JPH0674403B2 - Vulcanized adhesive composition and bonding method using the same - Google Patents
Vulcanized adhesive composition and bonding method using the sameInfo
- Publication number
- JPH0674403B2 JPH0674403B2 JP60120584A JP12058485A JPH0674403B2 JP H0674403 B2 JPH0674403 B2 JP H0674403B2 JP 60120584 A JP60120584 A JP 60120584A JP 12058485 A JP12058485 A JP 12058485A JP H0674403 B2 JPH0674403 B2 JP H0674403B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- adhesive composition
- nbr
- vulcanized adhesive
- 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.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、加硫接着剤組成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NBRとの間の接着に
有効に用いられる加硫接着剤組成物およびそれを用いる
接着方法に関する。TECHNICAL FIELD The present invention relates to a vulcanized adhesive composition and an adhesion method using the same. More specifically, it relates to a vulcanized adhesive composition effectively used for adhesion between metal and NBR and an adhesion method using the same.
〔従来の技術〕および〔発明が解決しようとする問題
点〕 従来から、金属とNBRとの加硫接着剤としてフェノール
樹脂系の接着剤が用いられているが、フェノール樹脂系
の加硫接着剤を用いた場合には、適度のベーキング処理
をしなければ、加硫成形時の熱と圧力で接着剤層が軟
化、流動し、接着目的を十分に達成し得ないという欠点
がみられた。[Prior Art] and [Problems to be Solved by the Invention] Conventionally, a phenol resin-based adhesive has been used as a vulcanization adhesive between metal and NBR. In the case of using, the adhesive layer was softened and flowed by heat and pressure at the time of vulcanization and the adhesive purpose could not be sufficiently achieved unless a proper baking treatment was performed.
このような接着剤層の軟化、流動を防止することができ
れば、フェノール樹脂系の接着剤が本来有するすぐれた
接着性が十分に発揮されることになるが、かかる接着剤
層の軟化、流動を防止するために、粒径が約１〜100μ
ｍの粒状無機物質、例えばカーボンブラック、シリカ、
タルク、炭酸カルシウム、酸化マグネシウム、酸化亜
鉛、酸化チタン、酸化鉛、けいそう土などを加硫接着剤
組成物中に添加することが、有効な解決手段であること
を本出願人は先に見出している（特開昭61−66766号公
報）。If such softening and flow of the adhesive layer can be prevented, the excellent adhesiveness originally possessed by the phenolic resin-based adhesive will be sufficiently exhibited. To prevent, the particle size is about 1-100μ
m granular inorganic material such as carbon black, silica,
The Applicant has previously found that adding talc, calcium carbonate, magnesium oxide, zinc oxide, titanium oxide, lead oxide, diatomaceous earth, etc. to the vulcanized adhesive composition is an effective solution. (Japanese Patent Laid-Open No. 61-66766).
この種の加硫接着剤は、例えば軟鋼板製金属缶にNBRを
焼付けたオイルシール、バルブ、ガスケット、パッキン
などの製造に用いられているが、この種の製品を温水環
境下で使用した場合、例えばオイルシール、金具入りパ
ッキンおよびガスケット、バルブなどであって、ラジエ
ーター内のシールやエンジン廻りの足まわりシール部な
ど、温度が上がりかつ雨水がかかる個所などに使用した
場合には、接着剥れという現象がみられ、こうした現象
の防止には、単に上記の如く粒状無機物質を添加したの
みだけでは必ずしも十分ではないことが新たに見出され
た。This type of vulcanized adhesive is used, for example, in the manufacture of oil seals, valves, gaskets, packings, etc. in which NBR is baked on a mild steel sheet metal can, but when this type of product is used in a hot water environment. , For example, oil seals, packings and gaskets with metal fittings, valves, etc., when used in places where the temperature rises and rainwater is encountered, such as seals inside the radiator and suspension parts around the engine, etc. It has been newly found that simply adding the particulate inorganic substance as described above is not sufficient to prevent such a phenomenon.
本発明者らは、このような新たな課題の解決方法を求め
て種々検討の結果、粒状無機物質として微粒子状粉末シ
リカ補強剤を用い、それを有機シラン表面処理剤と併用
することにより、かかる課題が効果的に解決されること
を見出した。As a result of various investigations for a solution to such a new problem, the present inventors have used a particulate powder silica reinforcing agent as a granular inorganic substance, and by using it together with an organic silane surface treating agent, We have found that the problems can be effectively solved.
〔問題点を解決するための手段〕および〔作用〕 従って、本発明は金属とNBRとの接着に用いられる加硫
接着剤組成物に係り、この加硫接着剤組成物は、ノボラ
ック型フェノール樹脂、ヘキサメチレンテトラミン硬化
剤、微粒子状粉末シリカ補強剤および有機シラン表面処
理剤を含有してなる。[Means for Solving Problems] and [Action] Therefore, the present invention relates to a vulcanized adhesive composition used for bonding a metal and NBR, and the vulcanized adhesive composition is a novolac type phenol resin. , Hexamethylenetetramine curing agent, fine powder silica reinforcing agent and organosilane surface treating agent.
本発明はまた、かかる加硫接着剤組成物を用いる金属と
NBRとの接着方法に係り、金属とNBRとの接着は、この加
硫接着剤組成物を金属上に塗布し、焼付け処理を行なっ
た後、NBRの未加硫配合物と接合させ、NBRの加硫温度で
加圧加硫することにより行われる。The invention also relates to metals using such vulcanized adhesive compositions.
Regarding the bonding method with NBR, the bonding between the metal and NBR is performed by applying this vulcanized adhesive composition onto the metal and performing a baking treatment, and then joining the unvulcanized compound of NBR, It is carried out by pressure vulcanization at a vulcanization temperature.
ノボラック型フェノール樹脂は、フェノールあるいはク
レゾール、キシレノールなどのアルキル置換フェノール
とこれに対してモル比１未満の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、本発明
においては融点が100℃前後、分子量が数100〜数1000程
度のものが一般に用いられる。Novolac-type phenol resin is a pine resin soluble in organic solvents such as alcohols and ketones by reacting phenol or an alkyl-substituted phenol such as cresol or xylenol with formaldehyde having a molar ratio of less than 1 in the presence of an acid catalyst. In the present invention, those having a melting point of about 100 ° C. and a molecular weight of several hundreds to several thousands are generally used.
ノボラック分子は、反応基（メチロール基）を有してい
ないので、単に加熱しただけでは分子間の縮合が起ら
ず、永久に熱可塑性を維持するが、硬化させるためのメ
チレン基供給源としてホルムアルデヒドまたはヘキサメ
チレンテトラミンを添加して加熱すると、不溶不融性と
なる。このような硬化剤としてのヘキサメチレンテトラ
ミンは、ノボラック型フェノール樹脂100重量部当り約
５〜20重量部の割合で用いられる。Since novolak molecules do not have a reactive group (methylol group), condensation between molecules does not occur simply by heating and permanently maintains thermoplasticity, but formaldehyde is used as a methylene group supply source for curing. Alternatively, when hexamethylenetetramine is added and heated, it becomes insoluble and infusible. Hexamethylenetetramine as such a curing agent is used in a proportion of about 5 to 20 parts by weight per 100 parts by weight of the novolac type phenol resin.
補強剤としての微粒子状粉末シリカは、粒径がやはり約
１〜100μｍの無水けい酸が、ノボラック型フェノール
樹脂100重量部当り約５〜50重量部の割合で一般に用い
られる。更に、このような微粒子状粉末シリカの表面処
理剤としての有機シラン、例えばアミノシラン、ビニル
シラン、エポキシシランなどの官能性基含有有機シラン
が、ノボラック型フェノール樹脂100重量部当り約0.5〜
４重量部の割合で用いられる。有機シランは、一般に微
粒子状粉末シリカと一緒に混合して用いられるが、これ
で予めシリカを処理した上で用いることもでき、このよ
うな態様も本発明に含まれる。As the fine particle powder silica as a reinforcing agent, silicic acid anhydride having a particle size of about 1 to 100 μm is generally used at a ratio of about 5 to 50 parts by weight per 100 parts by weight of the novolac type phenol resin. Further, an organic silane as a surface treatment agent for such fine powder silica, for example, aminosilane, vinylsilane, functional group-containing organic silane such as epoxysilane, about 0.5 ~ 100 parts by weight of novolak type phenolic resin.
Used in a proportion of 4 parts by weight. The organic silane is generally used as a mixture with the fine powder silica, but it is also possible to treat the silica with the silica in advance, and such an embodiment is also included in the present invention.
以上の各成分を必須成分とする本発明の加硫接着剤組成
物は、一般に有機溶剤分散液の形で調製されて用いられ
る。有機溶剤としては、微粒子状粉末シリカを除くこれ
らの各成分を溶解し得るものであれば任意のものを使用
し得るが、メタノールまたはメチルエチルケトンが好ん
で用いられる。The vulcanized adhesive composition of the present invention containing the above components as essential components is generally prepared and used in the form of an organic solvent dispersion. As the organic solvent, any solvent can be used as long as it can dissolve each of these components except the fine powder silica, but methanol or methyl ethyl ketone is preferably used.
接着に際しては、この加硫接着剤組成物の有機溶剤溶液
が金属、例えば軟鋼、ステンレススチール、黄銅などの
上に塗布され、それを約50〜60℃に加熱、乾燥させた
後、約120〜220℃に約５〜30分間加熱して、焼付処理が
行われる。その後、NBRの未加硫配合物と接合させ、NBR
の加硫温度である約160〜200℃に加熱しながら、金型な
どを用いて加圧加硫する。NBRの未加硫配合物として
は、例えば次のようなものが用いられる。At the time of adhesion, an organic solvent solution of the vulcanized adhesive composition is applied onto a metal, for example, mild steel, stainless steel, brass, etc., and heated to about 50 to 60 ° C. and dried, then about 120 to A baking process is performed by heating to 220 ° C. for about 5 to 30 minutes. After that, it was bonded with NBR unvulcanized compound,
While heating to a vulcanization temperature of about 160 to 200 ° C., pressure vulcanization is performed using a mold or the like. As the unvulcanized compound of NBR, for example, the following ones are used.
NBR（日本ゼオン製品ニポール1041） 100重量部 SRFカーボンブラック 40 酸化亜鉛 ５ ステアリン酸 １ ジオクチルフタレート ５ イオウ １ テトラメチルチウラムジスルフィド ２ 〔発明の効果〕 本発明に係る加硫接着剤組成物を用いて接着された金属
とNBRとの接着物は、室温乃至約120℃（100℃以上は加
圧下）の温水中に浸漬しても、接着剥れが全くみられな
いという顕著な効果を奏する。NBR (Nippon 1041 manufactured by Nippon Zeon Co., Ltd.) 100 parts by weight SRF carbon black 40 Zinc oxide 5 Stearic acid 1 Dioctylphthalate 5 Sulfur 1 Tetramethylthiuram disulfide 2 [Effect of the invention] Adhesion using the vulcanized adhesive composition according to the present invention The adhered material of the metal and NBR has a remarkable effect that no adhesion peeling is observed even when immersed in warm water at room temperature to about 120 ° C (under pressure at 100 ° C or higher).
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 ノボラック型フェノール樹脂 100重量部 ヘキサメチレンテトラミン 10 微粒子状粉末シリカ 50 （日本アエロジル製品アエロジル200） γ−アミノプロピルトリエトキシシラン ２ メタノール 1458 上記配合組成の加硫接着剤組成物の有機溶剤分散液をシ
ョットブラスト処理後トリクロルエタンで洗浄した軟鋼
板（表面粗さ10〜15μｍ）に塗布し、これを50℃で10分
間乾燥後、180℃で10分間焼付処理した。Example 1 100 parts by weight of novolac type phenolic resin Hexamethylenetetramine 10 Fine powder silica 50 (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) γ-aminopropyltriethoxysilane 2 Methanol 1458 Organic solvent dispersion of vulcanized adhesive composition having the above composition The solution was applied to a mild steel plate (surface roughness: 10 to 15 μm) that had been shot blasted and washed with trichloroethane, dried at 50 ° C. for 10 minutes, and then baked at 180 ° C. for 10 minutes.
この金属板に、前記配合例のNBR未加硫配合物を、JIS K
-6301 8・３頁 90°剥離法に従って接合させ、金型を用
いて180℃、４分間の加圧加硫を行なった。To this metal plate, the NBR unvulcanized compound of the above compounding example was JIS K
-6301 Page 8 ・ 3 Joined according to 90 ° peeling method, and pressure vulcanized at 180 ° C. for 4 minutes using a mold.
実施例２ 実施例１において、γ‐アミノプロピルトリエトキシシ
ランの代りに、同量のビニルトリエトキシシランが用い
られた。Example 2 In Example 1, the same amount of vinyltriethoxysilane was used instead of γ-aminopropyltriethoxysilane.
比較例１ 実施例１において、微粒子状粉末シリカおよび有機シラ
ンが用いられず、メタノールの使用量が1450重量部に変
更された。Comparative Example 1 In Example 1, fine particle powder silica and organosilane were not used, and the amount of methanol used was changed to 1450 parts by weight.
比較例２ 実施例１において、有機シランが用いられず、メタノー
ルの使用量が1460重量部に変更された。Comparative Example 2 In Example 1, the organosilane was not used, and the amount of methanol used was changed to 1460 parts by weight.
以上の各実施例および比較例において得られた加硫接着
物について、80℃、240時間温水浸漬試験を行ない、前
記剥離試験法による剥離強度および剥離後のゴム残り面
積がそれぞれ測定された。得られた結果は、次の表に示
される。The vulcanized adhesives obtained in each of the above Examples and Comparative Examples were subjected to a hot water immersion test at 80 ° C. for 240 hours, and the peel strength and the remaining rubber area after peeling were measured by the peel test method. The results obtained are shown in the following table.
表 例、測定項目 浸漬前 浸漬後 実施例１ 剥離力（kg/cm） 9.3 6.5 ゴム残り面積（％） 100 100 実施例２ 剥離力（kg/cm） 8.5 6.4 ゴム残り面積（％） 100 100 比較例１ 剥離力（kg/cm） 8.4 1.5 ゴム残り面積（％） 100 5 比較例２ 剥離力（kg/cm） 8.5 3.2 ゴム残り面積（％） 100 50Table example, measurement item Before immersion After immersion Example 1 Peeling force (kg / cm) 9.3 6.5 Rubber remaining area (%) 100 100 Example 2 Peeling force (kg / cm) 8.5 6.4 Rubber remaining area (%) 100 100 Comparison Example 1 Peeling force (kg / cm) 8.4 1.5 Rubber remaining area (%) 100 5 Comparative example 2 Peeling force (kg / cm) 8.5 3.2 Rubber remaining area (%) 100 50
Claims (4)
り、ヘキサメチレンテトラミン硬化剤５〜20重量部、微
粒子状粉末シリカ補強剤５〜50重量部および有機シラン
表面処理剤0.5〜４重量部を添加してなる、金属とNBRと
の接着に用いられる加硫接着剤組成物。1. Addition of 5 to 20 parts by weight of a hexamethylenetetramine curing agent, 5 to 50 parts by weight of a fine particle powder silica reinforcing agent, and 0.5 to 4 parts by weight of an organic silane surface treating agent per 100 parts by weight of a novolac type phenol resin. A vulcanized adhesive composition used for bonding a metal and NBR.
の範囲第１項記載の加硫接着剤組成物。2. The vulcanized adhesive composition according to claim 1, which is prepared in the form of an organic solvent dispersion.
り、ヘキサメチレンテトラミン硬化剤５〜20重量部、微
粒子状粉末シリカ補強剤５〜50重量部および有機シラン
表面処理剤0.5〜４重量部を添加してなる加硫接着剤組
成物を金属上に塗布し、焼付け処理を行なった後、NBR
の未加硫配合物を接合させ、NBRの加硫温度で加圧加硫
させることを特徴とする金属とNBRとの接着方法。3. Addition of 5 to 20 parts by weight of a hexamethylenetetramine curing agent, 5 to 50 parts by weight of a fine particle powder silica reinforcing agent and 0.5 to 4 parts by weight of an organic silane surface treating agent per 100 parts by weight of a novolac type phenol resin. After applying the vulcanized adhesive composition formed on the metal and baking it, NBR
A method for adhering a metal and NBR, which comprises joining the unvulcanized compound of 1. and vulcanizing under pressure at the vulcanizing temperature of NBR.
用いられる特許請求の範囲第３項記載の接着方法。4. The bonding method according to claim 3, wherein the vulcanized adhesive composition is used in the form of an organic solvent dispersion liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60120584A JPH0674403B2 (en) | 1985-06-05 | 1985-06-05 | Vulcanized adhesive composition and bonding method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60120584A JPH0674403B2 (en) | 1985-06-05 | 1985-06-05 | Vulcanized adhesive composition and bonding method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61278579A JPS61278579A (en) | 1986-12-09 |
| JPH0674403B2 true JPH0674403B2 (en) | 1994-09-21 |
Family
ID=14789892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60120584A Expired - Lifetime JPH0674403B2 (en) | 1985-06-05 | 1985-06-05 | Vulcanized adhesive composition and bonding method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674403B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2668972B2 (en) * | 1988-08-23 | 1997-10-27 | エヌオーケー株式会社 | Adhesion method between metal and NBR |
| US20060041059A1 (en) * | 2003-02-12 | 2006-02-23 | Nok Corporation | Water-based vulcanizable adhesive composition |
| JP4626223B2 (en) * | 2004-01-13 | 2011-02-02 | Ｎｏｋ株式会社 | Vulcanized adhesive composition |
| CN110637073B (en) * | 2017-05-25 | 2020-09-18 | Nok株式会社 | Vulcanized adhesive composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5346205A (en) * | 1976-10-08 | 1978-04-25 | Toshiba Corp | Data transmission system |
-
1985
- 1985-06-05 JP JP60120584A patent/JPH0674403B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61278579A (en) | 1986-12-09 |
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