JPH07103258B2 - Surface treatment method for vulcanized rubber moldings - Google Patents
Surface treatment method for vulcanized rubber moldingsInfo
- Publication number
- JPH07103258B2 JPH07103258B2 JP63063108A JP6310888A JPH07103258B2 JP H07103258 B2 JPH07103258 B2 JP H07103258B2 JP 63063108 A JP63063108 A JP 63063108A JP 6310888 A JP6310888 A JP 6310888A JP H07103258 B2 JPH07103258 B2 JP H07103258B2
- Authority
- JP
- Japan
- Prior art keywords
- vulcanized
- vulcanized rubber
- surface treatment
- treatment method
- molded article
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、加硫ゴム成形品の表面処理方法に関する。更
に詳しくは、加硫フッ素ゴム成形品の低摩擦化ならびに
非粘着化を達成させるための表面処理方法に関する。TECHNICAL FIELD The present invention relates to a surface treatment method for a vulcanized rubber molded article. More specifically, it relates to a surface treatment method for achieving low friction and detackification of a vulcanized fluororubber molded article.
〔従来の技術〕および〔発明が解決しようとする課題〕 加硫ゴムは、一般に摩擦抵抗が大きくまたは粘着性を有
することがあるため、加硫ゴム基材の有する他の好まし
い性質が十分に生かされず、使用用途に制限がみられ
る。このため、加硫ゴム成形品表面の低摩擦化ならびに
非粘着化の要請が、近年とみに高まっている。[Prior Art] and [Problems to be Solved by the Invention] Vulcanized rubber generally has large frictional resistance or may have tackiness, so that other preferable properties of the vulcanized rubber base material are sufficiently utilized. However, there are restrictions on the intended use. For this reason, demands for low friction and non-adhesion of the surface of vulcanized rubber molded products have been increasing in recent years.
加硫ゴム成形品表面の低摩擦化ならびに非粘着化のため
の従来技術としては、加硫ゴム表面を薬品により硬化処
理する方法、ポリテトラフルオロエチレンの樹脂分散液
を用いてコーティングする方法などがあるが、前者の方
法では硬化部分の化学構造が大きく変化し、その結果ゴ
ムの最大の特徴であるゴム状弾性が著しく失われるとい
う欠点がみられ、また後者の方法では噴霧塗布、刷毛塗
りなどの工程を必要とする以外に、基材との接合性も問
題となり易いなどの課題を抱えている。Conventional techniques for reducing the friction and detackifying the surface of the vulcanized rubber molded product include a method of curing the vulcanized rubber surface with a chemical and a method of coating with a resin dispersion of polytetrafluoroethylene. However, the former method has the drawback that the chemical structure of the cured part changes significantly, and as a result the rubber-like elasticity, which is the most characteristic feature of rubber, is significantly lost, and the latter method involves spray coating, brush coating, etc. In addition to the above process, there is a problem that the bondability with the base material is likely to become a problem.
本発明は、成形品全体の弾性などゴム本来の特性を実質
的に低下させることなく、加硫フッ素ゴム成形品表面の
低摩擦化ならびに非粘着化を達成させることを目的とし
ている。An object of the present invention is to achieve low friction and detackification of the surface of a vulcanized fluorinated rubber molded product without substantially deteriorating inherent properties of rubber such as elasticity of the entire molded product.
〔課題を解決するための手段〕 かかる本発明の目的は、表面に多官能性不飽和化合物お
よび有機過酸化物を付着させた加硫フッ素ゴム成形品を
該有機過酸化物分解温度に加熱する方法により達成され
る。[Means for Solving the Problems] An object of the present invention is to heat a vulcanized fluororubber molded article having a polyfunctional unsaturated compound and an organic peroxide adhered to its surface to the decomposition temperature of the organic peroxide. Achieved by the method.
加硫フッ素ゴム成形品表面に付着される多官能性不飽和
化合物としては、例えばトリアリルイソシアヌレート、
トリアリルシアヌレート、トリアクリルホルマール、ト
リアリルトリメリテート、N,N′−ｍ−フェニレンビス
マレイミド、ジプロパギルテレフタレート、ジアリルフ
タレート、テトラアリルテレフタルアミドなどの、放射
線照射あるいは有機過酸化物ラジカルによってラジカル
を発生させ、ポリマーラジカルと共架橋する化合物の少
くとも一種が用いられる。As the polyfunctional unsaturated compound attached to the surface of the vulcanized fluororubber molded article, for example, triallyl isocyanurate,
Irradiation or organic peroxide radicals such as triallyl cyanurate, triacrylic formal, triallyl trimellitate, N, N'-m-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide At least one compound that generates radicals and co-crosslinks with polymer radicals is used.
これらの多官能性不飽和化合物は、液状物であればそれ
をそのまま使用することもできるが、好ましくは可溶性
溶媒溶液として用いられる。そのための溶媒としては、
加硫フッ素ゴム成形品を溶解したりしないものが用いら
れるものの、成形品表面に数10μｍ程度浸透するように
ある程度加硫フッ素ゴム成形品を膨潤させるものが望ま
しい。実際には、アセトン、メチルエチルケトン、メタ
ノール、エタノール、トルエン、テトラヒドロフランな
どが、処理程度に応じた溶液濃度を形成するようにして
用いられる。Although these polyfunctional unsaturated compounds can be used as they are if they are liquids, they are preferably used as a soluble solvent solution. As a solvent for that,
Although a material which does not dissolve the vulcanized fluororubber molded article is used, it is desirable that the vulcanized fluororubber molded article swells to some extent so as to penetrate the surface of the molded article by about several tens of μm. In practice, acetone, methyl ethyl ketone, methanol, ethanol, toluene, tetrahydrofuran, etc. are used so as to form a solution concentration according to the degree of treatment.
表面処理は、多官能性不飽和化合物ラジカルとポリマー
ラジカルとの共架橋によるものと考えられるので、多官
能性不飽和化合物（溶液）中に有機過酸化物を溶解させ
ておき、不活性ガス雰囲気中で多官能性不飽和化合物付
着加硫フッ素ゴム成形品を、有機過酸化物が分解し、ラ
ジカルを発生させる温度に加熱することによって行われ
る。The surface treatment is considered to be due to the co-crosslinking of the polyfunctional unsaturated compound radical and the polymer radical. Therefore, the organic peroxide is dissolved in the polyfunctional unsaturated compound (solution) and the inert gas atmosphere is set. Among them, the polyfunctional unsaturated compound-adhered vulcanized fluororubber molded article is heated to a temperature at which organic peroxide decomposes to generate radicals.
有機過酸化物としては、例えばベンゾイルパーオキシ
ド、2,4−ジクロロベンゾイルパーオキシド、1,1−ジ
（第３ブチルパーオキシ）−3,3,5−トリメチルシクロ
ヘキサン、ｎ−ブチル−4,4−ビス（第３ブチルパーオ
キシ）バレレート、ジクミルパーオキシド、ジ第３ブチ
ルパーオキシジイソプロピルベンゼン、2,5−ジメチル
−2,5−ジ（第３ブチルパーオキシ）ヘキサン、2,5−ジ
メチル−2,5−ジ（第３ブチルパーオキシ）ヘキシン−
３などが用いられる。Examples of the organic peroxide include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di (tertiary butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4. -Bis (tertiary butylperoxy) valerate, dicumyl peroxide, ditertiary butylperoxydiisopropylbenzene, 2,5-dimethyl-2,5-di (tertiary butylperoxy) hexane, 2,5-dimethyl -2,5-Di (tertiary butylperoxy) hexyne-
3 or the like is used.
〔作用〕および〔発明の効果〕 多官能性不飽和化合物を用い、有機過酸化物ラジカルで
表面処理することにより、加硫フッ素ゴム成形品の表層
部分数μｍ〜数百μｍ程度が更に架橋されて高架橋密度
となり、局部的に硬化部分が形成されるものと考えられ
る。これにより、加硫フッ素ゴム成形品表面の低摩擦化
ならびに非粘着化が、成形品全体のフッ素ゴム本来の弾
性などを実質的に低下させることなく達成される。ま
た、硬化部分は、その組成が本質的に元のゴム組成に近
くしかも一体に形成されているため、単なるコーティン
グ膜とは異なり、剥離や亀裂などを生じさせない。[Function] and [Effects of the Invention] By using a polyfunctional unsaturated compound and surface-treating it with an organic peroxide radical, the surface layer portion of the vulcanized fluororubber molded product is further cross-linked in the order of several μm to several hundred μm. It is considered that a high cross-linking density results and locally hardened parts are formed. As a result, the surface of the vulcanized fluororubber molded article is reduced in friction and detackified without substantially reducing the inherent elasticity of the fluororubber molded article as a whole. In addition, since the composition of the cured part is essentially close to the original rubber composition and is integrally formed, unlike a simple coating film, peeling or cracking does not occur.
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.
加硫ゴム成形品の製造 （配合物Ａ） フッ素ゴム（ダイキン製品G801） 100重量部 MTカーボンブラック 30 2,5−ジメチル−2,5−ジ（第３ブチルパーオキシ）ヘキ
サン ２ トリアリルイソシアヌレート ４ （配合物Ｂ） EPM（日本合成ゴム製品EP11） 100 重量部 酸化亜鉛 ５ ステアリン酸 １ HAFカーボンブラック 50 ナフテン系オイル 10 ジクミルパーオキサイド 2.7 イオウ 0.3 上記各配合物について、180℃、10分間のプレス加硫お
よび200℃、24時間のオーブン加硫（配合物Ａのみ）を
行ない、100×100×2mmの加硫シートＡおよびＢを作製
した。Manufacture of vulcanized rubber molded products (Compound A) Fluororubber (Daikin product G801) 100 parts by weight MT carbon black 30 2,5-dimethyl-2,5-di (tertiary butylperoxy) hexane 2 triallyl isocyanurate 4 (Compound B) EPM (Japan Synthetic Rubber Product EP11) 100 parts by weight Zinc oxide 5 Stearic acid 1 HAF carbon black 50 Naphthene oil 10 Dicumyl peroxide 2.7 Sulfur 0.3 Press vulcanization and oven vulcanization at 200 ° C. for 24 hours (compound A only) were carried out to produce vulcanized sheets A and B of 100 × 100 × 2 mm.
実施例１〜２ 加硫シートＡ（実施例１）または加硫シートＢ（実施例
２）を、トリアリルイソシアヌレート−ベンゾイルパー
オキサイド（重量比2:1）混合物の50％アセトン溶液中
に10分間浸漬後引き上げ、室温に２時間放置した後、窒
素雰囲気下で180℃、２時間の加熱を行った。Examples 1-2 Vulcanized sheet A (Example 1) or vulcanized sheet B (Example 2) was added 10% in a 50% acetone solution of a triallyl isocyanurate-benzoyl peroxide (weight ratio 2: 1) mixture. After soaking for 1 minute, it was pulled up, left at room temperature for 2 hours, and then heated at 180 ° C. for 2 hours in a nitrogen atmosphere.
以上の各実施例で電子線照射処理された加硫シートにつ
いて、次の方法によりシート表面の動摩擦係数および粘
着力を測定した。また、加硫シートについて、180゜折
り曲げによるクラック発生の有無を観察した。得られた
結果は、後記表に示される。With respect to the vulcanized sheet subjected to the electron beam irradiation treatment in each of the above examples, the dynamic friction coefficient and the adhesive force of the sheet surface were measured by the following methods. In addition, the vulcanized sheet was observed for cracks due to 180 ° bending. The results obtained are shown in the table below.
動摩擦係数：クロムメッキされた球（直径2mm）と同じ
曲率を有する接触子に50gfの荷重をかけ、50mm/分の速
度で加硫シートを水平に移動させたときの値を測定 粘着力：直径16mmの円板状に加工した加硫シート（面積
2cm2）に4Kgf（2Kgf/cm2）の荷重を加え、125℃で15時
間6,6−ナイロン樹脂板に接触静置し、室温に戻した
後、それを引き離すのに要する力を測定 比較例１ 前記加硫シートＡについて、同様の測定を行った。Dynamic friction coefficient: A value of 50gf is applied to a contactor having the same curvature as a chrome-plated sphere (diameter 2mm), and the value is measured when the vulcanized sheet is moved horizontally at a speed of 50mm / min. Adhesion: Diameter Vulcanized sheet processed into a 16 mm disk shape (area
2cm 2 ) with a load of 4Kgf (2Kgf / cm 2 ), contact with the 6,6-nylon resin plate for 15 hours at 125 ° C, leave it at room temperature, and then measure the force required to pull it apart. Example 1 The same measurement was performed on the vulcanized sheet A.
比較例２ 前記加硫シートＢについて、同様の測定を行った。Comparative Example 2 The same measurement was performed on the vulcanized sheet B.
以上の各比較例での測定結果も、後記表に併記される。The measurement results in each of the above comparative examples are also shown in the table below.
表 例 動摩擦係数 粘着力（kgf/cm2） 実施例１ 0.4 2.2 〃 ２ 0.4 1.8 比較例１ 0.5 ＞５ 〃 ２ 0.5 ＞５ 以上の各実施例および比較例共、180゜折り曲げによる
クラックの発生はみられなかった。Table Example coefficient of dynamic friction adhesion (kgf / cm 2) Example 1 0.4 2.2 〃 2 0.4 1.8 Comparative Example 1 0.5> 5 〃 2 0.5> 5 above Examples and Comparative Examples both the occurrence of cracks due to bending 180 ° I couldn't see it.
Claims (1)
酸化物を付着させた加硫フッ素ゴム成形品を該有機過酸
化物分解温度に加熱することを特徴とする加硫ゴム成形
品の表面処理方法。1. A vulcanized rubber molded article, characterized in that a vulcanized fluororubber molded article having a polyfunctional unsaturated compound and an organic peroxide adhered to its surface is heated to the decomposition temperature of the organic peroxide. Surface treatment method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063108A JPH07103258B2 (en) | 1988-03-18 | 1988-03-18 | Surface treatment method for vulcanized rubber moldings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063108A JPH07103258B2 (en) | 1988-03-18 | 1988-03-18 | Surface treatment method for vulcanized rubber moldings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01240536A JPH01240536A (en) | 1989-09-26 |
| JPH07103258B2 true JPH07103258B2 (en) | 1995-11-08 |
Family
ID=13219765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63063108A Expired - Lifetime JPH07103258B2 (en) | 1988-03-18 | 1988-03-18 | Surface treatment method for vulcanized rubber moldings |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07103258B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998030622A1 (en) * | 1997-01-10 | 1998-07-16 | Nippon Valqua Industries, Ltd. | Process for producing surface-modified rubber, surface-modified rubber, and sealing material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3979845B2 (en) * | 2001-12-28 | 2007-09-19 | 日本バルカー工業株式会社 | Method for producing surface-modified fluororubber, obtained surface-modified fluororubber and use thereof |
| JP6181710B2 (en) * | 2015-06-19 | 2017-08-16 | 住友ゴム工業株式会社 | Catheter manufacturing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5029866B2 (en) * | 1972-05-09 | 1975-09-26 | ||
| JPS5247868A (en) * | 1975-10-16 | 1977-04-16 | Mitsubishi Petrochemical Co | Method of coating of polyolefine molded product |
| JPS5959728A (en) * | 1982-09-30 | 1984-04-05 | Nitto Electric Ind Co Ltd | Surface modification of plastic film or sheet |
| JPS59224330A (en) * | 1983-06-03 | 1984-12-17 | Sumitomo Chem Co Ltd | Improvement of oil resistance and organic solvent resistance of rubber product |
-
1988
- 1988-03-18 JP JP63063108A patent/JPH07103258B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998030622A1 (en) * | 1997-01-10 | 1998-07-16 | Nippon Valqua Industries, Ltd. | Process for producing surface-modified rubber, surface-modified rubber, and sealing material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01240536A (en) | 1989-09-26 |
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