JP2004098554A - Method for manufacturing composite material of metal and rubber - Google Patents
Method for manufacturing composite material of metal and rubber Download PDFInfo
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、金属・ゴム複合材料の製造法に関する。更に詳しくは、塗布型クロメート処理していない金属板上に水系NBR塗液を適用して金属・ゴム複合材料を製造する方法に関する。
【0002】
【従来の技術】
従来より、ガスケット等のシール製品としては、金属板上にゴムをコーティングして密封性を付与したものが使用されている。金属板上にコーティングするゴム層の厚みは数10〜数100μm程度であり、そのため従来は未加硫状態のゴム組成物を有機溶剤に溶解したコーティング液を用い、これをコーティング、乾燥および加硫して使用していた。しかしながら、近年環境問題等からゴムの溶解に使用されていた有機溶剤の使用が困難となりつつあり、水系ゴム塗液を用いる方向にある。
【0003】
従来の溶剤希釈タイプの製品から水系ゴム塗液に変更する場合には、従来のものと同等性能を発現し、しかもコスト的にも同等あるいはそれ以下であることが求められる。しかしながら、水系ゴム塗液タイプで従来の溶剤希釈タイプと同等性能を発現するのは容易ではなく、これが製品化する上での障害となっている。
【0004】
また、金属板とゴムとの接着力を上げるために、金属板表面に塗布型クロメート処理を施すことも行われているが、環境問題などの見地からクロムレス化も望まれている。特に、塗布型クロメート処理をしていない金属板を用い、水分散液のゴム塗液を適用する場合には、溶剤希釈タイプと同等性能を発現させることは容易ではない。
【0005】
【発明が解決しようとする課題】
本発明の目的は、塗布型クロメート処理していない金属板上に水系NBR塗液を適用して金属・ゴム複合材料を製造するに際し、従来の有機溶剤希釈タイプと同等の性能(物性、補強性、非粘着性など)を有するものの製造法を提供することにある。
【0006】
【課題を解決するための手段】
かかる本発明の目的は、塗布型クロメート処理していない金属板上に接着剤を塗布し、そこに結合アクリロニトリル量が30%以上のNBRの水性ラテックスと粒子径が5〜300nmのカーボンブラックの水分散液を含有する水系ゴム塗液を塗布、乾燥させた後、面圧0.1MPa以上でプレス加硫させて金属・ゴム複合材料を製造する方法によって達成される。
【0007】
【発明の実施の形態】
金属板としては、ステンレス鋼板、アルミニウム板、亜鉛鋼板等が用いられ、その厚さは限定されないが、一般には約0.1〜2.0mm程度のものが用いられる。十分な性能を発現させるためには、金属板表面をリン酸金属塩処理(ボンデ処理)した上で使用することが好ましく、その場合には塗膜の接着性を向上させるばかりではなく、金属板の耐腐食性向上にも寄与するようになる。
【0008】
金属板上には、ゴム層の形成に先立って、接着剤が塗布される。接着剤としては、フェノール系接着剤、シラン系またはチタネート系カップリング剤の少くとも一種が用いられる。フェノール系接着剤としては、フェノール・ホルムアルデヒド重縮合物が好んで用いられる。シラン系カップリング剤としては、ビニル基、アミノ基、メルカプト基等の官能基を有するメトキシシラン類およびエトキシシラン類が代表的な例として挙げられる。また、チタネート系カップリング剤としては、例えばイソプロピルトリイソステアロイルチタネート、イソプロピルトリデシルベンゼンスルホニルチタネート、イソプロピルトリス(ジオクチルパイロホスフェート)チタネート、テトライソプロピルビス(ジオクチルホスファイト)チタネート等が用いられる。これらを主成分とする接着剤中には、接着力向上のために、必要に応じてエラストマー等の高分子成分、シリカ等の無機添加物、有機金属触媒などが添加されていてもよい。これらの接着剤の金属板上への塗布は、ディッピング法、スプレー法、刷毛塗り法などの任意の方法で行なうことができ、その後所定温度での焼付け処理が行われる。
【0009】
接着剤が塗布された金属板上には、NBRの水性ラテックスとカーボンブラックの水分散液を含有する水系ゴム塗液が塗布される。水性ラテックスの形で用いられるNBRとしては、結合アクリロニトリル量が30%以上、好ましくは35%以上のNBRが用いられる。アクリロニトリルの結合量が30%より少ないものを用いた場合には、十分な物性および非粘着性の塗膜を形成させることができない。NBRは、環境衛生面から有機溶剤レスとするために、固型分濃度が約30〜60重量%の水性ラテックスとして用いられ、実際には市販品のNBR水性ラテックス、例えば日本ゼオン製品Nipolシリーズの1551、1561、1571、1571C、1571E、1571H、1571CL、LX511、LX513、LX517A、LX551等がそのまま用いられる。場合によっては、他のポリマーラテックス、例えばアクリルゴム水性ラテックス、フッ素ゴム水性ラテックスを併用することもできる。
【0010】
これらのNBR水性ラテックスと共に水系ゴム塗液を構成する成分であるカーボンブラックとしては、粒子径が5〜300nm、好ましくは20〜250nmのものが用いられる。粒子径がこれ以上のものを用いると、塗膜に十分な補強性および非粘着性を確保することができず、一方これ以下の粒子径のものを用いると、分散液の取り扱いが困難となる。このような範囲の粒子径を有するカーボンブラックとしては、SAF、ISAF、HAF、FEF、SRF、MT等のグレードのものが挙げられる。
【0011】
カーボンブラックは、水性ラテックス中のNBR100重量部に対し40〜160重量部、好ましくは60〜140重量部の割合で用いられ、形成される塗膜に十分な補強性および非粘着性を付与すると共に、廉価なカーボンブラックの配合割合を多くすることによって、製品の低コスト化をも達成せしめる。
【0012】
水系ゴム塗液中には、NBRの加硫に用いられるパーオキサイド系または硫黄系加硫剤、その他の必要な配合剤が添加されて用いられる。加硫剤の選定に際しては、加硫物性と加硫速度とが重要であるため、それらの点を考慮することが望ましい。加硫速度の点からは、約160〜260℃、好ましくは約180〜230℃の温度範囲において約5〜300秒、好ましくは約10〜200秒間で加硫するような加硫剤が望ましく、これを実現させるようなパーオキサイド系化合物の市販品としては、例えば日本油脂製品パーブチルZ、パーヘキサZ、パーブチルP、パークミルD、パーヘキサ25B、パーブチルC、パーブチルD、パークミルP等が挙げられ、また硫黄系化合物としては、硫黄の他に例えばテトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム類化合物、2−メチカプトベンゾチアゾール、ジベンゾチアジルジスルフィド等のチアゾール類化合物、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジブチルジチオカルバミン酸亜鉛等のジチオ酸塩類等が挙げられる。特にパーオキサイド系化合物を用いた場合には、塗膜の耐熱耐久性が向上する。これらの加硫剤、加硫促進剤以外にも、上記加硫条件を満足させるような加硫促進剤を組合せて使用してもよい。
【0013】
以上の各成分を含有する水系ゴム塗液の金属板上への塗布は、ロールコート法、ナイフコート法、フローコート法、ダイコート法、ディッピング法またはこれらの方法の組合せ方法等の公知の方法で行われる。塗布後には、約50〜250℃で数〜数10分間程度の乾燥が行われ、その後プレス加硫が行われる。
【0014】
プレス加硫は、0.1MPa以上、好ましくは約0.2〜10MPaの面圧をかけた状態で、約160〜260℃で約5〜300秒間加熱して行われ、金属板上に膜厚約20〜400μm、好ましくは約20〜200μmの加硫ゴム層を形成させる。
【0015】
このようにして行われる金属・ゴム複合材料の製造法は、例えば100m以上の長さを有する長尺金属板にも適用することができ、塗布型クロメート処理していない長尺の接着剤塗布金属板上に水系ゴム塗液を塗布する工程、水分を乾燥させる工程および金属板と塗膜とをプレスにより加硫接着させる工程という一連の工程を連続ライン方式として行なうことができ、この場合にも所望の物性、補強性、非粘着性などを備えた長尺金属・ゴム複合材料を得ることができる。
【0016】
【発明の効果】
本発明方法では、ゴム塗液として有機溶媒を用いず、また金属板の表面処理に塗布型クロメート処理を施していないにも拘らず、従来の有機溶媒希釈タイプゴム塗液あるいは塗布型クロメート処理金属板を用いた場合と同等の性能を示す金属・ゴム複合材料が得られる。
【0017】
より具体的には、次のような効果が得られる。
(1)加硫方式としてプレス加硫方式をとることにより、加硫温度にもよるが5〜300秒間という短時間で加硫接着が完了する。
(2)これによって、膜厚が20〜400μm程度と薄いにも拘らず、製品表面が平滑になり、シール性が向上するばかりではなく、大気中では加硫阻害が起るようなパーオキサイド加硫系でも加硫することができる。
(3)また、加硫時の熱による添加剤等の揮発散逸を抑えることができるので、環境衛生上有利になる。
(4)金属板上にクロム酸塩の化成皮膜を設けなくとも製品機能が良好となるのはプレス加硫方式をとったためと考えられる。
(5)短時間でのプレス加硫は、製造方式を連続ライン方式とすることを可能とし、これによって低コスト化も図られる。
【0018】
製法方式を連続ライン方式とすることに関連して、次のようなことがいえる。連続ライン方式では、バッチ毎のプレス加硫方式と違い、連続的にゴム製品をプレス加硫していく際に短時間加硫できなければならないことは勿論であるが、ゴムのプレス金型面への粘着という不具合が起らないようにしておくことも重要である。このような点が満足されていないと、製造速度が遅くなり、製品表面に異物が付着し易くなるなど品質の維持も難かしくなり、結果としてコストアップにつながってしまうが、本発明方法ではこのような点が十分に満足されるので、連続ライン方式を可能としているのである。
【0019】
このような特徴を有する本発明の金属・ゴム複合材料は、ガスケット等の液体や気体等の密封用シール製品として有効に用いることができる。
【0020】
【実施例】
次に、実施例について本発明を説明する。
【0021】
実施例1〜3、参考例1〜2、比較例1〜3
接着剤塗布鋼板I:ボンデ処理を施したSPCC鋼板上にフェノール系接着剤をディッピング法により塗布し、180℃で5分間の接着剤の焼付処理をした
接着剤塗布鋼板II:SUS鋼板(SUS304)上にシラン系接着剤(Dygussa社製品Dynasilan DAMO)をディッピング法により塗布し、60℃で20分間の乾燥後に180℃で5分間の焼付処理をした
接着剤塗布鋼板III:塗布型クロメート処理を施したSUS鋼板(SUS304)上にシラン系接着剤(Dynasilan DAMO)をディッピング法により塗布し、60℃で20分間の乾燥後に180℃で5分間の焼付処理をした
ゴム塗液A:NBR水性ラテックス(日本ゼオン製品Nipol 1571E;固形分濃度40重量%)250g中に攪拌下でHAFグレードのカーボンブラックの水分散物(カーボンブラック濃度:30重量%)200g、亜鉛華10g、硫黄系加硫剤の水分散物(日本ゼオン製品SD−1)6gを順次添加し、60分間攪拌を続けてゴム塗液を得た
ゴム塗液B:NBR水性ラテックス(日本ゼオン製品Nipol 1571C;固形分濃度45重量%)222g中に攪拌下でMTグレードのカーボンブラックとHAFグレードのカーボンブラックの水分散物(MT/HAF=7/3、カーボンブラック濃度:40重量%)200g、亜鉛華10g、パーオキサイド系加硫剤(日本油脂製品パーブチルP)の水分散物(パーオキサイド濃度:40重量%)8gを順次添加し、60分間攪拌を続けてゴム塗液を得た
ゴム塗液C:NBR水性ラテックス(日本ゼオン製品Nipol LX513;固形分濃度45重量%)222g中に攪拌下でHAFグレードのカーボンブラックの水分散物(カーボンブラック濃度:30重量%)200g、亜鉛華10g、硫黄系加硫剤の水分散物(SD−1)6gを順次添加し、60分間攪拌を続けてゴム塗液を得た
ゴム塗液D:NBR水性ラテックス(Nipol 1571E;固形分濃度40重量%)250g中に攪拌下でHAFグレードのカーボンブラックの水分散物(カーボンブラック濃度:30重量%)100g、亜鉛華10g、硫黄系加硫剤の水分散物(SD−1)6gを順次添加し、60分間攪拌を続けてゴム塗液を得た
ゴム塗液E:NBRポリマー(日本合成ゴム製品N220S)100gに対し、HAFグレードのカーボンブラック60g、亜鉛華10g、ステアリン酸1g、老化防止剤(3C) 1g、硫黄1g、促進剤TS−10 2.5gを混練し、得られた生地をトルエン525g中に溶解した
【0022】
上記接着剤焼付処理済みの鋼板I〜IIIを200×200mmの大きさに切断し、その上面に上記ゴム塗液A〜Eをナイフコーターで、乾燥後の塗膜厚みが60μmまたは100μmとなるように塗布した。次いで、80℃に加熱したホットプレート上で6分間の脱水乾燥を行ない、乾燥後の試料にSUS304板の当て板をかぶせ、200℃に加熱したプレス機を用いて、2MPa、2分間のプレス加硫を行った(ただし、比較例3〜4ではオーブン加硫が行われたが、200℃では揮発ガスの発生が顕著なため、180℃のオーブン加硫とした)。
【0023】
得られた試料について、次の各項目の測定または評価を行った。
型への非粘着性:SUS304板の剥れ易さで評価して、粘着性なしを〇、粘着性大を×と評価
ゴバン目試験(接着性):初期およびロングライフクーラント(トヨタ純正LLC)液中に130℃で72時間浸せきした後、ゴバン目テープ試験を実施し、評点10〜0で、初期は10、9が合格、浸せき後は8以上を合格とする
屈曲試験(塗膜の割れ抵抗性):JIS K−5400準拠;初期および130℃、50時間または200時間の熱暴露後に180°折曲げを実施し、割れや剥れが認められないときを〇、剥がれには至っていないが、部分的に割れが認められるときを△、これらが認められたときを×と評価
表面粗さ(表面平滑性):塗膜表面粗さを表面粗さ計で測定し、粗さRaおよび最大粗さRmaxを測定
【0024】
以上の測定および評価結果は、次の表に示される。なお、比較例3(加硫時間3分間)では加硫されず、また比較例4(加硫時間20分間)では加硫時に多量の悪臭ガスが発生した。
【0025】
以上の結果から、次のようなことがいえる。
(1)各実施例では水系ゴム塗液が用いられているが、塗布型クロメート処理を施した場合(参考例1)および溶剤希釈タイプの場合(参考例2)に相当する性能が得られている。
(2)プレス加硫の場合、比較例1〜2のゴム塗液では当て板への粘着性が大であった。
(3)初期ゴバン目評価はどれも殆んど問題なかったが、LLC液浸せき試験後の評価では比較例1、2、4にはゴム剥れがみられた。
(4)200時間の耐熱暴露試験では、比較例1、2、4でゴムの脆化に伴う破壊がみられた。
(5)オーブン加硫物では、プレス加硫物と比較して製品表面粗さが粗かった。
【0026】
実施例4
実施例3の条件を長さ1000mの接着剤焼付け処理済みの鋼板に適用し、ゴム溶液塗布−乾燥−加硫−巻取りの各工程が連続している連続ラインで実施したところ、製品機能評価結果は上記表の結果と変らなかった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a metal / rubber composite material. More specifically, the present invention relates to a method for producing a metal / rubber composite material by applying an aqueous NBR coating liquid on a metal plate that has not been subjected to a coating type chromate treatment.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, as a seal product such as a gasket, a product obtained by coating rubber on a metal plate to impart a sealing property has been used. The thickness of the rubber layer coated on the metal plate is about several tens to several hundreds of micrometers. Therefore, conventionally, a coating solution in which an unvulcanized rubber composition is dissolved in an organic solvent is used, and this is coated, dried and vulcanized. Had been used. However, in recent years, it has become difficult to use an organic solvent used for dissolving rubber due to environmental problems and the like, and there is a tendency to use an aqueous rubber coating solution.
[0003]
When changing from a conventional solvent-diluted type product to a water-based rubber coating solution, it is required that the performance be equivalent to that of the conventional product and that the cost be the same or less. However, it is not easy for the aqueous rubber coating liquid type to exhibit the same performance as the conventional solvent dilution type, and this is an obstacle to commercialization.
[0004]
Further, in order to increase the adhesive strength between the metal plate and the rubber, the surface of the metal plate is subjected to a coating type chromate treatment. However, from the viewpoint of environmental problems and the like, it is desired to reduce chrome. In particular, when a metal plate that has not been subjected to a coating-type chromate treatment is used and a rubber coating liquid of an aqueous dispersion is applied, it is not easy to exhibit the same performance as that of a solvent dilution type.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a metal-rubber composite material by applying an aqueous NBR coating liquid on a metal plate that has not been subjected to a coating type chromate treatment, and to obtain the same performance (physical properties, reinforcing properties, etc.) as a conventional organic solvent dilution type. , Non-adhesiveness, etc.).
[0006]
[Means for Solving the Problems]
An object of the present invention is to apply an adhesive onto a metal plate that has not been subjected to a coating-type chromate treatment, to which an aqueous latex of NBR having a bound acrylonitrile amount of 30% or more and water of carbon black having a particle diameter of 5 to 300 nm are used. This is achieved by a method of producing a metal-rubber composite material by applying and drying an aqueous rubber coating solution containing a dispersion, and then press vulcanizing at a surface pressure of 0.1 MPa or more.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
As the metal plate, a stainless steel plate, an aluminum plate, a zinc steel plate or the like is used, and its thickness is not limited, but generally about 0.1 to 2.0 mm is used. In order to achieve sufficient performance, it is preferable to use the metal plate surface after treating it with a metal phosphate (bonding treatment). In this case, not only is the adhesion of the coating film improved, but also the metal plate is used. Also contributes to the improvement of the corrosion resistance.
[0008]
An adhesive is applied on the metal plate prior to the formation of the rubber layer. As the adhesive, at least one kind of a phenol-based adhesive, a silane-based or a titanate-based coupling agent is used. As the phenol-based adhesive, a phenol-formaldehyde polycondensate is preferably used. Representative examples of the silane coupling agent include methoxysilanes and ethoxysilanes having a functional group such as a vinyl group, an amino group, and a mercapto group. As the titanate-based coupling agent, for example, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate and the like are used. If necessary, a polymer component such as an elastomer, an inorganic additive such as silica, an organometallic catalyst, or the like may be added to the adhesive containing these components as a main component to improve the adhesive strength. The application of the adhesive onto the metal plate can be performed by any method such as a dipping method, a spray method, and a brush coating method, and thereafter, a baking treatment is performed at a predetermined temperature.
[0009]
An aqueous rubber coating solution containing an aqueous latex of NBR and an aqueous dispersion of carbon black is applied on the metal plate to which the adhesive has been applied. As the NBR used in the form of the aqueous latex, an NBR having a bound acrylonitrile amount of 30% or more, preferably 35% or more is used. When an acrylonitrile having a bonding amount of less than 30% is used, it is impossible to form a coating film having sufficient physical properties and non-adhesiveness. NBR is used as an aqueous latex having a solid content of about 30 to 60% by weight in order to eliminate organic solvents from the viewpoint of environmental hygiene. Actually, a commercially available NBR aqueous latex, for example, a Nipol series of Nippon Zeon products 1551, 1561, 1571, 1571C, 1571E, 1571H, 1571CL, LX511, LX513, LX517A, LX551, etc. are used as they are. In some cases, another polymer latex, for example, an aqueous acrylic rubber latex or an aqueous fluororubber latex may be used in combination.
[0010]
Carbon black having a particle size of 5 to 300 nm, preferably 20 to 250 nm, is used as a component of the aqueous rubber coating liquid together with the NBR aqueous latex. If the particle size is larger than this, it is not possible to secure sufficient reinforcing properties and non-adhesion to the coating film, while if the particle size is smaller than this, it becomes difficult to handle the dispersion. . Examples of carbon black having a particle size in such a range include grades such as SAF, ISAF, HAF, FEF, SRF, and MT.
[0011]
Carbon black is used in an amount of 40 to 160 parts by weight, preferably 60 to 140 parts by weight, based on 100 parts by weight of NBR in the aqueous latex, and imparts sufficient reinforcing properties and non-adhesiveness to a coating film to be formed. By increasing the proportion of inexpensive carbon black, the cost of the product can be reduced.
[0012]
In the aqueous rubber coating liquid, a peroxide-based or sulfur-based vulcanizing agent used for vulcanizing NBR and other necessary compounding agents are added and used. When selecting a vulcanizing agent, vulcanization properties and vulcanization rate are important, and it is desirable to consider these points. From the viewpoint of the vulcanization rate, a vulcanizing agent which cures in a temperature range of about 160 to 260 ° C., preferably about 180 to 230 ° C. for about 5 to 300 seconds, preferably about 10 to 200 seconds is desirable. Commercially available peroxide-based compounds that achieve this are, for example, Nippon Oil and Fat Products Perbutyl Z, Perhexa Z, Perbutyl P, Parkmill D, Perhexa 25B, Perbutyl C, Perbutyl D, Parkmill P, and the like. As the system compound, in addition to sulfur, for example, thiurams such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, thiazoles such as 2-methylcaptobenzothiazole, dibenzothiazyl disulfide, and dimethyldithiocarbamic acid Zinc, diethyldithi Zinc carbamate, dithio acid salts such as zinc dibutyldithiocarbamate, and the like. In particular, when a peroxide compound is used, the heat resistance of the coating film is improved. In addition to these vulcanizing agents and vulcanization accelerators, vulcanization accelerators that satisfy the above vulcanization conditions may be used in combination.
[0013]
Application of the aqueous rubber coating solution containing the above components on a metal plate is performed by a known method such as a roll coating method, a knife coating method, a flow coating method, a die coating method, a dipping method or a combination method of these methods. Done. After the application, drying is performed at about 50 to 250 ° C. for about several to several tens of minutes, and then press vulcanization is performed.
[0014]
Press vulcanization is performed by heating at about 160 to 260 ° C. for about 5 to 300 seconds while applying a surface pressure of 0.1 MPa or more, preferably about 0.2 to 10 MPa. A vulcanized rubber layer of about 20 to 400 μm, preferably about 20 to 200 μm is formed.
[0015]
The method for producing a metal / rubber composite material performed in this manner can be applied to, for example, a long metal plate having a length of 100 m or more, and a long adhesive-coated metal that has not been subjected to a coating-type chromate treatment. A series of steps of applying a water-based rubber coating solution on a plate, drying a moisture, and vulcanizing and bonding a metal plate and a coating film by pressing can be performed as a continuous line method. A long metal / rubber composite material having desired physical properties, reinforcing properties, non-adhesiveness and the like can be obtained.
[0016]
【The invention's effect】
In the method of the present invention, a conventional organic solvent-diluted rubber coating liquid or a coating type chromate-treated metal is used, although an organic solvent is not used as the rubber coating liquid and the surface treatment of the metal plate is not subjected to the coating type chromate treatment. A metal / rubber composite material having the same performance as that obtained by using a plate is obtained.
[0017]
More specifically, the following effects can be obtained.
(1) By using a press vulcanization method as a vulcanization method, vulcanization bonding is completed in a short time of 5 to 300 seconds, depending on the vulcanization temperature.
(2) As a result, despite the thin film thickness of about 20 to 400 μm, not only does the product surface become smooth and the sealing property is improved, but also peroxide addition which causes vulcanization inhibition in the atmosphere is caused. Vulcanization can also be performed in a vulcanization system.
(3) Further, since the volatilization and dissipation of additives and the like due to heat during vulcanization can be suppressed, it is advantageous in environmental hygiene.
(4) It is considered that the reason why the product function is improved without providing the chromate chemical conversion film on the metal plate is that the press vulcanization method is employed.
(5) Press vulcanization in a short time enables the production system to be a continuous line system, thereby reducing costs.
[0018]
The following can be said in connection with making the manufacturing method a continuous line method. In the continuous line method, unlike the press vulcanization method for each batch, it is necessary to be able to vulcanize for a short time when continuously vulcanizing the rubber product. It is also important to avoid the problem of sticking to the surface. If these points are not satisfied, the production speed will be slow, and it will be difficult to maintain the quality, such as foreign substances easily adhering to the product surface, which will lead to an increase in cost. Since such points are sufficiently satisfied, the continuous line system is made possible.
[0019]
The metal / rubber composite material of the present invention having such characteristics can be effectively used as a sealing product for sealing a liquid or gas such as a gasket.
[0020]
【Example】
Next, the present invention will be described with reference to examples.
[0021]
Examples 1-3, Reference Examples 1-2, Comparative Examples 1-3
Adhesive-coated steel sheet I: An adhesive-coated steel sheet obtained by applying a phenolic adhesive to a bond-treated SPCC steel sheet by dipping and baking the adhesive at 180 ° C. for 5 minutes II: SUS steel sheet (SUS304) A silane-based adhesive (Dynasila DAMO manufactured by Dygussa) was applied thereon by a dipping method, dried at 60 ° C. for 20 minutes, and then baked at 180 ° C. for 5 minutes. A silane-based adhesive (Dynasilan DAMO) was applied to the SUS steel plate (SUS304) by dipping, dried at 60 ° C. for 20 minutes, and baked at 180 ° C. for 5 minutes. Rubber coating solution A: NBR aqueous latex ( Nippon Zeon product Nipol 1571E; solid content concentration 40% by weight) under stirring in 250 g 200 g of an aqueous dispersion of HAF-grade carbon black (carbon black concentration: 30% by weight), 10 g of zinc white, and 6 g of an aqueous dispersion of a sulfur-based vulcanizing agent (Nippon Zeon SD-1) are sequentially added and stirred for 60 minutes. A rubber coating liquid B was obtained by continuing to prepare a rubber coating liquid B: water of MT-grade carbon black and HAF-grade carbon black in 222 g of NBR aqueous latex (Nipol 1571C manufactured by Nippon Zeon; solids concentration: 45% by weight) under stirring. 200 g of a dispersion (MT / HAF = 7/3, carbon black concentration: 40% by weight), 10 g of zinc white, an aqueous dispersion of a peroxide-based vulcanizing agent (Nippon Oil & Fats product, Perbutyl P) (peroxide concentration: 40% by weight) ) 8 g was sequentially added, and stirring was continued for 60 minutes to obtain a rubber coating solution. Rubber coating solution C: NBR aqueous latex (product of Zeon Corporation) IPOL LX513; 200 g of an aqueous dispersion of HAF grade carbon black (carbon black concentration: 30 wt%), 10 g of zinc white, and an aqueous dispersion of a sulfur-based vulcanizing agent in 222 g of a solid content concentration of 45 wt% (solid content: 45 wt%). SD-1) 6 g were sequentially added and stirring was continued for 60 minutes to obtain a rubber coating solution. Rubber coating solution D: 250 g of NBR aqueous latex (Nipol 1571E; solid content concentration: 40% by weight) under HAF grade under stirring. 100 g of an aqueous dispersion of carbon black (carbon black concentration: 30% by weight), 10 g of zinc white, and 6 g of an aqueous dispersion of a sulfur-based vulcanizing agent (SD-1) are sequentially added, and stirring is continued for 60 minutes to prepare a rubber coating liquid. Rubber coating liquid E obtained: 100 g of NBR polymer (N220S manufactured by Nippon Synthetic Rubber), 60 g of HAF grade carbon black, 10 g of zinc white, 1 g of theearic acid, 1 g of antioxidant (3C), 1 g of sulfur, and 2.5 g of TS-10 accelerator were kneaded, and the resulting dough was dissolved in 525 g of toluene.
The steel plates I to III having been subjected to the adhesive baking treatment are cut into a size of 200 × 200 mm, and the rubber coating liquids A to E are coated on the upper surface thereof with a knife coater so that the coating thickness after drying becomes 60 μm or 100 μm. Was applied. Next, dehydration drying was performed for 6 minutes on a hot plate heated to 80 ° C., and the dried sample was covered with a SUS304 plate, and pressed at 2 MPa for 2 minutes using a press machine heated to 200 ° C. Sulfurization was performed (however, oven vulcanization was performed in Comparative Examples 3 and 4, but the generation of volatile gas was remarkable at 200 ° C, so that oven vulcanization was performed at 180 ° C).
[0023]
For the obtained sample, the following items were measured or evaluated.
Non-adhesiveness to mold: Evaluated by easiness of peeling of SUS304 plate, evaluated as non-adhesive, evaluated as Δ, and evaluated as large, evaluated as ×. After being immersed in the solution at 130 ° C. for 72 hours, a goban-mesh tape test was performed. Resistance): According to JIS K-5400; Initially and after 180 ° heat exposure at 130 ° C. for 50 hours or 200 hours, bending was performed at 180 °. , When cracks were partially observed, and x when these were observed Surface roughness (surface smoothness): The surface roughness of the coating film was measured with a surface roughness meter, and the roughness Ra and the maximum were measured. Measure roughness Rmax
The above measurement and evaluation results are shown in the following table. In Comparative Example 3 (vulcanization time of 3 minutes), no vulcanization was performed, and in Comparative Example 4 (vulcanization time of 20 minutes), a large amount of malodorous gas was generated during vulcanization.
[0025]
From the above results, the following can be said.
(1) Although a water-based rubber coating liquid is used in each of the examples, the performance equivalent to the case of applying the coating type chromate treatment (Reference Example 1) and the case of the solvent dilution type (Reference Example 2) is obtained. I have.
(2) In the case of press vulcanization, the rubber coating liquids of Comparative Examples 1 and 2 had high adhesiveness to the backing plate.
(3) Although there was almost no problem in the initial evaluation of the Goban pattern, rubber peeling was observed in Comparative Examples 1, 2, and 4 in the evaluation after the LLC liquid immersion test.
(4) In a heat exposure test for 200 hours, in Comparative Examples 1, 2, and 4, destruction due to embrittlement of rubber was observed.
(5) The product surface roughness of the oven vulcanized product was higher than that of the press vulcanized product.
[0026]
Example 4
When the conditions of Example 3 were applied to a steel plate having a length of 1000 m and subjected to an adhesive baking treatment, and the steps of rubber solution application-drying-vulcanization-winding were performed in a continuous line, product function evaluation was performed. The result was not different from the result in the above table.
Claims (10)
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