JPH0413790A - Vulcanizing adhesive compound - Google Patents
Vulcanizing adhesive compoundInfo
- Publication number
- JPH0413790A JPH0413790A JP11638190A JP11638190A JPH0413790A JP H0413790 A JPH0413790 A JP H0413790A JP 11638190 A JP11638190 A JP 11638190A JP 11638190 A JP11638190 A JP 11638190A JP H0413790 A JPH0413790 A JP H0413790A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- novolac type
- epoxy resin
- type epoxy
- novolak type
- 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.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims description 29
- 230000001070 adhesive effect Effects 0.000 title claims description 29
- 150000001875 compounds Chemical class 0.000 title abstract description 6
- 229920003986 novolac Polymers 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- -1 imidazole compound Chemical class 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005011 phenolic resin Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 21
- 238000009472 formulation Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002989 phenols Chemical class 0.000 abstract description 6
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000001879 gelation Methods 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical group CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 abstract 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229920001973 fluoroelastomer Polymers 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000010680 novolac-type phenolic resin Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 229920001967 Metal rubber Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 102220560985 Flotillin-2_E60C_mutation Human genes 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、加硫接着剤配合物に関する。更に詳しくは、
金属とフッ素ゴムとの間の接着などに有効に用いられる
加硫接着剤配合物に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to vulcanizable adhesive formulations. For more details,
This invention relates to a vulcanized adhesive compound that is effectively used for adhesion between metal and fluororubber.
従来、金属とフッ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や耐錆性に問題が
あり、特に２次加硫の温度が２００℃以上の場合には、
フッ素ゴムから発生したフッ化水素によって金属面での
剥れを発生することが多く、また腐食による錆発生とい
った問題もみられる。Traditionally, organic silane adhesives have been mainly used to bond metals and fluororubbers, but when bonding with this adhesive, there are problems with heat resistance and rust resistance after bonding. Yes, especially when the temperature of secondary vulcanization is 200℃ or higher,
Hydrogen fluoride generated from fluororubber often causes peeling on metal surfaces, and there are also problems such as rust caused by corrosion.
そこで１本出願人は先に、ノボラック型エポキシ樹脂、
ノボラック型フェノール樹脂およびノボラック型フエ、
ノール樹脂の硬化剤を含有する加硫接着剤配合物を提案
している（特開昭６２−１４１，０８２号公報）。Therefore, the applicant first developed a novolac type epoxy resin,
novolac type phenolic resin and novolac type fue,
proposed a vulcanized adhesive formulation containing a knoll resin curing agent (Japanese Unexamined Patent Publication No. 141,082/1982).
この加硫接着剤配合物では、ノボラック型フェノール樹
脂の硬化剤として、各種のアミン化合物またはリン化合
物が用いられており、これらの硬化剤化合物を含有する
加硫接着剤配合物を有機溶剤溶液の形に調製して用いた
場合には、上記の如き有機シラン系接着剤を用いたとき
にみられる問題点は克服し得るものの、有機溶剤溶液の
経時的安定性が十分ではなく、数日間でゲル化するなど
の新たな問題点がみられた。In this vulcanized adhesive formulation, various amine compounds or phosphorus compounds are used as curing agents for the novolac type phenolic resin, and the vulcanized adhesive formulation containing these curing agent compounds is mixed with an organic solvent solution. Although it is possible to overcome the problems seen when using an organic silane adhesive as described above, the stability of the organic solvent solution over time is not sufficient, and it can be used in a few days. New problems such as gelation were observed.
また、このようなゲル化傾向は、Ｐ−非置換フェノール
から導かれた低融点のノボラック型フェノール樹脂を用
いた場合にもみられることが判明した。It has also been found that such a tendency to gel is also observed when a low melting point novolak type phenol resin derived from P-unsubstituted phenol is used.
本発明の目的は、ノボラック型エポキシ樹脂およびノボ
ラック型フェノール樹脂を主成分とする加硫接着剤配合
物であって、有機溶剤溶液の形に調製した場合の経時的
安定性にすぐれたものを提供することにある。An object of the present invention is to provide a vulcanized adhesive formulation containing a novolac type epoxy resin and a novolac type phenolic resin as main components, which has excellent stability over time when prepared in the form of an organic solvent solution. It's about doing.
かかる目的を達成せしめる本発明の加硫接着剤配合物は
、ノボラック型エポキシ樹脂、ｐ−置換フェノールから
導かれたノボラック型フェノール樹脂および硬化触媒と
してのイミダゾール化合物を含有してなる。The vulcanized adhesive formulation of the present invention which achieves this object comprises a novolac type epoxy resin, a novolac type phenolic resin derived from p-substituted phenol, and an imidazole compound as a curing catalyst.
加硫接着剤配合物の一成分であるノボラック型エポキシ
樹脂は、次のような一般式で表わされるものである。The novolac type epoxy resin, which is one component of the vulcanizable adhesive formulation, is represented by the following general formula.
（以下余白） ノボラック型エポキシ樹脂は、接着剤の耐熱性。(Margin below) Novolac type epoxy resin is a heat resistant adhesive.
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、それほど非置換フェノールから導かれたノボ
ラック樹脂にエピクロルヒドリンによって代表されるエ
ピハロヒドリンを反応させ、フェ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ック型フェノール樹脂は
、次のような一般式で表わされるものである。It is a component used to further improve chemical resistance and adhesion, and is produced by reacting a novolac resin derived from unsubstituted phenol with epihalohydrin, typically epichlorohydrin, and converting the phenolic hydroxyl group into glycidyl ether. The other component, the novolac type phenol resin, is represented by the following general formula.
このように、ノボラック型フェノール樹脂は。In this way, novolac type phenolic resin.
アルキル、フェニルまたはρ−イソプロピルフェノール
基などでρ−位が置換されたフェ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、不溶不融のフェノー
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１０００程度のものが用い
られる。By reacting a phenol substituted at the ρ-position with an alkyl, phenyl or ρ-isopropylphenol group with formaldehyde under an acid catalyst, it is obtained as a pine resin-like substance that is soluble in organic solvents such as alcohols and ketones. By adding a curing agent such as an amine compound or a phosphorus compound to this and heating it, an insoluble and infusible phenol resin is formed. In the present invention, the melting point is about 100
A material having a temperature of about 150° C. and a molecular weight of about 1000 is used.
硬化触媒として用いられるイミダゾール化合物としては
１次のようなものが用いられる。The following imidazole compounds are used as curing catalysts.
２−メチルイミダゾール
２−エチル−４−メチルイミダゾール
２−ウンデシルイミダゾール
２−ヘプタデシルイミダゾール
２−フェニルイミダゾール
ｌ−ベンジルイミダゾール
１−ベンジル−２−メチルイミダゾールこれらの各成分
は、ノボラック型エポキシ樹脂１００重量部に対してノ
ボラック型フェノール樹脂が約３０〜６０重量部の割合
で、またノボラック型エポキシ樹脂１００重量部に対し
てそれの硬化触媒が約０．１〜５重量部の割合でそれぞ
れ用いられる。硬化触媒の配合割合がこれより少ないと
、樹脂の硬化が遅く、また耐熱性が劣り、接着性も低下
する。2-Methylimidazole 2-ethyl-4-methylimidazole 2-undecylimidazole 2-heptadecyl imidazole 2-phenylimidazole l-benzylimidazole 1-benzylimidazole 1-benzyl-2-methylimidazole Each of these components contains 100% by weight of novolac type epoxy resin. The novolac type phenol resin is used in an amount of about 30 to 60 parts by weight per part of the novolac type epoxy resin, and the curing catalyst thereof is used in an amount of about 0.1 to 5 parts by weight per 100 parts by weight of the novolac type epoxy resin. If the blending ratio of the curing catalyst is less than this, the curing of the resin will be slow, the heat resistance will be poor, and the adhesiveness will also be reduced.
逆に硬化触媒がこれより多い割合で用いられると。Conversely, if the curing catalyst is used in a higher proportion.
かえって有機溶剤溶液の経時的安定性が低下するように
なる。On the contrary, the stability of the organic solvent solution over time deteriorates.
以上の各成分を必須成分とする加硫接着剤配合物は、そ
のままあるいは有機溶剤溶液の形に調製して使用される
。有機溶剤としては、これらの各配合成分を溶解し得る
ものであれば任意のものを使用し得る。The vulcanized adhesive composition containing the above-mentioned components as essential components is used as it is or prepared in the form of an organic solvent solution. Any organic solvent can be used as long as it can dissolve each of these ingredients.
かかる加硫接着剤配合物は、金属とフッ素ゴムとの接着
に好適に使用されるが、その際のフッ素ゴムの加硫反応
を促進させるために、酸化マグネシウム、水酸化カルシ
ウムなどの２価金属の酸化物または水酸化物を、この接
着剤配合物中に少量添加しておくことも有効である。Such vulcanized adhesive formulations are suitably used for bonding metals and fluororubber, but in order to accelerate the vulcanization reaction of the fluororubber at that time, divalent metals such as magnesium oxide and calcium hydroxide are added. It may also be advantageous to add small amounts of oxides or hydroxides to the adhesive formulation.
この加硫接着剤配合物を金属とフッ素ゴムとの接着に用
いる場合には、この配合物溶液を金属上に塗布し、室温
で約３０〜６０分間風乾させた後、好ましくは約１００
〜２００℃で約１０〜３０分間加熱して焼付は処理を行
ない、その後金型内で未加硫のフッ素ゴムをその上に置
きあるいは注入するなどして金属と接触させ、フッ素ゴ
ムの加硫温度である約１５０〜２００℃で加圧加硫する
ことにより接着が行われる。When this vulcanized adhesive formulation is used for bonding metal and fluororubber, a solution of this formulation is applied onto the metal, air-dried for about 30 to 60 minutes at room temperature, and then preferably about 100%
Baking is performed by heating at ~200°C for about 10 to 30 minutes, and then unvulcanized fluororubber is placed on top of it in a mold or injected into contact with metal to cure the fluororubber. Adhesion is performed by pressure vulcanization at a temperature of approximately 150 to 200°C.
金属としては、軟鋼、ステンレススチール、アルミニウ
ム、アルミニウムダイキャスト、黄銅、亜鉛などが用い
られる。また、未加硫のフッ素ゴムは、それが加熱時に
加硫されるように、各種の加硫配合剤を添加した配合物
として用いられ、それの配合処方の例を示すと次の如く
である。As the metal, mild steel, stainless steel, aluminum, aluminum die-cast, brass, zinc, etc. are used. In addition, unvulcanized fluororubber is used as a compound with various vulcanizing additives added to it so that it is vulcanized when heated, and an example of the compounding recipe is as follows. .
（以下余白）
（配合例り
フッ素ゴム（デュポン社製品パイトンＥ６０Ｃ） １
００重量部Ｃａ（ＯＨ）２６
Ｍｇ０ ３訂
カーボンブラツク ３０（配合
例■）
フッ素ゴム（デュポン社製品パイトンＢ） １００
重量部ＰｂＯ１５
加硫剤（デュポン社製品ダイアックＮｏ、４）
３ＭＴカーボンブラック ２０
〔発明の効果〕
本発明に係る加硫接着剤配合物を用いて金属とフッ素ゴ
ムとの接着を行なうと、接着物は高温処理を行なった場
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安定
した効果を奏する。(Left below) (Blend example fluororubber (DuPont product Piton E60C) 1
00 parts by weight Ca (OH) 26 Mg0 3rd edition Carbon Black 30 (Blending example ■) Fluororubber (DuPont product Piton B) 100
Part by weight PbO15 Vulcanizing agent (DuPont product DIAC No. 4)
3MT carbon black 20
[Effects of the Invention] When a metal and fluororubber are bonded using the vulcanized adhesive composition of the present invention, the adhesive does not peel off from the metal surface even when subjected to high temperature treatment. Aluminum, copper,
It has a stable effect with almost no peeling even on metal surfaces such as zinc.
しかも、このような加硫接着剤配合物を有機溶剤溶液の
形に調製した上で用いた場合にも、それの経時的安定性
はすぐれており、ゲル化速度は著しく遅延化されている
。Moreover, even when such a vulcanized adhesive formulation is prepared in the form of an organic solvent solution and used, its stability over time is excellent and the gelation rate is significantly retarded.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
比較例
ノボラック型エポキシ樹脂（日本チバ・ガイギー製品Ｅ
ＣＮ １２９９）１００部（重量、以下同じ）、Ｐ−非
置換フェノールから導かれたノボラック型フェノール樹
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溶液を、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、１８
０℃で１０分間焼付は処理を行なった。Comparative example Novolac type epoxy resin (Japan Ciba Geigy product E
CN 1299) 100 parts (by weight, the same hereinafter), 100 parts of novolac type phenolic resin derived from P-unsubstituted phenol, 10 parts of hexamethylenetetramine, 1000 parts of methyl ethyl ketone and 1000 parts of methanol. was applied onto a mild steel plate treated with zinc phosphate coating, and after air-drying at room temperature for 30 minutes,
The baking process was carried out at 0°C for 10 minutes.
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ッ素ゴムを接
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。Next, on the mild steel plate on which the vulcanized adhesive composition was baked in this way, the above formulation example was applied. The unvulcanized fluororubber was brought into contact with the adhesive, pressure vulcanization was performed at 180°C for 8 minutes, and the vulcanized adhesive was heat-treated at 200°C for 22 hours.
実施例
ノボラック型エポキシ樹脂（ＥＣＮ １２９９ＨＯＯ部
、Ｐ−置換フェノールから導かれたノボラック型フェノ
ール樹脂（大日本インキ化学製品ＫＡｌ１７４ ；ビス
フェノールノボラックフェノール樹脂）４０部、２−エ
チル−４−メチルイミダゾール０．５部およびメチルエ
チルケトン２７０部からなる加硫接着剤配合物溶液を用
い、上記比較例と同様に処理した。Examples Novolac type epoxy resin (ECN 1299HOO parts, novolac type phenol resin derived from P-substituted phenol (Dainippon Ink Chemicals KAl174; bisphenol novolac phenol resin) 40 parts, 2-ethyl-4-methylimidazole 0.5 parts The same procedure as in the comparative example above was carried out using a solution of a vulcanized adhesive formulation consisting of 270 parts of methyl ethyl ketone and 270 parts of methyl ethyl ketone.
以上の比較例および実施例で得られた熱処理接着物につ
いて、 ＪＩＳ Ｋ−６３０１９０＠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
れがみられなかった面積）をそれぞれ測定すると共に、
用いられた加硫接着剤配合物溶液の粘度についても経時
的に測定した。得られた結果は、次の表に示される。Regarding the heat-treated adhesives obtained in the above comparative examples and examples, the peel force and remaining rubber area (area where no peeling was observed between the rubber and adhesive) according to JIS K-630190 @ peel test method were determined. In addition to measuring each,
The viscosity of the vulcanized adhesive formulation solution used was also measured over time. The results obtained are shown in the following table.
表 ｆ１且−− 剥離力（ｋｇｆ／ａｍ） ゴム残り面積（％） 溶液粘度 （ｃｐｓ） 初期 ６０℃、７日後 ｍ スＪ１鮮 １１．５ １２．５ ５．６ ３．５ ゲル化 ６．０table f1 and -- Peeling force (kgf/am) Rubber remaining area (%) Solution viscosity (cps) initial 60℃, 7 days later m Su J1 Sen 11.5 12.5 5.6 3.5 gelling 6.0
Claims (1)
ら導かれたノボラック型フェノール樹脂および硬化触媒
としてのイミダゾール化合物を含有してなる加硫接着剤
配合物。 ２、有機溶剤溶液の形で調製された請求項１記載の加硫
接着剤配合物。[Scope of Claims] 1. A vulcanized adhesive formulation comprising a novolac type epoxy resin, a novolac type phenol resin derived from p-substituted phenol, and an imidazole compound as a curing catalyst. 2. A vulcanized adhesive formulation according to claim 1 prepared in the form of an organic solvent solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11638190A JP2870118B2 (en) | 1990-05-02 | 1990-05-02 | Vulcanized adhesive compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11638190A JP2870118B2 (en) | 1990-05-02 | 1990-05-02 | Vulcanized adhesive compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0413790A true JPH0413790A (en) | 1992-01-17 |
| JP2870118B2 JP2870118B2 (en) | 1999-03-10 |
Family
ID=14685597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11638190A Expired - Lifetime JP2870118B2 (en) | 1990-05-02 | 1990-05-02 | Vulcanized adhesive compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2870118B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0688062A (en) * | 1992-09-04 | 1994-03-29 | Nok Corp | Vulcaniazable adhesive composition |
| JPH0718248A (en) * | 1993-06-30 | 1995-01-20 | Nok Corp | Fluororubber-coated gasket material |
| JPH1134226A (en) * | 1997-07-18 | 1999-02-09 | Nok Corp | Fluororubber-coated metal plate |
| JP2000017247A (en) * | 1998-07-03 | 2000-01-18 | Nok Corp | Adhesive composition for vulcanization |
| JP2003033983A (en) * | 2001-05-15 | 2003-02-04 | Tokai Rubber Ind Ltd | Fuel hose |
| JP2004076911A (en) * | 2002-08-22 | 2004-03-11 | Nok Corp | Rubber metal laminate gasket |
| JPWO2016163514A1 (en) * | 2015-04-10 | 2017-08-10 | 株式会社寺岡製作所 | Adhesive sheet |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4876683B2 (en) | 2006-04-13 | 2012-02-15 | Ｎｏｋ株式会社 | Acrylic rubber-metal composite |
| JP5011886B2 (en) | 2006-08-22 | 2012-08-29 | Ｎｏｋ株式会社 | Bonded piston seal |
-
1990
- 1990-05-02 JP JP11638190A patent/JP2870118B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0688062A (en) * | 1992-09-04 | 1994-03-29 | Nok Corp | Vulcaniazable adhesive composition |
| JPH0718248A (en) * | 1993-06-30 | 1995-01-20 | Nok Corp | Fluororubber-coated gasket material |
| JPH1134226A (en) * | 1997-07-18 | 1999-02-09 | Nok Corp | Fluororubber-coated metal plate |
| JP2000017247A (en) * | 1998-07-03 | 2000-01-18 | Nok Corp | Adhesive composition for vulcanization |
| JP2003033983A (en) * | 2001-05-15 | 2003-02-04 | Tokai Rubber Ind Ltd | Fuel hose |
| JP2004076911A (en) * | 2002-08-22 | 2004-03-11 | Nok Corp | Rubber metal laminate gasket |
| JPWO2016163514A1 (en) * | 2015-04-10 | 2017-08-10 | 株式会社寺岡製作所 | Adhesive sheet |
| JP2018021203A (en) * | 2015-04-10 | 2018-02-08 | 株式会社寺岡製作所 | Adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2870118B2 (en) | 1999-03-10 |
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