WO2018216380A1 - Vulcanizing adhesive composition - Google Patents
Vulcanizing adhesive composition Download PDFInfo
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- WO2018216380A1 WO2018216380A1 PCT/JP2018/015063 JP2018015063W WO2018216380A1 WO 2018216380 A1 WO2018216380 A1 WO 2018216380A1 JP 2018015063 W JP2018015063 W JP 2018015063W WO 2018216380 A1 WO2018216380 A1 WO 2018216380A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
Definitions
- the present invention relates to a vulcanized adhesive composition. More specifically, the present invention relates to a vulcanized adhesive composition that is effectively used for vulcanization adhesion between a metal and NBR.
- vulcanized adhesive compositions for NBR have existed in the past, but those consisting of phenolic resin and hexamethylenetetramine have been widely used for a long time because they are easy to prepare and inexpensive. I came.
- this vulcanized adhesive composition has a drawback in that it generates hexamethylenetetramine gas at the time of heat-drying and contaminates the inside or the vicinity of the drying furnace.
- coated other adhesive agents is dried in the same drying furnace, the hexamethylenetetramine which remains in a furnace may adhere and cause an adhesion
- the present applicant has added a novolac type phenol resin obtained from an m-cresol-p-cresol mixture as an adhesive component and an unmodified resol type phenol resin as a curing agent, and hexamethylenetetramine is a curing agent.
- a vulcanized adhesive between metal and acrylic rubber, which has a baking temperature range of about 100 to 200 ° C. Patent Document 1. This vulcanized adhesive may have a problem that it tends to cause poor adhesion due to insufficient curing.
- An object of the present invention is a vulcanized adhesive composition mainly composed of a phenolic resin and used for vulcanization adhesion between a metal and NBR, which not only prevents contamination of a mold and an adhesive, but also stably.
- the object is to provide an adhesive.
- An object of the present invention is to provide a vulcanized adhesive composition prepared as an organic solvent solution by adding 1 to 5 parts by weight of a silane coupling agent and 15 to 30 parts by weight of unvulcanized NBR per 100 parts by weight of a high-ortho type novolak phenol resin. Achieved by things.
- the vulcanized adhesive according to the present invention is used for vulcanization adhesion of various metals such as stainless steel plate, mild steel plate, galvanized copper plate, SPCC steel plate, copper plate, magnesium plate, aluminum plate, aluminum die cast plate and NBR.
- the adhesive coating becomes tack-free and reduces the incidence without causing defects such as mold contamination during rubber vulcanization and product contamination. It is possible to obtain a vulcanized adhesion state with a good rubber remaining area ratio.
- hexamethylenetetramine curing accelerator is blended as a phenolic resin curing agent, there is no contamination in the baking furnace and its surroundings. This is because a high-ortho type novolak phenol resin having high reactivity was used.
- the ortho type content calculated from the area of the ortho type derived absorption peak and the para type derived absorption peak by IR is 65% or more, preferably 70% or more, More preferably, 70 to 80% novolak phenol resin is used.
- Normal novolak phenol resin is called random type novolak phenol resin compared to high ortho type novolak phenol resin, but random type novolak phenol resin is inferior in curability compared with high ortho type novolak phenol resin and is high during processing. It often takes temperature and long time.
- the high-ortho type novolak phenol resin has high reactivity and can be suitably used as the main agent of the vulcanized adhesive of the present invention.
- High ortho type novolak phenol resin is one or more of m-cresol, p-cresol, 3,5-xylenol and 2,3,5-trimethylphenol, such as m-cresol, p-cresol and 3,5- It can be obtained by reacting these with aldehydes using three of xylenol or three of m-cresol, p-cresol and 2,3,5-trimethylphenol.
- aldehydes for example, formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, benzaldehyde, salicylaldehyde and the like are used, and preferably formaldehyde, acetaldehyde and salicylaldehyde are used.
- formaldehyde any of formaldehyde-generating substances such as aqueous formalin solution, paraformaldehyde, hemi-formal with alcohols, and trioxane can be used.
- the reaction between phenols and aldehydes is carried out using an acid catalyst at a reaction temperature of about 110 to 220 ° C., preferably about 120 to 150 ° C. By reacting at such a high reaction temperature, the reaction in the vicinity of the phenolic hydroxyl group occurs preferentially, and the ortho-ratio is increased.
- the acid catalyst weak acids such as oxalic acid and acetic acid are generally used, but divalent metal salts, oxides or hydroxides of divalent metals are also used, and these divalent metal compounds are acidic compounds such as the above weak acids. It can also be used in combination. Specifically, for example, zinc acetate, zinc hydroxide and the like are used.
- Patent Document 2 a reaction in which a trifunctional phenol monomer is used and a reaction is performed under a high pressure condition without using a catalyst has been proposed.
- a high-ortho type novolak phenol resin a commercially available product, for example, Showa Denko product Shonor BRM-7174H or the like is used as it is.
- a random type novolac phenolic resin or a resol type phenolic resin can be used in combination with up to about 25 parts by weight or less per 100 parts by weight thereof.
- silane coupling agent examples include those containing (meth) acryloxy group, mercapto group, vinyl group, epoxy group, amino group, chloropropyl group, etc., preferably methacryloxypropylmethyldimethoxysilane, methacryloxypropyltri Examples include methoxysilane, methacryloxypropylmethyldiethoxy group-containing silane, methacryloxysilane such as methacryloxypropyltriethoxysilane, and mercapto group-containing silane such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.
- silane coupling agents are used at a ratio of about 0.5 to 5 parts by weight, preferably about 1 to 3 parts by weight, per 100 parts by weight of the high-ortho type novolak phenol resin. If the ratio is less than this, the generation of fine blisters cannot be suppressed. On the other hand, if the ratio is larger than this, the water-resistant adhesiveness deteriorates.
- unvulcanized NBR those having an acrylonitrile (AN) content of about 20 to 40% by weight, preferably about 25 to 35% by weight are used. In general, those having the same or higher AN content as the NBR to be bonded are used.
- This unvulcanized NBR does not contain a vulcanizing component such as a vulcanizing agent.
- Unvulcanized NBR is used at a ratio of about 15 to 30 parts by weight, preferably about 20 to 28 parts by weight, per 100 parts by weight of the high-ortho type novolak phenol resin. If the amount used is less than this, the initial adhesiveness is lowered, and it becomes difficult to adhere to the NBR kneaded material having low reactivity. On the other hand, if it is used in a proportion higher than this, as shown in the results of Comparative Example 5 described later. Although the results of the peel test are satisfactory, the mold and molded product are contaminated, and the intended purpose of the present invention cannot be achieved.
- the vulcanized adhesive of the present invention having the above components as essential components is prepared as an organic solvent solution.
- organic solvent ketones such as acetone, methyl ethyl ketone (2-butanone) and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene are used alone or in combination.
- ketones and aromatic hydrocarbons are used as a mixture, the aromatic hydrocarbons are preferably used in a ratio of about 30 to 70 parts by weight per 100 parts by weight of the ketones.
- the vulcanized adhesive is prepared as a uniform solution by stirring and dissolving so that the solid content concentration in the organic solvent is about 3 to 10% by weight.
- the adhesive is first applied on a metal, dried at room temperature, and then heated and cured at about 100 to 160 ° C. Next, the unvulcanized NBR kneaded material is joined and pressure vulcanized at about 170 to 210 ° C. for about 3 to 8 minutes to bond the metal and the NBR.
- the adhesive molded product in which the metal and NBR are satisfactorily bonded include automotive parts such as oil seals and hub seals.
- Example 1 High ortho type novolac phenolic resin (Showa Denko products 100 parts by weight Shonor BRM-7174H; ortho type content 70-80%) Methacryloxypropyltrimethoxysilane 1 ⁇ NBR (JSR product N232S; AN content 35% by weight) 28 ⁇ Random type novolac phenolic resin 50 ⁇ (Load and ink product Chemlock TS1677-13; (Solid concentration 40% by weight) 2-butanone 4500 ⁇ The vulcanized adhesive prepared from each of the above components was applied onto a mild steel sheet treated with zinc phosphate, allowed to stand at room temperature for 5 minutes, and then dried at 140 ° C. for 10 minutes.
- an unvulcanized NBR kneaded material having the following composition was joined and pressure vulcanized at 180 ° C. for 4 minutes to obtain an adhesive molded product test piece.
- Unvulcanized NBR kneaded material NBR (Nippon ZEON product Nipol DN1042; AN content 34 wt%) 100 parts by weight
- FEF carbon black 40 ⁇
- Silica powder 20 ⁇ Zinc oxide 5 ⁇ Stearic acid 1 ⁇ Dioctyl phthalate 5 ⁇ Anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline) 1 ⁇
- Example 2 In Example 1, a vulcanized adhesive composition prepared from the following components was used. High ortho type novolac phenol resin (BRM-7174H) 100 parts by weight Mercaptopropyltrimethoxysilane 3 ⁇ Random type novolac phenolic resin 50 ⁇ (Chemlock TS1677-13) NBR (N232S) 28 ⁇ 2-butanone 4500 ⁇
- Example 1 a vulcanized adhesive prepared from the following components was used.
- High ortho type novolac phenol resin 100 parts by weight (Shonol BRM-7174H)
- Bisphenol A type epoxy resin (Mitsubishi Chemical JSR1004) 3 ⁇ NBR (JSR product N237; AN content 34% by weight) 21 ⁇ 2-butanone 2980 ⁇
- Example 2 a vulcanized adhesive prepared from the following components was used.
- High ortho type novolac phenolic resin BRM-7174H
- Bisphenol A type epoxy resin JSR1004
- JSR1004 3 ⁇ Random type novolac phenolic resin 52 ⁇ (Chemlock TS1677-13)
- NBR N232S
- 2-butanone 3540 ⁇
- Comparative Example 4 In Comparative Example 1, a vulcanized adhesive in which the amount of bisphenol A type epoxy resin was changed to 15 parts by weight and the amount of 2-butanone was changed to 3260 parts by weight was used.
- Comparative Example 5 In Comparative Example 2, a vulcanized adhesive in which the NBR amount was changed to 37 parts by weight and the 2-butanone amount was changed to 3820 parts by weight was used.
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Abstract
Provided is a vulcanizing adhesive composition prepared as an organic solvent solution by adding 1 to 5 parts by weight of a silane coupling agent and 15 to 30 parts by weight of unvulcanized NBR per 100 parts by weight of a high-ortho novolac phenolic resin having an ortho content rate calculated from a result of measurement by IR of 65% or more. This vulcanizing adhesive composition, which is used for vulcanized adhesion between metal and NBR, is not only capable of preventing contamination of molds and bonded articles but has stable adhesive properties and can be used effectively as an adhesive for vehicle components such as an oil seal or a hub seal.
Description
本発明は、加硫接着剤組成物に関する。さらに詳しくは、金属とNBRとの加硫接着に有効に用いられる加硫接着剤組成物に関する。
The present invention relates to a vulcanized adhesive composition. More specifically, the present invention relates to a vulcanized adhesive composition that is effectively used for vulcanization adhesion between a metal and NBR.
従来より種々のNBR用の加硫接着剤組成物が存在するが、これらの内フェノール樹脂とヘキサメチレンテトラミンとからなるものは、調合が容易でかつ廉価であることから、古くから広範囲に用いられてきた。しかしながら、この加硫接着剤組成物は、加熱乾燥時にヘキサメチレンテトラミンのガスを発生させ、乾燥炉内やその周辺を汚染してしまうという欠点がみられた。ここで、他の接着剤を塗布した金具を同じ乾燥炉内で乾燥させると、炉内に残存するヘキサメチレンテトラミンが付着して接着不具合をひき起こす場合がある。
Various types of vulcanized adhesive compositions for NBR have existed in the past, but those consisting of phenolic resin and hexamethylenetetramine have been widely used for a long time because they are easy to prepare and inexpensive. I came. However, this vulcanized adhesive composition has a drawback in that it generates hexamethylenetetramine gas at the time of heat-drying and contaminates the inside or the vicinity of the drying furnace. Here, when the metal fitting which apply | coated other adhesive agents is dried in the same drying furnace, the hexamethylenetetramine which remains in a furnace may adhere and cause an adhesion | attachment malfunction.
本出願人は、m-クレゾール-p-クレゾール混合物から得られたノボラック型フェノール樹脂を接着剤成分とし、これに未変性レゾール型フェノール樹脂を硬化剤として添加してなり、ヘキサメチレンテトラミンが硬化剤として使用されておらず、金属への焼付温度範囲が約100～200℃である、金属とアクリルゴムとの加硫接着剤を提案している(特許文献１)。この加硫接着剤は、硬化が不十分なことによる接着不良を起こし易いといった問題がみられる場合がある。
The present applicant has added a novolac type phenol resin obtained from an m-cresol-p-cresol mixture as an adhesive component and an unmodified resol type phenol resin as a curing agent, and hexamethylenetetramine is a curing agent. And a vulcanized adhesive between metal and acrylic rubber, which has a baking temperature range of about 100 to 200 ° C. (Patent Document 1). This vulcanized adhesive may have a problem that it tends to cause poor adhesion due to insufficient curing.
本発明の目的は、フェノール系樹脂を主体とし、金属とNBRとの加硫接着に用いられる加硫接着剤組成物であって、金型や接着物の汚染を防止できるばかりではなく、安定した接着性を示すものを提供することにある。
An object of the present invention is a vulcanized adhesive composition mainly composed of a phenolic resin and used for vulcanization adhesion between a metal and NBR, which not only prevents contamination of a mold and an adhesive, but also stably. The object is to provide an adhesive.
かかる本発明の目的は、ハイオルソ型ノボラックフェノール樹脂100重量部当りシランカップリング剤1～5重量部および未加硫のNBR15～30重量部を添加し、有機溶媒溶液として調製した加硫接着剤組成物によって達成される。
An object of the present invention is to provide a vulcanized adhesive composition prepared as an organic solvent solution by adding 1 to 5 parts by weight of a silane coupling agent and 15 to 30 parts by weight of unvulcanized NBR per 100 parts by weight of a high-ortho type novolak phenol resin. Achieved by things.
本発明に係る加硫接着剤は、これをステンレス鋼板、軟鋼板、亜鉛メッキ銅板、SPCC鋼板、銅板、マグネシウム板、アルミニウム板、アルミニウムダイキャスト板等の各種金属とNBRとの加硫接着に用いたとき、接着剤塗膜がタックフリーとなり、ゴム加硫成形時の金型汚染および製品汚染の原因となる微小ブリスターの発生といった不具合を生ぜずにその発生率を低下させ、90°剥離試験でのゴム残り面積率の良好な加硫接着状態を得ることを可能としている。
The vulcanized adhesive according to the present invention is used for vulcanization adhesion of various metals such as stainless steel plate, mild steel plate, galvanized copper plate, SPCC steel plate, copper plate, magnesium plate, aluminum plate, aluminum die cast plate and NBR. The adhesive coating becomes tack-free and reduces the incidence without causing defects such as mold contamination during rubber vulcanization and product contamination. It is possible to obtain a vulcanized adhesion state with a good rubber remaining area ratio.
本発明の加硫接着剤では、フェノール樹脂の硬化剤としてヘキサメチレンテトラミン硬化促進剤を配合していないので、それによる焼付炉やその周辺での汚染がみられない。このことは、高い反応性を有するハイオルソ型ノボラックフェノール樹脂を用いたことによる。
In the vulcanized adhesive of the present invention, since no hexamethylenetetramine curing accelerator is blended as a phenolic resin curing agent, there is no contamination in the baking furnace and its surroundings. This is because a high-ortho type novolak phenol resin having high reactivity was used.
また、従来の加硫接着剤は、NBR混練物との良好な接着性を得るために、高い配合比率でNBRを配合する必要があり、これによる金型や製品の汚染もみられたが(後記比較例５)、高い反応性を有するハイオルソ型ノボラックフェノール樹脂の使用によりNBRの配合比率を低下させることができる。
In addition, conventional vulcanized adhesives require NBR to be blended at a high blending ratio in order to obtain good adhesion to the NBR kneaded product, and this has caused mold and product contamination (see below). Comparative Example 5) By using a high-ortho type novolak phenol resin having high reactivity, the blending ratio of NBR can be reduced.
本発明においてハイオルソ型ノボラックフェノール樹脂としては、IR(赤外線吸収スペクトル)によるオルソ型由来吸収ピークおよびパラ型由来吸収ピークの面積から算出されるオルソ型含有率が65％以上、好ましくは70％以上、さらに好ましくは70～80％のノボラックフェノール樹脂が用いられる。
As the high ortho type novolak phenol resin in the present invention, the ortho type content calculated from the area of the ortho type derived absorption peak and the para type derived absorption peak by IR (infrared absorption spectrum) is 65% or more, preferably 70% or more, More preferably, 70 to 80% novolak phenol resin is used.
ハイオルソ型ノボラックフェノール樹脂に対して、通常のノボラックフェノール樹脂はランダム型ノボラックフェノール樹脂と呼称されているが、ランダム型ノボラックフェノール樹脂はハイオルソ型ノボラックフェノール樹脂と比較して硬化性に劣り、加工時に高い温度や長い時間を要する場合が多い。一方、ハイオルソ型ノボラックフェノール樹脂は高い反応性を有し、本発明の加硫接着剤の主剤として好適に用いることができる。
Normal novolak phenol resin is called random type novolak phenol resin compared to high ortho type novolak phenol resin, but random type novolak phenol resin is inferior in curability compared with high ortho type novolak phenol resin and is high during processing. It often takes temperature and long time. On the other hand, the high-ortho type novolak phenol resin has high reactivity and can be suitably used as the main agent of the vulcanized adhesive of the present invention.
ハイオルソ型ノボラックフェノール樹脂は、m-クレゾール、p-クレゾール、3,5-キシレノールおよび2,3,5-トリメチルフェノールの１種または２種以上、例えばm-クレゾール、p-クレゾールおよび3,5-キシレノールの３者またはm-クレゾール、p-クレゾールおよび2,3,5-トリメチルフェノールの３者を用い、これらをアルデヒド類と反応させることにより得られる。
High ortho type novolak phenol resin is one or more of m-cresol, p-cresol, 3,5-xylenol and 2,3,5-trimethylphenol, such as m-cresol, p-cresol and 3,5- It can be obtained by reacting these with aldehydes using three of xylenol or three of m-cresol, p-cresol and 2,3,5-trimethylphenol.
アルデヒド類としては、例えばホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、ベンズアルデヒド、サリチルアルデヒド等が用いられ、好ましくはホルムアルデヒド、アセトアルデヒド、サリチルアルデヒドが用いられる。ホルムアルデヒドとしては、ホルマリン水溶液、パラホルムアルデヒド、アルコール類とのヘミホルマール、トリオキサン等のホルムアルデヒド発生物質のいずれをも使用することができる。
As the aldehydes, for example, formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, benzaldehyde, salicylaldehyde and the like are used, and preferably formaldehyde, acetaldehyde and salicylaldehyde are used. As the formaldehyde, any of formaldehyde-generating substances such as aqueous formalin solution, paraformaldehyde, hemi-formal with alcohols, and trioxane can be used.
フェノール類とアルデヒド類との反応は、約110～220℃、好ましくは約120～150℃の反応温度で、酸触媒を用いて行われる。このような高温の反応温度で反応させることにより、フェノール性水酸基近傍での反応が優先的に起こり、オルト化率が高くなる。酸触媒としては、一般にシュウ酸、酢酸等の弱酸が用いられるが、2価金属塩、2価金属の酸化物または水酸化物も用いられ、これらの2価金属化合物は上記弱酸の如き酸性化合物と組合せて用いることもできる。具体的には、例えば酢酸亜鉛、水酸化亜鉛等が用いられる。また、3官能性フェノール系モノマーを用い、触媒を用いずに、高圧条件下で反応させる反応も提案されている(特許文献２)。
The reaction between phenols and aldehydes is carried out using an acid catalyst at a reaction temperature of about 110 to 220 ° C., preferably about 120 to 150 ° C. By reacting at such a high reaction temperature, the reaction in the vicinity of the phenolic hydroxyl group occurs preferentially, and the ortho-ratio is increased. As the acid catalyst, weak acids such as oxalic acid and acetic acid are generally used, but divalent metal salts, oxides or hydroxides of divalent metals are also used, and these divalent metal compounds are acidic compounds such as the above weak acids. It can also be used in combination. Specifically, for example, zinc acetate, zinc hydroxide and the like are used. In addition, a reaction in which a trifunctional phenol monomer is used and a reaction is performed under a high pressure condition without using a catalyst has been proposed (Patent Document 2).
かかるハイオルソ型ノボラックフェノール樹脂としては、実際には市販品、例えば昭和電工製品ショウノールBRM-7174H等がそのまま用いられる。また、ハイオルソ型ノボラックフェノール樹脂と共に、それの100重量部当り約25重量部以下までであればランダム型ノボラックフェノール樹脂やレゾール型フェノール樹脂を併用することもできる。
As such a high-ortho type novolak phenol resin, a commercially available product, for example, Showa Denko product Shonor BRM-7174H or the like is used as it is. In addition to the high-ortho type novolac phenolic resin, a random type novolac phenolic resin or a resol type phenolic resin can be used in combination with up to about 25 parts by weight or less per 100 parts by weight thereof.
シランカップリング剤としては、(メタ)アクリロキシ基、メルカプト基、ビニル基、エポキシ基、アミノ基、クロロプロピル基等を含有するものが挙げられ、好ましくはメタクリロキシプロピルメチルジメトキシシラン、メタクリロキシプロピルトリメトキシシラン、メタクリロキシプロピルメチルジエトキシ基含有シラン、メタクリロキシプロピルトリエトキシシラン等のメタクリロキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン等のメルカプト基含有シランが用いられる。
Examples of the silane coupling agent include those containing (meth) acryloxy group, mercapto group, vinyl group, epoxy group, amino group, chloropropyl group, etc., preferably methacryloxypropylmethyldimethoxysilane, methacryloxypropyltri Examples include methoxysilane, methacryloxypropylmethyldiethoxy group-containing silane, methacryloxysilane such as methacryloxypropyltriethoxysilane, and mercapto group-containing silane such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.
これらのシランカップリング剤は、ハイオルソ型ノボラックフェノール樹脂100重量部当り約0.5～5重量部、好ましくは約1～3重量部の割合で用いられる。これより少ない使用割合では微小ブリスターの発生を抑えることができず、一方これより多い割合で用いられると、耐水接着性が悪化するようになる。
These silane coupling agents are used at a ratio of about 0.5 to 5 parts by weight, preferably about 1 to 3 parts by weight, per 100 parts by weight of the high-ortho type novolak phenol resin. If the ratio is less than this, the generation of fine blisters cannot be suppressed. On the other hand, if the ratio is larger than this, the water-resistant adhesiveness deteriorates.
未加硫のNBRとしては、アクリロニトリル(AN)含量が約20～40重量％、好ましくは約25～35重量％のものが用いられる。一般には、接着されるべきNBRと同等またはよりAN含量の多いものが用いられる。この未加硫NBRは、加硫剤等の加硫系成分を含有していない。
As the unvulcanized NBR, those having an acrylonitrile (AN) content of about 20 to 40% by weight, preferably about 25 to 35% by weight are used. In general, those having the same or higher AN content as the NBR to be bonded are used. This unvulcanized NBR does not contain a vulcanizing component such as a vulcanizing agent.
未加硫NBRは、ハイオルソ型ノボラックフェノール樹脂100重量部当り約15～30重量部、好ましくは約20～28重量部の割合で用いられる。これよりも少ない使用割合では初期接着性が低下し、反応性が低いNBR混練物に対しては接着が困難となり、一方これより多い割合で用いられると、後記比較例５の結果に示される如く、剥離試験の結果は満足させるものの、金型や成型物に汚染がみられ、本発明所期の目的を達成することができない。
Unvulcanized NBR is used at a ratio of about 15 to 30 parts by weight, preferably about 20 to 28 parts by weight, per 100 parts by weight of the high-ortho type novolak phenol resin. If the amount used is less than this, the initial adhesiveness is lowered, and it becomes difficult to adhere to the NBR kneaded material having low reactivity. On the other hand, if it is used in a proportion higher than this, as shown in the results of Comparative Example 5 described later. Although the results of the peel test are satisfactory, the mold and molded product are contaminated, and the intended purpose of the present invention cannot be achieved.
以上の各成分を必須成分とする本発明の加硫接着剤は、有機溶媒溶液として調製される。有機溶媒としては、アセトン、メチルエチルケトン(2-ブタノン)、メチルイソブチルケトン等のケトン類、トルエン、キシレン等の芳香族炭化水素類が、単独であるいは混合して用いられる。ケトン類と芳香族炭化水素類とが混合して用いられる場合には、ケトン類100重量部に対し芳香族炭化水素類が約30～70重量部の割合で用いられることが好ましい。
The vulcanized adhesive of the present invention having the above components as essential components is prepared as an organic solvent solution. As the organic solvent, ketones such as acetone, methyl ethyl ketone (2-butanone) and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene are used alone or in combination. When ketones and aromatic hydrocarbons are used as a mixture, the aromatic hydrocarbons are preferably used in a ratio of about 30 to 70 parts by weight per 100 parts by weight of the ketones.
加硫接着剤は、有機溶媒中固形分濃度が約3～10重量％となるように攪拌、溶解して、均一な溶液として調製される。
The vulcanized adhesive is prepared as a uniform solution by stirring and dissolving so that the solid content concentration in the organic solvent is about 3 to 10% by weight.
本発明に係る加硫接着剤を用いて接着成形物を作製する際は、まず接着剤を金属上に塗布し、室温下で乾燥させた後、約100～160℃で加熱硬化させる。次いで、未加硫のNBR混練物を接合させ、約170～210℃で約3～8分間加圧加硫することにより、金属とNBRとの接着がなされる。金属とNBRが良好に接着された接着成形物としては、オイルシール、ハブシール等の自動車用部品が例示される。
When producing an adhesive molded product using the vulcanized adhesive according to the present invention, the adhesive is first applied on a metal, dried at room temperature, and then heated and cured at about 100 to 160 ° C. Next, the unvulcanized NBR kneaded material is joined and pressure vulcanized at about 170 to 210 ° C. for about 3 to 8 minutes to bond the metal and the NBR. Examples of the adhesive molded product in which the metal and NBR are satisfactorily bonded include automotive parts such as oil seals and hub seals.
次に、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 examples.
実施例１
ハイオルソ型ノボラックフェノール樹脂(昭和電工製品 100重量部
ショウノールBRM-7174H；オルソ型含有率 70～80％)
メタクリロキシプロピルトリメトキシシラン 1 〃
NBR(JSR製品N232S；AN含量35重量％) 28 〃
ランダム型ノボラックフェノール樹脂 50 〃
(ロード・インク製品ケムロックTS1677-13；
固形分濃度40重量％)
2-ブタノン 4500 〃
以上の各成分から調製された加硫接着剤を、リン酸亜鉛処理した軟鋼板上に塗布し、室温下に5分間放置した後、140℃で10分間乾燥処理した。 Example 1
High ortho type novolac phenolic resin (Showa Denko products 100 parts by weight Shonor BRM-7174H; ortho type content 70-80%)
Methacryloxypropyltrimethoxysilane 1 〃
NBR (JSR product N232S; AN content 35% by weight) 28 〃
Random type novolac phenolic resin 50 〃
(Load and ink product Chemlock TS1677-13;
(Solid concentration 40% by weight)
2-butanone 4500 〃
The vulcanized adhesive prepared from each of the above components was applied onto a mild steel sheet treated with zinc phosphate, allowed to stand at room temperature for 5 minutes, and then dried at 140 ° C. for 10 minutes.
ハイオルソ型ノボラックフェノール樹脂(昭和電工製品 100重量部
ショウノールBRM-7174H；オルソ型含有率 70～80％)
メタクリロキシプロピルトリメトキシシラン 1 〃
NBR(JSR製品N232S；AN含量35重量％) 28 〃
ランダム型ノボラックフェノール樹脂 50 〃
(ロード・インク製品ケムロックTS1677-13；
固形分濃度40重量％)
2-ブタノン 4500 〃
以上の各成分から調製された加硫接着剤を、リン酸亜鉛処理した軟鋼板上に塗布し、室温下に5分間放置した後、140℃で10分間乾燥処理した。 Example 1
High ortho type novolac phenolic resin (Showa Denko products 100 parts by weight Shonor BRM-7174H; ortho type content 70-80%)
Methacryloxypropyltrimethoxysilane 1 〃
NBR (JSR product N232S; AN content 35% by weight) 28 〃
Random type novolac phenolic resin 50 〃
(Load and ink product Chemlock TS1677-13;
(Solid concentration 40% by weight)
2-butanone 4500 〃
The vulcanized adhesive prepared from each of the above components was applied onto a mild steel sheet treated with zinc phosphate, allowed to stand at room temperature for 5 minutes, and then dried at 140 ° C. for 10 minutes.
この加硫接着剤塗布軟鋼板上に、下記配合の未加硫NBR混練物を接合させ、180℃で4分間の加圧加硫を行い、接着成形物試験片を得た。
未加硫NBR混練物：
NBR(日本ゼオン製品ニポールDN1042；AN含量34重量％) 100重量部
FEFカーボンブラック 40 〃
シリカ粉末 20 〃
酸化亜鉛 5 〃
ステアリン酸 1 〃
ジオクチルフタレート 5 〃
老化防止剤(2,2,4-トリメチル-1,2-ジヒドロキノリン) 1 〃
トリアリルイソシアヌレート(濃度70重量％) 0.8 〃 On this vulcanized adhesive coated mild steel sheet, an unvulcanized NBR kneaded material having the following composition was joined and pressure vulcanized at 180 ° C. for 4 minutes to obtain an adhesive molded product test piece.
Unvulcanized NBR kneaded material:
NBR (Nippon ZEON product Nipol DN1042; AN content 34 wt%) 100 parts by weight FEF carbon black 40 〃
Silica powder 20 〃
Zinc oxide 5 〃
Stearic acid 1 〃
Dioctyl phthalate 5 〃
Anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline) 1 〃
Triallyl isocyanurate (concentration 70% by weight) 0.8 〃
未加硫NBR混練物：
NBR(日本ゼオン製品ニポールDN1042；AN含量34重量％) 100重量部
FEFカーボンブラック 40 〃
シリカ粉末 20 〃
酸化亜鉛 5 〃
ステアリン酸 1 〃
ジオクチルフタレート 5 〃
老化防止剤(2,2,4-トリメチル-1,2-ジヒドロキノリン) 1 〃
トリアリルイソシアヌレート(濃度70重量％) 0.8 〃 On this vulcanized adhesive coated mild steel sheet, an unvulcanized NBR kneaded material having the following composition was joined and pressure vulcanized at 180 ° C. for 4 minutes to obtain an adhesive molded product test piece.
Unvulcanized NBR kneaded material:
NBR (Nippon ZEON product Nipol DN1042; AN content 34 wt%) 100 parts by weight FEF carbon black 40 〃
Silica powder 20 〃
Zinc oxide 5 〃
Stearic acid 1 〃
Dioctyl phthalate 5 〃
Anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline) 1 〃
Triallyl isocyanurate (concentration 70% by weight) 0.8 〃
実施例２
実施例１において、下記各成分から調製された加硫接着剤組成物が用いられた。
ハイオルソ型ノボラックフェノール樹脂(BRM-7174H) 100重量部
メルカプトプロピルトリメトキシシラン 3 〃
ランダム型ノボラックフェノール樹脂 50 〃
(ケムロックTS1677-13)
NBR(N232S) 28 〃
2-ブタノン 4500 〃 Example 2
In Example 1, a vulcanized adhesive composition prepared from the following components was used.
High ortho type novolac phenol resin (BRM-7174H) 100 parts by weight Mercaptopropyltrimethoxysilane 3 〃
Random type novolac phenolic resin 50 〃
(Chemlock TS1677-13)
NBR (N232S) 28 〃
2-butanone 4500 〃
実施例１において、下記各成分から調製された加硫接着剤組成物が用いられた。
ハイオルソ型ノボラックフェノール樹脂(BRM-7174H) 100重量部
メルカプトプロピルトリメトキシシラン 3 〃
ランダム型ノボラックフェノール樹脂 50 〃
(ケムロックTS1677-13)
NBR(N232S) 28 〃
2-ブタノン 4500 〃 Example 2
In Example 1, a vulcanized adhesive composition prepared from the following components was used.
High ortho type novolac phenol resin (BRM-7174H) 100 parts by weight Mercaptopropyltrimethoxysilane 3 〃
Random type novolac phenolic resin 50 〃
(Chemlock TS1677-13)
NBR (N232S) 28 〃
2-butanone 4500 〃
比較例１
実施例１において、下記各成分から調製された加硫接着剤が用いられた。
ハイオルソ型ノボラックフェノール樹脂 100重量部
(ショウノールBRM-7174H)
ビスフェノールA型エポキシ樹脂(三菱化学製品JSR1004) 3 〃
NBR(JSR製品N237；AN含量34重量％) 21 〃
2-ブタノン 2980 〃 Comparative Example 1
In Example 1, a vulcanized adhesive prepared from the following components was used.
High ortho type novolac phenol resin 100 parts by weight (Shonol BRM-7174H)
Bisphenol A type epoxy resin (Mitsubishi Chemical JSR1004) 3 〃
NBR (JSR product N237; AN content 34% by weight) 21 〃
2-butanone 2980 〃
実施例１において、下記各成分から調製された加硫接着剤が用いられた。
ハイオルソ型ノボラックフェノール樹脂 100重量部
(ショウノールBRM-7174H)
ビスフェノールA型エポキシ樹脂(三菱化学製品JSR1004) 3 〃
NBR(JSR製品N237；AN含量34重量％) 21 〃
2-ブタノン 2980 〃 Comparative Example 1
In Example 1, a vulcanized adhesive prepared from the following components was used.
High ortho type novolac phenol resin 100 parts by weight (Shonol BRM-7174H)
Bisphenol A type epoxy resin (Mitsubishi Chemical JSR1004) 3 〃
NBR (JSR product N237; AN content 34% by weight) 21 〃
2-butanone 2980 〃
比較例２
実施例１において、下記各成分から調製された加硫接着剤が用いられた。
ハイオルソ型ノボラックフェノール樹脂(BRM-7174H) 100重量部
ビスフェノールA型エポキシ樹脂(JSR1004) 3 〃
ランダム型ノボラックフェノール樹脂 52 〃
(ケムロックTS1677-13)
NBR(N232S) 25 〃
2-ブタノン 3540 〃 Comparative Example 2
In Example 1, a vulcanized adhesive prepared from the following components was used.
High ortho type novolac phenolic resin (BRM-7174H) 100 parts by weight Bisphenol A type epoxy resin (JSR1004) 3 部
Random type novolac phenolic resin 52 〃
(Chemlock TS1677-13)
NBR (N232S) 25 〃
2-butanone 3540 〃
実施例１において、下記各成分から調製された加硫接着剤が用いられた。
ハイオルソ型ノボラックフェノール樹脂(BRM-7174H) 100重量部
ビスフェノールA型エポキシ樹脂(JSR1004) 3 〃
ランダム型ノボラックフェノール樹脂 52 〃
(ケムロックTS1677-13)
NBR(N232S) 25 〃
2-ブタノン 3540 〃 Comparative Example 2
In Example 1, a vulcanized adhesive prepared from the following components was used.
High ortho type novolac phenolic resin (BRM-7174H) 100 parts by weight Bisphenol A type epoxy resin (JSR1004) 3 部
Random type novolac phenolic resin 52 〃
(Chemlock TS1677-13)
NBR (N232S) 25 〃
2-butanone 3540 〃
比較例３
ランダム型ノボラックフェノール樹脂 7 〃
(ケムロックTS1677-13)
レゾール型フェノール樹脂 3 〃
2-ブタノン 90 〃
ここで、レゾール型フェノール樹脂としては、特許文献１記載の参考例３に従い、m-クレゾール-p-クレゾール混合物とホルムアルデヒド水溶液とを水酸化バリウム・8水和物の存在下で、70℃で2時間反応させることにより得られたものを使用した。 Comparative Example 3
Random type novolac phenolic resin 7 〃
(Chemlock TS1677-13)
Resole type phenolic resin 3 〃
2-butanone 90 〃
Here, as the resol-type phenol resin, in accordance with Reference Example 3 described in Patent Document 1, an m-cresol-p-cresol mixture and an aqueous formaldehyde solution were mixed at 70 ° C. in the presence of barium hydroxide octahydrate at 70 ° C. What was obtained by making it react for time was used.
ランダム型ノボラックフェノール樹脂 7 〃
(ケムロックTS1677-13)
レゾール型フェノール樹脂 3 〃
2-ブタノン 90 〃
ここで、レゾール型フェノール樹脂としては、特許文献１記載の参考例３に従い、m-クレゾール-p-クレゾール混合物とホルムアルデヒド水溶液とを水酸化バリウム・8水和物の存在下で、70℃で2時間反応させることにより得られたものを使用した。 Comparative Example 3
Random type novolac phenolic resin 7 〃
(Chemlock TS1677-13)
Resole type phenolic resin 3 〃
2-butanone 90 〃
Here, as the resol-type phenol resin, in accordance with Reference Example 3 described in Patent Document 1, an m-cresol-p-cresol mixture and an aqueous formaldehyde solution were mixed at 70 ° C. in the presence of barium hydroxide octahydrate at 70 ° C. What was obtained by making it react for time was used.
比較例４
比較例１において、ビスフェノールA型エポキシ樹脂量を15重量部に、また2-ブタノン量を3260重量部にそれぞれ変更した加硫接着剤が用いられた。 Comparative Example 4
In Comparative Example 1, a vulcanized adhesive in which the amount of bisphenol A type epoxy resin was changed to 15 parts by weight and the amount of 2-butanone was changed to 3260 parts by weight was used.
比較例１において、ビスフェノールA型エポキシ樹脂量を15重量部に、また2-ブタノン量を3260重量部にそれぞれ変更した加硫接着剤が用いられた。 Comparative Example 4
In Comparative Example 1, a vulcanized adhesive in which the amount of bisphenol A type epoxy resin was changed to 15 parts by weight and the amount of 2-butanone was changed to 3260 parts by weight was used.
比較例５
比較例２において、NBR量を37重量部に、また2-ブタノン量を3820重量部にそれぞれ変更した加硫接着剤が用いられた。 Comparative Example 5
In Comparative Example 2, a vulcanized adhesive in which the NBR amount was changed to 37 parts by weight and the 2-butanone amount was changed to 3820 parts by weight was used.
比較例２において、NBR量を37重量部に、また2-ブタノン量を3820重量部にそれぞれ変更した加硫接着剤が用いられた。 Comparative Example 5
In Comparative Example 2, a vulcanized adhesive in which the NBR amount was changed to 37 parts by weight and the 2-butanone amount was changed to 3820 parts by weight was used.
以上の各実施例および比較例において、用いられた金型および接着成形物の汚染の有無、微小ブリスター発生率を目視で判定すると共に、得られた接着成形物について、JIS K-6301に準拠して90°剥離試験を実施し、ゴム残り面積率を測定した。また、接着成形物を純水に浸漬し、80℃で70時間加温後のゴム残り面積率を測定し、耐水接着性を評価した。評価結果および測定結果は、次の表に示される。なお、比較例4においては、加硫接着剤として機能しなかったため、微小ブリスター発生率は計測できなかった。
表
評価・測定項目 実１ 実２ 比１ 比２ 比３ 比４ 比５
汚染
金型 なし なし なし なし なし なし あり
接着成形物 なし なし なし なし なし なし あり
微小ブリスター発生率(％) <3 <3 30 15 40 － <3
ゴム残り面積率(％)
初期 100 100 100 100 50 0 100
純水浸漬後 70 80 60 80 20 0 70 In each of the above Examples and Comparative Examples, the presence or absence of contamination of the used mold and the adhesive molded product, and the occurrence rate of fine blisters were visually determined, and the obtained adhesive molded product conformed to JIS K-6301. A 90 ° peel test was conducted to measure the rubber remaining area ratio. Further, the adhesive molded product was immersed in pure water, and the area ratio of the rubber remaining after heating at 80 ° C. for 70 hours was measured to evaluate water-resistant adhesion. The evaluation results and measurement results are shown in the following table. In Comparative Example 4, since it did not function as a vulcanized adhesive, the occurrence rate of fine blisters could not be measured.
Table Evaluation / Measurement Items Actual 1 Actual 2 Ratio 1 Ratio 2 Ratio 3 Ratio 4 Ratio 5
Contamination Mold No No No No No No Yes Adhesive molding No No No No No No No Yes Small blister rate (%) <3 <3 30 15 40 － <3
Rubber remaining area ratio (%)
Initial 100 100 100 100 50 0 100
After immersion in pure water 70 80 60 80 20 0 70
表
評価・測定項目 実１ 実２ 比１ 比２ 比３ 比４ 比５
汚染
金型 なし なし なし なし なし なし あり
接着成形物 なし なし なし なし なし なし あり
微小ブリスター発生率(％) <3 <3 30 15 40 － <3
ゴム残り面積率(％)
初期 100 100 100 100 50 0 100
純水浸漬後 70 80 60 80 20 0 70 In each of the above Examples and Comparative Examples, the presence or absence of contamination of the used mold and the adhesive molded product, and the occurrence rate of fine blisters were visually determined, and the obtained adhesive molded product conformed to JIS K-6301. A 90 ° peel test was conducted to measure the rubber remaining area ratio. Further, the adhesive molded product was immersed in pure water, and the area ratio of the rubber remaining after heating at 80 ° C. for 70 hours was measured to evaluate water-resistant adhesion. The evaluation results and measurement results are shown in the following table. In Comparative Example 4, since it did not function as a vulcanized adhesive, the occurrence rate of fine blisters could not be measured.
Table Evaluation / Measurement Items Actual 1 Actual 2 Ratio 1 Ratio 2 Ratio 3 Ratio 4 Ratio 5
Contamination Mold No No No No No No Yes Adhesive molding No No No No No No No Yes Small blister rate (%) <3 <3 30 15 40 － <3
Rubber remaining area ratio (%)
Initial 100 100 100 100 50 0 100
After immersion in pure water 70 80 60 80 20 0 70
Claims (8)
- ハイオルソ型ノボラックフェノール樹脂100重量部当りシランカップリング剤0.5～5重量部および未加硫のNBR 15～30重量部を添加し、有機溶媒溶液として調製した加硫接着剤組成物。 A vulcanized adhesive composition prepared as an organic solvent solution by adding 0.5 to 5 parts by weight of a silane coupling agent and 15 to 30 parts by weight of unvulcanized NBR per 100 parts by weight of a high-ortho type novolak phenol resin.
- IRによる測定結果から算出されるオルソ型含有率が65％以上のハイオルソ型ノボラックフェノール樹脂が用いられた請求項１記載の加硫接着剤組成物。 The vulcanized adhesive composition according to claim 1, wherein a high-ortho-type novolac phenol resin having an ortho-type content calculated from IR measurement results of 65% or more is used.
- ハイオルソ型ノボラックフェノール樹脂100重量部当り25重量部以下のランダム型ノボラックフェノール樹脂またはレゾール型フェノール樹脂をさらに配合した請求項１記載の加硫接着剤組成物。 The vulcanized adhesive composition according to claim 1, further comprising 25 parts by weight or less of a random type novolak phenol resin or a resol type phenol resin per 100 parts by weight of a high ortho type novolak phenol resin.
- シランカップリング剤としてメタクリロキシ基含有シランおよびメルカプト基含有シランの少くとも一種が用いられた請求項１記載の加硫接着剤組成物。 The vulcanized adhesive composition according to claim 1, wherein at least one of methacryloxy group-containing silane and mercapto group-containing silane is used as the silane coupling agent.
- NBRポリマーとして、アクリロニトリル含量が20～40重量％のものが用いられた請求項１記載の加硫接着剤組成物。 The vulcanized adhesive composition according to claim 1, wherein the NBR polymer has an acrylonitrile content of 20 to 40% by weight.
- 金属とNBRとの加硫接着に用いられる請求項１乃至５のいずれかの請求項に記載の加硫接着剤組成物。 The vulcanized adhesive composition according to any one of claims 1 to 5, which is used for vulcanization adhesion between a metal and NBR.
- 請求項６記載の加硫接着剤組成物を用いて加硫接着された金属-NBRの接着成形物。 Metal-NBR adhesive molded product vulcanized and bonded using the vulcanized adhesive composition according to claim 6.
- オイルシールまたはハブシールである請求項７記載の接着成形物。 The adhesive molded product according to claim 7, which is an oil seal or a hub seal.
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| JP2018563938A JP6508442B1 (en) | 2017-05-25 | 2018-04-10 | Vulcanizing adhesive composition |
| CN201880032942.4A CN110637073B (en) | 2017-05-25 | 2018-04-10 | Vulcanized adhesive composition |
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| JP2017-103228 | 2017-05-25 | ||
| JP2017103228 | 2017-05-25 |
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| PCT/JP2018/015063 WO2018216380A1 (en) | 2017-05-25 | 2018-04-10 | Vulcanizing adhesive composition |
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| JP (1) | JP6508442B1 (en) |
| CN (1) | CN110637073B (en) |
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| JP2021109367A (en) * | 2020-01-09 | 2021-08-02 | 興国インテック株式会社 | Method for producing metal or resin-rubber adhesion body and novolak type phenol resin composition used in the method |
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|---|---|---|---|---|
| JPS4992186A (en) * | 1972-10-18 | 1974-09-03 | ||
| JPS4992187A (en) * | 1972-10-18 | 1974-09-03 | ||
| JPS61278579A (en) * | 1985-06-05 | 1986-12-09 | Nok Corp | Vulcanizing adhesive composition and method of bonding using the same |
| JPH111672A (en) * | 1997-06-12 | 1999-01-06 | Nok Corp | Vulcanizable adhesive composition |
| JP2003261850A (en) * | 2002-03-08 | 2003-09-19 | Nok Corp | Vulcanizing adhesive composition |
| JP2011098541A (en) * | 2009-11-09 | 2011-05-19 | Nok Corp | Rubber metal laminate |
| WO2018047467A1 (en) * | 2016-09-09 | 2018-03-15 | Nok株式会社 | Vulcanizing adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2821816T3 (en) * | 2014-02-07 | 2021-04-27 | Sumitomo Bakelite Co | Phenolic resin composition for friction material, friction material and brake |
| CN106046283B (en) * | 2015-06-18 | 2019-04-09 | 济南圣泉集团股份有限公司 | High ortho position benzylic ether phenolic resin, preparation method and applications are in the method for cold-box binder |
-
2018
- 2018-04-10 JP JP2018563938A patent/JP6508442B1/en active Active
- 2018-04-10 CN CN201880032942.4A patent/CN110637073B/en active Active
- 2018-04-10 WO PCT/JP2018/015063 patent/WO2018216380A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4992186A (en) * | 1972-10-18 | 1974-09-03 | ||
| JPS4992187A (en) * | 1972-10-18 | 1974-09-03 | ||
| JPS61278579A (en) * | 1985-06-05 | 1986-12-09 | Nok Corp | Vulcanizing adhesive composition and method of bonding using the same |
| JPH111672A (en) * | 1997-06-12 | 1999-01-06 | Nok Corp | Vulcanizable adhesive composition |
| JP2003261850A (en) * | 2002-03-08 | 2003-09-19 | Nok Corp | Vulcanizing adhesive composition |
| JP2011098541A (en) * | 2009-11-09 | 2011-05-19 | Nok Corp | Rubber metal laminate |
| WO2018047467A1 (en) * | 2016-09-09 | 2018-03-15 | Nok株式会社 | Vulcanizing adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6508442B1 (en) | 2019-05-08 |
| CN110637073B (en) | 2020-09-18 |
| CN110637073A (en) | 2019-12-31 |
| JPWO2018216380A1 (en) | 2019-06-27 |
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