JPH0488033A - Rubber having gas barrier property - Google Patents
Rubber having gas barrier propertyInfo
- Publication number
- JPH0488033A JPH0488033A JP20413090A JP20413090A JPH0488033A JP H0488033 A JPH0488033 A JP H0488033A JP 20413090 A JP20413090 A JP 20413090A JP 20413090 A JP20413090 A JP 20413090A JP H0488033 A JPH0488033 A JP H0488033A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- gas barrier
- barrier properties
- butadiene
- fluorination treatment
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 61
- 239000005060 rubber Substances 0.000 title claims abstract description 61
- 230000004888 barrier function Effects 0.000 title claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 12
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 10
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 5
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 5
- 229920001194 natural rubber Polymers 0.000 claims abstract description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 3
- 239000005062 Polybutadiene Substances 0.000 claims abstract 2
- 229920003049 isoprene rubber Polymers 0.000 claims abstract 2
- 229920002857 polybutadiene Polymers 0.000 claims abstract 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 30
- 239000011521 glass Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- VDETZMGKOHNVOT-UHFFFAOYSA-N butane;styrene Chemical compound CCCC.C=CC1=CC=CC=C1 VDETZMGKOHNVOT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はガスバリア性の高いゴム表面変性物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a rubber surface modified product with high gas barrier properties.
（従 来 の 技 術 ）
ゴムのガスバリア性はプラスチックのそれに比ヘー・般
に低い。その中で、ブチルゴム、アクリルニトリルブタ
ジェンゴム、チオコール等は比較的ガスバリア性が高い
が、これらのガスバリア性もポリ塩化ビニリデンと比較
すると１０３分の１〜１０２分の１程度しかない。(Conventional technology) The gas barrier properties of rubber are generally lower than those of plastics. Among them, butyl rubber, acrylonitrile butadiene rubber, thiocol, etc. have relatively high gas barrier properties, but their gas barrier properties are only about 1/103 to 1/102 when compared to polyvinylidene chloride.
ブチルゴム、アクリルニトリルブタジェンゴム等のガス
バリア性をさらに向上させるには、下記の二つの方法が
ある。There are two methods to further improve the gas barrier properties of butyl rubber, acrylonitrile butadiene rubber, etc.
■マイカ等の無機物を大量に添加する。■ Add large amounts of inorganic substances such as mica.
■成型物の表面に、有機溶媒に溶解したガスバリア性の
高いプラスチック（例えばナイロン、ポリ塩化ビニリデ
ン等）をコーティングする。(2) Coating the surface of the molded product with a plastic with high gas barrier properties (for example, nylon, polyvinylidene chloride, etc.) dissolved in an organic solvent.
しかしこれらも
■の方法は、ガスバリア性がもとのゴムの２倍程度にし
かならない上、ゴムがはく離し易くなる■の方法は、プ
ラスチック溶液の粘性のため成型物が互いに（つついて
しまうので数多く処理できない上、コーティング層とゴ
ムとの接着が弱いため、コーティング層かはがれ易い
等の問題点かあった。However, in method (2), the gas barrier properties are only about twice as high as those of the original rubber, and in method (2), the rubber peels off easily. In addition to not being able to process a large number of products, the adhesion between the coating layer and the rubber is weak, resulting in problems such as the coating layer peeling off easily.
一方、ゴムの高温におｉ）るガスバリア性の低下は、プ
ラスチックのそれに比べ大きいため、これを防ぐ目的で
、ゴムの表面に高温で高ガスバリア性のプラスチックフ
ィルム（テフロン等）を積層する方法があり、アルミ電
解コンデンサー用ゴム栓としての応用が考えられている
。ブチルゴムにテフロンを積層すると、１３０’Ｃでの
ガスバリア性は積層していないものの約１０倍となる。On the other hand, the gas barrier property of rubber (i) decreases significantly at high temperatures compared to that of plastics, so in order to prevent this, there is a method of laminating a plastic film (such as Teflon) with high gas barrier properties at high temperatures on the surface of the rubber. It is being considered for use as a rubber plug for aluminum electrolytic capacitors. When Teflon is laminated on butyl rubber, the gas barrier property at 130'C is approximately 10 times that of the one without lamination.
しかしこの方法も ○複雑な形状の成型物には積層できない。But this method also ○Cannot be laminated on molded products with complex shapes.
○積層物かはがれ易い。○Laminated materials peel off easily.
○テフロンを積層すると、組立作業性が悪くなる。○ If Teflon is layered, assembly workability will deteriorate.
○テフロンが高価な上、製造コストも高価なのでゴム栓
１−個当たりの値段か、積層していないものの約１０倍
となる。○Teflon is expensive and the manufacturing cost is also high, so the price per rubber stopper is about 10 times that of a non-laminated one.
等の問題点があった。There were problems such as.
このように、ガスバリア性の高いゴム成型物を作成する
ことは、これまでひとつの課題とされていた。As described above, creating a rubber molded product with high gas barrier properties has been a challenge until now.
（発明が解決しようとする問題点）
本発明はガスバリア性が高く、経時的にその性質か失わ
れず、廉価に作成できるゴム成型物を提供することを目
的さする。(Problems to be Solved by the Invention) An object of the present invention is to provide a rubber molded product that has high gas barrier properties, does not lose its properties over time, and can be produced at low cost.
（問題点を解決するための手段）
はじめにガスバリア性の他に要求される性質があれば、
そのゴムをベースゴムとして選択する３、例えばゴム弾
性が高く、かつガスバリア性のあるゴム成型物を所望す
る場合は、ベースゴムに天然ゴムを選択する。アルミ電
解コンデンサー用ゴム栓としては、アルミを腐食するよ
うなゴム（例えばクロロブレン等）はベースゴムとしな
い。特に要求される性質かない場合には、もともとガス
バリア性の高いブチルゴムやアクリルニトリルブタジェ
ンゴムをベースゴムとすれば、−層ガスバリア性か期待
できる。(Means for solving the problem) First, if there are any properties required in addition to gas barrier properties,
Select the rubber as the base rubber 3. For example, if a rubber molded product with high rubber elasticity and gas barrier properties is desired, natural rubber is selected as the base rubber. Rubbers that corrode aluminum (such as chloroprene) should not be used as the base rubber for rubber plugs for aluminum electrolytic capacitors. If there are no particularly required properties, if butyl rubber or acrylonitrile butadiene rubber, which already has high gas barrier properties, is used as the base rubber, it can be expected that the layer will have gas barrier properties.
これに成型等に必要な添加剤（加硫剤、加硫促進剤、充
填剤、補強剤等）を加え、所望の形状に成型する。Additives necessary for molding, etc. (vulcanizing agent, vulcanization accelerator, filler, reinforcing agent, etc.) are added to this and molded into the desired shape.
次に、成型物にフッ素化処理を施す。処理方法はまず、
耐圧容器に成型物を入れ、容器内の空気を排除する。次
にフッ素ガスを容量１０〜５０％、好ましくは容量２０
〜４０％含む不活性ガス（例えば窒素ガス、アルゴンガ
ス等）を流入して容器を常圧とし、３０分〜２時間、常
温で放置すれば良い。Next, the molded product is subjected to fluorination treatment. First, the processing method is
Place the molded product in a pressure-resistant container and eliminate the air inside the container. Next, add fluorine gas to 10 to 50% by volume, preferably 20% by volume.
The container may be brought to normal pressure by flowing an inert gas (for example, nitrogen gas, argon gas, etc.) containing ~40%, and left at room temperature for 30 minutes to 2 hours.
（作 用 ） ゴム成型物はフッ素ガスに曝すさ、表面がフ。(written by) The surface of rubber molded products becomes opaque when exposed to fluorine gas.
素化される。ゴム分子はフッ素化されると、気体の溶解
性が低下し、ガスバリア性が向」ニする。フッ素化処理
によって、もともとガスバリア性の高いブチルゴムやア
クリルニトリルブタジェンゴムで約３〜１０倍、天然ゴ
ムやスチレンブタジェンゴムでは約５０倍もガスバリア
性が向−トする。Be stripped down. When rubber molecules are fluorinated, gas solubility decreases and gas barrier properties are improved. Fluorination treatment improves the gas barrier properties of butyl rubber and acrylonitrile butadiene rubber, which already have high gas barrier properties, by about 3 to 10 times, and of natural rubber and styrene butadiene rubber, about 50 times.
またフッ素化処理すると、ゴム表面分子にフッ素か付加
もしくは置換するが、これによってゴムかアルミを腐食
するようなことはないので、アルミ電解コンデンサー用
ゴム栓に用いることができる。Furthermore, when fluorinated, fluorine is added to or replaced with molecules on the rubber surface, but this does not corrode the rubber or aluminum, so it can be used in rubber plugs for aluminum electrolytic capacitors.
一方、これまでフッ素化処理は、ゴムの粘着防止や摩擦
係数低下の目的で行われていた。本発明のフッ素化処理
成型物でもこれらの作用は表れるので、成型物の取り扱
い作業性か改善される。On the other hand, fluorination treatment has so far been carried out for the purpose of preventing rubber from sticking or lowering the coefficient of friction. Since these effects are also exhibited in the fluorinated molded product of the present invention, the handling efficiency of the molded product is improved.
（実 施 例 ）
例１）エチレンプロピレンジエンゴムにフッ素化処理を
施したアルミ電解コンデンサー用ゴム栓エチレンプロピ
レンジエンゴムｔｏｏｓにパーオキサイド１０部、充填
剤、補強剤等を加えて混練し、金型でアルミ電解コンデ
ンサー用ゴム栓を成型する。(Example) Example 1) 10 parts of peroxide, a filler, a reinforcing agent, etc. are added to ethylene propylene diene rubber too, which is a rubber stopper for aluminum electrolytic capacitors made of fluorinated ethylene propylene diene rubber, and then kneaded and molded. Molding rubber plugs for aluminum electrolytic capacitors.
成型品を耐圧容器に入れ、内部の空気を排除した後、３
５容量％のフッ素を含む窒素ガスを容器に充満し、約２
５０Ｃで１時間放置する。After placing the molded product in a pressure-resistant container and eliminating the air inside,
Fill the container with nitrogen gas containing 5% by volume of fluorine, and
Leave at 50C for 1 hour.
実験）上述のフッ素化処理ゴム栓と、未処理のエチレン
プロピレンジエンゴム（ＥＰＤＭ）のゴム栓とを用い、
ガスバリア性を次のように比較した。ガラス管にγ−ブ
チロラクトンを１０ｍｌ入れ、両ゴム栓で各々管を封口
し、１０００Ｃでの経時減量を測定した。その結果、フ
ッ素化処理ゴム栓を施したガラス管の重量減量率は未処
理の約５０分の１であった。（表１）表１１００°Ｃで
の重量減量率（％）
７日 ３０日
等を加えて混練し、金型でアルミ電解コンデンサ用ゴム
栓を成型する。Experiment) Using the above-mentioned fluorinated rubber stopper and an untreated ethylene propylene diene rubber (EPDM) rubber stopper,
Gas barrier properties were compared as follows. 10 ml of γ-butyrolactone was placed in a glass tube, each tube was sealed with both rubber stoppers, and the weight loss over time at 1000C was measured. As a result, the weight loss rate of the glass tube provided with the fluorinated rubber stopper was approximately 1/50 of that of the untreated glass tube. (Table 1) Table 1 Weight loss rate at 1100°C (%) 7 days, 30 days, etc., and knead, and mold a rubber plug for an aluminum electrolytic capacitor using a mold.
成型品を耐圧容器に入れ、内部の空気を排除した後、３
８容量％のフッ素を含む窒素ガスで常圧とし、約２５８
Ｃで１時間放置する。After placing the molded product in a pressure-resistant container and eliminating the air inside,
At normal pressure with nitrogen gas containing 8% by volume of fluorine, approximately 258
Leave at C for 1 hour.
実験）上述のフッ素化処理ゴム栓と、未処理のブチルゴ
ム（ポリサーＸ Ｌ １００００）のゴム栓とを用い、
ガスバリア性を次のように比較した。Experiment) Using the above-mentioned fluorinated rubber stopper and a rubber stopper made of untreated butyl rubber (Polycer XL 10000),
Gas barrier properties were compared as follows.
ガラス管にγ−ブチロラクトンを１．Ｑｍｌ入れ、両ゴ
ム栓で各々管を封目し、１３０８Ｃでの重量変化を経時
測定した。その結果、フッ素化処理ゴム栓を施したガラ
ス管の減量率は、未処理の約６分の１〜７分の１であっ
た。（表２）表２ １３０°Ｃでの重量減量率（％）例
２）ブチルゴムにフッ素化処理を施したアルミ電解コン
デンサー用ゴム栓
部分架橋ブチルゴム（ボリサーＸ Ｌ １００００）１
００部にパーオキサイド２部、充填剤、補強剤（効
果 ）
ゴムにフッ素化処理を施す技術は公知であるが、それは
主としてゴム特有の粘着性などを低下させる為のもので
あった。1. Add γ-butyrolactone to a glass tube. Qml was added, each tube was sealed with both rubber stoppers, and the weight change at 1308C was measured over time. As a result, the weight loss rate of the glass tube provided with the fluorinated rubber stopper was approximately 1/6 to 1/7 of that of the untreated glass tube. (Table 2) Table 2 Weight loss rate (%) at 130°C Example 2) Partially cross-linked butyl rubber for rubber plugs for aluminum electrolytic capacitors made by subjecting butyl rubber to fluorination treatment (Borisar XL 10000) 1
00 parts, 2 parts of peroxide, filler, reinforcing agent (effective
Although the technology of subjecting rubber to fluorination treatment is well known, it was mainly used to reduce the stickiness characteristic of rubber.
本発明はフッ素化処理によって、ゴム成型物の表面を変
性させてガスバリア性を付与したもので、該処理によっ
てガスバリア性は、ブチルゴムやアクリルニトリルブタ
ジェンゴムで未処理品の約３〜１０倍、天然ゴムやスチ
レンブタンエンゴムなとでは実に約５０倍にもなる。In the present invention, the surface of the rubber molded product is modified by fluorination treatment to impart gas barrier properties, and the gas barrier properties are approximately 3 to 10 times higher than that of untreated butyl rubber or acrylonitrile butadiene rubber. Natural rubber and styrene-butane rubber are about 50 times more effective.
上述のようにゴム表面が変性してガスバリア性となって
いるので、過酷な条件で長期間使用しても、従来のプラ
スチックコーテイング品等のようにガスバリア層がはが
れ落ちたりすることはない。As mentioned above, the rubber surface has been modified to provide gas barrier properties, so even if used for long periods of time under harsh conditions, the gas barrier layer will not peel off unlike conventional plastic coated products.
また、フッ素化処理は操作が簡単なため、製造工程のコ
ストは、ブチルゴムにテフロンを積層したゴム栓と比へ
ると約５分の工程度で済む。Further, since the fluorination treatment is easy to operate, the manufacturing process cost is only about 5 minutes compared to a rubber stopper made of butyl rubber laminated with Teflon.
さらには上述のようにフッ素化処理によってゴム特有の
粘着性なとが低下するので、減圧管の封口ゴムに本発明
を応用した場合、ゴム栓の組立作業性が大幅に改善され
る。Furthermore, as mentioned above, the fluorination treatment reduces the stickiness characteristic of rubber, so when the present invention is applied to sealing rubber for pressure reducing tubes, the workability of assembling the rubber stopper is greatly improved.
このように本発明のゴム表面変性物は、ガスバリア性が
高い、組立作業性が良い、アルミを腐食しない、という
特徴を持ち、特にアルミ電解コンデンサー用ゴム栓とし
て優れた性質を有している。As described above, the rubber surface modified product of the present invention has the characteristics of high gas barrier properties, good assembly workability, and does not corrode aluminum, and has particularly excellent properties as a rubber plug for an aluminum electrolytic capacitor.
Claims (1)
リア性を付与したゴム表面変性物。 ２）該ゴム表面変性物をアルミ電解コンデンサー用封口
ゴムに用いることを特徴とする特許請求の範囲第１項記
載のゴム表面変性物。 ３）ベースとなるゴムが、天然ゴム、イソプレンゴム、
スチレンブタジエンゴム、ブタジエンゴム、アクリルニ
トリルブタジエンゴム、ブチルゴム、エチレンプロピレ
ンジエンゴム、のいずれか１つ、もしくは２以上のブレ
ンドである特許請求の範囲第２項記載のゴム表面変性物
。[Scope of Claims] 1) A rubber surface-modified product that is provided with gas barrier properties by subjecting a rubber molded product to fluorination treatment. 2) The rubber surface modified product according to claim 1, wherein the rubber surface modified product is used as a sealing rubber for an aluminum electrolytic capacitor. 3) The base rubber is natural rubber, isoprene rubber,
The rubber surface modified product according to claim 2, which is any one of styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, and ethylene-propylene diene rubber, or a blend of two or more thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20413090A JPH0488033A (en) | 1990-08-01 | 1990-08-01 | Rubber having gas barrier property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20413090A JPH0488033A (en) | 1990-08-01 | 1990-08-01 | Rubber having gas barrier property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0488033A true JPH0488033A (en) | 1992-03-19 |
Family
ID=16485331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20413090A Pending JPH0488033A (en) | 1990-08-01 | 1990-08-01 | Rubber having gas barrier property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0488033A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012180458A (en) * | 2011-03-01 | 2012-09-20 | Bridgestone Corp | Gas-barrier material |
-
1990
- 1990-08-01 JP JP20413090A patent/JPH0488033A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012180458A (en) * | 2011-03-01 | 2012-09-20 | Bridgestone Corp | Gas-barrier material |
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