JPH05131124A - Production of hydrophilic fluoroplastic porous membrane - Google Patents
Production of hydrophilic fluoroplastic porous membraneInfo
- Publication number
- JPH05131124A JPH05131124A JP29426691A JP29426691A JPH05131124A JP H05131124 A JPH05131124 A JP H05131124A JP 29426691 A JP29426691 A JP 29426691A JP 29426691 A JP29426691 A JP 29426691A JP H05131124 A JPH05131124 A JP H05131124A
- Authority
- JP
- Japan
- Prior art keywords
- hydrophilic
- hydrophilic monomer
- pores
- alkyl group
- porous material
- 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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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
(57)【要約】
【目的】フッ素樹脂多孔体の細孔内に、特定の親水性モ
ノマーをグラフトおよび架橋することにより固定し、親
水性が高くその耐久性に優れ、かつ耐薬品性、耐溶剤
性、耐熱性などに優れた親水性フッ素樹脂多孔質膜とす
る。
【構成】 フッ素樹脂多孔体の細孔内に、構造式ＣＨ2
＝ＣＲ1 −（Ｒ1 はＨまたは炭素数 〜 のアルキル
基）を含む第３アミン若しくは第４アミン、または構造
式ＣＨ2 ＝ＣＲ1 −と−ＣＨ（Ｒ2 ）（Ｒ3 ）基
（Ｒ2 ，Ｒ3 は同一でも異なっていてもよい炭素数１〜
５のアルキル基）を含む親水性モノマー溶液を含浸した
後、紫外線照射を行い該親水性モノマーをグラフトおよ
び架橋する。(57) [Abstract] [Purpose] A specific hydrophilic monomer is fixed by grafting and crosslinking in the pores of the fluororesin porous material, and it has high hydrophilicity and excellent durability, as well as chemical resistance and resistance. The hydrophilic fluororesin porous film is excellent in solvent resistance and heat resistance. [Structure] The structural formula CH 2 is contained in the pores of the fluororesin porous material.
Or a tertiary amine containing ═CR 1 — (R 1 is H or an alkyl group having from 1 to 4 carbon atoms), or a structural formula CH 2 ═CR 1 — and —CH (R 2 ) (R 3 ) group (R 2 , R 3 may be the same or different and have 1 to 1 carbon atoms.
After impregnating a hydrophilic monomer solution containing an alkyl group of 5), UV irradiation is carried out to graft and crosslink the hydrophilic monomer.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、薬品、食品、水などの
液体の精密濾過や限外濾過に使用する液体用濾過膜、濾
過装置等に用いることができる親水性フッ素樹脂多孔質
膜の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a hydrophilic fluororesin porous membrane that can be used in liquid filtration membranes, filtration devices and the like used for microfiltration and ultrafiltration of liquids such as chemicals, foods and water. It relates to a manufacturing method.
【０００２】[0002]
【従来の技術】薬品、食品、水などの液体の精密濾過や
限外濾過において、微粒子の除去性能、液体の透過流
束、耐薬品性、耐圧性、耐熱性等が濾過膜の重要な選択
因子である。そのため、従来、ポリテトラフルオロエチ
レン（以下、ＰＴＦＥと略す）、ポリフッ化ビニリデン
等のフッ素樹脂、ポリエチレン、ポリプロピレン、ポリ
オレフィン等の高分子重合体からなる多孔質膜が選ばれ
ていた。2. Description of the Related Art In microfiltration and ultrafiltration of liquids such as chemicals, foods and water, fine particles removal performance, liquid permeation flux, chemical resistance, pressure resistance, heat resistance, etc. are important selections of filtration membranes. Is a factor. Therefore, conventionally, a porous film made of a fluororesin such as polytetrafluoroethylene (hereinafter abbreviated as PTFE) or polyvinylidene fluoride, or a polymer such as polyethylene, polypropylene or polyolefin has been selected.
【０００３】しかしながら、近年ではさらに親水化膜の
必要性が高まってきた。すなわち、例えば半導体工業に
おいて、シリコンウエハの洗浄は硝酸、フッ酸、硫酸等
で行われているが、循環洗浄した後の薬品の交換時に、
薬品を排出することによって濾過用カートリッジフィル
ター内に空気が流入する。However, in recent years, the need for a hydrophilic film has further increased. That is, for example, in the semiconductor industry, cleaning of silicon wafers is performed with nitric acid, hydrofluoric acid, sulfuric acid, etc., but when replacing chemicals after circulating cleaning,
Air flows into the filter cartridge filter by discharging the chemicals.
【０００４】そのため、フィルター内のＰＴＦＥ膜等の
疎水性膜の表面に空気が接し、フィルター装着時等に有
機溶媒等で膜を親水化処理した効果が消失するため、次
回に薬品を導入した際には、液体透過流束が激減する。
そのため、低い表面張力を有する液体で再度親水化しな
ければならないという問題があった。Therefore, air comes into contact with the surface of a hydrophobic membrane such as a PTFE membrane in the filter, and the effect of hydrophilic treatment of the membrane with an organic solvent when the filter is attached disappears. The liquid permeation flux is drastically reduced.
Therefore, there is a problem that the liquid having a low surface tension must be made hydrophilic again.
【０００５】そして、フッ素樹脂多孔体の親水化方法と
して界面活性剤を塗布する方法あるいは特開昭５６−６
３７７２号公報に記載されているようにポリビニルアル
コール、ポリエチレングリコールのような水溶性高分子
を多孔体の細孔内に含浸せしめ、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
離性放射線照射等により親水化する方法が知られてい
る。Then, as a method for making the fluororesin porous material hydrophilic, a method of applying a surfactant or JP-A-56-6 is used.
As described in Japanese Patent No. 3772, a water-soluble polymer such as polyvinyl alcohol or polyethylene glycol is impregnated into pores of a porous body, and the polymer is heat-treated, acetalized, esterified, dichromic acid. A method for making hydrophilic by treatment, irradiation with ionizing radiation, or the like is known.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、前記界
面活性剤を塗布する方法は、多孔体への界面活性剤の付
着力が充分でなく、活性剤が脱落し易く、親水性の耐久
性が乏しいという問題があった。However, in the method of applying the surfactant, the adhesive force of the surfactant to the porous body is not sufficient, the active agent easily falls off, and the hydrophilic durability is poor. There was a problem.
【０００７】また、特開昭５６−６３７７２号公報に提
案されている方法は、放射線の照射により多孔体の分解
劣化を生じ機械的強度の大巾な低下を生ずるばかりでな
く、熱処理、アセタール化、エステル化は水溶性ポリマ
ーの一部を疎水性とするので、親水度合が低下するとい
う問題があった。Further, the method proposed in Japanese Patent Laid-Open No. 56-63772 not only causes decomposition and deterioration of the porous material due to irradiation of radiation to cause a large decrease in mechanical strength, but also heat treatment and acetalization. However, the esterification makes a part of the water-soluble polymer hydrophobic so that there is a problem that the hydrophilicity is lowered.
【０００８】本発明は、前記従来技術課題を解決するた
め、親水性が高くその耐久性に優れ、かつ耐薬品性、耐
溶剤性、耐熱性などに優れた親水性フッ素樹脂多孔質膜
の製造方法を提供することを目的とする。In order to solve the above-mentioned problems of the prior art, the present invention provides a hydrophilic fluororesin porous membrane having high hydrophilicity and excellent durability as well as excellent chemical resistance, solvent resistance, heat resistance and the like. The purpose is to provide a method.
【０００９】[0009]
【課題を解決するための手段】前記目的を達成するた
め、本発明の親水性フッ素樹脂多孔質膜の製造方法は、
フッ素樹脂多孔体の細孔内に、構造式ＣＨ2 ＝ＣＲ1 −
（Ｒ1 はＨまたは炭素数１〜５のアルキル基）を含む第
３アミン若しくは第４アミン、又は構造式ＣＨ2 ＝ＣＲ
1 −と−ＣＨ（Ｒ2 ）（Ｒ3 ）基（Ｒ2 ，Ｒ3 は同一で
も異なっていてもよい炭素数１〜５のアルキル基）を含
む親水性モノマー溶液を含浸した後、紫外線照射を行い
該親水性モノマーをグラフト重合および架橋することを
特徴とする。In order to achieve the above object, the method for producing a hydrophilic fluororesin porous membrane of the present invention comprises:
Fluorine resin porous body within the pores, the structural formula CH 2 = CR 1 -
(R 1 is H or an alkyl group having 1 to 5 carbon atoms) containing a tertiary amine or a quaternary amine, or a structural formula CH 2 = CR
After impregnating a hydrophilic monomer solution containing 1- and -CH (R 2 ) (R 3 ) groups (R 2 and R 3 may be the same or different and each is an alkyl group having 1 to 5 carbon atoms), ultraviolet irradiation is performed. The hydrophilic monomer is graft-polymerized and cross-linked.
【００１０】前記構成においては、親水性モノマーが一
般式ＣＨ2 ＝ＣＲ1 −Ｘ（−ＣＨ3 ）n （ただし、Ｘは
ＣＯＮＨ−（ＣＨ2 ）m −Ｎ、ＣＯＮ、ＯＣＯＮ、ＣＯ
Ｏ−（ＣＨ2 ）m −Ｎ、またはＣＯＮＨＣＨ、ｍは１〜
１０の整数、ｎは２〜３の整数、Ｒ1 はＨまたは炭素数
１〜５のアルキル基）で示される物質であることが好ま
しい。In the above structure, the hydrophilic monomer has the general formula CH 2 = CR 1 -X (-CH 3 ) n (where X is CONH- (CH 2 ) m -N, CON, OCON, CO.
O- (CH 2) m -N or CONHCH, m is 1,
It is preferable that the substance is an integer of 10, n is an integer of 2 to 3, and R 1 is H or an alkyl group having 1 to 5 carbon atoms.
【００１１】[0011]
【作用】前記本発明の構成によれば、フッ素樹脂多孔体
の細孔内に、構造式ＣＨ2 ＝ＣＲ1 −（Ｒ1 はＨまたは
炭素数１〜５のアルキル基）を含む第３アミン若しくは
第４アミン、または構造式ＣＨ2 ＝ＣＲ1 −と−ＣＨ
（Ｒ2 ）（Ｒ3 ）基（Ｒ2 ，Ｒ3 は同一でも異なってい
てもよい炭素数１〜５のアルキル基）を含む親水性モノ
マー溶液を含浸した後、紫外線照射を行い該親水性モノ
マーをグラフト重合および架橋することにより、該親水
性モノマーが前記多孔体の細孔内に固定されているの
で、親水性が高くその耐久性に優れ、かつ耐薬品性、耐
溶剤性、耐熱性などに優れた親水性フッ素樹脂多孔質膜
とすることができる。According to the structure of the present invention, a tertiary amine containing the structural formula CH 2 = CR 1- (R 1 is H or an alkyl group having 1 to 5 carbon atoms) in the pores of the fluororesin porous material. or quaternary amine or a structural formula CH 2 = CR 1, - and -CH
After impregnating a hydrophilic monomer solution containing a (R 2 ) (R 3 ) group (R 2 and R 3 may be the same or different alkyl groups having 1 to 5 carbon atoms), ultraviolet irradiation is carried out to obtain the hydrophilic property. Since the hydrophilic monomer is fixed in the pores of the porous body by graft polymerization and crosslinking of the monomer, it has high hydrophilicity and excellent durability, and also has chemical resistance, solvent resistance, and heat resistance. It is possible to obtain a hydrophilic fluororesin porous film having excellent properties.
【００１２】また、親水性モノマーが一般式ＣＨ2 ＝Ｃ
Ｒ1 −Ｘ（−ＣＨ3 ）n （ただし、ＸはＣＯＮＨ−（Ｃ
Ｈ2 ）m −Ｎ、ＣＯＮ、ＯＣＯＮ、ＣＯＯ−（ＣＨ2 ）
m −Ｎ、またはＣＯＮＨＣＨ、ｍは１〜１０の整数、ｎ
は２〜３の整数、Ｒ1 はＨまたは炭素数１〜５のアルキ
ル基）で示される物質であるという本発明の好ましい構
成によれば、さらに親水性とその耐久性に優れた多孔膜
を得ることができる。Further, the hydrophilic monomer has the general formula CH 2 ═C
R 1 -X (-CH 3) n ( however, X is CONH- (C
H 2) m -N, CON, OCON, COO- (CH 2)
m- N, or CONHCH, m is an integer of 1 to 10, n
Is an integer of 2 to 3, and R 1 is a substance represented by H or an alkyl group having 1 to 5 carbon atoms. According to the preferred constitution of the present invention, a porous film further excellent in hydrophilicity and durability is obtained. Obtainable.
【００１３】[0013]
【実施例】以下実施例を用いて本発明をさらに具体的に
説明する。本発明者は、種々検討の結果、フッ素樹脂は
耐紫外線性が極めて優れており、フッ素樹脂多孔体の細
孔内に含浸せしめた特定の化学構造を有する親水性モノ
マーをグラフト及び架橋するために必要な線量の紫外線
を照射した場合、分解劣化を生ずることなく、かつ耐薬
品性、耐溶剤性、耐熱性に優れる該親水性モノマーを多
孔体の細孔内に強固に固定し得ることを見出し本発明を
完成するに至った。The present invention will be described in more detail with reference to the following examples. The present inventor, as a result of various studies, the fluororesin is extremely excellent in ultraviolet resistance, and in order to graft and crosslink a hydrophilic monomer having a specific chemical structure impregnated in the pores of the fluororesin porous material. It was found that the hydrophilic monomer, which is excellent in chemical resistance, solvent resistance, and heat resistance, can be firmly fixed in the pores of a porous body without causing decomposition and deterioration when irradiated with a necessary dose of ultraviolet rays. The present invention has been completed.
【００１４】即ち、本発明に係る親水性を有するフッ素
樹脂多孔体の製造法は、フッ素樹脂多孔体の細孔内にＣ
Ｈ2 ＝ＣＲ1 −基を有する第３アミンまたは第４アミン
またはＣＨ2 ＝ＣＲ1 −基とイソプロピル基を有する親
水性モノマーを含浸し、次いで紫外線の照射により親水
性モノマーをグラフト及び架橋して、該モノマーを前記
多孔体の細孔内に固定するのである。That is, in the method for producing a fluororesin porous material having hydrophilicity according to the present invention, C is introduced into the pores of the fluororesin porous material.
A hydrophilic monomer having a tertiary amine or a quaternary amine having an H 2 ═CR 1 — group or a CH 2 ═CR 1 — group and an isopropyl group is impregnated, and then the hydrophilic monomer is grafted and crosslinked by irradiation with ultraviolet rays. The monomer is fixed in the pores of the porous body.
【００１５】本発明に用いる多孔体は、通常ＰＴＦＥか
らなるものであるが、他のフッ素樹脂、例えば、テトラ
フルオロエチレンーヘキサフルオロプロピレン共重合体
（以下、ＦＥＰと称す）、エチレンーテトラフルオロエ
チレン共重合体、テトラフルオロエチレンーパーフルオ
ロアルキルビニルエーテル共重合体、フッ化ビニル樹
脂、フッ化ビニリデン樹脂、三フッ化塩化エチレン樹脂
等からなるものであってもよい。The porous material used in the present invention is usually made of PTFE, but other fluororesins such as tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP) and ethylene-tetrafluoroethylene. It may be composed of a copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a vinyl fluoride resin, a vinylidene fluoride resin, a trifluorochloroethylene resin, or the like.
【００１６】そして、この多孔体はシート状、棒状、チ
ューブ状等いずれの形状であってもよく、焼成品もしく
は未焼成品のいずれも使用し得る。また、この多孔体の
気孔率、細孔の孔径は用途に応じて種々設定できるが、
通常、前者は約２０〜８０％、後者は約０．０１〜１０
μｍである。The porous body may have any shape such as a sheet shape, a rod shape and a tube shape, and either a fired product or an unfired product may be used. Further, the porosity of this porous body, the pore size of the pores can be variously set according to the application,
Usually, the former is about 20-80% and the latter is about 0.01-10.
μm.
【００１７】なお、フッ素樹脂多孔体は種々の方法で得
ることができる。例えば、ＰＴＦＥ多孔体は特公昭５８
−２５３３２号公報、特公昭５１−１８９９１号公報、
特公昭４２−１３５６０号公報等に記載された延伸法、
あるいは特公昭４２−４９７４号公報に記載された起泡
剤を用いる方法等によって得ることができる。The fluororesin porous material can be obtained by various methods. For example, PTFE porous body is Japanese Patent Publication Sho 58
No. 25332, Japanese Patent Publication No. 51-18991,
The stretching method described in Japanese Examined Patent Publication No. 42-13560,
Alternatively, it can be obtained by a method using a foaming agent described in JP-B-42-4974.
【００１８】また、本発明に用いる親水性モノマーは、
分子内に親水性基を有し且つ架橋し得るモノマーであ
る。この親水性モノマーとしては、次の一般式ＣＨ2 ＝
ＣＲ1 −Ｘ（−ＣＨ3 ）n （但し、ＸはＣＯＮＨ−
（ＣＨ2）m −Ｎ，ＣＯＮ，ＯＣＯＮ，ＣＯＯ−（Ｃ
Ｈ2）m −Ｎ，ＣＯＮＨＣＨ，ｍは１〜１０、ｎは２〜
３、Ｒ1 はＨまたは炭素数１〜５のアルキル基）を用い
ることができる。この中で、ＸがＣＯＮＨ−（ＣＨ２）
3 Ｎ、ｎが２であるＮ、Ｎ−ジメチルアミノプロピル、
アクリルアミド、ｎが３つであるその４級塩タイプ、ま
たＸがＣＯＮ、ｎが２であるジメチルアクリルアミドが
特に好適に用いられる。The hydrophilic monomer used in the present invention is
It is a monomer having a hydrophilic group in the molecule and capable of crosslinking. As the hydrophilic monomer, the following general formula CH 2 =
CR 1 -X (-CH 3 ) n (where X is CONH-
(CH 2 ) m -N, CON, OCON, COO- (C
H 2) m -N, CONHCH, m is 1 to 10, n is 2
3, R 1 may be H or an alkyl group having 1 to 5 carbon atoms). In this, X is CONH- (CH2)
3 N, n is 2 N, N-dimethylaminopropyl,
Acrylamide, its quaternary salt type in which n is 3, and dimethylacrylamide in which X is CON and n is 2 are particularly preferably used.
【００１９】本発明の方法においては、先ず、フッ素樹
脂多孔体の細孔内親水性モノマーが含浸される。フッ素
樹脂多孔体の細孔内への親水性モノマーの含浸は、種々
の方法で行ない得るが、該多孔体が疎水性である点を考
慮し、下記の方法によるのが好ましいものである。 (1)(a)フッ素樹脂多孔体を、水との相溶性に優れ且つ表
面張力が３０dyne/cm 以下の有機溶媒（メタノール、エ
タノール、アセトン等）中に浸漬し、多孔体内に溶媒を
含浸せしめる第１工程。In the method of the present invention, first, the hydrophilic monomer in the pores of the fluororesin porous material is impregnated. The impregnation of the hydrophilic monomer into the pores of the fluororesin porous material can be carried out by various methods, but the following method is preferable in view of the fact that the porous material is hydrophobic. (1) (a) The fluororesin porous material is dipped in an organic solvent (methanol, ethanol, acetone, etc.) having excellent compatibility with water and a surface tension of 30 dyne / cm or less to impregnate the porous material with the solvent. First step.
【００２０】(b)次いで、これを水中に浸漬し、溶媒を
水と置換する（細孔内に水が含浸される）第２工程。 (c)その後、親水性モノマーの水溶液（モノマー濃度
は、通常、約０．０５〜１０重量％）中に多孔体を浸漬
し、該水溶液を多孔体の細孔内に含浸せしめる第３工
程。(B) Next, the second step of immersing this in water to replace the solvent with water (water is impregnated into the pores). (c) Then, the third step of immersing the porous body in an aqueous solution of a hydrophilic monomer (monomer concentration is usually about 0.05 to 10% by weight) to impregnate the aqueous solution into the pores of the porous body.
【００２１】以上、３工程を経て含浸する方法。 (2) 上記の如く低表面張力の有機溶媒に親水性モノマー
を混合して、３０ｄｙｎｅ／ｃｍ以下の溶液を調整し
て、フッ素樹脂多孔体に塗布、あるいは噴霧、あるいは
浸漬することによりフッ素樹脂多孔体の細孔内に該溶液
を含浸する方法。A method of impregnating through the above three steps. (2) As described above, a hydrophilic monomer is mixed with an organic solvent having a low surface tension to prepare a solution having a concentration of 30 dyne / cm or less, and the fluororesin porous material is coated with, sprayed on, or immersed in the fluororesin porous material. A method of impregnating the solution in the pores of the body.
【００２２】上記のような方法によって、多孔体の細孔
内に親水性ポリマーを含浸せしめると、多孔体の表面に
も親水性ポリマーが付着する。含浸工程において、多孔
体表面に付着した親水性ポリマーは拭き取り等により除
去してもよく、或いは付着させたままでもよい。親水性
モノマーを多孔体表面に付着させたまま、次工程の紫外
線照射を実施すると、多孔体の細孔内および表面に、架
橋された親水性モノマーが固定される。When the hydrophilic polymer is impregnated into the pores of the porous body by the method as described above, the hydrophilic polymer also adheres to the surface of the porous body. In the impregnation step, the hydrophilic polymer attached to the surface of the porous body may be removed by wiping or the like, or may be left attached. When ultraviolet irradiation in the next step is carried out with the hydrophilic monomer attached to the surface of the porous body, the crosslinked hydrophilic monomer is fixed in the pores and the surface of the porous body.
【００２３】本発明においては、上記含浸工程の後に行
われる紫外線照射の効率向上のため、紫外線増感剤を用
いるのが好ましい。該増感剤の具体例としては、安息香
酸ナトリウム、イソフタル酸、ベンゾフェノン、４−ヒ
ドロキシベンゾフェノン、２−メチルアンスラキノン、
ベンゾインアセトフェノン、ナフトキノン、アンスロン
等の芳香族ケトン、芳香族アルデヒド、芳香族カルボン
酸が挙げられる。これら増感剤の配合量は、親水性ポリ
マーの種類等によって変わり得るが、通常、親水性モノ
マー１００重量部に対し、約０．１〜１０重量部であ
る。In the present invention, it is preferable to use an ultraviolet sensitizer in order to improve the efficiency of ultraviolet irradiation performed after the impregnation step. Specific examples of the sensitizer include sodium benzoate, isophthalic acid, benzophenone, 4-hydroxybenzophenone, 2-methylanthraquinone,
Examples thereof include aromatic ketones such as benzoin acetophenone, naphthoquinone and anthrone, aromatic aldehydes and aromatic carboxylic acids. The blending amount of these sensitizers may vary depending on the type of hydrophilic polymer and the like, but is usually about 0.1 to 10 parts by weight with respect to 100 parts by weight of the hydrophilic monomer.
【００２４】このように紫外線増感剤を使用する場合
は、親水性モノマー水溶液中に配合し、該モノマーと共
にフッ素樹脂多孔体の細孔内に含浸せしめるのがよい
が、多孔体の細孔内に親水性モノマーを含浸せしめ、そ
の後該モノマーに増感剤を吸収せしめてもよい。When the UV sensitizer is used as described above, it is preferable that the UV sensitizer is blended in an aqueous solution of a hydrophilic monomer and impregnated into the pores of the fluororesin porous material together with the monomer. May be impregnated with a hydrophilic monomer, and then the monomer may be allowed to absorb a sensitizer.
【００２５】本発明の方法においては、上記のようにし
てフッ素樹脂多孔体の細孔内に親水性モノマーを含浸せ
しめた後、紫外線の照射により、該ポリマーが架橋さ
れ、多孔体の細孔内に固定される。In the method of the present invention, after the hydrophilic monomer is impregnated into the pores of the fluororesin porous material as described above, the polymer is cross-linked by the irradiation of ultraviolet rays, and the pores of the porous material are crosslinked. Fixed to.
【００２６】紫外線照射は高圧水銀ランプ、キセノンラ
ンプ、低圧水銀ランプ、メタルハライドランプ、カーボ
ンアーク灯等により行なうことができ、波長は１５０〜
６００ｎｍとするのが好ましい。照射時間は線源の出
力、照射距離、親水性ポリマーの種類、多孔体の形状等
種々の要因を考慮して設定するが、通常は約３０秒〜３
０分である。Ultraviolet irradiation can be carried out by a high pressure mercury lamp, a xenon lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc., and the wavelength is 150 to
It is preferably 600 nm. The irradiation time is set in consideration of various factors such as the output of the radiation source, the irradiation distance, the type of hydrophilic polymer, and the shape of the porous body, but it is usually about 30 seconds to 3 seconds.
0 minutes.
【００２７】紫外線照射の際に、紫外線吸収の少いポリ
エチレン、ポリプロピレン、ポリテトラフルオロエチレ
ン、ポリフッ化ビニリデン等の透明性フィルム（厚さ１
μｍ、好ましくは５〜５０μｍ）を用いて、親水性モノ
マー溶液を含浸した多孔体を上下方向から挟んでモノマ
ーの蒸発を防ぎ、また、酸素を遮断してもよい。A transparent film (thickness 1) of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, etc., which absorbs little ultraviolet light when irradiated with ultraviolet light.
The porous body impregnated with the hydrophilic monomer solution may be sandwiched from above and below to prevent evaporation of the monomer and to block oxygen.
【００２８】また、以上のように親水性モノマー含浸
後、紫外線照射により親水化された多孔質膜を、例えば
ディスク状、プリーツ状に加工し支持体に接着して、容
器内に組み込んでなるカートリッジフィルターや、平膜
状態でプレートとフレームにて支持するプレートタイプ
モジュール、中空糸膜モジュール等の瀘過装置とするこ
とができる。A cartridge which is obtained by impregnating the hydrophilic monomer as described above and then hydrophilizing the porous membrane by, for example, irradiating with ultraviolet rays is processed into a disc shape or a pleated shape, adhered to a support, and incorporated in a container. A filtration device such as a filter, a plate-type module in which a plate and a frame are supported in a flat membrane state, a hollow fiber membrane module, or the like can be used.
【００２９】また本発明の親水性を付与した多孔質支持
膜は、電池セパレーターなどにも応用することができ
る。以下、具体的実施例により本発明を更に詳細に説明
する。The hydrophilic supporting membrane of the present invention can be applied to battery separators and the like. Hereinafter, the present invention will be described in more detail with reference to specific examples.
【００３０】実施例１ 厚さ６０μｍ、細孔径０．１μｍ、気孔率７０％、縦お
よび横が各１０ｃｍのＰＴＦＥ多孔質シートをメタノー
ル中および水中に順次１０分間ずつ浸漬し、更に親水性
モノマー水溶液中に３０分間浸漬し、細孔内に親水性ポ
リマーを含浸させる。なお、親水性モノマー水溶液とし
ては、Ｎ、Ｎ−ジメチルアミノプロピルアクリルアミド
５ｗｔ％、ベンゾフェノン０．１ｗｔ％を溶解させたも
のを用いた。Example 1 A PTFE porous sheet having a thickness of 60 μm, a pore diameter of 0.1 μm, a porosity of 70%, and a length and width of 10 cm was immersed in methanol and water for 10 minutes respectively, and a hydrophilic monomer aqueous solution was further added. It is immersed in the solution for 30 minutes to impregnate the hydrophilic polymer in the pores. The hydrophilic monomer aqueous solution used was one in which 5 wt% of N, N-dimethylaminopropylacrylamide and 0.1 wt% of benzophenone were dissolved.
【００３１】含浸後、紙にてＰＴＦＥ多孔質シート上の
モノマーを払拭し、厚さ２５μｍのポリフッ化ビニリデ
ンシートにＰＴＦＥ多孔質シートを挟みカバーした。そ
の後、２ｋｗの高圧水銀ランプにより、距離１２ｃｍで
５分間ずつ多孔質シートの表裏各面に紫外線を照射し、
細孔内に架橋されたＮ、Ｎ−ジメチルアミノプロピルア
ミドが固定された親水性ＰＴＦＥ多孔質シートを得た。After the impregnation, the monomer on the PTFE porous sheet was wiped with paper, and the PTFE porous sheet was sandwiched and covered with a polyvinylidene fluoride sheet having a thickness of 25 μm. After that, a high pressure mercury lamp of 2 kW was used to irradiate the front and back surfaces of the porous sheet with ultraviolet rays for 5 minutes at a distance of 12 cm,
A hydrophilic PTFE porous sheet having crosslinked N, N-dimethylaminopropylamide fixed therein was obtained.
【００３２】なお、この親水性ＰＴＦＥ多孔質シート
は、細孔内へのポリビニルアルコールの固定により、基
材として用いた多孔質シートよりも、重量が６．１％増
加していた。The weight of the hydrophilic PTFE porous sheet was increased by 6.1% as compared with the porous sheet used as the substrate due to the fixing of polyvinyl alcohol in the pores.
【００３３】この親水性ＰＴＦＥ多孔質シートを圧力差
２３５ｍｍＨｇで透水試験に供したところ、純水の透過
流束は３．３ｃｍ3 ／（ｃｍ2 ・ｍｉｎ）であった。ま
た、該親水性多孔質シートを８０℃の熱水を１ｋｇ／ｃ
ｍ2 の加圧で３０分間透過させた後同様に試験したとこ
ろ、純水の透過流束は３．２ｃｍ3 ／（ｃｍ 2 ・ｍｉ
ｎ）であり、該親水性シートは親水性の耐久性が優れて
いることが確認された。また、エタノールとアセトンを
各々透過させた後、乾燥させ同様に透水試験したとこ
ろ、純水の透過流束は３．２ｃｍ3 ／（ｃｍ2・ｓｅ
ｃ）で、有機溶剤に対しても、耐久性が確認された。This hydrophilic PTFE porous sheet is used for pressure difference.
When subjected to a water permeability test at 235 mmHg, the permeation of pure water
Flux is 3.3 cm3/ (Cm2・ Min). Well
In addition, the hydrophilic porous sheet was treated with hot water at 80 ° C. at 1 kg / c.
m2It was permeated for 30 minutes under pressure and tested in the same way.
The permeation flux of pure water is 3.2 cm3/ (Cm 2・ Mi
n), and the hydrophilic sheet has excellent hydrophilic durability.
It was confirmed that In addition, ethanol and acetone
After permeating each, it was dried and similarly permeated.
The permeation flux of pure water is 3.2 cm3/ (Cm2・ Se
In c), durability was confirmed even with respect to organic solvents.
【００３４】因みに、基材として用いたＰＴＦＥ多孔質
シートでは透水が認められなかった。また、この膜の純
水透過実験を１．５ｋｇ／ｃｍ2 の加圧下で２ケ月行っ
たが親水性を維持していた。また、室温で硫酸（９７
％）フッ酸（５０％）に２ケ月浸漬しても親水性を維持
していた。Incidentally, no water permeation was observed in the PTFE porous sheet used as the base material. Further, a pure water permeation experiment of this membrane was carried out for 2 months under a pressure of 1.5 kg / cm 2 , but the hydrophilicity was maintained. In addition, sulfuric acid (97
%) Hydrophilicity was maintained even after immersion in hydrofluoric acid (50%) for 2 months.
【００３５】比較例１ 実施例１で用いたと同じＰＴＦＥ多孔質シートを界面活
性剤（ラウリルトリメチルアンモニウムクロライド）の
５重量％水溶液に３０分間浸漬して引き上げ、これを８
０℃で２時間乾燥した。Comparative Example 1 The same PTFE porous sheet used in Example 1 was immersed in a 5% by weight aqueous solution of a surfactant (lauryltrimethylammonium chloride) for 30 minutes and pulled up.
It was dried at 0 ° C. for 2 hours.
【００３６】この親水性多孔質シートを実施例１と同様
な透水試験に供したところ、透水量は３．６ｃｍ3 ／
（ｃｍ2 ・ｍｉｎ）（熱水処理前）および０ｃｍ3 ／
（ｃｍ2 ・ｍｉｎ）（熱水処理後）であった。When this hydrophilic porous sheet was subjected to the same water permeability test as in Example 1, the water permeability was 3.6 cm 3 /
(Cm 2 · min) (before hot water treatment) and 0 cm 3 /
(Cm 2 · min) (after hot water treatment).
【００３７】比較例２ 分子量２万のポリビニルアルコール２重量部を水１００
重量部に溶解した溶液中に、実施例１で用いたのと同じ
ＰＴＦＥ多孔質シートを３０分浸漬し、細孔内に上記溶
液を含浸させる。Comparative Example 2 2 parts by weight of polyvinyl alcohol having a molecular weight of 20,000 was added to 100 parts of water.
The same PTFE porous sheet used in Example 1 is dipped in a solution dissolved in parts by weight for 30 minutes to impregnate the solution with the solution.
【００３８】次に、これをホルムアルデヒド５重量部、
硫酸１５重量部、硫酸ナトリウム１５重量部および水６
５重量部から成る溶液（液温６０℃）に２分間浸漬し、
ポリビニルアルコールをアセタール化した。この親水性
多孔質シートの透水量は１．４ｃｍ3 ／（ｃｍ2 ・ｍｉ
ｎ）（熱水処理前）および１．１ｃｍ3 ／（ｃｍ2 ・ｍ
ｉｎ）（熱水処理後）であった。Next, 5 parts by weight of formaldehyde,
15 parts by weight of sulfuric acid, 15 parts by weight of sodium sulfate and 6 parts of water
Soak for 2 minutes in a solution consisting of 5 parts by weight (liquid temperature 60 ° C),
Polyvinyl alcohol was acetalized. The water permeability of this hydrophilic porous sheet is 1.4 cm 3 / (cm 2 · mi
n) (before hot water treatment) and 1.1 cm 3 / (cm 2 · m)
in) (after hot water treatment).
【００３９】実施例２ 親水性モノマー溶液を、イソプロピルアルコール７０重
量部、水３０重量部、Ｎ、Ｎ、ジメチルアクリルアミド
５重量部、ベンゾフェノン０．１重量部に調整し、ＰＴ
ＦＥ多孔質シートに塗布した以外は、実施例１と同じく
カバーをして紫外線照射を行った。実施例１と同様の耐
薬品性、瀘過特性が得られた。この親水膜を電池セパレ
ータとしての適用性を検討するためにＫＯＨの４０ｗｔ
％水溶液中での交流電圧低下法により、その電気抵抗を
測定した。結果は１．６ｍΩ／ｃｍ2 であり、電気抵抗
は低く、電池用セパレータとして適用できるものであっ
た。因みに、基材として用いたＰＴＦＥ多孔質シートの
電気抵抗は２２０ｍΩ／ｃｍ2 と高いものであった。Example 2 A hydrophilic monomer solution was adjusted to 70 parts by weight of isopropyl alcohol, 30 parts by weight of water, 5 parts by weight of N, N, dimethylacrylamide and 0.1 part by weight of benzophenone, and PT
Except that the FE porous sheet was applied, the same cover as in Example 1 was used and irradiation with ultraviolet rays was performed. The same chemical resistance and filtration characteristics as in Example 1 were obtained. To examine the applicability of this hydrophilic film as a battery separator, 40 wt% of KOH
%, Its electrical resistance was measured by an AC voltage drop method in an aqueous solution. The result was 1.6 mΩ / cm 2 , the electric resistance was low, and it was applicable as a battery separator. Incidentally, the electrical resistance of the PTFE porous sheet used as the base material was as high as 220 mΩ / cm 2 .
【００４０】[0040]
【発明の効果】本発明は多孔体の細孔内に含浸せしめら
れた親水性ポリマーを紫外線の照射により、架橋固定す
るようにしたので、多孔体の分解劣化を生ずることな
く、しかも簡単な操作で親水性フッ素樹脂多孔体を得る
ことができる。また、本発明の方法によって得られる親
水性多孔体は親水性が長期間持続する効果がある。INDUSTRIAL APPLICABILITY According to the present invention, the hydrophilic polymer impregnated in the pores of the porous body is crosslinked and fixed by the irradiation of ultraviolet rays, so that the decomposition and deterioration of the porous body do not occur and a simple operation is possible. Thus, a hydrophilic fluororesin porous material can be obtained. In addition, the hydrophilic porous body obtained by the method of the present invention has an effect of maintaining hydrophilicity for a long period of time.
Claims (2)
Ｈ2 ＝ＣＲ1 −（Ｒ1 はＨまたは炭素数１〜５のアルキ
ル基）を含む第３アミン若しくは第４アミン、または構
造式ＣＨ2 ＝ＣＲ1 −と−ＣＨ（Ｒ2 ）（Ｒ3 ）基（Ｒ
2，Ｒ3 は同一でも異なっていてもよい炭素数１〜５の
アルキル基）を含む親水性モノマー溶液を含浸した後、
紫外線照射を行い該親水性モノマーをグラフト重合およ
び架橋することを特徴とする親水性フッ素樹脂多孔質膜
の製造方法。1. The structural formula C is contained in the pores of the fluororesin porous material.
H 2 ═CR 1 — (R 1 is H or an alkyl group having 1 to 5 carbon atoms) containing a tertiary amine or a quaternary amine, or structural formulas CH 2 = CR 1 — and —CH (R 2 ) (R 3 ) Group (R
2 , R 3 may be the same or different, and after impregnating with a hydrophilic monomer solution containing a C 1-5 alkyl group),
A method for producing a hydrophilic fluororesin porous membrane, which comprises irradiating ultraviolet rays to graft-polymerize and crosslink the hydrophilic monomer.
1 −Ｘ（−ＣＨ3 ）n （ただし、ＸはＣＯＮＨ−（ＣＨ
2 ）m −Ｎ、ＣＯＮ、ＯＣＯＮ、ＣＯＯ−（ＣＨ2 ）m
−Ｎ、またはＣＯＮＨＣＨ、ｍは１〜１０の整数、ｎは
２〜３の整数、Ｒ1 はＨまたは炭素数１〜５のアルキル
基）で示される請求項１記載の親水性フッ素樹脂多孔質
膜の製造方法。2. The hydrophilic monomer has the general formula CH 2 = CR
1 -X (-CH 3) n (however, X is CONH- (CH
2 ) m- N, CON, OCON, COO- (CH 2 ) m
-N, or CONHCH, m is an integer of 1 to 10, n is an integer of 2 to 3, and R 1 is H or an alkyl group having 1 to 5 carbon atoms). Membrane manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29426691A JPH05131124A (en) | 1991-11-11 | 1991-11-11 | Production of hydrophilic fluoroplastic porous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29426691A JPH05131124A (en) | 1991-11-11 | 1991-11-11 | Production of hydrophilic fluoroplastic porous membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05131124A true JPH05131124A (en) | 1993-05-28 |
Family
ID=17805492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29426691A Pending JPH05131124A (en) | 1991-11-11 | 1991-11-11 | Production of hydrophilic fluoroplastic porous membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05131124A (en) |
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