JPH061876A - Method for producing hydrophilic porous fluororesin material - Google Patents
Method for producing hydrophilic porous fluororesin materialInfo
- Publication number
- JPH061876A JPH061876A JP18758492A JP18758492A JPH061876A JP H061876 A JPH061876 A JP H061876A JP 18758492 A JP18758492 A JP 18758492A JP 18758492 A JP18758492 A JP 18758492A JP H061876 A JPH061876 A JP H061876A
- Authority
- JP
- Japan
- Prior art keywords
- hydrophilic
- solution
- copolymer
- methyl alcohol
- alcohol
- 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
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
(57)【要約】
【目的】 含フッ素ビニルモノマー成分と含親水基ビニ
ルモノマー成分との親水性共重合体のメチルアルコール
溶液を多孔質フッ素樹脂材料に含浸させる親水性多孔質
フッ素樹脂材料の製造方法において、均一で安定な含浸
を行うことができ、かつ、十分な親水性を有する多孔質
フッ素樹脂材料を製造する方法の提供。
【構成】 含フッ素ビニルモノマー成分と含親水基ビニ
ルモノマー成分との親水性共重合体の有機溶媒溶液を多
孔質フッ素樹脂材料内に含浸させた後、該有機溶媒を除
去させる方法において、該有機溶媒として、（ａ）メチ
ルアルコールと、（ｂ）炭素数２〜４のアルコール及び
／又は炭素数３〜５のアルキルケトンとの混合物を用い
ることを特徴とする親水性多孔質フッ素樹脂材料の製造
方法。(57) [Abstract] [Purpose] Production of hydrophilic porous fluororesin material by impregnating a porous fluororesin material with a methyl alcohol solution of a hydrophilic copolymer of a fluorine-containing vinyl monomer component and a hydrophilic group-containing vinyl monomer component In the method, it is possible to provide a method for producing a porous fluororesin material capable of performing uniform and stable impregnation and having sufficient hydrophilicity. [Structure] In a method of impregnating a porous fluororesin material with an organic solvent solution of a hydrophilic copolymer of a fluorine-containing vinyl monomer component and a hydrophilic group-containing vinyl monomer component, and then removing the organic solvent, Use of a mixture of (a) methyl alcohol and (b) alcohol having 2 to 4 carbon atoms and / or alkyl ketone having 3 to 5 carbon atoms as a solvent, for producing a hydrophilic porous fluororesin material Method.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、親水性多孔質フッ素樹
脂材料の製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing a hydrophilic porous fluororesin material.
【０００２】[0002]
【従来技術及びその問題点】多孔質フッ素樹脂材料（以
下、材料とも言う）は、耐熱性及び耐薬品性に優れてお
り、分離膜として広く利用されている。ところが、多孔
質フッ素樹脂材料は一般に撥水性が大きく、水を容易に
透過させないため、水系の媒体に分散した粒子の分離膜
として適用することは困難である。水を容易に透過させ
るような多孔質フッ素樹脂材料を得るには、その細孔の
内面を親水化することが必要であり、このため各種の方
法が検討されている。このような方法として、例えば、
テトラフルオロエチレンのような含フッ素ビニルモノマ
ー成分とビニルアルコールのような含親水基ビニルモノ
マー成分との共重合体（以下、親水性共重合体とも言
う）をメチルアルコールを使って含浸させる方法があ
る。この方法の場合、親水性共重合体を単独で溶解さ
せ、かつ、多孔質フッ素樹脂材料に浸透しうる溶媒はメ
チルアルコールに限定される。しかし、実際にメチルア
ルコールを使って親水性共重合体を材料に含浸させる
と、含浸性が不安定であり、含浸むらが起こり易いとい
う問題がある。また、材料は撥水性であるため、メチル
アルコールに少量でも水分が混入すると材料への含浸性
はさらに低下し、さらに、メチルアルコール中の水分率
が約２重量％以上になると含浸は不可能となる。メチル
アルコールには強い吸水性があるため、含浸工程におけ
る溶液には厳重な水分管理が必要となる。一方、含浸・
乾燥後に得られる多孔質フッ素樹脂材料は、含浸溶液中
に全く水分が含まれていない場合にはあまり親水性が良
くなく、むしろ、含浸溶液中に水分が含まれている場合
の方が親水性が優れているという性状を示す。以上のよ
うに、親水性共重合体のメチルアルコール溶液を多孔質
フッ素樹脂材料に含浸させる方法においては、材料に対
する溶液の含浸性と得られる親水化材料の親水性との間
には相矛盾する重大な問題があり、従来の方法は、多孔
質フッ素樹脂材料の親水化技術として未だ不十分なもの
であった。2. Description of the Related Art Porous fluororesin materials (hereinafter also referred to as materials) have excellent heat resistance and chemical resistance and are widely used as separation membranes. However, since the porous fluororesin material generally has large water repellency and does not easily permeate water, it is difficult to apply it as a separation membrane for particles dispersed in an aqueous medium. In order to obtain a porous fluororesin material that allows water to easily pass through, it is necessary to make the inner surfaces of the pores hydrophilic, and various methods have been studied for this purpose. As such a method, for example,
There is a method in which a copolymer of a fluorine-containing vinyl monomer component such as tetrafluoroethylene and a hydrophilic group-containing vinyl monomer component such as vinyl alcohol (hereinafter, also referred to as a hydrophilic copolymer) is impregnated with methyl alcohol. . In the case of this method, the solvent capable of dissolving the hydrophilic copolymer alone and penetrating the porous fluororesin material is limited to methyl alcohol. However, when a material is actually impregnated with a hydrophilic copolymer using methyl alcohol, there is a problem that impregnation is unstable and uneven impregnation easily occurs. In addition, since the material is water repellent, impregnation into the material will be further reduced if a small amount of water is mixed into methyl alcohol, and impregnation becomes impossible when the water content in methyl alcohol is about 2% by weight or more. Become. Since methyl alcohol has a strong water absorption property, the solution in the impregnation step requires strict water management. On the other hand, impregnation
The porous fluororesin material obtained after drying is not very hydrophilic when the impregnating solution contains no water, but rather hydrophilic when the impregnating solution contains water. Is excellent. As described above, in the method for impregnating the porous fluororesin material with the methyl alcohol solution of the hydrophilic copolymer, there is a contradiction between the impregnability of the solution with respect to the material and the hydrophilicity of the resulting hydrophilic material. There is a serious problem, and the conventional method is still insufficient as a technique for hydrophilizing a porous fluororesin material.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、含フッ素ビ
ニルモノマー成分と含親水基ビニルモノマー成分との親
水性共重合体のメチルアルコール溶液を多孔質フッ素樹
脂材料に含浸させる親水性多孔質フッ素樹脂材料の製造
方法に見られる前記問題を解決し、均一で安定な含浸を
行うことができ、かつ、十分な親水性を有する多孔質フ
ッ素樹脂材料を効率よく得ることのできる方法を提供す
ることをその課題とする。DISCLOSURE OF THE INVENTION The present invention provides a hydrophilic porous fluorine in which a porous fluororesin material is impregnated with a methyl alcohol solution of a hydrophilic copolymer of a fluorine-containing vinyl monomer component and a hydrophilic group-containing vinyl monomer component. To provide a method capable of solving the above problems found in a method for producing a resin material, performing uniform and stable impregnation, and efficiently obtaining a porous fluororesin material having sufficient hydrophilicity. Is the task.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、含フッ素ビニルモノ
マー成分と含親水基ビニルモノマー成分との親水性共重
合体の有機溶媒溶液を多孔質フッ素樹脂材料内に含浸さ
せた後、該有機溶媒を除去させる方法において、該有機
溶媒として、（ａ）メチルアルコールと、（ｂ）炭素数
２〜４のアルコール及び／又は炭素数３〜５のアルキル
ケトンとの混合物を用いることを特徴とする親水性多孔
質フッ素樹脂材料の製造方法が提供される。また、本発
明によれば、含フッ素ビニルモノマー成分と含親水基ビ
ニルモノマー成分との親水性共重合体を有機溶媒に溶解
させた溶液を多孔質フッ素樹脂材料内に含浸させた後、
該有機溶媒を除去させる工程を２回又はそれ以上の回数
行う方法において、第１回目の工程における親水性共重
合体溶液の有機溶媒として、（ａ）メチルアルコール
と、（ｂ）炭素数２〜４のアルコール及び／又は炭素数
３〜５のアルキルケトンとの混合物を用い、第２回目以
降の少なくとも１回の工程における親水性共重合体溶液
の有機溶媒として、水を混在させたメチルアルコールを
用いるか又は（ａ）メチルアルコールと、（ｂ）炭素数
２〜４のアルコール及び／又は炭素数３〜５のアルキル
ケトンとの混合物に水を混在させたものを用いることを
特徴とする親水性多孔質フッ素樹脂材料の製造方法が提
供される。The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, a porous fluororesin material is impregnated with an organic solvent solution of a hydrophilic copolymer of a fluorine-containing vinyl monomer component and a hydrophilic group-containing vinyl monomer component, and then the organic solvent is removed. In the method, as the organic solvent, a mixture of (a) methyl alcohol and (b) an alcohol having 2 to 4 carbon atoms and / or an alkyl ketone having 3 to 5 carbon atoms is used as a hydrophilic porous material. A method for manufacturing a fluororesin material is provided. Further, according to the present invention, after impregnating a solution prepared by dissolving a hydrophilic copolymer of a fluorine-containing vinyl monomer component and a hydrophilic group-containing vinyl monomer component in an organic solvent into a porous fluororesin material,
In the method in which the step of removing the organic solvent is performed twice or more times, (a) methyl alcohol and (b) a carbon number of 2 to 2 are used as the organic solvent of the hydrophilic copolymer solution in the first step. Methyl alcohol mixed with water was used as an organic solvent for the hydrophilic copolymer solution in the second and subsequent steps at least once using a mixture of 4 alcohol and / or an alkyl ketone having 3 to 5 carbon atoms. Hydrophilicity characterized by using or using a mixture of (a) methyl alcohol and (b) alcohol having 2 to 4 carbon atoms and / or alkyl ketone having 3 to 5 carbon atoms with water. A method for manufacturing a porous fluororesin material is provided.
【０００５】本発明において用いる多孔質フッ素樹脂材
料の材質は特に限定されないが、通常は、ポリテトラフ
ルオロエチレンである。これ以外にも、テトラフルオロ
エチレン・ヘキサフルオロプロピレン共重合体、ポリフ
ッ化ビニル、ポリフッ化ビニリデン等のフッ素樹脂を材
質とするものも使用することができる。フッ素樹脂材料
に細孔を形成し、多孔質化する手段は、特に限定される
ものではなく、延伸、発泡、抽出等のいずれの手段によ
るものであってもよいが、細孔は連続して表裏に貫通し
ていることが必要である。本発明で用いる多孔質フッ素
樹脂材料は、ポリテトルラフルオロエチレンを延伸して
フィブリル化することによって多孔質化したものが最も
好ましい（特公昭５６−４５７７３号公報、特公昭５６
−１７２１６号公報）。多孔質フッ素樹脂材料は、空孔
率１５〜９５％、好ましくは７５〜９５％、細孔直径
０．０２〜３０μｍを有するものが好ましい。材料の形
態は、特にフィルム状のものに限定するものではなく、
チューブ、テープ、織物等の形態であってもよい。The material of the porous fluororesin material used in the present invention is not particularly limited, but it is usually polytetrafluoroethylene. In addition to this, it is also possible to use a material made of a fluororesin such as a tetrafluoroethylene / hexafluoropropylene copolymer, polyvinyl fluoride, or polyvinylidene fluoride. The means for forming pores in the fluororesin material to make it porous is not particularly limited, and may be any means such as stretching, foaming, and extraction, but the pores are continuous. It is necessary to penetrate both sides. The porous fluororesin material used in the present invention is most preferably made porous by stretching and fibrillating polytetrulafluoroethylene (JP-B-56-45773 and JP-B-56).
-17216). The porous fluororesin material preferably has a porosity of 15 to 95%, preferably 75 to 95% and a pore diameter of 0.02 to 30 μm. The form of the material is not particularly limited to the film-like one,
It may be in the form of a tube, a tape, a woven fabric or the like.
【０００６】本発明において用いる親水性共重合体は、
含フッ素ビニルモノマーと含親水基ビニルモノマーを必
須モノマー成分として含む共重合体である。含フッ素ビ
ニルモノマーとしては、テトラフルオロエチレン、ヘキ
サフルオロプロピレン、フッ化ビニル、フッ化ビニリデ
ン、モノクロロトリフルオロエチレン、ジクロロジフル
オロエチレン等が挙げられる。含親水基ビニルモノマー
としては、ビニルアルコール、アクリル酸、メタクリル
酸等が挙げられる。共重合体中の含親水基ビニルモノマ
ー成分の含有量は、共重合体が親水性を示すような割合
であればよく、通常、５０モル％以上、好ましくは７０
〜９９モル％の範囲である。本発明で用いる好ましい親
水性共重合体は、テトラフルオロエチレン・ビニルアル
コール共重合体である。この共重合体は、テトラフルオ
ロエチレン・ビニルアセテート共重合体をケン化処理す
ること等によって得ることができる。The hydrophilic copolymer used in the present invention is
It is a copolymer containing a fluorine-containing vinyl monomer and a hydrophilic group-containing vinyl monomer as essential monomer components. Examples of the fluorine-containing vinyl monomer include tetrafluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, monochlorotrifluoroethylene, dichlorodifluoroethylene and the like. Examples of the hydrophilic group-containing vinyl monomer include vinyl alcohol, acrylic acid, methacrylic acid and the like. The content of the hydrophilic group-containing vinyl monomer component in the copolymer may be such that the copolymer exhibits hydrophilicity, and is usually 50 mol% or more, preferably 70 mol% or more.
To 99 mol%. The preferred hydrophilic copolymer used in the present invention is a tetrafluoroethylene / vinyl alcohol copolymer. This copolymer can be obtained by saponifying a tetrafluoroethylene / vinyl acetate copolymer.
【０００７】この親水性共重合体を単独で溶解し、か
つ、材料に浸透しうる溶媒はメチルアルコールに限定さ
れる。ところが、親水性共重合体のメチルアルコール溶
液を実際に材料に含浸させると、溶液の含浸性が不安定
であり、含浸むらが起こりやすいという問題がある。さ
らに、溶液中に水が混入すると、材料に対する溶液の含
浸性が著しく低下するという問題を生じる。本発明で
は、これらの問題はいずれも解決される。本発明は、メ
チルアルコールに炭素数２〜４のアルコール及び／又は
炭素数３〜５のアルキルケトンのような、多孔質フッ素
樹脂材料に対して含浸性の優れた溶媒のうちいずれか一
つまたは任意の組合せを加え、２成分系以上の混合溶媒
とし、この混合溶媒による親水性共重合体の溶液を多孔
質フッ素樹脂材料に含浸させる方法である。この方法に
より、材料に対する含浸性は大きく向上し、含浸むらを
生じることなく、均一かつ安定に、材料に対する含浸処
理を行うことが可能となる。しかも溶液に多少の水分が
混入しても、溶液の含浸性が格別損われるようなことも
ない。メチルアルコールに混合させるアルコールとして
は、エチルアルコール、プロピルアルコール、イソプロ
ピルアルコール、ブチルアルコール等が挙げられる。ア
ルキルケトンとしては、アセトン、メチルエチルケト
ン、ジエチルケトン等が挙げられる。このうちで最も良
い組合せはメチルアルコールとエチルアルコールとの２
成分系の混合溶媒である。混合溶媒中のエチルアルコー
ル含有量は７０重量％未満が好ましく、さらに好ましく
は５０重量％以下である。メチルアルコール以外の有機
溶媒は親水性共重合体の貧溶媒であるため、混合溶媒中
の含有量が多くなれば、親水性共重合体の混合溶媒に対
する溶解性が低くなる。The solvent capable of dissolving the hydrophilic copolymer alone and penetrating the material is limited to methyl alcohol. However, when a material is actually impregnated with a methyl alcohol solution of a hydrophilic copolymer, there is a problem in that impregnation of the solution is unstable and uneven impregnation easily occurs. Further, when water is mixed in the solution, there arises a problem that the impregnation property of the solution into the material is significantly lowered. The present invention solves both of these problems. The present invention provides any one of solvents having excellent impregnation properties for a porous fluororesin material, such as an alcohol having 2 to 4 carbon atoms in methyl alcohol and / or an alkyl ketone having 3 to 5 carbon atoms, or This is a method in which an arbitrary combination is added to form a mixed solvent of two or more components, and a solution of the hydrophilic copolymer by the mixed solvent is impregnated into the porous fluororesin material. By this method, the impregnation property with respect to the material is significantly improved, and the impregnation treatment with respect to the material can be performed uniformly and stably without causing unevenness of the impregnation. Moreover, even if some water is mixed in the solution, the impregnating property of the solution is not particularly impaired. Examples of the alcohol mixed with methyl alcohol include ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Examples of the alkyl ketone include acetone, methyl ethyl ketone, diethyl ketone and the like. The best combination of these is 2 with methyl alcohol and ethyl alcohol
It is a mixed solvent of component systems. The content of ethyl alcohol in the mixed solvent is preferably less than 70% by weight, more preferably 50% by weight or less. Since the organic solvent other than methyl alcohol is a poor solvent for the hydrophilic copolymer, the higher the content in the mixed solvent, the lower the solubility of the hydrophilic copolymer in the mixed solvent.
【０００８】さらに好ましい方法は、前記２成分系以上
の混合溶媒に水を混在させた３成分系以上の混合溶媒に
よる親水性共重合体の溶液を多孔質フッ素樹脂材料に含
浸させる方法である。ここで、最も良い組合せはメチル
アルコールとエチルアルコールと水との３成分系の混合
溶媒である。この方法により、材料に対する含浸性は良
く、含浸むらを生じることなく、かつ、含浸・乾燥後に
得られる材料の親水性も十分発揮させることが可能とな
る。さらに好ましい方法としては、含浸処理を２回以上
の工程に分けて行う方法である。１回目の工程は含浸性
を優先して、前記２成分系以上の混合溶媒による親水性
共重合体の溶媒を多孔質フッ素樹脂材料に含浸させる。
ここで、最も良い組合せはメチルアルコールとエチルア
ルコールとの２成分系の混合溶媒である。そして、２回
目又はそれ以降の工程では親水性を十分発揮させるた
め、メチルアルコールに水を混在させた溶媒による親水
性共重合体の溶液を多孔質フッ素樹脂材料に含浸させ
る。このメチルアルコール溶媒には、さらに、炭素数２
〜４のアルコール及び／又は炭素数３〜５のアルキルケ
トンのような、多孔質フッ素樹脂材料に対して含浸性の
優れた溶媒のうちいずれか一つまたは任意の組合せが混
在していても良い。ここで、最も良い組合せは水を混在
させたメチルアルコールである。材料は１回目の含浸処
理で、既に相当程度の親水性が付与されているため、水
を混在させたメチルアルコール溶媒による溶液でも、十
分含浸可能である。溶媒中の水含有量は６０重量％未満
が好ましく、さらに好ましくは５〜３０重量％である。
５重量％未満では含浸・乾燥後の親水性を発揮させる効
果が不十分となり、３０重量％を超えると溶媒による溶
液の含浸性が不十分となる。さらに６０重量％を超える
と親水性共重合体の混合溶媒に対する溶解性が低くな
る。１回目の水を混在させていない溶液による含浸処理
においては、溶液に多少の水分が混入しても、含浸むら
を生じることなく、均一かつ安定に材料に対する含浸処
理を行うことができるという利点が得られ、また２回目
又はそれ以降の工程の水を混在させた溶液による含浸処
理においては、材料の親水性を著しく向上させうる利点
がある。この方法により、多孔質フッ素樹脂材料に対し
て、親水性共重合体を均一かつ安定に含浸させることが
でき、かつ、含浸・乾燥後に十分な親水性を有する材料
を得ることが可能となる。含浸処理を３回以上の工程に
分けて行う場合には、その途中の工程又は最終の工程で
水を混在させた溶媒による溶液で少なくとも１回以上含
浸処理を行う。A more preferable method is a method of impregnating a porous fluororesin material with a solution of a hydrophilic copolymer prepared by mixing a mixed solvent of two or more components and water with a mixed solvent of three or more components. Here, the best combination is a ternary mixed solvent of methyl alcohol, ethyl alcohol and water. By this method, the impregnation property with respect to the material is good, unevenness of the impregnation does not occur, and the hydrophilicity of the material obtained after the impregnation and drying can be sufficiently exhibited. A more preferable method is to carry out the impregnation treatment in two or more steps. In the first step, the porous fluororesin material is impregnated with the solvent of the hydrophilic copolymer by the mixed solvent of two or more components, giving priority to the impregnation property.
Here, the best combination is a binary solvent mixture of methyl alcohol and ethyl alcohol. In the second or subsequent steps, the porous fluororesin material is impregnated with a solution of the hydrophilic copolymer using a solvent in which methyl alcohol is mixed with water in order to sufficiently exhibit hydrophilicity. This methyl alcohol solvent also contains 2 carbon atoms.
~ 4 alcohol and / or C3-5 alkyl ketone, or any one or any combination of solvents having excellent impregnating property with respect to the porous fluororesin material may be mixed. . Here, the best combination is methyl alcohol mixed with water. Since the material has already been imparted with a considerable degree of hydrophilicity in the first impregnation treatment, it can be sufficiently impregnated even with a solution of a methyl alcohol solvent mixed with water. The water content in the solvent is preferably less than 60% by weight, more preferably 5 to 30% by weight.
If it is less than 5% by weight, the effect of exerting hydrophilicity after impregnation / drying is insufficient, and if it exceeds 30% by weight, impregnation of the solution with the solvent is insufficient. Further, if it exceeds 60% by weight, the solubility of the hydrophilic copolymer in the mixed solvent becomes low. In the first impregnation treatment with a solution in which water is not mixed, even if some water is mixed in the solution, there is an advantage that the impregnation treatment can be performed uniformly and stably on the material without causing uneven impregnation. In the impregnation treatment with the solution obtained and mixed with water in the second or subsequent step, there is an advantage that the hydrophilicity of the material can be remarkably improved. According to this method, the hydrophilic copolymer can be uniformly and stably impregnated into the porous fluororesin material, and a material having sufficient hydrophilicity after impregnation and drying can be obtained. When the impregnation treatment is performed in three or more steps, the impregnation treatment is performed at least once with a solution of a solvent mixed with water in the intermediate step or the final step.
【０００９】本発明で材料の含浸処理に用いる親水性共
重合体の溶液中濃度は、４重量％以下が好ましく、さら
に好ましくは０．１〜２重量％である。親水性共重合体
の濃度が４重量％を超えると、材料の細孔の目づまりが
生じるようになるので好ましくない。また、材料に対す
る親水性共重合体溶液の含浸処理は、塗布、散布、浸
漬、圧入、吸引等の各種の方法で行うことができる。含
浸処理後の溶媒の除去は、材料をピンフレームに固定
し、風乾させるか大気圧下の加熱、減圧下の加熱により
行うことができる。加熱温度は６０℃以下が良い。The concentration of the hydrophilic copolymer used for impregnation of the material in the present invention is preferably 4% by weight or less, more preferably 0.1 to 2% by weight. When the concentration of the hydrophilic copolymer exceeds 4% by weight, the pores of the material become clogged, which is not preferable. Further, the impregnation treatment of the hydrophilic copolymer solution with respect to the material can be performed by various methods such as coating, spraying, dipping, press fitting, and suction. The solvent can be removed after the impregnation treatment by fixing the material on a pin frame and air-drying, or heating under atmospheric pressure or heating under reduced pressure. The heating temperature is preferably 60 ° C or lower.
【００１０】[0010]
【発明の効果】本発明によれば、多孔質フッ素樹脂材料
に対する親水性共重合体溶液の含浸処理を、含浸むらな
く、均一かつ安定に行うことができ、親水性に優れた材
料を効率良く得ることができる。EFFECT OF THE INVENTION According to the present invention, the impregnation treatment of the hydrophilic copolymer solution into the porous fluororesin material can be carried out uniformly and stably without unevenness of impregnation, and a material excellent in hydrophilicity can be efficiently obtained. Obtainable.
【００１１】[0011]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。なお、以下の実施例及び比較例において、材料の
厚さと空孔率の測定及び親水性評価は、以下の方法によ
り行われた。 （１）厚さ 厚さは、１／１０００ｍｍの精度を有するダイアル測厚
ゲージにて測定した。 （２）空孔率 材料の空孔率は材料の密度を測定して得た。ポリテトラ
フルオロエチレンの真密度は２．２ｇ／ｃｍ3であると
して、以下の式を用いて空孔率を計算した。 空孔率（％）＝（２．２−材料の密度）÷２．２×１０
０ 含浸処理後の材料の空孔率の計算においては、真密度と
して２．２ｇ／ｃｍ3の代わりに２．１ｇ／ｃｍ3を採用
した。 （３）親水性評価法 親水性は高さ５ｃｍの所から水滴をサンプル全面に吹き
かけ、次の５段階にしたがって目視で評価した。 １．濡れない。（水が染み込まない。） ２．少し濡れる部分がある。 ３．半分程度は濡れる。 ４．斑もしくは筋状に濡れない部分が残る。 ５．全面が均一に良く濡れる。EXAMPLES Next, the present invention will be described in more detail by way of examples. In the following examples and comparative examples, measurement of material thickness and porosity and evaluation of hydrophilicity were performed by the following methods. (1) Thickness Thickness was measured with a dial thickness gauge having an accuracy of 1/1000 mm. (2) Porosity The porosity of the material was obtained by measuring the density of the material. The true density of polytetrafluoroethylene was 2.2 g / cm 3 , and the porosity was calculated using the following formula. Porosity (%) = (2.2-density of material) ÷ 2.2 × 10
0 In the calculation of the porosity of the material after the impregnation treatment, 2.1 g / cm 3 was adopted as the true density instead of 2.2 g / cm 3 . (3) Hydrophilicity evaluation method Hydrophilicity was visually evaluated according to the following five steps by spraying water droplets on the entire surface of the sample from a height of 5 cm. 1. Do not get wet (Water does not soak into it.) 2. There is a part that gets a little wet. 3. About half gets wet. 4. Spots or streaks that do not wet remain. 5. The entire surface is evenly and well wet.
【００１２】実施例１ テトラフルオロエチレン・ビニルアルコール共重合体
（テトラフルオロエチレン・ビニルアセテート共重合体
のケン化物；ケン化度１００％；フッ素含量２７重量
％；水酸基含有１４．５ミリモル／ｇ）を１リットルの
メチルアルコールに溶かし、これにエチルアルコール、
水を加え、溶液Ａ（上記共重合体１重量％；メチルアル
コール７９重量％；エチルアルコール２０重量％）と溶
液Ｂ（上記共重合体０．５重量％；メチルアルコール７
９．５重量％；水２０重量％）との２種類の含浸溶液を
調製した。厚さ４０μｍ、空孔率８０％の多孔質ポリテ
トラフルオロエチレン膜を、溶液Ａ中に浸漬して含浸処
理した後、ピンフレーム上で、６０℃で５分間乾燥し
た。さらに、溶液Ｂ中に浸漬して含浸処理した後、ピン
フレーム上で、６０℃で５分間乾燥した。２回の含浸処
理共に含浸性は良好であり、得られた多孔質膜は、厚さ
３０μｍ、空孔率７０％、親水性評価５であった。Example 1 Tetrafluoroethylene / vinyl alcohol copolymer (saponified tetrafluoroethylene / vinyl acetate copolymer; saponification degree 100%; fluorine content 27% by weight; hydroxyl group content 14.5 mmol / g) Is dissolved in 1 liter of methyl alcohol, and ethyl alcohol,
Water was added, and solution A (the above copolymer 1% by weight; methyl alcohol 79% by weight; ethyl alcohol 20% by weight) and solution B (the above copolymer 0.5% by weight; methyl alcohol 7)
9.5 wt%; 20 wt% water) were prepared. A porous polytetrafluoroethylene film having a thickness of 40 μm and a porosity of 80% was immersed in the solution A for impregnation treatment, and then dried on a pin frame at 60 ° C. for 5 minutes. Furthermore, after being immersed in the solution B for impregnation treatment, it was dried on a pin frame at 60 ° C. for 5 minutes. The impregnability was good in both impregnation treatments, and the resulting porous membrane had a thickness of 30 μm, a porosity of 70%, and a hydrophilicity rating of 5.
【００１３】実施例２ 実施例１で用いた共重合体を１リットルのメチルアルコ
ールに溶かし、これにエチルアルコール、水を加え、含
浸溶液（上記共重合体１重量％；メチルアルコール５９
重量％；エチルアルコール２０重量％；水２０重量％）
を調製した。厚さ４０μｍ、空孔率８０％の多孔質ポリ
テトラフルオロエチレン膜を、この溶液中に浸漬して含
浸処理した後、ピンフレーム上で、６０℃で５分間乾燥
した。溶液の含浸性は良好であり、得られた多孔質膜
は、厚さ３０μｍ、空孔率７０％、親水性評価５であっ
た。Example 2 The copolymer used in Example 1 was dissolved in 1 liter of methyl alcohol, ethyl alcohol and water were added thereto, and the impregnation solution (1% by weight of the above copolymer; methyl alcohol 59) was added.
% By weight; 20% by weight of ethyl alcohol; 20% by weight of water)
Was prepared. A porous polytetrafluoroethylene film having a thickness of 40 μm and a porosity of 80% was immersed in this solution for impregnation treatment, and then dried on a pin frame at 60 ° C. for 5 minutes. The impregnation property of the solution was good, and the obtained porous film had a thickness of 30 μm, a porosity of 70%, and a hydrophilicity rating of 5.
【００１４】実施例３ 実施例１で用いた共重合体を１リットルのメチルアルコ
ールに溶かし、これにエチルアルコールを加え、含浸溶
液（上記共重合体１重量％；メチルアルコール７９重量
％；エチルアルコール２０重量％）を調製した。厚さ４
０μｍ、空孔率８０％の多孔質ポリテトラフルオロエチ
レン膜を、この溶液中に浸漬して含浸処理した後、ピン
フレーム上で、６０℃で５分間乾燥した。溶液の含浸性
は良好であり、得られた多孔質膜は、厚さ３０μｍ、空
孔率７０％、親水性評価４であった。Example 3 The copolymer used in Example 1 was dissolved in 1 liter of methyl alcohol, ethyl alcohol was added thereto, and the impregnation solution (1% by weight of the above copolymer; 79% by weight of methyl alcohol; ethyl alcohol) was added. 20% by weight) was prepared. Thickness 4
A porous polytetrafluoroethylene membrane having a pore size of 0 μm and a porosity of 80% was immersed in this solution for impregnation treatment, and then dried on a pin frame at 60 ° C. for 5 minutes. The impregnation property of the solution was good, and the obtained porous film had a thickness of 30 μm, a porosity of 70%, and a hydrophilicity rating of 4.
【００１５】実施例４ 実施例１で用いた共重合体を１リットルのメチルアルコ
ールに溶かし、これにアセトン、水を加えて溶液Ａ（上
記共重合体１重量％；メチルアルコール７９重量％；ア
セトン２０重量％）と溶液Ｂ（上記共重合体０．５重量
％；メチルアルコール７９．５重量％；水２０重量％）
との２種類の含浸溶液を調製した。厚さ４０μｍ、空孔
率８０％の多孔質ポリテトラフルオロエチレン膜を溶液
Ａ中に浸漬して含浸処理した後、ピンフレーム上で、６
０℃で５分間乾燥した。さらに、溶液Ｂ中に浸漬して含
浸処理した後、ピンフレーム上で、６０℃で５分間乾燥
した。２回の含浸処理共に溶液の含浸性は良好であり、
得られた多孔質膜は、厚さ３０μｍ、空孔率７０％、親
水性評価５であった。Example 4 The copolymer used in Example 1 was dissolved in 1 liter of methyl alcohol, and acetone and water were added thereto to prepare a solution A (1% by weight of the above copolymer; 79% by weight of methyl alcohol; acetone). 20% by weight) and solution B (0.5% by weight of the above copolymer; 79.5% by weight of methyl alcohol; 20% by weight of water)
Two kinds of impregnation solutions were prepared. A porous polytetrafluoroethylene film having a thickness of 40 μm and a porosity of 80% was immersed in the solution A for impregnation treatment, and then 6 on the pin frame.
It was dried at 0 ° C. for 5 minutes. Furthermore, after being immersed in the solution B for impregnation treatment, it was dried on a pin frame at 60 ° C. for 5 minutes. Both the two impregnation treatments have good solution impregnation properties,
The obtained porous film had a thickness of 30 μm, a porosity of 70%, and a hydrophilicity rating of 5.
【００１６】比較例１ 実施例１で用いた共重合体を１リットルのメチルアルコ
ールに溶かし、１重量％メチルアルコール溶液を調製
し、含浸溶液とした。厚さ４０μｍ、空孔率８０％の多
孔質ポリテトラフルオロエチレン膜を、この溶液中に浸
漬して含浸処理したが、溶液は多孔質膜に均一にはしみ
込まず、一部に含浸むらができた。その後、ピンフレー
ム上で、６０℃で５分間乾燥した。得られた多孔質膜を
親水性評価３であった。Comparative Example 1 The copolymer used in Example 1 was dissolved in 1 liter of methyl alcohol to prepare a 1 wt% methyl alcohol solution, which was used as an impregnation solution. A porous polytetrafluoroethylene membrane having a thickness of 40 μm and a porosity of 80% was dipped in this solution for impregnation treatment, but the solution did not uniformly permeate into the porous membrane and uneven impregnation could occur in part. It was Then, it dried at 60 degreeC for 5 minutes on the pin frame. The obtained porous film had a hydrophilicity rating of 3.
【００１７】比較例２ 実施例１で用いた共重合体を１リットルのメチルアルコ
ールに溶かし、これに水を加えて、含浸溶液（上記共重
合体１重量％；メチルアルコール７９重量％；水２０重
量％）を調製した。厚さ４０μｍ、空孔率８０％の多孔
質ポリテトラフルオロエチレン膜を、この溶液中に浸漬
したが、溶液は多孔質膜にしみ込まなかった。その後、
ピンフレーム上で、６０℃で５分間乾燥したが、得られ
た多孔質膜は親水性評価１であった。Comparative Example 2 The copolymer used in Example 1 was dissolved in 1 liter of methyl alcohol, water was added thereto, and an impregnation solution (1% by weight of the above copolymer; 79% by weight of methyl alcohol; water 20) was added. Wt%) was prepared. A porous polytetrafluoroethylene membrane having a thickness of 40 μm and a porosity of 80% was immersed in this solution, but the solution did not soak into the porous membrane. afterwards,
After drying on a pin frame at 60 ° C. for 5 minutes, the resulting porous film had a hydrophilicity rating of 1.
Claims (6)
ビニルモノマー成分との親水性共重合体の有機溶媒溶液
を多孔質フッ素樹脂材料内に含浸させた後、該有機溶媒
を除去させる方法において、該有機溶媒として、（ａ）
メチルアルコールと、（ｂ）炭素数２〜４のアルコール
及び／又は炭素数３〜５のアルキルケトンとの混合物を
用いることを特徴とする親水性多孔質フッ素樹脂材料の
製造方法。1. A method of impregnating a porous fluororesin material with an organic solvent solution of a hydrophilic copolymer of a fluorine-containing vinyl monomer component and a hydrophilic group-containing vinyl monomer component, and then removing the organic solvent, As the organic solvent, (a)
A method for producing a hydrophilic porous fluororesin material, which comprises using a mixture of methyl alcohol and (b) an alcohol having 2 to 4 carbon atoms and / or an alkyl ketone having 3 to 5 carbon atoms.
ルアルコールとの混合物である請求項１の方法。2. The method of claim 1 wherein the organic solvent is a mixture of methyl alcohol and ethyl alcohol.
又は２の方法。3. Water mixed in the organic solvent.
Or the method of 2.
ビニルモノマー成分との親水性共重合体を有機溶媒に溶
解させた溶液を多孔質フッ素樹脂材料内に含浸させた
後、該有機溶媒を除去させる工程を２回又はそれ以上の
回数行う方法において、第１回目の工程における親水性
共重合体溶液の有機溶媒として、（ａ）メチルアルコー
ルと、（ｂ）炭素数２〜４のアルコール及び／又は炭素
数３〜５のアルキルケトンとの混合物を用い、第２回目
以降の少なくとも１回の工程における親水性共重合体溶
液の有機溶媒として、水を混在させたメチルアルコール
を用いるか又は（ａ）メチルアルコールと、（ｂ）炭素
数２〜４のアルコール及び／又は炭素数３〜５のアルキ
ルケトンとの混合物に水を混在させたものを用いること
を特徴とする親水性多孔質フッ素樹脂材料の製造方法。4. A porous fluororesin material is impregnated with a solution of a hydrophilic copolymer of a fluorine-containing vinyl monomer component and a hydrophilic group-containing vinyl monomer component dissolved in an organic solvent, and then the organic solvent is removed. In the method in which the step of performing the step is performed twice or more times, (a) methyl alcohol, (b) an alcohol having 2 to 4 carbon atoms and / or an organic solvent of the hydrophilic copolymer solution in the first step. Alternatively, a mixture with an alkyl ketone having 3 to 5 carbon atoms is used, and methyl alcohol mixed with water is used as an organic solvent of the hydrophilic copolymer solution in at least one step after the second step, or (a ) A mixture of methyl alcohol and (b) an alcohol having 2 to 4 carbon atoms and / or an alkyl ketone having 3 to 5 carbon atoms mixed with water is used. A method for producing a porous fluororesin material.
チレン・ビニルアルコール共重合体である請求項１〜４
のいずれかの方法。5. The hydrophilic copolymer is a tetrafluoroethylene / vinyl alcohol copolymer, and the hydrophilic copolymer is a copolymer of tetrafluoroethylene and vinyl alcohol.
Either way.
ポリテトラフルオロエチレンである請求項１〜５のいず
れかの方法。6. The method according to claim 1, wherein the porous fluororesin material is expanded porous polytetrafluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18758492A JP3286696B2 (en) | 1992-06-22 | 1992-06-22 | Method for producing hydrophilic porous fluororesin material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18758492A JP3286696B2 (en) | 1992-06-22 | 1992-06-22 | Method for producing hydrophilic porous fluororesin material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH061876A true JPH061876A (en) | 1994-01-11 |
| JP3286696B2 JP3286696B2 (en) | 2002-05-27 |
Family
ID=16208668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18758492A Expired - Fee Related JP3286696B2 (en) | 1992-06-22 | 1992-06-22 | Method for producing hydrophilic porous fluororesin material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3286696B2 (en) |
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