JPH0730183B2 - Adhesion method between vulcanized rubber and other materials - Google Patents
Adhesion method between vulcanized rubber and other materialsInfo
- Publication number
- JPH0730183B2 JPH0730183B2 JP60179469A JP17946985A JPH0730183B2 JP H0730183 B2 JPH0730183 B2 JP H0730183B2 JP 60179469 A JP60179469 A JP 60179469A JP 17946985 A JP17946985 A JP 17946985A JP H0730183 B2 JPH0730183 B2 JP H0730183B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- resin
- butadiene
- copolymer
- vulcanized rubber
- 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 - Fee Related
Links
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は加硫ゴムと他材料との接着方法に関し、詳しく
は加硫ゴム表面に低温プラズマガス処理を施し、該処理
面と他材料とを接着する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a method for adhering a vulcanized rubber to another material. More specifically, the surface of the vulcanized rubber is subjected to low-temperature plasma gas treatment, and the treated surface and other materials are treated. It relates to a method of adhering.
＜従来技術＞ 従来、加硫ゴムと他材料との接着は極性の比較的大きい
ニトリロゴム、クロロプレンゴムなどの場合はエポキシ
樹脂、ウレタン樹脂系接着剤を用いてある程度は可能で
あった。<Prior Art> Conventionally, vulcanized rubber and other materials can be bonded to some extent by using epoxy resin or urethane resin adhesive in the case of nitrilo rubber or chloroprene rubber having relatively large polarity.
また、極性の抵い天然ゴム、ポリブタジエンゴム、スチ
レン−ブタジエン共重合体ゴム等では表面を研摩した
り、硫酸あるいはクロム酸などで表面を処理したり、あ
るいは有機ハロゲン化合物、次亜塩素酸、ハロゲンガス
等で表面を処理した後、接着剤を塗布することが行われ
た。In the case of polar polar natural rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, etc., the surface is polished, the surface is treated with sulfuric acid or chromic acid, or an organic halogen compound, hypochlorous acid, halogen is used. After treating the surface with gas or the like, an adhesive was applied.
かかる化学的手段も通常反応性に富んだ二重結合を多く
含むゴムには有効であるが、エチレン−プロピレン系ゴ
ム、ブチルゴムのような飽和度の高いゴム、無極性ゴム
に対しては有効な表面処理といえることがきわめて少な
いのが実情である。Such chemical means is also effective for rubbers containing a large amount of double bonds, which are usually highly reactive, but is effective for highly saturated rubbers such as ethylene-propylene rubber and butyl rubber, and nonpolar rubbers. The reality is that surface treatment is extremely rare.
また、上述の従来技術は効果が僅少であるか、処理が繁
雑であったり、有機溶剤の使用、過激な薬剤・ガスの使
用等安全衛生上から望ましくないものであった。Further, the above-mentioned conventional techniques are not desirable from the viewpoint of safety and hygiene, such as little effect, complicated treatment, use of organic solvent, and extreme use of chemicals and gas.
またこのような処理はゴム層の表面を数μにわたって化
学的に変質させるため動的な歪みに対して弱くなり、し
ばしば致命的な亀裂を生じることがあった。In addition, such a treatment chemically deteriorates the surface of the rubber layer over several μm, so that it becomes weak against dynamic strain and often causes a fatal crack.
＜発明の目的＞ 本発明者らは従来技術に於ける問題点を解決、克服する
新しい手段として低温プラズマガス処理法を鋭意研究の
結果、特定のプラズマガスが特定のゴム配合物に対して
みわめて有効な処理効果をもたらし、特定の低温プラズ
マガスで処理したゴム配合物表面と他材料との間に高い
接着力が得られることを見出し、本発明の完成に至った
ものである。<Purpose of the Invention> As a result of intensive studies on the low-temperature plasma gas treatment method as a new means for solving and overcoming the problems in the prior art, the present inventors found that a specific plasma gas was found to be present in a specific rubber compound. The inventors have found that an effective treatment effect is brought about and a high adhesive force can be obtained between the surface of a rubber compound treated with a specific low temperature plasma gas and other materials, and the present invention has been completed.
本発明方法によれば高い接着力が得られ、従来表面処理
が困難であった、ブチル系ゴムにも有効であるほか、処
理表面が動的な変化に耐え、ゴム本来の性質を損なわな
いというきわめてすぐれた効果が得られる。またこの処
理が本質的にドライプロセスであり、クローズトシステ
ム中で行われるので、安全衛生上と観点からもきわめて
望ましいものである。According to the method of the present invention, it is possible to obtain a high adhesive force, and it is effective for butyl-based rubber, which has been difficult to surface-treat in the past, and the treated surface withstands a dynamic change and does not impair the original properties of the rubber. Very good effect can be obtained. Moreover, since this treatment is essentially a dry process and is performed in a closed system, it is extremely desirable from the viewpoint of safety and health.
本発明方法により得られた加硫（架橋）ゴムと樹脂との
複合体あるいは樹脂を介して金属、セラミック等と複合
された物品は、コンベアベルト、防振ゴム、ホース、ブ
ッシュ、カップリング等の工業用品、スポーツ用品、玩
具、家庭用品等に広く用いられる。The composite of vulcanized (crosslinked) rubber and resin obtained by the method of the present invention or an article composited with metal, ceramic or the like through a resin is used as a conveyor belt, anti-vibration rubber, hose, bush, coupling, etc. Widely used in industrial goods, sports goods, toys, household goods, etc.
＜発明の構成＞ 本発明は、ポリイソプレンゴム、ポリブタジエンゴム、
スチレン−ブタジエン共重合体ゴム、ブタジエン−アク
リロニトリル共重合体ゴム、ブチルゴム、ハロゲン化ブ
チルゴム、クロロプレンゴム、イソブチレン−イソプレ
ン共重合体ゴム、ポリノルボルネンゴム、ポリペンテナ
マー、ブタジエン−アクリロニトリル−メタクリル酸エ
ステル共重合体ゴム、ブタジエン−ビニルピリジン共重
合体ゴム、ブタジエン−スチレン−ビニルピリジン共重
合体ゴムのゴム単体またはこれらのブレンド物、または
上記ゴムに塩化ビニルを混合した配合物からなる加硫ゴ
ムの表面に酸素、空気、アルゴン、ヘリウム、窒素、二
酸化炭素、一酸化炭素の単体または混合ガスによる低温
プラズマガス処理を施し、該処理面と他材料とを接着す
る加硫ゴムと他材料との接着方法である。<Structure of the Invention> The present invention relates to a polyisoprene rubber, a polybutadiene rubber,
Styrene-butadiene copolymer rubber, butadiene-acrylonitrile copolymer rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, isobutylene-isoprene copolymer rubber, polynorbornene rubber, polypentenamer, butadiene-acrylonitrile-methacrylic acid ester copolymer rubber , Butadiene-vinyl pyridine copolymer rubber, butadiene-styrene-vinyl pyridine copolymer rubber rubber alone or a blend thereof, or oxygen on the surface of a vulcanized rubber comprising a mixture of the above rubber and vinyl chloride, This is a method for adhering a vulcanized rubber and another material in which a low-temperature plasma gas treatment is performed with a simple substance or a mixed gas of air, argon, helium, nitrogen, carbon dioxide, and carbon monoxide, and the treated surface is adhered to another material.
本発明方法に於いて用いられる加硫ゴム配合物として
は、ポリイソプレンゴム、ポリブタジエンゴム、スチレ
ン−ブタジエン共重合体ゴム、アクリロニトリル−ブタ
ジエン共重合体ゴム、ブチルゴム、ハロゲン化ブチルゴ
ム、クロロプレンゴム、イソブチレン−イソプレン共重
合体ゴム、ポリノルボルネンゴム、ポリペンテナマー、
ブタジエン−アクリロニトリル−メタクリル酸エステル
共重合体ゴム、ブタジエン−ビニルピリジン共重合体ゴ
ム、ブタジエン−スチレン−ビニルピリジン共重合体ゴ
ム等のゴム単体あるいはそれらのブレンド物、あるいは
上記ゴムに塩化ビニル等を混合した配合物に加硫（架橋
剤）、促進剤、促進助剤、さらにはゴム工業に於いて通
常使用される充填剤、補強剤、老化防止剤、着色剤等を
加えたものがあげられる。The vulcanized rubber compound used in the method of the present invention includes polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, isobutylene- Isoprene copolymer rubber, polynorbornene rubber, polypentenamer,
Butadiene-acrylonitrile-methacrylic acid ester copolymer rubber, butadiene-vinyl pyridine copolymer rubber, butadiene-styrene-vinyl pyridine copolymer rubber or other rubber alone or a blend thereof, or a mixture of the above rubber with vinyl chloride or the like. Vulcanization (crosslinking agent), accelerators, accelerator aids, and fillers, reinforcing agents, antiaging agents, colorants and the like which are commonly used in the rubber industry are added to the above-mentioned compound.
上記の配合剤とゴムは、ロールミル、バンバリー等の混
合機でブレンドされ、該ブレンド物は熱プレス等適当な
手段により加硫、架橋とともに成型される。The above compounding agent and rubber are blended by a mixer such as a roll mill or Banbury, and the blended product is molded together with vulcanization and crosslinking by an appropriate means such as hot pressing.
上記の如くにして得られた加硫ゴムは次に低温プラズマ
ガスに１〜数百秒間さらされる。低温プラズマガスは通
常用いられる各種の方法によって発生される。電源とし
て高周波を用いる場合は電極を処理槽の外部（但しこの
とき処理槽は絶縁体）に設置して放電をおこすことも可
能であるが、内部に電極を設ける方式は直流〜高周波の
広い範囲にわたり採用できる。またマイクロ波を用いて
プラズマガスを発生させることもできる。The vulcanized rubber obtained as described above is then exposed to a low temperature plasma gas for 1 to several hundred seconds. The low temperature plasma gas is generated by various commonly used methods. When a high frequency is used as the power supply, it is possible to place the electrode outside the processing tank (however, the processing tank is an insulator at this time) to generate discharge, but the method of installing the electrode inside is wide range from DC to high frequency. It can be used over a wide range. Alternatively, microwaves can be used to generate plasma gas.
本発明に於いては、12.56MHzの高周波を用いて低温プラ
ズマガス処理を行った。In the present invention, low temperature plasma gas treatment was performed using a high frequency of 12.56 MHz.
すなわち本発明に於いては添付図面に示す如く、真空弁
（13）を介して真空ポンプ（14）により処理槽（７）内
部を１×10-2Torr前後まで排気減圧し、次に真空弁
（３）又は（４）を介してガスボンベ（１）又は気化器
（２）により槽（７）内に所定ガスを真空計（６）によ
り、0.05〜10Torr程度になるように導入する。次に電源
（12）よりマッチングボックス（11）を経て13.56MHzの
高周波電力を印加して外部電極（８）と対向アース電極
（９）間にて槽（７）内に低温プラズマを発生させ、予
め槽（７）内に設置した被処理体（10）すなわち加硫ゴ
ム表面を１〜数百秒間処理する。That is, in the present invention, as shown in the accompanying drawings, the inside of the processing tank (7) is evacuated to a pressure of about 1 × 10 -2 Torr by a vacuum pump (14) through a vacuum valve (13), and then the vacuum valve is used. Through (3) or (4), a gas cylinder (1) or a vaporizer (2) introduces a predetermined gas into the tank (7) with a vacuum gauge (6) so that the pressure is about 0.05 to 10 Torr. Next, high frequency power of 13.56MHz is applied from the power source (12) through the matching box (11) to generate low temperature plasma in the tank (7) between the external electrode (8) and the opposing earth electrode (9). The object (10) to be treated, that is, the surface of the vulcanized rubber, which is previously installed in the tank (7), is treated for 1 to several hundred seconds.
本発明方法に於いて好適に用いられる処理ガスは酸素、
アルゴン、ヘリウム、窒素、空気、炭酸ガス、一酸化炭
素、等の単独または混合ガスである。The processing gas preferably used in the method of the present invention is oxygen,
It is a single gas or a mixed gas of argon, helium, nitrogen, air, carbon dioxide, carbon monoxide, and the like.
プラズマガス処理されたゴム表面と接合される樹脂とし
てはエポキシ樹脂、ウレタン樹脂、ポリアミド樹脂、エ
チレン−酢酸ビニル共重合体、エチレン−アクリル酸共
重合体、ポリエステル樹脂、フェノール樹脂、アクリル
樹脂、ABS樹脂、AES樹脂等の単独または配合物が用いら
れる。樹脂は硬化前の液状物、溶融物、半溶融物、溶液
の状態でゴム表面に塗布され、ついで加熱、冷却、溶媒
の除去法により接合が完成される。As the resin to be bonded to the rubber surface treated with plasma gas, epoxy resin, urethane resin, polyamide resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, polyester resin, phenol resin, acrylic resin, ABS resin , AES resin, etc., alone or in combination. The resin is applied to the surface of the rubber in a liquid state, a molten state, a semi-molten state or a solution state before being cured, and then the joining is completed by heating, cooling and a method of removing the solvent.
＜実 施 例＞ 以下に実施例により本発明をより詳細に説明する。<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例 １ シス−１、４−ポリブタジエンゴム（日本合成ゴム株式
会社JSRBR01）100重量部にカーボンブラックHAF30重量
部、酸化亜鉛５重量部、ステアリン酸１重量部を10分間
ロールミン上で添加混練し、ついで加硫促進剤DM1重量
部、イオウ1.5重量部を同じロールミルで添加し、厚さ
約2mmの未加硫ゴムシートを得た。次にこのシートをモ
ールドに入れ、160℃、15分間加熱、加圧して加硫ゴム
シートを作成した。Example 1 100 parts by weight of cis-1,4-polybutadiene rubber (JSRBR01, Japan Synthetic Rubber Co., Ltd.), 30 parts by weight of carbon black HAF, 5 parts by weight of zinc oxide, and 1 part by weight of stearic acid were added and kneaded on rollmin for 10 minutes, Then, 1 part by weight of vulcanization accelerator DM and 1.5 parts by weight of sulfur were added by the same roll mill to obtain an unvulcanized rubber sheet having a thickness of about 2 mm. Next, this sheet was put into a mold and heated and pressed at 160 ° C. for 15 minutes to prepare a vulcanized rubber sheet.
このシートから５×7.5cmの試験片を切り出し、ヘキサ
ンにて清拭後、添附図面に示すプラズマ処理槽（７）の
中央に位置させた。ついで真空弁（13）を介し真空ポン
プ（14）を用いて１×10-2Torrまで処理槽（７）内を排
気し、次に真空弁（３）及び（５）をあけてガスボンベ
（１）より空気を導入して1Torrとした後、高周波13.56
MHzの電極（12）からマッチングボックス（11）を通じ
て電極（８）に100w、60秒間電力を印加し、処理槽内の
ガスをプラズマ化してゴム表面を処理した。A test piece of 5 × 7.5 cm was cut out from this sheet, wiped with hexane, and placed in the center of the plasma treatment tank (7) shown in the attached drawing. Then, the inside of the processing tank (7) was evacuated to 1 × 10 -2 Torr through the vacuum valve (13) using the vacuum pump (14), and then the vacuum valves (3) and (5) were opened to open the gas cylinder (1 ) And introduce air to 1 Torr, then high frequency 13.56
Power was applied from the MHz electrode (12) to the electrode (8) through the matching box (11) for 100 w for 60 seconds, and the gas in the treatment tank was turned into plasma to treat the rubber surface.
この処理シートから１×7.5cmの短冊試験片を切り出
し、プラズマガス処理面に共重合ナイロン（白楊社ナイ
コートMT−25）のアルコール溶液を塗布し、不織布で裏
打ちした後、乾燥して接着試験片を得た。A 1 × 7.5 cm strip test piece was cut out from this treated sheet, and the plasma gas treated surface was coated with an alcohol solution of copolymerized nylon (Hakutosha Nycoat MT-25), lined with a non-woven fabric, and then dried to obtain an adhesive test piece. Got
次に試験片をインストロン型引張試験機を用いゴム−ナ
イロン間の180゜剥離接着力を引張速度50mm/minで測定
した。この試験片の接着力は10kg/25mmであり、破壊は
ブタジエン層でおこった。なおプラズマガス処理を施さ
ない場合の接着力は0.1kg/25mmであった。Next, the test piece was measured for the 180 ° peeling adhesive force between the rubber and the nylon using an Instron type tensile tester at a pulling speed of 50 mm / min. The adhesive strength of this test piece was 10 kg / 25 mm, and the fracture occurred in the butadiene layer. The adhesive strength without plasma gas treatment was 0.1 kg / 25 mm.
実施例 ２ シス−１、４−ポリブタジエンにかえて天然ゴム、スチ
レン−ブタジエン共重合体ゴムSBR1500（日本合成ゴム
株式会社）、ブタジエン−アクリロニトリル共重合体ゴ
ムJRSN230S（日本合成ゴム株式会社）、１、２−ポリブ
タジエン、クロロプレンゴム、ブチルゴム、EPDMを用い
て実施例１と同様の試験を行った。結果は第１表に示す
通りであった。Example 2 Instead of cis-1,4-polybutadiene, natural rubber, styrene-butadiene copolymer rubber SBR1500 (Japan Synthetic Rubber Co., Ltd.), butadiene-acrylonitrile copolymer rubber JRSN230S (Japan Synthetic Rubber Co., Ltd.), 1, The same test as in Example 1 was conducted using 2-polybutadiene, chloroprene rubber, butyl rubber and EPDM. The results are as shown in Table 1.
実施例 ３ 実施例１の処理ガスである酸素を空気及びアルゴンにか
え、また被着体樹脂をナイロン溶液からウレタン樹脂に
かえて試験を行った。ウレタン樹脂として両末端にイソ
シアナート機を有するポリエーテル樹脂（デュポン社Ｌ
−213）を用い、該樹脂を減圧下に加熱して脱泡、脱水
し、硬化剤として４、４−メチレンビスオルソクロルア
ニリンを加えてゴムのプラズマガス処理面に積層し、10
0℃、３時間加熱、硬化させてゴム−ウレタン積層体を
作成した。接着力試験は実施例１と同様な方法でおこな
った。結果は第２表に示す通りであった。 Example 3 The test was carried out by changing the treatment gas of Example 1, oxygen, to air and argon, and changing the adherend resin from a nylon solution to a urethane resin. Polyether resin having an isocyanate machine at both ends as a urethane resin (DuPont L
-213), the resin is heated under reduced pressure for defoaming and dehydration, and 4,4-methylenebisorthochloroaniline is added as a curing agent and laminated on the plasma gas-treated surface of the rubber.
A rubber-urethane laminate was prepared by heating and curing at 0 ° C. for 3 hours. The adhesive strength test was performed in the same manner as in Example 1. The results are shown in Table 2.
実施例 ４ ゴムとしてブタジエン−アクリロニトリル共重合体ゴム
N230を用い、処理ガスとして窒素ガスを用いた。プラズ
マ処理条件はガス圧1Torr、電力10w、処理時間30秒であ
った。被着体樹脂として共重合ナイロン（ナイコートMT
−25）を用いた。結果は接着力が6.9kg/25mmであった。 Example 4 Butadiene-acrylonitrile copolymer rubber as rubber
N230 was used and nitrogen gas was used as a processing gas. The plasma treatment conditions were a gas pressure of 1 Torr, an electric power of 10 w, and a treatment time of 30 seconds. Copolymerized nylon as adherend resin (Nycoat MT
-25) was used. As a result, the adhesive force was 6.9 kg / 25 mm.
実施例 ５ ゴムとしてスチレン−ブタジエン共重合体ゴム、シス−
１、４−ポリブタジエンゴム、１、２−ポリブタジエン
ゴム、ブタジエン−アクリロニトリル共重合体ゴムN220
S（アクリロニトリル40％）、同N250S（アクリロニトリ
ル20％）、ブタジエン−アクリロニトリル共重合体ゴム
と塩化ビニルとのブレンド物（日本合成ゴム株式会社NV
72）を、また被着体樹脂として共重合ナイロンCM8000
（東レ株式会社）用いた。Example 5 Styrene-butadiene copolymer rubber, cis-
1,4-polybutadiene rubber, 1,2-polybutadiene rubber, butadiene-acrylonitrile copolymer rubber N220
Blend of S (acrylonitrile 40%), N250S (acrylonitrile 20%), butadiene-acrylonitrile copolymer rubber and vinyl chloride (Nippon Synthetic Rubber NV
72), and copolymer nylon CM8000 as the adherend resin.
(Toray Industries, Inc.) was used.
この場合、ナイロンフィルムを加硫ゴムのプラズマ処理
面に密着させ、130℃、５分間予熱し、さらに５分間圧
着した。接着テストは実施例１と全く同様に行った。結
果は第３表に示す通りであった。In this case, the nylon film was brought into close contact with the plasma-treated surface of the vulcanized rubber, preheated at 130 ° C. for 5 minutes, and further pressure-bonded for 5 minutes. The adhesion test was performed exactly as in Example 1. The results are shown in Table 3.
実施例 ６ ゴム種としてブタジエン−アクリロニトリル共重合体ゴ
ムN230Sを用い。実施例１と全く同様にして加硫ゴムシ
ートを得た。次にこのシートの一方側を酸素にてプラズ
マガス処理（1Torr×100w、60秒）した。 Example 6 A butadiene-acrylonitrile copolymer rubber N230S is used as a rubber type. A vulcanized rubber sheet was obtained in exactly the same manner as in Example 1. Next, one side of this sheet was subjected to plasma gas treatment with oxygen (1 Torr × 100 w, 60 seconds).
また比較のため上記加硫ゴムシートの他方側に湿式表面
処理（トリクロルイソシアヌレートの１％アセトン溶液
を塗布）した。For comparison, the other surface of the vulcanized rubber sheet was subjected to wet surface treatment (coating with a 1% acetone solution of trichloroisocyanurate).
次に上記シートより巾1cm、長さ10cmの短冊状試験片を
切り出し、平衡型疲労試験機を用い試験片の長手方向に
30％の引張歪を１分500回の割で繰返して与え、表面状
態を観察した。結果は第４表に示す通りであった。Next, a strip test piece with a width of 1 cm and a length of 10 cm was cut out from the above sheet, and was placed in the longitudinal direction of the test piece using a balanced fatigue tester.
A surface strain was observed by repeatedly applying a tensile strain of 30% every 500 times for 1 minute. The results are shown in Table 4.
第４表から明らかなように、プラズマガス処理したゴム
は繰返し大変形に耐え、全く亀裂が生じなかった。 As is clear from Table 4, the plasma gas treated rubber withstood repeated large deformations and no cracks occurred.
実施例 ７ 実施例６で得たゴム表面に共重合ナイロン（ナイコート
MT25）を塗布、積層し、同様にして動的歪を与えた。結
果は第５表に示す通りであった。Example 7 The surface of the rubber obtained in Example 6 was copolymerized with nylon (nycoat).
MT25) was applied, laminated, and similarly subjected to dynamic strain. The results are shown in Table 5.
第５表より明らかなように、プラズマ処理による接着性
向上は動的用途に於いて耐屈曲亀裂性に非常にすぐれて
いるという従来全く知られなかった結果が見出された。 As is clear from Table 5, it has been found that the improvement in adhesion by plasma treatment is very excellent in flex crack resistance in dynamic applications, which has never been known.
添附図面は本発明方法の実施にあたり使用される低温プ
ラズマガス処理装置の一例を示す概略図である。 なお、図示された主要部と符号との対応関係は以下の通
りである。 １……ガスボンベ、２……気化器、３、４、13……真空
弁、６……真空計、７……処理槽、８……外部電極、９
……対向アース電極、10……被処理体、11……マッチン
グボックス、12……高周波電源、14……真空ポンプThe accompanying drawings are schematic views showing an example of a low-temperature plasma gas processing apparatus used for carrying out the method of the present invention. The correspondence between the illustrated main parts and reference numerals is as follows. 1 ... Gas cylinder, 2 ... Vaporizer, 3, 4, 13 ... Vacuum valve, 6 ... Vacuum gauge, 7 ... Processing tank, 8 ... External electrode, 9
...... Counter grounding electrode, 10 ...... Processing object, 11 …… Matching box, 12 …… High frequency power supply, 14 …… Vacuum pump
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭52−28577（ＪＰ，Ａ) 特公 昭51−24369（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-52-28577 (JP, A) JP-B-51-24369 (JP, B1)
Claims (3)
ム、スチレン−ブタジエン共重合体ゴム、ブタジエン−
アクリロニトリル共重合体ゴム、ブチルゴム、ハロゲン
化ブチルゴム、クロロプレンゴム、イソブチレン−イソ
プレン共重合体ゴム、ポリノルボルネンゴム、ポリペン
テナマー、ブタジエン−アクリロニトリル−メタクリル
酸エステル共重合体ゴム、ブタジエン−ビニルピリジン
共重合体ゴム、ブタジエン−スチレン−ビニルピリジン
共重合体ゴムのゴム単体またはこれらのブレンド物、ま
たは上記ゴムに塩化ビニルを混合した配合物からなる加
硫ゴムの表面に酸素、空気、アルゴン、ヘリウム、窒
素、二酸化炭素、一酸化炭素の単体または混合ガスによ
る低温プラズマガス処理を施し、該処理面と他材料とを
接着することを特徴とする加硫ゴムと他材料との接着方
法。1. Polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, butadiene-
Acrylonitrile copolymer rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, isobutylene-isoprene copolymer rubber, polynorbornene rubber, polypentenamer, butadiene-acrylonitrile-methacrylic acid ester copolymer rubber, butadiene-vinylpyridine copolymer rubber, Oxygen, air, argon, helium, nitrogen, carbon dioxide on the surface of a vulcanized rubber composed of a rubber simple substance of butadiene-styrene-vinylpyridine copolymer rubber or a blend thereof, or a mixture of the above rubber and vinyl chloride. A method for adhering a vulcanized rubber to another material, which comprises subjecting the treated surface to another material by performing low-temperature plasma gas treatment with a simple substance or a mixed gas of carbon monoxide.
いて、他材料がエポキシ樹脂、ウレタン樹脂、ポリアミ
ド樹脂、ポリエステル樹脂、エチレン−酢酸ビニル共重
合体樹脂、フェノール樹脂、ポリ（メタ）アクリル樹
脂、ポリシアノアクリレート樹脂、エチレン−アクリル
酸共重合体樹脂、ABS樹脂、AES樹脂、あるいはそれらの
ブレンド物であることを特徴とする加硫ゴムと他材料と
の接着方法。2. The bonding method according to claim 1, wherein the other material is epoxy resin, urethane resin, polyamide resin, polyester resin, ethylene-vinyl acetate copolymer resin, phenol resin, poly (meta). ) A method for adhering a vulcanized rubber to another material, which is an acrylic resin, a polycyanoacrylate resin, an ethylene-acrylic acid copolymer resin, an ABS resin, an AES resin, or a blend thereof.
いて、低温プラズマガスで処理した加硫ゴム表面に他材
料を接着する際、上記の低温プラズマで処理した加硫ゴ
ム表面に、接着剤としてエポキシ樹脂、ウレタン樹脂、
ポリアミド樹脂、ポリエステル樹脂、エチレン−酢酸ビ
ニル共重合体樹脂、フェノール樹脂、ポリ（メタ）アク
リル樹脂、ポリシアノアクリレート樹脂、エチレン−ア
クリル酸共重合体樹脂、ABS樹脂、AES樹脂、あるいはそ
れらのブレンド物を塗布することを特徴とする加硫ゴム
と他材料との接着方法。3. The bonding method according to claim 1, wherein when another material is bonded to the surface of the vulcanized rubber treated with the low temperature plasma gas, the surface of the vulcanized rubber treated with the low temperature plasma is adhered. , Epoxy resin, urethane resin, as adhesive
Polyamide resin, polyester resin, ethylene-vinyl acetate copolymer resin, phenol resin, poly (meth) acrylic resin, polycyanoacrylate resin, ethylene-acrylic acid copolymer resin, ABS resin, AES resin, or blends thereof. A method for adhering a vulcanized rubber to another material, which comprises applying
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60179469A JPH0730183B2 (en) | 1985-08-16 | 1985-08-16 | Adhesion method between vulcanized rubber and other materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60179469A JPH0730183B2 (en) | 1985-08-16 | 1985-08-16 | Adhesion method between vulcanized rubber and other materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6241233A JPS6241233A (en) | 1987-02-23 |
| JPH0730183B2 true JPH0730183B2 (en) | 1995-04-05 |
Family
ID=16066390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60179469A Expired - Fee Related JPH0730183B2 (en) | 1985-08-16 | 1985-08-16 | Adhesion method between vulcanized rubber and other materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730183B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008531330A (en) * | 2005-02-22 | 2008-08-14 | ビーエーエスエフ ソシエタス・ヨーロピア | Articles containing polystyrene and thermoplastic polyurethane |
Families Citing this family (5)
| 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 |
| US5939160A (en) * | 1997-02-25 | 1999-08-17 | Sealand Technology, Inc. | Low odor permeable hose |
| US6495259B1 (en) | 1999-11-03 | 2002-12-17 | Alliant Techsystems Inc. | Rubber-epoxy bonding via an interfacial layer containing acrylates |
| WO2014196312A1 (en) * | 2013-06-03 | 2014-12-11 | Nok株式会社 | Resin-rubber composite |
| JP2022070004A (en) * | 2020-10-26 | 2022-05-12 | 三菱電線工業株式会社 | Rubber composition and rubber member obtained by crosslinking the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5124369A (en) * | 1974-08-19 | 1976-02-27 | Toshiba Machine Co Ltd | Inryoekitaino reikyakuchushutsusochi |
| DE2538055C3 (en) * | 1975-08-27 | 1978-07-13 | Chemische Werke Huels Ag, 4370 Marl | Process for improving the adhesiveness of the surface of vulcanized articles made from ethylene-α-olefin-diene terpolymers |
-
1985
- 1985-08-16 JP JP60179469A patent/JPH0730183B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008531330A (en) * | 2005-02-22 | 2008-08-14 | ビーエーエスエフ ソシエタス・ヨーロピア | Articles containing polystyrene and thermoplastic polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6241233A (en) | 1987-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0606014B1 (en) | Surface treating method | |
| US4337111A (en) | Method of obtaining strong and durable adhesion to rubber through chemical covalent bonds | |
| US6013153A (en) | Process for surface treatment of vulcanized rubber and process for production of rubber-based composite material | |
| JPH0730183B2 (en) | Adhesion method between vulcanized rubber and other materials | |
| JP2001260235A (en) | Rubber and metal bonding method and structure using the same | |
| EP0788870B1 (en) | Process for surface treatment of vulcanized rubber and process for production of rubber-based composite material | |
| JP3661723B2 (en) | Method for producing rubber-based composite material | |
| US4349403A (en) | Method for bonding elastomers to steel | |
| JPH0625261B2 (en) | Adhesion method between vulcanized rubber and other materials | |
| JPH07171930A (en) | Rubber composite and production thereof | |
| US5069927A (en) | Adhesively-bonded coated composites of highly saturated elastomers | |
| JP2001162722A (en) | Polyamide/rubber composite | |
| JPH04145139A (en) | Surface-treating method of fluorine based member and method for bonding fluorine based member | |
| US5902861A (en) | Method of making rubber | |
| WO2001027196A1 (en) | Rubber composition, composite material, and process for producing composite material | |
| JPH05202208A (en) | Method of surface-treating vulcanized rubber | |
| JP2004251368A (en) | Manufacturing method for seat ring for valve, and manufacturing method for valve element | |
| JP3819045B2 (en) | Laminate of resin and rubber and method for producing the same | |
| JP2790342B2 (en) | Bonding method between vulcanized rubber and urethane elastomer | |
| US20120082851A1 (en) | Hybrid adhesive | |
| JPH08118547A (en) | Cooling medium transport hose and manufacture thereof | |
| JPS6239236A (en) | Laminate of vulcanized rubber and other adherend | |
| JP2939290B2 (en) | Coating composites bonded with highly saturated elastomeric adhesives | |
| Chang et al. | Bonding elastomer layers together by a surface oxidation reaction | |
| JPH06298971A (en) | Surface treatment for fluorine resin molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |