JPH07145253A - Method for improving water repellency of molded article of polytetrafluoroethylene - Google Patents
Method for improving water repellency of molded article of polytetrafluoroethyleneInfo
- Publication number
- JPH07145253A JPH07145253A JP16201793A JP16201793A JPH07145253A JP H07145253 A JPH07145253 A JP H07145253A JP 16201793 A JP16201793 A JP 16201793A JP 16201793 A JP16201793 A JP 16201793A JP H07145253 A JPH07145253 A JP H07145253A
- Authority
- JP
- Japan
- Prior art keywords
- polytetrafluoroethylene
- molded article
- water repellency
- fluorine gas
- contact angle
- 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 65
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 65
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 32
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 230000003746 surface roughness Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 27
- 239000007789 gas Substances 0.000 description 25
- 238000000465 moulding Methods 0.000 description 7
- 238000007788 roughening Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリテトラフルオロエチ
レン成形体の撥水性を向上させる方法に関する。FIELD OF THE INVENTION The present invention relates to a method for improving the water repellency of a polytetrafluoroethylene molded article.
【０００２】[0002]
【従来の技術】含フッ素高分子は、耐薬品性、低摩擦
性、難燃性、耐熱性等を有するため、広く産業上のあら
ゆる分野で利用されている。ところで、半導体産業の分
野においては、フロンによる洗浄が一般的であったが、
環境問題よりフロンに代えて超純水による洗浄が行われ
るようになってきている。そのため、半導体製造工程で
冶具や部品、装置類に撥水性の良好なポリテトラフルオ
ロエチレン、テトラフルオロエチレン−パーフルオロア
ルキルビニルエーテル共重合体、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等の含フッ素高
分子材料が利用されている。しかし、これらの含フッ素
高分子材料の撥水性の指標である水との接触角は110゜
程度であり、水切れが悪く乾燥工程が必要であるという
問題がある。Fluorine-containing polymers are widely used in all industrial fields because they have chemical resistance, low friction, flame retardancy, heat resistance and the like. By the way, in the field of the semiconductor industry, cleaning with chlorofluorocarbon was common,
Due to environmental problems, cleaning with ultrapure water has been performed instead of CFCs. Therefore, in the semiconductor manufacturing process, jigs, parts, and devices have high water-repellent properties such as polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer. Molecular materials are used. However, the contact angle with water, which is an index of water repellency of these fluorine-containing polymer materials, is about 110 °, and there is a problem that water is not drained and a drying step is required.
【０００３】[0003]
【発明が解決しようとする課題】そこで、本発明者ら
が、含フッ素高分子成形体の表面を機械的又は電気的処
理によって粗し、次いで当該表面にフッ素ガスを接触さ
せることにより、撥水性の優れた含フッ素高分子成形体
が得られることを見出し、先に出願した特願平５−５９
２６号の方法によれば、ポリテトラフルオロエチレン成
形体においては、最高155゜の接触角を有する撥水性表
面が得られる。Therefore, the present inventors roughened the surface of the fluoropolymer molding by mechanical or electrical treatment, and then contacted the surface with fluorine gas to obtain water repellency. Of the above-mentioned Japanese Patent Application No. 5-59
According to the method of No. 26, a water repellent surface having a contact angle of 155 ° at the maximum can be obtained in the polytetrafluoroethylene molded body.
【０００４】しかしながら、この方法によって得られた
ものも未だ充分とは言えず、更に優れた撥水性を有する
含フッ素高分子成形体を得る方法が望まれていた。However, the product obtained by this method is not yet satisfactory, and a method for obtaining a fluoropolymer molding having further excellent water repellency has been desired.
【０００５】[0005]
【課題を解決するための手段】かかる実情において、本
発明者らは更に鋭意検討を行った結果、含フッ素高分子
成形体の一つであるポリテトラフルオロエチレン成形体
をポリテトラフルオロエチレンの融点以上、分解点未満
の温度で熱処理すれば、高い撥水性が得られることを見
出し、本発明を完成した。Under these circumstances, the inventors of the present invention have made further studies and as a result, found that one of the fluorine-containing polymer molded bodies was a polytetrafluoroethylene molded body, which had a melting point of polytetrafluoroethylene. As described above, they have found that high water repellency can be obtained by heat treatment at a temperature below the decomposition point, and completed the present invention.
【０００６】すなわち、本発明はポリテトラフルオロエ
チレン成形体をポリテトラフルオロエチレン融点以上、
分解点未満の温度で熱処理することを特徴とするポリテ
トラフルオロエチレン成形体の撥水性向上方法を提供す
るものである。That is, according to the present invention, a molded product of polytetrafluoroethylene has a melting point of polytetrafluoroethylene or higher,
The present invention provides a method for improving water repellency of a polytetrafluoroethylene molded article, which comprises heat treatment at a temperature lower than the decomposition point.
【０００７】本発明方法の熱処理の対象はポリテトラフ
ルオロエチレン成形体である。他の含フッ素高分子成形
体は、本発明における温度で熱処理行うと、水との接触
角が低下する傾向にあり、更には成形体の形状が崩れた
り、発泡が生じたりするため使用することができない。
実際、テトラフルオロエチレン−パーフルオロアルキル
ビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエ
チレン−エチレン共重合体（ＥＴＦＥ）、ポリフッ化ビ
ニリデン（ＰＶＤＦ）、テトラフルオロエチレン−へキ
サフルオロプロピレン共重合体（ＦＥＰ） 等の溶融樹
脂は特に溶融粘度が低いため、融点以上に加熱すると、
溶融、発泡して成形体の形状を大幅に崩していた。The object of the heat treatment of the method of the present invention is a polytetrafluoroethylene molded body. Other fluorine-containing polymer moldings, when subjected to heat treatment at the temperature in the present invention, tends to have a reduced contact angle with water, and further, the shape of the molding may collapse, or foaming may occur, so use it. I can't.
In fact, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) Since molten resins such as have a particularly low melt viscosity, when heated above the melting point,
It melted and foamed, and the shape of the molded body was largely destroyed.
【０００８】これに対し、ポリテトラフルオロエチレン
は融点以上での溶融粘度が1011poiseと他の含フッ素高
分子成形体に比べて非常に高いため、この成形体を融点
以上に加熱しても形状をそのまま留めることができる。On the other hand, polytetrafluoroethylene has a melt viscosity of 10 11 poise above the melting point, which is much higher than that of other fluoropolymer moldings, and therefore even if this molding is heated above the melting point. The shape can be retained as it is.
【０００９】本発明方法におけるポリテトラフルオロエ
チレン成形体とは、ポリテトラフルオロエチレンの原料
粉末を予備成形しフリーベーキング法又はホットモール
ディング法によって焼成し、次いで機械加工により成形
したものであり、その形体もフィルム、シートその他の
各種形状の成形品が挙げられる。また、これらの成形体
を製造するにあたって、各種配合剤、添加剤、加工助剤
を配合することは何等差し支えない。The polytetrafluoroethylene molded product in the method of the present invention is a product in which a raw material powder of polytetrafluoroethylene is preliminarily molded, fired by a free baking method or a hot molding method, and then molded by machining, and the shape thereof is obtained. Also, a film, a sheet and other molded articles of various shapes can be mentioned. In addition, in producing these molded products, it is safe to add various compounding agents, additives and processing aids.
【００１０】このように成形されたポリテトラフルオロ
エチレン成形体をポリテトラフルオロエチレンの融点以
上、分解点未満の温度で熱処理する。融点以上、分解点
未満の温度とは、常圧においては327〜399℃の範囲の温
度である。熱処理の温度が融点未満ではポリテトラフル
オロエチレン成形体の表面が全く溶融しないため撥水性
の向上が得られず、また、分解点以上では ポリテトラ
フルオロエチレン成形体の熱分解が避けられない。本発
明における好ましい熱処理温度は340〜380℃である。更
に、熱処理の時間はポリテトラフルオロエチレン成形体
の大きさや厚みによって影響され、小さく薄いものは短
時間でよいが、大きく厚いものは長時間を必要とする。The polytetrafluoroethylene molded body thus molded is heat-treated at a temperature above the melting point of polytetrafluoroethylene and below the decomposition point. The temperature above the melting point and below the decomposition point is a temperature in the range of 327 to 399 ° C. under normal pressure. If the temperature of the heat treatment is lower than the melting point, the surface of the polytetrafluoroethylene molded product is not melted at all, so that the water repellency cannot be improved, and if it is above the decomposition point, thermal decomposition of the polytetrafluoroethylene molded product cannot be avoided. The preferred heat treatment temperature in the present invention is 340 to 380 ° C. Further, the heat treatment time is affected by the size and thickness of the polytetrafluoroethylene molded product, and a small and thin one may take a short time, but a large and thick one requires a long time.
【００１１】この熱処理によってポリテトラフルオロエ
チレン成形体の表面に径が数μm程度の球状物ができ
る。この球状物の径の大きさは一概に規定できないが、
0.5〜5.0μmが好ましい。本発明方法においてはこの球
状物によって、ポリテトラフルオロエチレン成形体の表
面に数μm程度の凹凸ができ、撥水性が向上するものと
思われる。従って、冶具等が接触していると、その場所
には球状物が生成しないため撥水性が期待できず、撥水
性を施す面には冶具等が接触しないようにする必要があ
る。例えば、ポリテトラフルオロエチレンシートを金属
板に挟み350℃で熱処理しても、本来のポリテトラフル
オロエチレンの接触角110°しか得られず、撥水性の向
上は見られない。By this heat treatment, spherical particles having a diameter of about several μm are formed on the surface of the polytetrafluoroethylene molded body. Although the size of the diameter of this spherical object cannot be specified unconditionally,
0.5 to 5.0 μm is preferable. In the method of the present invention, it is considered that this spherical material causes irregularities of about several μm on the surface of the polytetrafluoroethylene molded article, and thus improves the water repellency. Therefore, if a jig or the like is in contact, a spherical object is not formed at that location, so that water repellency cannot be expected, and it is necessary to prevent the jig or the like from contacting the surface to which water repellency is applied. For example, even if a polytetrafluoroethylene sheet is sandwiched between metal plates and heat-treated at 350 ° C., only the original contact angle of polytetrafluoroethylene of 110 ° is obtained, and no improvement in water repellency is observed.
【００１２】本発明の方法は上記のような熱処理のみで
ポリテトラフルオロエチレン成形体の撥水性を上げるこ
とができるが、熱処理とポリテトラフルオロエチレン成
形体をフッ素ガスと接触させる処理とを併用することに
よってポリテトラフルオロエチレンの末端基をフッ素化
し、更に撥水性を向上することができる。ここで用いら
れるフッ素ガスは、単独で又は窒素、アルゴン等の不活
性ガスと混合しても使用することができる。不活性ガス
との混合で用いる際の不活性ガスの濃度は10〜90％が好
ましい。また、フッ素ガス濃度と接触時間とは、相互に
密接に関係があり、高濃度であれば短時間で充分であ
り、低濃度の場合には長時間を要する。また、フッ素ガ
ス容器中へのポリテトラフルオロエチレン成形体の充填
量が少なければ短時間、低濃度で充分であり、充填量が
多ければ長時間、高濃度を要する。例えば、フッ素ガス
濃度は10〜500torr、接触時間は10分〜１時間が好まし
い。フッ素ガスとの接触は、例えばポリテトラフルオロ
エチレン成形体を気密容器に入れ、空気を除去してフッ
素ガス又はフッ素ガスと不活性ガスとの混合ガスを挿入
することによって実施される。In the method of the present invention, the water repellency of the polytetrafluoroethylene molded article can be increased only by the above heat treatment, but the heat treatment and the treatment of bringing the polytetrafluoroethylene molded article into contact with fluorine gas are used in combination. This makes it possible to fluorinate the end groups of polytetrafluoroethylene and further improve water repellency. The fluorine gas used here can be used alone or as a mixture with an inert gas such as nitrogen or argon. When used as a mixture with an inert gas, the concentration of the inert gas is preferably 10 to 90%. Further, the fluorine gas concentration and the contact time are closely related to each other, and a high concentration requires a short time, and a low concentration requires a long time. In addition, if the filling amount of the polytetrafluoroethylene molded body in the fluorine gas container is small, a low concentration is sufficient for a short time, and if the filling amount is large, a high concentration is required for a long time. For example, the fluorine gas concentration is preferably 10 to 500 torr, and the contact time is preferably 10 minutes to 1 hour. The contact with the fluorine gas is carried out, for example, by placing the polytetrafluoroethylene molded body in an airtight container, removing the air, and inserting the fluorine gas or the mixed gas of the fluorine gas and the inert gas.
【００１３】本発明においては、ポリテトラフルオロエ
チレン成形体にフッ素ガスを接触させてから熱処理する
こともできるが、双方の操作を同時に行うのが経済的に
も操作性からも好ましい。In the present invention, it is possible to bring the polytetrafluoroethylene molded product into contact with fluorine gas and then heat it, but it is preferable to carry out both operations simultaneously from the economical and operability point of view.
【００１４】また、本発明方法においてはポリテトラフ
ルオロエチレン成形体の表面を前もって粗しておき、次
いで熱処理と必要に応じてフッ素ガス接触処理を行え
ば、撥水性を更に向上することができる。In the method of the present invention, the water repellency can be further improved by roughening the surface of the polytetrafluoroethylene molded product in advance and then subjecting it to heat treatment and, if necessary, fluorine gas contact treatment.
【００１５】当該表面を粗す手段としては機械的処理が
好ましく、例えば、ワイヤーブラシ、ベルトサンダー、
ショットブラスト等による処理を行うことができる。ア
ルゴンスパッタリングのような電気的処理を施して表面
を粗すことも考えられるが、本発明の熱処理を行うと接
触角が小さくなって撥水性が低下するため好ましくな
い。これは、スパッタリングにより生成したポリテトラ
フルオロエチレン成形体表面の針状物が、融点以上で加
熱すると溶融し、平坦な面となるためである。Mechanical treatment is preferable as means for roughening the surface, for example, wire brush, belt sander,
Processing such as shot blasting can be performed. It is possible to roughen the surface by performing an electrical treatment such as argon sputtering, but the heat treatment of the present invention is not preferable because the contact angle becomes small and the water repellency decreases. This is because the needle-shaped material on the surface of the polytetrafluoroethylene molded body generated by sputtering is melted when heated above the melting point to form a flat surface.
【００１６】上述の機械的処理により粗したポリテトラ
フルオロエチレン成形体の表面は、分子鎖が切断される
と共に凹凸ができ、この凹凸が熱処理によって溶融し
て、適度な大きさの球状体となり、撥水性の向上に寄与
すると考えられる。この、表面の凹凸の大きさは一概に
規定できないが、JIS B 0601「表面粗さの定義と表示」
の方法により示せば、機械的エネルギーを用いた場合、
Ra（中心線平均粗さ）は0.5〜50.0μmが好ましく、特に
2.0〜15.0μmが好ましい。On the surface of the polytetrafluoroethylene molded body roughened by the above mechanical treatment, the molecular chain is cut and irregularities are formed, and the irregularities are melted by heat treatment to become spherical bodies of appropriate size, It is considered to contribute to the improvement of water repellency. The size of the surface irregularities cannot be specified unconditionally, but JIS B 0601 “Definition and display of surface roughness”
If mechanical energy is used,
Ra (center line average roughness) is preferably 0.5 to 50.0 μm,
2.0 to 15.0 μm is preferable.
【００１７】また、表面粗し処理を施したポリテトラフ
ルオロエチレン成形体を用いる場合に、熱処理をしてか
ら表面粗し処理を行うことも考えられ得るが、この操作
順序によると、熱処理によって生成した凹凸を表面粗し
処理によって潰してしまうため、撥水性の向上効果は得
ることができない。また、フッ素ガス接触処理を行って
から表面粗し処理を行うという操作手順は、表面粗しに
よってポリテトラフルオロエチレン成形体の分子鎖が切
断されて生成した末端基をフッ素ガスでフッ素化して撥
水性の向上が得るという効果が得られず、好ましくな
い。Further, when the surface-roughened polytetrafluoroethylene molded product is used, it may be considered that the surface-roughening treatment is carried out after the heat treatment. Since the roughened surface is crushed by the surface roughening treatment, the effect of improving water repellency cannot be obtained. In addition, the operation procedure in which the surface roughening treatment is performed after the fluorine gas contact treatment is performed, the surface group is cut off the molecular chain of the polytetrafluoroethylene molded product, and the generated end group is fluorinated with fluorine gas to repel the end group. It is not preferable because the effect of improving the aqueous property cannot be obtained.
【００１８】[0018]
【作用及び発明の効果】本発明方法によると、ポリテト
ラフルオロエチレン成形体は熱処理を受けて表面に数μ
mの凹凸が生成し、液体との付着面積が小さくなるため
撥水性が向上すると考えられる。これは、前述したよう
にポリテトラフルオロエチレン成形体に特有の性質であ
る。また、この凹凸を生成させる熱処理にフッ素ガス接
触処理を併用することによってポリテトラフルオロエチ
レンの末端基をフッ素化して、低表面エネルギー基であ
る-CF3基を実質的に生成させ、撥水性を更に向上するこ
とができる。更には、予めポリテトラフルオロエチレン
成形体の表面を機械的処理によって粗すことにより、表
面に末端基を増加させると共に、凹凸を作り、次いで行
われる熱処理によって更に細かな凹凸が生成して撥水性
が向上し、またフッ素ガスと接触させることにより、末
端基をフッ素化して、今までにない優れた撥水性を得る
ことができる。According to the method of the present invention, the polytetrafluoroethylene molded article is subjected to heat treatment to give a surface of several μm.
It is considered that the water repellency is improved because the unevenness of m is generated and the adhesion area with the liquid is reduced. This is a characteristic peculiar to the polytetrafluoroethylene molded body as described above. In addition, by using a fluorine gas contact treatment in combination with the heat treatment for generating the irregularities, the terminal group of polytetrafluoroethylene is fluorinated, and a low surface energy group, -CF 3 group, is substantially generated, and water repellency is improved. It can be further improved. Furthermore, the surface of the polytetrafluoroethylene molded product is roughened by mechanical treatment in advance to increase the number of end groups on the surface and also to form irregularities, and the subsequent heat treatment produces finer irregularities, resulting in water repellency. And the contact with fluorine gas makes it possible to fluorinate the terminal group and obtain an unprecedentedly excellent water repellency.
【００１９】本発明方法によれば、熱処理という簡便な
方法でポリテトラフルオロエチレン成形体の水に対する
接触角を、従来知られているポリテトラフルオロエチレ
ンの接触角よりも更に高い値、すなわち最高値で168°
に達させることができる。かくして得られたポリテトラ
フルオロエチレン成形体は優れた撥水性を有するため、
かかる特性を必要とする種々の用途に好適に用いられ
る。According to the method of the present invention, the contact angle of the polytetrafluoroethylene molded body with water is higher than the conventionally known contact angle of polytetrafluoroethylene by the simple method of heat treatment, that is, the maximum value. At 168 °
Can be reached. Since the polytetrafluoroethylene molded body thus obtained has excellent water repellency,
It is preferably used for various applications requiring such characteristics.
【００２０】[0020]
【実施例】次に、実施例と比較例により本発明を具体的
に説明するが、本発明は下記の実施例に限定されるもの
ではない。EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００２１】実施例１ 厚さ１mm、幅40mm、長さ50mmのポリテトラフルオロエチ
レンシートを下記に示した各条件に設定し、内径55mm、
長さ600mmの円柱状ニッケル製反応器に入れ、外部加熱
により各種温度で熱処理し、冷却速度100℃／hrの条件
で室温まで冷却した。その後、各ポリテトラフルオロエ
チレンシートについて撥水性の程度を水に対する接触角
を測定することにより求めた。その結果を図１に示す。Example 1 A polytetrafluoroethylene sheet having a thickness of 1 mm, a width of 40 mm and a length of 50 mm was set under the respective conditions shown below, and an inner diameter of 55 mm,
It was placed in a cylindrical nickel reactor having a length of 600 mm, heat-treated at various temperatures by external heating, and cooled to room temperature at a cooling rate of 100 ° C / hr. Then, the degree of water repellency of each polytetrafluoroethylene sheet was determined by measuring the contact angle with water. The result is shown in FIG.
【００２２】（処理方法） １・・・ポリテトラフルオロエチレンシートを各種温度
で10分間加熱処理した。 ２・・・ポリテトラフルオロエチレンシートを各種温度
でフッ素ガス100torrを接触させながら10分間加熱処理
した。 ３・・・ポリテトラフルオロエチレンシートに菊川鉄鋼
所製ベルトサンダー（M648）を用いて表面粗しを行い
（ベルトは＃240ベルトを用いた）、各種温度で10分間
加熱処理した。尚、JIS B 0601に準じて表面粗さ形状測
定機サーコム300B（東京精密社製）で測定したところ、
Ra（中心線平均粗さ）は3.2μmであった。 ４・・・３と同じポリテトラフルオロエチレンシートを
各種温度でフッ素ガス100torrと接触させながら10分間
加熱処理した。 ５・・・100torrのフッ素ガスで200℃にて10分間処理し
たポリテトラフルオロエチレンシートを、各種温度で10
分間処理した。(Treatment Method) 1 ... The polytetrafluoroethylene sheet was heat-treated at various temperatures for 10 minutes. 2. The polytetrafluoroethylene sheet was heat-treated at various temperatures for 10 minutes while contacting with 100 torr of fluorine gas. 3. The surface of the polytetrafluoroethylene sheet was roughened using a belt sander (M648) manufactured by Kikugawa Steel Co., Ltd. (a belt # 240 was used), and heat-treated at various temperatures for 10 minutes. In addition, according to JIS B 0601, when measured with a surface roughness shape measuring instrument Cercom 300B (manufactured by Tokyo Seimitsu Co., Ltd.),
Ra (center line average roughness) was 3.2 μm. The same polytetrafluoroethylene sheet as in 4 ... 3 was heat-treated for 10 minutes at various temperatures while being brought into contact with 100 torr of fluorine gas. 5 ・ ・ ・ Polytetrafluoroethylene sheet treated with 100 torr of fluorine gas at 200 ℃ for 10 minutes at various temperatures
Processed for a minute.
【００２３】（接触角測定方法）接触角の測定は、接触
角測定機（協和界面化学(株)、CA-S150型）を用いて行
った。測定は、マイクロシリンジによりマイクロヘッド
で径を１mmに統一した蒸留水の水滴を試料表面に滴下
し、平衡接触角を読み取った。接触角の値は10個の測定
結果の平均値により決定した。(Method of measuring contact angle) The contact angle was measured by using a contact angle measuring machine (CA-S150 type, manufactured by Kyowa Interface Science Co., Ltd.). For the measurement, water droplets of distilled water having a uniform diameter of 1 mm were dropped on the sample surface by a micro-syringe with a micro syringe, and the equilibrium contact angle was read. The value of the contact angle was determined by the average value of 10 measurement results.
【００２４】（結果）図１から明らかなように、１では
320℃まで接触角の変化はほとんどないが、340℃で急激
に接触角が向上した。２では200℃で接触角は５°程度
向上し、320℃までほとんど変化がないが、340℃で急激
に接触角は向上した。表面粗しと熱処理を施した３は、
320℃まではほとんど変化がないが、同様に340℃から急
激に接触角が向上した。４は、フッ素ガスと接触させて
いるため200℃で接触角が155°まで向上し、320℃で接
触角は10°程度低下した。しかし、340℃で処理すると2
00℃で処理したときよりも更に接触角は向上し、168°
と最も高い撥水性を示した。５はフッ素ガスに接触させ
たシートを後から熱処理したものであるが、同時に行っ
た１と同じ接触角が得られている。(Results) As is apparent from FIG. 1, in 1
There was almost no change in contact angle up to 320 ° C, but the contact angle improved sharply at 340 ° C. In No. 2, the contact angle was improved by about 5 ° at 200 ° C and hardly changed up to 320 ° C, but the contact angle was sharply improved at 340 ° C. The surface-roughened and heat-treated 3 is
Although there was almost no change up to 320 ° C, the contact angle also drastically improved from 340 ° C. In No. 4, the contact angle improved to 155 ° at 200 ° C because it was in contact with fluorine gas, and the contact angle decreased about 10 ° at 320 ° C. However, when treated at 340 ° C, 2
The contact angle is further improved compared to when treated at 00 ° C, 168 °
And showed the highest water repellency. In No. 5, a sheet that was brought into contact with fluorine gas was heat-treated later, and the same contact angle as in No. 1 obtained at the same time was obtained.
【００２５】以上のことから、340〜399℃で熱処理する
と接触角は急激に向上する。また、熱処理と同時にフッ
素ガスを接触させると更に接触角は大きくなり、更に、
表面粗しを施したポリテトラフルオロエチレン成形体を
用いると最も接触角が大きくなり、撥水性が向上するこ
とがわかる。From the above, when the heat treatment is performed at 340 to 399 ° C., the contact angle sharply improves. Also, when the fluorine gas is brought into contact with the heat treatment at the same time, the contact angle is further increased.
It can be seen that when the surface-roughened polytetrafluoroethylene molded product is used, the contact angle becomes the largest and the water repellency is improved.
【図１】 図１は実施例１において、それぞれ異なる条
件においてポリテトラフルオロエチレンシートを温度を
変えて熱処理したときの接触角を示す図である。図中の
１は熱処理のみ、２はフッ素ガスと接触させながら熱処
理、３は表面粗しを行なった後に熱処理、４は表面粗し
を行なった後にフッ素ガスを接触させながら熱処理、５
はフッ素ガスを接触させた後に熱処理をしたことを示
す。FIG. 1 is a diagram showing a contact angle when heat-treating a polytetrafluoroethylene sheet at different temperatures under different conditions in Example 1. In the figure, 1 is heat treatment only, 2 is heat treatment in contact with fluorine gas, 3 is heat treatment after surface roughening, 4 is heat treatment while contacting fluorine gas after surface roughening, and 5 is heat treatment.
Indicates that heat treatment was performed after contacting with fluorine gas.
フロントページの続き (72)発明者 下村 正篤 東京都八王子市南陽台２−６−８ (72)発明者 小野 雅宏 埼玉県川口市大字赤井488 (72)発明者 渡辺 信淳 京都府長岡京市うぐいす台136Front page continuation (72) Inventor Masaatsu Shimomura 2-6-8 Nanyodai, Hachioji, Tokyo (72) Inventor Masahiro Ono 488 Akai, Kawaguchi City, Saitama Prefecture (72) Inventor Nobuyoshi Watanabe 136 Uguisudai, Nagaokakyo, Kyoto Prefecture
Claims (4)
リテトラフルオロエチレンの融点以上、分解点未満の温
度で熱処理することを特徴とするポリテトラフルオロエ
チレン成形体の撥水性向上方法。1. A method for improving water repellency of a polytetrafluoroethylene molded article, which comprises heat-treating the polytetrafluoroethylene molded article at a temperature not lower than the melting point of polytetrafluoroethylene and lower than the decomposition point.
リテトラフルオロエチレンの融点以上、分解点未満の温
度でフッ素ガスと接触させることを特徴とするポリテト
ラフルオロエチレン成形体の撥水性向上方法。2. A method for improving water repellency of a polytetrafluoroethylene molded article, which comprises contacting the polytetrafluoroethylene molded article with fluorine gas at a temperature not lower than the melting point of polytetrafluoroethylene and lower than the decomposition point.
ッ素ガスと接触させた後、ポリテトラフルオロエチレン
の融点以上、分解点未満の温度で熱処理することを特徴
とするポリテトラフルオロエチレン成形体の撥水性向上
方法。3. The water repellency of a polytetrafluoroethylene molded article, which is characterized in that after the polytetrafluoroethylene molded article is brought into contact with fluorine gas, it is heat-treated at a temperature not lower than the melting point of polytetrafluoroethylene and lower than the decomposition point. How to improve.
械的処理によって表面粗しを施されているものである請
求項１〜３いずれか１項記載のポリテトラフルオロエチ
レン成形体の撥水性向上方法。4. The method for improving water repellency of a polytetrafluoroethylene molded article according to claim 1, wherein the polytetrafluoroethylene molded article is surface-roughened by mechanical treatment.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16201793A JPH07145253A (en) | 1993-06-30 | 1993-06-30 | Method for improving water repellency of molded article of polytetrafluoroethylene |
| KR1019940000534A KR940018419A (en) | 1993-01-18 | 1994-01-13 | Fluorine-containing polymer molded article having improved water repellency and cleaning jig prepared therefrom |
| DE4401363A DE4401363A1 (en) | 1993-01-18 | 1994-01-18 | Fluorine-contg polymer having improved water repellence |
| US08/450,990 US5599489A (en) | 1993-01-18 | 1995-05-25 | Preparing molded articles of fluorine-containing polymer with increased water-repellency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16201793A JPH07145253A (en) | 1993-06-30 | 1993-06-30 | Method for improving water repellency of molded article of polytetrafluoroethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07145253A true JPH07145253A (en) | 1995-06-06 |
Family
ID=15746477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16201793A Pending JPH07145253A (en) | 1993-01-18 | 1993-06-30 | Method for improving water repellency of molded article of polytetrafluoroethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07145253A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001190344A (en) * | 2000-01-14 | 2001-07-17 | Matsushita Electric Ind Co Ltd | Artificial marble and kitchen counter, bathtub, or washing floor using the same |
| WO2001079337A1 (en) * | 2000-04-19 | 2001-10-25 | Daikin Industries, Ltd. | Molded fluoroelastomer with excellent detachability and process for producing the same |
| JP2014126279A (en) * | 2012-12-26 | 2014-07-07 | Mitsubishi Electric Corp | Outdoor unit of air conditioner |
| JP2015505725A (en) * | 2011-12-13 | 2015-02-26 | ザルトリウス ステディム ビオテック ゲーエムベーハー | Hydrophobic or oleophobic microporous polymer membrane with structurally induced beading effect |
-
1993
- 1993-06-30 JP JP16201793A patent/JPH07145253A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001190344A (en) * | 2000-01-14 | 2001-07-17 | Matsushita Electric Ind Co Ltd | Artificial marble and kitchen counter, bathtub, or washing floor using the same |
| WO2001079337A1 (en) * | 2000-04-19 | 2001-10-25 | Daikin Industries, Ltd. | Molded fluoroelastomer with excellent detachability and process for producing the same |
| US7125598B2 (en) | 2000-04-19 | 2006-10-24 | Daikin Industries, Ltd. | Molded fluoroelastomer with excellent detachability and process for producing the same |
| KR100743409B1 (en) * | 2000-04-19 | 2007-07-30 | 다이낑 고오교 가부시키가이샤 | Molded fluoroelastomer with excellent detachability and process for producing the same |
| CN100345893C (en) * | 2000-04-19 | 2007-10-31 | 大金工业株式会社 | Molded fluoro elastomer with excellent detachability and process for producing the same |
| JP2015505725A (en) * | 2011-12-13 | 2015-02-26 | ザルトリウス ステディム ビオテック ゲーエムベーハー | Hydrophobic or oleophobic microporous polymer membrane with structurally induced beading effect |
| JP2014126279A (en) * | 2012-12-26 | 2014-07-07 | Mitsubishi Electric Corp | Outdoor unit of air conditioner |
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