JPS6181473A - Vulcanizable adhesive composition and bonding method using same - Google Patents
Vulcanizable adhesive composition and bonding method using sameInfo
- Publication number
- JPS6181473A JPS6181473A JP20349784A JP20349784A JPS6181473A JP S6181473 A JPS6181473 A JP S6181473A JP 20349784 A JP20349784 A JP 20349784A JP 20349784 A JP20349784 A JP 20349784A JP S6181473 A JPS6181473 A JP S6181473A
- Authority
- JP
- Japan
- Prior art keywords
- fluororubber
- metal
- resin
- phenolic resin
- vulcanized
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 239000000853 adhesive Substances 0.000 title claims description 36
- 230000001070 adhesive effect Effects 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 7
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 13
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 13
- 238000009472 formulation Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 10
- 229920001967 Metal rubber Polymers 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000005011 phenolic resin Substances 0.000 abstract description 10
- 229920003986 novolac Polymers 0.000 abstract description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 229920001568 phenolic resin Polymers 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 5
- -1 amine compound Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 239000013040 bath agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 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
- 241000021559 Dicerandra Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000010654 Melissa officinalis Nutrition 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- OZXRLJIEKITDLN-UHFFFAOYSA-M benzyl(triethyl)phosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC1=CC=CC=C1 OZXRLJIEKITDLN-UHFFFAOYSA-M 0.000 description 1
- 239000010951 brass 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
- 229910002091 carbon monoxide Inorganic materials 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
- 238000004512 die casting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts 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
- 239000012207 thread-locking agent Substances 0.000 description 1
- WPPGURUIRLDHAB-UHFFFAOYSA-M triethyl(hexadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC WPPGURUIRLDHAB-UHFFFAOYSA-M 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
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、加硫接着剤配合物およびそれを用いる接着方
法に関する。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およびそ
れを用いる接着方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to vulcanized adhesive formulations and adhesive methods using the same. More specifically, the present invention relates to a vulcanized adhesive compound that is effectively used for adhesion between metal and fluororubber, and an adhesion method using the same.
従来、金属とフッ素ゴムとの間の接着には、主として有
機シラン糸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
１／Ｃ２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７ツ化水素によって金属面での剥れ
全発生することが多い０
〔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っても金
属−フッ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０
〔問題点を解決するための手段〕および〔作用〕従って
、本発明は加硫接着剤配合物に係り、この加硫接着剤配
合物は、ポリアミドイミド樹脂、ノボラック型フェノー
ル樹脂および該ノボラック型フェノール樹脂の硬化剤を
含有してなる。Conventionally, organic silane thread adhesives have been mainly used for adhesion between metals and fluororubber, but when this adhesive is used for adhesion, there are problems with heat resistance after adhesion. /C When the secondary vulcanization temperature is 200°C or higher, hydrogen heptadide generated from the fluororubber often causes peeling on the metal surface.0 [Problems to be solved by the invention] As a result of various studies in search of an adhesive formulation that would provide sufficient adhesive strength between metal and fluororubber even when heat treated at high temperatures, the present inventors discovered a vulcanized compound containing the following components: It has been found that an adhesive formulation satisfactorily satisfies these objectives. [Means for Solving the Problems] and [Operation] Accordingly, the present invention relates to a vulcanized adhesive formulation, and relates to a vulcanized adhesive formulation. The sulfur adhesive formulation comprises a polyamideimide resin, a novolac type phenolic resin, and a curing agent for the novolac type phenolic resin.
本発明はまた、かかる加硫接着剤配合物を用いる金属と
フッ素ゴムとの接着方法に係り、金属とフッ素ゴムとの
接着は、この加硫接着剤配合物を金属上に塗布し、必要
に応じて焼付は処理を行なった後、未加硫のフッ素ゴム
と接触させ、フッ素ゴムの加硫温度で加圧加硫すること
により行われる。The present invention also relates to a method of adhering metal and fluororubber using such a vulcanized adhesive composition, and the adhesion between metal and fluororubber is achieved by applying the vulcanized adhesive composition onto the metal and applying the vulcanized adhesive composition to the metal. Accordingly, baking is carried out by, after the treatment, contacting with unvulcanized fluororubber and vulcanizing under pressure at the vulcanization temperature of the fluororubber.
Ｄｎｎ接接着剤配合物一成分であるポリアミドイミド樹
脂は、次のような一般式で表わされるものである。The polyamideimide resin that is one component of the Dnn adhesive formulation is represented by the following general formula.
Ｒ” ＣｎＨ２ｎ （ｎは正の整数） ０ 、 Ｓ、ＣＯ Ｒ’ ： Ｃ！ｎＨ２，（ｎは正の整数）ｏ、ｓ、ｃ。R” CnH2n (n is a positive integer) 0, S, CO R’: C! nH2, (n is a positive integer) o, s, c.
このように、ポリアミドイミド硲脂は、ポリイミド樹脂
の主鎖中にアミド結合を導入し、この結合の導入により
ポリイミド樹脂にたわみ性を付与し、加工性を向上させ
たものであり、例えば次のようにして合成される。In this way, polyamide-imide balm has an amide bond introduced into the main chain of a polyimide resin, and the introduction of this bond gives the polyimide resin flexibility and improves processability. It is synthesized in this way.
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Ｏ
Ｒ５、Ｒ４：水素原子またはアルキル基このように、ノ
ボラック現フェノール樹脂は、フェノールあるいはアル
キル置換、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
機浴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、
分子量が約数万程度のものが用いられる。In addition, the novolak type phenolic resin, which is another component, is represented by the following general formula. By reacting phenol and formaldehyde in the presence of an acid catalyst, it is obtained as a resin-like substance that is soluble in organic bath agents such as alcohol and ketones, and a hardening agent such as an amine compound or phosphorus compound is added to this and heated. This forms an insoluble and infusible phenolic resin. In the present invention, the melting point is about 100 to 150°C,
Those with a molecular weight of about several tens of thousands are used.
ノボラック型フェ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。Amine compounds or phosphorus compounds are generally used as curing agents for novolac type phenolic resins.
アミン化合物としては、次の一般式で表わされＨ２Ｍ＋
０ｎＨ２ニーＮＨｆｃｊｎＨ２ニーＮＨ２ａ：Ｑまたは
２５程度迄の正の整数
ｎ：正の整数
Ｈ２Ｎ−Ｒ，−ＮＨ。The amine compound is represented by the following general formula and H2M+
0nH2 NHfcjnH2 NH2a: Q or a positive integer up to about 25 n: Positive integer H2N-R, -NH.
また、リン化合物としては、次の一般式で表わされるよ
うなものが用いられる。Further, as the phosphorus compound, one represented by the following general formula is used.
Ｒ，＋Ｐ −０ヤｑ４
ｂ：２以上の整数
Ｒ４：ヒドロキシル基またはア
ルキル基
これらの各成分は、ポリアミドイミド樹脂１００重量部
に対してノボラック型フェノール樹脂が約５〜５０重量
部の割合で、またノボラック型フェノール樹脂１００重
量部に対してそれの硬化剤が約５〜３０重重部の割合で
それぞれ用いられる。R, +P −0 yq4 b: an integer of 2 or more R4: hydroxyl group or alkyl group These components include a novolak type phenol resin in a proportion of about 5 to 50 parts by weight per 100 parts by weight of the polyamide-imide resin; The curing agent is used in an amount of about 5 to 30 parts by weight per 100 parts by weight of the novolac type phenolic resin.
ノボラック型フェノール樹脂の配合割合がこれより少な
いと、フッ素ゴムなどとの結合力が弱く、反応性が低下
する。これは、ポリアミドイミド樹脂の硬化速度が遅い
ため、ゴムとの結合が開始される前に、接着剤層が流さ
れるためと考えられる。If the blending ratio of the novolac type phenol resin is less than this, the bonding force with fluororubber etc. will be weak and the reactivity will be reduced. This is thought to be due to the slow curing speed of the polyamide-imide resin, which causes the adhesive layer to be washed away before bonding with the rubber begins.
逆に、ノボラック型フェノール樹脂がこれより多い割合
で用いられると、相対的にポリアミドイミド樹脂の割合
が少なくなり、耐熱性が低下するようＫなる。On the other hand, if the novolac type phenol resin is used in a larger proportion than this, the proportion of the polyamide-imide resin will be relatively small, and the K will decrease so that the heat resistance will decrease.
以上の各成分を必須成分とする加硫接着剤配合物は、一
般に有機溶剤溶液の形に調製して使用される。有機浴剤
としては、これらの各配合成分を浴解し得るものであれ
ば任意のものを使用し得るが、特にジメチルホルムアミ
ドが好んで用いられる。A vulcanized adhesive composition containing the above-mentioned components as essential components is generally prepared and used in the form of an organic solvent solution. As the organic bath agent, any organic bath agent can be used as long as it can bath-dissolve each of these components, but dimethylformamide is particularly preferably used.
かかる加硫接着剤配合物は、金属とフッ素ゴムとの接層
に好適に使用されるが、その際の７ツ素ゴムの加硫反応
全促進させるために、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、あるいは
ベンジルトリエチルアンモニウムプロミド、ヘキサデシ
ルトリエチルアンモニウムクロリド、ベンジルトリエチ
ルホスホニウムクロリドなどのオニウム塩を、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 a vulcanized adhesive compound is suitably used for bonding metal and fluororubber, but in order to accelerate the entire vulcanization reaction of the heptad rubber at that time, magnesium oxide, calcium hydroxide, etc. are added. Small amounts of divalent metal oxides or hydroxides or onium salts such as benzyltriethylammonium bromide, hexadecyltriethylammonium chloride, benzyltriethylphosphonium chloride may also be added to the adhesive formulation. be.
この加硫接着剤配合物を金属とフッ素ゴムとの接層に用
いる場合には、この配合物の溶液を金属上に塗布し、一
旦約１２０〜１５０℃で乾燥させた後、好ましくは約２
３０〜２５０℃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
素ゴムの加硫濃度である約１５０〜２００℃で加圧加硫
することにより接着が行われる。When this vulcanizable adhesive formulation is used to bond metal and fluororubber, a solution of this formulation is applied onto the metal and once dried at about 120 to 150°C, preferably about 2
Baking is carried out by heating at 30 to 250°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 sulfur concentration of approximately 150 to 200°C.
金ｌｌ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２．３の配合処方を示すと次
の如くである。As the gold, mild steel, stainless steel, aluminum, aluminum die-casting, brass, zinc, etc. are used. In addition, unvulcanized fluororubber is used as a compound with various vulcanizing additives added so that it is vulcanized when heated, and the compounding recipe in 2.3 is as follows. It is.
（配合例Ｉ）
フッ素ゴム（デュポン社製品パイトン”６００）
１００重量部０ａ（ＯＨ）、
６Ｍｇ０
３ＭＴカーボンブラック
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Ａ４）３ＭＴカーボ
ンブラック ２０（配合例■）
フッ素ゴム（ダイキン工業製品ダイエルＧ９０２）
１００ 重量部加硫剤（日本油脂製品パーへキサ２
５Ｂ−４０）２トリアリルイソシアネート
４ＭＴ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、
亜鉛などの金槁面でも殆んど剥れを生じないという効果
を奏する。(Blend Example I) Fluororubber (DuPont product Paiton"600)
100 parts by weight 0a (OH),
6Mg0
3MT carbon black 30 (formulation example ■) Fluororubber (DuPont product Paiton B)
100 parts by weight PbO15 Vulcanizing agent (DuPont product DIAC A4) 3MT carbon black 20 (Composition example ■) Fluororubber (Daikin Industries product Daiel G902)
100 parts by weight Vulcanizing agent (NOF Perhexa 2
5B-40) 2triallyl isocyanate
4MT carbon black
20 [Effects of the Invention] When the vulcanized adhesive composition of the present invention is used to bond metal and fluororubber, the adhesive will peel off from the metal surface even when subjected to high temperature treatment. Aluminum, copper,
It has the effect that almost no peeling occurs even on metal surfaces such as zinc.
このような効果は、フッ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
フッ素ガスから発生するフッ化水素による金属の腐食を
も有効に防止する。This effect is exhibited regardless of the type of vulcanizing agent used for fluororubber, such as amine-based, polyol-based, or peroxide-based vulcanizing agents. It also provides high heat resistance and effectively prevents corrosion of metals due to hydrogen fluoride generated from fluorine gas during heating.
本発明に係る接着剤配合物を用いての金属とフッ素ゴム
との加硫！Ｉ’ｍは、オイルシール、パルプステムシー
ル、リードパルプ、パルプ部品などの製造に好適に適用
されるが、金属とフッ素ゴムとの接着以外にも、金属と
ニトリルゴム、フッ素ゴムシート同士あるいはポリアミ
ド樹脂成形品とフッ素ゴムとの接着などにも使用するこ
とができる。Vulcanization of metal and fluororubber using the adhesive formulation according to the invention! I'm is suitably applied to the production of oil seals, pulp stem seals, lead pulp, pulp parts, etc., but it can also be used to bond metals and nitrile rubber, fluororubber sheets to each other, or polyamide. It can also be used to bond resin molded products and fluororubber.
次に１実施例について本発明を説明する。 Next, the present invention will be described with reference to one embodiment.
実施例１
ポリアミドイミド樹脂（玉押石油化学製品ケルイミド５
００） １００部（重量、以下同じ）、ノボラツク型
フェノール樹脂（群栄化学工業製品）２０部、ヘキサメ
チレンジアミン５部およびジメチルホルムアミド１５０
部からなる加硫接着剤配合物を、リン酸亜鉛被膜処理を
施した軟綱板に塗布し、１２０℃で１０分間乾燥後、２
３０℃で１０分間焼付は処理を行なった。Example 1 Polyamide-imide resin (tamashi petrochemical product Kelimide 5
00) 100 parts (weight, same below), 20 parts of novolac type phenol resin (Gun-ei Chemical Industry Products), 5 parts of hexamethylene diamine, and 150 parts of dimethylformamide
A vulcanized adhesive formulation consisting of 100% of
Baking treatment was carried out at 30° 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Ｉよりなる未加硫のフッ素ゴムを接
触させ、１８０℃で８分間の加圧加硫を行ない、加硫さ
れた接着物を２００℃で２２時間熱処理した。Next, the unvulcanized fluororubber made from Formulation Example I was brought into contact with the mild steel plate on which the vulcanized adhesive composition had been baked in this way, and pressure vulcanization was performed at 180°C for 8 minutes. The vulcanized adhesive was heat treated at 200°C for 22 hours.
実施例２
実施例１において、次の各成分からなる加硫接着剤配合
物が用いられた。Example 2 In Example 1, a vulcanized adhesive formulation was used consisting of the following components:
ポリアミドイミド樹脂（ケルイミド５００）
１００部ノボラック型フェノール樹脂（ＰＳＩＦ ２８
０３） ４０トリエチレンテトラミン
４ジメチルホルムアミド
１４０実施例３
実施例１において、次の各成分からなる加硫接着剤配合
物が用いられた。Polyamideimide resin (Kelimide 500)
100 parts novolac type phenolic resin (PSIF 28
03) 40 triethylenetetramine
4 dimethylformamide
140 Example 3 In Example 1, a vulcanized adhesive formulation consisting of the following components was used.
ポリアミドイミド樹脂（ケルイミド５００）
１００ 部ノボラック型フェノール樹脂（オタラ
イト工業製品）３０ビロリン酸
８ジメチルホルムアミド
１５０実施例４
ポリアミ ドイミ ド樹脂（ケルイミ ド５００）
１００部、／ボラック型フェノール樹脂（オタライト工
業製品）３０８、ｐ−フェニレンジアミン８部およびジ
メチルホルムアミド１４０部からなる加硫液↓
着剤配合を、実施例１の軟鋼板に塗布し、１２０℃で１
０分間乾燥後、２３０℃で１５分間焼付は処理を行なっ
た。Polyamideimide resin (Kelimide 500)
100 parts novolac type phenolic resin (Otalite Industrial Product) 30 birophosphoric acid
8 dimethylformamide
150 Example 4 Polyamide Doimide Resin (Kelimide 500)
100 parts of a vulcanizing solution consisting of 308 parts of Borac-type phenolic resin (Otalite Industrial Products), 8 parts of p-phenylenediamine, and 140 parts of dimethylformamide↓ The adhesive formulation was applied to the mild steel plate of Example 1 and heated at 120°C. 1
After drying for 0 minutes, baking was performed at 230° C. for 15 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分間の加圧加硫を行ない、加硫さ
れた接着物を２００℃で２４時間熱処理した。Next, on the mild steel plate on which the vulcanized adhesive composition was baked in this way, an unvulcanized fluororubber consisting of the above formulation example was brought into contact, and pressure vulcanization was performed at 180 ° C. for 8 minutes. The vulcanized adhesive was heat treated at 200° C. for 24 hours.
比較例 妻。Comparative example wife.
実施例１において、リン酸亜鉛被膜処理軟鋼と未加硫の
フッ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詩間の熱処理を行なった。In Example 1, adhesion between zinc phosphate coated mild steel and unvulcanized fluororubber was carried out using an organic silane adhesive, and the pressure vulcanization was performed at 180°C for 8 minutes and the pressure vulcanized product was vulcanized for 22 hours at 200°C. Heat treatment was performed.
以上の各実施例および比較例で得られた熱処理ｔｉＩｓ
物につい１、ＴＸＳ 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）をそれぞれ測定した。得
られた結果は、次の表に示される。Heat treated tiIs obtained in each of the above Examples and Comparative Examples
For each product, the peel force and remaining rubber area (area where no peeling was observed between the rubber and adhesive) were measured using the TXS K-630190' peel test method. The results obtained are shown in the following table.
表table
Claims (1)
脂および該ノボラック型フェノール樹脂の硬化剤を含有
してなる加硫接着剤配合物。 ２、有機浴剤溶液の形で調製された特許請求の範囲第１
項記載の加硫接着剤配合物。 ３、ポリアミドイミド樹脂、ノボラック型フェノール樹
脂および該ノボラック型フェ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
焼付け処理を行なった後、未加硫のフッ素ゴムと接触さ
せ、フッ素ゴムの加硫温度で加圧加硫することを特徴と
する金属とフッ素ゴムとの接着方法。 ４、加硫接着剤配合物が有機浴剤浴液の形で用いられる
特許請求の範囲第３項記載の接着方法。[Scope of Claims] 1. A vulcanized adhesive formulation containing a polyamideimide resin, a novolac type phenolic resin, and a curing agent for the novolac type phenolic resin. 2. Claim 1 prepared in the form of an organic bath solution
Vulcanized adhesive formulations as described in Section. 3. After applying a vulcanized adhesive formulation containing a polyamide-imide resin, a novolac type phenolic resin, and a curing agent for the novolac type phenolic resin onto the metal, and performing a baking process if necessary, unvulcanized A method for adhering metal and fluororubber, characterized by contacting the metal with fluororubber and vulcanizing under pressure at the vulcanization temperature of the fluororubber. 4. Adhesion method according to claim 3, wherein the vulcanized adhesive formulation is used in the form of an organic bath solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20349784A JPS6181473A (en) | 1984-09-28 | 1984-09-28 | Vulcanizable adhesive composition and bonding method using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20349784A JPS6181473A (en) | 1984-09-28 | 1984-09-28 | Vulcanizable adhesive composition and bonding method using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6181473A true JPS6181473A (en) | 1986-04-25 |
Family
ID=16475133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20349784A Pending JPS6181473A (en) | 1984-09-28 | 1984-09-28 | Vulcanizable adhesive composition and bonding method using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6181473A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6284154A (en) * | 1985-10-07 | 1987-04-17 | Youbea Le-Ron Kogyo Kk | Polyamide imide resin composition |
| US7901141B2 (en) * | 2005-02-14 | 2011-03-08 | Nsk Ltd. | Hub unit bearing |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58187478A (en) * | 1982-04-26 | 1983-11-01 | Nok Corp | Vulcanizable adhesive composition and bonding method using the same |
-
1984
- 1984-09-28 JP JP20349784A patent/JPS6181473A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58187478A (en) * | 1982-04-26 | 1983-11-01 | Nok Corp | Vulcanizable adhesive composition and bonding method using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6284154A (en) * | 1985-10-07 | 1987-04-17 | Youbea Le-Ron Kogyo Kk | Polyamide imide resin composition |
| US7901141B2 (en) * | 2005-02-14 | 2011-03-08 | Nsk Ltd. | Hub unit bearing |
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