JP3146647B2 - Surface treatment method for vulcanized rubber - Google Patents
Surface treatment method for vulcanized rubberInfo
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- JP3146647B2 JP3146647B2 JP18029292A JP18029292A JP3146647B2 JP 3146647 B2 JP3146647 B2 JP 3146647B2 JP 18029292 A JP18029292 A JP 18029292A JP 18029292 A JP18029292 A JP 18029292A JP 3146647 B2 JP3146647 B2 JP 3146647B2
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- Prior art keywords
- rubber
- vulcanized rubber
- gas
- surface treatment
- treatment
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、特に加硫ゴムに他材料
を接合するなどのことを目的として加硫ゴムを表面処理
する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for surface-treating vulcanized rubber for the purpose of bonding other materials to the vulcanized rubber.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】加硫ゴ
ムの表面処理は、加硫ゴムと他のゴム材料や金属、樹脂
等の他材料と接合して複合材料を製造したり、加硫ゴム
に塗装を施すための前処理などとして採用されており、
従来種々の表面処理方法が知られている。2. Description of the Related Art Surface treatment of vulcanized rubber involves bonding a vulcanized rubber to another rubber material, a metal, a resin, or another material to produce a composite material, It is used as a pre-treatment for painting rubber.
Conventionally, various surface treatment methods are known.
【０００３】例えば、加硫ゴムに接着性を付与するため
に加硫ゴムの表面を強酸、強酸化剤で強力に酸化して表
面全体に微細な亀裂を発生させる方法が知られている
が、この方法は強酸、強酸化剤の取扱いに十分な注意を
要し、また強酸、強酸化剤によって加硫ゴムの物性が著
しく損なわれ、しかも十分な接着力を与え難いという問
題点がある。[0003] For example, a method is known in which the surface of a vulcanized rubber is strongly oxidized with a strong acid or a strong oxidizing agent to impart fine cracks to the entire surface in order to impart adhesiveness to the vulcanized rubber. This method requires sufficient care in handling a strong acid and a strong oxidizing agent, and has a problem that physical properties of the vulcanized rubber are significantly impaired by the strong acid and the strong oxidizing agent, and that it is difficult to provide a sufficient adhesive force.
【０００４】また、加硫ゴムを塩素ガスにさらす塩素処
理法、擬ハロゲン化合物を用いて表面処理する方法（特
公昭５２−３６９１０号公報参照）も提案されている。
これらの方法は、いずれもゴム中の二重結合を攻撃し、
Ｃｌ基を形成して接着しやすい表面にする表面処理方法
であるが、これらの方法で加硫ゴムの表面処理を行った
場合、例えば金属や樹脂などの他材料と複合化して防振
ゴム（ＮＲ／ＳＢＲ系）を製造する際に被処理表面が樹
脂化してしまうので、接着性、耐熱性が不良になるとい
う問題点がある。また、被処理表面が黄変するという問
題点もあり、例えばこの方法を用いてバラタ材（トラン
スポリイソプレン）を主成分とする加硫ゴムからなるゴ
ルフボール本体に表面処理を施し、塗装してゴルフボー
ルを製造した場合、ゴルフボールの外観が損なわれると
いう問題点がある。更に、塩素ガスや擬ハロゲン化合物
は環境破壊を引き起こすという問題点もある。Further, a chlorination method in which vulcanized rubber is exposed to chlorine gas, and a method in which surface treatment is performed using a pseudohalogen compound (see Japanese Patent Publication No. 52-36910) have also been proposed.
All of these methods attack double bonds in rubber,
This is a surface treatment method for forming a Cl group to make the surface easy to adhere. When surface treatment of the vulcanized rubber is performed by these methods, for example, the vulcanized rubber is compounded with another material such as a metal or a resin to form a vibration-proof rubber ( When manufacturing (NR / SBR type), the surface to be processed becomes resin, and thus there is a problem that the adhesiveness and the heat resistance become poor. Further, there is also a problem that the surface to be processed is yellowed. For example, using this method, a golf ball body made of a vulcanized rubber mainly composed of a balata material (trans polyisoprene) is subjected to a surface treatment, which is then painted. When a golf ball is manufactured, there is a problem that the appearance of the golf ball is impaired. Further, there is a problem that chlorine gas and pseudohalogen compounds cause environmental destruction.
【０００５】更に別の表面処理方法として、Ｏ2やＣＦ4
とＯ2との混合ガス等のガスを用い、低圧グロープラズ
マ処理法により加硫ゴムの表面をエッチング酸化して活
性化する方法がある。しかし、低圧グロープラズマ処理
では、処理むらの少ない均一な表面処理ができるが、低
圧プラズマ処理は通常１０Ｔｏｒｒ以下の低圧において
行われるため、これを工業的に実施する場合、大型の真
空装置が必要となり、また、連続処理を行うためには、
設備費や処理コストが大きくなる。更に、減圧雰囲気中
では加硫ゴム表面からオイル、水等が放出され、このた
めプラズマ処理において目的とする性能や機能が得られ
ない場合もある。As another surface treatment method, O 2 or CF 4
There is a method in which a surface of a vulcanized rubber is activated by etching and oxidation by a low-pressure glow plasma treatment method using a gas such as a mixed gas of O 2 and O 2 . However, in the low-pressure glow plasma treatment, a uniform surface treatment with little processing unevenness can be performed. However, since the low-pressure plasma treatment is usually performed at a low pressure of 10 Torr or less, a large-scale vacuum apparatus is required when performing this industrially. In order to perform continuous processing,
Equipment costs and processing costs increase. Furthermore, in a reduced pressure atmosphere, oil, water, and the like are released from the surface of the vulcanized rubber, so that the desired performance or function may not be obtained in the plasma treatment.
【０００６】本発明は上記事情に鑑みなされたもので、
加硫ゴムの表面を簡単に表面処理することができ、かつ
加硫ゴム表面に良好な接着性を付与し、他の材料と接合
して良好な複合材料を得ることができる加硫ゴムの表面
処理方法を提供することを目的とする。The present invention has been made in view of the above circumstances,
Surface of vulcanized rubber that can easily surface-treat the surface of vulcanized rubber, imparts good adhesion to the surface of the vulcanized rubber, and joins with other materials to obtain a good composite material It is an object to provide a processing method.
【０００７】[0007]
【課題を解決するための手段及び作用】本発明者は上記
目的を達成するため鋭意検討を行った結果、酸素原子を
含むガスとハロゲン原子を含むガスを用いて加硫ゴムの
表面を大気圧プラズマ処理した場合、溶剤を用いていな
いのでクリーンな環境で簡単に表面処理を行うことがで
き、低圧グロープラズマ処理した場合などの従来法と比
較してはるかに良好な接着性表面を有する加硫ゴムを得
ることができ、また、ごく表面のみに処理が施されるた
め加硫ゴム自体の物性を損なうことがないことを知見
し、本発明をなすに至った。The present inventors have conducted intensive studies to achieve the above object, and as a result, the surface of the vulcanized rubber was subjected to atmospheric pressure using a gas containing oxygen atoms and a gas containing halogen atoms. When plasma treatment is used, surface treatment can be easily performed in a clean environment because no solvent is used, and vulcanization with a much better adhesive surface compared to conventional methods such as low pressure glow plasma treatment The present inventors have found that a rubber can be obtained, and that only the surface is treated, so that the physical properties of the vulcanized rubber itself are not impaired, and the present invention has been accomplished.
【０００８】従って、本発明は、加硫ゴムの表面を酸素
原子を含むガスとハロゲン原子を含むガスを用いて大気
圧プラズマ処理することを特徴とする加硫ゴムの表面処
理方法を提供する。Accordingly, the present invention provides a method for treating the surface of a vulcanized rubber, wherein the surface of the vulcanized rubber is subjected to an atmospheric pressure plasma treatment using a gas containing an oxygen atom and a gas containing a halogen atom.
【０００９】以下、本発明を更に詳しく説明すると、本
発明の加硫ゴムの表面処理方法は、酸素原子を含むガス
とハロゲン原子を含むガスを用いて加硫ゴムの表面を大
気圧プラズマ処理するものである。Hereinafter, the present invention will be described in more detail. In the surface treatment method for vulcanized rubber according to the present invention, the surface of the vulcanized rubber is subjected to atmospheric pressure plasma treatment using a gas containing oxygen atoms and a gas containing halogen atoms. Things.
【００１０】ここで、大気圧プラズマ法で処理される加
硫ゴムとしては、特に制限されるものではなく、ＮＲ
（天然ゴム）系、ＳＢＲ（スチレン・ブタジエンゴム）
系、ＩＲ（イソプレンゴム）系、ＮＢＲ（アクリロニト
リル・ブタジエンゴム）系、ＥＰＭ（エチレン・プロピ
レンゴム）系、ＥＰＤＭ（エチレン・プロピレン・ジエ
ンゴム）系、ＢＲ（ブタジエンゴム）系、ＩＩＲ（ブチ
ルゴム）系、ＣＲ（クロロプレンゴム）系等のいずれの
加硫ゴムにも適用することができる。また、加硫ゴムの
形状は板状、シート状、球状、筒状、柱状、ブロック状
等のいかなる形状であっても差し支えない。Here, the vulcanized rubber treated by the atmospheric pressure plasma method is not particularly limited.
(Natural rubber), SBR (Styrene-butadiene rubber)
System, IR (isoprene rubber) system, NBR (acrylonitrile butadiene rubber) system, EPM (ethylene propylene rubber) system, EPDM (ethylene propylene diene rubber) system, BR (butadiene rubber) system, IIR (butyl rubber) system, It can be applied to any vulcanized rubber such as CR (chloroprene rubber). The vulcanized rubber may have any shape such as a plate, a sheet, a sphere, a tube, a column, and a block.
【００１１】本発明に係る表面処理方法で用いる反応ガ
スのうち酸素原子を含むガスとしては、Ｏ2，Ｈ2Ｏ，Ｃ
Ｏ2等のガス、アルコール類，ケトン類，エーテル類等
の酸素含有有機物のガスなどが挙げられ、このうち特に
Ｏ2が好適に使用される。Among the reaction gases used in the surface treatment method according to the present invention, the gases containing oxygen atoms include O 2 , H 2 O, C
Gases such as O 2 , and gases of oxygen-containing organic substances such as alcohols, ketones, and ethers, and the like are mentioned. Of these, O 2 is particularly preferably used.
【００１２】また、ハロゲン原子を含むガスとしては、
Ｆ2，Ｃｌ2，Ｂｒ2，Ｉ2等の単体ガス、ＨＦ，ＨＣｌ，
ＨＢｒ，ＨＩ等のハロゲン化水素、ＣＦ4，ＣＣｌＦ3，
ＣＣｌ2Ｆ2，Ｃ2Ｆ6等のフロン、ＣＢｒＦ3等のハロ
ン、ＣＨＣｌＦ2，ＣＨＢｒＦ2，ＣＨＣｌ3，ＣＨ2Ｃｌ
2，ＣＨ3ＣＣｌ3，ＣＣｌ4等のハロゲン化炭化水素、Ｓ
Ｆ6などが挙げられる。このうち取扱いの容易性の点か
らフロン、ハロンやハロゲン化炭化水素が好適に使用さ
れ、上記酸素を含むガスとの組み合わせは、取扱いの容
易性の点から下記のものが特に好ましい。Further, as the gas containing a halogen atom,
Simple gases such as F 2 , Cl 2 , Br 2 , I 2 , HF, HCl,
Hydrogen halides such as HBr and HI, CF 4 , CCIF 3 ,
Freon such as CCl 2 F 2 , C 2 F 6 , halon such as CBrF 3 , CHClF 2 , CHBrF 2 , CHCl 3 , CH 2 Cl
Halogenated hydrocarbons such as 2 , CH 3 CCl 3 and CCl 4 , S
Such as the F 6 and the like. Of these, chlorofluorocarbon, halon, and halogenated hydrocarbons are preferably used from the viewpoint of easy handling, and the following combinations with the above-mentioned gas containing oxygen are particularly preferable from the viewpoint of easy handling.
【００１３】 Ｏ2＋ＣＣｌ2Ｆ2，Ｏ2＋ＣＣｌＦ3，Ｏ2＋ＣＨＣｌ
Ｆ2， Ｏ2＋ＣＢｒＦ3，Ｏ2＋ＣＦ4，Ｏ2＋ＣＦ4＋ＣＨＣ
ｌ3， Ｏ2＋ＣＦ4＋ＣＨ2Ｃｌ2，Ｏ2＋ＣＦ4＋ＣＣｌ4， Ｏ2＋ＣＦ4＋ＣＨ3ＣＣｌ3 O 2 + CCl 2 F 2 , O 2 + CCLF 3 , O 2 + CHCl
F 2 , O 2 + CBrF 3 , O 2 + CF 4 , O 2 + CF 4 + CHC
l 3 , O 2 + CF 4 + CH 2 Cl 2 , O 2 + CF 4 + CCl 4 , O 2 + CF 4 + CH 3 CCl 3
【００１４】なお、酸素原子とハロゲン原子とを同時に
含むガスは、その１種を単独で使用することができる。The gas containing both oxygen atoms and halogen atoms can be used alone.
【００１５】上記反応ガスを用いて表面処理を行う場
合、大気圧プラズマを安定的に得るためには、上記反応
ガスを大気圧グロー放電しやすいガスで希釈することが
好ましい。このようなガスとして具体的にはヘリウム，
アルゴン，ネオンのような不活性ガス、窒素、水素等の
汎用ガス、種々の有機物のガスなどの１種又は２種以上
のガスの混合物を用いることができる。このうち特にヘ
リウムが好ましく用いられる。In the case where the surface treatment is performed using the above-mentioned reaction gas, it is preferable to dilute the above-mentioned reaction gas with a gas which can be easily glow-discharged under atmospheric pressure in order to stably obtain an atmospheric pressure plasma. Specifically, such a gas is helium,
An inert gas such as argon or neon, a general-purpose gas such as nitrogen or hydrogen, or a mixture of one or more gases such as various organic gases can be used. Of these, helium is particularly preferably used.
【００１６】これらのガスは必ずしも常温でガス状であ
る必要はなく、供給の方法は放電領域温度や常温での状
態（固体、液体、気体）などにより、選定される。即
ち、放電領域の温度や常温においてガス状である場合
は、これをそのまま処理容器内へ流入させることがで
き、また、液状である場合は、蒸気圧が比較的高ければ
その蒸気をそのまま流入してもよいし、その液体を不活
性ガス等でバブリングして流入してもよいし、被処理物
である加硫ゴムの表面に塗布して用いることもできる。
一方、ガス状でなく、しかも蒸気圧が比較的低い場合に
は、加熱することによりガス状又は蒸気圧が高い状態に
して用いることができる。These gases do not necessarily need to be in a gaseous state at room temperature, and the method of supply is selected depending on the discharge area temperature, the state at room temperature (solid, liquid, gas) and the like. That is, if the gas is gaseous at the temperature of the discharge region or normal temperature, it can be flowed into the processing vessel as it is, and if it is liquid, the vapor flows as it is if the vapor pressure is relatively high. Alternatively, the liquid may be bubbled in with an inert gas or the like and then flowed in. Alternatively, the liquid may be applied to the surface of a vulcanized rubber which is an object to be processed and used.
On the other hand, when it is not gaseous and the vapor pressure is relatively low, it can be used in a gaseous or vapor pressure state by heating.
【００１７】本発明に係る大気圧プラズマの発生方法と
しては、大気圧付近の圧力でグロー放電を発生させ得る
方法であれば、いかなる方法も採用することができる。
電圧の印加方法は、大きく分けて直流、交流の２通りあ
るが、工業的には交流放電の方が容易である。As the method of generating the atmospheric pressure plasma according to the present invention, any method can be employed as long as it can generate a glow discharge at a pressure near the atmospheric pressure.
The method of applying a voltage can be roughly classified into two types, DC and AC. However, industrially, AC discharge is easier.
【００１８】内部電極型の交流放電を採用した場合、安
定した大気圧プラズマを容易に得るため、電極の少なく
とも一方を絶縁体で被覆することが推奨される。また、
処理室がガラス等の絶縁体からなる場合には外部電極方
式を採用することもできる。また、コイル型方式による
放電や導波管型方式による放電も可能である。なお、直
流放電の場合、電極からの直接の電子流入により直流グ
ローを形成、安定化させるため、高電圧印加側電極及び
接地側電極共に絶縁体で被覆しない方がよい。When an internal electrode type AC discharge is adopted, it is recommended to coat at least one of the electrodes with an insulator in order to easily obtain stable atmospheric pressure plasma. Also,
When the processing chamber is made of an insulator such as glass, an external electrode method can be employed. Further, a discharge by a coil type system and a discharge by a waveguide type system are also possible. In the case of a DC discharge, in order to form and stabilize a DC glow by direct inflow of electrons from the electrodes, it is better not to cover both the high voltage application side electrode and the ground side electrode with an insulator.
【００１９】本発明に係る表面処理の実施に用いる製造
装置例を説明すると、例えば図１に示すような装置が挙
げられる。即ち、この装置はプラズマ放電領域が形成さ
れる処理室１内に被処理物２を収容し、この処理室１内
に酸素原子を含むガスとハロゲン原子を含むガス及びこ
のガスを希釈するためのガスをガス供給管３から供給す
ると共に、電極４，４にプラズマ放電領域を形成するこ
とにより表面処理を行うものである。なお、上記電極
４，４は絶縁体で被覆され、互いに所定間隔離間して対
向配置され、一方の電極４には交流電源５が接続されて
いると共に、他方の電極４は接地されており、これら電
極４，４間に被処理物２（加硫ゴム）が配置されて表面
処理が行われるものである。なお、６はガス排出管（排
気系）である。An example of a manufacturing apparatus used for carrying out the surface treatment according to the present invention will be described. For example, an apparatus as shown in FIG. In other words, this apparatus accommodates a workpiece 2 in a processing chamber 1 in which a plasma discharge region is formed, and a gas for containing an oxygen atom, a gas containing a halogen atom, and a gas for diluting the gas in the processing chamber 1. A gas is supplied from the gas supply pipe 3 and a surface treatment is performed by forming a plasma discharge region on the electrodes 4 and 4. Note that the electrodes 4 and 4 are covered with an insulator, and are arranged facing each other with a predetermined distance therebetween. An AC power supply 5 is connected to one of the electrodes 4 and the other electrode 4 is grounded. An object 2 (vulcanized rubber) is disposed between the electrodes 4 and 4 to perform a surface treatment. Reference numeral 6 denotes a gas exhaust pipe (exhaust system).
【００２０】本発明により表面処理された加硫ゴムの表
面は高度に接着し易い表面に改質されているため、例え
ば加熱、圧着、加熱圧着などの公知の方法により加硫ゴ
ム表面に他の部材を容易に接着することができる。Since the surface of the vulcanized rubber surface-treated according to the present invention has been modified to a surface that is highly adhesive, the surface of the vulcanized rubber can be applied to the surface of the vulcanized rubber by a known method such as heating, crimping, and heat crimping. The members can be easily bonded.
【００２１】この場合、他の部材としては、プラスチッ
ク、ゴム、金属、セラミック等、有機質固体、無機質固
体のいずれであってもよく、また、その形状は板状、シ
ート状、繊維状、ブロック状等のいかなる形状であって
も差し支えない。In this case, the other member may be any of an organic solid and an inorganic solid such as plastic, rubber, metal, ceramic and the like, and may have a plate-like, sheet-like, fibrous, or block-like shape. Any shape such as is acceptable.
【００２２】表面処理された加硫ゴムと他の部材とを接
合する場合、一般的には接着剤を用いるが、この接着剤
としては、例えばシラン系カップリング剤、アミノシラ
ン系カップリング剤、エポキシ系，ウレタン系，フェノ
ール系，アクリル系，ゴム系接着剤などが用いられ、加
硫ゴムと接合する他の部材の種類やその表面状態、接着
の方法により適宜選定することができる。なお、部材の
種類や加硫ゴムの表面処理条件によっては接着剤を用い
ずに直接接着することも可能である。When joining the surface-treated vulcanized rubber to another member, an adhesive is generally used. Examples of the adhesive include a silane coupling agent, an aminosilane coupling agent, and an epoxy. , Urethane-based, phenol-based, acrylic-based, rubber-based adhesives and the like can be used, and can be appropriately selected depending on the type of other members to be joined to the vulcanized rubber, the surface state thereof, and the bonding method. In addition, depending on the type of the member and the surface treatment conditions of the vulcanized rubber, it is also possible to directly bond without using an adhesive.
【００２３】本発明方法は種々の加硫ゴム複合材料の製
造に適用されるが、特に、ゴルフボール、防振ゴム、再
生タイヤ等の製造に好適に採用される。Although the method of the present invention is applied to the production of various vulcanized rubber composite materials, it is particularly suitably applied to the production of golf balls, vibration-isolating rubber, recycled tires and the like.
【００２４】[0024]
【実施例】以下、実施例と比較例を示し、本発明を具体
的に説明するが、本発明は下記の実施例に制限されるも
のではない。EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
【００２５】［実施例１〜１４、比較例１〜１２］図１
に示した大気圧グロー放電装置を用い、下記に示す配合
のゴム組成物を加硫した加硫ゴムの表面処理を表１に示
す条件で行い、被処理加硫ゴムについて下記の実験を行
った（実施例１〜１４）。また、比較のため未処理の加
硫ゴム（比較例１）、擬ハロゲン化合物処理した加硫ゴ
ム（比較例２）、表１に示す条件で低圧グロープラズマ
処理した加硫ゴム（比較例３〜１２）について下記の実
験を行った。結果を表１に併記する。[Examples 1 to 14, Comparative Examples 1 to 12] FIG.
The surface treatment of a vulcanized rubber obtained by vulcanizing a rubber composition having the composition shown below was performed under the conditions shown in Table 1 using the atmospheric pressure glow discharge device shown in Table 1. (Examples 1 to 14). For comparison, untreated vulcanized rubber (Comparative Example 1), vulcanized rubber treated with a pseudohalogen compound (Comparative Example 2), and vulcanized rubber treated with low-pressure glow plasma under the conditions shown in Table 1 (Comparative Examples 3 to 5) The following experiment was performed for 12). The results are also shown in Table 1.
【００２６】 実験１ トランスポリイソプレン ３０部 ＳＢＲ（日本合成ゴム社製，１５０２） ５０ ＮＲ ２０ 硫黄 １ 亜鉛華 ５ Ｎｏｃｒａｃ ＮＳ−６（大内新興化学工業（株）製） １ からなるゴム組成物を加硫した後、１０×６０×３ｍｍ
の試験片を作製した。表１に示す処理条件（実施例１〜
９、比較例１〜７）でそれぞれ２枚ずつ表面処理し、処
理面にウレタン系接着剤を塗布した後、塗布面同士を重
ね合わせ接着し、図２に示すようにＴ字剥離テストを行
い、接着力を測定した。なお、図２において７は加硫ゴ
ム試験片、８はウレタン系接着剤である。 Experiment 1 A rubber composition comprising 30 parts of trans polyisoprene SBR (produced by Nippon Synthetic Rubber Co., Ltd., 1502) 50 NR 20 sulfur 1 zinc white 5 Nocrac NS-6 (produced by Ouchi Shinko Chemical Industry Co., Ltd.) 1 After vulcanization, 10 × 60 × 3mm
Was prepared. Processing conditions shown in Table 1 (Examples 1 to
9, each of the comparative examples 1 to 7) is subjected to a surface treatment, and after applying a urethane-based adhesive to the treated surface, the applied surfaces are overlapped and adhered to each other, and a T-shaped peel test is performed as shown in FIG. And the adhesive strength was measured. In FIG. 2, 7 is a vulcanized rubber test piece, and 8 is a urethane-based adhesive.
【００２７】実験２ 実験１と同様の加硫ゴム試験片の表面を表１に示す処理
条件（実施例２〜９）で表面処理し、処理面にウレタン
系接着剤を塗布してポリエステル系不織布と接着し、図
３に示すように１８０°剥離テストを行い、接着力を測
定した。なお、図３において９は不織布である。 Experiment 2 The surface of a vulcanized rubber specimen similar to that in Experiment 1 was subjected to surface treatment under the treatment conditions shown in Table 1 (Examples 2 to 9), and a urethane-based adhesive was applied to the treated surface to form a polyester-based nonwoven fabric. And a 180 ° peel test was performed as shown in FIG. 3 to measure the adhesive strength. In FIG. 3, reference numeral 9 denotes a nonwoven fabric.
【００２８】 実験３ ＳＢＲ（日本合成ゴム社製，１５０２） ５０部 ＮＲ ５０ カーボンブラック ６０ 硫黄 ２ 亜鉛華 ５ 老化防止剤（注１） １ 加硫促進剤（注２） １ （注１）Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミ
ン（ＤＰＰＤ） （注２）Ｎ−オキシジエチレン−２−ベンゾチアゾール
（ＮＯＢＳ） からなるゴム組成物を加硫した後、３４×７５×５ｍｍ
の試験片を作製した。表１に示す処理条件（実施例３〜
９、比較例１，２，４〜７）でそれぞれ２枚ずつ表面処
理し、処理面にフェノール系接着剤を塗布した後、塗布
面同士を重ね合わせ、１５０℃で３０分間加熱圧着し接
着させた。実験１と同様に図２に示すＴ字剥離テストを
行い、接着力を測定した。 Experiment 3 SBR (produced by Nippon Synthetic Rubber Co., Ltd., 1502) 50 parts NR 50 carbon black 60 sulfur 2 zinc white 5 antioxidant (Note 1) 1 vulcanization accelerator (Note 2) 1 (Note 1) N, N'-diphenyl-p-phenylenediamine (DPPD) (Note 2) After vulcanizing a rubber composition composed of N-oxydiethylene-2-benzothiazole (NOBS), 34 × 75 × 5 mm
Was prepared. Processing conditions shown in Table 1 (Examples 3 to
9, each of two sheets in Comparative Examples 1, 2, 4 to 7) was subjected to a surface treatment, a phenolic adhesive was applied to the treated surfaces, the applied surfaces were overlapped, and heated and pressed at 150 ° C. for 30 minutes for bonding. Was. The T-peel test shown in FIG. 2 was performed in the same manner as in Experiment 1, and the adhesive strength was measured.
【００２９】 実験４ ＮＢＲ（日本合成ゴム社製，Ｎ２３０５） １００部 カーボンブラック ６０ 硫黄 ２ 亜鉛華 ５ 老化防止剤（注３） １ 加硫促進剤（注４） １ 鉱物油 ２ （注３）Ｎ−フェニル−Ｎ’−イソプロピル−ｐ−フェ
ニレンジアミン（ＮＯＣＲＡＣ ８１０−ＮＡ） （注４）テトラメチルチウラムモノサルファイド（ＴＭ
ＴＭ） からなるゴム組成物を１５０℃，２０分の条件で加硫し
た後、３４×７５×５ｍｍの試験片を作製した。表１に
示す処理条件（実施例８〜１２、比較例１０〜１４）で
表面処理し、処理面にフェノール系接着剤を塗布し、１
５０℃で３０分間オーブン中で熱処理した後、樹脂イン
ジェクションマシンを用い、ガラス繊維充填ナイロン
（充填率５０％）を上記フェノール樹脂接着剤上に射出
成形した。図３に示したのと同様の１８０゜剥離テスト
を行い、ゴム破壊（面積％）を測定した。 Experiment 4 NBR (N2305, manufactured by Nippon Synthetic Rubber Co., Ltd.) 100 parts Carbon black 60 Sulfur 2 Zinc white 5 Antioxidant (Note 3) 1 Vulcanization accelerator (Note 4) 1 Mineral oil 2 (Note 3) N -Phenyl-N'-isopropyl-p-phenylenediamine (NOCRAC 810-NA) (Note 4) Tetramethylthiuram monosulfide (TM
After vulcanizing the rubber composition comprising TM) at 150 ° C. for 20 minutes, a 34 × 75 × 5 mm test piece was prepared. Surface treatment was carried out under the treatment conditions shown in Table 1 (Examples 8 to 12 and Comparative Examples 10 to 14), and a phenolic adhesive was applied to the treated surface.
After heat treatment in an oven at 50 ° C. for 30 minutes, glass fiber-filled nylon (filling rate: 50%) was injection-molded on the phenolic resin adhesive using a resin injection machine. A 180 ° peel test similar to that shown in FIG. 3 was performed, and the rubber fracture (area%) was measured.
【００３０】[0030]
【表１】 [Table 1]
【００３１】表１からわかるように、低圧グロープラズ
マ処理の場合（比較例８〜１２）、処理時間が０．５〜
２分まではゴム破壊が増加するが、処理時間が２分より
も長くなるとゴム破壊が減少するため接着性が悪くな
り、しかもゴム破壊の最高値を示す２分間処理でもゴム
破壊は１００面積％には至らない。一方、大気圧プラズ
マ処理の場合（実施例１０〜１４）、０．５分間処理で
ゴム破壊は１００面積％になり、処理時間を長くしても
接着性は変わらない。これは低圧グロープラズマ処理の
場合、ゴムを減圧下で長時間プラズマ雰囲気中にさらす
とゴムの温度が上昇してゴム中のガスが発生し、このガ
スが表面処理を妨げるのに対し、大気圧プラズマ処理は
ゴムを減圧下に入れないためゴム中からガスが発生せ
ず、安定した表面処理を行うことができるためと考えら
れる。As can be seen from Table 1, in the case of the low-pressure glow plasma treatment (Comparative Examples 8 to 12), the treatment time was 0.5 to
Rubber breakage increases up to 2 minutes, but if the treatment time is longer than 2 minutes, the rubber breakage decreases and the adhesion deteriorates, and the rubber breakage is 100% by area even with the 2 minute treatment showing the highest value of rubber breakage. Does not reach. On the other hand, in the case of the atmospheric pressure plasma treatment (Examples 10 to 14), the rubber destruction becomes 100 area% by the treatment for 0.5 minutes, and the adhesiveness does not change even if the treatment time is extended. In the case of low-pressure glow plasma treatment, when rubber is exposed to a plasma atmosphere for a long time under reduced pressure, the temperature of the rubber rises and gas in the rubber is generated. It is considered that the plasma treatment does not generate the gas from the rubber because the rubber is not put under the reduced pressure, so that a stable surface treatment can be performed.
【００３２】[0032]
【発明の効果】本発明によれば、クリーンな環境で簡単
に加硫ゴムの表面処理を行うことができ、低圧グロープ
ラズマ処理した場合と比較してはるかに良好な接着性表
面を有する加硫ゴムを得ることができ、また、ごく表面
のみに処理が施されるため加硫ゴム自体の物性を損なう
ことがない。According to the present invention, it is possible to easily perform surface treatment of a vulcanized rubber in a clean environment, and to obtain a vulcanized rubber having a much better adhesive surface than that obtained by a low-pressure glow plasma treatment. Rubber can be obtained, and since only the surface is treated, the physical properties of the vulcanized rubber itself are not impaired.
【図１】本発明の実施例に用いる大気圧プラズマ放電装
置の一例を示す概略図である。FIG. 1 is a schematic view showing an example of an atmospheric pressure plasma discharge device used in an embodiment of the present invention.
【図２】本発明の実施例及び比較例におけるＴ字剥離テ
ストの説明図である。FIG. 2 is an explanatory diagram of a T-shaped peel test in Examples and Comparative Examples of the present invention.
【図３】本発明の実施例及び比較例における１８０゜剥
離テストの説明図である。FIG. 3 is an explanatory diagram of a 180 ° peel test in Examples and Comparative Examples of the present invention.
１ 処理室 ２ 被処理物 ３ ガス供給管 ４ 電極 ５ 交流電源 ６ ガス排出管 ７ 加硫ゴム試験片 ８ ウレタン系接着剤 ９ 不織布 DESCRIPTION OF SYMBOLS 1 Processing chamber 2 Processing object 3 Gas supply pipe 4 Electrode 5 AC power supply 6 Gas discharge pipe 7 Vulcanized rubber test piece 8 Urethane adhesive 9 Non-woven fabric
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉川 雅人 東京都小平市小川東町３−５−９−202 (72)発明者 内藤 壽夫 神奈川県川崎市宮前区馬絹969−１ (72)発明者 岡崎 幸子 東京都杉並区高井戸東２−20−11 (72)発明者 小駒 益弘 埼玉県和光市下新倉843−15 (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 7/00 C08J 5/12 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masato Yoshikawa 3-5-9-202, Ogawahigashi-cho, Kodaira-shi, Tokyo (72) Inventor Toshio Naito 969-1 Makin, Miyamae-ku, Kawasaki-shi, Kanagawa-ken Sachiko 2-20-11 Takaido East, Suginami-ku, Tokyo (72) Inventor Masuhiro 843-15 Shimo-Nikura, Wako-shi, Saitama (58) Field surveyed (Int.Cl. 7 , DB name) C08J 7/00 C08J 5 / 12
Claims (1)
ハロゲン原子を含むガスを用いて大気圧プラズマ処理す
ることを特徴とする加硫ゴムの表面処理方法。1. A method for surface treating a vulcanized rubber, wherein the surface of the vulcanized rubber is subjected to an atmospheric pressure plasma treatment using a gas containing an oxygen atom and a gas containing a halogen atom.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18029292A JP3146647B2 (en) | 1991-08-20 | 1992-06-15 | Surface treatment method for vulcanized rubber |
| GB9217744A GB2259185B (en) | 1991-08-20 | 1992-08-19 | Method and apparatus for surface treatment |
| US07/932,382 US5316739A (en) | 1991-08-20 | 1992-08-19 | Method and apparatus for surface treatment |
| DE4227631A DE4227631B4 (en) | 1991-08-20 | 1992-08-20 | Method and device for surface treatment |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23218391 | 1991-08-20 | ||
| JP3-232183 | 1991-08-20 | ||
| JP18029292A JP3146647B2 (en) | 1991-08-20 | 1992-06-15 | Surface treatment method for vulcanized rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05202208A JPH05202208A (en) | 1993-08-10 |
| JP3146647B2 true JP3146647B2 (en) | 2001-03-19 |
Family
ID=26499870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18029292A Expired - Lifetime JP3146647B2 (en) | 1991-08-20 | 1992-06-15 | Surface treatment method for vulcanized rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3146647B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5647939A (en) * | 1994-12-05 | 1997-07-15 | Integrated Liner Technologies, Inc. | Method of bonding a cured elastomer to plastic and metal surfaces |
| JP2007217559A (en) * | 2006-02-16 | 2007-08-30 | Toyo Tire & Rubber Co Ltd | Bonding method of vulcanized rubber and unvulcanized rubber |
| WO2010058648A1 (en) * | 2008-11-22 | 2010-05-27 | 淀川ヒューテック株式会社 | Surface modification process using microplasma and bonding process using microplasma |
| WO2014196312A1 (en) | 2013-06-03 | 2014-12-11 | Nok株式会社 | Resin-rubber composite |
-
1992
- 1992-06-15 JP JP18029292A patent/JP3146647B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05202208A (en) | 1993-08-10 |
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