JPH04153231A - Composite film of polytetrafluoroethylene and preparation thereof - Google Patents
Composite film of polytetrafluoroethylene and preparation thereofInfo
- Publication number
- JPH04153231A JPH04153231A JP27854690A JP27854690A JPH04153231A JP H04153231 A JPH04153231 A JP H04153231A JP 27854690 A JP27854690 A JP 27854690A JP 27854690 A JP27854690 A JP 27854690A JP H04153231 A JPH04153231 A JP H04153231A
- Authority
- JP
- Japan
- Prior art keywords
- polytetrafluoroethylene
- water
- composite membrane
- monomer
- soluble vinyl
- 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.)
- Pending
Links
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 25
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 5
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 4
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 102000004190 Enzymes Human genes 0.000 abstract description 3
- 108090000790 Enzymes Proteins 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000010559 graft polymerization reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000012510 hollow fiber Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229930091051 Arenine Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
上の
本発明は、複合材料に関し、特に、表面改質されたポリ
テトラフルオロエチレン系複合膜とその製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to composite materials, and particularly to a surface-modified polytetrafluoroethylene composite membrane and a method for manufacturing the same.
の が しよ゛ る
近年、機会的強度や耐薬品性などに優れた材料を担体な
いしは基質とし、これに機能性ポリマーをグラフトした
複合材料の開発が試みられている。In recent years, attempts have been made to develop composite materials in which functional polymers are grafted onto a carrier or substrate made of a material with excellent mechanical strength and chemical resistance.
その一つとして、担体（基質）として各種の物理的また
は化学的性質に優れているポリテトラフルオロエチレン
に、金属イオン吸着能や酵素固定能を有するポリマーを
グラフトした、高機能性複合材料の出現が期待さ九てい
る。しかしながら、従来よりポリテトラフルオロエチレ
ンなどの低エネルギー表面へのポリマーのグラフトは困
難とされており未だ実質的な成功例は見られない。One example of this is the emergence of highly functional composite materials in which polytetrafluoroethylene, which has excellent physical and chemical properties as a carrier (substrate), is grafted with polymers capable of adsorbing metal ions and immobilizing enzymes. There are nine expected. However, it has been considered difficult to graft a polymer onto a low-energy surface such as polytetrafluoroethylene, and no substantial success story has been seen yet.
本発明の目的は、このような従来の技術常識を打ち破り
、ポリテトラフルオロエチレンにポリマ特に、各種の機
能性を発揮し得る水溶性ビニルポワマーを結合させた高
機能性材料を得ることにある。The purpose of the present invention is to overcome such conventional technical common sense and to obtain a highly functional material in which polytetrafluoroethylene is bonded with a polymer, particularly a water-soluble vinyl polymer capable of exhibiting various functions.
四の および
本発明者は、上述の目的を達成するため研究を重ねた結
果、低圧気体プラズマの化学反応性を利用することによ
り、ポリテトラフルオロエチレン膜の表面に、水溶性ビ
ニルポリマーを結合させた複合膜が得られることを見い
だした。As a result of repeated research in order to achieve the above-mentioned object, the present inventors have succeeded in bonding a water-soluble vinyl polymer to the surface of a polytetrafluoroethylene film by utilizing the chemical reactivity of low-pressure gas plasma. It was found that a composite membrane can be obtained.
すなわち、本発明に従えば、水溶性ビニルモノマーの水
溶液を調製して充分な脱気を行う工程、テトラフルオロ
エチレン膜に不活性ガスのプラズマを照射して膜の表面
処理を行う工程、および、表面処理を終了した後直ちに
、表面処理後の膜をモノマー水溶液に接触させてモノマ
ーを重合すせる工程を含むことを特徴とするポリテトラ
フルオロエチレン複合膜の製造方法が提供される。That is, according to the present invention, a step of preparing an aqueous solution of a water-soluble vinyl monomer and sufficiently degassing it, a step of irradiating the tetrafluoroethylene membrane with an inert gas plasma to perform a surface treatment of the membrane, and There is provided a method for producing a polytetrafluoroethylene composite membrane, which includes the step of bringing the surface-treated membrane into contact with an aqueous monomer solution to polymerize the monomer immediately after the surface treatment is completed.
プラズマガスを重合に利用する技術としては、プラズマ
を重合を開始するためのエネルギー源に使用して超高分
子量のポリマーの調製を試みた例がある［厚目ら、 「
分析化学Ｊ ３８，１２，７３７（１９８９）コ。As a technique that uses plasma gas for polymerization, there is an example of an attempt to prepare ultra-high molecular weight polymers by using plasma as an energy source to initiate polymerization [Atsume et al.
Analytical Chemistry J 38, 12, 737 (1989).
しかし、本発明の方法は、そのような技術とは全く趣を
異にし、プラズマによってモノマーを直接活性化するの
ではなく、ポリテトラフルオロエチレンの表面にプラズ
マによるエネルギーを与え表面を親水化し、そこに水溶
性ビニルモノマーを導入してその表面をグラフト化する
ことに成功したものである。However, the method of the present invention is completely different from such techniques; instead of directly activating monomers with plasma, plasma energy is applied to the surface of polytetrafluoroethylene to make the surface hydrophilic. They succeeded in grafting the surface by introducing a water-soluble vinyl monomer into the material.
本発明の方法においてプラズマガスを発生させるのに用
いられる不活性ガスの好ましい例はアルゴンであり、一
般に、１０〜１０００Ｐａの圧力下においてプラズマ放
電をポリテトラフルオロエチレンの膜に照射する。A preferred example of an inert gas used to generate the plasma gas in the method of the invention is argon, and the polytetrafluoroethylene membrane is generally irradiated with a plasma discharge under a pressure of 10 to 1000 Pa.
本発明において用いる水溶性ビニルモノマー（ないしは
ポリマー）は、特に限定的なものではなく得るべき複合
材料の機能性に応じて選択されるが、好ましい水溶性ビ
ニルモノマーの例は、アクリルアミドまたはアクリル酸
である。その他に、メチルメタクリレートまたはＥ−カ
プロラクタムなども採用できる。The water-soluble vinyl monomer (or polymer) used in the present invention is not particularly limited and is selected depending on the functionality of the composite material to be obtained. Preferred examples of water-soluble vinyl monomers include acrylamide and acrylic acid. be. In addition, methyl methacrylate or E-caprolactam can also be used.
本発明の方法においては、水溶性ビニルモノマーの濃度
を比較的高濃度にＩＮ製して、表面処理後のポリテトラ
フルオロエチレンを接触させる。好ましいモノマー濃度
はＩＭ〜ＩＯＭである。調製したモノマー溶液は、充分
に脱気を行い、溶存酸素を除去することが重要である。In the method of the present invention, a water-soluble vinyl monomer is prepared at a relatively high concentration and brought into contact with polytetrafluoroethylene after surface treatment. The preferred monomer concentration is between IM and IOM. It is important that the prepared monomer solution is sufficiently degassed to remove dissolved oxygen.
ポリテトラフルオロエチレンの膜は、中空糸やラシヒリ
ング状の材料として提供される。これらの材料は、プラ
ズマ放電による表面処理工程を受ける前に超音波などに
より充分に洗浄しておくことが重要である。Polytetrafluoroethylene membranes are provided as hollow fiber or Raschig ring materials. It is important to thoroughly clean these materials using ultrasonic waves or the like before undergoing a surface treatment process using plasma discharge.
本発明の方法によれば、ポリテトラフルオロエチレンの
表面に、ポリアクリルアミドやポリアクリル酸などの水
溶性ビニルポリマーが物理的に付着しているのではなく
、化学的結合によって強力に結びついていることが種々
の測定結果により確認されている。かくして、本発明は
、ポリテトラフルオロエチレン膜の表面に、水溶性ビニ
ルポリマーが化学結合していることから成る複合膜も提
供する。According to the method of the present invention, water-soluble vinyl polymers such as polyacrylamide and polyacrylic acid are not physically attached to the surface of polytetrafluoroethylene, but are strongly bonded by chemical bonds. has been confirmed by various measurement results. Thus, the present invention also provides a composite membrane comprising a water-soluble vinyl polymer chemically bonded to the surface of a polytetrafluoroethylene membrane.
本発明によって得られる複合膜は、金属イオンの濃縮分
離、酵素固定化、液／液分離などの多くの用途に用いら
れる高機能性材料となり得るものである。The composite membrane obtained by the present invention can be a highly functional material used in many applications such as concentration and separation of metal ions, enzyme immobilization, and liquid/liquid separation.
以下、実施例に沿って本発明を説明するが、本発明はこ
の実施例によって制限されるものではない
尖１１例
本発明において使用するプラズマグラフト重合装置を第
１図に示す。電極１は４２０厘ｍの銅板をガラス管反応
容器の周りに固定しプラズマを発生させた。モノマーは
市販のアクリルアミド（ＡＡＭ）とアクリル＊ （ＡＡ
）をそのまま使用し所定濃度の水溶液を作成調製して容
器４に入れた後、液体窒素による凍結融解を３回繰り返
してモノマー溶液中に溶存しているガスの脱気を充分に
行った。The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.The plasma graft polymerization apparatus used in the present invention is shown in FIG. 1. Electrode 1 was a 420 mm copper plate fixed around a glass tube reaction vessel to generate plasma. The monomers are commercially available acrylamide (AAM) and acrylic* (AA
) was used as it was to prepare an aqueous solution of a predetermined concentration and put it into the container 4, and then freezing and thawing with liquid nitrogen was repeated three times to sufficiently degas the gas dissolved in the monomer solution.
基質は外径２．０ｍｍ、内径１．１ｍｍ、平均孔径０．
２μｍのテトラフルオロエチレン中空糸を用いジクロロ
エタン中で１０分間超音波洗浄した後、−昼夜真空乾燥
を行い重合装置のサンプル管２内にセットし真空排気し
た（図中矢印３の方向）。その後アルゴンガスを約１０
０Ｐａになるように装置内に導入しながら（図中矢印５
の方向）１０ｋＨｚのプラズマ放電を１０分間表面に照
射し重合系を排気系と切り放した後、直ちにモノマー溶
液と接触させ２５℃で後重合を行った。得られたグラフ
ト重合物は３Ｍ塩酸で洗浄し、水洗して真空乾燥した後
金属イオン吸着能を測定しＥＳＣＡ （島津ＥＳＣＡ−
７５０） 。The substrate has an outer diameter of 2.0 mm, an inner diameter of 1.1 mm, and an average pore size of 0.
After carrying out ultrasonic cleaning in dichloroethane for 10 minutes using a 2 μm tetrafluoroethylene hollow fiber, it was vacuum dried day and night, set in sample tube 2 of a polymerization apparatus, and evacuated (in the direction of arrow 3 in the figure). Then add argon gas for about 10 minutes.
While introducing it into the device so that the pressure is 0 Pa (arrow 5 in the figure)
After irradiating the surface with a 10 kHz plasma discharge for 10 minutes to separate the polymerization system from the exhaust system, it was immediately brought into contact with the monomer solution and post-polymerized at 25°C. The obtained graft polymer was washed with 3M hydrochloric acid, water and vacuum dried, and then the metal ion adsorption capacity was measured using ESCA (Shimadzu ESCA-
750).
ＳＥＭ（日本電子製ＪＳ呵−７２００） 、 および
ＦＴ−ＩＲ（Ｎｉｃｏｌｅｊ製Ｔｙｐｅ ５ＤＸＢ）を
用いた表面解析を行った。Surface analysis was performed using SEM (JS-7200 manufactured by JEOL) and FT-IR (Type 5DXB manufactured by Nicolej).
３．５ＭのＡＡＭ溶液で３０分間グラフトを行ったポリ
テトラフルオロエチレン中空糸（グラフト率３００％）
の外側および内側表面の断面ＳＥＭ写真によれば、外側
表面をポリアクリルアミドのグラフト重合物が被ってい
ることが明らかに確認できるが、内側ではその表面は無
処理のものと比較して変化は観察されなかった。これよ
りプラズマグラフト重合ではアルゴンガスプラズマの照
射によって中空糸の外側表面のみに活性点が発生しモノ
マー溶液との接触によってそこからグラフト重合が進行
するものと思われる。Polytetrafluoroethylene hollow fiber grafted with 3.5M AAM solution for 30 minutes (grafting rate 300%)
According to cross-sectional SEM photographs of the outer and inner surfaces of the It wasn't done. This suggests that in plasma graft polymerization, active sites are generated only on the outer surface of the hollow fiber by irradiation with argon gas plasma, and graft polymerization proceeds from there upon contact with the monomer solution.
一般にポリアクリルアミドは水溶性であるが今回のグラ
フト重合で得られた樹脂は架橋剤を使用していないにも
関わらす水不溶性のポリマーが得られ、熱水洗浄や塩酸
洗浄によってもその表面形態や大幅な重量変化は観察さ
れなかった。また同様な結果はモノマーをアクリル酸に
代えた場合にも観察された。これは、ポリテトラフルオ
ロエチレン中空糸の表面にポリアクリルアミドやポリア
クリル酸などの水溶性ビニルポリマーが物理的に付着し
ているのではなく化学結合によって強力に結びつきその
分子量は超巨大高分子に成っていることを示唆している
。Generally, polyacrylamide is water-soluble, but the resin obtained through this graft polymerization is water-insoluble even though no crosslinking agent is used, and its surface morphology remains unchanged even after washing with hot water or hydrochloric acid. No significant weight change was observed. Similar results were also observed when the monomer was replaced with acrylic acid. This is because water-soluble vinyl polymers such as polyacrylamide and polyacrylic acid are not physically attached to the surface of polytetrafluoroethylene hollow fibers, but are strongly bonded by chemical bonds and have a molecular weight that makes them ultra-huge polymers. This suggests that
第２図は３．０ＭのＡＡＭ溶液で３０分間グラフトを行
ったポリテトラフルオロエチレンフィルムの表面をＡＴ
Ｒプローブにより観察したＩＲスペクトルである。（ｂ
）は無処理の表面（ａ）をグラフト重合した後のスペク
トルで１６００ｃｍ−’付近にアミドのＣ＝Ｏ伸縮振動
やＮ−Ｈ変角振動に基づくピークが、さらに３４００ｃ
ｍ−’付近にはＮＨ伸縮振動に基づくピークが下地層の
ポリテトラフルオロエチレンのピークとあわせて観察さ
れた。（Ｃ）は（ｂ）と（ａ）の差スペクトルを示した
ものであるがこのスペクトルはプラズマ開始重合によっ
て得られた樹脂のものと同一であった。Figure 2 shows the surface of a polytetrafluoroethylene film grafted with a 3.0M AAM solution for 30 minutes.
This is an IR spectrum observed using an R probe. (b
) is the spectrum after graft polymerization of the untreated surface (a), and there is a peak based on the C=O stretching vibration and N-H bending vibration of the amide near 1600 cm-', and an additional peak at 3400 cm-'.
A peak based on NH stretching vibration was observed in the vicinity of m-' together with a peak of polytetrafluoroethylene of the base layer. (C) shows the difference spectrum between (b) and (a), and this spectrum was the same as that of the resin obtained by plasma initiated polymerization.
グラフト処理後のサンプルのＥＳＣＡのＣＩＳナロース
キャンスペクトルを第３図に示した。未処理の表面には
２９３ｅＶに−ＣＦ２−基によるケミカルシフトが顕著
であるのに対してグラフト処理後の表面にはこのケミカ
ルシフトは見られず２８９および２８６ｅＶにそれぞれ
＞Ｃ＝○、−ＣＨ−に相当するピークが観察された。よ
って今回のプラズマグラフト重合で得られた複合膜はポ
リテトラフルオロエチレン上にプラズマ開始重合によっ
て得られるものと同様なグラフトポリマーが形成された
ことが明白になった。またこのグラフト重合物の金属イ
オン吸着能を検討したところ、Ｐｄ（ＩＩ）やＣｕ（Ｉ
Ｉ）などの異なる金属イオン間の吸着ｐｌ＋に差がみら
れた。FIG. 3 shows the ESCA CIS narrow scan spectrum of the sample after the grafting treatment. On the untreated surface, there is a significant chemical shift due to the -CF2- group at 293 eV, whereas this chemical shift is not observed on the surface after the grafting treatment, and >C=○ and -CH- at 289 and 286 eV, respectively. A peak corresponding to . Therefore, it is clear that in the composite membrane obtained by this plasma graft polymerization, a graft polymer similar to that obtained by plasma-initiated polymerization was formed on polytetrafluoroethylene. In addition, when the metal ion adsorption ability of this graft polymer was investigated, it was found that Pd(II), Cu(I),
Differences were observed in adsorption pl+ between different metal ions such as I).
第１図は、本発明の複合膜を製造するのに好適な装置の
例である。
第２図は、本発明の複合膜の表面のＩＲスペクトルの例
である。
第３図は、本発明の複合膜のＥＳＣＡスペクトルの例で
ある。
第
図
波
数（Ｃｍ−’）
第
図FIG. 1 is an example of an apparatus suitable for producing the composite membrane of the present invention. FIG. 2 is an example of the IR spectrum of the surface of the composite membrane of the present invention. FIG. 3 is an example of the ESCA spectrum of the composite membrane of the present invention. Figure wave number (Cm-') Figure
Claims (6)
ニルポリマーが化学結合していることを特徴とするポリ
テトラフルオロエチレン複合膜。(1) A polytetrafluoroethylene composite membrane characterized in that a water-soluble vinyl polymer is chemically bonded to the surface of polytetrafluoroethylene.
たはポリアクリル酸である特許請求の範囲第（１）項に
記載のポリテトラフルオロエチレン複合膜。(2) The polytetrafluoroethylene composite membrane according to claim (1), wherein the water-soluble vinyl polymer is polyacrylamide or polyacrylic acid.
脱気を行う工程、テトラフルオロエチレン膜に不活性ガ
スのプラズマを照射して該膜の表面処理を行う工程、お
よび、前記表面処理の終了直後に、表面処理した膜を前
記モノマーの水溶液を接触させて該モノマーを重合させ
る工程を含むことを特徴とする、ポリテトラフルオロエ
チレン膜の表面に水溶性ビニルポリマーが化学結合して
いるポリテトラフルオロエチレン複合膜の製造方法。(3) a step of preparing an aqueous solution of a water-soluble vinyl monomer and sufficiently degassing; a step of irradiating the tetrafluoroethylene membrane with inert gas plasma to treat the surface of the membrane; A polytetrafluoroethylene film in which a water-soluble vinyl polymer is chemically bonded to the surface of the polytetrafluoroethylene film, comprising the step of bringing the surface-treated film into contact with an aqueous solution of the monomer to polymerize the monomer immediately after the completion of the surface treatment. A method for producing a tetrafluoroethylene composite membrane.
３）項に記載の複合膜の製造方法。(4) Claim No. 1 in which the inert gas is argon (
3) The method for producing a composite membrane according to item 3).
ある特許請求の範囲第（４）項に記載の複合膜の製造方
法。(5) The method for producing a composite membrane according to claim (4), wherein the concentration of the monomer aqueous solution to be prepared is 1M to 10M.
を充分に洗浄する工程を含む特許請求の範囲第（３）項
〜第（５）項のいずれかに記載の複合膜の製造方法。(6) The method for manufacturing a composite membrane according to any one of claims (3) to (5), including the step of thoroughly cleaning the tetrafluoroethylene membrane before plasma irradiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27854690A JPH04153231A (en) | 1990-10-16 | 1990-10-16 | Composite film of polytetrafluoroethylene and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27854690A JPH04153231A (en) | 1990-10-16 | 1990-10-16 | Composite film of polytetrafluoroethylene and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04153231A true JPH04153231A (en) | 1992-05-26 |
Family
ID=17598766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27854690A Pending JPH04153231A (en) | 1990-10-16 | 1990-10-16 | Composite film of polytetrafluoroethylene and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04153231A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048065A1 (en) * | 1999-12-28 | 2001-07-05 | Hitoshi Kanazawa | Method of modifying polymeric material and use thereof |
| WO2020261459A1 (en) * | 2019-06-26 | 2020-12-30 | 株式会社日立ハイテク | Fluorine resin membrane surface treatment method and fluorine resin membrane |
-
1990
- 1990-10-16 JP JP27854690A patent/JPH04153231A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048065A1 (en) * | 1999-12-28 | 2001-07-05 | Hitoshi Kanazawa | Method of modifying polymeric material and use thereof |
| US6830782B2 (en) | 1999-12-28 | 2004-12-14 | Hitoshi Kanazawa | Hydrophilic polymer treatment of an activated polymeric material and use thereof |
| KR100752245B1 (en) * | 1999-12-28 | 2007-08-29 | 카나자와 히토시 | Modification method of polymer material and its use |
| WO2020261459A1 (en) * | 2019-06-26 | 2020-12-30 | 株式会社日立ハイテク | Fluorine resin membrane surface treatment method and fluorine resin membrane |
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