JP3358342B2 - Hydrophilic membrane and method for producing the same - Google Patents
Hydrophilic membrane and method for producing the sameInfo
- Publication number
- JP3358342B2 JP3358342B2 JP28047494A JP28047494A JP3358342B2 JP 3358342 B2 JP3358342 B2 JP 3358342B2 JP 28047494 A JP28047494 A JP 28047494A JP 28047494 A JP28047494 A JP 28047494A JP 3358342 B2 JP3358342 B2 JP 3358342B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- water
- solvent
- polyvinyl acetal
- 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.)
- Expired - Lifetime
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、疎水性多孔質膜に、ポ
リビニルアセタールジエチルアミノアセテートを付着保
持させることによる親水化膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic membrane obtained by adhering and holding polyvinyl acetal diethylaminoacetate on a hydrophobic porous membrane.
【０００２】[0002]
【従来の技術】ポリオレフィンに代表される疎水性多孔
質膜は、化学的安定性が高いこと等の利点を有し、水ま
たは水溶液の分離精製、処理等の分野や医療分野で利用
されている。しかし、そのままでは水との親和性が乏し
いので、水または水溶液を処理する用途に用いる場合に
は、予め親水化する必要がある。疎水性多孔質膜の親水
化処理のための方法としては、例えば、アルコール、ケ
トン等の有機溶剤によって、疎水性多孔質膜の外表面、
微細孔内表面を湿潤処理した後、有機溶剤を水で置換す
る方法がある。また、水可溶性親水性高分子や界面活性
剤等の親水化剤を疎水性多孔質膜表面に保持させること
による親水化方法もある。2. Description of the Related Art Hydrophobic porous membranes represented by polyolefins have advantages such as high chemical stability, and are used in fields such as separation and purification of water or aqueous solution, treatment, and medical fields. . However, if it is used as it is, it has a poor affinity for water, so that it needs to be hydrophilized in advance when used for treating water or an aqueous solution. As a method for hydrophilizing the hydrophobic porous membrane, for example, an organic solvent such as alcohol and ketone, the outer surface of the hydrophobic porous membrane,
There is a method of replacing the organic solvent with water after wetting the inner surface of the micropores. There is also a method of hydrophilization by retaining a hydrophilic agent such as a water-soluble hydrophilic polymer or a surfactant on the surface of the hydrophobic porous membrane.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、有機溶
剤による親水化方法は、疎水性多孔質膜を常に湿潤状態
に保持する必要があり、その維持管理が煩雑となってい
る。また、水可溶性親水性高分子による親水化方法は該
微細孔表面に保持させた親水化剤が水に溶けだし、その
ような状態の多孔質膜は一旦乾燥すると、親水性を失っ
てしまうので、このような用途では好ましくない。界面
活性剤による親水化方法も水への溶出が懸念される他、
雑菌による資化を受けやすいといった問題がある。本発
明はこれらの問題を解決することを目的とする。However, in the method for hydrophilizing with an organic solvent, it is necessary to keep the hydrophobic porous membrane in a wet state at all times, and the maintenance and management thereof are complicated. Further, in the method of hydrophilization using a water-soluble hydrophilic polymer, the hydrophilizing agent held on the surface of the micropores is dissolved in water, and the porous membrane in such a state loses hydrophilicity once dried, Such a use is not preferable. In addition to the fear of elution into water,
There is a problem that it is susceptible to assimilation by various bacteria. The present invention aims to solve these problems.
【０００４】[0004]
【課題を解決するための手段】本発明者らはこれらの問
題点を改良する方法として、親水性部分を有する高分子
であって、かつ膜成分樹脂に対して親和性があり、疎水
性多孔質膜に保持させた際の被処理水中への溶出が生じ
にくい化合物を、親水性−疎水性のバランスを考慮して
選定し、多孔質膜微細孔表面上に付着保持させる方法を
鋭意検討した結果、本発明を完成させるに至った。Means for Solving the Problems As a method for solving these problems, the present inventors have proposed a polymer having a hydrophilic portion, having an affinity for a membrane component resin, and a hydrophobic porous material. A compound that hardly dissolves into the water to be treated when retained on the porous membrane was selected in consideration of the balance between hydrophilicity and hydrophobicity, and a method for adhering and retaining the compound on the microporous surface of the porous membrane was studied. As a result, the present invention has been completed.
【０００５】本発明は、片面から他の面に連通している
微細孔を少なくとも一部に有する熱可塑性樹脂からなる
膜において、ポリビニルアセタールジエチルアミノアセ
テートを該微細孔を有する膜の少なくとも一部に付着保
持させて親水性を付与したことを特徴とする親水化膜に
関する。また、該熱可塑性樹脂が疎水性熱可塑性樹脂の
ポリエチレン、ポリプロピレン、ポリフロロエチレン、
ポリアクリロニトリル、ポリエチレンテレフタレート、
ポリスルホン、ポリアミド及びポリイミドから選ばれた
少なくとも１種の物質または２種以上の共重合体または
２種以上の混合物である親水化膜の製法に関する。According to the present invention, there is provided a film made of a thermoplastic resin having at least a portion of micropores communicating from one surface to the other surface, wherein polyvinyl acetal diethylaminoacetate is attached to at least a portion of the film having the micropores. The present invention relates to a hydrophilized film characterized by holding and imparting hydrophilicity. Further, the thermoplastic resin is a hydrophobic thermoplastic resin polyethylene, polypropylene, polyfluoroethylene,
Polyacrylonitrile, polyethylene terephthalate,
The present invention relates to a method for producing a hydrophilized membrane which is at least one substance selected from polysulfone, polyamide and polyimide, or two or more copolymers or a mixture of two or more substances.
【０００６】本発明における疎水性多孔質膜としては、
中空糸膜、平膜、管状膜等の任意の形態を用いることが
できる。疎水性多孔質膜の素材は、ポリエチレン等前記
記載の単量体または共重合体である。The hydrophobic porous membrane in the present invention includes:
Arbitrary forms such as a hollow fiber membrane, a flat membrane, and a tubular membrane can be used. The material of the hydrophobic porous membrane is the above-described monomer or copolymer such as polyethylene.
【０００７】本発明で用いるポリビニルアセタールジエ
チルアミノアセテートは、下記一般式で示され、The polyvinyl acetal diethylaminoacetate used in the present invention is represented by the following general formula:
【０００８】[0008]
【化１】 Embedded image
【０００９】式中、Ｒ＝ＣＨ3 であり、窒素含有量が１
〜４重量％、平均分子量が１０，０００〜７５，０００
のものが好ましい。Wherein R = CH 3 and the nitrogen content is 1
-4% by weight, average molecular weight of 10,000-75,000
Are preferred.
【００１０】本発明の親水化膜の製造方法は、ポリビニ
ルアセタールジエチルアミノアセテートをアルコール
系、ケトン系、芳香族系等の溶媒の単独または混合溶
媒、あるいはその含水溶媒、好ましくは、メチルアルコ
ール、エチルアルコール、イソプロピルアルコールまた
はアセトンの１種または２種以上の混合物、あるいはそ
の含水物に溶解し、浸漬液を調整する。浸漬液の濃度
は、１〜５ｗｔ／ｖｏｌ％が好ましい。浸漬液が常温で
粘性が高い場合は、適宜加温して浸漬液の粘度を下げて
浸漬処理を行うことができる。 次いで、疎水性多孔質
膜を浸漬し、膜の貫通微細孔内にも十分溶液を行き渡ら
せた後、乾燥して溶媒を除去する。乾燥手段は、溶媒の
種類により風乾、減圧乾燥、加熱乾燥など通常の方法を
適宜用いることができる。膜上の親水化剤の量を示す担
持率は次式であらわされ、本発明における親水化剤の担
持率は５〜４０重量％が好ましい。 担持率（重量％）＝親水化剤量（ｇ）／疎水糸重量
（ｇ）×１００The method for producing a hydrophilized film according to the present invention is characterized in that polyvinyl acetal diethylaminoacetate is used alone or in a mixture of solvents such as alcohols, ketones and aromatics, or a water-containing solvent thereof, preferably methyl alcohol, ethyl alcohol. Isopropyl alcohol or acetone, or a mixture of two or more of them, or a hydrate thereof to prepare an immersion liquid. The concentration of the immersion liquid is preferably 1 to 5 wt / vol%. When the immersion liquid has a high viscosity at room temperature, the immersion treatment can be performed by appropriately heating to lower the viscosity of the immersion liquid. Next, the hydrophobic porous membrane is immersed, the solution is sufficiently spread even in the through-holes of the membrane, and then the solvent is removed by drying. As a drying means, an ordinary method such as air drying, reduced pressure drying, and heat drying can be appropriately used depending on the type of the solvent. The loading rate indicating the amount of the hydrophilic agent on the membrane is represented by the following formula, and the loading rate of the hydrophilic agent in the present invention is preferably 5 to 40% by weight. Loading ratio (% by weight) = amount of hydrophilic agent (g) / weight of hydrophobic yarn (g) × 100
【００１１】[0011]
【実施例】以下に実施例及び比較例によって本発明を更
に詳細に説明する。The present invention will be described in more detail with reference to the following Examples and Comparative Examples.
【００１２】実施例１ ポリビニルアセタールジエチルアミノアセテート〔商品
名：ＡＥＡ三共、三共（株）製〕２重量部をエタノール
９０容量部、及び蒸留水１０容量部の混合物に溶解し浸
漬液とし、その中へポリプロピレン多孔質中空糸膜〔宇
部興産（株）製，平均孔径０．３μｍ，空孔率７０％〕
を３０秒間浸漬した。その後、風乾により溶剤の除去を
行い、担持率１２％の親水化膜を得た。この親水化処理
した中空糸膜を１００本束ねて末端をウレタン樹脂で固
め、有効面積１００ｃｍ2 の膜モジュールを作成した。
この膜モジュールに水圧１ｋｇ／ｃｍ2 をかけて水を濾
過したところ透水量は６５ｃｃ／ｍ2 ・ｍｉｎであり、
優れた透水性を示した。また、水圧１ｋｇ／ｃｍ2 で５
リットルの水を濾過した後、完全に乾燥させた後も透水
性の低下はみられなかった。Example 1 2 parts by weight of polyvinyl acetal diethylaminoacetate (trade name: AEA Sankyo, Sankyo Co., Ltd.) was dissolved in a mixture of 90 parts by volume of ethanol and 10 parts by volume of distilled water to form an immersion liquid. Polypropylene porous hollow fiber membrane [Ube Industries, Ltd., average pore diameter 0.3 μm, porosity 70%]
For 30 seconds. Thereafter, the solvent was removed by air drying to obtain a hydrophilic film having a loading of 12%. One hundred hollow fiber membranes subjected to the hydrophilic treatment were bundled and the ends were solidified with a urethane resin to prepare a membrane module having an effective area of 100 cm 2 .
When water was filtered by applying a water pressure of 1 kg / cm 2 to the membrane module, the water permeability was 65 cc / m 2 · min,
It showed excellent water permeability. In addition, water pressure 1 kg / cm 2
After filtration of 1 liter of water and complete drying, no decrease in water permeability was observed.
【００１３】比較例１ 実施例１で用いたのと同様のポリプロピレン多孔質中空
糸膜を用いて、これを親水化処理することなく、実施例
１と同様の膜モジュールを作成し、水を濾過しようとし
たが、水は全く透過しなかった。Comparative Example 1 Using the same polypropylene porous hollow fiber membrane as used in Example 1, a membrane module similar to that of Example 1 was prepared without hydrophilizing the same, and water was filtered. Attempted, but no water permeated.
【００１４】実施例２ ポリビニルアセタールジエチルアミノアセテート〔商品
名：ＡＥＡ三共、三共（株）製〕２重量部をメタノール
９０容量部、及び蒸留水１０容量部に溶解した浸漬液を
用いる以外は、実施例１と同様の親水化処理を行った。
実施例１と同様の膜モジュールによる透水性評価の結
果、７５ｃｃ／ｍ2 ・ｍｉｎの透水量を得た。Example 2 Example 2 was repeated except that an immersion liquid obtained by dissolving 2 parts by weight of polyvinyl acetal diethylaminoacetate (trade name: AEA, manufactured by Sankyo and Sankyo KK) in 90 parts by volume of methanol and 10 parts by volume of distilled water was used. The same hydrophilic treatment as in Example 1 was performed.
As a result of the water permeability evaluation using the same membrane module as in Example 1, a water permeability of 75 cc / m 2 · min was obtained.
【００１５】[0015]
【発明の効果】本発明の親水化ポリオレフィン多孔質膜
は濾過後に多孔質膜が乾燥されても透水性能の低下が認
められず、耐久性のある親水性が付与された多孔質膜で
ある。The porous polyolefin membrane of the present invention is a porous membrane having a durable hydrophilic property without a decrease in water permeability even when the porous membrane is dried after filtration.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭48−36080（ＪＰ，Ａ) 特開 昭54−117380（ＪＰ，Ａ) 特開 昭62−23403（ＪＰ，Ａ) 特開 昭62−201939（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 61/00 - 71/82 510 C02F 1/44 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-48-36080 (JP, A) JP-A-54-117380 (JP, A) JP-A-62-23403 (JP, A) JP-A-62 201939 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B01D 61/00-71/82 510 C02F 1/44
Claims (4)
少なくとも一部に有する熱可塑性樹脂からなる膜におい
て、ポリビニルアセタールジエチルアミノアセテートを
該微細孔を有する膜の少なくとも一部に付着保持させて
親水性を付与したことを特徴とする親水化膜。1. A film made of a thermoplastic resin having at least a portion of micropores communicating from one surface to the other surface, wherein polyvinyl acetal diethylaminoacetate is adhered and held on at least a portion of the film having the micropores. A hydrophilic film characterized by imparting hydrophilicity to the film.
ン、ポリプロピレン、ポリフロロエチレン、ポリアクリ
ロニトリル、ポリエチレンテレフタレート、ポリスルホ
ン、ポリアミド及びポリイミドから選ばれた少なくとも
１種の物質または２種以上の共重合体または２種以上の
混合物であることを特徴とする請求項１記載の親水化
膜。2. The thermoplastic resin is a hydrophobic resin of at least one substance selected from polyethylene, polypropylene, polyfluoroethylene, polyacrylonitrile, polyethylene terephthalate, polysulfone, polyamide and polyimide, or a copolymer of two or more kinds thereof. The hydrophilic film according to claim 1, wherein the film is a mixture of two or more kinds.
セテートをアルコール系、ケトン系、芳香族系溶媒、ま
たはそれらの混合溶媒、あるいはその含水溶媒に溶解し
たものを浸漬液とし、片面から他の面に連通している微
細孔を有する熱可塑性樹脂からなる膜を浸漬し、微細孔
の少なくとも一部に該ポリビニルアセタールジエチルア
ミノアセテートを付着保持させることを特徴とする親水
化膜の製法。3. An immersion liquid obtained by dissolving polyvinyl acetal diethylaminoacetate in an alcohol-based, ketone-based, aromatic-based solvent, or a mixed solvent thereof, or a water-containing solvent thereof, and communicating from one side to the other side. A method for producing a hydrophilized film, characterized by immersing a film made of a thermoplastic resin having fine pores and adhering and holding the polyvinyl acetal diethylaminoacetate in at least a part of the fine pores.
ール、イソプロピルアルコール、アセトンのうちの１種
または２種以上の混合物、あるいはその含水溶媒である
ことを特徴とする請求項３記載の親水化膜の製法。4. The method according to claim 3, wherein the solvent is one or a mixture of two or more of methyl alcohol, ethyl alcohol, isopropyl alcohol, and acetone, or a water-containing solvent thereof. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28047494A JP3358342B2 (en) | 1994-11-15 | 1994-11-15 | Hydrophilic membrane and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28047494A JP3358342B2 (en) | 1994-11-15 | 1994-11-15 | Hydrophilic membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08131790A JPH08131790A (en) | 1996-05-28 |
| JP3358342B2 true JP3358342B2 (en) | 2002-12-16 |
Family
ID=17625586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28047494A Expired - Lifetime JP3358342B2 (en) | 1994-11-15 | 1994-11-15 | Hydrophilic membrane and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3358342B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019193918A (en) * | 2018-05-01 | 2019-11-07 | 宇部興産株式会社 | Composite membrane for gas separation |
-
1994
- 1994-11-15 JP JP28047494A patent/JP3358342B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08131790A (en) | 1996-05-28 |
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