JPH06312486A - Laminate and its usage - Google Patents
Laminate and its usageInfo
- Publication number
- JPH06312486A JPH06312486A JP5102591A JP10259193A JPH06312486A JP H06312486 A JPH06312486 A JP H06312486A JP 5102591 A JP5102591 A JP 5102591A JP 10259193 A JP10259193 A JP 10259193A JP H06312486 A JPH06312486 A JP H06312486A
- Authority
- JP
- Japan
- Prior art keywords
- laminate
- film
- rubber layer
- crosslinked
- rubber
- 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
Landscapes
- Closures For Containers (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は架橋されたフッ素樹脂フ
ィルムとゴムとの積層体、その積層体を用いた電解コン
デンサ、あるいは液体（医薬液や化学液）容器用栓に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate of a crosslinked fluororesin film and rubber, an electrolytic capacitor using the laminate, or a stopper for a liquid (medicinal liquid or chemical liquid) container.
【０００２】[0002]
【従来の技術】電解コンデンサの封口や液体容器用栓と
してフッ素樹脂フィルムとゴム層との積層体を用いるこ
とは既に知られている。2. Description of the Related Art It is already known to use a laminate of a fluororesin film and a rubber layer for sealing an electrolytic capacitor or as a stopper for a liquid container.
【０００３】例えば、実公昭４３−２３０１７号公報に
はコンデンサ素子を内装したケースの開口部をフッ素樹
脂とゴムとの積層体で封止した電解コンデンサが記載さ
れている。このコンデンサは図２に示すように、アルミ
ニウム等から成るケース３内に電極およびセパレータ等
より成るコンデンサ素子４が内装され、その開口部はフ
ッ素樹脂フィルム１とゴム層２との積層体により封止さ
れている。なお、５はコンデンサ素子４の電極とケース
３を電気的に接続する接続線、６、７はリード線であ
る。For example, Japanese Utility Model Publication No. 4323017 discloses an electrolytic capacitor in which an opening of a case containing a capacitor element is sealed with a laminate of fluororesin and rubber. As shown in FIG. 2, in this capacitor, a capacitor element 4 including electrodes and a separator is internally provided in a case 3 made of aluminum or the like, and an opening portion thereof is sealed with a laminated body of a fluororesin film 1 and a rubber layer 2. Has been done. In addition, 5 is a connecting wire for electrically connecting the electrode of the capacitor element 4 and the case 3, and 6 and 7 are lead wires.
【０００４】また、特公平２−４０４９１号公報には、
図３に示すようにゴム層２とエチレン−テトラフルオロ
エチレン共重合体（以下、「ＥＴＦＥ」という）フィル
ム８から成る積層体を所定形状に賦形した医薬用ゴム栓
が記載されている。In Japanese Patent Publication No. 2-40491,
As shown in FIG. 3, there is described a medicinal rubber stopper in which a laminate comprising a rubber layer 2 and an ethylene-tetrafluoroethylene copolymer (hereinafter referred to as “ETFE”) film 8 is formed into a predetermined shape.
【０００５】[0005]
【発明が解決しようとする課題】上記電解コンデンサや
医薬用ゴム栓はゴム層とフッ素樹脂との積層体によりγ
−ブチルラクトン、ジメチルホルムアミド等の電解液や
医薬液の透過漏出を阻止しようとするものであるが、例
えばＥＴＦＥはこれらの液により膨潤する傾向があり、
その電解液透過阻止性能は未だ満足すべきものではな
い。DISCLOSURE OF THE INVENTION The electrolytic capacitor and the rubber stopper for medical use are formed by a laminated body of a rubber layer and a fluororesin.
-It is intended to prevent permeation and leakage of electrolytic solutions such as butyl lactone and dimethylformamide and pharmaceutical solutions. For example, ETFE tends to swell due to these solutions,
Its electrolyte permeation blocking performance is not yet satisfactory.
【０００６】[0006]
【課題を解決するための手段】本発明者は従来技術の有
する上記問題を解決するため鋭意研究の結果、フッ素樹
脂とゴム層との積層体において、フッ素樹脂を架橋する
ことにより電解液や医薬液の透過漏出を極少にできるこ
とを見出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive research to solve the above problems of the prior art, the present inventor has found that in a laminate of a fluororesin and a rubber layer, the fluororesin is crosslinked to form an electrolytic solution or a medicine. The inventors have found that permeation and leakage of liquid can be minimized, and have completed the present invention.
【０００７】即ち、本発明はフッ素樹脂フィルムとゴム
層との積層体であり、前記フッ素樹脂フィルムが架橋さ
れていることを特徴とする積層体に関するものである。That is, the present invention relates to a laminate of a fluororesin film and a rubber layer, which is characterized in that the fluororesin film is crosslinked.
【０００８】図１は本発明に係る積層体の実例を示し、
フッ素樹脂フィルム１とゴム層２とから成り、該フッ素
樹脂フィルム１は架橋されている。このように本発明に
おいてはフッ素樹脂フィルムを架橋するので、該フッ素
樹脂フィルムとしてはＥＴＦＥ、エチレン−クロロトリ
フルオロエチレン共重合体（以下、「ＥＣＴＦＥ」とい
う）あるいはポリフッ化ビニリデンのような架橋し得る
フッ素樹脂から成るフィルムを用いる。FIG. 1 shows an example of a laminate according to the present invention,
It comprises a fluororesin film 1 and a rubber layer 2, and the fluororesin film 1 is crosslinked. As described above, since the fluororesin film is crosslinked in the present invention, the fluororesin film may be crosslinked such as ETFE, ethylene-chlorotrifluoroethylene copolymer (hereinafter referred to as "ECTFE") or polyvinylidene fluoride. A film made of fluororesin is used.
【０００９】本発明においてはかようにフッ素樹脂フィ
ルムが架橋されていることが重要であり、架橋フィルム
を用いることにより電解液や医薬液の透過漏出を極少に
できる。In the present invention, it is important that the fluororesin film is crosslinked as described above, and the use of the crosslinked film can minimize the permeation and leakage of the electrolytic solution and the medicinal solution.
【００１０】フッ素樹脂フィルムの架橋はガンマ線、エ
ックス線、電子線のような放射線を照射する方法等で行
うことができる。このとき架橋助剤として予めフィルム
中にトリアリルイソシアヌレートやトリメチロールプロ
パンアクリレートのような多官能モノマーを配合しても
よい。放射線照射法により架橋する場合の照射量は、通
常、１〜５０メガラッドであり、多官能モノマーを使用
する場合、その配合量は、通常、フッ素樹脂１００重量
部に対し５重量部以下とする。そして、フッ素樹脂フィ
ルムの架橋はゴム層との積層の前、後あるいは積層中の
いずれで行ってもよいが、ゴム層がブチルゴムのような
耐放射線性に乏しい場合に放射線照射法を採用するとき
は、積層前に架橋しておくのが好ましい。Crosslinking of the fluororesin film can be carried out by a method of irradiating with radiation such as gamma rays, X rays or electron rays. At this time, a polyfunctional monomer such as triallyl isocyanurate or trimethylolpropane acrylate may be previously mixed in the film as a crosslinking aid. The irradiation amount in the case of crosslinking by the irradiation method is usually 1 to 50 megarads, and when a polyfunctional monomer is used, the compounding amount thereof is usually 5 parts by weight or less with respect to 100 parts by weight of the fluororesin. The cross-linking of the fluororesin film may be carried out before, after or during the lamination with the rubber layer, but when the radiation irradiation method is adopted when the rubber layer is poor in radiation resistance such as butyl rubber. Is preferably crosslinked before lamination.
【００１１】一方、フッ素樹脂フィルムと積層されるゴ
ム層は特に限定されず、例えば、ブチルゴム（ＩＩ
Ｒ）、エチレンプロピレンターポリマー（ＥＰＤＭ）、
エピクロロヒドリンゴム、イソプレンゴム（ＩＲ）、ブ
タジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢ
Ｒ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、ク
ロロプレンゴム（ＣＲ）、シリコーンゴム等の合成ゴム
あるいは天然ゴムのいずれも用いることができる。On the other hand, the rubber layer laminated with the fluororesin film is not particularly limited. For example, butyl rubber (II
R), ethylene propylene terpolymer (EPDM),
Epichlorohydrin rubber, isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SB
R), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), silicone rubber, or other synthetic rubber or natural rubber can be used.
【００１２】フッ素樹脂フィルムとゴム層との積層方法
としては、フッ素樹脂フィルムと未加硫のゴム層を重ね
合わせて加熱加圧することにより、ゴム層を加硫すると
共に両者を接合する方法が既に知られており、本発明の
積層体もこの方法により得ることができる。この積層に
際し、両者の接合強度を向上させるため、フッ素樹脂フ
ィルム表面にコロナ放電処理、スパッタエッチング処理
（この方法やそれに用いる装置については特公昭５３−
２２１０８号公報、特公昭５６−１３３６号公報、特公
昭５６−１３３７号公報、特公昭５６−１３３８号公報
等に詳細に記載されている）、火炎処理等の公知の接着
処理を施すことができる。As a method for laminating the fluororesin film and the rubber layer, a method of vulcanizing the rubber layer and joining the two by superposing the fluororesin film and the unvulcanized rubber layer on each other and applying heat and pressure has already been used. Known laminates of the invention can also be obtained by this method. At the time of this lamination, in order to improve the bonding strength between the two, a corona discharge treatment and a sputter etching treatment are performed on the surface of the fluororesin film.
No. 22108, Japanese Patent Publication No. 56-1336, Japanese Patent Publication No. 56-1337, Japanese Patent Publication No. 56-1338, etc.), flame treatment or other known adhesion treatment can be applied. .
【００１３】そして、フッ素樹脂とゴム層との積層体を
医薬液や化学液等を収納する容器の栓に用いるため、所
定の形状に賦形する場合は、加硫と接合に際して金型を
用い、同時に賦形することも知られている（例えば、特
公平２−４０４９１号公報）。従って、本発明に係る積
層体にこの方法を適用することにより、所定形状に賦形
された液体容器用栓を得ることができる。なお、ＥＴＦ
ＥフィルムあるいはＥＣＴＦＥフィルムは架橋前あるい
は架橋後にかかわらず賦形性がよいので、この点で好ま
しい。Since a laminate of a fluororesin and a rubber layer is used as a stopper of a container for containing a medical liquid, a chemical liquid, etc., when shaping it into a predetermined shape, a mold is used for vulcanization and bonding. It is also known to shape at the same time (for example, Japanese Patent Publication No. 2-40491). Therefore, by applying this method to the laminate according to the present invention, it is possible to obtain a stopper for a liquid container shaped into a predetermined shape. In addition, ETF
The E film or ECTFE film is preferable in this respect because it has good shapeability before or after crosslinking.
【００１４】本発明に係る積層体を用いた電解コンデン
サの構造は前記図２に示すのと同様に、アルミニウム等
から成るケース内に電極およびセパレータ等から成るコ
ンデンサ素子が内装され、その開口部を積層体により封
止したものであってよい。勿論、リード線やコンデンサ
素子とケースを電気的に接続する接続線は適宜配備す
る。The structure of the electrolytic capacitor using the laminated body according to the present invention is similar to that shown in FIG. 2, in which a case made of aluminum or the like is internally provided with a capacitor element composed of electrodes and a separator and the like, and its opening is It may be sealed with a laminate. Of course, a lead wire or a connecting wire for electrically connecting the capacitor element and the case is appropriately provided.
【００１５】[0015]
【実施例】以下、実施例により本発明を更に詳細に説明
する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００１６】実施例１ 厚さ１００μｍのＥＴＦＥフィルムに電子線を５メガラ
ッド照射して架橋する（この架橋フィルムを試料１とす
る）。次に、雰囲気ガスとしてアルゴンガスを用い、雰
囲気圧０．１Ｔｏｒｒで１３．５６ＭＨｚの高周波電圧
を印加し、放電電力２Ｗａｔｔ／ｃｍ2 で架橋ＥＴＦＥ
フィルムの片面を３秒間スパッタエッチング処理する。
そして、該フィルムのスパッタエッチング処理面にプラ
イマー液（株式会社東洋化学研究所製、商品名メタロッ
クＧ）を塗布する。Example 1 An ETFE film having a thickness of 100 μm is irradiated with an electron beam of 5 megarads to be crosslinked (this crosslinked film is referred to as Sample 1). Next, using argon gas as an atmosphere gas, a high frequency voltage of 13.56 MHz was applied at an atmosphere pressure of 0.1 Torr, and a cross-linked ETFE was formed at a discharge power of 2 Watt / cm 2.
Sputter etch one side of the film for 3 seconds.
Then, a primer solution (trade name: METALLOCK G, manufactured by Toyo Kagaku Kenkyusho Co., Ltd.) is applied to the sputter-etched surface of the film.
【００１７】一方、これとは別にＮＢＲ１００重量部に
対し加硫剤（化薬ヌーリー株式会社製、商品名パーカド
ックス）２重量部を配合した組成物から成る未加硫のゴ
ム板（厚さ２ｍｍ）を用意する。On the other hand, separately from this, an unvulcanized rubber plate (thickness: 2 mm) made of a composition in which 2 parts by weight of a vulcanizing agent (product name: Percadox, manufactured by Kayaku Nouri Co., Ltd.) is mixed with 100 parts by weight of NBR. ) Is prepared.
【００１８】そして、上記ＥＴＦＥフィルムのプライマ
ー液塗布面にゴム板を重ね合わせ、温度１５０℃、圧力
２ｋｇ／ｃｍ2 の条件で３０分間加熱加圧することによ
り、ゴムを加硫すると共に両者を接合して積層体を得
た。Then, a rubber plate is placed on the primer liquid-coated surface of the ETFE film and heated and pressed for 30 minutes at a temperature of 150 ° C. and a pressure of 2 kg / cm 2 to vulcanize the rubber and bond them together. To obtain a laminate.
【００１９】実施例２ ＥＴＦＥフィルムに対し電子線を１０メガラッドあるい
は２０メガラッド照射して２枚の架橋フィルムを用意す
る（１０メガラッド照射品を試料２、２０メガラッド照
射品を試料３とする）。これら架橋フィルムを用いるこ
と以外は実施例１と同様に作業して２種類の積層体を得
た。Example 2 Two crosslinked films were prepared by irradiating an ETFE film with an electron beam at 10 megarads or 20 megarads (10 megarad-irradiated product is sample 2 and 20 megarad-irradiated product is sample 3). The same operation as in Example 1 was carried out except that these crosslinked films were used to obtain two kinds of laminates.
【００２０】実施例３ ＥＴＦＥフィルムに代えてＥＣＴＦＥフィルムを用い、
このＥＣＴＦＥフィルムに対する電子線の照射量を５メ
ガラッド、１０メガラッドあるいは２０メガラッド照射
して３枚の架橋フィルムを用意する（５メガラッド照射
品を試料４、１０メガラッド照射品を試料５、２０メガ
ラッド照射品を試料６とする）。これら架橋フィルムを
用いること以外は実施例１と同様に作業して３種類の積
層体を得た。Example 3 An ECTFE film was used in place of the ETFE film,
This ECTFE film is irradiated with an electron beam of 5 megarads, 10 megarads or 20 megarads to prepare three crosslinked films (5 megarads are sample 4, 10 megarads are samples 5 and 20 megarads are samples 5 and 20 megarads). Is referred to as Sample 6). The same operation as in Example 1 was carried out except that these crosslinked films were used to obtain three kinds of laminates.
【００２１】比較例１ ＥＴＦＥフィルムに対する電子線照射を行わないこと
（未照射のＥＴＦＥフィルムを試料７とする）以外は実
施例１と同様に作業して積層体を得た。Comparative Example 1 A laminate was obtained in the same manner as in Example 1 except that the ETFE film was not irradiated with an electron beam (the unirradiated ETFE film was used as Sample 7).
【００２２】比較例２ ＥＣＴＦＥフィルムに対する電子線照射を行わないこと
（未照射のＥＣＴＦＥフィルムを試料８とする）以外は
実施例３と同様に作業して積層体を得た。Comparative Example 2 A laminate was obtained in the same manner as in Example 3 except that the ECTFE film was not irradiated with an electron beam (unirradiated ECTFE film was used as Sample 8).
【００２３】上記実施例および比較例において用いたフ
ィルム（試料１〜８）について、下記要領により透過漏
出阻止試験を行い、得られた結果を表１に示す。The films (Samples 1 to 8) used in the above Examples and Comparative Examples were subjected to a permeation leakage prevention test according to the following procedure, and the results obtained are shown in Table 1.
【００２４】Ａ．透過漏出阻止試験 各フィルムから縦、横が各々１０ｃｍの矩形片２枚を切
出し、それを合わせ３方を熱シール（シール部の幅は１
０ｍｍ）して袋状とし、次に、１０ｇのγ−ブチルラク
トンを収納した後開口部を熱シール（シール部の幅は１
０ｍｍ）して密封体とする。そして、この密封体を１０
０℃の雰囲気中に１カ月放置し、密封体の重量減少を秤
量してγ−ブチルラクトンの透過量（ｇ／ｃｍ2 ・ｄａ
ｙ）を算出した。A. Permeation Leakage Prevention Test Two rectangular pieces with a length of 10 cm and a width of 10 cm were cut out from each film, and the three pieces were combined and heat-sealed (the width of the sealing part was 1
(0 mm) to form a bag, and after containing 10 g of γ-butyl lactone, the opening is heat-sealed (the width of the sealing part is 1).
0 mm) to make a sealed body. And this sealed body is 10
After leaving it in an atmosphere of 0 ° C. for 1 month, the weight loss of the sealed body is weighed and the amount of permeation of γ-butyl lactone (g / cm 2 · da) is measured.
y) was calculated.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明は上記のように構成され、フッ素
樹脂フィルムを架橋してゴム層と積層するようにしたの
で、電解液や医薬液のような液体の透過漏出を有効に阻
止できる。EFFECTS OF THE INVENTION Since the present invention is constructed as described above and the fluororesin film is cross-linked and laminated with the rubber layer, it is possible to effectively prevent the permeation and leakage of a liquid such as an electrolytic solution or a medicinal solution.
【図１】本発明に係る積層体の実例を示す正面図であ
る。FIG. 1 is a front view showing an example of a laminate according to the present invention.
【図２】フッ素樹脂とゴム層との積層体を用いて開口部
を封止した電解コンデンサの実例を示す断面図である。FIG. 2 is a cross-sectional view showing an actual example of an electrolytic capacitor whose opening is sealed with a laminate of a fluororesin and a rubber layer.
【図３】フッ素樹脂とゴム層との積層体から成る医薬用
ゴム栓の実例を示す断面図である。FIG. 3 is a cross-sectional view showing an example of a medical rubber stopper made of a laminate of a fluororesin and a rubber layer.
１ フッ素樹脂フィルム ２ ゴム層 1 Fluororesin film 2 Rubber layer
Claims (4)
であり、前記フッ素樹脂フィルムが架橋されていること
を特徴とする積層体。1. A laminate comprising a fluororesin film and a rubber layer, wherein the fluororesin film is crosslinked.
フルオロエチレン共重合体、エチレン−クロロトリフル
オロエチレン共重合体またはポリフッ化ビニリデンのい
ずれかである請求項１記載の積層体。2. The laminate according to claim 1, wherein the fluororesin film is any one of ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer and polyvinylidene fluoride.
部を架橋されたフッ素樹脂フィルムとゴム層との積層体
により封止したことを特徴とする電解コンデンサ。3. An electrolytic capacitor characterized in that an opening of a case containing a capacitor element is sealed with a laminate of a crosslinked fluororesin film and a rubber layer.
との積層体から成る液体容器用栓。4. A stopper for a liquid container comprising a laminate of a crosslinked fluororesin film and a rubber layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5102591A JPH06312486A (en) | 1993-04-28 | 1993-04-28 | Laminate and its usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5102591A JPH06312486A (en) | 1993-04-28 | 1993-04-28 | Laminate and its usage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06312486A true JPH06312486A (en) | 1994-11-08 |
Family
ID=14331482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5102591A Pending JPH06312486A (en) | 1993-04-28 | 1993-04-28 | Laminate and its usage |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06312486A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109881A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Sealer for electrolytic capacitor and method of manufacturing same |
| JP2011146494A (en) * | 2010-01-14 | 2011-07-28 | Shin-Etsu Chemical Co Ltd | Sealing body for electrolytic capacitor |
| JP2012245790A (en) * | 2001-06-04 | 2012-12-13 | Saint-Gobain Performance Plastics Corp | Multilayer polymeric article with intercrosslinked polymer layer and method of making the same |
-
1993
- 1993-04-28 JP JP5102591A patent/JPH06312486A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012245790A (en) * | 2001-06-04 | 2012-12-13 | Saint-Gobain Performance Plastics Corp | Multilayer polymeric article with intercrosslinked polymer layer and method of making the same |
| JP2003109881A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Sealer for electrolytic capacitor and method of manufacturing same |
| JP2011146494A (en) * | 2010-01-14 | 2011-07-28 | Shin-Etsu Chemical Co Ltd | Sealing body for electrolytic capacitor |
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