JPH0776060A - Thermally plastic fluorine resin and rubber adhesive compound and its manufacture - Google Patents
Thermally plastic fluorine resin and rubber adhesive compound and its manufactureInfo
- Publication number
- JPH0776060A JPH0776060A JP22351893A JP22351893A JPH0776060A JP H0776060 A JPH0776060 A JP H0776060A JP 22351893 A JP22351893 A JP 22351893A JP 22351893 A JP22351893 A JP 22351893A JP H0776060 A JPH0776060 A JP H0776060A
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- Prior art keywords
- rubber
- rubber composition
- fluororesin
- adhesive
- butadiene copolymer
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は熱可塑性弗素樹脂とゴム
との接着複合体及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composite of a thermoplastic fluororesin and rubber and a method for producing the same.
【０００２】[0002]
【従来の技術】熱可塑性弗素樹脂（以下、弗素樹脂と略
す）は、耐薬品性，耐候性，耐ガスバリア性，耐油性，
食品安全性等多くの優れた物性を有する柔軟な加工し易
い熱可塑性樹脂であり、耐蝕機器分野，食品・衛生分
野，電気・電線分野等で用途開発が進んでいる。一方、
ゴムは、弗素樹脂に比べると高い弾性を有し、しかも安
価である。2. Description of the Related Art Thermoplastic fluororesins (hereinafter abbreviated as fluororesins) have chemical resistance, weather resistance, gas barrier resistance, oil resistance,
It is a flexible and easy-to-process thermoplastic resin that has many excellent physical properties such as food safety, and its application development is progressing in the fields of corrosion-resistant equipment, food / sanitation, electric / electric wires, etc. on the other hand,
Rubber has higher elasticity than fluororesin and is inexpensive.
【０００３】したがって、弗素樹脂とゴムを接合して接
着複合体にすることができれば、弗素樹脂と各ゴムのそ
れぞれ特長を保有する工業的メリットの大きい材料にす
ることが可能である。たとえば、ゴム製ホースの外表面
に弗素樹脂層を接合すれば、優れた耐候性，耐熱劣化
性、耐ガスバリア性等を付与することが可能になる。ま
たゴム製ベルトの表面に弗素樹脂層を接着すれば、耐油
性や耐薬品性を向上させることが可能になる。Therefore, if the fluororesin and the rubber can be joined to form an adhesive composite, it is possible to make the material having the advantages of the fluororesin and each of the rubbers, which has great industrial advantages. For example, by bonding a fluororesin layer to the outer surface of a rubber hose, it becomes possible to impart excellent weather resistance, heat deterioration resistance, gas barrier resistance, and the like. Further, if a fluororesin layer is adhered to the surface of the rubber belt, oil resistance and chemical resistance can be improved.
【０００４】しかしながら、弗素樹脂とゴムとは、接着
性に乏しく、強固に接着することができなかった。従
来、弗素樹脂の接着剤としてイソシアナート系接着剤が
知られているが、この接着剤は、静的接着性は良好であ
るものの、動的接着性に劣るため屈曲等の曲げ変形を受
けると容易に剥離し、耐久性のある接着力が得られるも
のではなかった。However, the fluororesin and the rubber have poor adhesiveness and cannot be firmly bonded. Conventionally, an isocyanate-based adhesive has been known as an adhesive for a fluororesin, but this adhesive has good static adhesiveness, but is inferior in dynamic adhesiveness, and therefore is subject to bending deformation such as bending. It was easily peeled off, and a durable adhesive force was not obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、弗素
樹脂とゴムとが強固に接着し、かつ優れた動的接着性を
有する弗素樹脂／ゴム接着複合体及びその製造方法を提
供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a fluororesin / rubber adhesive composite in which a fluororesin and rubber are firmly adhered and which has excellent dynamic adhesion, and a method for producing the same. It is in.
【０００６】[0006]
【課題を解決するための手段】このような目的を達成す
る本発明の弗素樹脂／ゴム接着複合体は、弗素樹脂と、
水素添加アクリロニトリル−ブタジエン共重合体ゴム
（以下、水素添加ＮＢＲと略す）にメタクリル酸と酸化
亜鉛との混合物又はメタクリル酸亜鉛及び有機過酸化物
を配合したゴム組成物（以下、変性ＮＢＲゴム組成物と
称する）とを接着一体化したことを特徴とする。The fluororesin / rubber adhesive composite of the present invention which achieves the above object comprises a fluororesin and
A rubber composition obtained by blending a hydrogenated acrylonitrile-butadiene copolymer rubber (hereinafter abbreviated as hydrogenated NBR) with a mixture of methacrylic acid and zinc oxide or zinc methacrylate and an organic peroxide (hereinafter, modified NBR rubber composition (Referred to as) and are integrally bonded.
【０００７】また、本発明の他の弗素樹脂／ゴム接着複
合体は、弗素樹脂と、ブチルゴム（以下、ＩＩＲと略
す），アクリロニトリル−ブタジエン共重合体ゴム（以
下、ＮＢＲと略す），アクリルゴム（以下、ＡＣＭと略
す），クロロスルホン化ポリエチレンゴム（以下、ＣＳ
Ｍと略す）及びヒドリンゴム（以下、ＣＨＣと略す）か
らなる群から選ばれたゴムを主成分とするゴム組成物と
を、接着層として変性ＮＢＲゴム組成物を介して接着一
体化したことを特徴とするものである。Another fluororesin / rubber adhesive composite of the present invention comprises a fluororesin, butyl rubber (hereinafter abbreviated as IIR), acrylonitrile-butadiene copolymer rubber (hereinafter abbreviated as NBR), acrylic rubber ( Hereinafter, abbreviated as ACM), chlorosulfonated polyethylene rubber (hereinafter, CS)
M) and hydrin rubber (hereinafter abbreviated as CHC), and a rubber composition containing a rubber as a main component selected from the group consisting of a rubber and a hydrin rubber (hereinafter abbreviated as CHC) are bonded and integrated via a modified NBR rubber composition as an adhesive layer. It is what
【０００８】本発明の弗素樹脂／ゴム接着複合体の製造
方法は、弗素樹脂と、ＩＩＲ，ＮＢＲ，ＡＣＭ，ＣＳ
Ｍ，ＣＨＣからなる群から選ばれたゴムを主成分とする
未加硫ゴム組成物との間に、未加硫の変性ＮＢＲゴム組
成物を介在させて、前記未加硫ゴム組成物を双方ともに
加硫すると同時に、接着一体化することを特徴とするも
のである。The method for producing a fluororesin / rubber adhesive composite of the present invention comprises a fluororesin, IIR, NBR, ACM and CS.
Both the unvulcanized rubber composition is obtained by interposing an unvulcanized modified NBR rubber composition between the unvulcanized rubber composition containing a rubber selected from the group consisting of M and CHC as a main component. It is characterized in that they are both vulcanized and bonded together at the same time.
【０００９】このように変性ＮＢＲゴム組成物は、弗素
樹脂に対し優れた接着性を有するため、弗素樹脂との接
着複合体にすることができると共に、さらにこの変性Ｎ
ＢＲゴム組成物を接着層とすれば、ＩＩＲ，ＮＢＲ，Ａ
ＣＭ，ＣＳＭ，ＣＨＣからなる群から選ばれたゴムを主
成分とするゴム組成物との接着複合体にすることができ
る。As described above, the modified NBR rubber composition has excellent adhesiveness to the fluororesin, so that it can be made into an adhesive composite with the fluororesin, and the modified NBR rubber composition can be further improved.
If the BR rubber composition is used as the adhesive layer, IIR, NBR, A
An adhesive composite with a rubber composition containing a rubber selected from the group consisting of CM, CSM and CHC as a main component can be obtained.
【００１０】本発明において、熱可塑性弗素樹脂とは、
柔軟性セグメントの弗素ゴムからなる幹ポリマーに結晶
性の弗素樹脂からなる枝ポリマーをグラフト共重合した
樹脂をいう。好ましくは、弗素ゴムにポリビニリデンフ
ロライドをグラフト共重合したポリマーが挙げられる。
具体的には、セントラル硝子社から製造販売されている
“セフラルソフトＧ１５０”（商品名）を例示すること
ができる。In the present invention, the thermoplastic fluororesin means
A resin obtained by graft-copolymerizing a branch polymer made of a crystalline fluororesin with a trunk polymer made of fluororubber of the flexible segment. Preferred is a polymer obtained by graft-copolymerizing polyvinylidene fluoride on fluororubber.
Specifically, "Sefraral Soft G150" (trade name) manufactured and sold by Central Glass Co., Ltd. can be exemplified.
【００１１】また、弗素樹脂と複合させるゴム組成物と
しては、ＩＩＲ，ＮＢＲ，ＡＣＭ，ＣＳＭ，ＣＨＣから
なる群から選ばれたゴムを主成分とするゴム組成物があ
る。これらゴム組成物は、いずれも特に限定されるもの
ではなく公知のものを使用することができる。本発明に
おいて、弗素樹脂の複合相手のゴムとして又は接着層と
して使用される変性ＮＢＲゴム組成物には、エチレン性
不飽和ニトリル単位を１０〜６０重量部含有し、共役ジ
エン単位を３０重量部以下を含有する水素添加ＮＢＲ１
００重量部に対し、メタクリル酸亜鉛を２０〜２００重
量部配合し、さらに有機過酸化物を０．５〜２０重量部
配合したものが挙げられる。具体的には日本ゼオン社か
ら製造販売されているＺＳＣ２２９５（商品名）があ
る。メタクリル酸亜鉛は、その原料のメタクリル酸と酸
化亜鉛を、メタクリル酸／酸化亜鉛のモル比が１／０．
５〜１／３の範囲になるように配合することもできる。
この場合、上記水素添加ＮＢＲ１００重量部に対してメ
タクリル酸を２０〜６０重量部、酸化亜鉛を１０〜６０
重量部の範囲で配合することが望ましい。As a rubber composition to be combined with a fluororesin, there is a rubber composition containing a rubber selected from the group consisting of IIR, NBR, ACM, CSM and CHC as a main component. These rubber compositions are not particularly limited, and known ones can be used. In the present invention, the modified NBR rubber composition used as the rubber of the composite partner of the fluororesin or as the adhesive layer contains 10 to 60 parts by weight of the ethylenically unsaturated nitrile unit and 30 parts by weight or less of the conjugated diene unit. Hydrogenated NBR1 containing
For example, 20 to 200 parts by weight of zinc methacrylate and 0.5 to 20 parts by weight of organic peroxide are added to 100 parts by weight. Specifically, there is ZSC2295 (trade name) manufactured and sold by Nippon Zeon Co., Ltd. Zinc methacrylate has a methacrylic acid / zinc oxide molar ratio of 1/0.
It is also possible to mix it so as to be in the range of 5 to 1/3.
In this case, methacrylic acid is 20 to 60 parts by weight and zinc oxide is 10 to 60 parts by weight with respect to 100 parts by weight of the hydrogenated NBR.
It is desirable to mix in the range of parts by weight.
【００１２】本発明の接着複合体において、変性ＮＢＲ
ゴム組成物は、それ自身が弗素樹脂との複合体のゴム層
を構成できるばかりでなく、弗素樹脂に対してＩＩＲ，
ＮＢＲ，ＡＣＭ，ＣＳＭ，ＣＨＣからなる群から選ばれ
たゴムを主成分とするゴム組成物を接着させる接着剤と
しての機能を有する。すなわち、ＩＩＲ，ＮＢＲ，ＡＣ
Ｍ，ＣＳＭ，ＣＨＣを主成分とするゴム組成物は、いず
れも弗素樹脂に直接接着させることはできないが、変性
ＮＢＲゴム組成物を介して接着させることが可能になる
のである。In the adhesive composite of the present invention, the modified NBR
The rubber composition not only can itself form the rubber layer of the composite with the fluororesin,
It has a function as an adhesive for adhering a rubber composition containing a rubber selected from the group consisting of NBR, ACM, CSM and CHC as a main component. That is, IIR, NBR, AC
None of the rubber compositions containing M, CSM, and CHC as the main components can be directly adhered to the fluororesin, but they can be adhered via the modified NBR rubber composition.
【００１３】本発明の接着複合体の製造方法において、
変性ＮＢＲゴム組成物は未加硫状態で接着処理に供す
る。未加硫状態であることにより、これを加熱下に加硫
させると、未加硫の変性ＮＢＲゴム組成物が架橋反応を
起こして弗素樹脂との間、ゴム組成物同士の間で強固に
接着するようになる。この変性ＮＢＲゴム組成物を接着
剤として使用するときは、厚さ１０μｍ〜１．０ｍｍの
フィルム状にして使用することが望ましい。その厚さを
１０μｍ以上にすることにより接着強度を高めることが
できる。しかし、接着強度は１．０ｍｍ以上の厚さで飽
和するようになるので、上限を１．０ｍｍにするのが経
済的である。In the method for producing the adhesive composite of the present invention,
The modified NBR rubber composition is subjected to an adhesive treatment in an unvulcanized state. Since it is in an unvulcanized state, when it is vulcanized under heating, the unvulcanized modified NBR rubber composition undergoes a crosslinking reaction to firmly bond it with the fluororesin and between the rubber compositions. Come to do. When the modified NBR rubber composition is used as an adhesive, it is desirable to use it as a film having a thickness of 10 μm to 1.0 mm. The adhesive strength can be increased by setting the thickness to 10 μm or more. However, since the adhesive strength is saturated at a thickness of 1.0 mm or more, it is economical to set the upper limit to 1.0 mm.
【００１４】他方、ＩＩＲ，ＮＢＲ，ＣＳＭ，ＡＣＭ，
ＣＨＣを主成分とするゴム組成物も接着処理するとき
は、それぞれ未加硫状態で使用する。加硫済みのときは
変性ＮＢＲゴム組成物に対する接着性が低下するからで
ある。接着条件としては、未加硫の変性ＮＢＲゴム組成
物及び上記ＩＩＲ，ＮＢＲ，ＣＳＭ，ＡＣＭ，ＣＨＣを
主成分とするゴム組成物がそれぞれ加硫する条件下、好
ましくは１６０〜１８０℃、１５〜３０分間、プレス下
に加熱するのがよい。On the other hand, IIR, NBR, CSM, ACM,
When a rubber composition containing CHC as a main component is also subjected to an adhesive treatment, it is used in an unvulcanized state. This is because when vulcanized, the adhesion to the modified NBR rubber composition decreases. The adhesion conditions are such that the unvulcanized modified NBR rubber composition and the rubber composition containing IIR, NBR, CSM, ACM, and CHC as the main components are vulcanized, preferably 160 to 180 ° C. and 15 to 150 ° C. It is better to heat under the press for 30 minutes.
【００１５】[0015]
実施例 市販の弗素樹脂（セントラル硝子社製“セフラルソフト
Ｇ１５０”）からなる樹脂板を切断して１５０ｍｍ×５
０ｍｍ×２. ５ｍｍの樹脂板を製作した。水素添加ＮＢ
Ｒとメタクリル酸亜鉛を主成分として含有するゴム組成
物（日本ゼオン社製ＺＳＣ−２２９５）８５重量％に、
水素添加ＮＢＲ（日本ゼオン社製ＺＥＴＰＯＬ２０２
０）１５重量％を添加混練した後、この混合物１００重
量部に対して４，４−ビス（α，α−ジメチルベンジ
ル）ジフェニルアミン（老化防止剤，Ｎａｕｇａｒｄ−
４４５）１．５重量部、１，３−ビスターシャリーブチ
ルパーオキシ−イソプロピルベンゼン（化薬アクゾ社製
有機過酸化物“パーカドックス１４／４０“）５重量部
を、それぞれ添加配合して未加硫の変性ＮＢＲゴム組成
物を調製し、このゴム組成物から１５０ｍｍ×５０ｍｍ
×０．５ｍｍのフィルムを作製した。Example A resin plate made of a commercially available fluororesin (“Sefraral Soft G150” manufactured by Central Glass Co., Ltd.) was cut to 150 mm × 5.
A resin plate of 0 mm x 2.5 mm was manufactured. Hydrogenated NB
To a rubber composition containing R and zinc methacrylate as main components (ZSC-2295 manufactured by Zeon Corporation) to 85% by weight,
Hydrogenated NBR (ZETPOL202 manufactured by Zeon Corporation)
0) After adding and kneading 15% by weight, 4,4-bis (α, α-dimethylbenzyl) diphenylamine (anti-aging agent, Naugard-) was added to 100 parts by weight of this mixture.
445) 1.5 parts by weight, 5 parts by weight of 1,3-Bistersharybutylperoxy-isopropylbenzene (organic peroxide "Perkadox 14/40" manufactured by Kayaku Akzo Co., Ltd.) are added and blended, respectively, and unadded. A sulfur-modified NBR rubber composition was prepared, and 150 mm × 50 mm was prepared from this rubber composition.
A film of × 0.5 mm was produced.
【００１６】表１に示す配合組成のＡＣＭ，ＮＢＲ，Ｃ
ＨＣ，ＩＩＲ，ＣＳＭをそれぞれ含有する５種類の未加
硫ゴム組成物１〜５を調製し、これらゴム組成物１〜５
を用いて、それぞれ１５０ｍｍ×５０ｍｍ×２. ５ｍｍ
の未加硫ゴムシートに成形した。 表１中の数値は、いずれも重量部である。ACM, NBR, C having the composition shown in Table 1
Five kinds of unvulcanized rubber compositions 1 to 5 respectively containing HC, IIR and CSM were prepared, and these rubber compositions 1 to 5 were prepared.
150 mm x 50 mm x 2.5 mm
Was molded into an unvulcanized rubber sheet. All the numerical values in Table 1 are parts by weight.
【００１７】＊１：日本ゼオン社製ＮＩＰＯＬ ＡＲ
７２ＬＳ ＊２：日本ゼオン社製ＧＥＣＨＲＯＮ ３１０２ ＊３：ハイパロン−４０ ＊４：Ｐb3Ｏ4 （レビタルマスター） ＊５：４，４−ビス（α，α−ジメチルベンジル）ジフ
ェニルアミン（老化防止剤４４５） ＊６：ジブチルジチオカルバミン酸ニッケル（老化防止
剤ＮＢＣ） ＊７：Ｎ−フェニル−Ｎ’−イソプロピル−ｐ−フェニ
レンジアミン（老化防止剤３Ｃ） ＊８：脂肪酸ソーダ石鹸（ノンサールＳＮ−１） ＊９：脂肪酸カリ石鹸（ノンサールＴＫ−１） ＊10：エチレンチオウレアのマスター（レビタルマスタ
ー＃２２） ＊11：ベンゾチアジルジスルフィド ＊12：ジペンタメチレンチウラムテトラサルファイド ＊13：Ｎ−ｔ−ブチル−２−ベンゾチアゾールスルフェ
ンアミド ＊14：テトラメチルチウラムモノスルフィド 上記弗素樹脂板に、それぞれ変性ＮＢＲゴム組成物から
なる未加硫ゴムフィルムを積層し、１７０℃，２０分間
加熱して加硫すると同時に接着させた。また、上記弗素
樹脂板と上記５種類のゴム組成物１〜５からなる未加硫
ゴムシートとの間に、それぞれ前記変性ＮＢＲゴム組成
物の未加硫ゴムフィルムを介在させ、上記と同条件下に
加熱して加硫すると同時に接着させた。得られた５種類
の接着複合体の接着性を下記の方法により評価した結
果、いずれも接着性良好（○）であった。* 1: NIPOL AR manufactured by Nippon Zeon Co., Ltd.
72LS * 2: Nippon Zeon Co., Ltd. GECHRON 3102 * 3: Hypalon -40 * 4: Pb 3 O 4 ( Levi barrel master) * 5: 4,4-bis (alpha, alpha-dimethylbenzyl) diphenylamine (Antioxidant 445 ) * 6: Nickel dibutyldithiocarbamate (anti-aging agent NBC) * 7: N-phenyl-N'-isopropyl-p-phenylenediamine (anti-aging agent 3C) * 8: Fatty acid soda soap (Nonsar SN-1) * 9 : Potassium fatty acid soap (Nonsar TK-1) * 10: Ethylenethiourea master (Revital Master # 22) * 11: Benzothiazyl disulfide * 12: Dipentamethylene thiuram tetrasulfide * 13: Nt-butyl-2 -Benzothiazole sulfenamide * 14: Tetramethyl thiuram monosulfide An unvulcanized rubber film made of a modified NBR rubber composition was laminated on each fat plate and heated at 170 ° C. for 20 minutes to be vulcanized and simultaneously adhered. In addition, the unvulcanized rubber film of the modified NBR rubber composition is interposed between each of the fluororesin plate and the unvulcanized rubber sheet composed of the five types of rubber compositions 1 to 5 under the same conditions as above. It was heated under to be vulcanized and simultaneously bonded. As a result of evaluating the adhesiveness of the obtained five kinds of adhesive composites by the following method, all of them were good in adhesiveness (◯).
【００１８】接着性の評価方法：熱可塑性弗素樹脂接着
複合体の接着性は、接着力の大きさで評価するのは正確
ではない、。そこで、幅約２０ｍｍのサンプルを作製し
て剥離テストを行い、乾麺剥離を起こった場合は、たと
え接着力が高くても不良（×）と評価した。他方、界面
剥離を起こさなかった場合は、複合体の接着界面を中心
にして約０．５ｍｍの厚さのシートを剃刀で切り出し、
その接着界面付近に剃刀で傷を入れて剥離テストを行
い、シートが内部で凝集破壊を起こすほどに強固に接着
している場合を接着性良好 (○) と評価した。 Adhesiveness evaluation method : The adhesiveness of the thermoplastic fluororesin adhesive composite is not accurately evaluated by the magnitude of the adhesive strength. Therefore, a sample having a width of about 20 mm was prepared, and a peeling test was performed. When dry noodle peeling occurred, it was evaluated as poor (x) even if the adhesive strength was high. On the other hand, when the interfacial peeling did not occur, a sheet with a thickness of about 0.5 mm was cut out with a razor centering on the adhesive interface of the composite,
A peeling test was performed by making a scratch with a razor near the bonding interface, and the case where the sheet was firmly bonded so as to cause cohesive failure inside was evaluated as good adhesion (◯).
【００１９】[0019]
【発明の効果】本発明によれば、弗素樹脂に対する複合
相手として変性ＮＢＲゴム組成物を使用することによ
り、弗素樹脂と上記変性ＮＢＲゴム組成物とが強固に接
着した接着複合体を得ることができる。また、上記変性
ＮＢＲゴム組成物を接着層とすることにより、弗素樹脂
とＩＩＲ，ＮＢＲ，ＡＣＭ，ＣＳＭ，ＣＨＣとがそれぞ
れ強固に接着し、かつ優れた動的接着性を有する接着複
合体を得ることができる。According to the present invention, by using a modified NBR rubber composition as a composite partner for a fluororesin, an adhesive composite in which the fluororesin and the modified NBR rubber composition are firmly adhered can be obtained. it can. Further, by using the modified NBR rubber composition as an adhesive layer, a fluororesin and IIR, NBR, ACM, CSM, CHC are firmly adhered to each other, and an adhesive composite having excellent dynamic adhesiveness is obtained. be able to.
Claims (3)
ニトリル−ブタジエン共重合体ゴムにメタクリル酸と酸
化亜鉛との混合物又はメタクリル酸亜鉛及び有機過酸化
物を配合したゴム組成物とを接着一体化した熱可塑性弗
素樹脂／ゴム接着複合体。1. A thermoplastic fluororesin and a rubber composition comprising a hydrogenated acrylonitrile-butadiene copolymer rubber and a mixture of methacrylic acid and zinc oxide or a mixture of zinc methacrylate and an organic peroxide are bonded and integrated. Thermoplastic fluororesin / rubber adhesive composite.
リロニトリル−ブタジエン共重合体ゴム，アクリルゴ
ム，クロロスルホン化ポリエチレンゴム及びヒドリンゴ
ムからなる群から選ばれたゴムを主成分とするゴム組成
物とを、接着層として水素添加アクリロニトリル−ブタ
ジエン共重合体ゴムにメタクリル酸と酸化亜鉛との混合
物又はメタクリル酸亜鉛及び有機過酸化物を配合したゴ
ム組成物を介して接着一体化した熱可塑性弗素樹脂／ゴ
ム接着複合体。2. A rubber composition comprising a thermoplastic fluororesin and a rubber selected from the group consisting of butyl rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber, chlorosulfonated polyethylene rubber and hydrin rubber as a main component, Thermoplastic Fluororesin / Rubber Adhesion Adhering and Integrating Through Hydrogenated Acrylonitrile-Butadiene Copolymer Rubber as Adhesion Layer via Rubber Composition Combining Methacrylic Acid and Zinc Oxide or Zinc Methacrylate and Organic Peroxide Complex.
リロニトリル−ブタジエン共重合体ゴム，アクリルゴ
ム，クロロスルホン化ポリエチレンゴム及びヒドリンゴ
ムからなる群から選ばれたゴムを主成分とする未加硫ゴ
ム組成物との間に、水素添加アクリロニトリル−ブタジ
エン共重合体ゴムにメタクリル酸と酸化亜鉛との混合物
又はメタクリル酸亜鉛及び有機過酸化物を配合した未加
硫ゴム組成物を介在させて、前記未加硫のゴム組成物を
双方ともに加硫すると同時に、接着一体化する熱可塑性
弗素樹脂／ゴム接着複合体の製造方法。3. An unvulcanized rubber composition comprising a thermoplastic fluororesin and a rubber selected from the group consisting of butyl rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber, chlorosulfonated polyethylene rubber and hydrin rubber as main components. And an unvulcanized rubber composition containing a mixture of methacrylic acid and zinc oxide or zinc methacrylate and an organic peroxide in a hydrogenated acrylonitrile-butadiene copolymer rubber. A method for producing a thermoplastic fluororesin / rubber adhesive composite, in which both rubber compositions are vulcanized and bonded together at the same time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22351893A JP3193540B2 (en) | 1993-09-08 | 1993-09-08 | Thermoplastic fluororesin / rubber adhesive composite and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22351893A JP3193540B2 (en) | 1993-09-08 | 1993-09-08 | Thermoplastic fluororesin / rubber adhesive composite and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0776060A true JPH0776060A (en) | 1995-03-20 |
| JP3193540B2 JP3193540B2 (en) | 2001-07-30 |
Family
ID=16799402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22351893A Expired - Fee Related JP3193540B2 (en) | 1993-09-08 | 1993-09-08 | Thermoplastic fluororesin / rubber adhesive composite and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3193540B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006132325A1 (en) * | 2005-06-10 | 2006-12-14 | Nok Corporation | Rubber blend composition |
| KR20180052424A (en) * | 2016-11-10 | 2018-05-18 | 주식회사 화인 | Method of manufacturing a rubber sheet and the rubber sheet for a bag manufactured by the method |
-
1993
- 1993-09-08 JP JP22351893A patent/JP3193540B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006132325A1 (en) * | 2005-06-10 | 2006-12-14 | Nok Corporation | Rubber blend composition |
| JPWO2006132325A1 (en) * | 2005-06-10 | 2009-01-08 | Nok株式会社 | Blend rubber composition |
| JP4795342B2 (en) * | 2005-06-10 | 2011-10-19 | Ｎｏｋ株式会社 | Blend rubber composition |
| KR20180052424A (en) * | 2016-11-10 | 2018-05-18 | 주식회사 화인 | Method of manufacturing a rubber sheet and the rubber sheet for a bag manufactured by the method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3193540B2 (en) | 2001-07-30 |
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