JPH0586987B2

JPH0586987B2 -

Info

Publication number: JPH0586987B2
Application number: JP60279235A
Authority: JP
Inventors: Shoji Hagiwara; Rikito Eguchi
Original assignee: Nok Corp
Current assignee: Nok Corp
Priority date: 1985-12-13
Filing date: 1985-12-13
Publication date: 1993-12-15
Also published as: JPS62141082A

Description

[Detailed description of the invention]

〔産業上の利用分野〕本発明は、金属とフツ素ゴムとの接着方法に関
する。更に詳しくは、加硫接着剤配合物を用いた
金属とフツ素ゴムとの接着方法に関する。〔従来の技術〕従来、金属とフツ素ゴムとの間の接着には、主
として有機シラン系接着剤が使用されているが、
この接着剤を用いて接着した場合には接着後の耐
熱性に問題があり、特に２次加硫の温度が200℃
以上の場合には、フツ素ゴムから発生したフツ化
水素によつて金属面での剥れを発生することが多
い。〔発明が解決しようとする問題点〕そこで、本発明者は、高い温度で熱処理を行な
つても金属−フツ素ゴム間で十分な接着力が得ら
れるような接着剤配合物を求めて種々検討の結
果、次の各成分を含有する加硫接着剤配合物がか
かる目的を十分に満足させるものであることを見
出した。〔問題点を解決するための手段〕および〔作用〕従つて、本発明は金属とフツ素ゴムとの接着方
法に係り、金属とフツ素ゴムとの接着は、ノボラ
ツク型エポキシ樹脂、ノボラツク型フエノール樹
脂および該ノボラツク型フエノール樹脂の硬化剤
を含有する加硫接着剤配合物を金属上に塗布し、
必要に応じて焼付け処理を行なつた後、未加硫の
フツ素ゴムと接触させ、フツ素ゴムの加硫温度で
加圧加硫することにより行われる。加硫接着剤配合物の一成分であるノボラツク型
エポキシ樹脂は、次のような一般式で表わされる
ものである。 [Industrial Application Field] The present invention relates to a method for bonding metal and fluororubber. More specifically, the present invention relates to a method of bonding metal and fluororubber using a vulcanized adhesive composition. [Prior Art] Conventionally, organic silane adhesives have been mainly used for adhesion between metals and fluorocarbon rubber.
When bonding with this adhesive, there is a problem with heat resistance after bonding, especially when the temperature of secondary vulcanization is 200℃.
In the above cases, hydrogen fluoride generated from the fluororubber often causes peeling on the metal surface. [Problems to be Solved by the Invention] Therefore, the present inventor conducted various efforts in search of an adhesive compound that would provide sufficient adhesive strength between metal and fluoro rubber even when heat-treated at high temperatures. As a result of investigation, it has been found that a vulcanized adhesive formulation containing the following components fully satisfies these objectives. [Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a method of bonding metal and fluoro rubber, and the bonding between metal and fluoro rubber is performed using novolac type epoxy resin, novolac type phenol. applying a vulcanized adhesive formulation containing a resin and a curing agent of the novolac type phenolic resin onto the metal;
After carrying out a baking treatment as necessary, it is brought into contact with unvulcanized fluororubber and vulcanized under pressure at the vulcanization temperature of the fluororubber. The novolak type epoxy resin, which is a component of the vulcanizable adhesive formulation, is represented by the following general formula.

【化】ノボラツク型エポキシ樹脂は、接着剤の耐熱
性、耐薬品性、接着性を更に改善させるために用
いられる成分であり、それはノボラツク樹脂にエ
ピクロルヒドリンによつて代表されるエピハロヒ
ドリンを反応させ、フエノール性水酸基をグリシ
ジルエーテル化することによって製造される。また、他の一成分であるノボラツク型フエノー
ル樹脂は、次のような一般式で表わされるもので
ある。[Chemical] Novolac-type epoxy resin is a component used to further improve the heat resistance, chemical resistance, and adhesive properties of adhesives.It is a component that is used to further improve the heat resistance, chemical resistance, and adhesive properties of adhesives. It is produced by converting a hydroxyl group into glycidyl ether. The other component, novolac type phenolic resin, is represented by the following general formula.

【化】このように、ノボラツク型フエノール樹脂は、
フエノールあるいはアルキル置換フエノールとホ
ルムアルデヒドとを酸触媒下で反応させることに
より、アルコール、ケトンなどの有機溶剤に可溶
な松やに状物として得られ、これにアミン化合物
あるいはリン化合物などの硬化剤を加えて加熱す
ることによって、不溶不融のフエノール樹脂を形
成する。本発明においては、融点が約100〜150℃
程度、分子量が約数万程度のものが用いられる。ノボラツク型フエノール樹脂の硬化剤として
は、アミン化合物またはリン化合物が一般に用い
られる。アミン化合物としては、次の一般式で表わされ
るようなものが用いられる。（ａ） H_zＮ（C_oH_zoNH）_nC_oH_zoNH_z ｍ：０または25程度迄の正の整数ｎ：正の整数（ｂ） H_zＮ−R₃−NH_z R₃：[C] In this way, novolac type phenolic resin is
By reacting phenol or alkyl-substituted phenol with formaldehyde under an acid catalyst, it is obtained as a resin-like substance that is soluble in organic solvents such as alcohols and ketones. By heating, an insoluble and infusible phenolic resin is formed. In the present invention, the melting point is approximately 100 to 150°C.
Those with a molecular weight of about tens of thousands are used. Amine compounds or phosphorus compounds are generally used as curing agents for novolak type phenolic resins. As the amine compound, those represented by the following general formula are used. (a) H _z N (C _o H _zo NH) _n C _o H _zo NH _z m: Positive integer up to 0 or 25 n: Positive integer (b) H _z N−R ₃ −NH _z R ₃ :

【formula】

【式】【formula】

【formula】〔Effect of the invention〕

ノボラック型エポキシ樹脂とノボラツク型フエ
ノール樹脂とを主成分とする加硫接着剤配合物を
用いて金属とフツ素ゴムとの接着を行なうと、接
着物は高温処理を行なつた場合にも金属面での剥
れを生ずることがなく、特にこのような場合にし
ばしば剥れがみられたアルミニウム、銅、亜鉛な
どの金属面でも殆んど剥れを生じないという効果
を奏する。このような効果は、フツ素ゴムの加硫剤として
アミン系、ポリオール系、パーオキサイド系など
の各種加硫剤を用いた場合にもその種類を問わず
に発揮され、接着物に安定した接着性と高い耐熱
性とを付与し、また加熱時にフツ素ガスから発生
するフツ化水素による金属の腐食をも有効に防止
する。本発明方法によつて行われる金属とフツ素ゴム
との加硫接着は、オイルシール、バルブステムシ
ール、リードバルブ、バルブ部品などの製造に好
適に適用される。〔実施例〕次に、実施例について本発明を説明する。実施例１ノボラツク型エポキシ樹脂（日本チバ・ガイギ
ー製品ECN1299）100部（重量、以下同じ）、ノ
ボラツク型フエノール樹脂100部、ヘキサメチレ
ンテトラミン10部、メチルエチルケトン1000部お
よびメタノール1000部からなる加硫接着剤配合物
を、リン酸亜鉛被膜処理を施した軟鋼板上に塗布
し、室温で30分間風乾後、180℃で10分間焼付け
処理を行なつた。次に、このようにして加硫接着剤配合物を焼付
けた軟鋼板上に、前記配合例よりなる未加硫の
フツ素ゴムを接触させ、180℃で８分間加圧加硫
を行ない、加硫された接着物を200℃で22時間熱
処理した。実施例２実施例１において、未加硫のフツ素ゴムとし
て、前記配合例のものが用いられた。比較例実施例１において、リン酸亜鉛被膜処理軟鋼板
と未加硫のフツ素ゴムとの接着を有機シラン系接
着剤を用いて行ない、180℃で８分間の加圧加硫
物について、200℃で22時間の熱処理を行なつた。以上の各実施例および比較例で得られた熱処理
接着物について、JIS Ｋ−6301 90°剥離試験法に
よる剥離力ならびにゴム残り面積（ゴムと接着剤
との間に剥れがみられなかつた面積）をそれぞれ
測定した。得られた結果は、次の表に示される。 When bonding metal and fluoro rubber using a vulcanized adhesive compound containing a novolac type epoxy resin and a novolac type phenolic resin as main components, the bonded material remains stable on the metal surface even when subjected to high temperature treatment. In particular, it has the effect of hardly causing any peeling even on metal surfaces such as aluminum, copper, zinc, etc., which often peel off in such cases. This effect is exhibited regardless of the type of vulcanizing agent used for fluoro rubber, such as amine, polyol, or peroxide, and provides stable adhesion to the adhesive. In addition, it effectively prevents corrosion of metals due to hydrogen fluoride generated from fluorine gas during heating. The vulcanization bonding of metal and fluoro rubber performed by the method of the present invention is suitably applied to the production of oil seals, valve stem seals, reed valves, valve parts, and the like. [Example] Next, the present invention will be explained with reference to an example. Example 1 Vulcanized adhesive consisting of 100 parts of novolac type epoxy resin (ECN1299 manufactured by Nippon Ciba Geigy) (weight, same hereinafter), 100 parts of novolac type phenolic resin, 10 parts of hexamethylenetetramine, 1000 parts of methyl ethyl ketone and 1000 parts of methanol. The formulation was applied onto a mild steel plate treated with a zinc phosphate coating, air-dried at room temperature for 30 minutes, and then baked at 180°C for 10 minutes. Next, on the mild steel plate on which the vulcanized adhesive composition was baked, an unvulcanized fluoro rubber made from the above formulation example was brought into contact, and pressure vulcanization was performed at 180°C for 8 minutes. The sulfurized adhesive was heat treated at 200°C for 22 hours. Example 2 In Example 1, as the unvulcanized fluororubber, the one in the formulation example described above was used. Comparative Example In Example 1, the zinc phosphate coated mild steel sheet and the unvulcanized fluoro rubber were bonded using an organosilane adhesive, and the pressure vulcanizate was cured at 180°C for 8 minutes. Heat treatment was performed at ℃ for 22 hours. Regarding the heat-treated adhesives obtained in each of the above Examples and Comparative Examples, the peel force and remaining rubber area (area where no peeling was observed between the rubber and adhesive) were determined by the JIS K-6301 90° peel test method. ) were measured respectively. The results obtained are shown in the following table.

【table】

Claims

[Scope of Claims] 1. The ratio of novolak type phenolic resin to 100 parts by weight of novolak type epoxy resin is 40 to 100 parts by weight, and the curing agent thereof is 5 to 30 parts by weight to the novolak type phenolic resin. A method of applying a vulcanizable adhesive composition to a metal, contacting it with unvulcanized fluorocarbon rubber, and vulcanizing it under pressure at the vulcanization temperature of the fluorocarbon rubber. Adhesion method with fluoro rubber. 2. Adhesion method according to claim 1, in which the vulcanized adhesive formulation is used in the form of an organic solvent solution. 3 A additive in which the novolak type phenolic resin is used in a ratio of 40 to 100 parts by weight to 100 parts by weight of the novolak type epoxy resin, and the curing agent thereof is used in a ratio of 5 to 30 parts by weight to the novolak type phenolic resin. A sulfur adhesive formulation is applied to the metal, subjected to a baking process, and then brought into contact with unvulcanized fluorocarbon rubber.
A method of bonding metal and fluoro rubber characterized by pressure vulcanization at the vulcanization temperature of fluoro rubber. 4. Adhesion method according to claim 3, in which the vulcanized adhesive formulation is used in the form of an organic solvent solution.