JP2000229227A - Porous polymer membrane provided with hydrophilic property and its production - Google Patents
Porous polymer membrane provided with hydrophilic property and its productionInfo
- Publication number
- JP2000229227A JP2000229227A JP3253699A JP3253699A JP2000229227A JP 2000229227 A JP2000229227 A JP 2000229227A JP 3253699 A JP3253699 A JP 3253699A JP 3253699 A JP3253699 A JP 3253699A JP 2000229227 A JP2000229227 A JP 2000229227A
- Authority
- JP
- Japan
- Prior art keywords
- porous polymer
- polymer membrane
- hydrophilic
- resin material
- hydrophilized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は親水化多孔質高分子
膜とその製造方法に関するもので、さらに詳しく言え
ば、医療用の無菌水の製造、飲料水または食品製造用の
精製水の製造に適した親水化多孔質高分子膜とその製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic porous polymer membrane and a method for producing the same, and more particularly, to the production of sterile water for medical use and purified water for drinking water or food production. The present invention relates to a suitable hydrophilized porous polymer membrane and a method for producing the same.
【０００２】[0002]
【従来の技術】医療用の無菌水の製造、飲料水または食
品製造用の精製水の製造に適した親水化多孔質高分子膜
は、これらの製造過程の濾過や電解で使用され、乾燥と
湿潤を反復させても親水性を維持することが必須とされ
ている。2. Description of the Related Art Hydrophilized porous polymer membranes suitable for the production of sterile water for medical use, purified water for the production of drinking water or food are used for filtration and electrolysis in these production processes, and for drying and drying. It is essential to maintain hydrophilicity even after repeated wetting.
【０００３】上記した用途に用いられる親水化多孔質高
分子膜には素材が親水性材料からなるものと撥水性材料
からなるものとがあり、前者のものとしては酢酸セルロ
ース膜等があり、後者のものとしてはポリエチレンやポ
リプロピレンなどのポリオレフィン系のもの、ポリ塩化
ビニルやポリフッ化ビニリデンなどのビニル系のもの、
ポリスルホンなどのエンジニアリングプラスチック系の
もの等がある。There are two types of hydrophilic porous polymer membranes used for the above-mentioned applications: those made of a hydrophilic material and those made of a water-repellent material. The former includes a cellulose acetate membrane and the like. The thing of the polyolefin type such as polyethylene and polypropylene, the vinyl type such as polyvinyl chloride and polyvinylidene fluoride,
There are engineering plastics such as polysulfone.
【０００４】親水性材料からなるものは、素材自体が親
水性を有しているため、特別な処理を施さずに使用でき
るという長所があるが、素材の物理的、化学的強度が小
さいため、取扱いに注意を要するという欠点がある。ま
た、撥水性材料からなるものは、素材の物理的、化学的
強度が大きく、使用目的に応じて種々の選択ができると
いう長所があるが、素材に親水性を付与するための処理
を行わなければならないという欠点がある。そして、こ
のような素材に親水性を付与するのにも多様な方法があ
る。たとえば、撥水性材料からなる素材に界面活性剤を
塗布して乾燥させることによって親水化する方法、ポリ
ビニルアルコールやポリエチレングリコールのような水
溶性高分子を膜の細孔内に含浸させ、該高分子を熱処
理、アセタール化処理、エステル化処理、重クロム酸処
理、電離性放射線照射によって親水化する方法などがあ
る。A material made of a hydrophilic material has an advantage that it can be used without special treatment because the material itself has hydrophilicity. However, since the material has a small physical and chemical strength, There is a disadvantage that care must be taken in handling. In addition, a material made of a water-repellent material has the advantage that the material has a large physical and chemical strength and can be variously selected according to the purpose of use. However, a treatment for imparting hydrophilicity to the material must be performed. There is a disadvantage that it must be done. There are various methods for imparting hydrophilicity to such a material. For example, a method of applying a surfactant to a material made of a water-repellent material and drying the material to make it hydrophilic, or impregnating pores of a membrane with a water-soluble polymer such as polyvinyl alcohol or polyethylene glycol, Heat treatment, acetalization treatment, esterification treatment, dichromic acid treatment, and a method of hydrophilizing by ionizing radiation irradiation.
【０００５】[0005]
【発明が解決しようとする課題】親水性材料を素材とす
るものは、素材の物理的、化学的強度が小さいため、長
期間の使用に耐えられないという問題があり、撥水性材
料を素材とするものに、界面活性剤を塗布して乾燥させ
ることによって親水性を付与したものでは、長期間の使
用によって界面活性剤が溶出して親水性が失われるとい
う問題があり、水溶性高分子を膜の細孔内に含浸させ、
該高分子を熱処理、アセタール化処理、エステル化処
理、重クロム酸処理、電離性放射線照射することによっ
て親水性を付与したものでは、親水化のための工程が複
雑であり、コストが高くなるという問題がある。A material made of a hydrophilic material has a problem that the material cannot be used for a long time because the material has low physical and chemical strength. In the case where the surfactant is applied and dried to impart hydrophilicity, there is a problem that the surfactant is eluted by long-term use and the hydrophilicity is lost. Impregnated into the pores of the membrane,
In the case where the polymer is made hydrophilic by heat treatment, acetalization treatment, esterification treatment, dichromic acid treatment, or irradiation with ionizing radiation, the process for hydrophilization is complicated and the cost increases. There's a problem.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するた
め、請求項１記載の発明は、基材に樹脂材料と親水性高
分子を含有させたことを特徴とする親水化多孔質高分子
膜であり、これにより、複雑な親水化のための工程を必
要とせず、長期間の使用に耐えることができる親水化多
孔質高分子膜を得ることができる。According to a first aspect of the present invention, there is provided a hydrophilized porous polymer membrane comprising a base material containing a resin material and a hydrophilic polymer. This makes it possible to obtain a hydrophilized porous polymer membrane that does not require complicated steps for hydrophilization and can withstand long-term use.
【０００７】また、請求項２記載の発明は、樹脂材料は
ポリ塩化ビニル樹脂または塩素化ポリ塩化ビニル樹脂の
少なくとも一方からなることを特徴とする請求項１記載
の親水化多孔質高分子膜であり、これにより、物理的、
化学的強度が大きい親水化多孔質高分子膜を得ることが
できる。According to a second aspect of the present invention, the resin material is made of at least one of a polyvinyl chloride resin and a chlorinated polyvinyl chloride resin. Yes, this allows physical,
A hydrophilized porous polymer membrane having high chemical strength can be obtained.
【０００８】また、請求項３記載の発明は、親水性高分
子はセルロース誘導体であることを特徴とする請求項１
または２記載の親水化多孔質高分子膜であり、これによ
り、長期間使用しても、親水性が保持できる親水化多孔
質高分子膜を得ることができる。[0008] The invention according to claim 3 is characterized in that the hydrophilic polymer is a cellulose derivative.
Or the hydrophilized porous polymer membrane described in 2 above, whereby a hydrophilized porous polymer membrane capable of maintaining hydrophilicity even after long-term use can be obtained.
【０００９】また、請求項４記載の発明は、基材は織布
または不織布であることを特徴とする請求項１〜３のい
ずれか一項記載の親水化多孔質高分子膜であり、これに
より、物理的強度が大きく、柔軟性にすぐれた親水化多
孔質高分子膜を得ることができる。According to a fourth aspect of the present invention, there is provided the hydrophilic porous polymer membrane according to any one of the first to third aspects, wherein the base material is a woven fabric or a nonwoven fabric. This makes it possible to obtain a hydrophilic porous polymer membrane having high physical strength and excellent flexibility.
【００１０】また、請求項５記載の発明は、親水性高分
子は樹脂材料の少なくとも３重量％含有させたことを特
徴とする請求項１〜４記載の親水化多孔質高分子膜であ
り、これにより、医療用の無菌水の製造過程、飲料水ま
たは食品製造用の精製水の製造過程の濾過や電解に対応
できる程度の親水性を確保することができ、長期間の使
用や乾燥と湿潤を反復させても親水性が保持できる親水
化多孔質高分子膜を得ることができる。According to a fifth aspect of the present invention, there is provided the hydrophilic porous polymer membrane according to the first to fourth aspects, wherein the hydrophilic polymer is contained at least 3% by weight of the resin material. As a result, it is possible to ensure hydrophilicity enough to cope with filtration and electrolysis in the manufacturing process of sterile water for medical use, the manufacturing process of purified water for drinking water or food production, and to use and dry and wet for a long time. Can be obtained to obtain a hydrophilized porous polymer membrane that can maintain hydrophilicity even when the above is repeated.
【００１１】また、請求項６記載の発明は、溶剤に樹脂
材料と親水性高分子としてのセルロース誘導体とを溶解
させ、これに非溶剤を添加して混合し、得られた混合液
を基材に塗布して乾燥させることを特徴とする親水化多
孔質高分子膜の製造方法であり、これにより、親水性高
分子としてのセルロース誘導体を均一に保持させた親水
化多孔質高分子膜を得ることができる。[0011] The invention according to claim 6 is to dissolve a resin material and a cellulose derivative as a hydrophilic polymer in a solvent, add a non-solvent thereto and mix the resultant, and obtain a mixed liquid as a substrate. A method for producing a hydrophilized porous polymer membrane, characterized in that it is coated and dried to obtain a hydrophilized porous polymer membrane in which a cellulose derivative as a hydrophilic polymer is uniformly held. be able to.
【００１２】また、請求項７記載の発明は、請求項６記
載の多孔質高分子膜の製造方法において、セルロース誘
導体は樹脂材料の少なくとも３重量％含有させたことを
特徴とするものであり、これにより、医療用の無菌水の
製造過程、飲料水または食品製造用の精製水の製造過程
の濾過や電解に対応できる程度の親水性が確保でき、長
期間の使用や乾燥と湿潤を反復させても親水性が保持で
きる親水化多孔質高分子膜を容易に製造することができ
る。According to a seventh aspect of the present invention, in the method for producing a porous polymer membrane according to the sixth aspect, the cellulose derivative is contained in at least 3% by weight of the resin material. As a result, it is possible to secure hydrophilicity enough to cope with filtration and electrolysis in the manufacturing process of sterile water for medical use, the manufacturing process of purified water for drinking water or food production, and to repeatedly use and dry and wet for a long time. Thus, a hydrophilic porous polymer membrane that can maintain hydrophilicity can be easily produced.
【００１３】[0013]
【発明の実施の形態】以下、本発明をその実施の形態に
基づいて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on its embodiments.
【００１４】本発明の実施の形態に係る親水化多孔質高
分子膜の特徴は、基材に樹脂材料と親水性高分子を含有
させたことである。A feature of the hydrophilized porous polymer membrane according to the embodiment of the present invention is that a base material contains a resin material and a hydrophilic polymer.
【００１５】前記樹脂材料はポリ塩化ビニル樹脂または
塩素化ポリ塩化ビニル樹脂の少なくとも一方からなり、
前記親水性高分子には、セルロースにアセチル基、ヘキ
サヒドロフタレート基のような疎水性基が導入されたセ
ルロースアセテートヘキサヒドロフタレート、水溶性セ
ルロース誘導体の一つであるヒドロキシプロピルメチル
セルロースの基本骨格にカルボキシベンゾイル基、アセ
チル基、サクシネート基、ヘキサヒドロフタレート基の
ような疎水性基が導入された、水溶性でないセルロース
誘導体の一つであるヒドロキシプロピルメチルセルロー
スフタレート等が用いられる。The resin material comprises at least one of a polyvinyl chloride resin and a chlorinated polyvinyl chloride resin,
The hydrophilic polymer includes cellulose acetate hexahydrophthalate in which a hydrophobic group such as acetyl group and hexahydrophthalate group is introduced into cellulose, and carboxy group is added to the basic skeleton of hydroxypropyl methylcellulose which is one of water-soluble cellulose derivatives. Hydroxypropyl methylcellulose phthalate, which is one of the non-water-soluble cellulose derivatives into which a hydrophobic group such as a benzoyl group, an acetyl group, a succinate group, and a hexahydrophthalate group has been introduced, is used.
【００１６】また、本発明の実施の形態に係る親水化多
孔質高分子膜の製造方法の特徴は、溶剤に樹脂材料と親
水性高分子としてのセルロース誘導体とを溶解させ、こ
れに非溶剤を添加して混合し、得られた混合液を基材に
塗布して乾燥させることである。The feature of the method for producing a hydrophilic porous polymer membrane according to the embodiment of the present invention is that a resin material and a cellulose derivative as a hydrophilic polymer are dissolved in a solvent, and a non-solvent is added thereto. It is to add and mix, apply the resulting mixture to a substrate, and dry it.
【００１７】本発明の実施の形態に係る親水化多孔質高
分子膜Ａ１として、４０℃の温度下で、溶剤としてのテ
トラヒドロフラン１２６．０ｇに、樹脂材料としての塩
素化ポリ塩化ビニル樹脂１８ｇ．０と親水性高分子とし
てのヒドロキシプロピルメチルセルロースフタレート
０．２７ｇ（親水性高分子は樹脂材料の１．５重量％に
相当）とを溶解させ、これに非溶剤としてのイソプロピ
ルアルコール５６．０ｇを徐々に添加し、３０℃の温度
下で、２４時間攪拌して混合させ、得られた混合液を、
厚さが０．０８ｍｍ、目付けが４０ｇ／ｍ2 のポリエス
テル製不織布に塗布し、温度が３０℃、湿度が７５％の
雰囲気下で乾燥させたものを、同Ａ２として、親水性高
分子としてのヒドロキシプロピルメチルセルロースフタ
レートを０．５４ｇ（親水性高分子は樹脂材料の３．０
重量％に相当）溶解させたものを、同Ａ３として、親水
性高分子としてのヒドロキシプロピルメチルセルロース
フタレートを０．８１ｇ（親水性高分子は樹脂材料の
４．５重量％に相当）溶解させたものを、同Ａ４とし
て、親水性高分子としてのヒドロキシプロピルメチルセ
ルロースフタレートを１．０８ｇ（親水性高分子は樹脂
材料の６．０重量％に相当）溶解させたものをそれぞれ
準備し、従来の親水化多孔質高分子膜Ｂとして、４０℃
の温度下で、溶剤としてのテトラヒドロフラン１２６．
０ｇに、樹脂材料としての塩素化ポリ塩化ビニル樹脂１
８．０ｇを添加し、４８時間攪拌して溶解させ、これに
非溶剤としてのイソプロピルアルコール５６．０ｇを徐
々に添加し、３０℃の温度下で、２４時間攪拌して混合
させ、得られた混合液を、厚さが０．０８ｍｍ、目付け
が４０ｇ／ｍ2 のポリエステル製不織布に塗布し、温度
が３０℃、湿度が７５％の雰囲気下で乾燥させた後、界
面活性剤としてのショ糖脂肪酸エステルを溶解させたイ
ソプロピルアルコール中に浸漬して親水化処理したもの
を準備した。As the hydrophilized porous polymer membrane A1 according to the embodiment of the present invention, 18 g of a chlorinated polyvinyl chloride resin as a resin material was added to 126.0 g of tetrahydrofuran as a solvent at a temperature of 40 ° C. 0 and 0.27 g of hydroxypropylmethylcellulose phthalate as a hydrophilic polymer (the hydrophilic polymer is equivalent to 1.5% by weight of the resin material), and 56.0 g of isopropyl alcohol as a non-solvent is gradually added thereto. , And stirred and mixed at a temperature of 30 ° C. for 24 hours.
What was applied to a non-woven fabric made of polyester having a thickness of 0.08 mm and a basis weight of 40 g / m 2 and dried in an atmosphere at a temperature of 30 ° C. and a humidity of 75% was designated as A2 as a hydrophilic polymer. 0.54 g of hydroxypropyl methylcellulose phthalate (the hydrophilic polymer is 3.0 of resin material)
A3 was prepared by dissolving 0.81 g of hydroxypropylmethylcellulose phthalate as a hydrophilic polymer (the hydrophilic polymer was equivalent to 4.5% by weight of the resin material). A4 was prepared by dissolving 1.08 g of hydroxypropylmethylcellulose phthalate as a hydrophilic polymer (the hydrophilic polymer was equivalent to 6.0% by weight of the resin material) as A4. 40 ° C. as the porous polymer membrane B
At a temperature of 126.
0g, chlorinated polyvinyl chloride resin 1 as resin material
8.0 g was added and dissolved by stirring for 48 hours, and 56.0 g of isopropyl alcohol as a non-solvent was gradually added thereto, followed by stirring and mixing at a temperature of 30 ° C. for 24 hours to obtain. The mixture is applied to a polyester nonwoven fabric having a thickness of 0.08 mm and a basis weight of 40 g / m 2 , dried under an atmosphere of a temperature of 30 ° C. and a humidity of 75%, and then sucrose as a surfactant. What was hydrophilized by immersing in isopropyl alcohol in which a fatty acid ester was dissolved was prepared.
【００１８】（評価試験１）上記した本発明の実施の形
態に係る親水化多孔質高分子膜Ａ３と従来の親水化多孔
質高分子膜Ｂとについて、膜からの溶出物を比較するた
め、各々を、２ミリリットル／ｃｍ2 の割合で、温度が
６０℃の蒸留水に３０分間浸漬し、浸漬液の過マンガン
酸カリウム消費量を測定した。(Evaluation Test 1) In order to compare the eluted substances from the hydrophilicized porous polymer membrane A3 according to the embodiment of the present invention and the conventional hydrophilicized porous polymer membrane B, Each was immersed in distilled water at a temperature of 60 ° C. for 30 minutes at a rate of 2 ml / cm 2 , and the amount of potassium permanganate consumed by the immersion liquid was measured.
【００１９】この評価試験１によれば、親水化多孔質高
分子膜Ａ３では過マンガン酸カリウムの消費量が０．６
ｍｇ／リットルであったのに対し、親水化多孔質高分子
膜Ｂではそれが５．５ｍｇ／リットルであった。同様の
試験を親水化処理をしていない従来の膜で行ったとこ
ろ、０．６ｍｇ／リットルであった。According to this evaluation test 1, the consumption of potassium permanganate was 0.6 in the hydrophilic porous polymer membrane A3.
mg / L, whereas that of the hydrophilic porous polymer membrane B was 5.5 mg / L. When the same test was performed on a conventional membrane that had not been subjected to a hydrophilic treatment, the result was 0.6 mg / liter.
【００２０】（評価試験２）上記した本発明の実施の形
態に係る親水化多孔質高分子膜Ａ３と従来の親水化多孔
質高分子膜Ｂとについて、膜からの溶出物を比較するた
め、各々を、２ミリリットル／ｃｍ2 の割合で、沸騰し
た蒸留水に３０分間浸漬し、浸漬液の過マンガン酸カリ
ウム消費量を測定した。(Evaluation Test 2) In order to compare the eluted substances from the hydrophilic porous polymer membrane A3 according to the embodiment of the present invention and the conventional hydrophilic porous polymer membrane B, Each was immersed in boiling distilled water at a rate of 2 ml / cm 2 for 30 minutes, and the amount of potassium permanganate consumed by the immersion liquid was measured.
【００２１】この評価試験２によれば、親水化多孔質高
分子膜Ａ３では過マンガン酸カリウムの消費量が０．６
ｍｇ／リットルであったのに対し、親水化多孔質高分子
膜Ｂではそれが４．１ｍｇ／リットルであった。同様の
試験を親水化処理をしていない従来の膜で行ったとこ
ろ、０．６ｍｇ／リットルであった。According to this evaluation test 2, the consumption of potassium permanganate was 0.6% in the hydrophilic porous polymer membrane A3.
mg / L, whereas that of the hydrophilized porous polymer membrane B was 4.1 mg / L. When the same test was performed on a conventional membrane that had not been subjected to a hydrophilic treatment, the result was 0.6 mg / liter.
【００２２】（評価試験３）上記した本発明の実施の形
態に係る親水化多孔質高分子膜Ａ３と従来の親水化多孔
質高分子膜Ｂとについて、乾燥と湿潤とを反復させたこ
とによる親水性の劣化を比較するため、各々を、常温の
水道水を５リットル／分で流した流水中に１２時間浸漬
し、その後４０℃に設定した温風乾燥機中で３０分間乾
燥させ、その後常温の水道水中に浮かせる過程を反復さ
せた。(Evaluation Test 3) Drying and wetting were repeated for the hydrophilic porous polymer membrane A3 according to the embodiment of the present invention and the conventional hydrophilic porous polymer membrane B. In order to compare the deterioration of hydrophilicity, each was immersed in running water of normal temperature tap water at a flow rate of 5 L / min for 12 hours, and then dried in a hot air dryer set at 40 ° C. for 30 minutes. The process of floating in tap water at room temperature was repeated.
【００２３】この評価試験３によれば、親水化多孔質高
分子膜Ｂでは８４時間後に濡れなくなったのに対し、親
水化多孔質高分子膜Ａ３では９６時間後も一瞬にして濡
れることがわかった。According to this evaluation test 3, it was found that the hydrophilic porous polymer membrane B did not wet after 84 hours, whereas the hydrophilic porous polymer membrane A3 instantly became wet after 96 hours. Was.
【００２４】（評価試験４）上記した本発明の実施の形
態に係る親水化多孔質高分子膜Ａ３と従来の親水化多孔
質高分子膜Ｂとについて、乾燥と湿潤とを反復させたこ
とによる親水性の劣化を比較するため、各々を、網籠に
入れて７５℃の水道水を満たした攪拌器付の恒温水槽中
に浸漬して６時間攪拌し、その後４０℃に設定した温風
乾燥機中で３０分間乾燥させ、その後常温の水道水中に
浮かせる過程を反復させた。(Evaluation Test 4) Drying and wetting were repeated for the hydrophilic porous polymer membrane A3 according to the embodiment of the present invention and the conventional hydrophilic porous polymer membrane B. To compare the deterioration of hydrophilicity, each was put in a net basket, immersed in a constant temperature water tank with a stirrer filled with 75 ° C tap water, stirred for 6 hours, and then dried with hot air set at 40 ° C. The process of drying in a machine for 30 minutes and then floating in normal-temperature tap water was repeated.
【００２５】この評価試験４によれば、親水化多孔質高
分子膜Ｂでは１８時間後に濡れなくなったのに対し、親
水化多孔質高分子膜Ａ３では２４時間後も一瞬にして濡
れることがわかった。According to this evaluation test 4, it was found that the hydrophilic porous polymer membrane B did not wet after 18 hours, whereas the hydrophilic porous polymer membrane A3 instantly became wet after 24 hours. Was.
【００２６】（評価試験５）上記した本発明の実施の形
態に係る親水化多孔質高分子膜Ａ１，Ａ２，Ａ３，Ａ４
と従来の親水化多孔質高分子膜Ｂとを電解隔膜として使
用した場合の親水性の劣化を比較するため、各々に電
極、スペーサーを配して電解セルを組み立て、これらを
互いに並列に接続し、水道水の電解に供した。電解の条
件は直流１０Ｖの定電圧を印加し、１０分ごとに各電解
セルの電流値を測定するとともに、１時間ごとに電解セ
ルをビーカーから取り出し、４０℃に設定した温風乾燥
機中で６０分間乾燥させた後再度ビーカー内に浸漬して
電解を継続するという過程を反復させた。(Evaluation Test 5) The hydrophilized porous polymer membranes A1, A2, A3, A4 according to the embodiment of the present invention described above.
In order to compare the deterioration of hydrophilicity when using the conventional hydrophilic polymer porous membrane B with the conventional hydrophilic polymer membrane B, electrodes and spacers were arranged on each of them to assemble an electrolytic cell, and these were connected in parallel with each other. For tap water electrolysis. The electrolysis conditions were as follows: apply a constant voltage of DC 10 V, measure the current value of each electrolytic cell every 10 minutes, take out the electrolytic cell from the beaker every hour, and in a hot air dryer set at 40 ° C. After drying for 60 minutes, the process of immersing in a beaker again to continue electrolysis was repeated.
【００２７】この評価試験５によれば、親水化多孔質高
分子膜Ｂでは、最初の電解開始直後の電流は０．０８０
Ａであり、３０分後の電流は０．０６４Ａであり、２回
目の電解開始直後の電流は０．０４０Ａであり、３回目
の電解開始直後の電流は０．０３６Ａで、その後１時間
はほぼ一定に推移したのに対し、親水化多孔質高分子膜
Ａ１，Ａ２，Ａ３，Ａ４では、いずれも３回目の電解が
終了するまでほぼ一定に推移したが、親水化多孔質高分
子膜Ａ１は、親水化多孔質高分子膜Ａ２，Ａ３，Ａ４に
比較して親水性高分子の含有量が小さいために電解時の
電流は小さく推移したことがわかった。なお、電解に使
用した水道水の電導度は０．３３ｍＳ／ｃｍ2 で、ほぼ
一定であった。According to this evaluation test 5, in the hydrophilic porous polymer membrane B, the current immediately after the start of the first electrolysis was 0.080.
A, the current after 30 minutes is 0.064 A, the current immediately after the start of the second electrolysis is 0.040 A, the current immediately after the start of the third electrolysis is 0.036 A, and after that, approximately one hour after that. On the other hand, in the hydrophilized porous polymer membranes A1, A2, A3, and A4, they all remained almost constant until the third electrolysis was completed. On the other hand, it was found that the current during electrolysis was small because the content of the hydrophilic polymer was small as compared with the hydrophilic porous polymer membranes A2, A3 and A4. The electric conductivity of tap water used for electrolysis was 0.33 mS / cm 2 , which was almost constant.
【００２８】上記した評価試験１〜５から、本発明に係
る親水化多孔質高分子膜Ａ１，Ａ２，Ａ３，Ａ４は、種
々の過酷な試験によっても親水性は失われないことがわ
かるとともに、評価試験５から、電解に対応できる程度
の親水性を得るためには、親水性高分子は少なくとも３
重量％含有させるとよいことがわかる。From the evaluation tests 1 to 5 described above, it is found that the hydrophilic porous polymer membranes A1, A2, A3, and A4 according to the present invention do not lose their hydrophilicity even after various severe tests. From the evaluation test 5, in order to obtain hydrophilicity enough to cope with electrolysis, the hydrophilic polymer should be at least 3
It is understood that it is better to make the content by weight%.
【００２９】また、上記した評価試験１〜５では、塩素
化ポリ塩化ビニル樹脂１８．０ｇを用いて平均孔径が
０．９μｍの親水化多孔質高分子膜を作製したが、樹脂
を多くすれば作製しようとする膜の平均孔径を小さくす
ることができ、樹脂を少なくすれば作製しようとする膜
の平均孔径を大きくすることができるので、必要に応じ
て増減すればよいことは言うまでもない。また、塩素化
ポリ塩化ビニル樹脂に代えてポリ塩化ビニル樹脂を用い
てもよく、これらを混合させてもよい。In the above evaluation tests 1 to 5, a hydrophilized porous polymer membrane having an average pore diameter of 0.9 μm was prepared using 18.0 g of chlorinated polyvinyl chloride resin. The average pore diameter of the film to be produced can be reduced, and the average pore diameter of the film to be produced can be increased by reducing the amount of the resin. Needless to say, the average pore diameter may be increased or decreased as necessary. Further, a polyvinyl chloride resin may be used instead of the chlorinated polyvinyl chloride resin, and these may be mixed.
【００３０】また、上記した評価試験１〜５に供した親
水化多孔質高分子膜は、溶剤としてテトラヒドロフラン
を用いたが、ジメチルホルムアミドやジメチルスルホキ
シド等を用いてもよく、非溶剤としてイソプロピルアル
コールを用いたが、メチルアルコールやエチルアルコー
ル等を用いてもよい。In the hydrophilized porous polymer membranes used in the evaluation tests 1 to 5, tetrahydrofuran was used as a solvent, but dimethylformamide, dimethylsulfoxide, or the like may be used. Although used, methyl alcohol or ethyl alcohol may be used.
【００３１】[0031]
【発明の効果】上記した如く、本発明の親水化多孔質高
分子膜は、基材に樹脂材料と親水性高分子を含有させ、
該親水性高分子にセルロース誘導体を使用しているの
で、長期間使用しても親水性を維持することができると
ともに、濾液中に親水性高分子が溶出することもなく、
医療用の無菌水の製造や飲料水または食品製造用の精製
水の製造といった高純度の水を得るのに寄与することが
できる。As described above, the hydrophilic porous polymer membrane of the present invention comprises a base material containing a resin material and a hydrophilic polymer,
Since the cellulose derivative is used for the hydrophilic polymer, the hydrophilicity can be maintained even when used for a long time, and the hydrophilic polymer does not elute in the filtrate.
It can contribute to obtaining high-purity water such as the production of sterile water for medical use and the production of drinking water or purified water for food production.
【００３２】また、本発明の親水化多孔質高分子膜の製
造方法は、溶剤に樹脂材料と親水性高分子としてのセル
ロース誘導体とを溶解させ、これに非溶剤を添加して混
合し、得られた混合液を基材に塗布しているから、親水
性高分子を均一に保持させた膜を、複雑な工程を経るこ
となく作製することができ、コストの削減に寄与するこ
とができる。In the method for producing a hydrophilized porous polymer membrane according to the present invention, a resin material and a cellulose derivative as a hydrophilic polymer are dissolved in a solvent, and a non-solvent is added thereto and mixed. Since the obtained mixed solution is applied to the base material, a film in which the hydrophilic polymer is uniformly held can be manufactured without going through a complicated process, which can contribute to cost reduction.
【図１】本発明の実施の形態に係る親水化多孔質高分子
膜Ａ１，Ａ２，Ａ３，Ａ４と従来の親水化多孔質高分子
膜Ｂとを電解に用いた時の電流値の推移を示す図であ
る。FIG. 1 shows the transition of the current value when hydrophilized porous polymer membranes A1, A2, A3 and A4 according to an embodiment of the present invention and a conventional hydrophilized porous polymer membrane B are used for electrolysis. FIG.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０８Ｌ 1:02 27:06 (72)発明者 林 信夫 大阪府高槻市城西町６番６号 株式会社ユ アサコーポレーション内 Ｆターム(参考） 4D006 GA01 GA16 HA93 JA42Z MA03 MA22 MB02 MB09 MC16 MC26 MC27 NA10 NA60 NA64 PB06 PB24 PC11 PC41 PC52 4F074 AA02 AA35 AD04 AH03 BA73 CB37 CB47 DA20 DA24 DA54 DA59 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme Court II (Reference) // C08L 1:02 27:06 (72) Inventor Nobuo Hayashi 6-6 Josaicho, Takatsuki City, Osaka Stock 4D006 GA01 GA16 HA93 JA42Z MA03 MA22 MB02 MB09 MC16 MC26 MC27 NA10 NA60 NA64 PB06 PB24 PC11 PC41 PC52 4F074 AA02 AA35 AD04 AH03 BA73 CB37 CB47 DA20 DA24 DA54 DA59
Claims (7)
せたことを特徴とする親水化多孔質高分子膜。1. A hydrophilized porous polymer membrane comprising a base material containing a resin material and a hydrophilic polymer.
素化ポリ塩化ビニル樹脂の少なくとも一方からなること
を特徴とする請求項１記載の親水化多孔質高分子膜。2. The hydrophilic porous polymer membrane according to claim 1, wherein the resin material is made of at least one of a polyvinyl chloride resin and a chlorinated polyvinyl chloride resin.
ことを特徴とする請求項１または２記載の親水化多孔質
高分子膜。3. The hydrophilized porous polymer membrane according to claim 1, wherein the hydrophilic polymer is a cellulose derivative.
徴とする請求項１〜３のいずれか一項記載の親水化多孔
質高分子膜。4. The hydrophilized porous polymer membrane according to claim 1, wherein the substrate is a woven or nonwoven fabric.
重量％含有させたことを特徴とする請求項１〜４のいず
れか一項記載の親水化多孔質高分子膜。5. The method according to claim 1, wherein the hydrophilic polymer comprises at least three of the resin materials.
The hydrophilized porous polymer membrane according to any one of claims 1 to 4, which is contained by weight%.
セルロース誘導体とを溶解させ、これに非溶剤を添加し
て混合し、得られた混合液を基材に塗布して乾燥させる
ことを特徴とする親水化多孔質高分子膜の製造方法。6. A method in which a resin material and a cellulose derivative as a hydrophilic polymer are dissolved in a solvent, a non-solvent is added thereto and mixed, and the resulting mixture is applied to a substrate and dried. A method for producing a hydrophilized porous polymer membrane.
製造方法において、セルロース誘導体は樹脂材料の少な
くとも３重量％含有させることを特徴とする親水化多孔
質高分子膜の製造方法。7. The method for producing a hydrophilicized porous polymer membrane according to claim 6, wherein the cellulose derivative is contained in at least 3% by weight of the resin material.
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| JP3253699A JP4395904B2 (en) | 1999-02-10 | 1999-02-10 | Hydrophilized porous polymer membrane and method for producing the same |
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Cited By (7)
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|---|---|---|---|---|
| JP2007007488A (en) * | 2005-06-28 | 2007-01-18 | Ebara Corp | Water treatment method and apparatus using separation membrane |
| JP2011110472A (en) * | 2009-11-25 | 2011-06-09 | Fujifilm Corp | Microporous membrane of crystalline polymer, method of producing the same, and filter for use in filtration |
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1999
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007007488A (en) * | 2005-06-28 | 2007-01-18 | Ebara Corp | Water treatment method and apparatus using separation membrane |
| JP4671784B2 (en) * | 2005-06-28 | 2011-04-20 | 荏原エンジニアリングサービス株式会社 | Water treatment method and apparatus using separation membrane |
| CN101485961B (en) * | 2009-01-08 | 2013-01-30 | 杭州水处理技术研究开发中心有限公司 | Method for preparing polyvinylidene fluoride hollow fiber alloy film |
| JP2011110472A (en) * | 2009-11-25 | 2011-06-09 | Fujifilm Corp | Microporous membrane of crystalline polymer, method of producing the same, and filter for use in filtration |
| US9193815B2 (en) | 2010-03-04 | 2015-11-24 | Sekisui Chemical Co., Ltd. | Polymer membrane for water treatment and method for manufacture of same |
| JP5655963B1 (en) * | 2013-02-20 | 2015-01-21 | 東洋紡株式会社 | Polymeric porous flat membrane sheet made of polyvinylidene fluoride |
| WO2014199871A1 (en) * | 2013-06-11 | 2014-12-18 | 東洋紡株式会社 | Porous polymer flat-film sheet for mbr |
| WO2017111294A1 (en) * | 2015-12-24 | 2017-06-29 | 롯데정밀화학 주식회사 | Hydroxypropyl methylcellulose phthalate particles, and preparation method therefor |
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|---|---|
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