JPH06293837A - Production of porous film of hydrophilic fluororesin - Google Patents
Production of porous film of hydrophilic fluororesinInfo
- Publication number
- JPH06293837A JPH06293837A JP8043593A JP8043593A JPH06293837A JP H06293837 A JPH06293837 A JP H06293837A JP 8043593 A JP8043593 A JP 8043593A JP 8043593 A JP8043593 A JP 8043593A JP H06293837 A JPH06293837 A JP H06293837A
- Authority
- JP
- Japan
- Prior art keywords
- hydrophilic
- compound
- fluororesin
- porous body
- fluororesin porous
- 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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Links
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- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、親水性フッ素樹脂多孔
質膜の製造方法に関する。さらに詳しくは、薬品、食
品、水などの液体の精密ろ過や限外ろ過に使用する液体
用ろ過膜、ろ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。TECHNICAL FIELD The present invention relates to a method for producing a hydrophilic fluororesin porous membrane. More specifically, it relates to a method for producing a hydrophilic fluororesin porous membrane that can be used in a filtration membrane for liquids used for microfiltration or ultrafiltration of liquids such as chemicals, foods, and water, and a filtration device.
【０００２】[0002]
【従来の技術】薬品、食品、水などの液体の精密ろ過や
限外ろ過において、ろ過膜の重要な選択因子となるの
は、微粒子の除去性能、液体の透過流束、耐薬品性、耐
圧性、耐熱性等である。従来選ばれていたのは、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
多孔質膜である。2. Description of the Related Art In microfiltration and ultrafiltration of liquids such as chemicals, foods, and water, important factors for selecting a filtration membrane are fine particle removal performance, liquid permeation flux, chemical resistance, and pressure resistance. And heat resistance. Conventionally, a porous film made of polytetrafluoroethylene (hereinafter abbreviated as PTFE), a fluororesin such as polyvinylidene fluoride, or a high-molecular polymer such as polyethylene, polypropylene, or polyolefin is used.
【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ろ過用カートリッジフ
ィルター内に空気が流れ込む。However, in recent years, the need for a hydrophilic film has further increased. That is, for example, in the semiconductor industry, silicon wafers are washed with nitric acid, hydrofluoric acid, sulfuric acid, etc., but when the chemicals are exchanged after circulating cleaning, the chemicals are discharged to remove air from the filtration cartridge filter. Flows in.
【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に、
次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 the hydrophobic membrane such as the PTFE membrane in the filter, and the effect of hydrophilic treatment of the membrane with an organic solvent when the filter is attached disappears.
Then, when the chemical is introduced, 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】フッ素樹脂多孔体の親水化方法としては、
界面活性剤を塗布する方法あるいは特開昭５６−６３７
７２号公報に記載されているようにポリビニールアルコ
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させ、前記高分子を熱処理、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。As a method for making the fluororesin porous body hydrophilic,
A method of applying a surfactant or JP-A-56-637.
No. 72, a water-soluble polymer such as polyvinyl alcohol or polyethylene glycol is impregnated into the pores of a porous body, and the polymer is heat-treated, acetalized, esterified, heavy chromium. A method of making hydrophilic by acid treatment, irradiation of ionizing radiation, etc. is known.
【０００６】また、特開平２−１９６８３４号公報に開
示してあるように、フッ素樹脂の表面改質にＡｒＦレー
ザーを照射して親水化する方法が知られている。Further, as disclosed in Japanese Patent Laid-Open No. 2-196834, there is known a method of irradiating an surface of a fluororesin with an ArF laser to make it hydrophilic.
【０００７】[0007]
【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、界面活性剤が多孔体に十分
付着しないため脱落しやすく、親水性が保持されにくい
という問題があった。However, the method of applying the surfactant has a problem that the surfactant is not sufficiently adhered to the porous body and thus is easily removed and hydrophilicity is difficult to be retained.
【０００８】また、特開昭５６−６３７７２号公報に記
載の方法は、放射線照射により多孔体の分解劣化を生
じ、機械的強度が著しく低下する。さらに、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, in the method described in JP-A-56-63772, the irradiation of radiation causes decomposition and deterioration of the porous body, resulting in a marked decrease in mechanical strength. Further, the heat treatment, acetalization, and esterification make a part of the water-soluble polymer hydrophobic, so that there is a problem that the hydrophilicity is lowered.
【０００９】また、特開平２−１９６８３４号公報に記
載の方法は、表面層の改質であり、多孔体の内部に至る
全体の親水化は不十分であった。Further, the method described in Japanese Patent Application Laid-Open No. 2-196834 is a modification of the surface layer, and the hydrophilization of the whole inside the porous body was insufficient.
【００１０】本発明は、前記従来技術の問題点を解決す
るため、親水性およびその耐久性に優れ，耐薬品性、耐
圧性、耐熱性等に優れ，かつ安価に製造することのでき
る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 is excellent in hydrophilicity and its durability, excellent in chemical resistance, pressure resistance, heat resistance and the like, and hydrophilic in that it can be manufactured at low cost. It is an object to provide a method for producing a fluororesin porous film.
【００１１】[0011]
【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，
フッ素原子との結合エネルギーが１２８ｋｃａｌ／ｍｏ
ｌ以上の原子と親水基を有する化合物の存在下で、フッ
素樹脂多孔体にエキシマレーザーを照射して親水化する
という構成を備えたものである。すなわち、エキシマレ
ーザーを照射することによりフッ素樹脂のＣ−Ｆ結合
（１２８ｋｃａｌ／ｍｏｌ）を切る。この際、後で述べ
るようにＣ−Ｆ結合エネルギー（１２８ｋｃａｌ／ｍｏ
ｌ）以上の原子を存在させることにより、切断されたフ
ッ素原子は前記原子と結合され、トラップされる。フッ
素原子は電気陰性度が４．０と大きいので、好ましくは
炭素原子（電気陰性度：２．５）より電気陰性度が小さ
い原子を存在させることでＣ−Ｆ間の再結合を阻むこと
ができる。また、その原子とフッ素原子との結合は、そ
の結合エネルギーがＣ−Ｆ結合（１２８ｋｃａｌ／ｍｏ
ｌ）より高いので、再切断されにくい。したがって、フ
ッ素樹脂のフッ素原子の一部を親水性官能基と置換する
ことができる。In order to achieve the above object, the method for producing a hydrophilic fluororesin porous membrane of the present invention comprises:
The binding energy with the fluorine atom is 128 kcal / mo
In the presence of a compound having 1 or more atoms and a hydrophilic group, the fluororesin porous material is irradiated with an excimer laser to make it hydrophilic. That is, the C—F bond (128 kcal / mol) of the fluororesin is cut by irradiating the excimer laser. At this time, as described later, the C—F bond energy (128 kcal / mo)
l) By allowing the above atoms to exist, the cleaved fluorine atom is bonded to the atom and trapped. Since the fluorine atom has a large electronegativity of 4.0, it is preferable to prevent the recombination between C and F by allowing an atom having an electronegativity smaller than that of the carbon atom (electronegativity: 2.5) to exist. it can. The bond energy between the atom and the fluorine atom is C—F bond (128 kcal / mo).
Since it is higher than l), it is less likely to be cut again. Therefore, a part of the fluorine atoms of the fluororesin can be replaced with the hydrophilic functional group.
【００１２】前記構成においては、化合物がアルミニウ
ム化合物、ホウ素化合物またはリチウム化合物であるこ
とが好ましい。また、前記構成においては、エキシマレ
ーザーがＡｒＦレーザーであることが好ましい。In the above constitution, the compound is preferably an aluminum compound, a boron compound or a lithium compound. Further, in the above structure, the excimer laser is preferably an ArF laser.
【００１３】[0013]
【作用】前記本発明の構成によれば、親水性が高くその
耐久性に優れ、かつ耐薬品性、耐溶剤性、耐熱性等に優
れた親水性フッ素樹脂多孔質膜を安価に提供することが
できる。また，放電処理のような真空操作が必要なく、
簡便に親水性フッ素樹脂多孔質膜を得ることができる。According to the constitution of the present invention, it is possible to inexpensively provide a hydrophilic fluororesin porous film having high hydrophilicity, excellent durability, chemical resistance, solvent resistance, heat resistance and the like. You can Also, there is no need for vacuum operation such as discharge processing,
A hydrophilic fluororesin porous membrane can be easily obtained.
【００１４】また、化合物がアルミニウム化合物、ホウ
素化合物またはリチウム化合物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
た親水性フッ素樹脂多孔質膜を提供することができる。Further, according to the preferable constitution of the present invention in which the compound is an aluminum compound, a boron compound or a lithium compound, it is possible to provide a hydrophilic fluororesin porous membrane which is more excellent in hydrophilicity and durability thereof. .
【００１５】また，エキシマレーザーがＡｒＦレーザー
であると，フッ素樹脂のＣ−Ｆ結合を切断するのに好都
合である。When the excimer laser is an ArF laser, it is convenient for cutting the C--F bond of the fluororesin.
【００１６】[0016]
【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。本発明者らは、種々検討の結果、特定原子と
親水基を有する化合物の存在下で、フッ素樹脂多孔体に
エキシマレーザーを照射することにより、フッ素樹脂多
孔体のフッ素原子の一部を親水性官能基と置換しフッ素
樹脂多孔質膜を作製した。そして、その膜は親水性が高
く、その耐久性に優れ、かつ耐薬品性、耐溶剤性、耐熱
性などに優れることを見いだし本発明を完成するに至っ
た。EXAMPLES The present invention will be described in more detail with reference to the following examples. As a result of various studies, the inventors of the present invention irradiate an excimer laser on a fluororesin porous material in the presence of a compound having a specific atom and a hydrophilic group, thereby making part of the fluorine atoms of the fluororesin porous material hydrophilic. Substitution with a functional group was performed to produce a fluororesin porous membrane. The inventors have found that the film has high hydrophilicity, excellent durability, chemical resistance, solvent resistance, heat resistance, etc., and completed the present invention.
【００１７】本発明に用いる多孔体は、フッ素樹脂から
なるものであれば特に限定されず、通常ＰＴＦＥからな
るものである。また、他のフッ素樹脂、例えばテトラフ
ルオロエチレン−ヘキサフルオロプロピレン共重合体、
エチレン−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−パーフルオロアルキルビニールエーテ
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 not particularly limited as long as it is made of a fluororesin, and is usually made of PTFE. In addition, other fluororesins such as tetrafluoroethylene-hexafluoropropylene copolymer,
It may be composed of an ethylene-tetrafluoroethylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a vinyl fluoride resin, a vinylidene fluoride resin, a trifluoroethylene chloride resin, or the like.
【００１８】そして、この多孔体はシート状、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うる。また、この多孔体の気孔
率、細孔の公称孔径は用途に応じて種々設定できるが、
通常、気孔率は２０〜８０％，公称孔径は約０．０１〜
１０μｍが好ましい。The porous material may have any shape such as a sheet shape or a tube shape, and either a fired product or a non-fired product may be used. Further, the porosity of this porous body, the nominal pore diameter of the pores can be variously set according to the application,
Generally, the porosity is 20 to 80% and the nominal pore size is about 0.01 to
10 μm is preferable.
【００１９】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 Patent Publication No. 42-13560,
Alternatively, it can be obtained by a method using a foaming agent described in JP-B-42-4974.
【００２０】また、本発明に用いる化合物は、フッ素原
子との結合エネルギーが１２８ｋｃａｌ／ｍｏｌ以上で
あり、電気陰性度が２．５より小さなアルミニウム（フ
ッ素原子との結合エネルギー：１５８ｋｃａｌ／ｍｏ
ｌ、電気陰性度：１．５）、ホウ素（１８３ｋｃａｌ／
ｍｏｌ，２．０），カルシウム（１３４ｋｃａｌ／ｍｏ
ｌ，１．０），バリウム（１３９ｋｃａｌ／ｍｏｌ，
０．９），リチウム（１３９ｋｃａｌ／ｍｏｌ，１．
０）等の原子を有する水酸化アルミニウム、ホウ酸、ホ
ウ酸アンモニウム、水酸化リチウム、水酸化カルシウ
ム、水酸化バリウム等の化合物を用いることができる。
本発明においてはこれら化合物の水溶液が好ましく用い
られる。また、溶質の溶解度を上げるために、水酸化ナ
トリウム、水酸化カリウム等のアルカリ塩を添加しても
よい。The compound used in the present invention has a binding energy with a fluorine atom of 128 kcal / mol or more and an electronegativity of aluminum smaller than 2.5 (binding energy with a fluorine atom: 158 kcal / mo).
1, electronegativity: 1.5), boron (183 kcal /
mol, 2.0), calcium (134 kcal / mo)
1, 1.0), barium (139 kcal / mol,
0.9), lithium (139 kcal / mol, 1.
Compounds such as aluminum hydroxide, boric acid, ammonium borate, lithium hydroxide, calcium hydroxide and barium hydroxide having atoms such as 0) can be used.
In the present invention, aqueous solutions of these compounds are preferably used. Further, an alkali salt such as sodium hydroxide or potassium hydroxide may be added to increase the solubility of the solute.
【００２１】本発明において上記化合物を存在させる方
法としては、フッ素樹脂フィルムに好ましくは上記化合
物の水溶液を含浸、塗布などにより接触させる方法があ
げられる。In the present invention, the method of allowing the above compound to be present includes a method of contacting the fluororesin film with an aqueous solution of the above compound, preferably by impregnation or coating.
【００２２】本発明の方法では、まず、フッ素樹脂多孔
体の細孔内に化合物水溶液が含浸される。フッ素樹脂多
孔体は有機溶媒に浸漬、または有機溶媒中で超音波洗浄
等を行ったものを用いてもよい。In the method of the present invention, first, the compound aqueous solution is impregnated into the pores of the fluororesin porous material. The fluororesin porous material may be used after being immersed in an organic solvent or subjected to ultrasonic cleaning in an organic solvent.
【００２３】フッ素樹脂多孔体の細孔内への化合物水溶
液の含浸は、種々の方法で行いうるが、この多孔体が疎
水性である点を考慮して、下記の方法を採用することが
好ましい。 （１）（ａ）フッ素樹脂多孔体を、水との相溶性に優れ
かつ表面張力が３０ｄｙｎｅ／ｃｍ以下の有機溶媒（メ
タノール、エタノール、アセトン、エーテル、イソプロ
ピルアルコール等）に浸漬し、多孔体内に溶媒を含浸さ
せる第１工程。 （ｂ）次いで、これを水に浸漬し、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、化合物溶液に多孔体を浸漬し、水を該水
溶液と置換する（細孔内に該水溶液が含浸される）第３
工程。 以上、３工程を経て含浸する方法。Impregnation of the aqueous solution of the compound into the pores of the fluororesin porous material can be carried out by various methods, but it is preferable to adopt the following method in consideration of the fact that the porous material is hydrophobic. . (1) (a) The fluororesin porous body is immersed in an organic solvent (methanol, ethanol, acetone, ether, isopropyl alcohol, etc.) having excellent compatibility with water and having a surface tension of 30 dyne / cm or less, and then is immersed in the porous body. The first step of impregnating with a solvent. (B) Next, the second step of immersing this in water to replace the solvent with water (water is impregnated into the pores). (C) After that, the porous body is immersed in the compound solution, and water is replaced with the aqueous solution (the pores are impregnated with the aqueous solution) Third
Process. The method of impregnating through the above three steps.
【００２４】（２）上記のごとく低表面張力の有機溶媒
に化合物を混合して、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
るいはフッ素樹脂多孔体を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。(2) The compound is mixed with an organic solvent having a low surface tension as described above to prepare a solution of 30 dyne / cm or less, which is applied to or sprayed on the fluororesin porous body, or the fluororesin porous body is dipped. By impregnating the solution into the pores of the fluororesin porous material.
【００２５】上記のような方法によって、多孔体の細孔
内に化合物溶液を含浸させることができる。By the method as described above, the compound solution can be impregnated into the pores of the porous body.
【００２６】前記水溶液を含浸中に次工程のエキシマレ
ーザーを照射すると、フッ素樹脂多孔体のフッ素原子の
一部が親水基と置換される。エキシマレーザーはＡｒ
Ｆ，Ｘｅ2 、Ｆ2 、Ａｒ2 、ＫｒＣｌレーザー等の、光
子エネルギーが１２８ｋＪ／ｍｏｌ以上のレーザーを用
いることで、Ｃ−Ｆ結合を切断して親水基と置換するこ
とができるが、特にＡｒＦレーザーを用いるのが好まし
い。照射時間は出力、照射距離、発振繰り返し数、化合
物水溶液の種類、濃度、多孔体の形状，厚さ等種々の要
因を考慮して設定するが、通常は約１０秒〜３０分であ
る。When the excimer laser of the next step is irradiated during the impregnation of the aqueous solution, a part of the fluorine atoms of the fluororesin porous material is replaced with the hydrophilic group. Excimer laser is Ar
By using a laser having a photon energy of 128 kJ / mol or more, such as an F, Xe 2 , F 2 , Ar 2 , or KrCl laser, the C—F bond can be cleaved and replaced with a hydrophilic group. It is preferable to use a laser. The irradiation time is set in consideration of various factors such as output, irradiation distance, number of oscillation repetitions, kind of aqueous solution of compound, concentration, shape and thickness of porous body, but is usually about 10 seconds to 30 minutes.
【００２７】以下、具体的な実施例により本発明をさら
に詳細に説明する。 実施例１ 厚さ６０μｍ、公称孔径０．１μｍ、気孔率７５％、縦
横の長さがそれぞれ１０ｃｍのＰＴＦＥ多孔性シートを
メタノールおよび水に順次１０分ずつ浸漬し、さらに化
合物水溶液に１０分浸漬し、細孔内に化合物水溶液を含
浸させた。ここで、化合物水溶液として、４．１重量％
ホウ酸水溶液を用いた。水溶液含浸状態でＡｒＦレーザ
ーをエネルギー密度２００ｍＪ／ｃｍ2 、繰り返し５０
パルス／秒で１２０秒照射した後、純水で洗浄し、次い
で乾燥し親水性フッ素樹脂多孔質膜を得た。The present invention will be described in more detail with reference to specific examples. Example 1 A PTFE porous sheet having a thickness of 60 μm, a nominal pore size of 0.1 μm, a porosity of 75%, and a length and width of 10 cm was immersed in methanol and water for 10 minutes each, and further immersed in a compound aqueous solution for 10 minutes. The compound aqueous solution was impregnated into the pores. Here, as a compound aqueous solution, 4.1% by weight
A boric acid aqueous solution was used. ArF laser with energy density of 200 mJ / cm 2 , repeatedly 50 times in an aqueous solution impregnated state.
After irradiating with pulse / second for 120 seconds, it was washed with pure water and then dried to obtain a hydrophilic fluororesin porous membrane.
【００２８】この膜を純水に浸漬したところ、速やかに
吸水した。さらにこの膜をＥＳＣＡ（electron spectro
scopy for chemical analysis ）により表面分析を行っ
たところ、親水化処理前のＯ／Ｃの比が０に対して親水
化処理後は０．１８であった。また、Ｆ／Ｃの値が各々
２．０と０．２８であったことから、フッ素原子が親水
基と置換したことを確認できた。また、波形解析を行っ
たところ、−ＣＦ2 −結合（２９２ｅＶ）の炭素原子数
を１００とすると、−Ｃ−Ｏ−結合（２８６ｅＶ）が６
３、−Ｃ＝Ｏ（２８８ｅＶ）結合が１１であり、親水性
官能基が存在していることを確認した。処理前にはそれ
ら官能基は存在しなかった。When this membrane was immersed in pure water, it immediately absorbed water. Furthermore, this film is applied to ESCA (electron spectro
Surface analysis by scopy for chemical analysis) showed that the O / C ratio before the hydrophilic treatment was 0, whereas it was 0.18 after the hydrophilic treatment. Further, since the F / C values were 2.0 and 0.28, respectively, it could be confirmed that the fluorine atom was replaced with the hydrophilic group. In addition, when a waveform analysis was performed, assuming that the number of carbon atoms of the —CF 2 — bond (292 eV) was 100, the number of —C—O— bonds (286 eV) was 6.
3, -C = O (288 eV) bond was 11, and it was confirmed that a hydrophilic functional group was present. Prior to treatment, these functional groups were absent.
【００２９】この膜を、フッ酸（５０重量％）、塩酸
（３６重量％）、硫酸（９７重量％）に室温で１日浸漬
後、水で洗浄、乾燥後も親水性を維持していた。また、
エタノール、アセトンで洗浄、乾燥後も親水性を維持し
ていた。The membrane was kept hydrophilic even after being immersed in hydrofluoric acid (50% by weight), hydrochloric acid (36% by weight) and sulfuric acid (97% by weight) at room temperature for 1 day, washed with water and dried. . Also,
It remained hydrophilic even after washing with ethanol and acetone and drying.
【００３０】この親水性フッ素樹脂多孔質膜を圧力差２
３５ｍｍＨｇで透水試験に供したところ、純水の透過流
束は３．５ｃｍ3 ／ｃｍ2 ／ｍｉｎであった。親水化処
理を行わない膜は純水に濡れないために０であり、その
膜をエタノールにより湿潤させた後、測定した純水の透
過流束は３．５ｃｍ3 ／ｃｍ2 ／ｍｉｎであった。した
がって、親水化処理したことによる膜の透過流束の低下
はみられなかった。This hydrophilic fluororesin porous membrane is provided with a pressure difference of 2
When subjected to a water permeability test at 35 mmHg, the permeation flux of pure water was 3.5 cm 3 / cm 2 / min. The membrane which was not subjected to the hydrophilic treatment was 0 because it was not wet with pure water, and the permeation flux of pure water measured after wetting the membrane with ethanol was 3.5 cm 3 / cm 2 / min. . Therefore, no reduction in the permeation flux of the membrane due to the hydrophilization treatment was observed.
【００３１】この親水性フッ素樹脂多孔質膜にテトラエ
トキシシランを接触させた後、洗浄し、Ｘ線マイクロア
ナライザーで観察したところ、多孔体孔内までＳｉ原子
が存在しており、親水化していることを確認した。Tetraethoxysilane was brought into contact with this hydrophilic fluororesin porous membrane, washed, and observed with an X-ray microanalyzer. As a result, Si atoms were present even in the pores of the porous body, and they were hydrophilized. It was confirmed.
【００３２】実施例２ 実施例１と同様に、化合物溶液として２Ｎ水酸化リチウ
ム水溶液を用いた以外は、同じ方法でレーザー照射し
た。得られた膜は洗浄、乾燥後も純水に浸漬すると吸水
した。また，膜性能も実施例１とほぼ同様であった。Example 2 Laser irradiation was carried out in the same manner as in Example 1 except that 2N aqueous lithium hydroxide solution was used as the compound solution. The obtained film absorbed water when immersed in pure water even after being washed and dried. The membrane performance was also almost the same as in Example 1.
【００３３】実施例３ 実施例１と同様に、化合物溶液として１Ｎ水酸化アルミ
ニウムと１Ｎ水酸化ナトリウムの混合水溶液を用い、同
じ方法でレーザー照射した。このとき、溶液を含浸した
膜をその水溶液中に沈めてＡｒＦレーザーをエネルギー
密度１００ｍＪ／ｃｍ2 、繰り返し５０パルス／秒で４
０秒照射した。得られた膜は洗浄、乾燥後も純水に浸漬
すると吸水した。また，膜性能も実施例１とほぼ同様で
あった。Example 3 As in Example 1, laser irradiation was carried out by the same method using a mixed aqueous solution of 1N aluminum hydroxide and 1N sodium hydroxide as a compound solution. At this time, the film impregnated with the solution was immersed in the aqueous solution, and an ArF laser was used at an energy density of 100 mJ / cm 2 at a repetition rate of 50 pulses / second for 4
It was irradiated for 0 seconds. The obtained film absorbed water when immersed in pure water even after being washed and dried. The membrane performance was also almost the same as in Example 1.
【００３４】比較例 実施例１と同様の多孔質膜を用い、化合物溶液を使用し
ない以外は、実施例１と同じ方法でレーザー照射した。
得られた膜は洗浄、乾燥後に純水に浸漬しても親水化さ
れていなかった。Comparative Example Laser irradiation was carried out in the same manner as in Example 1 except that the same porous membrane as in Example 1 was used and no compound solution was used.
The obtained film was not hydrophilized even if it was washed and dried and then immersed in pure water.
【００３５】[0035]
【発明の効果】以上説明した通り、本発明によれば、フ
ッ素樹脂多孔体のフッ素原子を親水基で置換することに
より、親水性が高くその耐久性に優れ、かつ耐薬品性、
耐溶剤性、耐熱性等に優れた親水性フッ素樹脂多孔質膜
を安価に提供することができる。また，放電処理のよう
な真空操作が必要なく、簡便に親水性フッ素樹脂多孔質
膜を得ることができる。As described above, according to the present invention, by replacing the fluorine atom of the fluororesin porous material with a hydrophilic group, the hydrophilicity is high and the durability is excellent, and the chemical resistance,
A hydrophilic fluororesin porous membrane having excellent solvent resistance, heat resistance, etc. can be provided at low cost. Further, the hydrophilic fluororesin porous film can be easily obtained without the need for vacuum operation such as electric discharge treatment.
【００３６】また、化合物の溶液がアルミニウム化合
物、ホウ素化合物またはリチウム化合物の水溶液である
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親水性フッ素樹脂多孔質膜を提供す
ることができる。Further, according to the preferable constitution of the present invention in which the solution of the compound is an aqueous solution of an aluminum compound, a boron compound or a lithium compound, a hydrophilic fluororesin porous film further excellent in hydrophilicity and durability thereof is provided. can do.
【００３７】また，エキシマレーザーがＡｒＦレーザー
であると，フッ素樹脂のＣ−Ｆ結合を切断するのに好都
合である。When the excimer laser is an ArF laser, it is convenient for cutting the C—F bond of the fluororesin.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浦入 正勝 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内 (72)発明者 野田 謙 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内 (72)発明者 松本 憲嗣 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masakatsu Urairi 1-2-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (72) Inventor Ken Ken Noda 1-2-1 Shimohozumi, Ibaraki City, Osaka Prefecture No. Nitto Denko Corporation (72) Inventor Kenji Matsumoto 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation
Claims (3)
ｋｃａｌ／ｍｏｌ以上の原子と親水基を有する化合物の
存在下で、フッ素樹脂多孔体にエキシマレーザーを照射
して親水化することからなる親水性フッ素樹脂多孔質膜
の製造方法。1. The binding energy with a fluorine atom is 128.
A method for producing a hydrophilic fluororesin porous membrane, which comprises irradiating a fluororesin porous body with an excimer laser to make it hydrophilic in the presence of a compound having at least kcal / mol atoms and a hydrophilic group.
合物またはリチウム化合物である請求項１に記載の親水
性フッ素樹脂多孔質膜の製造方法。2. The method for producing a hydrophilic fluororesin porous film according to claim 1, wherein the compound is an aluminum compound, a boron compound or a lithium compound.
る請求項１に記載の親水性フッ素樹脂多孔質膜の製造方
法。3. The method for producing a hydrophilic fluororesin porous film according to claim 1, wherein the excimer laser is an ArF laser.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08043593A JP3340501B2 (en) | 1993-04-07 | 1993-04-07 | Method for producing hydrophilic fluororesin porous membrane |
| EP94910522A EP0644227B1 (en) | 1993-03-23 | 1994-03-23 | Solid surface modifying method and apparatus |
| PCT/JP1994/000463 WO1994021715A1 (en) | 1993-03-23 | 1994-03-23 | Solid surface modifying method and apparatus |
| DE69432966T DE69432966T2 (en) | 1993-03-23 | 1994-03-23 | METHOD AND DEVICE FOR MODIFYING SOLID SURFACES |
| US08/888,862 US6117497A (en) | 1993-03-23 | 1997-07-07 | Solid surface modification method and apparatus |
| US09/639,006 US6689426B1 (en) | 1993-03-23 | 2000-08-15 | Solid surface modification method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08043593A JP3340501B2 (en) | 1993-04-07 | 1993-04-07 | Method for producing hydrophilic fluororesin porous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06293837A true JPH06293837A (en) | 1994-10-21 |
| JP3340501B2 JP3340501B2 (en) | 2002-11-05 |
Family
ID=13718192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08043593A Expired - Lifetime JP3340501B2 (en) | 1993-03-23 | 1993-04-07 | Method for producing hydrophilic fluororesin porous membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3340501B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182516A (en) * | 2002-12-02 | 2004-07-02 | Tokai Univ | Method of photochemically modifying solid material surface |
| DE102007006634A1 (en) | 2007-02-06 | 2008-08-07 | Laser-Laboratorium Göttingen e.V. | Modifying PTFE surface to create roughness and improve adhesion properties, e.g. to biological cells or chemical adhesive, by direct material ablation using pulsed laser light |
| US10981138B2 (en) | 2016-04-13 | 2021-04-20 | M Hikari & Energy Laboratory Co., Ltd. | Electrochemical reactor using ion on/off surface switch |
-
1993
- 1993-04-07 JP JP08043593A patent/JP3340501B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182516A (en) * | 2002-12-02 | 2004-07-02 | Tokai Univ | Method of photochemically modifying solid material surface |
| DE102007006634A1 (en) | 2007-02-06 | 2008-08-07 | Laser-Laboratorium Göttingen e.V. | Modifying PTFE surface to create roughness and improve adhesion properties, e.g. to biological cells or chemical adhesive, by direct material ablation using pulsed laser light |
| US10981138B2 (en) | 2016-04-13 | 2021-04-20 | M Hikari & Energy Laboratory Co., Ltd. | Electrochemical reactor using ion on/off surface switch |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3340501B2 (en) | 2002-11-05 |
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