JP3181329B2 - Porous fluororesin material containing metal - Google Patents
Porous fluororesin material containing metalInfo
- Publication number
- JP3181329B2 JP3181329B2 JP27693491A JP27693491A JP3181329B2 JP 3181329 B2 JP3181329 B2 JP 3181329B2 JP 27693491 A JP27693491 A JP 27693491A JP 27693491 A JP27693491 A JP 27693491A JP 3181329 B2 JP3181329 B2 JP 3181329B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- inorganic compound
- porous fluororesin
- fluororesin material
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/034—Organic insulating material consisting of one material containing halogen
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属を含有する多孔質
ふっ素樹脂材料及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-containing porous fluororesin material and a method for producing the same.
【０００２】[0002]
【従来の技術及びその問題点】従来、多数の微細孔を有
する多孔質ふっ素樹脂材料は知られいる。また、この材
料の細孔内表面に化学メッキにより金属膜を形成するこ
とも知られている（特公表昭６０−５００９０６号）。
この公知方法は、材料に親水化処理を施した後、活性化
処理、化学メッキ処理を施す方法で、材料は常に湿潤状
態に保持される。しかし、この方法においては、多孔質
ふっ素樹脂材料が乾燥してしまうと、元の大きに比べ約
４分の３くらいの大きさに縮み、また、しわも生じると
いう問題があり、製品歩留まりに大きく影響する。ま
た、この公知方法で製造した金属膜を有する材料は、分
解触媒用等の触媒膜としても使用可能であるが、安定し
た触媒能力を発揮するものではなかった。一方、触媒と
しては、一般的にアルミナ、シリカ、ジルコニア等のセ
ラミックスを担体として、これに、白金、パラジウム、
ニッケル、銅等の金属や、これらの金属酸化物等を触媒
金属として担持したものがよく知られている。そして、
触媒作用は、この担体と、この担体に担持する金属触媒
の相互作用により大きく変化する。2. Description of the Related Art Conventionally, a porous fluororesin material having a large number of micropores has been known. It is also known that a metal film is formed on the inner surface of the pores of this material by chemical plating (Japanese Patent Publication No. 60-500906).
In this known method, a material is subjected to a hydrophilic treatment, followed by an activation treatment and a chemical plating treatment, and the material is always kept in a wet state. However, in this method, when the porous fluororesin material is dried, it shrinks to about three-quarters of the original size and also has a problem that wrinkles are generated. Affect. Further, the material having a metal film produced by this known method can be used as a catalyst film for a decomposition catalyst, but does not exhibit a stable catalytic ability. On the other hand, as a catalyst, generally, ceramics such as alumina, silica, and zirconia as a carrier, platinum, palladium,
Metals such as nickel and copper, and those carrying these metal oxides and the like as catalyst metals are well known. And
The catalytic action is greatly changed by the interaction between the carrier and the metal catalyst supported on the carrier.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の金属
を有する多孔質ふっ素樹脂材料において、触媒材として
も十分に使用し得る金属を含有する多孔質ふっ素樹脂材
料及びその製造方法を提供することをその課題とする。SUMMARY OF THE INVENTION The present invention provides a porous fluororesin material containing a metal which can be sufficiently used as a catalyst material in a conventional porous fluororesin material having a metal, and a method for producing the same. That is the subject.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく研究を重ねた結果、多孔質ふっ素樹脂材料
の少なくとも微細孔内表面に、無機化合物を付着させる
ことにより、非常に撥水性の高い多孔質ふっ素樹脂材料
といえども親水化することができ、かつ、乾燥しても縮
み現象がまったく発生しないことを見いだすとともに、
その無機化合物を介して金属膜を付着結合したものは、
触媒材として十分な特性を持っていることを見いだし、
本発明を完成するに至った。即ち、本発明によれば、微
細孔を有する多孔質ふっ素樹脂材料において、該材料の
微細孔内に無機化合物を付着結合させるとともに、該無
機化合物に金属状態の金属を付着結合させたことを特徴
とする金属を含有する多孔質ふっ素樹脂材料が提供され
る。また、本発明によれば、微細孔を有する多孔質ふっ
素樹脂材料において、該材料の微細孔内に無機化合物を
付着結合させるとともに、該無機化合物に金属状態の金
属を付着結合させ、該金属を酸化して金属酸化物とした
ことを特徴とする金属酸化物を含有する多孔質ふっ素樹
脂材料が提供される。 さらに、本発明によれば、微細孔
を有する多孔質ふっ素樹脂材料の微細孔内に無機化合物
を付着結合させたのち、該無機化合物に金属を金属状態
で付着結合させることを特徴とする金属を含有する多孔
質ふっ素樹脂材料の製造方法が提供される。Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that very small amounts of inorganic compounds can be attached to at least the inner surfaces of the pores of the porous fluororesin material. In addition to finding that even a porous fluororesin material with high water repellency can be made hydrophilic, and that no shrinkage phenomenon occurs even when dried,
A metal film attached and bonded via the inorganic compound is
Found that it has sufficient properties as a catalyst material,
The present invention has been completed. That is, according to the present invention, the porous fluororesin material having fine <br/> pores, with deposit bond an inorganic compound in the material of the fine pores, deposition couple of metallic state metals inorganic compound A porous fluororesin material containing a metal is provided. Further, according to the present invention, a porous filter having fine pores is provided.
In a resin material, an inorganic compound is contained in micropores of the material.
In addition to bonding and bonding, the inorganic compound
Attach and bond the genus and oxidize the metal to metal oxide
Fluorine tree containing metal oxide characterized by the following:
A grease material is provided. Furthermore, according to the present invention, it allowed to attach for binding the inorganic compound in the porous fine holes of fluorine resin material having fine pores, the metal a metal state inorganic compound
The present invention provides a method for producing a metal-containing porous fluororesin material, wherein the porous fluororesin material contains a metal.
【０００５】本発明において基材として用いる多孔質ふ
っ素樹脂材料（以下、単に材料とも言う）は、平均細孔
直径が１００μｍ以下の連続した微細孔（透孔）を有す
るもので、その細孔を形成させる手段も特に限定され
ず、延伸や拡張、発泡、抽出等が採用される。また、ふ
っ素樹脂の種類は特に限定されず、各種のものが用いら
れる。本発明で用いる好ましいふっ素樹脂は、ポリテト
ラフルオロエチレンであるが、その他、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も使用し得る。本
発明においては、多孔質ポリテトラフルオロエチレン、
特に延伸された多孔質ポリテトラフルオロエチレンの使
用が好ましい。本発明で基材として好ましく用いる多孔
質ふっ素樹脂材料は、ポリテトラフルオロエチレンの延
伸物からなり、平均細孔直径：１００μｍ以下、好まし
くは５０μｍ以下、空孔率：１５〜９５％、好ましくは
５０〜９５％を有するものである。このような基材につ
いては、特公昭５６−４５７７３号、特公昭５６−１７
２１６号、米国特許第４１８７３９０号に詳述されてい
る。[0005] The porous fluororesin material (hereinafter, also simply referred to as a material) used as a substrate in the present invention has continuous fine pores (pores) having an average pore diameter of 100 µm or less. The means for forming is not particularly limited, and stretching, expansion, foaming, extraction, or the like is employed. The type of fluororesin is not particularly limited, and various types are used. The preferred fluororesin used in the present invention is polytetrafluoroethylene, but in addition, tetrafluoroethylene / hexafluoropropylene copolymer, polyvinyl fluoride, polyvinylidene fluoride and the like can also be used. In the present invention, porous polytetrafluoroethylene,
In particular, the use of stretched porous polytetrafluoroethylene is preferred. The porous fluororesin material preferably used as the substrate in the present invention is made of a stretched product of polytetrafluoroethylene, and has an average pore diameter of 100 μm or less, preferably 50 μm or less, and a porosity of 15 to 95%, preferably 50%. ~ 95%. Such base materials are described in JP-B-56-45773 and JP-B-56-17.
216 and U.S. Pat. No. 4,187,390.
【０００６】本発明において材料に付着結合させる無機
化合物は、水不溶性ないし水難溶性のものであればよ
く、各種金属の酸化物、水酸化物、炭酸塩、亜硫酸塩等
が包含される。また、金属としては、Ｃａ，Ｍｇ，Ｂａ
等のアルカリ土類金属の他、Ｃｕ，Ａｌ，Ｇａ，Ｓｉ，
Ｓｎ，Ｐｂ，Ｔｉ，Ｚｒ，Ｂｉ，Ｖ，Ｍｏ，Ｗ，Ｍｎ，
Ｆｅ，Ｃｏ，Ｎｉ，Ｐｄ等が挙げられ、その種類は特に
限定されない。材料に対して無機化合物を付着結合させ
る方法としては、従来公知の方法が適用される。一般的
には、可溶性化合物の溶液を材料に含浸させ、この状態
においてその化合物を不溶性のものに変換させればよ
い。この場合、可溶性化合物を不溶性無機化合物に変換
させる方法としては、加熱、加水分解、ｐＨ調整の他、
可溶性化合物を不溶性無機化合物に変換させる反応試薬
と反応させる方法等がある。本発明における材料に無機
化合物を付着結合させる好ましい方法の１つは、金属ア
ルコキシドの有機溶媒溶液を材料に含浸させた後、その
金属アルコキシドを加水分解し、無機化合物へ変換する
方法（特開昭５２−１２７４７９号、特開昭５３−１２
９２６１号等）である。本発明における無機化合物とし
て、ＳｉＯ2、Ａｌ2Ｏ3、ＺｒＯ2、ＴｉＯ2等の酸化物
を用いる場合には、これらの酸化物は触媒担体として作
用するので、これらの酸化物表面に金属を付着結合させ
ることにより、触媒機能を持った材料を得ることができ
る。材料に対する無機化合物の付着結合量は、材料に対
し、１０〜０．１重量％、好ましくは３〜０．５重量％
である。In the present invention, the inorganic compound to be adhered to the material is not limited to water-insoluble or hardly water-soluble, and includes oxides, hydroxides, carbonates and sulfites of various metals. As the metal, Ca, Mg, Ba
Other than alkaline earth metals such as Cu, Al, Ga, Si,
Sn, Pb, Ti, Zr, Bi, V, Mo, W, Mn,
Examples include Fe, Co, Ni, and Pd, and the type is not particularly limited. As a method for adhering an inorganic compound to a material, a conventionally known method is applied. In general, a solution of a soluble compound may be impregnated into a material, and in this state, the compound may be converted into an insoluble compound. In this case, as a method of converting the soluble compound into an insoluble inorganic compound, in addition to heating, hydrolysis, and pH adjustment,
There is a method in which a soluble compound is reacted with a reaction reagent that converts the compound into an insoluble inorganic compound. One of the preferred methods for adhering and bonding an inorganic compound to a material in the present invention is to impregnate the material with an organic solvent solution of a metal alkoxide and then hydrolyze the metal alkoxide to convert the metal alkoxide to an inorganic compound (Japanese Patent Laid-Open No. 52-127479, JP-A-53-12
9261). When oxides such as SiO 2 , Al 2 O 3 , ZrO 2 , and TiO 2 are used as the inorganic compound in the present invention, since these oxides act as catalyst carriers, a metal is deposited on the surface of these oxides. A material having a catalytic function can be obtained by bonding. The amount of the inorganic compound attached to the material is 10 to 0.1% by weight, preferably 3 to 0.5% by weight, based on the material.
It is.
【０００７】このようにして得られた、無機化合物を付
着結合させた多孔質ふっ素樹脂材料は、特開昭５３−１
２９２６１号で示されるように完全に親水化されたもの
である。また、このような材料は、湿潤、乾燥行程を繰
り返しても、寸法変化が格段に小さくなり、湿潤状態で
行う化学メッキ法に使用する基材として最適品になる。
寸法変化が格段に小さくなる理由は、多孔質ふっ素樹脂
材料の細孔内に寸法変化の小さいセラミックスが付着結
合しているためであると考えられる。本発明において
は、前記のようにして無機化合物を付着結合させた材料
に対し、金属を金属状態でその無機化合物を介し付着結
合させる。金属の付着方法としては、従来公知の方法、
例えば、化学メッキ法、金属蒸着法（スパッタリング、
イオンプレーティング、ＣＶＤも含む）を使用すること
もできるし、金属コロイドを表面に付着させる方法を用
いることもできる。化学メッキ法により無機化合物に金
属膜を形成した場合、そのメッキ厚さは、通常、約１０
Åから１μｍ、好ましくは５００Åから５０００Åであ
る。金属コロイドは、直径５０００Å以下、好ましくは
１００Å以下のものがよい。無機化合物には、プラスに
帯電した金属コロイドがよく付着する傾向があり、コロ
イドを用いることにより、金属を無機化合物に容易に付
着させることができる。The thus obtained porous fluororesin material to which an inorganic compound is adhered and bonded is disclosed in JP-A-53-1.
It was completely hydrophilized as shown in No. 29261. In addition, such a material has a remarkably small dimensional change even if the wet and dry processes are repeated, and is an optimal product as a substrate used in a chemical plating method performed in a wet state.
It is considered that the reason why the dimensional change is significantly reduced is that ceramics having a small dimensional change are adhered and bonded in the pores of the porous fluororesin material. In the present invention, a metal is adhered and bonded in a metallic state via the inorganic compound to the material to which the inorganic compound is adhered and bonded as described above. As a method for attaching metal, a conventionally known method,
For example, chemical plating, metal deposition (sputtering,
(Including ion plating and CVD), and a method of attaching a metal colloid to the surface can also be used. When a metal film is formed on an inorganic compound by a chemical plating method, the plating thickness is usually about 10
Å to 1 μm, preferably 500 to 5000 °. The metal colloid has a diameter of 5000 ° or less, preferably 100 ° or less. Positively charged metal colloids tend to adhere well to inorganic compounds, and by using colloids, metals can be easily adhered to inorganic compounds.
【０００８】材料の中の無機化合物に金属を付着結合さ
せる場合、その金属は、無機化合物上に膜状に結合させ
得る他、その無機化合物の細孔内に選択的に付着結合さ
せることもできる。無機化合物の細孔内に金属を付着結
合させたものは、触媒として好適のものである。無機化
合物の細孔内に金属を選択的に付着結合させる方法とし
ては、従来の触媒調製法に採用されている一般的方法を
用いることができる。例えば、触媒活性金属の可溶性化
合物の溶液を材料に含浸させた後、その金属化合物を水
素還元する方法や、還元雰囲気中で熱分解する方法等が
ある。この場合、金属の担持量は、無機化合物に対し、
５〜３０重量％程度である。本発明において、材料中の
無機化合物を介して付着結合された金属は、必要に応
じ、酸素と反応させて酸化物とすることができ、また、
硫化水素と反応させて硫化物とすることができる。When a metal is bonded to an inorganic compound in a material, the metal can be bonded to the inorganic compound in the form of a film, or can be selectively bonded to pores of the inorganic compound. . An inorganic compound in which a metal is adhered and bonded in the pores is suitable as a catalyst. As a method for selectively attaching and bonding a metal to the pores of the inorganic compound, a general method employed in a conventional catalyst preparation method can be used. For example, there is a method of impregnating a material with a solution of a soluble compound of a catalytically active metal and then reducing the metal compound with hydrogen, or a method of thermally decomposing the metal compound in a reducing atmosphere. In this case, the amount of supported metal is based on the amount of the inorganic compound.
It is about 5 to 30% by weight. In the present invention, the metal attached and bonded via the inorganic compound in the material can be reacted with oxygen to form an oxide, if necessary,
It can be reacted with hydrogen sulfide to form a sulfide.
【０００９】[0009]
【発明の効果】本発明の金属を含有する多孔質ふっ素樹
脂材料は、多孔質ふっ素樹脂材料を基材として、その微
細孔内に無機化合物が付着し、更にその無機化合物に金
属状態の金属が付着した構造を有する。このような構成
のものは、特に膜状触媒として有利に用いられる。たと
えば、本発明の材料は、オゾンの分解触媒として使用可
能である。従来よりオゾンの分解能力を有する公知の触
媒として、ＣｕＯ，Ａｇ2Ｏ、ＮｉＯ、Ｐｔ、Ｐｂ等が
あり、その担体としては、ＴｉＯ2、ＳｉＯ2、ＺｒＯ2
等が挙げられる。本発明では、無機化合物としてＴｉＯ
2、ＳｉＯ2、ＺｒＯ2等の無機酸化物を用い、そして、
金属として、ＣｕＯ、Ａｇ2Ｏ、ＮｉＯ、Ｐｔ、Ｐｂ等
を用いることにより、膜状のオゾン分解触媒を得ること
ができる。ところで、オゾンは非常に腐食性の高いガス
であるために、高濃度の場合従来は汎用の有機物を使用
することが不可能であったが、本構成の材料では、耐食
性のあるふっ素樹脂を使用しているために十分使用に耐
えうる。触媒以外の応用分野においては、本発明の材料
は、導電性濾過膜、センサー膜、電磁シールド体、導電
性衣服材料、フレキシブルプリント基板、アンテナ材料
としても有利に用いることができる。本発明の材料は、
シート、チューブ、ワイヤー、ケーブル、棒状、ヤー
ン、織物、繊維、筒等の各種の形状で用いることができ
る。The porous fluororesin material containing a metal of the present invention exhibits, a porous fluororesin material as the substrate, the inorganic compound is adhered within the micropores, further gold its inorganic compounds
It has a structure with a metal of the genus state attached. Such a structure is particularly advantageously used as a film catalyst. For example, the material of the present invention can be used as an ozone decomposition catalyst. As known catalyst having a decomposition capability of conventionally ozone, CuO, Ag 2 O, NiO , Pt, there is Pb and the like, as the carrier thereof, TiO 2, SiO 2, ZrO 2
And the like. In the present invention, TiO is used as the inorganic compound.
2 , using an inorganic oxide such as SiO 2 or ZrO 2 , and
By using CuO, Ag 2 O, NiO, Pt, Pb, or the like as a metal, a film-like ozone decomposition catalyst can be obtained. By the way, since ozone is a highly corrosive gas, it has not been possible to use general-purpose organic substances at high concentrations in the past. It can withstand use enough. In application fields other than the catalyst, the material of the present invention can be advantageously used as a conductive filtration membrane, a sensor membrane, an electromagnetic shield, a conductive garment material, a flexible printed board, and an antenna material. The material of the present invention
It can be used in various shapes such as sheets, tubes, wires, cables, rods, yarns, fabrics, fibers, and tubes.
【００１０】[0010]
【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。Next, the present invention will be described in more detail with reference to examples.
【００１１】実施例１ 多孔質ポリテトラフルオロエチレン上に、以下のように
して、ジルコニアを付着結合させ、その上に金属銅を付
着結合させた。まず、厚さ４０μｍ、空孔率８０％、平
均細孔直径０．２μｍの多孔質ポリテトラフルオロエチ
レンフィルム（ジャパンゴアテックス（株）製）を、エ
タノールで十分に希釈さたジルコニウムブチレート（化
学式：Ｚｒ（ＯＣ4Ｈ9）4、松本製薬工業（株）製）の
中に浸し、その後、約２０分間蒸留水（常温）の中に入
れ水と反応させ、２６０℃、２時間で乾燥させる次に、
この基材を活性化後、無電解銅メッキ液（上村工業
（株）製、高速無電解銅メッキ液ＥＬＣ−ＳＰ）の中に
約１０分間浸して銅メッキした。Example 1 Zirconia was adhered and bonded onto porous polytetrafluoroethylene in the following manner, and metallic copper was bonded thereon. First, a porous polytetrafluoroethylene film (manufactured by Japan Gore-Tex Co., Ltd.) having a thickness of 40 μm, a porosity of 80%, and an average pore diameter of 0.2 μm was prepared by sufficiently diluting ethanol with zirconium butyrate (chemical formula). : Zr (OC 4 H 9 ) 4 , manufactured by Matsumoto Pharmaceutical Co., Ltd.), then put in distilled water (normal temperature) for about 20 minutes, reacted with water, and dried at 260 ° C. for 2 hours. next,
After activating this substrate, it was immersed in an electroless copper plating solution (high-speed electroless copper plating solution ELC-SP, manufactured by Uemura Kogyo KK) for about 10 minutes to perform copper plating.
【００１２】実施例２ 実施例１で示した多孔質ポリテトラフルオロエチレン上
に、以下のようにして、ジルコニアを付着結合させ、そ
の上に酸化銅を付着結合させた。実施例１と同様にし
て、まず多孔質ポリテトラフルオロエチレンフィルム上
にジルコニアを付着結合させ、更に銅を付着結合させ
る。次に、この基材を、２６０℃、１時間空気中で加熱
して、銅を酸化銅に変換した。 実施例３ 実施例１で示した多孔質ポリテトラフルオロエチレン上
に、以下のようにしてジルコニアを付着結合させ、その
上に酸化銀を付着結合させた。実施例１と同様にして、
まず多孔質ポリテトラフルオロエチレンフィルム上にジ
ルコニアを付着結合させた。次に、この基材を銀コロイ
ド液（戸田工業（株）製、ＴＳＣ−１１１、コロイド直
径約５０Å）中に約１時間浸して銀コロイドをジルコニ
ア上に付着させ、更に、２６０℃、１時間大気中で加熱
して、銀を酸化銀に変換した。Example 2 Zirconia was adhered and bonded onto the porous polytetrafluoroethylene shown in Example 1 as follows, and copper oxide was bonded thereon. In the same manner as in Example 1, first, zirconia is adhered and bonded onto the porous polytetrafluoroethylene film, and further copper is bonded and bonded. Next, the substrate was heated in air at 260 ° C. for 1 hour to convert copper to copper oxide. Example 3 Zirconia was adhered and bonded onto the porous polytetrafluoroethylene shown in Example 1 in the following manner, and silver oxide was bonded thereon. In the same manner as in Example 1,
First, zirconia was attached and bonded on a porous polytetrafluoroethylene film. Next, this substrate was immersed in a silver colloid solution (manufactured by Toda Kogyo Co., Ltd., TSC-111, colloid diameter: about 50 °) for about 1 hour to allow the silver colloid to adhere to the zirconia, and further at 260 ° C. for 1 hour. Heating in air converted silver to silver oxide.
【００１３】比較例１ 実施例１で示した多孔質ポリテトラフルオロエチレン上
に、特表昭６０−５００９０５号公報に記載の方法に従
って、以下のようにして酸化銅を付着結合させた。ま
ず、多孔質ポリテトラフルオロエチレンフィルムを界面
活性剤（住友スリーエム（株）製、ＦＣ−１７０Ｃ）の
５ｗｔ％水溶液に浸し、その後、常温で１２時間かけて
乾燥させ、親水性フィルムとした。次に、このフィルム
に対して実施例１と同様にして活性化し、銅メッキした
後、実施例２と同じ条件下で空気中で加熱し、銅を酸化
銅に変換した。Comparative Example 1 Copper oxide was adhered to the porous polytetrafluoroethylene shown in Example 1 according to the method described in Japanese Patent Publication No. Sho 60-500905 as follows. First, a porous polytetrafluoroethylene film was immersed in a 5 wt% aqueous solution of a surfactant (FC-170C, manufactured by Sumitomo 3M Limited), and then dried at room temperature for 12 hours to obtain a hydrophilic film. Next, the film was activated and copper-plated in the same manner as in Example 1, and then heated in air under the same conditions as in Example 2 to convert copper to copper oxide.
【００１４】（オゾンの分解試験）次に、前記実施例２
及び３で得られた膜を用いて、オゾンに対する分解触媒
能力の試験を行つた。試験方法は、オゾン発生機から一
定の濃度のオゾンを発生させ、下記反応条件で上記膜を
通過させ、通過後のオゾン濃度をオゾン分析計にて測定
した。その結果をもとに、次式によりオゾン分解率Ｒを
求めた。その結果を表１に示す。 Ｒ＝（Ｉ−Ｏ）／Ｉ×１００（％） （式中、Ｉは入り口のオゾン濃度を示し、Ｏは膜通過後
のオゾン濃度を示す） (1) 反応条件 オゾン温度…２５℃ 入り口のオゾン濃度…１０ｐｐｍ ＳＶ（Ｉ／Ｈ）…１０００００(Ozone decomposition test)
Using the membranes obtained in Steps (1) and (2), the ability of the catalyst to decompose ozone was tested. In the test method, a certain concentration of ozone was generated from an ozone generator, passed through the membrane under the following reaction conditions, and the ozone concentration after passing was measured by an ozone analyzer. Based on the result, the ozone decomposition rate R was determined by the following equation. Table 1 shows the results. R = (IO) / I × 100 (%) (where I represents the ozone concentration at the entrance, and O represents the ozone concentration after passing through the membrane) (1) Reaction conditions Ozone temperature: 25 ° C. Ozone concentration: 10 ppm SV (I / H): 100000
【００１５】[0015]
【表１】 [Table 1]
【００１６】（膜の縮み試験）次に金属を付着させる前
の親水化材料を、水に浸し、乾燥させたときの寸法変化
及びしわの発生試験を行う。その結果を表２に示す。サ
ンプルは下記の通りである。 サンプル１：ポリテトラフルオロエチレン膜に、実施例
１と同様にしてジルコニアを付着させたもの サンプル２：ポリテトラフルオロエチレン膜そのもの 上記サンプルに使用したポリテトラフルオロエチレン膜
は、すベて実施例１で使用したものと同じものを用い、
また、ジルコニア付着量は０．５ｗｔ％とした。尚、サ
ンプル２は、水に浸す前にエタノールで膜を親水化させ
た。(Film Shrinkage Test) Next, a dimensional change and a wrinkle generation test are performed when the hydrophilic material before the metal is attached is immersed in water and dried. Table 2 shows the results. The sample is as follows. Sample 1: Zirconia adhered to a polytetrafluoroethylene film in the same manner as in Example 1 Sample 2: Polytetrafluoroethylene film itself The polytetrafluoroethylene films used in the above samples were all of Example 1. Use the same ones used in
The zirconia adhesion amount was 0.5 wt%. Note that the membrane of Sample 2 was hydrophilized with ethanol before being immersed in water.
【００１７】[0017]
【表２】 [Table 2]
【００１８】尚、縮み度は、膜から１×１０ｃｍに切り
だしたサンプルを水に浸し、乾燥後の長片の長さをＤ
（ｃｍ）としたとき、式（（１０−Ｄ）／１０）×１０
０（％）で算出したものである。しわの状態は、乾燥後
の膜の状態を観察し、下記の指標で表した。 Ａ…全く変化なし、Ｂ…少ししわができる、Ｃ…たくさ
んしわができる。The degree of shrinkage is determined by immersing a sample cut into 1 × 10 cm from the membrane in water, and measuring the length of the long piece after drying by D.
(Cm), the formula ((10−D) / 10) × 10
It is calculated as 0 (%). The state of the wrinkles was indicated by the following index by observing the state of the film after drying. A: No change, B: A little wrinkle, C: A lot of wrinkles.
Claims (5)
おいて、該材料の微細孔内に無機化合物を付着結合させ
るとともに、該無機化合物に金属状態の金属を付着結合
させたことを特徴とする金属を含有する多孔質ふっ素樹
脂材料。1. A porous fluororesin material having fine pores, with deposit bond an inorganic compound in the material of the fine pores, characterized in that deposited bonds the metallic state metals inorganic compound A porous fluororesin material containing metal.
たもの、金属コロイドの付着により形成されたものまた
は蒸着により形成されたものである請求項１の多孔質ふ
っ素樹脂材料。2. The porous fluororesin material according to claim 1, wherein said metal is formed by electroless plating, formed by depositing a metal colloid, or formed by vapor deposition.
て付着結合する請求項１又は２の材料。Wherein said metal is a material according to claim 1 or 2, deposited binding metal film on the inorganic compound.
おいて、該材料の微細孔内に無機化合物を付着結合させ
るとともに、該無機化合物に金属状態の金属を付着結合
させ、該金属を酸化して金属酸化物としたことを特徴と
する金属酸化物を含有する多孔質ふっ素樹脂材料。4. A porous fluororesin material having fine pores.
In this case, an inorganic compound is adhered and bonded in the micropores of the material.
And bond metal in a metallic state to the inorganic compound
Characterized in that the metal is oxidized into a metal oxide.
A porous fluororesin material containing a metal oxide .
微細孔内に無機化合物を付着結合させたのち、該無機化
合物に金属を金属状態で付着結合させることを特徴とす
る金属を含有する多孔質ふっ素樹脂材料の製造方法。5. After the inorganic compound was deposited bond in the fine pores of the porous fluororesin material having fine pores, containing a metal, characterized in that depositing coupled metallic state metals in inorganic compound A method for producing a porous fluororesin material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27693491A JP3181329B2 (en) | 1991-09-27 | 1991-09-27 | Porous fluororesin material containing metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27693491A JP3181329B2 (en) | 1991-09-27 | 1991-09-27 | Porous fluororesin material containing metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0586224A JPH0586224A (en) | 1993-04-06 |
| JP3181329B2 true JP3181329B2 (en) | 2001-07-03 |
Family
ID=17576447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27693491A Expired - Fee Related JP3181329B2 (en) | 1991-09-27 | 1991-09-27 | Porous fluororesin material containing metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3181329B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5891402A (en) * | 1994-03-02 | 1999-04-06 | W. L. Gore & Associates, Inc. | Catalyst retaining apparatus and use in an ozone filter |
| JP2001513832A (en) * | 1997-02-26 | 2001-09-04 | インテグメント テクノロジーズ，インク． | Polymer composites and methods of making and using the same |
| JP2008063415A (en) * | 2006-09-06 | 2008-03-21 | Sumitomo Electric Ind Ltd | Porous resin material, method for producing the same, laminate sheet material and inspection unit |
| JP4811680B2 (en) * | 2008-03-05 | 2011-11-09 | 株式会社豊田中央研究所 | Ozone decomposition removal catalyst, method for producing the same, and ozone decomposition removal method |
| JP5354399B2 (en) * | 2011-06-17 | 2013-11-27 | 株式会社豊田中央研究所 | Ozone decomposition removal catalyst, method for producing the same, and ozone decomposition removal method |
-
1991
- 1991-09-27 JP JP27693491A patent/JP3181329B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0586224A (en) | 1993-04-06 |
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