JP2005315418A - Gasket material - Google Patents
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- JP2005315418A JP2005315418A JP2005098323A JP2005098323A JP2005315418A JP 2005315418 A JP2005315418 A JP 2005315418A JP 2005098323 A JP2005098323 A JP 2005098323A JP 2005098323 A JP2005098323 A JP 2005098323A JP 2005315418 A JP2005315418 A JP 2005315418A
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- rubber layer
- foaming
- gasket
- gasket material
- foamed
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- 239000000463 material Substances 0.000 title claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 64
- 238000005187 foaming Methods 0.000 claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000004088 foaming agent Substances 0.000 claims description 17
- 241001441571 Hiodontidae Species 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920001821 foam rubber Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010013642 Drooling Diseases 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 208000008630 Sialorrhea Diseases 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- Gasket Seals (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
本発明は、車両のエンジンに装着されるガスケットを形成するためのガスケット用素材に関する。 The present invention relates to a gasket material for forming a gasket to be mounted on a vehicle engine.
車両のエンジンに装着されるメタルガスケット、特にヘッドガスケット用として、ステンレス鋼板にゴム層を積層したゴムコーティングステンレス鋼板が一般的である。このようなヘッドガスケットに用いられるゴム層は、エンジン運転中に高面圧下で２００℃に近い温度まで加熱されるため、熱と圧力によるゴム層のヘタリが小さい、未発泡のゴム層を用いるのが一般的である（例えば、特許文献１参照）。 A rubber coated stainless steel plate in which a rubber layer is laminated on a stainless steel plate is generally used for a metal gasket, particularly a head gasket, to be mounted on a vehicle engine. Since the rubber layer used for such a head gasket is heated to a temperature close to 200 ° C. under high surface pressure during engine operation, an unfoamed rubber layer is used which has a small settling due to heat and pressure. Is common (see, for example, Patent Document 1).
このように未発泡のゴム層を用いたメタルガスケットは、ビードを備えることで優れたシール性を発現するが、一般にフランジの面粗度が１２．５Ｒａ以下のときに優れたシール性を発揮するが、それ以上では十分なシール性を確保できないことがあり、更にはメタルガスケットは、ビード（浮き彫り加工）部にボルト加重を集中させることでシールさせるため、ビードラインを跨って鋳巣（鋳造時の気泡に基づく表面の微細な凹部；図１参照）が存在すると十分なシール性が得られないことがある。 As described above, a metal gasket using an unfoamed rubber layer exhibits an excellent sealing property by providing a bead, but generally exhibits an excellent sealing property when the surface roughness of the flange is 12.5 Ra or less. However, there are cases where sufficient sealability cannot be secured beyond that, and metal gaskets are sealed by concentrating the bolt load on the bead (relief processing) part. If there are fine concave portions on the surface based on the bubbles of the surface (see FIG. 1), sufficient sealing properties may not be obtained.
また、発泡させたゴム層を積層したメタルガスケットも知られている（例えば、特許文献２参照）。この発泡ゴム層を積層したメタルガスケットは、面粗度の粗いフランジや鋳巣をシールすることができるが、一般に発泡前のゴム層が約７０μｍ以上の厚さがないと、発泡すること（特に発泡倍率が２倍以上）が困難となる。また、発泡ゴム層を積層したメタルガスケットは、発泡前のゴム層が厚いため、高温・高圧下で発泡ゴム層がへたり、ボルトの軸力が低下してしまう。更に、発泡ゴム層を得るには、一般にマイクロカプセル法、化学発泡剤を用いた加熱分解法があるが、マイクロカプセル法で得られた発泡ゴム層は発泡倍率が小さいため、鋳巣シールへの効果は小さく、また発泡ゴム層の多くが独泡（発泡セルが独立した気泡）であることから、低温（マイナス温度下）で独泡の収縮があり、ボルトの軸力低下を引き起こしたり、シール面圧が低いときは、発泡ゴム層が完全に漬れ切らないために、使用中に発泡ゴム層がへたってボルトが応力緩和するという問題がある。 A metal gasket in which foamed rubber layers are laminated is also known (for example, see Patent Document 2). The metal gasket laminated with the foamed rubber layer can seal a flange or a cast hole having a rough surface, but generally foams unless the rubber layer before foaming has a thickness of about 70 μm or more (especially The expansion ratio is 2 times or more). Moreover, since the rubber layer before foaming is thick in the metal gasket which laminated | stacked the foam rubber layer, a foam rubber layer will sag under high temperature and a high pressure, and the axial force of a bolt will fall. Furthermore, in order to obtain a foamed rubber layer, there are generally a microcapsule method and a thermal decomposition method using a chemical foaming agent. However, since the foamed rubber layer obtained by the microcapsule method has a low foaming ratio, The effect is small, and most of the foamed rubber layer is closed-celled (bubbles with independent foamed cells), so the closed-cell shrinkage occurs at low temperature (under minus temperature), causing a decrease in the axial force of the bolt, and sealing. When the surface pressure is low, the foamed rubber layer is not completely immersed, so that there is a problem that the foamed rubber layer falls during use and the bolts relieve stress.
上記のように、未発泡ゴム層を積層したガスケットは高温・高圧下によるゴム層のへたりは無いが鋳巣や面粗度の粗いフランジのシールには向かず、また、発泡ゴム層を積層したガスケットはへたりの問題を抱えている。従って本発明は、高温・高圧下でゴム層のヘタリがなく、且つ低温でのゴム層の収縮がなく、鋳巣や面粗度の粗いフランジを良好にシールするガスケットを得るためのガスケット素材を提供することを目的とする。 As mentioned above, gaskets with a non-foamed rubber layer laminated have no rubber layer sag under high temperature and high pressure, but are not suitable for seals in casting holes or flanges with rough surface roughness. The gasket has a problem of drooling. Therefore, the present invention provides a gasket material for obtaining a gasket that does not have a rubber layer settling under high temperature and high pressure, does not shrink the rubber layer at low temperature, and seals a cast hole or a flange having a rough surface. The purpose is to provide.
本発明者らは、このような従来の問題点に着目し、特にヘッドガスケットとしての使用を可能にすることを目的に、ゴム配合中のポリマー（ムーニー値、配合量）、発泡剤（種類、配合量）、加硫剤（加硫剤の種類）、加硫促進剤（加硫促進剤の種類）を鋭意検討した結果、発泡前のゴム層を薄くし（１５〜５０μｍ）、発泡ゴム層に含まれる全気泡の占める体積と連泡の占める体積との比率が８０％以上とすることにより、高温・高圧下でゴムフローがなく、低温での発泡層の収縮が小さく、鋳巣や面粗度の粗いフランジを良好にシールできることを見出した。尚、連泡とは発泡セルが連続で繋がった気泡である。本発明は、このような知見に基づくものである。 The present inventors pay attention to such conventional problems, and in particular for the purpose of enabling the use as a head gasket, a polymer (Mooney value, blending amount), a foaming agent (kind, Compounding amount), vulcanizing agent (type of vulcanizing agent), and vulcanization accelerator (type of vulcanizing accelerator), as a result of intensive studies, the rubber layer before foaming was thinned (15-50 μm), and the foamed rubber layer By making the ratio of the volume occupied by all bubbles and the volume occupied by continuous bubbles contained in 80% or more, there is no rubber flow under high temperature and high pressure, and the shrinkage of the foamed layer at low temperature is small, so It has been found that a rough flange can be well sealed. The open cell is a bubble in which foam cells are continuously connected. The present invention is based on such knowledge.
即ち、本発明は、鋼板の両面または片面に発泡ゴム層が形成され、車両のエンジンに装着されるガスケットを形成するためのガスケット用素材において、前記発泡ゴム層の発泡前におけるゴム層厚さが１５〜５０μｍで、かつ発泡倍率が２〜４倍であることを特徴とするガスケット用素材を提供する。特に、前記発泡ゴム層が、ムーニー値１０〜７０のポリマーを２０〜７０質量％、加熱分解型の化学発泡剤を２０〜６０質量％の割合で含有するゴムコンパウンドを発泡させてなり、かつ該発泡ゴム層の８０％以上が連泡であることが好ましい。尚、発泡倍率とは、発泡前のゴム層の厚さに対する発泡後のゴム層の厚さの比率である。 That is, according to the present invention, a foam rubber layer is formed on both sides or one side of a steel plate, and a gasket material for forming a gasket to be mounted on a vehicle engine has a rubber layer thickness before foaming of the foam rubber layer. Provided is a gasket material characterized by being 15 to 50 μm and an expansion ratio of 2 to 4 times. In particular, the foamed rubber layer is obtained by foaming a rubber compound containing 20 to 70% by mass of a polymer having a Mooney value of 10 to 70 and 20 to 60% by mass of a thermal decomposition type chemical foaming agent, and It is preferable that 80% or more of the foamed rubber layer is open-celled. The expansion ratio is the ratio of the thickness of the rubber layer after foaming to the thickness of the rubber layer before foaming.
本発明のガスケット用素材を用いることにより、高温・高圧下でゴム層のヘタリがなく、且つ低温でのゴム層の収縮がなく、鋳巣や面粗度の粗いフランジを良好にシールし得るガスケットが得られる。 By using the gasket material of the present invention, there is no rubber layer settling under high temperature and high pressure, there is no shrinkage of the rubber layer at low temperature, and a gasket that can satisfactorily seal a flange with a rough cast surface or rough surface Is obtained.
以下、本発明に関して詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のガスケット用素材は、鋼板の両面または片面に発泡ゴム層が形成されたものである。発泡ゴム層を形成するゴムコンパウンドには、ムーニー値１０〜７０のポリマーがゴムコンパウンド全量の２０〜７０質量％（請求項２に一致）の割合で配合されることが好ましい。より好ましくは、ムーニー値が２０〜６０で、配合量がゴムコンパウンド全量の２０〜６０質量％である。このようなポリマーの配合により、発泡ゴム層のへたりを効果的に抑えることができる。 The gasket material of the present invention has a foam rubber layer formed on both sides or one side of a steel plate. The rubber compound forming the foamed rubber layer is preferably blended with a polymer having a Mooney value of 10 to 70 in a proportion of 20 to 70% by mass (corresponding to claim 2) of the total amount of the rubber compound. More preferably, the Mooney value is 20 to 60, and the blending amount is 20 to 60% by mass of the total amount of the rubber compound. By blending such a polymer, it is possible to effectively suppress the sag of the foamed rubber layer.
ポリマーの種類は、ムーニー値が前記の範囲であれば制限されず、従来からゴム層を積層したガスケットに使用されているＮＢＲ、ＨＮＢＲ、フッ素ゴム、ＥＰＤＭ、アクリルゴム等を使用でき、ＮＢＲ、ＨＮＢＲ、フッ素ゴムを用いるのが好ましい。また、ＮＢＲは、耐油性を持たせるため、ＡＮ値（ＮＢＲ中のアクリロニトル基の含有量）が３９〜５２までのものを用いるのが好ましく、４０〜４８までのものがより好ましい。 The type of polymer is not limited as long as the Mooney value is in the above range, and NBR, HNBR, fluororubber, EPDM, acrylic rubber, etc. that have been used for gaskets laminated with a rubber layer can be used. NBR, HNBR Fluorine rubber is preferably used. Moreover, in order to give oil resistance to NBR, it is preferable to use an AN value (content of acrylonitrile group in NBR) of 39 to 52, more preferably 40 to 48.
また、ゴムコンパウンドには、加熱分解型の化学発泡剤が配合される。この加熱分解型の発泡剤の種類は限定されないが、発泡温度が１２０℃以上のものがよい。更に、１５０〜２１０℃のものが最良である。また、配合量はゴムコンパウンド全量の２０〜６０質量％の割合で配合されることが好ましく、より好ましくは１５〜３５質量％である。 The rubber compound is blended with a thermal decomposition type chemical foaming agent. The kind of the heat decomposable foaming agent is not limited, but a foaming temperature of 120 ° C. or higher is preferable. Furthermore, the thing of 150-210 degreeC is the best. Moreover, it is preferable to mix | blend the compounding quantity in the ratio of 20-60 mass% of rubber compound whole quantity, More preferably, it is 15-35 mass%.
また、ゴムコンパウンドには加硫剤及び加硫促進剤が添加される。加硫剤は、加硫密度が高くなるように多量に配合されるのが好ましく、硫黄加硫の場合、１．５〜４．５ｐｈｒで用いられるのが好ましい。また、加硫促進剤は、キュラストデータ（１５０℃）でＴ５０までの時間が４分以内で立ち上がる高速のものを用いるのが好ましい。尚、キュラストデータ（１５０℃）でＴ５０までの時間とは、キュラスト試験機を用い１５０℃で加硫を行った際に、ゴムの加硫程度がＴ５０に達するまでに要する時間である。 Moreover, a vulcanizing agent and a vulcanization accelerator are added to the rubber compound. The vulcanizing agent is preferably blended in a large amount so as to increase the vulcanization density. In the case of sulfur vulcanization, it is preferably used at 1.5 to 4.5 phr. As the vulcanization accelerator, it is preferable to use a high-speed vulcanization accelerator that rises within 4 minutes until T50 in the curast data (150 ° C.). The time to T50 in the curast data (150 ° C.) is the time required for the degree of rubber vulcanization to reach T50 when vulcanized at 150 ° C. using a curast tester.
上記のゴムコンパウンドは、有機溶剤に溶解させて塗布液とされ、鋼板に塗布される。有機溶剤は上記のゴムコンパウンドを溶解できるものであれば制限されるものではないが、トルエン等の芳香族炭化水素系溶剤（ケトン系も可）１０〜９０質量％に対し、エステル系溶剤を１０〜９０質量％の割合で混合したものを例示できる。そして、この有機溶剤に上記のゴムコンパウンドを固形分濃度１０〜６０質量％となるように溶解する。 The above rubber compound is dissolved in an organic solvent to form a coating solution, which is applied to the steel sheet. The organic solvent is not limited as long as it can dissolve the above rubber compound, but 10 to 90% by mass of the ester solvent is 10 to 90% by mass of an aromatic hydrocarbon solvent such as toluene (ketone type is also acceptable). What mixed in the ratio of -90 mass% can be illustrated. And said rubber compound is melt | dissolved in this organic solvent so that it may become solid content concentration 10-60 mass%.
鋼板は特定されず、ステンレス鋼板（フェライト系／マルテンサイト系／オーステナイト系ステンレス）、ＳＰＣＣ鋼板、アルミニウム鋼板等の従来よりガスケットに使用されている鋼板を使用することができる。通常、これらの鋼板は、アルカリ脱脂した後、クロメート処理剤または、ノンクロメート処理剤等の防錆皮膜を形成させる化成処理を施した上で用いられるが、本発明においても同様の処理が施されてもよい。また、ＳＰＣＣ鋼板ではリン酸亜鉛、リン酸鉄皮膜を形成させる場合もあるが、本発明においても同様の皮膜が形成されていてもよい。また、表面をショットブラスト、スコッチブラスト等で粗面化した鋼板も用いることができる。 The steel plate is not specified, and steel plates conventionally used for gaskets such as stainless steel plates (ferritic / martensitic / austenite stainless steel), SPCC steel plates, aluminum steel plates and the like can be used. Normally, these steel sheets are used after being subjected to a chemical conversion treatment for forming a rust-proof film such as a chromate treatment agent or a non-chromate treatment agent after alkali degreasing, but the same treatment is also carried out in the present invention. May be. In addition, although zinc phosphate and iron phosphate films may be formed on SPCC steel sheets, similar films may be formed in the present invention. Further, a steel plate whose surface is roughened by shot blast, scotch blast, or the like can also be used.
ゴムコンパウンドを含有する塗布液の塗布方法にも制限がないが、塗布厚を制御できる方法が好ましく、スキマコーターやロールコーター等が好適である。塗布厚は１５〜５０μｍであり、その後、約１５０〜２４０℃で５〜１５分間熱処理して発泡剤を発泡させ、発泡ゴム層を形成する。このとき、得られる発泡ゴム層の発泡倍率は２〜４倍で、８０％以上が連泡となるように、用いる加硫剤や発泡剤、加熱時間等の発泡条件を調整する。発泡倍率を２〜４倍に自由に変えるには、上記したムーニー値を有するポリマーと、上記した加硫剤及び発泡剤とを上記で規定した配合とすることにより達成することができ、特に、この発泡倍率はポリマーのムーニー値と加硫速度に依存する。これは、ポリマーのムーニー値が低いと発泡ガスによるポリマーの変形が大きくなり、逆にムーニー値が高いと発泡ガスによるポリマーの変形が小さくなるためである。加硫速度に関しては速度が速いと、発泡ガスによってポリマーが膨張変形する前に加硫が進行する為、発泡倍率が抑えられる。逆に加硫速度が遅いと加硫によるゴムの硬化速度より、発泡ガスによるポリマーの変形が優先する為発泡倍率が大きくなる。例えば、ムーニー値２０〜４０のポリマーと、速度の遅い加硫促進剤（キュラストデータ：１５０℃加硫でＴ５０までの立ち上がり時間が５〜６分程度）と、発泡分解温度の低い発泡剤とを組み合わせると発泡倍率が大きくなり、逆にムーニー値が４０〜６０のポリマーと加硫速度が速い加硫促進剤（キュラストデータ：１５０℃加硫でＴ５０までの立ち上がり時間が１〜３分程度）と、発泡分解温度の高い発泡剤とを組み合わせると発泡倍率が小さくなる。このように、ポリマー、加硫促進剤及び発泡剤の組み合わせにより、発泡倍率を自由にコントロールすることができる。 Although there is no restriction | limiting in the application | coating method of the coating liquid containing a rubber compound, The method which can control application | coating thickness is preferable and a skimmer coater, a roll coater, etc. are suitable. The coating thickness is 15 to 50 μm, and then the foaming agent is foamed by heat treatment at about 150 to 240 ° C. for 5 to 15 minutes to form a foamed rubber layer. At this time, the foaming ratio of the foamed rubber layer to be obtained is 2 to 4 times, and the foaming conditions such as the vulcanizing agent, the foaming agent, and the heating time to be used are adjusted so that 80% or more is open-celled. In order to freely change the expansion ratio to 2 to 4 times, it can be achieved by blending the polymer having the Mooney value described above, the vulcanizing agent and the foaming agent described above, and in particular, This expansion ratio depends on the Mooney value of the polymer and the vulcanization rate. This is because when the Mooney value of the polymer is low, the deformation of the polymer due to the foaming gas increases, and conversely, when the Mooney value is high, the deformation of the polymer due to the foaming gas decreases. With regard to the vulcanization speed, if the speed is high, vulcanization proceeds before the polymer expands and deforms by the foaming gas, so that the expansion ratio can be suppressed. Conversely, if the vulcanization rate is low, the foaming ratio increases because the deformation of the polymer by the foaming gas has priority over the curing rate of the rubber by vulcanization. For example, a polymer having a Mooney value of 20 to 40, a slow vulcanization accelerator (curast data: rise time to T50 by vulcanization at 150 ° C. of about 5 to 6 minutes), a foaming agent having a low foaming decomposition temperature, When combined, the expansion ratio becomes large, and conversely, a polymer having a Mooney value of 40 to 60 and a vulcanization accelerator with a fast vulcanization rate (curast data: rise time to T50 with vulcanization at 150 ° C. is about 1 to 3 minutes. ) And a foaming agent having a high foaming decomposition temperature, the foaming ratio is reduced. Thus, the expansion ratio can be freely controlled by the combination of the polymer, the vulcanization accelerator and the foaming agent.
このようにして得られるガスケット用素材は、後述される実施例に示すように、高温・高圧下でゴム層のヘタリがなく、かつ低温でのゴム層の収縮がなく、鋳巣や面粗度の粗いフランジを良好にシールし得る。 The gasket material thus obtained, as shown in the examples to be described later, has no rubber layer settling under high temperature and high pressure, and there is no shrinkage of the rubber layer at low temperature. The rough flange can be well sealed.
以下に実施例および比較例を挙げて本発明を更に説明するが、本発明はこれにより何ら限定されるものではない。 Examples The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto.
（実施例１〜３、比較例１〜７）
［試料の作製］
表１に示すようにポリマー、発泡剤、加硫剤及び加硫促進剤を配合したゴムコンパウンドを、固形分濃度４０質量％となるようにトルエンと酢酸エチルとの混合有機溶剤に溶解し、塗布液を調製した。そして、ノンクロム処理したステンレス鋼板にプライマー処理を施し、塗布液をロールコーターで塗布した後（塗布厚は表１の通り）、２１０℃で１０分間熱処理して試料を得た。
各試料について、以下の評価を行った。
(Examples 1-3, Comparative Examples 1-7)
[Sample preparation]
As shown in Table 1, a rubber compound containing a polymer, a foaming agent, a vulcanizing agent, and a vulcanization accelerator is dissolved in a mixed organic solvent of toluene and ethyl acetate so that the solid content concentration is 40% by mass, and then applied. A liquid was prepared. And the primer process was performed to the stainless steel plate which carried out the non-chromium treatment, and after apply | coating a coating liquid with a roll coater (application | coating thickness is as Table 1), it heat-processed for 10 minutes at 210 degreeC, and obtained the sample.
Each sample was evaluated as follows.
［評価方法］
１．発泡倍率
発泡倍率の測定は、発泡前のゴム層の厚さと発泡後のゴム層の厚さをマイクロメーターで測定し、以下の式から発泡倍率を算出した。
[Evaluation methods]
1. Foaming ratio The foaming ratio was measured by measuring the thickness of the rubber layer before foaming and the thickness of the rubber layer after foaming with a micrometer, and calculating the foaming ratio from the following formula.
２．連泡率の測定
試料を水中に浸漬し、これを真空脱気して発泡ゴム層のセル中に水を置換させる。水中置換後の重量が一定になるまで試験を行い、以下の式から連泡率を算出した。
2. Measurement of open cell ratio A sample is immersed in water and vacuum degassed to replace water in the foam rubber layer cell. The test was conducted until the weight after substitution in water was constant, and the open cell ratio was calculated from the following formula.
３．耐熱フロー性
試料を、面圧１００ＭＰａ、１５０℃×２２Ｈｒの条件で放置し、試験後の試料の外観をマイクロスコープで観察し、下記基準で評価した。
評価基準
○：ゴムフローなし
×：ゴムフローあり
3. Heat-resistant flow property The sample was allowed to stand under conditions of a surface pressure of 100 MPa and 150 ° C. × 22 Hr, and the appearance of the sample after the test was observed with a microscope and evaluated according to the following criteria.
Evaluation criteria ○: No rubber flow ×: With rubber flow
４．トルクダウン率
各サンプルを下記の試験を行い、トルクダウン率を評価した。
（１）サンプルをフランジにセットし、ボルトをトルクレンチを用いて締め込み、締め込んだ時のトルク値（初期のトルク値）を測定した。
（２）（１）の状態でサンプルを−35℃に冷却した。 その状態で、ボルトとフランジの接面にマーキングを施し、ボルトを外した。
（３）再度、ボルトをトルクレンチを用いて、マーキング部まで締め込み、その時のトルク値（−35℃まで冷却した時のトルク値）を測定した。
また、試料の初期（常温）のトルク値と、−３５℃まで冷却した時のトルク値とを比較し、以下の式からトルクダウン率を算出した。
4). Torque down rate Each sample was subjected to the following test to evaluate the torque down rate.
(1) The sample was set on the flange, the bolt was tightened with a torque wrench, and the torque value (initial torque value) when tightened was measured.
(2) The sample was cooled to −35 ° C. in the state of (1). In that state, markings were made on the contact surfaces of the bolt and flange, and the bolt was removed.
(3) The bolt was tightened to the marking part again using a torque wrench, and the torque value at that time (torque value when cooled to -35 ° C.) was measured.
Further, the initial torque value (normal temperature) of the sample was compared with the torque value when cooled to -35 ° C., and the torque down rate was calculated from the following equation.
５．シール試験
配合１〜１０を用いて、以下の表２〜３に示す形状を有する実施例１〜３及び比較例１〜７のガスケットを作成した。そして、それぞれのガスケットを表２に示すフランジに組み込み、以下に記す評価を行った。
・鋳巣シール試験
（１）図１に示すように、試料をハーフビード形状が高さ０．２ｍｍ×幅１．５ｍｍで、ハーフビードのセンター径がφ５１．５ｍｍに加工してガスケットとし、これを鋳巣（φ２．５ｍｍ×深さ２．５ｍｍ）を設けたフランジに鋳巣位置がハーフビードセンターの位置になるよう組み付け、ビード線圧１０Ｎ／ｍｍの条件で締め込む。
（２）（１）の状態で、フランジの中央にあるノズルから空気（２００ＫＰａ）を送り込み、漏れ量を測定した。
・面粗度シール試験
（１）試料をハーフビード形状が高さ０．２ｍｍ×幅１．５ｍｍで、ハーフビードのセンター径がφ５１．５ｍｍに加工してガスケットとし、これを面粗度５０Ｒａのフランジに、鋳巣位置がφ５１．５の箇所になるよう組み付け、ビード線圧１０Ｎ／ｍｍの条件で締め込む。
（２）（１）の状態で、フランジの中央にあるノズルから空気（２００ＫＰａ）を送り込み、漏れ量を測定した。
5). Seal Test Using Examples 1 to 10, gaskets of Examples 1 to 3 and Comparative Examples 1 to 7 having shapes shown in Tables 2 to 3 below were created. Each gasket was incorporated in the flange shown in Table 2 and evaluated as follows.
・ Cavity seal test (1) As shown in FIG. 1, the sample was processed into a half bead shape having a height of 0.2 mm × width of 1.5 mm and a half bead having a center diameter of φ51.5 mm to form a gasket. It is assembled to a flange provided with a nest (φ2.5 mm × depth 2.5 mm) so that the cast nest is located at the half bead center, and is tightened under the condition of a bead linear pressure of 10 N / mm.
(2) In the state of (1), air (200 KPa) was sent from the nozzle at the center of the flange, and the amount of leakage was measured.
・ Surface roughness seal test (1) The sample was processed into a half bead shape with a height of 0.2 mm × width of 1.5 mm and a half bead center diameter of φ51.5 mm to form a gasket, which was used as a flange with a surface roughness of 50 Ra. Then, the cast hole is assembled so that the position of the casting hole is φ51.5, and tightened under the condition of a bead linear pressure of 10 N / mm.
(2) In the state of (1), air (200 KPa) was sent from the nozzle at the center of the flange, and the amount of leakage was measured.
上記各測定及び各試験の結果を、表３にまとめて示す。尚、各シール試験の評価は、空気漏れが無い場合を「○」、空気漏れが発生した場合を「×」とした。 The results of the above measurements and tests are summarized in Table 3. In the evaluation of each seal test, “◯” indicates that there is no air leak, and “X” indicates that there is an air leak.
表３から、本発明に従う発泡ゴム層を有する実施例の試料は、耐熱フロー製、トルクダウン率、シール試験の何れに対しても良好な結果が得られることがわかる。これに対し、発泡前のゴム層厚が過大である比較例１の試料は耐熱フロー性が悪く、トルクダウン率も若干劣る。比較例２の試料はマイクロカプセル型の発泡剤を用いたことから、連泡率が低く、トルクダウン率も劣っている。ムーニー値が過大の比較例３の試料は、発泡倍率が低く、シール性能に劣っている。発泡剤量が過小の比較例４の試料も発泡倍率が低く、シー性能に劣っている。ポリマー量が過小の比較例５の試料は連泡率が低く、耐熱フロー性に劣り、トルクダウン率が最も大きい。比較例６の試料はマイクロカプセル型の発泡剤を用い、かつ発泡前のゴム層が過大であることから、発泡倍率及び連泡率が最低で、シール性能にも劣っている。比較例７の試料は発泡剤を使用しないため、シール性に劣っている。 From Table 3, it can be seen that the sample of the example having the foamed rubber layer according to the present invention gives good results for any of heat-resistant flow, torque-down rate, and seal test. On the other hand, the sample of Comparative Example 1 in which the rubber layer thickness before foaming is excessive has poor heat resistance flow properties, and the torque down rate is slightly inferior. Since the sample of Comparative Example 2 used a microcapsule-type foaming agent, the open cell rate was low and the torque down rate was also inferior. The sample of Comparative Example 3 having an excessive Mooney value has a low expansion ratio and inferior sealing performance. The sample of Comparative Example 4 having an excessively small amount of foaming agent also has a low foaming ratio and is inferior in sea performance. The sample of Comparative Example 5 having an excessively small amount of polymer has a low open cell ratio, inferior heat-resistant flow properties, and the largest torque-down rate. Since the sample of Comparative Example 6 uses a microcapsule type foaming agent and the rubber layer before foaming is excessive, the foaming ratio and the open cell ratio are the lowest and the sealing performance is poor. Since the sample of Comparative Example 7 does not use a foaming agent, it has poor sealing properties.
Claims (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011099558A (en) * | 2009-10-07 | 2011-05-19 | Nichias Corp | Gasket material |
| WO2013011918A1 (en) | 2011-07-19 | 2013-01-24 | Nok株式会社 | Gasket material |
| CN113993935A (en) * | 2019-06-17 | 2022-01-28 | 霓佳斯株式会社 | Pad for disc brake and disc brake |
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| JPH07286165A (en) * | 1994-04-19 | 1995-10-31 | Nok Corp | Gasket material and its production |
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| JP2003171489A (en) * | 2001-12-05 | 2003-06-20 | Nitto Denko Corp | Rubber foamed material for sealing |
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| JPH0612870U (en) * | 1992-07-21 | 1994-02-18 | 日本ラインツ株式会社 | Metal cylinder head gasket |
| JPH07286165A (en) * | 1994-04-19 | 1995-10-31 | Nok Corp | Gasket material and its production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011099558A (en) * | 2009-10-07 | 2011-05-19 | Nichias Corp | Gasket material |
| WO2013011918A1 (en) | 2011-07-19 | 2013-01-24 | Nok株式会社 | Gasket material |
| US9381721B2 (en) | 2011-07-19 | 2016-07-05 | Nok Corporation | Gasket material |
| CN113993935A (en) * | 2019-06-17 | 2022-01-28 | 霓佳斯株式会社 | Pad for disc brake and disc brake |
| CN113993935B (en) * | 2019-06-17 | 2024-06-28 | 霓佳斯株式会社 | Pad for disc brake and disc brake |
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