〜
１２０μｍの厚みを有するものが望ましい。The thickness of the ion exchange membrane of the present invention is usually from 10 to 150 μm from the viewpoint of reducing the membrane resistance in the entire thickness and imparting necessary mechanical strength.
Are preferred, more preferably 15 to
Those having a thickness of 120 μm are desirable.
【００３１】更に、本発明のイオン交換膜においては、
微細孔を除く微多孔性膜表面にも実質的にイオン交換樹
脂が存在しないことが好ましい。即ち、微多孔性膜表面
にイオン交換樹脂が存在する場合、該表面のイオン交換
樹脂に吸着堆積した巨大有機イオンが陥没部位の周縁部
から内部に向かってせり出し、その結果、膜抵抗を上昇
させるおそれがある。また、イオン交換膜の取り扱い
上、かかる微多孔性膜表面にイオン交換樹脂が存在しな
い方が好ましい。Further, in the ion exchange membrane of the present invention,
It is preferable that the ion exchange resin does not substantially exist on the surface of the microporous membrane except for the micropores. That is, when the ion exchange resin is present on the surface of the microporous membrane, the giant organic ions adsorbed and deposited on the ion exchange resin on the surface protrude from the periphery of the depressed portion toward the inside, thereby increasing the membrane resistance. There is a risk. Further, in handling the ion exchange membrane, it is preferable that the ion exchange resin does not exist on the surface of the microporous membrane.
【００３２】尚、上記のように、微多孔性膜表面にイオ
ン交換樹脂が存在しない場合、イオン交換膜の厚みは、
実質的に微多孔性膜の厚みとなる。As described above, when no ion exchange resin is present on the surface of the microporous membrane, the thickness of the ion exchange membrane is
Substantially the thickness of the microporous membrane.
【００３３】本発明における微多孔性膜は、一般に、熱
可塑性樹脂よりなり、表裏を連通する微細孔を多数有す
るものが特に制限なく使用される。The microporous membrane of the present invention is generally made of a thermoplastic resin and has a large number of fine pores communicating between the front and back, and is used without any particular limitation.
【００３４】上記熱可塑性樹脂としては、実質的にイオ
ン交換基を持たないものが好適であり、例えば、ポリ塩
化ビニル、塩化ビニル−酢酸ビニル共重合体、塩化ビニ
ル−塩化ビニリデン共重合体、塩化ビニル−オレフィン
重合体等の塩化ビニル系樹脂；ポリテトラフルオロエチ
レン、ポリトリフルオロエチレン、ポリクロロトリフル
オロエチレン、ポリ（テトラフルオロエチレンーヘキサ
フルオロプロピレン）、ポリ（テトラフルオロエチレン
−ペルフルオロアルキルエーテル）等のフッ素系樹脂；
ナイロン６、ナイロン６６等のポリアミド樹脂等からな
るものが、制限無く使用される。機械的強度、化学的安
定性、耐薬品性に優れていることから、ポリオレフィン
樹脂を用いるのが特に好ましい。ポリオレフィン樹脂と
しては、エチレン、プロピレン、１−ブテン、１−ペン
テン、１−ヘキセン、３−メチル−１−ブテン、４−メ
チル−１−ペンテン、５−メチル−１−ヘプテン等のα
−オレフィンの単独重合体又は共重合体が挙げられる。
このうち、本発明では、ポリエチレン、ポリプロピレン
が好ましく、特にポリエチレンが好ましい。As the above-mentioned thermoplastic resin, those having substantially no ion-exchange group are preferable. For example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, chloride Vinyl chloride resins such as vinyl-olefin polymers; polytetrafluoroethylene, polytrifluoroethylene, polychlorotrifluoroethylene, poly (tetrafluoroethylene-hexafluoropropylene), poly (tetrafluoroethylene-perfluoroalkyl ether), etc. Fluorine resin;
What consists of polyamide resins, such as nylon 6, nylon 66, etc. is used without restriction. It is particularly preferable to use a polyolefin resin because of its excellent mechanical strength, chemical stability and chemical resistance. Examples of the polyolefin resin include α, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, and 5-methyl-1-heptene.
-Olefin homopolymers or copolymers.
Among them, in the present invention, polyethylene and polypropylene are preferred, and polyethylene is particularly preferred.
【００３５】前記イオン交換膜表面に存在する微細孔の
孔径、該微細孔の占める面積等は、母材である微多孔性
膜の性状によって殆ど決定される。The pore size of the micropores existing on the surface of the ion exchange membrane, the area occupied by the micropores, and the like are almost determined by the properties of the microporous membrane as the base material.
【００３６】従って、本発明において好適に使用される
微多孔性膜としては、前記範囲の微細孔の孔径、微細孔
の占める面積等を有するものである。Accordingly, the microporous membrane suitably used in the present invention has a pore diameter in the above range, an area occupied by the micropores, and the like.
【００３７】尚、上記微多孔性膜表面における特性は、
通気度に主として反映されるが、かかる通気度として
は、２０〜１５００秒／１００ｍｌ、好ましい範囲で１
００〜１０００秒／１００ｍｌとなる。The characteristics of the microporous membrane surface are as follows:
Although mainly reflected in the air permeability, the air permeability is 20 to 1500 seconds / 100 ml, preferably 1
It becomes 00-1000 seconds / 100 ml.
【００３８】また、微多孔性膜は、前記好適な膜抵抗を
達成するために、その空隙率が２０〜９０％、好適には
３０〜７０％のものが好適に使用される。Further, the microporous membrane having a porosity of 20 to 90%, preferably 30 to 70% is suitably used in order to achieve the above-mentioned preferable membrane resistance.
【００３９】即ち、上記空隙率が２０％未満の場合、膜
の空隙内にイオン交換樹脂を十分充填することが容易で
はなく、更に、単位容積あたりのイオン交換樹脂量が少
なくなり十分なイオン交換能が発揮されず、その結果、
膜抵抗が高くなる。一方９０％を超えると単位容積あた
りのイオン交換樹脂量が多くなり、実用に供した場合、
イオン交換樹脂の膨潤収縮によって、寸法安定性を欠き
機械的強度も低下するため、好ましくない。That is, when the porosity is less than 20%, it is not easy to sufficiently fill the pores of the membrane with the ion exchange resin, and further, the amount of the ion exchange resin per unit volume is reduced, resulting in a sufficient ion exchange resin. Not work, and as a result,
The film resistance increases. On the other hand, if it exceeds 90%, the amount of ion exchange resin per unit volume increases, and when it is put to practical use,
The swelling and shrinking of the ion exchange resin is not preferable because it lacks dimensional stability and lowers mechanical strength.
【００４０】上記空隙率は、独立気泡を除いたもので、
後記の延伸法による製造方法によって得られる微多孔性
膜は殆ど独立気泡は存在しない。The above porosity excludes closed cells.
The microporous membrane obtained by the production method by the stretching method described later has almost no closed cells.
【００４１】これらの微多孔性膜の製造方法は特に限定
されず、公知の種々の方法によって製造することができ
る。例えば、熱可塑性樹脂、好ましくは、結晶性を有す
る熱可塑性樹脂に対して、延伸後に除去が可能な添加剤
を分散せしめ、これを一軸又は二軸に、該熱可塑性樹脂
の融点以下に加熱しながら延伸した後、上記添加剤を除
去することによる、公知の延伸法による微多孔性膜の製
造方法が挙げられる。The method for producing these microporous membranes is not particularly limited, and can be produced by various known methods. For example, for a thermoplastic resin, preferably, a thermoplastic resin having crystallinity, an additive that can be removed after stretching is dispersed, and this is uniaxially or biaxially heated to a melting point of the thermoplastic resin or lower. After the stretching, a method for producing a microporous membrane by a known stretching method by removing the above-mentioned additives is exemplified.
【００４２】上記添加剤としては、パラフィン、無機粉
体等の公知の添加剤が挙げられ、延伸後の添加剤の除去
方法も、溶剤による抽出、酸による溶解等、公知の方法
が特に制限なく実施される。Examples of the above-mentioned additives include known additives such as paraffin and inorganic powder. The method of removing the additives after stretching is not particularly limited. Will be implemented.
【００４３】このような延伸法により製造される微多孔
性膜は、表層に厚み約０．０１〜２μｍ、一般には、
０．３〜１．５μｍのスキン層を形成し易く、図１に概
念的に示したように、表面に微細な細孔を有しながら、
内部に存在する比較的大きな空洞部により適度に大きい
空隙率を達成し易い。The microporous membrane produced by such a stretching method has a thickness of about 0.01 to 2 μm on the surface layer, generally,
It is easy to form a skin layer of 0.3 to 1.5 μm, and as shown conceptually in FIG. 1, while having fine pores on the surface,
It is easy to achieve a moderately high porosity due to the relatively large cavity present inside.
【００４４】従って、上記微多孔性膜を本発明の母材と
して使用することにより、表面の微細孔による耐汚染防
止効果に優れるのみでなく、該スキン層の厚みの近傍と
なるように、充填されたイオン交換樹脂の露出面の陥没
深度を調節することによって、上記スキン層における微
細孔部分の抵抗を無くし、一層低抵抗のイオン交換膜を
実現することが可能である。Therefore, by using the microporous membrane as a base material of the present invention, not only the effect of preventing contamination due to micropores on the surface is excellent, but also the filling so that the thickness becomes close to the thickness of the skin layer. By adjusting the depressed depth of the exposed surface of the ion-exchange resin, the resistance of the microporous portion in the skin layer can be eliminated, and an ion-exchange membrane having a lower resistance can be realized.
【００４５】本発明において、微多孔性膜の空隙内に充
填されるイオン交換樹脂は、公知のイオン交換樹脂が特
に制限なく使用される。例えば、炭化水素系又はフッ素
系の材質より成り、陽イオン交換機能及び／又は陰イオ
ン交換能を有する樹脂である。In the present invention, as the ion exchange resin filled in the voids of the microporous membrane, a known ion exchange resin is used without any particular limitation. For example, a resin made of a hydrocarbon-based or fluorine-based material and having a cation exchange function and / or an anion exchange ability.
【００４６】上記炭化水素系の材質としては、スチレン
系樹脂、アクリル系樹脂等が、また、フッ素系の材質と
しては、パーフロオロカーボン系樹脂等が挙げられる。The hydrocarbon-based material includes styrene-based resin and acrylic resin, and the fluorine-based material includes perfluorocarbon-based resin.
【００４７】また、イオン交換能は、イオン交換基の存
在により発現するが、かかるイオン交換基としては、水
溶液中で負又は正の電荷となり得る官能基なら特に制限
されるものではない。The ion-exchange ability is exhibited by the presence of an ion-exchange group, but the ion-exchange group is not particularly limited as long as it is a functional group that can be negatively or positively charged in an aqueous solution.
【００４８】具体的には、陽イオン交換基の場合には、
スルホン酸基、カルボン酸基、ホスホン酸基等が挙げら
れ、一般的に、強酸性基であるスルホン酸基が好適に用
いられる。Specifically, in the case of a cation exchange group,
Examples thereof include a sulfonic acid group, a carboxylic acid group, and a phosphonic acid group. Generally, a sulfonic acid group that is a strongly acidic group is suitably used.
【００４９】また、陰イオン交換基の場合には、１〜３
級アミノ基、４級アンモニウム基、ピリジル基、イミダ
ゾール基、４級ピリジニウム基等が挙げられ、一般的
に、強塩基性基である４級アンモニウム基や４級ピリジ
ニウム基が好適に用いられる。In the case of an anion exchange group, 1 to 3
Examples include a quaternary amino group, a quaternary ammonium group, a pyridyl group, an imidazole group, and a quaternary pyridinium group. Generally, a quaternary ammonium group or a quaternary pyridinium group, which is a strongly basic group, is preferably used.
【００５０】本発明のイオン交換膜の製造方法は、特に
制限されないが、代表的な製造方法を例示すれば、下記
の方法が挙げられる。The method for producing the ion exchange membrane of the present invention is not particularly limited, but the following method may be mentioned as a typical production method.
【００５１】即ち、本発明によれば、微多孔性膜の空隙
内に、イオン交換基導入可能な官能基又はイオン交換基
を有する単量体、架橋性単量体、および重合開始剤を含
有する単量体組成物を含浸せしめた後、該単量体組成物
を重合せしめてイオン交換樹脂又はイオン交換樹脂前駆
体を生成し、次いで、該微細孔内の微多孔性膜表面近傍
に存在するイオン交換樹脂又はイオン交換樹脂前駆体を
除去することを特徴とするイオン交換膜の製造方法が提
供される。That is, according to the present invention, a monomer having a functional group capable of introducing an ion exchange group or an ion exchange group, a crosslinkable monomer, and a polymerization initiator are contained in the voids of the microporous membrane. After impregnating with the monomer composition to be formed, the monomer composition is polymerized to produce an ion exchange resin or an ion exchange resin precursor, which is then present near the surface of the microporous membrane in the micropores. The present invention provides a method for producing an ion-exchange membrane, which comprises removing an ion-exchange resin or an ion-exchange resin precursor.
【００５２】上記イオン交換樹脂の充填方法は、特に制
限されず公知の技術、例えば、イオン交換基が導入可能
な官能基又はイオン交換基を有する単量体、架橋性単量
体および重合開始剤からなる単量体組成物を空隙内に含
浸させた後、単量体組成物を重合し、必要に応じて陽イ
オン交換基や陰イオン交換基を導入する方法等が挙げら
れる。The method of filling the ion exchange resin is not particularly limited, and is a known technique, for example, a monomer having a functional group into which an ion exchange group can be introduced or an ion exchange group, a crosslinkable monomer, and a polymerization initiator. After impregnating the voids with the monomer composition consisting of, the monomer composition is polymerized and, if necessary, a cation exchange group or an anion exchange group is introduced.
【００５３】上記単量体組成物は、分子量が低いため微
多孔性膜の空隙に充填しやすく、また、その硬化物であ
るイオン交換樹脂は、空隙に隙間なく高い密度で充填す
ることができるため好適である。Since the monomer composition has a low molecular weight, it can be easily filled in the voids of the microporous membrane, and the cured product of the ion exchange resin can be filled in the voids at a high density without any gaps. Therefore, it is suitable.
【００５４】この製造方法において、イオン交換基が導
入可能な官能基を有する単量体又はイオン交換基を有す
る単量体としては、従来公知であるイオン交換樹脂の製
造において用いられている炭化水素系単量体が特に限定
されずに使用される。具体的には、陽イオン交換基が導
入可能な官能基を有する単量体としては、スチレン、ビ
ニルトルエン、ビニルキシレン、α−メチルスチレン、
ビニルナフタレン、α−ハロゲン化スチレン類等が挙げ
られる。また、陽イオン交換基を有する単量体として
は、α−ハロゲン化ビニルスルホン酸、スチレンスルホ
ン酸、ビニルスルホン酸等のスルホン酸系単量体、メタ
クリル酸、アクリル酸、無水マレイン酸等のカルボン酸
系単量体、ビニルリン酸等のホスホン酸系単量体、それ
らの塩類およびエステル類等が用いられる。In this production method, the monomer having a functional group into which an ion-exchange group can be introduced or the monomer having an ion-exchange group includes hydrocarbons used in the production of conventionally known ion-exchange resins. A system monomer is used without any particular limitation. Specifically, as a monomer having a functional group into which a cation exchange group can be introduced, styrene, vinyl toluene, vinyl xylene, α-methyl styrene,
Vinyl naphthalene, α-halogenated styrenes and the like. Examples of the monomer having a cation exchange group include sulfonic acid monomers such as α-halogenated vinyl sulfonic acid, styrene sulfonic acid, and vinyl sulfonic acid; and carboxylic acids such as methacrylic acid, acrylic acid, and maleic anhydride. Acid monomers, phosphonic acid monomers such as vinyl phosphoric acid, and salts and esters thereof are used.
【００５５】一方、陰イオン交換基が導入可能な官能基
を有する単量体としては、スチレン、ビニルトルエン、
クロロメチルスチレン、ビニルピリジン、ビニルイミダ
ゾール、α−メチルスチレン、ビニルナフタレン等が挙
げられる。また、陰イオン交換基を有する単量体として
は、ビニルベンジルトリメチルアミン、ビニルベンジル
トリエチルアミン等のアミン系単量体、ビニルピリジ
ン、ビニルイミダゾール等の含窒素複素環系単量体、そ
れらの塩類およびエステル類等が用いられる。On the other hand, monomers having a functional group into which an anion exchange group can be introduced include styrene, vinyl toluene,
Chloromethylstyrene, vinylpyridine, vinylimidazole, α-methylstyrene, vinylnaphthalene and the like can be mentioned. Examples of the monomer having an anion exchange group include amine monomers such as vinylbenzyltrimethylamine and vinylbenzyltriethylamine, nitrogen-containing heterocyclic monomers such as vinylpyridine and vinylimidazole, salts and esters thereof. And the like are used.
【００５６】また、架橋性単量体としては、特に制限さ
れるものではないが、例えば、ジビニルベンゼン類、ジ
ビニルスルホン、ブタジエン、クロロプレン、ジビニル
ビフェニル、トリビニルベンゼン類、ジビニルナフタリ
ン、ジアリルアミン、ジビニルピリジン類等のジビニル
化合物が用いられる。The crosslinkable monomer is not particularly restricted but includes, for example, divinylbenzenes, divinylsulfone, butadiene, chloroprene, divinylbiphenyl, trivinylbenzenes, divinylnaphthalene, diallylamine and divinylpyridine. A divinyl compound such as a compound is used.
【００５７】本発明では、上記したイオン交換基が導入
可能な官能基を有する単量体又はイオン交換基を有する
単量体や架橋性単量体の他に、必要に応じてこれらの単
量体と共重合可能な他の単量体を添加しても良い。こう
した他の単量体としては、例えば、スチレン、アクリロ
ニトリル、メチルスチレン、アクロレイン、メチルビニ
ルケトン、ビニルビフェニル等が用いられる。In the present invention, in addition to the above-mentioned monomer having a functional group into which an ion-exchange group can be introduced, a monomer having an ion-exchange group and a crosslinkable monomer, if necessary, Other monomers copolymerizable with the polymer may be added. Examples of such other monomers include styrene, acrylonitrile, methylstyrene, acrolein, methylvinylketone, and vinylbiphenyl.
【００５８】次に、本発明における重合開始剤として
は、従来公知のものが特に制限なく使用される。こうし
た重合開始剤の具体例としては、オクタノイルパーオキ
シド、ラウロイルパーオキシド、ｔ−ブチルパーオキシ
−２−エチルヘキサノエート、ベンゾイルパーオキシ
ド、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチル
パーオキシラウレート、ｔ−ヘキシルパーオキシベンゾ
エート、ジ−ｔ−ブチルパーオキシド等の有機過酸化物
が用いられる。Next, as the polymerization initiator in the present invention, conventionally known ones are used without any particular limitation. Specific examples of such a polymerization initiator include octanoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, and t-butylperoxy. Organic peroxides such as laurate, t-hexylperoxybenzoate and di-t-butyl peroxide are used.
【００５９】本発明において、単量体組成物を構成する
各成分の配合割合は、一般には、イオン交換基が導入可
能な官能基を有する単量体又はイオン交換基を有する単
量体１００重量部に対して、架橋性単量体を０．１〜５
０重量部、好適には１〜４０重量部、これらの単量体と
共重合可能な他の単量体を０〜１００重量部使用するの
が好適である。また、重合開始剤は、イオン交換基が導
入可能な官能基を有する単量体又はイオン交換基を有す
る単量体１００重量部対して、０．１〜２０重量部、好
適には０．５〜１０重量部配合させるのが好ましい。In the present invention, the mixing ratio of each component constituting the monomer composition is generally 100 parts by weight of a monomer having a functional group into which an ion exchange group can be introduced or 100 parts by weight of a monomer having an ion exchange group. Parts to 0.1 to 5 parts of the crosslinking monomer.
It is preferred to use 0 parts by weight, preferably 1 to 40 parts by weight, and 0 to 100 parts by weight of other monomers copolymerizable with these monomers. The polymerization initiator is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 100 parts by weight, based on 100 parts by weight of a monomer having a functional group into which an ion exchange group can be introduced or 100 parts by weight of a monomer having an ion exchange group. It is preferable to mix 10 to 10 parts by weight.
【００６０】上記単量体組成物を微多孔性膜の空隙部に
充填する方法は特に制限されないが、一般には微多孔性
膜を単量体組成物に浸漬する方法や単量体組成物を微多
孔性膜に塗布、スプレーする方法が採用される。この
時、粘度等の性状により、単量体組成物を微多孔性膜の
空隙内に充分充填することが困難な場合には、単量体組
成物に微多孔性膜を減圧下で接触させ、充填する方法を
採ることもできる。The method of filling the voids of the microporous membrane with the above monomer composition is not particularly limited, but generally, the method of immersing the microporous membrane in the monomer composition or the method of filling the monomer composition is used. A method of applying and spraying on a microporous membrane is employed. At this time, if it is difficult to sufficiently fill the monomer composition into the voids of the microporous membrane due to properties such as viscosity, the microporous membrane is brought into contact with the monomer composition under reduced pressure. Alternatively, a filling method may be employed.
【００６１】単量体組成物を上記したように微多孔性膜
に充填させたのち重合する方法は、一般に、ポリエステ
ル等のフィルムに挟んで加圧下で常温から昇温する方法
が好ましい。こうした重合条件は、関与する重合開始剤
の種類、単量体組成物の組成等によって左右されるもの
であり、公知の条件より適宜選択して決定すればよい。As a method of polymerizing the monomer composition after filling it in the microporous membrane as described above, it is generally preferable to raise the temperature from room temperature under pressure while sandwiching a film of polyester or the like. Such polymerization conditions depend on the type of polymerization initiator involved, the composition of the monomer composition, and the like, and may be determined by appropriately selecting from known conditions.
【００６２】以上のように重合されて得られる膜状物
は、必要に応じてこれを、公知の例えば、陽イオン交換
膜であれば、スルホン化、クロルスルホン化、ホスホニ
ウム化、加水分解等の処理、陰イオン交換膜であれば、
アミノ化、アルキル化等の処理により所望のイオン交換
基を導入して、イオン交換膜とすることができる。The membrane obtained by polymerization as described above may be used, if necessary, in the case of a known cation exchange membrane, for example, sulfonation, chlorosulfonation, phosphoniumation, hydrolysis and the like. If the treatment, anion exchange membrane,
A desired ion exchange group can be introduced by a treatment such as amination or alkylation to form an ion exchange membrane.
【００６３】次いで、微細孔内の微多孔性膜表面近傍に
存在するイオン交換樹脂又はイオン交換樹脂前駆体を除
去し、必要に応じて、イオン交換膜を導入することによ
り、本発明のイオン交換膜が得られる。Next, the ion-exchange resin or the ion-exchange resin precursor present near the surface of the microporous membrane in the micropores is removed, and if necessary, an ion-exchange membrane is introduced. A film is obtained.
【００６４】即ち、上記のイオン交換樹脂の除去は、イ
オン交換樹脂に対して行っても良く、或いは、イオン交
換基を導入前のイオン交換樹脂前駆体に対して行っても
良い。That is, the above-mentioned removal of the ion exchange resin may be performed on the ion exchange resin, or may be performed on the ion exchange resin precursor before the ion exchange group is introduced.
【００６５】上記イオン交換樹脂を除去する方法として
は、何ら制限はされないが、例えば、コロナ放電処理や
プラズマエッチング処理等が挙げられる。プラズマエッ
チング処理の場合、例えば、酸素又は、酸素／アルゴン
混合の雰囲気下でプラズマ処理することにより所望の深
さまでイオン交換樹脂をエッチング除去することが可能
である。また、過酸化水素、オゾン、濃硝酸、濃硫酸、
重クロム酸カリウム、塩素、ヨウ素、次亜塩素酸ナトリ
ウムなどの酸化剤を膜表面に接触させることによって
も、膜表面のイオン交換樹脂が除去できる。特に酸化剤
を用いる方法は簡便であり、好適に用いられる。The method for removing the ion-exchange resin is not particularly limited, and examples thereof include a corona discharge treatment and a plasma etching treatment. In the case of the plasma etching treatment, for example, the ion exchange resin can be etched and removed to a desired depth by performing a plasma treatment in an atmosphere of oxygen or a mixture of oxygen and argon. Also, hydrogen peroxide, ozone, concentrated nitric acid, concentrated sulfuric acid,
The ion exchange resin on the membrane surface can also be removed by contacting the membrane surface with an oxidizing agent such as potassium dichromate, chlorine, iodine or sodium hypochlorite. In particular, a method using an oxidizing agent is simple and is preferably used.
【００６６】本発明のイオン交換膜を簡便に得るために
好適な方法として、前記単量体組成物に、更に、溶媒や
平均分子量５００〜１００００の重合体のいずれか一
方、又は両方を添加して得られた組成物を微多孔性膜の
空隙内に充填した後、該組成物を硬化させ、次いで、必
要に応じてイオン交換基を導入する方法がある。As a preferred method for easily obtaining the ion-exchange membrane of the present invention, one or both of a solvent and a polymer having an average molecular weight of 500 to 10,000 are further added to the monomer composition. After filling the obtained composition into the voids of the microporous membrane, the composition is cured, and then, if necessary, an ion exchange group is introduced.
【００６７】この製造方法によれば、微細孔内の表面近
傍のイオン交換樹脂は、特殊な除去手段を採用しなくと
も、イオン交換基導入工程において容易に除去される。
また、イオン交換基導入工程が必要ない場合には、溶剤
と接触せしめることによって、微細孔内の微多孔性膜表
面近傍のイオン交換樹脂を簡単に除去することができ
る。According to this manufacturing method, the ion-exchange resin in the vicinity of the surface in the micropores is easily removed in the ion-exchange group introduction step without employing any special removing means.
When the ion-exchange group introduction step is not necessary, the ion-exchange resin in the vicinity of the surface of the microporous membrane in the micropores can be easily removed by contact with a solvent.
【００６８】本製造方法において、溶媒は、単量体組成
物の重合反応の進行に伴い、いわゆるミクロ相分離を引
き起こすため、最表面部に当たる、微細孔内の微多孔性
膜表面近傍のイオン交換樹脂は極めてポーラスな多孔体
となる。そして、かかるポーラス構造に起因する機械的
強度の低さ故に、イオン交換基導入工程や簡単な溶剤処
理によって脱落し易く、該部分を容易に除去することが
できる。In the present production method, the solvent causes so-called microphase separation with the progress of the polymerization reaction of the monomer composition, so that the ion exchange near the surface of the microporous membrane in the fine pores, which corresponds to the outermost surface, is performed. The resin becomes an extremely porous body. Then, due to the low mechanical strength due to the porous structure, the porous structure is easily dropped off by an ion exchange group introduction step or a simple solvent treatment, and the portion can be easily removed.
【００６９】一方、平均分子量５００〜１００００の重
合体は、単量体組成物の微多孔膜への充填工程におい
て、分子が大きいため単量体の重合の過程において表面
に押し出され、最表面部に当たる、微細孔内の微多孔性
膜表面近傍に偏在する。そして、これらの重合体はイオ
ン交換基導入工程などで使用される溶剤によって抽出除
去することができ、その結果、やはり微細孔内における
膜表面近傍のイオン交換樹脂の除去が容易となる。On the other hand, the polymer having an average molecular weight of 500 to 10000 is extruded to the surface in the course of polymerization of the monomer because the molecules are large in the step of filling the microporous membrane with the monomer composition, and , Which are localized near the surface of the microporous membrane in the micropores. These polymers can be extracted and removed with a solvent used in the ion-exchange group introduction step and the like, and as a result, the ion-exchange resin in the vicinity of the membrane surface in the micropores can be easily removed.
【００７０】これらの作用は、溶媒および平均分子量５
００〜１００００の重合体を併用することでより効果的
となる。すなわち、溶媒のみを用いて微細孔内の表面近
傍のイオン交換樹脂を完全に除去するには、多量の溶媒
を添加することが必要となり、その結果、膜内部に残存
するイオン交換樹脂が更にポーラスになり、イオン選択
性に低下を来たす。また、平均分子量５００〜１０００
０の重合体のみを用いた場合には、該重合体の抽出除去
が不完全になり易く、その結果、有機汚染の防止効果を
充分に発現できなくなる。These effects are based on the solvent and the average molecular weight of 5
It is more effective to use a polymer of from 00 to 10,000 in combination. That is, in order to completely remove the ion-exchange resin near the surface in the micropores using only the solvent, it is necessary to add a large amount of the solvent, and as a result, the ion-exchange resin remaining inside the membrane becomes more porous. , Resulting in a decrease in ion selectivity. Further, the average molecular weight is 500 to 1000.
When only the polymer of 0 is used, extraction and removal of the polymer tend to be incomplete, and as a result, the effect of preventing organic contamination cannot be sufficiently exhibited.
【００７１】従って、溶媒および平均分子量５００〜１
００００の重合体を併用した場合には、膜表面近傍に偏
在する重合体が、溶媒が抜けてポーラスになったイオン
交換樹脂から簡単に抽出されるため、有機汚染防止効果
が十分に発現され、更に、溶媒添加量を低減できるた
め、膜内部に残存するイオン交換樹脂が過度にポーラス
とならず、イオン選択性の低下も防ぐことができる。Accordingly, the solvent and the average molecular weight are from 500 to 1
When a polymer of 0000 is used in combination, a polymer unevenly distributed in the vicinity of the membrane surface is easily extracted from a porous ion-exchange resin from which a solvent has been removed, so that an organic pollution preventing effect is sufficiently exhibited. Furthermore, since the amount of solvent added can be reduced, the ion exchange resin remaining inside the membrane does not become excessively porous, and a decrease in ion selectivity can be prevented.
【００７２】本製造方法において、前記単量体組成物に
添加される溶媒としては、単量体組成物を重合させる際
に、重合反応に関与しない溶媒であれば何ら制限される
こと無く使用可能である。具体的には、メタノール、エ
タノール、ｉ−ブタノール、２−エトキシエタノール等
のアルコール類、ヘキサン、シクロヘキサン、ヘプタ
ン、ｉ−オクタン等の脂肪族炭化水素類、オクタン酸等
の脂肪酸類、ジメチルオクチルアミン等のアミン類、ト
ルエン、キシレン、ナフタレン等の芳香族炭化水素類、
シクロヘキサノン、メチルエチルケトン等のケトン類、
ジベンジルエーテル、ジエチレングリコールジメチルエ
ーテル等のエーテル類、メチレンクロライド、クロロホ
ルム、エチレンブロマイド等のハロゲン化炭化水素類、
ジブチルフタレート、ジオクチルフタレート、ジメチル
イソフタレート、ジブチルアジペート、トリエチルシト
レート、アセチルトリブチルシトレート、ジブチルセバ
ケート等の芳香族酸や脂肪族酸のアルコールエステル類
やアルキルリン酸エステル等が挙げられる。これらは、
単量体組成物との溶解性や重合温度等を勘案して適宜選
択されるが、ｉ−ブタノール、２−エトキシエタノー
ル、ジベンジルエーテル、ジオクチルフタレート、アセ
チルトリブチルシトレート等が特に好適である。また、
これらを数種類を併用することも可能である。In the present production method, the solvent added to the monomer composition can be used without any limitation as long as it does not participate in the polymerization reaction when polymerizing the monomer composition. It is. Specifically, alcohols such as methanol, ethanol, i-butanol and 2-ethoxyethanol, aliphatic hydrocarbons such as hexane, cyclohexane, heptane and i-octane, fatty acids such as octanoic acid, dimethyloctylamine and the like Amines, toluene, xylene, aromatic hydrocarbons such as naphthalene,
Ketones such as cyclohexanone and methyl ethyl ketone,
Dibenzyl ether, ethers such as diethylene glycol dimethyl ether, methylene chloride, chloroform, halogenated hydrocarbons such as ethylene bromide,
Examples thereof include alcoholic esters of aromatic acids and aliphatic acids such as dibutyl phthalate, dioctyl phthalate, dimethyl isophthalate, dibutyl adipate, triethyl citrate, acetyl tributyl citrate, and dibutyl sebacate, and alkyl phosphate esters. They are,
It is appropriately selected in consideration of the solubility with the monomer composition, the polymerization temperature and the like, but i-butanol, 2-ethoxyethanol, dibenzyl ether, dioctyl phthalate, acetyltributyl citrate and the like are particularly preferable. Also,
These can be used in combination of several types.
【００７３】次いで、前記単量体組成物に添加される重
合体としては、具体的には、スチレン−ブタジエン共重
合体、アクリロニトリル−ブタジエン共重合体、ポリブ
タジエン、ポリエチレングリコール、ポリプロピレング
リコール等が挙げられる。Next, specific examples of the polymer to be added to the monomer composition include styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polybutadiene, polyethylene glycol, polypropylene glycol and the like. .
【００７４】これらも、また、単量体組成物との溶解性
等を勘案して、適宜選択されるが、ポリブタジエン、ポ
リプロピレングリコールが特に好適である。 これら重
合体の平均分子量は５００〜１００００、好ましくは５
００〜６０００である。即ち、平均分子量が５００以下
の場合、膜表面近傍に偏在しにくくなり、有機汚染防止
効果やイオン選択性が不十分となる。また、平均分子量
が１００００以上の場合には、抽出除去が困難になり、
有機汚染防止効果が不十分となり好ましくない。上記溶
媒、平均分子量５００〜１００００の重合体の前記単量
体組成物への配合割合は、イオン交換基導入可能な官能
基又はイオン交換基を有する単量体、架橋性単量体およ
び重合開始剤の合計１００重量部に対し、溶媒は１５〜
１５０重量部、好ましくは２０〜１２０重量部である。
即ち、溶媒の配合量が１５重量部未満では、有機汚
染防止効果が十分でなく、１５０重量部を超える場合に
は、イオン選択性が低下する。These are also appropriately selected in consideration of the solubility with the monomer composition and the like, but polybutadiene and polypropylene glycol are particularly preferred. The average molecular weight of these polymers is from 500 to 10,000, preferably 5
00 to 6000. That is, when the average molecular weight is 500 or less, it is difficult to be unevenly distributed in the vicinity of the membrane surface, and the organic contamination preventing effect and ion selectivity become insufficient. When the average molecular weight is 10,000 or more, extraction and removal becomes difficult,
The effect of preventing organic contamination is insufficient, which is not preferable. The compounding ratio of the solvent, the polymer having an average molecular weight of 500 to 10,000 to the monomer composition is determined by a functional group capable of introducing an ion-exchange group or a monomer having an ion-exchange group, a cross-linkable monomer, and polymerization initiation. For a total of 100 parts by weight of the agent, the solvent is 15 to
It is 150 parts by weight, preferably 20 to 120 parts by weight.
That is, if the amount of the solvent is less than 15 parts by weight, the effect of preventing organic contamination is not sufficient. If the amount exceeds 150 parts by weight, ion selectivity is reduced.
【００７５】また、平均分子量５００〜１００００の重
合体は、イオン交換基導入可能な官能基又はイオン交換
基を有する単量体、架橋性単量体および重合開始剤の合
計１００重量部に対し、５〜１００重量部、好ましくは
１０〜７０重量部である。Further, the polymer having an average molecular weight of 500 to 10000 is based on 100 parts by weight of a total of a monomer having a functional group capable of introducing an ion exchange group or an ion exchange group, a crosslinkable monomer and a polymerization initiator. It is 5 to 100 parts by weight, preferably 10 to 70 parts by weight.
【００７６】即ち、平均分子量５００〜１００００の重
合体の配合量が５重量部未満では有機汚染防止効果が十
分でなく、１００重量部を超える場合には、単量体組成
物の微多孔性膜への充填が不十分になり、さらにイオン
選択性の低下を来たし好ましくない。That is, if the amount of the polymer having an average molecular weight of 500 to 10,000 is less than 5 parts by weight, the effect of preventing organic contamination is not sufficient. If the amount exceeds 100 parts by weight, the microporous film of the monomer composition is obtained. Insufficiently, the ion selectivity is lowered, which is not preferable.
【００７７】以上のような、溶媒や平均分子量５００〜
１００００の重合体を添加した単量体組成物は、前記製
造方法の説明に記載された方法により微多孔性膜に充填
され、次いで硬化される。得られた膜状物には、引き続
き、前記したイオン交換基の導入方法によって、必要に
応じてイオン交換基が導入される。As described above, the solvent and the average molecular weight are 500 to
The monomer composition containing 10,000 polymers is filled in the microporous membrane by the method described in the above description of the production method, and then cured. Subsequently, ion-exchange groups are introduced into the obtained film-like material according to the method for introducing ion-exchange groups described above, if necessary.
【００７８】イオン交換基の導入工程において、微細孔
内の膜表面近傍のイオン交換樹脂が除去される場合に
は、更なる除去工程を必要とすること無く、本発明のイ
オン交換膜が得られ、膜表面近傍のイオン交換樹脂の除
去が充分でない場合には、添加した溶剤や平均分子量５
００〜１００００の重合体の性情に応じた抽出工程を施
すことでイオン交換樹脂を除去し、本発明のイオン交換
膜を得ることができる。In the step of introducing ion-exchange groups, when the ion-exchange resin in the vicinity of the membrane surface in the micropores is removed, the ion-exchange membrane of the present invention can be obtained without requiring a further removal step. If the ion exchange resin in the vicinity of the membrane surface is not sufficiently removed, the added solvent or the average molecular weight 5
The ion exchange resin is removed by performing an extraction step according to the nature of the polymer of 00 to 10000, and the ion exchange membrane of the present invention can be obtained.
【００７９】また、この製造方法においても、イオン交
換樹脂又はイオン交換樹脂前駆体の除去は、イオン交換
基導入の前であっても、後であってもよい。Also in this production method, the ion exchange resin or the ion exchange resin precursor may be removed before or after the ion exchange group is introduced.
【００８０】[0080]
【発明の効果】以上の説明より理解されるように、本発
明のイオン交換膜は、微細孔において、上記イオン交換
樹脂が微多孔性膜表面より陥没した位置で露出した構造
を有することにより、極めて優れた耐有機汚染性を有し
ながら、低い膜抵抗や良好なイオン選択性などを有し、
基本性能にも優れたイオン交換膜である。As will be understood from the above description, the ion exchange membrane of the present invention has a structure in which the above-mentioned ion exchange resin is exposed at a position depressed from the surface of the microporous membrane in the micropores. While having extremely good organic contamination resistance, it has low membrane resistance and good ion selectivity,
It is an ion exchange membrane with excellent basic performance.
【００８１】従って、耐有機汚染性を必要とする用途は
勿論、耐有機汚染性を必要としない用途においても、制
限なく使用することができる。Therefore, the present invention can be used without limitation not only in applications that require organic contamination resistance but also in applications that do not require organic contamination resistance.
【００８２】特に、食品、医薬品、農薬などの合成工程
における電気透析用の隔膜として、或いは、機能性セパ
レーター等のその他の用途にも有効に使用することがで
きる。In particular, it can be effectively used as a diaphragm for electrodialysis in the synthesis process of foods, pharmaceuticals, agricultural chemicals and the like, or for other uses such as a functional separator.
【００８３】[0083]
【実施例】以下、本発明を更に詳細に説明するため実施
例を挙げるが、本発明はこれらの実施例に限定されるも
のではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００８４】なお、実施例、比較例に示すイオン交換膜
の特性は、以下の方法により測定した。The characteristics of the ion exchange membranes shown in Examples and Comparative Examples were measured by the following methods.
【００８５】１）微多孔性膜表面からイオン交換樹脂の
露出面までの陥没深度 電子顕微鏡（ＳＥＭ）によってイオン交換膜表面を観察
し、微多孔性膜の表面全面を覆うイオン交換樹脂層がな
いことを確認した後、イオン交換膜の表面粗さを走査型
レーザー顕微鏡（レーザーテック社製、１Ｌｍ２１型）
で測定した。得られた粗さ分布図において、ピーク部と
隣接する最深部の高低差を測り、長さ３０μｍに渡って
測定した高低差の平均値を陥没深度とした。1) Depression depth from the surface of the microporous membrane to the exposed surface of the ion exchange resin The surface of the ion exchange membrane is observed by an electron microscope (SEM), and there is no ion exchange resin layer covering the entire surface of the microporous membrane. After confirming this, the surface roughness of the ion exchange membrane was measured using a scanning laser microscope (manufactured by Lasertec, 1Lm21 type).
Was measured. In the obtained roughness distribution map, the height difference between the peak portion and the deepest portion adjacent to the peak portion was measured, and the average value of the height difference measured over a length of 30 μm was defined as the depression depth.
【００８６】２）イオン交換容量および含水率 イオン交換膜を１ｍｏｌ／Ｌ−ＨＣｌに１０時間以上浸
漬する。2) Ion exchange capacity and water content The ion exchange membrane is immersed in 1 mol / L-HCl for 10 hours or more.
【００８７】その後、陽イオン交換膜の場合には、１ｍ
ｏｌ／Ｌ−ＮａＣｌで水素イオン型をナトリウムイオン
型に置換させ、遊離した水素イオンを電位差滴定装置
（ＣＯＭＴＩＴＥ−９００、平沼産業株式会社製）で定
量した（Ａｍｏｌ）。一方、陰イオン交換膜の場合に
は、１ｍｏｌ／Ｌ−ＮａＮＯ3で塩素イオン型を硝酸イ
オン型に置換させ、遊離した塩素イオンを電位差滴定装
置（ＣＯＭＴＩＴＥ−９００、平沼産業株式会社製）で
定量した（Ａｍｏｌ）。Thereafter, in the case of a cation exchange membrane, 1 m
The hydrogen ion type was replaced with a sodium ion type with ol / L-NaCl, and the released hydrogen ions were quantified with a potentiometric titrator (COMMITE-900, manufactured by Hiranuma Sangyo Co., Ltd.) (Amol). On the other hand, in the case of an anion exchange membrane, the chloride ion type is replaced with a nitrate ion type with 1 mol / L-NaNO 3 , and the liberated chloride ion is quantified with a potentiometric titrator (COMTITE-900, manufactured by Hiranuma Sangyo Co., Ltd.). (Amol).
【００８８】次に、同じイオン交換膜を１ｍｏｌ／Ｌ−
ＨＣｌに４時間以上浸漬し、イオン交換水で十分に水洗
した後膜を取り出しティッシュペーパー等で表面の水分
をふき取り湿潤時の重さ（Ｗｇ）を測定した。次に、膜
を減圧乾燥機に入れ６０℃で５時間乾燥させた。膜を取
り出し乾燥時の重さ（Ｄｇ）を測定した。Next, the same ion exchange membrane was added at 1 mol / L-
After being immersed in HCl for 4 hours or more and thoroughly washed with ion-exchanged water, the membrane was taken out, the surface water was wiped off with a tissue paper or the like, and the wet weight (Wg) was measured. Next, the membrane was placed in a vacuum drier and dried at 60 ° C. for 5 hours. The film was taken out and the weight (Dg) at the time of drying was measured.
【００８９】イオン交換容量と含水率は次式により算出
した。The ion exchange capacity and the water content were calculated by the following equations.
【００９０】イオン交換容量＝Ａ×１０００／Ｗ ［ｍ
ｍｏｌ／ｇ−乾燥膜］ 含水率＝１００×（Ｗ−Ｄ）／Ｄ ［％］ ３）膜抵抗の測定 白金黒電極版を有する２室セル中にイオン交換膜を挟
み、イオン交換膜の両側に３ｍｏｌ／Ｌ−Ｈ2ＳＯ4溶液
を満たし、交流ブリッジ（周波数１０００サイクル/
秒）により２５℃における電極間の抵抗を測定し、該電
極間抵抗とイオン交換膜を設置しない場合の電極間抵抗
との差により求めた。上記測定に使用する膜は、あらか
じめ３ｍｏｌ／Ｌ−Ｈ2ＳＯ4溶液中で平衡にしたものを
用いた。Ion exchange capacity = A × 1000 / W [m
mol / g-dry membrane] Water content = 100 × (WD) / D [%] 3) Measurement of membrane resistance An ion exchange membrane is sandwiched in a two-chamber cell having a platinum black electrode plate, and both sides of the ion exchange membrane Is filled with a 3 mol / L-H 2 SO 4 solution, and an AC bridge (frequency: 1000 cycles /
), The resistance between the electrodes at 25 ° C was measured, and the resistance was determined from the difference between the resistance between the electrodes and the resistance between the electrodes without the ion exchange membrane. Film for use in the above measurement, used was equilibrated in advance with 3mol / L-H 2 SO 4 solution.
【００９１】４）耐有機汚染性の測定 陰イオン交換膜では、得られた陰イオン交換膜をコンデ
ショニングした後、銀、塩化銀電極を有する二室セルに
該イオン交換膜を挟み、その陽極室には０．０５ｍｏｌ
／Ｌ−ＮａＣｌ溶液を入れ、陰極室には１０００ｐｐｍ
のドデシルベンゼンスルホン酸ナトリウムと０．０５ｍ
ｏｌ／Ｌ−ＮａＣｌの混合溶液を入れた。両室の液を１
５００ｒｐｍの回転速度で攪拌し、０．２Ａ／ｄｍ2の
電流密度で電気透析を行った。4) Measurement of resistance to organic contamination In the anion exchange membrane, after conditioning the obtained anion exchange membrane, the ion exchange membrane was sandwiched in a two-chamber cell having silver and silver chloride electrodes. 0.05 mol in the room
/ L-NaCl solution, 1000ppm in the cathode chamber
Sodium dodecylbenzenesulfonate with 0.05m
ol / L-NaCl mixed solution. 1 liquid in both chambers
The mixture was stirred at a rotation speed of 500 rpm, and electrodialysis was performed at a current density of 0.2 A / dm 2 .
【００９２】この時、両膜表面の近傍に白金線を固定
し、膜間電圧を測定した。通電中に有機汚染が起こると
膜間電圧が上昇してくる。通電を開始して３０分後の膜
間電圧を測定し、有機汚染物質を添加した場合と添加し
ない場合の電圧差（ΔＥ）をとって膜の汚染性の尺度と
した。At this time, a platinum wire was fixed near the surfaces of both films, and the voltage between the films was measured. If organic contamination occurs during energization, the transmembrane voltage will increase. The transmembrane voltage was measured 30 minutes after the start of energization, and the voltage difference (ΔE) between the case where the organic contaminant was added and the case where the organic contaminant was not added was used as a measure of the film's contamination.
【００９３】陽イオン交換膜では、上記方法において、
有機汚染物質をドデシルベンゼンスルホン酸ナトリウム
から分子量２０００のポリエチレンイミンに変え、同様
にして耐有機汚染性を測定した。In the cation exchange membrane, in the above method,
The organic contaminant was changed from sodium dodecylbenzenesulfonate to polyethyleneimine having a molecular weight of 2000, and the organic contaminant resistance was measured in the same manner.
【００９４】５）酸、アルカリの透過速度 陰イオン交換膜では、陰イオン交換膜で区切られたアク
リル樹脂製の二室セルを用い、一室（原液室）に２５℃
の１ｍｏｌ／Ｌ−硫酸と０．５ｍｏｌ／Ｌ−硫酸マグネ
シウムを含む液を入れ、もう一室（透析液室）には２５
℃のイオン交換水を入れた。5) Permeation Rate of Acid and Alkali In the anion exchange membrane, a two-chamber cell made of an acrylic resin separated by an anion exchange membrane was used, and one chamber (stock solution chamber) was kept at 25 ° C.
Of a solution containing 1 mol / L-sulfuric acid and 0.5 mol / L-magnesium sulfate, and 25 ml in another chamber (dialysis fluid chamber).
C. Ion exchange water was added.
【００９５】次いで、攪拌しにより両室を攪拌し一定時
間後に透析液室の液を抜き取り、電位差滴定によって硫
酸の透過量を、原子吸光光度計によって硫酸マグネシウ
ムの透過量をそれぞれ測定した。Next, the two chambers were agitated by stirring, and after a certain period of time, the liquid in the dialysate chamber was withdrawn, and the permeation amount of sulfuric acid was measured by potentiometric titration, and the permeation amount of magnesium sulfate was measured by an atomic absorption spectrophotometer.
【００９６】また、陽イオン交換膜では、上記方法にお
いて１ｍｏｌ／Ｌ−硫酸と０．５ｍｏｌ／Ｌ−硫酸マグ
ネシウムを含む液を３ｍｏｌ／Ｌ−水酸化ナトリウムと
０．５ｍｏｌ／Ｌ−水酸化アルミニウムを含む液に変え
て同様な操作を行い、水酸化ナトリウムと水酸化アルミ
ニウムの透過量を測定した。それぞれの物質の透過速度
は次式により求めた。Further, in the cation exchange membrane, a solution containing 1 mol / L-sulfuric acid and 0.5 mol / L-magnesium sulfate in the above-mentioned method was mixed with 3 mol / L-sodium hydroxide and 0.5 mol / L-aluminum hydroxide. The same operation was carried out using a different solution, and the permeation amount of sodium hydroxide and aluminum hydroxide was measured. The permeation rate of each substance was determined by the following equation.
【００９７】Ｕ＝Ａ／（Ｔ・Ｓ・ΔＣ） Ｕ：酸又はアルカリの透過速度［mol/Hr・m2・(mol/L)］ Ａ：酸又はアルカリの透過量［ｍｏｌ］ Ｔ：攪拌時間［Ｈｒ］ Ｓ：有効膜面積［ｍ2］ ΔＣ：攪拌前後の両室の酸又はアルカリの対数平均濃度
差［mol／Ｌ］ 実施例１ クロロメチルスチレン９０重量部、ジビニルベンゼン１
０重量部、過酸化ベンゾイル５重量部、スチレンオキサ
イド３重量部よりなる単量体組成物を調製した。この単
量体組成物４００ｇを５００ｍｌのガラス容器に入れ、
ここに厚み２５μｍの重量平均分子量１０万のポリエチ
レンよりなり、延伸法によって得られた市販の微多孔性
膜（２０ｃｍ×２０ｃｍ）を浸漬して、微多孔性膜の空
隙に単量体組成物を充填した。U = A / (TS · ΔC) U: Permeation rate of acid or alkali [mol / Hr · m 2 · (mol / L)] A: Permeation amount of acid or alkali [mol] T: Stirring Time [Hr] S: Effective membrane area [m 2 ] ΔC: Logarithmic average concentration difference of acid or alkali in both chambers before and after stirring [mol / L] Example 1 90 parts by weight of chloromethylstyrene, divinylbenzene 1
A monomer composition comprising 0 parts by weight, 5 parts by weight of benzoyl peroxide, and 3 parts by weight of styrene oxide was prepared. Put 400 g of this monomer composition in a 500 ml glass container,
A commercially available microporous membrane (20 cm × 20 cm) made of polyethylene having a thickness of 25 μm and having a weight average molecular weight of 100,000 and obtained by a stretching method is immersed therein, and the monomer composition is filled in the voids of the microporous membrane. Filled.
【００９８】用いた微多孔性膜は、表面の微細孔の最大
径１μｍ、平均孔径０．０４μｍ、空隙率４５％、微細
孔の面積占有率１５％、通気度４１５秒／１００ｍｌで
あった。The microporous membrane used had a maximum diameter of the fine pores on the surface of 1 μm, an average pore diameter of 0.04 μm, a porosity of 45%, an area occupation rate of the fine pores of 15%, and an air permeability of 415 sec / 100 ml.
【００９９】続いて、多孔質膜を単量体組成物中から取
り出し、１００μｍのポリエステルフィルムを剥離材と
して多孔質膜の両側を被覆した後、０．４ＭＰａの窒素
加圧下、８０℃で８時間加熱重合した。得られた膜状物
を３０％トリメチルアミン水溶液１０部、水５部、アセ
トン５部よりなるアミノ化浴中、室温で５時間反応せし
め４級アンモニウム型陰イオン交換膜を得た。Subsequently, the porous film was taken out of the monomer composition, and both sides of the porous film were covered with a 100 μm polyester film as a release material. Then, at 80 ° C. for 8 hours under a nitrogen pressure of 0.4 MPa. Heat polymerization was performed. The resulting film was reacted at room temperature for 5 hours in an amination bath comprising 10 parts of a 30% aqueous solution of trimethylamine, 5 parts of water and 5 parts of acetone to obtain a quaternary ammonium type anion exchange membrane.
【０１００】次いで、該陰イオン交換膜を１ｗｔ％の次
亜塩素酸ナトリウム水溶液に、室温中、２４時間浸漬し
て膜表面のイオン交換樹脂を除去した。Next, the anion exchange membrane was immersed in a 1 wt% aqueous solution of sodium hypochlorite at room temperature for 24 hours to remove the ion exchange resin on the membrane surface.
【０１０１】得られたイオン交換膜の膜表面をＳＥＭで
観察したところ、微多孔性膜表面特有の微細孔構造が観
察され、更に、１ｗｔ％過マンガン酸カリウム水溶液に
イオン交換膜を浸漬してＭｎＯ4 -にイオン交換し、ＳＥ
Ｍ−ＥＤＳで膜表面におけるＭｎ元素の定状分析を行っ
た結果、Ｍｎに帰属するピークが観察されなかったこと
から、膜表面のイオン交換樹脂が除去されていることが
確認された。When the membrane surface of the obtained ion exchange membrane was observed by SEM, a fine pore structure peculiar to the surface of the microporous membrane was observed. Further, the ion exchange membrane was immersed in a 1 wt% aqueous solution of potassium permanganate. MnO 4 - to ion exchange, SE
As a result of performing a routine analysis of Mn element on the film surface by M-EDS, no peak attributed to Mn was observed, and it was confirmed that the ion exchange resin on the film surface was removed.
【０１０２】得られた陰イオン交換膜の陥没深度、イオ
ン交換容量、含水率、膜抵抗、耐有機汚染性、硫酸と硫
酸マグネシウムの透過速度を測定した。これらの結果を
表１に示す。The depth of depression, ion exchange capacity, water content, membrane resistance, resistance to organic contamination, and permeation rate of sulfuric acid and magnesium sulfate of the obtained anion exchange membrane were measured. Table 1 shows the results.
【０１０３】比較例１ 次亜塩素酸ナトリウム水溶液による処理を行わない点を
除き実施例１と同様にして陰イオン交換膜を得た。この
イオン交換膜について、ＳＥＭ観察を行った結果、膜表
面に微多孔性膜特有の微細孔構造は観察されず、更に、
ＭｎＯ4 -型にイオン交換した膜の膜表面にＭｎ元素の存
在が確認されたことから、イオン交換樹脂が膜表面に露
出していることが確認された。Comparative Example 1 An anion exchange membrane was obtained in the same manner as in Example 1 except that the treatment with the aqueous sodium hypochlorite solution was not performed. As a result of SEM observation of this ion exchange membrane, no microporous structure peculiar to the microporous membrane was observed on the membrane surface.
The existence of Mn element was confirmed on the surface of the membrane ion-exchanged to the MnO 4 - type, confirming that the ion-exchange resin was exposed on the membrane surface.
【０１０４】得られた陰イオン交換膜は、実施例１と同
様に特性を測定した。結果を表１に示す。The properties of the obtained anion exchange membrane were measured in the same manner as in Example 1. Table 1 shows the results.
【０１０５】実施例２ スチレン９０重量部、ジビニルベンゼン１０重量部、過
酸化ベンゾイル５重量部、アセチルクエン酸トリブチル
１０重量部よりなる単量体組成物を調製した。この単量
体組成物を実施例１と同様にして、厚み３０μｍの重量
平均分子量２５万のポリエチレンよりなり、延伸法によ
って得られた市販の微多孔性膜に充填した。Example 2 A monomer composition comprising 90 parts by weight of styrene, 10 parts by weight of divinylbenzene, 5 parts by weight of benzoyl peroxide and 10 parts by weight of tributyl acetylcitrate was prepared. This monomer composition was filled in a commercially available microporous membrane made of polyethylene having a thickness of 30 μm and having a weight average molecular weight of 250,000 in the same manner as in Example 1.
【０１０６】用いた微多孔性膜は、表面の微細孔の最大
径１μｍ、平均孔径０．０２μｍ、空隙率３７％、微細
孔の面積占有率１７％、通気度６００秒／１００ｍｌで
あった。The microporous membrane used had a maximum diameter of the fine pores on the surface of 1 μm, an average pore diameter of 0.02 μm, a porosity of 37%, an area occupation rate of the fine pores of 17%, and an air permeability of 600 seconds / 100 ml.
【０１０７】続いて、多孔質膜を単量体組成物中から取
り出し、１００μｍのポリエステルフィルムを剥離材と
して多孔質膜の両側を被覆した後、０．４ＭＰａの窒素
加圧下、８０℃で８時間加熱重合した。得られた膜状物
を９８％濃硫酸と純度９０％以上のクロロスルホン酸の
１：１（重量比）の混合物中に４０℃で４５分間浸漬
し、スルホン酸型陽イオン交換膜を得た。Subsequently, the porous film was taken out of the monomer composition, and both sides of the porous film were covered with a 100 μm polyester film as a release material. Then, at 80 ° C. for 8 hours under a nitrogen pressure of 0.4 MPa. Heat polymerization was performed. The obtained membrane was immersed in a 1: 1 (weight ratio) mixture of 98% concentrated sulfuric acid and chlorosulfonic acid having a purity of 90% or more at 40 ° C. for 45 minutes to obtain a sulfonic acid type cation exchange membrane. .
【０１０８】次いで、該陰イオン交換膜を１ｗｔ％のＦ
ｅＣｌ2水溶液に、室温で２４時間浸漬してＦｅ2+型と
した後、２ｗｔ％Ｈ2Ｏ2水溶液に室温で３０分間浸漬し
て、膜表面のイオン交換樹脂を除去した。Next, the anion exchange membrane was changed to 1 wt% F
After being immersed in an aqueous solution of eCl 2 for 24 hours at room temperature to form an Fe 2+ type, it was immersed in an aqueous solution of 2 wt% H 2 O 2 for 30 minutes at room temperature to remove the ion exchange resin on the membrane surface.
【０１０９】得られたイオン交換膜の膜表面をＳＥＭで
観察したところ、微多孔性膜表面特有の微細孔構造が観
察され、更に、１ｗｔ％ＦｅＣｌ2水溶液に浸漬してＦ
ｅ2+型にイオン交換し、ＳＥＭ−ＥＤＳで膜表面におけ
るＦｅ元素の定状分析を行った結果、Ｆｅに帰属するピ
ークが観察されなかったことから、膜表面のイオン交換
樹脂が除去されていることが確認された。[0109] When a film surface of the obtained ion-exchange membrane was observed by SEM, microporous membrane surface unique microporous structure is observed, further, was immersed in 1 wt% FeCl 2 solution F
After ion-exchange to e 2+ type and performing a routine analysis of Fe element on the film surface by SEM-EDS, no peak attributed to Fe was observed, so the ion-exchange resin on the film surface was removed. It was confirmed that.
【０１１０】得られた陰イオン交換膜の陥没深度、イオ
ン交換容量、含水率、膜抵抗、耐有機汚染性、水酸化ナ
トリウムと水酸化アルミニウムの透過速度を測定した。
これらの結果を表２に示す。The depth of depression, ion exchange capacity, water content, membrane resistance, resistance to organic contamination, and permeation speed of sodium hydroxide and aluminum hydroxide of the obtained anion exchange membrane were measured.
Table 2 shows the results.
【０１１１】比較例２ Ｈ2Ｏ2水溶液による処理を行わない点を除き実施例２と
同様にして陽イオン交換膜を得た。Comparative Example 2 A cation exchange membrane was obtained in the same manner as in Example 2 except that the treatment with the H 2 O 2 aqueous solution was not performed.
【０１１２】このイオン交換膜について、ＳＥＭ観察を
行った結果、膜表面に微多孔性膜特有の微細孔構造は観
察されず、更に、Ｆｅ2+型にイオン交換した膜の膜表面
にＦｅ元素の存在が確認されたことから、イオン交換樹
脂が膜表面に露出していることが確認された。As a result of SEM observation of this ion exchange membrane, no microporous structure peculiar to the microporous membrane was observed on the membrane surface, and further, Fe element was added to the membrane surface of the ion-exchanged membrane of Fe 2+ type. It was confirmed that the ion-exchange resin was exposed on the membrane surface.
【０１１３】得られた陰イオン交換膜は、実施例２と同
様に特性を測定した。結果を表２に示す。The characteristics of the obtained anion exchange membrane were measured in the same manner as in Example 2. Table 2 shows the results.
【０１１４】実施例３〜７ 表３に示す重量平均分子量１０万のポリエチレンよりな
り、延伸法によって得られた市販の微多孔性膜に、表３
に示す単量体組成物を実施例１と同様にして充填した。Examples 3 to 7 Commercially available microporous membranes made of polyethylene having a weight average molecular weight of 100,000 and obtained by a stretching method as shown in Table 3
Was filled in the same manner as in Example 1.
【０１１５】続いて、多孔質膜を単量体組成物中から取
り出し、１００μｍのポリエステルフィルムを剥離材と
して多孔質膜の両側を被覆した後、０．４ＭＰａの窒素
加圧下、４５℃で３時間−７５℃で５時間加熱重合し
た。Subsequently, the porous film was taken out of the monomer composition, and both sides of the porous film were covered with a 100 μm polyester film as a release material. Then, the mixture was heated at 45 ° C. for 3 hours under a nitrogen pressure of 0.4 MPa. Heat polymerization was carried out at -75 ° C for 5 hours.
【０１１６】得られた膜状物をヨウ化メチルとｎ−ヘキ
サンの１：３（重量比）の混合物中に３０℃で２４時間
浸漬し、ピリジニウム型陰イオン交換膜を得た。The obtained membrane was immersed in a mixture of methyl iodide and n-hexane at a ratio of 1: 3 (weight ratio) at 30 ° C. for 24 hours to obtain a pyridinium type anion exchange membrane.
【０１１７】これらの陰イオン交換膜の表面をＳＥＭ観
察したところ、いずれの陰イオン交換膜においても、実
施例１と同様に膜表面からイオン交換樹脂が除去されて
いることが確認された。When the surfaces of these anion exchange membranes were observed by SEM, it was confirmed that the ion exchange resin was removed from the surface of each of the anion exchange membranes as in Example 1.
【０１１８】このピリジニウム型陰イオン交換膜のイオ
ン交換樹脂部の陥没深度、膜厚、イオン交換容量、含水
率、膜抵抗、硫酸と硫酸マグネシウムの透過速度、耐有
機汚染性を測定した。この結果を表４に示した。The depth of depression, film thickness, ion exchange capacity, water content, membrane resistance, permeation rate of sulfuric acid and magnesium sulfate, and organic stain resistance of this pyridinium type anion exchange membrane were measured. The results are shown in Table 4.
【０１１９】比較例３ 表３の微多孔性膜Ａを用い、４−ビニルピリジン６６重
量部、スチレン３０重量部、ジビニルベンゼン４重量部
およびｔ−ブチルパーオキシエチルヘキサノエート５重
量部よりなる単量体組成物を用いた以外は、実施例３〜
７と同様にしてピリジニウム型陰イオン交換膜を得た。Comparative Example 3 Using the microporous membrane A shown in Table 3, was composed of 66 parts by weight of 4-vinylpyridine, 30 parts by weight of styrene, 4 parts by weight of divinylbenzene and 5 parts by weight of t-butylperoxyethylhexanoate. Except that the monomer composition was used, Examples 3 to
In the same manner as in 7, a pyridinium-type anion exchange membrane was obtained.
【０１２０】この陰イオン交換膜の表面をＳＥＭ観察し
たところ、比較例１と同様に膜表面にイオン交換樹脂が
露出していることが確認された。When the surface of this anion exchange membrane was observed by SEM, it was confirmed that the ion exchange resin was exposed on the membrane surface as in Comparative Example 1.
【０１２１】このピリジニウム型陰イオン交換膜は、実
施例３〜７と同様にして特性を測定した。結果を表４に
示す。The characteristics of this pyridinium type anion exchange membrane were measured in the same manner as in Examples 3 to 7. Table 4 shows the results.
【０１２２】[0122]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 [Table 3]
【表４】 [Table 4]
【図１】 本発明のイオン交換樹脂を概念的に示す断面
図FIG. 1 is a sectional view conceptually showing an ion exchange resin of the present invention.
【図２】 従来のイオン交換樹脂を概念的に示す断面図FIG. 2 is a sectional view conceptually showing a conventional ion exchange resin.
【符号の説明】 １ 微多孔性膜 ２ 微細孔 ３ イオン交換樹脂 ４ 微多孔性膜表面 Ａ 陥没深度[Description of Signs] 1 Microporous membrane 2 Micropores 3 Ion exchange resin 4 Microporous membrane surface A Depression depth
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D006 GA17 MA03 MA12 MA22 MA23 MA24 MA40 MB07 MC22X MC23 MC26 MC27 MC28 MC30 MC54 NA34 NA54 NA66 PA01 PB12 PB13 PB27 PC11 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D006 GA17 MA03 MA12 MA22 MA23 MA24 MA40 MB07 MC22X MC23 MC26 MC27 MC28 MC30 MC54 NA34 NA54 NA66 PA01 PB12 PB13 PB27 PC11
Claims (7)
充填されて成り、該微多孔性膜の少なくとも片面に存在
する微細孔において、上記イオン交換樹脂が微多孔性膜
表面より陥没した位置で露出したことを特徴とするイオ
ン交換膜。An ion exchange resin is filled in voids of a microporous membrane, and the ion exchange resin is depressed from the surface of the microporous membrane in micropores present on at least one surface of the microporous membrane. An ion-exchange membrane exposed at a position.
ィルムよりなる請求項１記載のイオン交換膜。2. The ion exchange membrane according to claim 1, wherein the microporous membrane comprises a stretched polyolefin film.
ｍ以下であり、且つ、微細孔の占める面積が全面積の３
〜６０％である請求項１記載のイオン交換膜。3. The method according to claim 1, wherein the maximum diameter of the micropores is 5 μm on the membrane surface.
m and the area occupied by the micropores is 3% of the total area.
The ion-exchange membrane according to claim 1, wherein the amount is from 60% to 60%.
入可能な官能基又はイオン交換基を有する単量体、架橋
性単量体、および重合開始剤を含有する単量体組成物を
含浸せしめた後、該単量体組成物を重合せしめてイオン
交換樹脂又はイオン交換樹脂前駆体を生成し、次いで、
該微細孔内の膜表面近傍に存在するイオン交換樹脂又は
イオン交換樹脂前駆体を除去することを特徴とするイオ
ン交換膜の製造方法。4. A monomer composition containing a monomer having a functional group capable of introducing an ion-exchange group or an ion-exchange group, a crosslinkable monomer, and a polymerization initiator in the space of the microporous membrane. After impregnation, the monomer composition is polymerized to produce an ion exchange resin or an ion exchange resin precursor,
A method for producing an ion-exchange membrane, comprising removing an ion-exchange resin or an ion-exchange resin precursor existing near the membrane surface in the micropores.
体の除去手段が、微多孔性膜の表面を酸化剤と接触させ
る方法である請求項４記載のイオン交換膜の製造方法。5. The method for producing an ion exchange membrane according to claim 4, wherein the means for removing the ion exchange resin or the ion exchange resin precursor is a method of bringing the surface of the microporous membrane into contact with an oxidizing agent.
ある請求項５記載のイオン交換膜の製造方法。6. The method according to claim 5, wherein the oxidizing agent is hydrogen peroxide or hypochlorous acid.
び通気度が２０〜１５００秒／１００ｃｃであり、且つ
膜表面における最大孔径が５μｍ以下である請求項４〜
９記載のイオン交換膜の製造方法。7. The microporous membrane according to claim 4, wherein the porosity is 20 to 80%, the air permeability is 20 to 1500 sec / 100 cc, and the maximum pore size on the membrane surface is 5 μm or less.
10. The method for producing an ion exchange membrane according to item 9.
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