JP3305778B2 - Hydrophilized polysulfone-based resin hollow fiber membrane and method for producing the same - Google Patents
Hydrophilized polysulfone-based resin hollow fiber membrane and method for producing the sameInfo
- Publication number
- JP3305778B2 JP3305778B2 JP32419092A JP32419092A JP3305778B2 JP 3305778 B2 JP3305778 B2 JP 3305778B2 JP 32419092 A JP32419092 A JP 32419092A JP 32419092 A JP32419092 A JP 32419092A JP 3305778 B2 JP3305778 B2 JP 3305778B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- fiber membrane
- polysulfone
- resin hollow
- based resin
- 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.)
- Expired - Fee Related
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- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、親水化ポリスルホン系
樹脂中空糸膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic polysulfone resin hollow fiber membrane.
【０００２】[0002]
【従来の技術】ポリスルホン系樹脂製の中空糸膜は、耐
熱性、耐薬品性が優れているために、様々な用途に使用
されている。しかし、ポリスルホン系樹脂膜は疎水性で
あるために、膜が汚れやすく透水低下が起こりやすい。
ポリスルホン系樹脂膜の親水化方法としては、特開昭５
３−１３６７９号公報、特開昭５９−１９６３２２号公
報ではスルホン酸基を、特開昭５７−１７４１０４号公
報ではポリマー主鎖にポリエチレンイミンポリマー類
を、それぞれ導入もしくはグラフトして親水化してい
る。これらの親水化ポリスルホン膜は、水に溶けたり、
製造方法が複雑のため高価で実用的でない等の問題点が
あった。2. Description of the Related Art Hollow fiber membranes made of polysulfone resins are used for various purposes because of their excellent heat resistance and chemical resistance. However, since the polysulfone-based resin membrane is hydrophobic, the membrane is easily contaminated and water permeability tends to decrease.
As a method for hydrophilizing a polysulfone-based resin membrane, Japanese Unexamined Patent Publication No.
In JP-A-3-13679 and JP-A-59-196322, a sulfonic acid group is introduced, and in JP-A-57-174104, a polyethyleneimine polymer is introduced or grafted into the polymer main chain to make the polymer hydrophilic. These hydrophilic polysulfone membranes dissolve in water,
There were problems such as being expensive and impractical due to the complicated manufacturing method.
【０００３】また、特開昭６２ー１２５８０２号公報は
親水性ポリマーであるビニル系重合体のポリビニルピロ
リドンをポリスルホン系樹脂にブレンドしている。しか
し、ポリビニルピロリドンは水に溶けやすく、使用して
いると効果がなくなってしまうという問題点があった。Japanese Patent Application Laid-Open No. Sho 62-125802 discloses that a polyvinyl polymer, polyvinylpyrrolidone, which is a hydrophilic polymer, is blended with a polysulfone resin. However, there is a problem that polyvinylpyrrolidone is easily soluble in water and loses its effect when used.
【０００４】[0004]
【発明が解決しょうとする課題】本発明の目的は、ポリ
スルホン系樹脂中空糸膜を安価で恒久的に親水化する製
造方法および親水化ポリスルホン中空糸膜を提供するに
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide a production method for inexpensively and permanently hydrophilizing a polysulfone resin hollow fiber membrane and to provide a hydrophilic polysulfone hollow fiber membrane.
【０００５】[0005]
【課題を解決するための手段】上記問題点を解決するた
めに、本発明者は鋭意検討した結果、ポリスルホン系樹
脂中空糸膜の細孔表面の少なくとも一部にエチレン−ビ
ニルアルコール共重合体を一定量保持させてやればよい
ことを見いだし、本発明を完成させた。すなわち、本発
明は、ポリスルホン系樹脂中空糸膜の細孔表面にエチレ
ン−ビニルアルコール共重合体が０．１〜５重量％保持
されている親水化ポリスルホン系樹脂中空糸膜にあり、
さらに、ポリスルホン系樹脂中空糸膜を、エチレン−ビ
ニルアルコール共重合体が０．１〜２重量％溶解した、
メタノール、エタノール、イソプロパノールから選ばれ
るアルコールと水との混合溶液に浸漬した後、水で凝固
せずに乾燥することを特徴とする親水化ポリスルホン系
樹脂中空糸膜の製造方法である。Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies. As a result, an ethylene-vinyl alcohol copolymer was coated on at least a part of the pore surface of a polysulfone resin hollow fiber membrane. The inventors have found that it is necessary to keep a certain amount, and completed the present invention. That is, the present invention resides in a hydrophilized polysulfone-based resin hollow fiber membrane in which 0.1 to 5% by weight of an ethylene-vinyl alcohol copolymer is held on the pore surface of the polysulfone-based resin hollow fiber membrane,
Further, the polysulfone resin hollow fiber membrane, an ethylene - vinyl alcohol copolymer is dissolved 0.1 to 2% by weight,
Selected from methanol, ethanol and isopropanol
Immersed in a mixed solution of alcohol and water , then solidified with water
A method for producing a hydrophilic polysulfone-based resin hollow fiber membrane, characterized by drying without drying.
【０００６】以下、本発明を説明する。ポリスルホン系
樹脂としては、ポリスルホン樹脂、ポリエーテルスルホ
ン樹脂及びこれらの樹脂と他の樹脂との混合物が使用出
来る。また、エチレン−ビニルアルコール共重合体とし
ては、ランダム、ブロック、グラフト等いずれのタイプ
の共重合体であっても良いが、該重合体のエチレン含量
は２０〜５０モル％の範囲が好ましい。エチレン含量が
２０モル％未満では、ポリスルホン樹脂への接着性が悪
く、５０モル％を超えると親水性が失われて好ましくな
い。エチレンビニル−アルコール共重合体の保持量とし
ては、膜重量に対して、０．１〜５重量％が好ましい。
０．１重量％未満では、親水性の効果が少なく、５重量
％を超えると膜の透水量が低下する。Hereinafter, the present invention will be described. As the polysulfone resin, a polysulfone resin, a polyether sulfone resin, and a mixture of these resins with other resins can be used. In addition, the ethylene-vinyl alcohol copolymer may be any type of copolymer such as random, block, and graft, but the ethylene content of the polymer is preferably in the range of 20 to 50 mol%. If the ethylene content is less than 20 mol%, the adhesion to the polysulfone resin is poor, and if it exceeds 50 mol%, hydrophilicity is lost, which is not preferable. The amount of the ethylene vinyl-alcohol copolymer retained is preferably 0.1 to 5% by weight based on the weight of the film.
If it is less than 0.1% by weight, the effect of hydrophilicity is small, and if it exceeds 5% by weight, the water permeability of the membrane decreases.
【０００７】本発明のエチレン−ビニルアルコール共重
合体をポリスルホン系樹脂の細孔に保持させる方法とし
ては、エチレン−ビニルアルコール共重合体をメタノー
ル、エタノール、イソプロパノール等のアルコール類と
水との混合溶液に溶解させておいて、該溶液中にポリス
ルホン系樹脂中空糸膜を浸漬してから、乾燥すればよ
い。As a method for retaining the ethylene-vinyl alcohol copolymer of the present invention in the pores of a polysulfone resin, a method of mixing the ethylene-vinyl alcohol copolymer with an alcohol such as methanol, ethanol or isopropanol and water. , The polysulfone-based resin hollow fiber membrane is immersed in the solution, and then dried.
【０００８】[0008]
【実施例】以下、実施例に従い、本発明を説明する。The present invention will be described below with reference to examples.
【０００９】[0009]
【実施例１〜４、比較例１】日本合成化学（株）製のエ
チレン−ビニルアルコール共重合体樹脂ソアノールＤ２
９０８（エチレン含量２９モル％）をイソプロピルアル
コールと水の５０重量％ずつの混合溶液に溶かし、表１
に示す各種の濃度のエチレン−ビニルアルコール溶液を
作成し、これらの溶液に、内径０．７５ｍｍ、外径１．
２２ｍｍ、空孔率７５％、平均孔径０．２５μｍ、透水
量９０００リットル／ｍ2 ・ｈｒ・ｋｇ／ｃｍ2 ａｔ２
５℃のポリスルホン樹脂中空糸膜を６０℃で１０分間浸
漬し、乾燥して、表１に示すような各種の付着重量
（％）で、エチレン−ビニルアルコール共重合体を被覆
した膜（実施例１〜実施例４）を製作し、透水量と協和
界面科学（株）のＣＡ−Ａ型接触角計で傾斜法による後
退角による接触角を測定し、表１に示した。Examples 1-4, Comparative Example 1 Soarnol D2, an ethylene-vinyl alcohol copolymer resin manufactured by Nippon Synthetic Chemical Co., Ltd.
908 (ethylene content: 29 mol%) was dissolved in a mixed solution of isopropyl alcohol and water at 50% by weight.
The ethylene-vinyl alcohol solutions having various concentrations shown in Table 1 were prepared, and the inside diameter was 0.75 mm and the outside diameter was 1.
22 mm, porosity 75%, average pore diameter 0.25 μm, water permeability 9000 l / m 2 · hr · kg / cm 2 at2
A polysulfone resin hollow fiber membrane at 5 ° C. is immersed at 60 ° C. for 10 minutes, dried, and coated with an ethylene-vinyl alcohol copolymer at various adhesion weights (%) as shown in Table 1 (Examples). 1 to 4) were manufactured, and the amount of water permeation and the contact angle of the CA-A type contact angle meter of Kyowa Interface Science Co., Ltd. were measured by the receding angle by the tilt method.
【００１０】また、この実施例で使用した基材膜で、エ
チレン−ビニルアルコール共重合体樹脂の被覆処理を施
していない膜の値を比較例１として示した。このよう
に、エチレン−ビニルアルコール共重合体が少量保持さ
れると膜の接触角は著しく小さくなることが判る。The value of the base film used in this example, which was not coated with the ethylene-vinyl alcohol copolymer resin, is shown as Comparative Example 1. Thus, it can be seen that when a small amount of the ethylene-vinyl alcohol copolymer is held, the contact angle of the film becomes extremely small.
【００１１】[0011]
【実施例５、比較例２】上記の実施例３の膜と比較例１
で使用した基材膜でモジュールを製作して、導電率０．
１μｓ／ｃｍ、０．２μｍ以上の微粒子数が約１００個
／ミリリットルの純水を１ｋｇ／ｃｍ2 の圧力で、回収
率９５％で１ケ月間濾過したところ、上記の実施例３の
膜は透水保持率が９２％であったのに対して、比較例１
の基材膜では６１％に低下していた。Example 5 and Comparative Example 2 The film of Example 3 described above and Comparative Example 1
A module is manufactured using the substrate film used in step (1), and the conductivity is set to 0.
Pure water containing 1 μs / cm and 0.2 μm or more of fine particles having a particle count of about 100 particles / milliliter was filtered at a pressure of 1 kg / cm 2 for one month at a recovery rate of 95%. Comparative Example 1 had a retention of 92%.
In the case of the base material film, it was reduced to 61%.
【００１２】[0012]
【実施例６】上記の実施例３の膜を、４０℃の純水に３
月間浸漬した後、恒量になるまで、６０℃で乾燥して重
量を測定した結果、重量減少は０．１９重量％であり、
後退角による接触角は変わらなかった。[Embodiment 6] The membrane of the above-mentioned embodiment 3 was placed in pure water at 40 ° C for
After being immersed for a month, it was dried at 60 ° C. and weighed until it reached a constant weight. As a result, the weight loss was 0.19% by weight.
The contact angle due to the receding angle did not change.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【発明の効果】本発明の親水化ポリスルホン系樹脂中空
糸膜は、優れた親水性を有しており、しかも、長期間使
用しても親水性が損なわれず、透水量も低下しない。The hydrophilized polysulfone-based resin hollow fiber membrane of the present invention has excellent hydrophilicity, and its hydrophilicity is not impaired even after long-term use, and the water permeability does not decrease.
Claims (3)
にエチレン−ビニルアルコール共重合体が０．１〜５重
量％保持されていることを特徴とする親水化ポリスルホ
ン系樹脂中空糸膜。1. A hydrophilic polysulfone-based resin hollow fiber membrane characterized in that an ethylene-vinyl alcohol copolymer is held at 0.1 to 5% by weight on the surface of pores of the polysulfone-based resin hollow fiber membrane.
とを特徴とする請求項１記載の親水化ポリスルホン系樹2. The hydrophilized polysulfone-based tree according to claim 1, wherein
脂中空糸膜。Fat hollow fiber membrane.
ン−ビニルアルコール共重合体が０．１〜２重量％溶解
した、メタノール、エタノール、イソプロパノールから
選ばれるアルコールと水との混合溶液に浸漬した後、水
で凝固せずに乾燥することを特徴とする親水化ポリスル
ホン系樹脂中空糸膜の製造方法。The 3. A polysulfone resin hollow fiber membrane, an ethylene - vinyl alcohol copolymer is dissolved 0.1 to 2 wt%
From methanol, ethanol and isopropanol
After immersed in a mixed solution of alcohol and water is selected, the water
A method for producing a hydrophilic polysulfone-based resin hollow fiber membrane, wherein the membrane is dried without coagulation .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32419092A JP3305778B2 (en) | 1992-12-03 | 1992-12-03 | Hydrophilized polysulfone-based resin hollow fiber membrane and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32419092A JP3305778B2 (en) | 1992-12-03 | 1992-12-03 | Hydrophilized polysulfone-based resin hollow fiber membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06170193A JPH06170193A (en) | 1994-06-21 |
| JP3305778B2 true JP3305778B2 (en) | 2002-07-24 |
Family
ID=18163081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32419092A Expired - Fee Related JP3305778B2 (en) | 1992-12-03 | 1992-12-03 | Hydrophilized polysulfone-based resin hollow fiber membrane and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3305778B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140032949A (en) * | 2010-12-27 | 2014-03-17 | 도레이 카부시키가이샤 | Hollow fiber membrane module and method for producing chemicals |
| CN105597562B (en) * | 2015-12-22 | 2018-04-20 | 贵州省材料产业技术研究院 | The method being modified using ultrasonic in-situ polymerization to polymer separation film |
-
1992
- 1992-12-03 JP JP32419092A patent/JP3305778B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06170193A (en) | 1994-06-21 |
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