JPH0724964A - Laminate consisting of fluororesin and epichlorohydrin rubber - Google Patents
Laminate consisting of fluororesin and epichlorohydrin rubberInfo
- Publication number
- JPH0724964A JPH0724964A JP19419993A JP19419993A JPH0724964A JP H0724964 A JPH0724964 A JP H0724964A JP 19419993 A JP19419993 A JP 19419993A JP 19419993 A JP19419993 A JP 19419993A JP H0724964 A JPH0724964 A JP H0724964A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- epichlorohydrin rubber
- fuel
- laminate
- surface tension
- 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
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車用等の燃料の移
送に使われる燃料用ホース等に有用なフッ素樹脂とエピ
クロルヒドリンゴムとからなる積層物に関するものであ
り、ガソリン、メタノール等の燃料のガス遮断性に優
れ、メタノールハイドロカーボン規制等の公害対策上も
有用なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate composed of a fluororesin and epichlorohydrin rubber which is useful for a fuel hose used for transferring fuel for automobiles and the like. It has excellent gas barrier properties and is useful for pollution control such as methanol hydrocarbon regulations.
【０００２】[0002]
【従来の技術】従来ガソリン等の燃料ホースでは、燃料
のバリヤー性が比較的高いナイロン−１１等の樹脂類や
エピクロルヒドリンゴム等のゴム類等が積層されてホー
スが使用されていた。2. Description of the Related Art Conventionally, in a fuel hose for gasoline or the like, a hose has been used in which resins such as nylon-11 having a relatively high fuel barrier property and rubbers such as epichlorohydrin rubber are laminated.
【０００３】[0003]
【発明が解決しようとする課題】従来ガソリン等の燃料
ホースでは、微量ながらも燃料油が大気中に揮発してい
た。また、エピクロルヒドリンゴムと燃料油に対するバ
リヤー性の優れたフッ素樹脂とを接着することができな
かった。In a conventional fuel hose such as gasoline, a small amount of fuel oil was volatilized in the atmosphere. Further, it has not been possible to bond the epichlorohydrin rubber and the fluororesin having excellent barrier properties against fuel oil.
【０００４】[0004]
【課題を解決するための手段】本発明は、従来の技術が
有する上述の欠点を解決するために成されたものであ
り、手段としてはフッ素樹脂の接着表面を表面張力を３
０ダイン以上に高めたのち、シラン系またはエポキシ系
接着層を介してエピクロルヒドリンゴムを密着させ、高
い接着剥離強度を有し、フッ素樹脂の燃料油に対するバ
リヤー性を生かした燃料用ホース等に有用な積層物を提
供するものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art. As means, the adhesive surface of a fluororesin has a surface tension of 3 or less.
After increasing to 0 dyne or more, epichlorohydrin rubber is adhered through a silane-based or epoxy-based adhesive layer, and has high adhesive peel strength, which is useful for fuel hoses, etc. that make the best use of the barrier property of fluororesin to fuel oil. A laminate is provided.
【０００５】本発明において用いられるフッ素樹脂とし
ては、エチレン−テトラフルオロエチレン共重合体、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）エチレン共重合体等のＥＴＦＥ系共重合体（以下
単にＥＴＦＥと略す）、ポリテトラフルオロエチレン、
テトラフルオロエチレン−ヘキサフルオロプロピレン系
共重合体、テトラフルオロエチレン−（パーフルオロア
ルキル）ビニルエーテル系共重合体またはフッ化ビニリ
デン系共重合体等が挙げられ、以下においては、ＥＴＦ
Ｅを代表例として説明する。The fluororesin used in the present invention is an ETFE copolymer such as an ethylene-tetrafluoroethylene copolymer or an ethylene-tetrafluoroethylene- (perfluoroalkyl) ethylene copolymer (hereinafter simply referred to as ETFE). ), Polytetrafluoroethylene,
Examples thereof include a tetrafluoroethylene-hexafluoropropylene-based copolymer, a tetrafluoroethylene- (perfluoroalkyl) vinyl ether-based copolymer, a vinylidene fluoride-based copolymer and the like.
E will be described as a typical example.
【０００６】本発明において、燃料ホースの場合燃料の
透過性を低下させるものとして、内管にＥＴＦＥを使用
する。ホースとしての柔軟性を付与するために、室温に
おける曲げ弾性率２×１０4 ｋｇ／ｃｍ2 のＥＴＦＥが
用いられる。中でも６×１０3 ｋｇ／ｃｍ2 以下のもの
が好適に用いられる。また、外装被覆材としては、エピ
クロルヒドリンゴムが用いられる。ホースを補強するた
めに、外装材内部に布あるいはワイヤーからなる補強材
を配置するのが好ましい。内管のＥＴＦＥチューブの厚
みは、２０〜３００ミクロンで、２０ミクロン以下であ
れば燃料油に対するバリヤー性が十分発揮されず、３０
０ミクロンを超えると柔軟性が著しく低下するため好ま
しくない。In the present invention, in the case of a fuel hose, ETFE is used for the inner tube as a means for lowering the fuel permeability. ETFE having a flexural modulus of 2 × 10 4 kg / cm 2 at room temperature is used to impart flexibility as a hose. Among them, those having a density of 6 × 10 3 kg / cm 2 or less are preferably used. In addition, epichlorohydrin rubber is used as the exterior covering material. In order to reinforce the hose, it is preferable to dispose a reinforcing material made of cloth or wire inside the exterior material. The thickness of the ETFE tube as the inner tube is 20 to 300 μm. If the thickness is 20 μm or less, the barrier property against fuel oil is not sufficiently exhibited,
If it exceeds 0 micron, the flexibility is remarkably reduced, which is not preferable.
【０００７】ＥＴＦＥチューブの表面張力を３０ダイン
以上に高めるための方法としては、ナトリウムエッチン
グ処理またはコロナ放電処理が例示される。中でもその
簡便さからコロナ放電処理が好ましい。外装材であるエ
ピクロルヒドリンゴムとＥＴＦＥの接着には、エポキシ
系の接着剤またはアミノシラン、ビニルシラン等の有機
シラン系接着剤が用いられ、なかでも、有機シラン系接
着剤を用いるのが好ましい。特にアルコール系有機溶剤
を含有するシラン系接着剤が好ましい。接着方法につい
ては、加硫接着を行うのがよいが、低融点タイプのＥＴ
ＦＥを用いる場合には、加硫接着を必要としない。As a method for increasing the surface tension of the ETFE tube to 30 dyne or more, sodium etching treatment or corona discharge treatment is exemplified. Of these, corona discharge treatment is preferable because of its simplicity. An epoxy-based adhesive or an organic silane-based adhesive such as aminosilane or vinylsilane is used to bond the epichlorohydrin rubber, which is the outer packaging material, to ETFE, and among them, it is preferable to use the organic silane-based adhesive. Particularly, a silane-based adhesive containing an alcohol-based organic solvent is preferable. Regarding the bonding method, vulcanization bonding is preferable, but low melting point type ET
When using FE, no vulcanization adhesion is required.
【０００８】本発明では、内管に燃料油に対するバリヤ
ー性が高いＥＴＦＥ等のフッ素樹脂を用い、その表面を
処理した後、エピクロルヒドリンゴムと接着剤を用いて
一体化しており、燃料油の揮発が著しく抑えられてい
る。また、ＥＴＦＥとエピクロルヒドリンゴムとの密着
力も高い接着剥離強度を有し、長時間にわたり維持され
る。In the present invention, a fluororesin such as ETFE having a high barrier property against fuel oil is used for the inner pipe, and after the surface is treated, it is integrated with epichlorohydrin rubber and an adhesive to prevent the fuel oil from volatilizing. Remarkably suppressed. Also, the adhesion between ETFE and epichlorohydrin rubber has a high adhesive peel strength and is maintained for a long time.
【０００９】[0009]
【実施例】本発明を実施例により具体的に説明する。な
お、実施例中「部」とは重量部を示す。EXAMPLES The present invention will be specifically described with reference to examples. In addition, "part" in an Example shows a weight part.
【００１０】実施例１ ＣＯＰ５５ＡＸ（テトラフルオロエチレン／エチレン／
（パーフルオロブチル）エチレン、旭硝子製）を押出機
を用いてチューブ化し、その表面にコロナ処理を行った
チューブに接着剤としてビニルシラン、アミノシランの
混合シラン系カップリング剤（商品名：ケムロック６０
７ ロード・ファー・イースト製）を塗布し、その上に
エピクロルヒドリンゴム（商品名：Ｇｅｃｈｒｏｎ−３
１０３日本ゼオン製）を積層し、温度１５０℃で３０分
間加硫して２層の積層チューブを得た。この積層チュー
ブの剥離強度は、８．５ｋｇ／ｃｍだった。また、燃料
油Ｃに４０℃で７０時間浸漬後の剥離強度は７．９ｋｇ
／ｃｍだった。Example 1 COP55AX (tetrafluoroethylene / ethylene /
(Perfluorobutyl) ethylene, manufactured by Asahi Glass Co., Ltd., was made into a tube using an extruder, and the surface of the tube was corona-treated. A mixed silane coupling agent of vinylsilane and aminosilane was used as an adhesive (trade name: Chemloc 60
7 Road Far East Co., Ltd. is applied, and epichlorohydrin rubber (trade name: Gechron-3)
103 Nippon Zeon) was laminated and vulcanized at a temperature of 150 ° C. for 30 minutes to obtain a two-layer laminated tube. The peel strength of this laminated tube was 8.5 kg / cm. The peel strength after immersion in fuel oil C at 40 ° C for 70 hours is 7.9 kg.
It was / cm.
【００１１】実施例２ 実施例１の積層する相手剤として、カーボンをエピクロ
ルヒドリンゴム１００部に対して、５０部混合したエピ
クロルヒドリンゴムのコンパウンドを用いる以外は、実
施例１と同様にして２層チューブを得た。この積層体の
剥離強度は、７．２ｋｇ／ｃｍだった。Example 2 A two-layer tube was prepared in the same manner as in Example 1 except that 50 parts of carbon was mixed with 100 parts of epichlorohydrin rubber as the compounding agent for lamination in Example 1 except that a compound of epichlorohydrin rubber was used. Obtained. The peel strength of this laminate was 7.2 kg / cm.
【００１２】実施例３ 接着剤としてシラン系でなくエポキシ樹脂系接着剤（東
亜合成社製Ｓ−１０）を用いる以外は、実施例１と同様
に積層チューブを作成した。このチューブの剥離強度は
３．０ｋｇ／ｃｍであった。Example 3 A laminated tube was prepared in the same manner as in Example 1 except that an epoxy resin adhesive (S-10 manufactured by Toagosei Co., Ltd.) was used as the adhesive instead of the silane adhesive. The peel strength of this tube was 3.0 kg / cm.
【００１３】比較例１ 実施例１で接着剤を用いない以外は、実施例１と同様に
積層チューブを作成した。このチューブの剥離強度は
１．２ｋｇ／ｃｍであった。Comparative Example 1 A laminated tube was prepared in the same manner as in Example 1 except that the adhesive was not used in Example 1. The peel strength of this tube was 1.2 kg / cm.
【００１４】[0014]
【発明の効果】本発明の積層物は、フッ素樹脂とエピク
ロルヒドリンゴムとが強固に接着した耐燃料油性に優れ
た複層ホースとして特に有用である。本発明による工業
的利益は極めて大きい。本発明により得られる積層体
は、耐燃料油性以外にも耐薬品性、耐溶剤性、ガスバリ
ヤー性、溌油性、溌水性、耐候性、防水性、防汚性等の
付与により各種産業分野への応用展開が可能である。INDUSTRIAL APPLICABILITY The laminate of the present invention is particularly useful as a multi-layer hose in which a fluororesin and epichlorohydrin rubber are firmly adhered and which is excellent in fuel oil resistance. The industrial benefits of the present invention are enormous. The laminate obtained by the present invention can be applied to various industrial fields by imparting chemical resistance, solvent resistance, gas barrier property, oil repellency, water repellency, weather resistance, waterproofness, antifouling property, etc. in addition to fuel oil resistance. It is possible to develop the application of.
Claims (2)
ン以上に処理したものと、エピクロルヒドリンゴムと
を、シラン系またはエポキシ系接着剤を介して密着させ
た積層物。1. A laminate in which an adhesive surface of a fluororesin having a surface tension of 30 dynes or more and epichlorohydrin rubber are adhered to each other via a silane-based or epoxy-based adhesive.
チレン系共重合体である請求項１の積層物。2. The laminate according to claim 1, wherein the fluororesin is an ethylene-tetrafluoroethylene copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19419993A JPH0724964A (en) | 1993-07-09 | 1993-07-09 | Laminate consisting of fluororesin and epichlorohydrin rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19419993A JPH0724964A (en) | 1993-07-09 | 1993-07-09 | Laminate consisting of fluororesin and epichlorohydrin rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0724964A true JPH0724964A (en) | 1995-01-27 |
Family
ID=16320607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19419993A Pending JPH0724964A (en) | 1993-07-09 | 1993-07-09 | Laminate consisting of fluororesin and epichlorohydrin rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0724964A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007125694A (en) * | 2005-10-05 | 2007-05-24 | Togawa Rubber Co Ltd | Fuel hose and its manufacturing method |
| CN103712001A (en) * | 2013-11-27 | 2014-04-09 | 天津鹏翎胶管股份有限公司 | High-barrier nylon pipeline for automobile and method for manufacturing high-barrier nylon pipeline |
| TWI564160B (en) * | 2012-03-23 | 2017-01-01 | 富智康（香港）有限公司 | Bingd agent, method of surface treatment using the binding agent and product manufactured by the method |
-
1993
- 1993-07-09 JP JP19419993A patent/JPH0724964A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007125694A (en) * | 2005-10-05 | 2007-05-24 | Togawa Rubber Co Ltd | Fuel hose and its manufacturing method |
| TWI564160B (en) * | 2012-03-23 | 2017-01-01 | 富智康（香港）有限公司 | Bingd agent, method of surface treatment using the binding agent and product manufactured by the method |
| CN103712001A (en) * | 2013-11-27 | 2014-04-09 | 天津鹏翎胶管股份有限公司 | High-barrier nylon pipeline for automobile and method for manufacturing high-barrier nylon pipeline |
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