JPH1087863A - Surface treating solution for fluororubber vulcanizate and method for surface-treating fluororubber therewith - Google Patents
Surface treating solution for fluororubber vulcanizate and method for surface-treating fluororubber therewithInfo
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- JPH1087863A JPH1087863A JP26028296A JP26028296A JPH1087863A JP H1087863 A JPH1087863 A JP H1087863A JP 26028296 A JP26028296 A JP 26028296A JP 26028296 A JP26028296 A JP 26028296A JP H1087863 A JPH1087863 A JP H1087863A
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- Prior art keywords
- fluororubber
- vulcanizate
- surface treatment
- treatment liquid
- weight
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フッ素ゴム加硫物
の表面処理液およびそれを用いた表面処理方法に関し、
特に、表面の粘着性を低下させる処理に用いられる表面
処理液およびそれを用いた表面処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment solution for vulcanized fluororubber and a surface treatment method using the same.
In particular, the present invention relates to a surface treatment liquid used for a treatment for reducing surface tackiness and a surface treatment method using the same.
【０００２】[0002]
【従来の技術】フッ素ゴム加硫物は、優れたゴム弾性に
加えて、耐熱性、耐油性および耐オゾン性にも優れてお
り、バルブ、パッキン、シーリング材として幅広く用い
られている。そして、これらのものは、シール性を保持
するために用いられることが多く、通常、金属やプラス
チックと接触する状態で用いられる。2. Description of the Related Art In addition to excellent rubber elasticity, fluororubber vulcanizates have excellent heat resistance, oil resistance and ozone resistance, and are widely used as valves, packings and sealing materials. These materials are often used to maintain sealing properties, and are usually used in a state of contact with metal or plastic.
【０００３】しかしながら、フッ素ゴム加硫物は、その
表面が粘着性を有するが故に、金属やプラスチックと接
触した状態が長時間に亘ると、フッ素ゴム加硫物と金属
等が互いに接着してしまい、例えば、開閉バルブの弁と
して用いた場合、開閉バルブとしての本来の開閉機能が
正常に作用しないとか、またパッキンとして用いた場合
に、定期的に行われる交換作業が困難となるといった問
題を有していた。[0003] However, since the surface of the vulcanized fluororubber has tackiness, if the state of contact with metal or plastic is prolonged, the vulcanized fluororubber and metal or the like will adhere to each other. For example, when used as a valve of an opening / closing valve, there is a problem that the original opening / closing function as the opening / closing valve does not work properly, and when used as a packing, it is difficult to perform a regular replacement work. Was.
【０００４】このような問題を解決するために、特公平
６−１５６３２号公報には、含ハロゲンゴム加硫物の表
面に、トリアジンチオール、アルカリ及びオニウム塩を
含有する溶液を付着させて表面処理する方法が提案され
ている。この提案によれば、ゴム加硫物の表面層の分子
網目鎖濃度を高めて固着強度を減少させ、非粘着性およ
び低摩擦性を付与することができ上記の問題が解決でき
るとされている。[0004] In order to solve such a problem, Japanese Patent Publication No. 6-15632 discloses a surface treatment by adhering a solution containing a triazine thiol, an alkali and an onium salt to the surface of a halogenated rubber vulcanizate. A way to do that has been proposed. According to this proposal, it is said that the molecular network chain concentration of the surface layer of the rubber vulcanizate can be increased to reduce the fixing strength, to impart non-adhesiveness and low frictional properties, and to solve the above problem. .
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
提案では、ゴム表面の粘着性の低下はある程度期待でき
るものの、より確実に上記の問題を解決するために、さ
らなるゴム表面の粘着性の低下が要望されている。However, in the above proposal, although a decrease in the adhesiveness of the rubber surface can be expected to some extent, in order to solve the above problem more reliably, the adhesiveness of the rubber surface must be further reduced. Requested.
【０００６】このような実状のもとに本発明は創案され
たものであって、その目的は、従来技術よりさらにゴム
表面の粘着性の低下を可能ならしめるフッ素ゴム加硫物
の表面処理液およびそれを用いた表面処理方法を提供す
ることにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a surface treatment solution for a vulcanized fluororubber which can further reduce the tackiness of the rubber surface compared to the prior art. And a surface treatment method using the same.
【０００７】[0007]
【課題を解決するための手段】上記の課題を解決するた
めに、本願に係る発明者らが、特に、ゴム表面の架橋密
度を高くするために用いる架橋剤に注目して鋭意研究し
た結果、架橋剤としてジチオール化合物を用いることに
より、従来よりましてゴム表面の粘着性の低下が実現で
きるということを見いだし本発明に想到したのである。
すなわち、本発明は、フッ素ゴム加硫物の表面に付着さ
せ粘着性を低下させるために用いられる処理液であっ
て、当該処理液は、溶媒中に、架橋剤と、アルカリと、
オニウム塩を含有してなり、前記架橋剤がジチオール化
合物であるように構成される。Means for Solving the Problems In order to solve the above problems, the inventors of the present application have conducted intensive studies, particularly focusing on a crosslinking agent used for increasing the crosslinking density on the rubber surface. The present inventors have found that the use of a dithiol compound as a cross-linking agent makes it possible to reduce the adhesiveness of the rubber surface more than in the past, and conceived the present invention.
That is, the present invention is a treatment liquid used to reduce the adhesion by adhering to the surface of a fluororubber vulcanizate, the treatment liquid is a solvent, a crosslinking agent, and an alkali,
An onium salt is contained, and the crosslinking agent is a dithiol compound.
【０００８】好ましい態様として、前記ジチオール化合
物が下記式（１）の構造式で示されるように構成され
る。In a preferred embodiment, the dithiol compound is constituted as shown by the following structural formula (1).
【０００９】[0009]
【化２】 式（１）中、Ｒ1 ，Ｒ2 ，Ｒ3 ，およびＲ4 は、それぞ
れ、水素または炭素数１〜８のアルキル基を示し、これ
らはそれぞれ同一でも異なっていてもよい。Embedded image In the formula (1), R 1 , R 2 , R 3 , and R 4 each represent hydrogen or an alkyl group having 1 to 8 carbon atoms, which may be the same or different.
【００１０】好ましい態様として、前記溶媒がグリコー
ル類であるように構成される。In a preferred embodiment, the solvent is a glycol.
【００１１】好ましい態様として、前記溶媒１００重量
部に対して、架橋剤の含有量が、０．０５〜１０．０重
量部、アルカリの含有量が、０．０１〜５．０重量部、
オニウム塩の含有量が０．１〜３０．０重量部であるよ
うに構成される。In a preferred embodiment, the content of the crosslinking agent is 0.05 to 10.0 parts by weight, and the content of the alkali is 0.01 to 5.0 parts by weight, based on 100 parts by weight of the solvent.
The onium salt content is 0.1 to 30.0 parts by weight.
【００１２】また、本発明のフッ素ゴム加硫物の表面処
理方法は、上記の表面処理液を、被処理物であるフッ素
ゴム加硫物の表面に付着させた後、熱処理することによ
って構成される。Further, the method for surface treating a vulcanized fluororubber of the present invention is constituted by adhering the above-mentioned surface treatment liquid to the surface of a vulcanized fluororubber to be treated, followed by heat treatment. You.
【００１３】さらに、本発明のフッ素ゴム加硫物の表面
処理方法は、前記熱処理の後、洗浄し、しかる後、再熱
処理するように構成される。Further, the surface treatment method for a fluororubber vulcanizate of the present invention is configured so that after the above-mentioned heat treatment, cleaning is performed, and then re-heat treatment is performed.
【００１４】[0014]
【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。Embodiments of the present invention will be described below in detail.
【００１５】本発明の表面処理液は、被処理体であるフ
ッ素ゴム加硫物の表面に付着させ、表面の粘着性を低下
させるために用いられる処理液であって、この処理液
は、溶媒中に架橋剤と、アルカリと、オニウム塩とを含
有している。The surface treating solution of the present invention is a treating solution used to adhere to the surface of a vulcanizate of a fluororubber as an object to be treated and to reduce the tackiness of the surface. It contains a crosslinking agent, an alkali, and an onium salt.
【００１６】架橋剤は、ゴム表面の架橋密度を上げて低
粘着性を図るために用いられるものであって、本発明に
おいては、ジチオール化合物が用いられる。具体的に
は、下記式（１）の構造式で示されるものが好適例とし
て挙げられる。The cross-linking agent is used to increase the cross-linking density on the rubber surface to achieve low tackiness. In the present invention, a dithiol compound is used. Specifically, those represented by the structural formula of the following formula (1) are mentioned as preferred examples.
【００１７】[0017]
【化３】 上記式（１）中、Ｒ1 ，Ｒ2 ，Ｒ3 ，およびＲ4 は、そ
れぞれ、水素または炭素数１〜８のアルキル基を示す。
これらはそれぞれ同一であってもよいし異なっていても
よい。Embedded image In the above formula (1), R 1 , R 2 , R 3 and R 4 each represent hydrogen or an alkyl group having 1 to 8 carbon atoms.
These may be the same or different.
【００１８】上記式（１）において、下記構造式で示さ
れる化合物（６−メチルキノキサリン−２，３−ジチオ
カーバメイト）が具体的好適例として挙げられる。In the above formula (1), a compound represented by the following structural formula (6-methylquinoxaline-2,3-dithiocarbamate) is a specific preferred example.
【００１９】[0019]
【化４】 このような架橋剤を用いることによって、従来よりまし
てゴム表面の粘着性を低下させることができる。もちろ
ん、シール性を維持するための弾性とのバランスも非常
に良い。Embedded image By using such a cross-linking agent, the tackiness of the rubber surface can be reduced more than before. Of course, the balance with the elasticity for maintaining the sealing property is also very good.
【００２０】このような架橋剤の含有量は、溶媒１００
重量部に対して、０．０５〜１０．０重量部、好ましく
は０．２〜３．０重量部とされる。この含有量が多くな
り過ぎると、反応過剰となり表面が過度に硬化してしま
いシール性が低下するという不都合が生じ、また含有量
が少な過ぎると、反応が不十分となり満足のいく低粘着
効果が得られないという不都合が生じる。[0020] The content of such a crosslinking agent is 100
It is 0.05 to 10.0 parts by weight, preferably 0.2 to 3.0 parts by weight, based on parts by weight. If this content is too large, the reaction will be excessive and the surface will be hardened excessively, resulting in a problem that the sealing property will be reduced.If the content is too small, the reaction will be insufficient and a satisfactory low tack effect will be obtained. The disadvantage that it cannot be obtained occurs.
【００２１】溶媒としては、例えば、水；エタノールや
イソプロパノールなどのアルコール；エチレングリコー
ルやジエチレングリコール、トリエチレングリコール等
のポリエチレングリコール、プロピレングリコールやジ
プロピレングリコール、トリプロピレングリコール等の
ポリプロピレングリコールなどのグリコール類が用いら
れる。これらの中でも、エチレングリコール、ジエチレ
ングリコール、プロピレングリコール、ジプロピレング
リコールなどのグリコール類を用いるのが特に好まし
い。グリコール類を用いることによって、ゴム表面の粘
着性の低下はもちろんのこと、表面処理条件に多少の変
動が生じたとしても、処理後得られる粘着性を示す物性
値のバラツキが少なくなり、その点で処理条件の設定が
極めて容易となり、安定した処理が行われ、処理後の製
品歩留も良好となる。Examples of the solvent include water; alcohols such as ethanol and isopropanol; polyethylene glycols such as ethylene glycol, diethylene glycol and triethylene glycol; and glycols such as polypropylene glycol such as propylene glycol, dipropylene glycol and tripropylene glycol. Used. Among these, it is particularly preferable to use glycols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. The use of glycols not only reduces the tackiness of the rubber surface, but also reduces the variation in physical properties indicating the tackiness obtained after the treatment, even if the surface treatment conditions slightly fluctuate. This makes it very easy to set processing conditions, performs stable processing, and improves the product yield after processing.
【００２２】アルカリは上記架橋剤とのアルカリ塩を形
成し、後述するオニウム塩との反応を促進させるために
含有される。アルカリの好適例としては、ＮａＯＨ、Ｌ
ｉＯＨ、ＫＯＨ等が挙げられる。The alkali is contained to form an alkali salt with the above-mentioned cross-linking agent and to promote a reaction with an onium salt described later. Preferred examples of the alkali include NaOH, L
iOH, KOH and the like.
【００２３】このようなアルカリの含有量は、前記溶媒
１００重量部に対して、０．０１〜５．０重量部、好ま
しくは０．１〜１．０重量部とされる。この含有量が多
くなり過ぎると、反応過剰となり表面が過度に硬化して
しまいシール性が低下するという不都合が生じ、また含
有量が少な過ぎると、反応が不十分となり、満足のいく
低粘着効果が得られないという不都合が生じる。The content of such an alkali is 0.01 to 5.0 parts by weight, preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the solvent. If this content is too large, the reaction will be excessive and the surface will be hardened excessively, resulting in a problem that the sealing property will be reduced.If the content is too small, the reaction will be insufficient and a satisfactory low tack effect will be obtained. Is not obtained.
【００２４】オニウム塩は、上記の架橋剤とフッ素ゴム
加硫物の反応を促進させるために添加され、具体的には
テトラブチルアンモニウムブロミド、トリブチルベンジ
ルアンモニウムクロリド、トリメチルベンジルアンモニ
ウムフロウライド、テトラブチルスルホニウムブロミ
ド、トリフェニルブチルホスホニウムアイオダイド、ト
リブチルベンジルホスホニウムブロミド等が挙げられ
る。The onium salt is added to promote the reaction between the above crosslinking agent and the vulcanized fluororubber, and specifically, tetrabutylammonium bromide, tributylbenzylammonium chloride, trimethylbenzylammonium fluoride, tetrabutylsulfonium Bromide, triphenylbutylphosphonium iodide, tributylbenzylphosphonium bromide and the like.
【００２５】このようなオニウム塩の含有量は、前記溶
媒１００重量部に対して、０．１〜３０．０重量部、好
ましくは０．５〜５．０重量部とされる。この含有量が
多くなり過ぎると、反応過剰となり表面が過度に硬化し
てしまいシール性が低下するという不都合が生じ、また
含有量が少な過ぎると、反応が不十分となり、満足のい
く低粘着効果が得られないという不都合が生じる。The content of such an onium salt is 0.1 to 30.0 parts by weight, preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of the solvent. If this content is too large, the reaction will be excessive and the surface will be hardened excessively, resulting in a problem that the sealing property will be reduced.If the content is too small, the reaction will be insufficient and a satisfactory low tack effect will be obtained. Is not obtained.
【００２６】本発明の表面処理液で処理される被処理体
であるフッ素ゴムとしては、例えば、フッ化ビニリデン
−六フッ化プロピレン共重合体、フッ化ビニリデン−六
フッ化プロピレン−四フッ化エチレン三元共重合体、フ
ッ化ビニリデン−四フッ化エチレン−パーフルオロビニ
ルメチルエーテル三元共重合体等が挙げられる。The fluororubber to be treated with the surface treating solution of the present invention includes, for example, vinylidene fluoride-propylene hexafluoride copolymer, vinylidene fluoride-propylene hexafluoride-tetrafluoroethylene. Ternary copolymers, vinylidene fluoride-ethylene tetrafluoride-perfluorovinyl methyl ether terpolymers and the like can be mentioned.
【００２７】上記のフッ素ゴム加硫物は、公知の一般的
な種々の方法によって製造される。すなわち、加硫剤、
有機ないし金属の促進剤、安定剤、可塑剤等を添加して
一般的な加硫条件で加硫することによってフッ素ゴム加
硫物を得ることができる。さらに添加剤として、カーボ
ンブラック、シリカ等の充填剤を含有させてもよい。The fluororubber vulcanizates described above are produced by various known general methods. That is, vulcanizing agents,
A vulcanized fluororubber can be obtained by adding an organic or metal accelerator, a stabilizer, a plasticizer, and the like and vulcanizing under general vulcanizing conditions. Further, fillers such as carbon black and silica may be contained as additives.
【００２８】次いで、上記の表面処理液を用いたフッ素
ゴム加硫物の表面処理方法について説明する。Next, a method for surface treating a vulcanized fluororubber using the above surface treating solution will be described.
【００２９】まず最初に、上記の表面処理液を、被処理
体であるフッ素ゴム加硫物の表面に付着させる。付着に
際しては、表面処理液の溶液中にフッ素ゴム加硫物表面
を浸漬させたり（浸漬法）、フッ素ゴム加硫物の表面に
表面処理液を吹き付けたり（吹き付け法）、フッ素ゴム
加硫物の表面（一部分または全部）に表面処理液を塗布
したりする方法（塗布法）等が挙げられ、これらは、フ
ッ素ゴム加硫物の用途によって適宜選定すればよい。First, the above surface treatment liquid is adhered to the surface of a fluororubber vulcanizate which is an object to be treated. When adhering, the surface of the fluororubber vulcanizate is immersed in a solution of the surface treatment liquid (immersion method), or the surface treatment liquid is sprayed on the surface of the fluororubber vulcanizate (spraying method). Or a method (coating method) of applying a surface treatment liquid to the surface (partially or entirely), and these may be appropriately selected depending on the use of the fluororubber vulcanizate.
【００３０】このように表面処理液を付着処理されたフ
ッ素ゴム加硫物は、その後、熱処理される。熱処理条件
は、温度２０〜１５０℃程度、処理時間５〜２４０分程
度とされる。浸漬法により付着処理が行われた場合に
は、通常さらに、未反応物を除去するために水またはア
ルコールで洗浄が行われ、しかる後、もう一度、温度８
０〜２６０℃程度、処理時間０．５〜２４時間程度の条
件で再熱処理され、処理が完了する。また、塗布法によ
り付着処理が行われた場合には、通常、最初の熱処理が
行われた後、水またはアルコールで洗浄が行われ、しか
る後乾燥して処理が完了する。The fluororubber vulcanizate to which the surface treatment liquid has been adhered in this way is then subjected to a heat treatment. The heat treatment conditions are a temperature of about 20 to 150 ° C. and a processing time of about 5 to 240 minutes. When the adhesion treatment is performed by the immersion method, washing is usually further performed with water or alcohol to remove unreacted substances, and thereafter, once again at a temperature of 8 ° C.
The heat treatment is performed again under the conditions of about 0 to 260 ° C and the processing time of about 0.5 to 24 hours, and the processing is completed. In addition, when the adhesion treatment is performed by a coating method, usually, after the first heat treatment is performed, washing is performed with water or alcohol, and then the treatment is completed by drying.
【００３１】[0031]
【実施例】以下、具体的実施例を挙げて本発明をさらに
詳細に説明する。The present invention will be described below in further detail with reference to specific examples.
【００３２】（実施例１）まず最初に、下記に示す要領
でフッ素ゴム加硫物およびゴム加硫物の表面処理液を、
それぞれ作製し、準備した。(Example 1) First, a fluororubber vulcanizate and a surface treatment liquid of a rubber vulcanizate were treated in the following manner.
Each was prepared and prepared.
【００３３】フッ素ゴム加硫物の作製 フッ化ビニリデン−六フッ化プロピレン−四フッ化エチ
レン三元共重合体（ダイエルＧ−５０１、ダイキン工業
（株）社製）１００重量部、酸化マグネシウム（キョー
ワマグ＃３０、協和化学工業（株）社製）１５重量部、
カーボンブラック（サーマックスＭＴ、Cancarb 社製）
１０重量部からなるマスターバッチに、加硫剤（Ｖ−
１：ヘキサメチレンジアミンカルバメート、ダイキン工
業（株）社製）０．８重量部を加えて混合し、これを１
５０℃、１０分間熱加硫してフッ素ゴム加硫物を得た。Preparation of fluorinated rubber vulcanizate 100 parts by weight of vinylidene fluoride-propylene hexafluoride-ethylene tetrafluoride terpolymer (Daiel G-501, manufactured by Daikin Industries, Ltd.), magnesium oxide (Kyowa Mag) # 30, manufactured by Kyowa Chemical Industry Co., Ltd.) 15 parts by weight,
Carbon black (Thermax MT, manufactured by Cancarb)
A master batch consisting of 10 parts by weight is mixed with a vulcanizing agent (V-
0.8 part by weight (1: hexamethylene diamine carbamate, manufactured by Daikin Industries, Ltd.) was added and mixed.
The composition was thermally cured at 50 ° C. for 10 minutes to obtain a vulcanized fluororubber.
【００３４】表面処理液の作製 ジエチレングリコール１０００ｇに、下記構造式で示さ
れるジチオール化合物（商品名：ダイソネットＸＬ−２
１，ダイソー（株）社製）を６ｇ、ＮａＯＨを２ｇ、テ
トラブチルアンモニウムブロミドを１３ｇ、それぞれ加
えて、１００℃で４時間攪拌し、表面処理液を作製し
た。Preparation of Surface Treatment Solution To 1000 g of diethylene glycol was added a dithiol compound represented by the following structural formula (trade name: Daisonet XL-2).
6g, 1, 2 g of NaOH and 13 g of tetrabutylammonium bromide were added, and the mixture was stirred at 100 ° C for 4 hours to prepare a surface treatment liquid.
【００３５】[0035]
【化５】 具体的表面処理操作に基づくサンプルの作製 上記の表面処理液に上記のフッ素ゴム加硫物を１３０℃
で６０分間浸漬させ（熱処理）、その後、フッ素ゴム加
硫物の表面をメタノール水溶液で洗浄し、乾燥させ、し
かる後、２００℃、４時間の再熱処理を施し、実施例１
のサンプルを作製した。Embedded image Preparation of Sample Based on Specific Surface Treatment Operation The above fluororubber vulcanizate was added to the above surface treatment solution at 130 ° C.
(Heat treatment) for 60 minutes, and then the surface of the vulcanized fluororubber was washed with an aqueous methanol solution and dried, and then subjected to a reheat treatment at 200 ° C. for 4 hours.
Was prepared.
【００３６】このようにして作製した実施例１のサンプ
ルについて下記の要領でゴム表面の粘着性試験を行い、
粘着力（固着力）を求めた。The thus prepared sample of Example 1 was subjected to an adhesion test on the rubber surface in the following manner.
The adhesive strength (adhesive strength) was determined.
【００３７】（ゴム表面の粘着性試験）表面処理したフ
ッ素ゴム加硫物を接触面積約１ｃｍ2 のドーナツ状に加
工して、ＰＢＴ（ポリブチレンテレフタレート）板と接
触させ、１ｋｇの荷重をかけて、温度６０℃、湿度８０
％の雰囲気下で７２時間放置した。その後、ストログラ
フ（（株）東洋精機製作所社製、Ｗ２−Ｃ型）を用いて
固着強度を測定し、粘着力の測定試験とした。(Tackiness test on rubber surface) The vulcanizate of surface-treated fluororubber was processed into a donut shape having a contact area of about 1 cm 2 , contacted with a PBT (polybutylene terephthalate) plate, and applied with a load of 1 kg. , Temperature 60 ° C, humidity 80
% Atmosphere for 72 hours. Thereafter, the adhesion strength was measured using a strograph (W2-C type, manufactured by Toyo Seiki Seisaku-sho, Ltd.), and a measurement test of the adhesive strength was performed.
【００３８】上記の手法を用いて得られた粘着力（固着
力）の平均値は、２７６ｇ／ｃｍ2であった。また、各
サンプルは程好いゴム弾性を有しており、表面の粘着を
防止するための表面硬化と、シール性を維持するための
弾性とのバランスが非常に良いものとなっていることが
確認できた。The average value of the adhesive force (adhesive force) obtained using the above method was 276 g / cm 2 . In addition, each sample has moderate rubber elasticity, confirming that the balance between surface hardening to prevent sticking of the surface and elasticity to maintain sealing properties is very good. did it.
【００３９】（比較例１）上記実施例１の表面処理液中
の架橋剤を、６−ジブチルアミノ−１，３，５−トリア
ジン−２，４−ジチオール（トリアジン化合物）に変え
た。それ以外は、上記実施例１と同様にして、比較例１
サンプルを作製した。その後、上記実施例１と同様な手
法で比較例１サンプルの評価を行った。その結果、得ら
れた粘着力（固着力）の平均値は、４７７ｇ／ｃｍ2 で
あり、上記実施例１と比べて、約２０１ｇ／ｃｍ2 ほど
粘着力は高い値を示した。Comparative Example 1 The cross-linking agent in the surface treating solution of Example 1 was changed to 6-dibutylamino-1,3,5-triazine-2,4-dithiol (triazine compound). Except for this, Comparative Example 1 was performed in the same manner as in Example 1 above.
A sample was prepared. Thereafter, the sample of Comparative Example 1 was evaluated in the same manner as in Example 1 described above. As a result, the average value of the obtained pressure-sensitive adhesive force (anchoring force) is 477 g / cm 2, as compared with Example 1, adhesive strength approximately 201g / cm 2 showed a high value.
【００４０】（実施例２）上記実施例１の表面処理液中
の溶媒であるジエチレングリコールを水に変え、浸漬温
度を１００℃とした。それ以外は、上記実施例１と同様
にして実験を行った。(Example 2) Diethylene glycol as a solvent in the surface treatment solution of Example 1 was changed to water, and the immersion temperature was set to 100 ° C. Other than that, the experiment was performed in the same manner as in Example 1.
【００４１】その結果、得られた粘着力（固着力）の平
均値は、約零ｇ／ｃｍ2 であり、極めて低い粘着力を示
していたが、表面硬化が著しく進んでおり、表面に亀裂
を生じていることが確認された。なお、温度、時間等の
処理条件を種々変えていくと上記実施例１の結果に近い
物性のものが得られることが確認できたが、このものは
処理条件の変動に極めて敏感であり、処理の安定性とい
う面を考慮に入れると溶媒として水よりもグリコール類
を用いることが望ましいことがわかった。As a result, the average value of the obtained adhesive force (adhesive force) was about 0 g / cm 2 , indicating an extremely low adhesive force, but the surface hardening was remarkably advanced, and the surface had cracks. Was confirmed. In addition, it was confirmed that when the processing conditions such as temperature and time were variously changed, physical properties close to the results of Example 1 were obtained. However, this was extremely sensitive to the fluctuation of the processing conditions. In view of the stability of the compound, it was found that it is desirable to use glycols rather than water as the solvent.
【００４２】[0042]
【発明の効果】以上の結果より、本発明の効果は明らか
である。すなわち、本発明のフッ素ゴム加硫物の表面処
理液は、溶媒中にジチオール化合物からなる架橋剤と、
アルカリと、オニウム塩を含有させるように構成してい
るので、従来技術よりさらにゴム表面の粘着性の低下を
可能にすることができた。もちろん、程好いゴム弾性を
も有しており、表面の粘着を防止するための表面硬化
と、シール性を維持するための弾性とのバランスも非常
に良い。The effects of the present invention are apparent from the above results. That is, the surface treatment liquid of the vulcanized fluororubber of the present invention is a cross-linking agent comprising a dithiol compound in a solvent,
Since the composition is configured to contain an alkali and an onium salt, it is possible to further reduce the tackiness of the rubber surface as compared with the prior art. Of course, the rubber has moderate rubber elasticity, and the balance between surface hardening for preventing surface adhesion and elasticity for maintaining sealing properties is very good.
Claims (6)
性を低下させるために用いられる処理液であって、 当該処理液は、溶媒中に、架橋剤と、アルカリと、オニ
ウム塩を含有してなり、 前記架橋剤がジチオール化合物であることを特徴とする
フッ素ゴム加硫物の表面処理液。Claims: 1. A treatment liquid used for reducing the adhesion by adhering to the surface of a vulcanized fluororubber, wherein the treatment liquid contains a crosslinking agent, an alkali, and an onium salt in a solvent. Wherein the cross-linking agent is a dithiol compound.
構造式で示される請求項１記載のフッ素ゴム加硫物の表
面処理液。 【化１】 式（１）中、Ｒ1 ，Ｒ2 ，Ｒ3 ，およびＲ4 は、それぞ
れ、水素または炭素数１〜８のアルキル基を示し、これ
らはそれぞれ同一でも異なっていてもよい。2. The surface treatment liquid for a vulcanized fluororubber according to claim 1, wherein the dithiol compound is represented by the following structural formula (1). Embedded image In the formula (1), R 1 , R 2 , R 3 , and R 4 each represent hydrogen or an alkyl group having 1 to 8 carbon atoms, which may be the same or different.
または請求項２に記載のフッ素ゴム加硫物の表面処理
液。3. The solvent according to claim 1, wherein the solvent is a glycol.
Or the surface treatment liquid of the fluororubber vulcanizate according to claim 2.
含有量が、０．０５〜１０．０重量部、アルカリの含有
量が、０．０１〜５．０重量部、オニウム塩の含有量
が，０．１〜３０．０重量部である請求項１ないし請求
項３のいずれかに記載のフッ素ゴム加硫物の表面処理
液。4. A method according to claim 1, wherein the content of the crosslinking agent is 0.05 to 10.0 parts by weight, the content of the alkali is 0.01 to 5.0 parts by weight, and the amount of the onium salt is 100 parts by weight of the solvent. The surface treatment liquid for a vulcanized fluororubber product according to any one of claims 1 to 3, wherein the content is 0.1 to 30.0 parts by weight.
に記載の表面処理液を、被処理物であるフッ素ゴム加硫
物の表面に付着させた後、熱処理することを特徴とする
フッ素ゴム加硫物の表面処理方法。5. A fluorine-containing composition, wherein the surface treatment liquid according to claim 1 is attached to the surface of a vulcanizate of a fluororubber which is an object to be treated, and then heat-treated. Surface treatment method for rubber vulcanizates.
熱処理してなる請求項５に記載のフッ素ゴム加硫物の表
面処理方法。6. The surface treatment method for a vulcanized fluororubber according to claim 5, wherein the heat treatment is followed by washing and then reheating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26028296A JP3592000B2 (en) | 1996-09-09 | 1996-09-09 | Surface treatment liquid for vulcanized fluororubber and surface treatment method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26028296A JP3592000B2 (en) | 1996-09-09 | 1996-09-09 | Surface treatment liquid for vulcanized fluororubber and surface treatment method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1087863A true JPH1087863A (en) | 1998-04-07 |
| JP3592000B2 JP3592000B2 (en) | 2004-11-24 |
Family
ID=17345889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26028296A Expired - Fee Related JP3592000B2 (en) | 1996-09-09 | 1996-09-09 | Surface treatment liquid for vulcanized fluororubber and surface treatment method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3592000B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265476A (en) * | 2005-03-25 | 2006-10-05 | Mitsui Chemicals Inc | Polymer molded item |
| WO2013123156A1 (en) | 2012-02-15 | 2013-08-22 | 3M Innovative Properties Company | Fluoropolymer composition comprising a cross - linkable fluorinated elastomer and a ptfe of low melting point |
-
1996
- 1996-09-09 JP JP26028296A patent/JP3592000B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265476A (en) * | 2005-03-25 | 2006-10-05 | Mitsui Chemicals Inc | Polymer molded item |
| WO2013123156A1 (en) | 2012-02-15 | 2013-08-22 | 3M Innovative Properties Company | Fluoropolymer composition comprising a cross - linkable fluorinated elastomer and a ptfe of low melting point |
| US9458314B2 (en) | 2012-02-15 | 2016-10-04 | 3M Innovative Properties Company | Fluoropolymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3592000B2 (en) | 2004-11-24 |
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