WO2015019807A1 - Seal for gasoline engine - Google Patents
Seal for gasoline engine Download PDFInfo
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- WO2015019807A1 WO2015019807A1 PCT/JP2014/068817 JP2014068817W WO2015019807A1 WO 2015019807 A1 WO2015019807 A1 WO 2015019807A1 JP 2014068817 W JP2014068817 W JP 2014068817W WO 2015019807 A1 WO2015019807 A1 WO 2015019807A1
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- WIPO (PCT)
- Prior art keywords
- seal
- gasoline engine
- sealing device
- lip
- crankshaft
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1009—Fluorinated polymers, e.g. PTFE
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/16—Sealings between relatively-moving surfaces
- F16J15/32—Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings
- F16J15/3284—Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings characterised by their structure; Selection of materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/16—Sealings between relatively-moving surfaces
- F16J15/34—Sealings between relatively-moving surfaces with slip-ring pressed against a more or less radial face on one member
- F16J15/3496—Sealings between relatively-moving surfaces with slip-ring pressed against a more or less radial face on one member use of special materials
Definitions
- the present invention relates to a gasoline engine seal. More specifically, the present invention relates to a gasoline engine seal that is effectively used as a lip-type end face seal of an engine crankshaft sealing device.
- a sealing device for a crankshaft of an engine such as an automobile is, for example, a liquid leaking from an annular gap between a housing and a rotating shaft as two members in which a sealing device as shown in FIG. The oil is sealed.
- This sealing device is slidably sealingly contacted with a metal ring 6 fitted and fixed to the inner periphery of the housing and a sealing counterpart surface of a flange portion extending radially outward of a slinger 5 attached to the outer periphery of the rotary shaft.
- a lip-type end face seal 3 is slidably sealingly contacted with a metal ring 6 fitted and fixed to the inner periphery of the housing and a sealing counterpart surface of a flange portion extending radially outward of a slinger 5 attached to the outer periphery of the rotary shaft.
- end face seals tend to have a smaller lip reaction force than shaft lip seals, which reduces sliding torque and achieves fuel efficiency in automobiles.
- fluororesins or fluororubbers such as polytetrafluoroethylene, which have higher heat resistance than FVMQ, the followability is poor and leakage occurs under high engine speed.
- Patent Document 1 the packing material for the crankshaft sealing device of a gasoline engine is required to have excellent lip following properties in addition to heat resistance that can withstand high heat such as 230 ° C.
- An object of the present invention is to provide a seal that can be effectively used as a packing material for a sealing device for a crankshaft of a gasoline engine, etc., by allowing the fluid to continue to be satisfactorily sealed even under high temperature and high rotation. is there.
- An object of the present invention is that the loss tangent tan ⁇ at a frequency of 80 Hz and an ambient temperature of 100 ° C. is 0.13 or less, and consists of a vulcanized product of vinylidene fluoride-tetrafluoroethylene-perfluoro (methyl vinyl ether) terpolymer.
- a gasoline engine used as a lip-type end face seal of a sealing device for sealing an annular gap between a housing and a rotating shaft, as two members that are assembled concentrically and relatively rotatably together, for an engine crankshaft Achieved with a seal.
- Lip followability is caused by compression and tensile deformation from the slinger to the lip, but since rubber is a viscoelastic body, it will move under the influence of viscosity when compression and tension are applied from the slinger. A delay occurs, resulting in a gap between the slinger and the lip.
- the physical property representing the viscosity of the rubber is tan ⁇ , and thus the present invention has been completed by paying attention to this value.
- the seal for gasoline engines according to the present invention has excellent heat resistance and can keep fluid sealed well even at high temperatures. Therefore, it is suitably used as a packing material for a seal device for a crankshaft of a gasoline engine. It is done.
- a loss tangent tan ⁇ (80Hz, 100 ° C) is 0.13 or less fluororubber.
- tan ⁇ 80 Hz, 100 ° C.
- Reference Example 2 and Comparative Example 1 below durability required for a seal for a crankshaft of a gasoline engine used under high-speed sliding and The lip following ability cannot be satisfied.
- the loss tangent tan ⁇ is generated when the sinusoidal stress and strain act on the viscoelastic body, and the strain occurs later than the stress, but the loss angle (the delay angle of the strain phase relative to this stress) ( The tangent of ⁇ ), which is a measure of the amount of energy dissipated as heat during deformation.
- the value of loss tangent (tan ⁇ ) of a rubber molded product is measured by performing a dynamic viscoelasticity test in which a load of sinusoidal vibration is applied to the rubber molded product.
- Examples of the rubber having tan ⁇ (80 Hz, 100 ° C.) of 0.13 or less and capable of withstanding high heat such as 230 ° C. include fluororubber containing perfluoro (methyl vinyl ether) [FMVE] as a copolymer unit.
- a fluororubber a VdF-TFE-FMVE terpolymer, for example, a copolymer composition of VdF 55 to 80 mol%, TFE 10 to 30 mol%, FMVE 1 to 25 mol% is used.
- commercially available products such as DuPont Viton GFLT, GLT505, GLT305, and GLT600S can be used as they are.
- the sealing material which is a vulcanized molded product, cannot achieve the followability intended by the present invention.
- a polyfunctional unsaturated compound in combination as a crosslinking aid, and this is preferably about 0.5 to 10 parts by weight, preferably 100 parts by weight per 100 parts by weight of the terpolymer. About 1 to 8 parts by weight are used.
- the polyfunctional unsaturated compound include triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and the like.
- Preparation of the rubber composition to be crosslinked is carried out by kneading using a kneader such as an intermix, kneader, Banbury mixer or an open roll, and molding (crosslinking or vulcanization) is performed by a known method, for example, It is generally performed by heating at about 150 to 200 ° C for about 3 to 60 minutes using an injection molding machine, compression molding machine, vulcanizing press, etc., and at about 150 to 250 ° C for about 1 to 24 hours as necessary. Secondary crosslinking (secondary vulcanization) is also performed by heating to a certain extent.
- a kneader such as an intermix, kneader, Banbury mixer or an open roll
- molding crosslinking or vulcanization
- Secondary crosslinking is also performed by heating to a certain extent.
- FIG. 3 is an engine as a liquid leaking from an annular gap between the housing and the rotating shaft as two members concentrically and relatively rotatably assembled to each other. It seals the sealing object such as oil and gear oil.
- This sealing device is slidably sealingly contacted with a metal ring 6 fitted and fixed to the inner periphery of the housing and a sealing counterpart surface of a flange portion extending radially outward of a slinger 5 attached to the outer periphery of the rotary shaft.
- a fluorinated rubber seal made of vulcanized VdF-TFE-FMVE is used as this end face seal.
- Example VdF-TFE-FMVE terpolymer (DuPont product Viton GLT600S) 100 parts by weight Carbon black (Tokai carbon product Seast GSO) 20 ⁇ 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 2 ⁇ (Nippon Oil & Fat Products Perhexa 25B-40; Silica mixture) Triallyl isocyanurate 2 ⁇ (Nippon Kasei Co., Ltd .; calcium silicate mixture)
- the FMVE copolymer fluororubber composition comprising the above components is subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 200 ° C. for 15 hours, and the lip seal of the sealing device shown in FIG.
- Vulcanization molding was carried out, and further a sealing device was produced, and normal physical properties, tan ⁇ , heat resistance, lip following property and seal durability evaluation were performed.
- Normal state physical properties (hardness): JIS K6253 (1997) conforming to ISO 7169: 2004
- Compliant tan ⁇ Measured under conditions of initial strain 3%, strain amplitude 0.03%, frequency 80Hz, ambient temperature 100 ° C using viscoelasticity spectrometer manufactured by Toyo Seiki Seisakusho JIS K6257 (ISO 188 compatible) 2003), hardness change after 10 hours at 230 ° C is evaluated as ⁇ , and 10 points or more is evaluated as ⁇ .
- Lip followability after rotation at 25 ° C at 100rpm, 1000rpm or 8000rpm
- the lip tip lift is less than 0.1mm, ⁇ is less than 0.1mm and less than 0.3mm, and 0.3mm and more is evaluated as x.
- the lip tip lift is a metal ring as shown in Fig. 1. Set the sealing device with a part removed on a rotating tester, and measure the displacement of the lip tip and slinger surface with a laser displacement meter when the slinger fitted at an angle of about 1 ° rotates ( (See Fig.
- Reference example 2 In Reference Example 1, 100 parts by weight of JSR product JSR220S (acrylonitrile content 41%) was used as the acrylonitrile-butadiene copolymer in the rubber composition.
- the FMVE non-copolymerized fluororubber composition having the following composition was subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 200 ° C. for 15 hours. The end face seal was vulcanized and sealed.
- Comparative Example 2 In the examples, instead of the FMVE copolymer fluororubber composition, a silicone rubber composition having the following composition was subjected to a primary vulcanization at 180 ° C. for 10 minutes and a secondary vulcanization at 170 ° C. for 10 hours. Seal vulcanization and sealing devices were made.
Abstract
A seal which is for use in a gasoline engine, particularly in a crankshaft for the engine, which exhibits a loss tangent, tanδ, of 0.13 or less at a frequency of 80Hz and an ambient temperature of 100ºC and is made of a cured product of a vinylidene fluoride-tetrafluoroethylene-perfluoro(methyl vinyl ether) terpolymer, and which is used as a lip-type end-face seal for a sealing device for sealing the annular space between two members that are assembled in such a state that the members can rotate freely, relatively and concentrically with each other, namely, a housing and a rotating shaft. This seal for a gasoline engine can continue to prevent the leakage of a fluid sufficiently even under high-temperature and high-revolution conditions, and therefore can be effectively used as a packing material for a sealing device for a crankshaft for a gasoline engine or the like.
Description
本発明は、ガソリンエンジン用シールに関する。さらに詳しくは、エンジンのクランクシャフト用密封装置のリップ型端面シールとして有効に用いられるガソリンエンジン用シールに関する。
The present invention relates to a gasoline engine seal. More specifically, the present invention relates to a gasoline engine seal that is effectively used as a lip-type end face seal of an engine crankshaft sealing device.
密封装置(オイルシール)は、自動車、産業機械等の分野で重要な機械部品として広く用いられている。自動車等のエンジンのクランクシャフト用密封装置は、例えば図３に示されるような密封装置が互いに同心的に相対回転自在に組み付けられる２部材としてのハウジングと回転軸間の環状の隙間より漏れる液体としての油をシールするものである。この密封装置は、ハウジングの内周に嵌合固定される金属環６と、回転軸の外周に取り付けられるスリンガー５の半径方向外方に伸びるフランジ部のシール相手面に摺動自在に密封接触するリップ型の端面シール３とから構成されている。
Sealing devices (oil seals) are widely used as important machine parts in fields such as automobiles and industrial machinery. A sealing device for a crankshaft of an engine such as an automobile is, for example, a liquid leaking from an annular gap between a housing and a rotating shaft as two members in which a sealing device as shown in FIG. The oil is sealed. This sealing device is slidably sealingly contacted with a metal ring 6 fitted and fixed to the inner periphery of the housing and a sealing counterpart surface of a flange portion extending radially outward of a slinger 5 attached to the outer periphery of the rotary shaft. And a lip-type end face seal 3.
一般にオイルシール材料としては、ニトリルゴム〔NBR〕あるいはアクリルゴム〔ACM〕等の材料が使用されている。しかるにガソリンエンジン内の油温は耐久試験時に100℃程度まで達しており、オイルシールの摺動面温度はそれ以上になると予想されることから、エンジンシール用途では耐熱温度が100～120℃のNBR、120～160℃のACM、120～150℃の水素化NBRは耐熱性の点より使用されず、例えばディーゼルエンジンのクランクシャフト用密封装置のパッキン材としては耐熱性にすぐれた同温度が180～200℃シリコーンゴム〔FVMQ〕あるいは同温度が200～250℃と高いフッ素ゴム〔FKM〕を用いたリップ型端面シールが用いられている。
Generally, materials such as nitrile rubber [NBR] or acrylic rubber [ACM] are used as the oil seal material. However, the oil temperature in the gasoline engine has reached about 100 ° C during endurance tests, and the sliding surface temperature of the oil seal is expected to be higher than that. For engine seal applications, the NBR has a heat-resistant temperature of 100 to 120 ° C. , 120-160 ° C ACM and 120-150 ° C hydrogenated NBR are not used because of their heat resistance. For example, as a packing material for a sealing device for a crankshaft of a diesel engine, the same temperature with excellent heat resistance is 180- Lip-type end face seals using 200 ° C. silicone rubber [FVMQ] or fluoro rubber [FKM] having a high temperature of 200 to 250 ° C. are used.
ガソリンエンジンのクランクシャフト用シールでは、ディーゼルエンジンに比べてさらに高温雰囲気下となるため、FVMQではやはり耐熱性の点で対応が難しいといった問題がある。
¡Crankshaft seals for gasoline engines are in a higher temperature atmosphere than diesel engines, so FVMQ still has a problem that it is difficult to cope with in terms of heat resistance.
ここで端面シールは軸リップシールに比べてリップ反力が小さいといった傾向があり、これによって摺動トルクが低減されて自動車では省燃費が実現されることとなるが、その一方で、端面シール材料としてFVMQに比べてさらに耐熱性の高い、ポリテトラフルオロエチレンなど一般的に用いられているフッ素樹脂あるいはフッ素ゴムを用いると、ガソリンエンジンの高回転下では追随性が悪く漏れが生じてしまうという問題があった(特許文献１)。従って、ガソリンエンジンのクランクシャフト用密封装置のパッキン材としては、例えば230℃といった高熱に耐えうる耐熱性に加えてリップ追随性にすぐれていることが必要とされる。
Here, end face seals tend to have a smaller lip reaction force than shaft lip seals, which reduces sliding torque and achieves fuel efficiency in automobiles. When using fluororesins or fluororubbers such as polytetrafluoroethylene, which have higher heat resistance than FVMQ, the followability is poor and leakage occurs under high engine speed. (Patent Document 1). Therefore, the packing material for the crankshaft sealing device of a gasoline engine is required to have excellent lip following properties in addition to heat resistance that can withstand high heat such as 230 ° C.
本発明の目的は、高温高回転下においても良好に流体を密封し続けることを可能とすることにより、ガソリンエンジンのクランクシャフト用密封装置等のパッキン材として有効に用いられるシールを提供することにある。
An object of the present invention is to provide a seal that can be effectively used as a packing material for a sealing device for a crankshaft of a gasoline engine, etc., by allowing the fluid to continue to be satisfactorily sealed even under high temperature and high rotation. is there.
かかる本発明の目的は、周波数80Hz、雰囲気温度100℃での損失正接tanδが0.13以下であり、フッ化ビニリデン-テトラフルオロエチレン-パーフルオロ(メチルビニルエーテル)3元共重合体の加硫物よりなる、エンジンのクランクシャフト用であって、互いに同心的に相対回転自在に組み付けられる２部材としての、ハウジングと回転軸間の環状の隙間をシールする密封装置のリップ型の端面シールとして用いられるガソリンエンジン用シールによって達成される。
An object of the present invention is that the loss tangent tan δ at a frequency of 80 Hz and an ambient temperature of 100 ° C. is 0.13 or less, and consists of a vulcanized product of vinylidene fluoride-tetrafluoroethylene-perfluoro (methyl vinyl ether) terpolymer. A gasoline engine used as a lip-type end face seal of a sealing device for sealing an annular gap between a housing and a rotating shaft, as two members that are assembled concentrically and relatively rotatably together, for an engine crankshaft Achieved with a seal.
リップの追随性はスリンガーからリップへ圧縮および引張方向の変形が与えられることにより生じるが、ゴムは粘弾性体であることから、スリンガーからの圧縮、引張が与えられた際に粘性の影響で動的遅れが発生し、その結果スリンガーとリップの間で隙間が生じることとなる。本発明は、このゴムの粘性を表す物性がtanδであることからこの値に着目して発明を完成するに至ったものである。
Lip followability is caused by compression and tensile deformation from the slinger to the lip, but since rubber is a viscoelastic body, it will move under the influence of viscosity when compression and tension are applied from the slinger. A delay occurs, resulting in a gap between the slinger and the lip. In the present invention, the physical property representing the viscosity of the rubber is tan δ, and thus the present invention has been completed by paying attention to this value.
本発明に係るガソリンエンジン用シールは、耐熱性にすぐれており、高温下においても良好に流体を密封し続けることを可能とするので、ガソリンエンジンのクランクシャフト用密封装置のパッキン材として好適に用いられる。
The seal for gasoline engines according to the present invention has excellent heat resistance and can keep fluid sealed well even at high temperatures. Therefore, it is suitably used as a packing material for a seal device for a crankshaft of a gasoline engine. It is done.
エンジンのクランクシャフト用であって、互いに同心的に相対回転自在に組み付けられる２部材としての、ハウジングと回転軸間の環状の隙間をシールする密封装置のリップ型の端面シールとしては、損失正接tanδ(80Hz、100℃)は0.13以下のフッ素ゴムが用いられる。tanδ(80Hz、100℃)が0.13以上のものを用いると、後記参考例２および比較例１に示される通り、高速摺動下で用いられるガソリンエンジンのクランクシャフト用シールに要求される耐久性およびリップ追随性を満足させることはできない。
As a lip-type end face seal of a sealing device for sealing an annular gap between a housing and a rotating shaft, which is used for an engine crankshaft and is assembled concentrically and relatively rotatably, a loss tangent tanδ (80Hz, 100 ° C) is 0.13 or less fluororubber. When tan δ (80 Hz, 100 ° C.) is 0.13 or more, as shown in Reference Example 2 and Comparative Example 1 below, durability required for a seal for a crankshaft of a gasoline engine used under high-speed sliding and The lip following ability cannot be satisfied.
ここで損失正接tanδは、粘弾性体に正弦波形の応力とひずみが作用する場合に、ひずみが応力よりも遅れて生じることとなるが、この応力に対するひずみの位相の遅れ角度である損失角(δ)の正接であって、変形の間に熱として散逸されるエネルギー量の尺度となるものである。ゴム成形物の損失正接(tanδ)の値は、ゴム成形物に正弦振動の荷重を付与する動的粘弾性試験を行うことによって測定される。
Here, the loss tangent tan δ is generated when the sinusoidal stress and strain act on the viscoelastic body, and the strain occurs later than the stress, but the loss angle (the delay angle of the strain phase relative to this stress) ( The tangent of δ), which is a measure of the amount of energy dissipated as heat during deformation. The value of loss tangent (tan δ) of a rubber molded product is measured by performing a dynamic viscoelasticity test in which a load of sinusoidal vibration is applied to the rubber molded product.
tanδ(80Hz、100℃)が0.13以下であり、かつ230℃といった高熱に耐えうるゴムとしてはパーフルオロ(メチルビニルエーテル)〔FMVE〕を共重合単位として含有するフッ素ゴムが挙げられる。かかるフッ素ゴムとしては、VdF-TFE-FMVE 3元共重合体、例えばその共重合組成がVdF 55～80モル％、TFE 10～30モル％、FMVEが1～25モル％のものが用いられ、実際には市販品、例えばデュポン社製品バイトンGFLT、GLT505、GLT305、GLT600S等をそのまま用いることができる。FMVEが共重合されていないフッ素ゴムを用いた場合には、その加硫成形品であるシール材は本発明の目的とする追随性を達成することができない。
Examples of the rubber having tanδ (80 Hz, 100 ° C.) of 0.13 or less and capable of withstanding high heat such as 230 ° C. include fluororubber containing perfluoro (methyl vinyl ether) [FMVE] as a copolymer unit. As such a fluororubber, a VdF-TFE-FMVE terpolymer, for example, a copolymer composition of VdF 55 to 80 mol%, TFE 10 to 30 mol%, FMVE 1 to 25 mol% is used, In practice, commercially available products such as DuPont Viton GFLT, GLT505, GLT305, and GLT600S can be used as they are. In the case of using a fluororubber that is not copolymerized with FMVE, the sealing material, which is a vulcanized molded product, cannot achieve the followability intended by the present invention.
フッ素ゴム加硫物は、カーボンブラックによって代表される補強剤、タルク、クレー、グラファイト、けい酸カルシウムなどの充填剤、ステアリン酸、パルミチン酸、パラフィンワックスなどの加工助剤、酸化亜鉛、酸化マグネシウムなどの受酸剤、加硫剤、老化防止剤、可塑剤などのゴム工業で一般に使用されている各種配合剤が、必要に応じて適宜添加され、加硫成形することにより得られる。
Fluoro rubber vulcanizates include reinforcing agents such as carbon black, fillers such as talc, clay, graphite, calcium silicate, processing aids such as stearic acid, palmitic acid, paraffin wax, zinc oxide, magnesium oxide, etc. Various compounding agents generally used in the rubber industry such as acid acceptors, vulcanizing agents, anti-aging agents, and plasticizers are appropriately added as necessary, and obtained by vulcanization molding.
VdF-TFE-FMVE 3元共重合体の加硫は、好ましくは3元共重合体中に導入された架橋性基(臭素基および／またはヨウ素基)を利用し、有機過酸化物によって行われ、密封装置のリップ型端面シールが成形される。
VdF-TFE-FMVE terpolymer is preferably vulcanized with an organic peroxide using a crosslinkable group (bromine group and / or iodine group) introduced into the terpolymer. The lip type end face seal of the sealing device is molded.
有機過酸化物としては、例えば第3ブチルパーオキサイド、ジクミルパーオキサイド、第3ブチルクミルパーオキサイド、1,1-ジ(第3ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、2,5-ジメチル-2,5-ジ(第3ブチルパーオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(第3ブチルパーオキシ)ヘキシン-3、1,3-ジ(第3ブチルパーオキシイソプロピル)ベンゼン、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、第3ブチルパーオキシベンゾエート、第3ブチルパーオキシイソプロピルカーボネート、n-ブチル-4,4-ジ(第3ブチルパーオキシ)バレレートなどが3元共重合体100重量部当り約0.5～4重量部、好ましくは約0.5～2重量部の割合で用いられる。
Examples of the organic peroxide include tertiary butyl peroxide, dicumyl peroxide, tertiary butyl cumyl peroxide, 1,1-di (tertiary butyl peroxy) -3,3,5-trimethylcyclohexane, 2, 5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-di (tert-butylperoxy) Oxyisopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, n-butyl-4,4-di (tertiary 3) Butyl peroxy) valerate or the like is used at a ratio of about 0.5 to 4 parts by weight, preferably about 0.5 to 2 parts by weight, per 100 parts by weight of the terpolymer.
有機過酸化物架橋剤を用いた場合には、多官能性不飽和化合物を架橋助剤として併用することが好ましく、これは3元共重合体100重量部当り約0.5～10重量部、好ましくは約1～8重量部の割合で用いられる。多官能性不飽和化合物としては、例えばトリアリルイソシアヌレート、トリアリルシアヌレート、トリメチルアリルイソシアヌレート、エチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレートなどが用いられる。
When an organic peroxide crosslinking agent is used, it is preferable to use a polyfunctional unsaturated compound in combination as a crosslinking aid, and this is preferably about 0.5 to 10 parts by weight, preferably 100 parts by weight per 100 parts by weight of the terpolymer. About 1 to 8 parts by weight are used. Examples of the polyfunctional unsaturated compound include triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and the like.
架橋成形されるゴム組成物の調製は、インタミックス、ニーダ、バンバリーミキサなどの混練機またはオープンロールなどを用いて混練することによって行われ、成形(架橋または加硫)は、公知の方法、例えば射出成形機、圧縮成形機、加硫プレスなどを用いて、一般に約150～200℃で約3～60分間加熱することによって行われ、必要に応じて約150～250℃で約1～24時間程度加熱する二次架橋(二次加硫)も行われる。
Preparation of the rubber composition to be crosslinked is carried out by kneading using a kneader such as an intermix, kneader, Banbury mixer or an open roll, and molding (crosslinking or vulcanization) is performed by a known method, for example, It is generally performed by heating at about 150 to 200 ° C for about 3 to 60 minutes using an injection molding machine, compression molding machine, vulcanizing press, etc., and at about 150 to 250 ° C for about 1 to 24 hours as necessary. Secondary crosslinking (secondary vulcanization) is also performed by heating to a certain extent.
密封装置としては、例えば図３に示されるようなものが挙げられ、これは互いに同心的に相対回転自在に組み付けられる２部材としての、ハウジングと回転軸間の環状の隙間より漏れる液体としてのエンジン油やギア油等の密封対象をシールするものである。この密封装置は、ハウジングの内周に嵌合固定される金属環６と、回転軸の外周に取り付けられるスリンガー５の半径方向外方に伸びるフランジ部のシール相手面に摺動自在に密封接触するリップ型の端面シール３とから構成されており、加硫形成されたVdF-TFE-FMVEよりなるフッ素ゴム製シールは、この端面シールとして用いられる。
An example of the sealing device is as shown in FIG. 3, which is an engine as a liquid leaking from an annular gap between the housing and the rotating shaft as two members concentrically and relatively rotatably assembled to each other. It seals the sealing object such as oil and gear oil. This sealing device is slidably sealingly contacted with a metal ring 6 fitted and fixed to the inner periphery of the housing and a sealing counterpart surface of a flange portion extending radially outward of a slinger 5 attached to the outer periphery of the rotary shaft. A fluorinated rubber seal made of vulcanized VdF-TFE-FMVE is used as this end face seal.
次に、実施例について本発明を説明する。
Next, the present invention will be described with reference to examples.
実施例
VdF-TFE-FMVE 3元共重合体(デュポン社製品バイトンGLT600S) 100重量部
カーボンブラック(東海カーボン製品シーストGSO) 20 〃
2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン 2 〃
(日本油脂製品パーヘキサ25B-40;シリカ混合物)
トリアリルイソシアヌレート 2 〃
(日本化成製品タイク；ケイ酸カルシウム混合物)
以上の各成分よりなるFMVE共重合フッ素ゴム組成物について、180℃、10分間の一次加硫、および200℃、15時間の二次加硫を行い、図３に示される密封装置のリップシールを加硫成形し、さらに密封装置を作製して、常態物性、tanδ、耐熱性、リップ追随性およびシール耐久評価を行った。
常態物性(硬さ)：ISO 7169：2004に対応するJIS K6253(1997)準拠
常態物性(100％モジュラス、破断強度、破断時伸び)：ISO 37：2011に対
応するJIS K6251
(2010)準拠
tanδ：東洋精機製作所製粘弾性スペクトロメータを用い、初期歪3％、歪
振幅0.03％、周波数80Hz、雰囲気温度100℃の条件下で測定
耐熱性：ISO 188に対応するJIS K6257(2003)に準拠し、230℃、500時間後
における硬さ変化が10ポイント未満のものを○、10ポイント以上
のものを×と評価
リップ追随性：25℃で100rpm、1000rpmまたは8000rpmで回転後のリップ先
端の浮き量が0.1mm未満のものを○、0.1以上0.3mm未満の
ものを△、0.3mm以上のものを×と評価
リップ先端の浮き量は、図１に示されるように金属環の一
部を切除した密封装置を回転試験機にセットし、約１°傾
けて嵌合させたスリンガーが回転した際のリップ先端部お
よびスリンガー面の変位量をレーザー変位計により計測し
(図２参照)、それらの変位差を算出することにより行われ
た
シール耐久評価：端面シール(内径75mm、外径110mm、幅9.5mm)のダストリ
ップを切除したうえで密封装置を回転試験機にセットし
、潤滑油(トヨタ純正キャッスルオイルSN級0W-20)を回
転軸を中心とした状態で密封して、油温120℃、回転数
8000rpmの条件下で120時間を上限として油漏れが生じる
までの時間を測定 Example VdF-TFE-FMVE terpolymer (DuPont product Viton GLT600S) 100 parts by weight Carbon black (Tokai carbon product Seast GSO) 20 〃
2,5-dimethyl-2,5-di (t-butylperoxy)hexane 2〃
(Nippon Oil & Fat Products Perhexa 25B-40; Silica mixture)
Triallyl isocyanurate 2 〃
(Nippon Kasei Co., Ltd .; calcium silicate mixture)
The FMVE copolymer fluororubber composition comprising the above components is subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 200 ° C. for 15 hours, and the lip seal of the sealing device shown in FIG. Vulcanization molding was carried out, and further a sealing device was produced, and normal physical properties, tan δ, heat resistance, lip following property and seal durability evaluation were performed.
Normal state physical properties (hardness): JIS K6253 (1997) conforming to ISO 7169: 2004 Normal state physical properties (100% modulus, breaking strength, elongation at break): JIS K6251 conforming to ISO 37: 2011
(2010) Compliant tanδ: Measured under conditions ofinitial strain 3%, strain amplitude 0.03%, frequency 80Hz, ambient temperature 100 ° C using viscoelasticity spectrometer manufactured by Toyo Seiki Seisakusho JIS K6257 (ISO 188 compatible) 2003), hardness change after 10 hours at 230 ° C is evaluated as ○, and 10 points or more is evaluated as ×. Lip followability: after rotation at 25 ° C at 100rpm, 1000rpm or 8000rpm The lip tip lift is less than 0.1mm, ○ is less than 0.1mm and less than 0.3mm, and 0.3mm and more is evaluated as x. The lip tip lift is a metal ring as shown in Fig. 1. Set the sealing device with a part removed on a rotating tester, and measure the displacement of the lip tip and slinger surface with a laser displacement meter when the slinger fitted at an angle of about 1 ° rotates ( (See Fig. 2) Seal endurance evaluation performed by calculating the difference: After cutting off the dust lip of the end face seal (inner diameter 75 mm, outer diameter 110 mm, width 9.5 mm), the sealing device was set on a rotating tester and lubricating oil (Toyota Sealed with genuine castle oil SN class 0W-20) centered on the rotating shaft, and measured the time until oil leakage occurs up to 120 hours under conditions of oil temperature 120 ° C and rotation speed 8000rpm
VdF-TFE-FMVE 3元共重合体(デュポン社製品バイトンGLT600S) 100重量部
カーボンブラック(東海カーボン製品シーストGSO) 20 〃
2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン 2 〃
(日本油脂製品パーヘキサ25B-40;シリカ混合物)
トリアリルイソシアヌレート 2 〃
(日本化成製品タイク；ケイ酸カルシウム混合物)
以上の各成分よりなるFMVE共重合フッ素ゴム組成物について、180℃、10分間の一次加硫、および200℃、15時間の二次加硫を行い、図３に示される密封装置のリップシールを加硫成形し、さらに密封装置を作製して、常態物性、tanδ、耐熱性、リップ追随性およびシール耐久評価を行った。
常態物性(硬さ)：ISO 7169：2004に対応するJIS K6253(1997)準拠
常態物性(100％モジュラス、破断強度、破断時伸び)：ISO 37：2011に対
応するJIS K6251
(2010)準拠
tanδ：東洋精機製作所製粘弾性スペクトロメータを用い、初期歪3％、歪
振幅0.03％、周波数80Hz、雰囲気温度100℃の条件下で測定
耐熱性：ISO 188に対応するJIS K6257(2003)に準拠し、230℃、500時間後
における硬さ変化が10ポイント未満のものを○、10ポイント以上
のものを×と評価
リップ追随性：25℃で100rpm、1000rpmまたは8000rpmで回転後のリップ先
端の浮き量が0.1mm未満のものを○、0.1以上0.3mm未満の
ものを△、0.3mm以上のものを×と評価
リップ先端の浮き量は、図１に示されるように金属環の一
部を切除した密封装置を回転試験機にセットし、約１°傾
けて嵌合させたスリンガーが回転した際のリップ先端部お
よびスリンガー面の変位量をレーザー変位計により計測し
(図２参照)、それらの変位差を算出することにより行われ
た
シール耐久評価：端面シール(内径75mm、外径110mm、幅9.5mm)のダストリ
ップを切除したうえで密封装置を回転試験機にセットし
、潤滑油(トヨタ純正キャッスルオイルSN級0W-20)を回
転軸を中心とした状態で密封して、油温120℃、回転数
8000rpmの条件下で120時間を上限として油漏れが生じる
までの時間を測定 Example VdF-TFE-FMVE terpolymer (DuPont product Viton GLT600S) 100 parts by weight Carbon black (Tokai carbon product Seast GSO) 20 〃
2,5-dimethyl-2,5-di (t-butylperoxy)
(Nippon Oil & Fat Products Perhexa 25B-40; Silica mixture)
(Nippon Kasei Co., Ltd .; calcium silicate mixture)
The FMVE copolymer fluororubber composition comprising the above components is subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 200 ° C. for 15 hours, and the lip seal of the sealing device shown in FIG. Vulcanization molding was carried out, and further a sealing device was produced, and normal physical properties, tan δ, heat resistance, lip following property and seal durability evaluation were performed.
Normal state physical properties (hardness): JIS K6253 (1997) conforming to ISO 7169: 2004 Normal state physical properties (100% modulus, breaking strength, elongation at break): JIS K6251 conforming to ISO 37: 2011
(2010) Compliant tanδ: Measured under conditions of
参考例１
実施例において、FMVE共重合フッ素ゴム組成物の代わりに下記配合よりなるNBR組成物について、180℃、10分間の一次加硫および150℃、3時間の二次加硫が行われ、リップシールが加硫成形された。
アクリロニトリル・ブタジエン共重合体 100重量部
(JSR製品JSR260S；アクリロニトリル含量 15％)
カーボンブラック(シーストGSO) 40 〃
酸化亜鉛(堺化学工業製品酸化亜鉛１種) 5 〃
ステアリン酸・パルミチン酸混合物 1.5 〃
(ミヨシ油脂製品ステアリン酸)
2,2,4-トリメチル-1,2-ジヒドロキノリン重合物 2 〃
(川口化学工業製品老防RD)
硫黄(鶴見化学工業製品コロイド硫黄A) 0.5 〃
テトラメチルチウラムジスルフィド 3 〃
(ゼオン化成製品レビタルマスターTT70N；アクリロニトリル・
ブタジエン共重合物-ステアリン酸混合物マスターバッチ)
N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド 2 〃
(ゼオン化成製品レビタルマスターCZ70N；アクリロニトリル・
ブタジエン共重合物-ステアリン酸混合物マスターバッチ) Reference example 1
In the examples, instead of the FMVE copolymer fluororubber composition, an NBR composition having the following composition was subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 150 ° C. for 3 hours, and the lip seal was Vulcanized and molded.
Acrylonitrile-butadiene copolymer 100 parts by weight (JSR product JSR260S; acrylonitrile content 15%)
Carbon black (seeded GSO) 40 〃
Zinc oxide (Zinc oxide, one type of chemical product) 5 〃
Stearic acid / palmitic acid mixture 1.5 〃
(Miyoshi oil product stearic acid)
2,2,4-Trimethyl-1,2-dihydroquinoline polymer 2
(Kawaguchi Chemical Industry Products RD)
Sulfur (Tsurumi Chemical Industries colloidal sulfur A) 0.5 〃
Tetramethylthiuram disulfide 3 〃
(Zeon Chemical Product Levital Master TT70N; Acrylonitrile
(Butadiene copolymer-stearic acid mixture masterbatch)
N-cyclohexyl-2-benzothiazolylsulfenamide 2 フ ェ ン
(Zeon Chemical Product Levital Master CZ70N; Acrylonitrile
(Butadiene copolymer-stearic acid mixture masterbatch)
実施例において、FMVE共重合フッ素ゴム組成物の代わりに下記配合よりなるNBR組成物について、180℃、10分間の一次加硫および150℃、3時間の二次加硫が行われ、リップシールが加硫成形された。
アクリロニトリル・ブタジエン共重合体 100重量部
(JSR製品JSR260S；アクリロニトリル含量 15％)
カーボンブラック(シーストGSO) 40 〃
酸化亜鉛(堺化学工業製品酸化亜鉛１種) 5 〃
ステアリン酸・パルミチン酸混合物 1.5 〃
(ミヨシ油脂製品ステアリン酸)
2,2,4-トリメチル-1,2-ジヒドロキノリン重合物 2 〃
(川口化学工業製品老防RD)
硫黄(鶴見化学工業製品コロイド硫黄A) 0.5 〃
テトラメチルチウラムジスルフィド 3 〃
(ゼオン化成製品レビタルマスターTT70N；アクリロニトリル・
ブタジエン共重合物-ステアリン酸混合物マスターバッチ)
N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド 2 〃
(ゼオン化成製品レビタルマスターCZ70N；アクリロニトリル・
ブタジエン共重合物-ステアリン酸混合物マスターバッチ) Reference example 1
In the examples, instead of the FMVE copolymer fluororubber composition, an NBR composition having the following composition was subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 150 ° C. for 3 hours, and the lip seal was Vulcanized and molded.
Acrylonitrile-butadiene copolymer 100 parts by weight (JSR product JSR260S; acrylonitrile content 15%)
Carbon black (seeded GSO) 40 〃
Zinc oxide (Zinc oxide, one type of chemical product) 5 〃
Stearic acid / palmitic acid mixture 1.5 〃
(Miyoshi oil product stearic acid)
2,2,4-Trimethyl-1,2-
(Kawaguchi Chemical Industry Products RD)
Sulfur (Tsurumi Chemical Industries colloidal sulfur A) 0.5 〃
(Zeon Chemical Product Levital Master TT70N; Acrylonitrile
(Butadiene copolymer-stearic acid mixture masterbatch)
N-cyclohexyl-2-
(Zeon Chemical Product Levital Master CZ70N; Acrylonitrile
(Butadiene copolymer-stearic acid mixture masterbatch)
参考例２
参考例１において、ゴム組成物中のアクリロニトリル・ブタジエン共重合体として、JSR製品JSR220S(アクリロニトリル含量 41％)100重量部が用いられた。 Reference example 2
In Reference Example 1, 100 parts by weight of JSR product JSR220S (acrylonitrile content 41%) was used as the acrylonitrile-butadiene copolymer in the rubber composition.
参考例１において、ゴム組成物中のアクリロニトリル・ブタジエン共重合体として、JSR製品JSR220S(アクリロニトリル含量 41％)100重量部が用いられた。 Reference example 2
In Reference Example 1, 100 parts by weight of JSR product JSR220S (acrylonitrile content 41%) was used as the acrylonitrile-butadiene copolymer in the rubber composition.
比較例１
実施例において、FMVE共重合フッ素ゴム組成物の代わりに、下記配合よりなるFMVE非共重合フッ素ゴム組成物について、180℃、10分間の一次加硫および200℃、15時間の二次加硫が行われ、端面シールの加硫成形および密封装置の作製が行われた。
VdF-HFP共重合体(デュポン製品バイトンA500) 100重量部
カーボンブラック(シーストGSO) 15 〃
酸化マグネシウム(協和化学工業製品キョーワマグ150) 3 〃
水酸化カルシウム(近江化学工業製品CALDIC 2000) 6 〃
4,4´-(ヘキサフルオロイソプロピリデン)ジフェノール 2 〃
(ダイム共栄製品CHEMINOX AF-50)
トリフェニル(フェニルメチル)フォスフォニウムクロライド 1 〃
(ダイム共栄製品CHEMINOX B-35F) Comparative Example 1
In the examples, instead of the FMVE copolymerized fluororubber composition, the FMVE non-copolymerized fluororubber composition having the following composition was subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 200 ° C. for 15 hours. The end face seal was vulcanized and sealed.
VdF-HFP copolymer (DuPont Viton A500) 100 parts by weight Carbon black (Seast GSO) 15 〃
Magnesium oxide (Kyowa Chemical Industry Kyowa Mag 150) 3 〃
Calcium hydroxide (Omi Chemical Co., Ltd.CALDIC 2000) 6 〃
4,4´- (Hexafluoroisopropylidene)diphenol 2 〃
(Dime Kyoei Product CHEMINOX AF-50)
Triphenyl (phenylmethyl)phosphonium chloride 1 〃
(Dime Kyoei Product CHEMINOX B-35F)
実施例において、FMVE共重合フッ素ゴム組成物の代わりに、下記配合よりなるFMVE非共重合フッ素ゴム組成物について、180℃、10分間の一次加硫および200℃、15時間の二次加硫が行われ、端面シールの加硫成形および密封装置の作製が行われた。
VdF-HFP共重合体(デュポン製品バイトンA500) 100重量部
カーボンブラック(シーストGSO) 15 〃
酸化マグネシウム(協和化学工業製品キョーワマグ150) 3 〃
水酸化カルシウム(近江化学工業製品CALDIC 2000) 6 〃
4,4´-(ヘキサフルオロイソプロピリデン)ジフェノール 2 〃
(ダイム共栄製品CHEMINOX AF-50)
トリフェニル(フェニルメチル)フォスフォニウムクロライド 1 〃
(ダイム共栄製品CHEMINOX B-35F) Comparative Example 1
In the examples, instead of the FMVE copolymerized fluororubber composition, the FMVE non-copolymerized fluororubber composition having the following composition was subjected to primary vulcanization at 180 ° C. for 10 minutes and secondary vulcanization at 200 ° C. for 15 hours. The end face seal was vulcanized and sealed.
VdF-HFP copolymer (DuPont Viton A500) 100 parts by weight Carbon black (Seast GSO) 15 〃
Magnesium oxide (Kyowa Chemical Industry Kyowa Mag 150) 3 〃
Calcium hydroxide (Omi Chemical Co., Ltd.CALDIC 2000) 6 〃
4,4´- (Hexafluoroisopropylidene)
(Dime Kyoei Product CHEMINOX AF-50)
Triphenyl (phenylmethyl)
(Dime Kyoei Product CHEMINOX B-35F)
比較例２
実施例において、FMVE共重合フッ素ゴム組成物の代わりに、下記配合よりなるシリコーンゴム組成物について、180℃、10分間の一次加硫および170℃、10時間の二次加硫が行われ、リップシールの加硫成形および密封装置の作製が行われた。
ジメチルシリコーンゴム-フロロシリコーンゴム共重合体 100重量部
(信越化学工業FE2611U)
カーボンブラック(シーストGSO) 15 〃
ジメチルシリコーンオイル(信越化学工業製品WETTER-No.5) 1 〃
2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン 25 2 〃
(ダイム共栄製品C-8) Comparative Example 2
In the examples, instead of the FMVE copolymer fluororubber composition, a silicone rubber composition having the following composition was subjected to a primary vulcanization at 180 ° C. for 10 minutes and a secondary vulcanization at 170 ° C. for 10 hours. Seal vulcanization and sealing devices were made.
100 parts by weight of dimethyl silicone rubber-fluoro silicone rubber copolymer (Shin-Etsu Chemical FE2611U)
Carbon black (seeded GSO) 15 〃
Dimethyl silicone oil (Shin-Etsu Chemical WETTER-No.5) 1 〃
2,5-Dimethyl-2,5-bis (t-butylperoxy) hexane 25 2 〃
(Dime Kyoei Product C-8)
実施例において、FMVE共重合フッ素ゴム組成物の代わりに、下記配合よりなるシリコーンゴム組成物について、180℃、10分間の一次加硫および170℃、10時間の二次加硫が行われ、リップシールの加硫成形および密封装置の作製が行われた。
ジメチルシリコーンゴム-フロロシリコーンゴム共重合体 100重量部
(信越化学工業FE2611U)
カーボンブラック(シーストGSO) 15 〃
ジメチルシリコーンオイル(信越化学工業製品WETTER-No.5) 1 〃
2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン 25 2 〃
(ダイム共栄製品C-8) Comparative Example 2
In the examples, instead of the FMVE copolymer fluororubber composition, a silicone rubber composition having the following composition was subjected to a primary vulcanization at 180 ° C. for 10 minutes and a secondary vulcanization at 170 ° C. for 10 hours. Seal vulcanization and sealing devices were made.
100 parts by weight of dimethyl silicone rubber-fluoro silicone rubber copolymer (Shin-Etsu Chemical FE2611U)
Carbon black (seeded GSO) 15 〃
Dimethyl silicone oil (Shin-Etsu Chemical WETTER-No.5) 1 〃
2,5-Dimethyl-2,5-bis (t-butylperoxy) hexane 25 2 〃
(Dime Kyoei Product C-8)
以上の実施例、各参考例および比較例で得られた結果は次の表に示される。
表
測定・評価項目 実施例 参考例１ 参考例２ 比較例１ 比較例２
常態物性
硬さHs (Duro A) 75 74 78 75 81
100％モジュラス(MPa) 6.9 5.9 6.2 4.0 5.2
破断強度 (MPa) 13.1 17.2 18.2 11.3 5.9
破断時伸び (％) 390 370 480 240 170
tanδ (80Hz、100℃) 0.0632 0.105 0.137 0.147 0.0897
耐熱性 ○ × × ○ ×
リップ追随性 100rpm ○ ○ ○ △ ○
1000rpm ○ ○ △ × ○
8000rpm ○ ○ × × ○
耐久時間 (時間) >120 >120 18 3 >120 The results obtained in the above Examples, Reference Examples and Comparative Examples are shown in the following table.
table
Measurement / Evaluation Items Example Reference Example 1 Reference Example 2 Comparative Example 1 Comparative Example 2
Normal physical properties Hardness Hs (Duro A) 75 74 78 75 81
100% modulus (MPa) 6.9 5.9 6.2 4.0 5.2
Breaking strength (MPa) 13.1 17.2 18.2 11.3 5.9
Elongation at break (%) 390 370 480 240 170
tanδ (80Hz, 100 ° C) 0.0632 0.105 0.137 0.147 0.0897
Heat resistance ○ × × ○ ×
Lip followability 100rpm ○ ○ ○ △ ○
1000rpm ○ ○ △ × ○
8000rpm ○ ○ × × ○
Endurance time (hours)>120> 120 18 3> 120
表
測定・評価項目 実施例 参考例１ 参考例２ 比較例１ 比較例２
常態物性
硬さHs (Duro A) 75 74 78 75 81
100％モジュラス(MPa) 6.9 5.9 6.2 4.0 5.2
破断強度 (MPa) 13.1 17.2 18.2 11.3 5.9
破断時伸び (％) 390 370 480 240 170
tanδ (80Hz、100℃) 0.0632 0.105 0.137 0.147 0.0897
耐熱性 ○ × × ○ ×
リップ追随性 100rpm ○ ○ ○ △ ○
1000rpm ○ ○ △ × ○
8000rpm ○ ○ × × ○
耐久時間 (時間) >120 >120 18 3 >120 The results obtained in the above Examples, Reference Examples and Comparative Examples are shown in the following table.
table
Measurement / Evaluation Items Example Reference Example 1 Reference Example 2 Comparative Example 1 Comparative Example 2
Normal physical properties Hardness Hs (Duro A) 75 74 78 75 81
100% modulus (MPa) 6.9 5.9 6.2 4.0 5.2
Breaking strength (MPa) 13.1 17.2 18.2 11.3 5.9
Elongation at break (%) 390 370 480 240 170
tanδ (80Hz, 100 ° C) 0.0632 0.105 0.137 0.147 0.0897
Heat resistance ○ × × ○ ×
Lip followability 100rpm ○ ○ ○ △ ○
1000rpm ○ ○ △ × ○
8000rpm ○ ○ × × ○
Endurance time (hours)>120> 120 18 3> 120
以上の結果より、80Hz、100℃でのtanδが0.13以上の参考例２および比較例１では所望のリップ追随性を満足させることができないが、tanδが0.13以下の実施例、参考例１、比較例２では良好なリップ追随性を示すとともに、耐久性についても120時間以上であることが確認され、このうちFMVE共重合フッ素ゴム組成物を用いた実施例のみが230℃、500時間といった高温条件下での使用にも耐えうる耐熱性を示すことが確認された。
Based on the above results, Reference Example 2 and Comparative Example 1 in which tan δ at 80 Hz and 100 ° C. is 0.13 or more cannot satisfy the desired lip followability, but Examples and Reference Example 1 in which tan δ is 0.13 or less are compared. In Example 2, it was confirmed that the lip following property was good and the durability was 120 hours or more. Of these, only the example using the FMVE copolymer fluororubber composition was at a high temperature condition of 230 ° C. and 500 hours. It was confirmed to show heat resistance that can withstand use underneath.
１ 密封装置
２ シールリップ
３ 端面シール
４ ダストシール
５ スリンガー
６ 金属環
７ 回転軸
８ レーザー変位計 DESCRIPTION OFSYMBOLS 1 Sealing device 2 Seal lip 3 End face seal 4 Dust seal 5 Slinger 6 Metal ring 7 Rotating shaft 8 Laser displacement meter
２ シールリップ
３ 端面シール
４ ダストシール
５ スリンガー
６ 金属環
７ 回転軸
８ レーザー変位計 DESCRIPTION OF
Claims (3)
- 周波数80Hz、雰囲気温度100℃での損失正接tanδが0.13以下であり、フッ化ビニリデン-テトラフルオロエチレン-パーフルオロ(メチルビニルエーテル)3元共重合体の加硫物よりなる、エンジンのクランクシャフト用であって、互いに同心的に相対回転自在に組み付けられる２部材としてのハウジングと回転軸間の環状の隙間をシールする密封装置のリップ型の端面シールとして用いられるガソリンエンジン用シール。 Loss tangent tanδ at a frequency of 80 Hz and an ambient temperature of 100 ° C is 0.13 or less, and it is made of a vulcanized product of vinylidene fluoride-tetrafluoroethylene-perfluoro (methyl vinyl ether) terpolymer. A gasoline engine seal that is used as a lip-type end face seal of a sealing device that seals an annular gap between a housing and a rotary shaft that are concentrically mounted so as to be relatively rotatable relative to each other.
- 密封装置が、ハウジングの内周に嵌合固定される金属環と、回転軸の外周に取り付けられるスリンガーの半径方向外方に伸びるフランジ部のシール相手面に摺動自在に密封接触するリップ型の端面シールとから構成されている請求項１記載のガソリンエンジン用シール。 The sealing device is a lip-shaped seal that slidably comes into contact with the seal mating surface of the flange that extends radially outward of the slinger attached to the outer periphery of the rotating shaft and the metal ring that is fitted and fixed to the inner periphery of the housing. The gasoline engine seal according to claim 1, comprising an end face seal.
- 請求項１または２記載のガソリンエンジン用シールを、エンジンのクランクシャフト用シールとして用いた密封装置。 A sealing device using the gasoline engine seal according to claim 1 or 2 as a seal for an engine crankshaft.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015530773A JP6515805B2 (en) | 2013-08-09 | 2014-07-15 | Gasoline engine seal |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-166246 | 2013-08-09 | ||
| JP2013166246 | 2013-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015019807A1 true WO2015019807A1 (en) | 2015-02-12 |
Family
ID=52461146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2014/068817 WO2015019807A1 (en) | 2013-08-09 | 2014-07-15 | Seal for gasoline engine |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6515805B2 (en) |
| WO (1) | WO2015019807A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139970A (en) * | 1996-11-08 | 1998-05-26 | Nok Corp | Fluororubber composition |
| JP2002138181A (en) * | 2000-11-06 | 2002-05-14 | Nok Corp | Fluorinated rubber blend |
| JP2004316681A (en) * | 2003-04-11 | 2004-11-11 | Komatsu Ltd | Oil seal |
| US20070048476A1 (en) * | 2005-08-31 | 2007-03-01 | Freudenberg-Nok General Partnership | Assemblies sealed with multilayer composite compression seals having a layer of dispersed fluoroelastomer in thermoplastic |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050167928A1 (en) * | 2004-02-04 | 2005-08-04 | Park Edward H. | Dynamic seal using vulcanization of fluorocarbon elastomers |
-
2014
- 2014-07-15 JP JP2015530773A patent/JP6515805B2/en active Active
- 2014-07-15 WO PCT/JP2014/068817 patent/WO2015019807A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139970A (en) * | 1996-11-08 | 1998-05-26 | Nok Corp | Fluororubber composition |
| JP2002138181A (en) * | 2000-11-06 | 2002-05-14 | Nok Corp | Fluorinated rubber blend |
| JP2004316681A (en) * | 2003-04-11 | 2004-11-11 | Komatsu Ltd | Oil seal |
| US20070048476A1 (en) * | 2005-08-31 | 2007-03-01 | Freudenberg-Nok General Partnership | Assemblies sealed with multilayer composite compression seals having a layer of dispersed fluoroelastomer in thermoplastic |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6515805B2 (en) | 2019-05-22 |
| JPWO2015019807A1 (en) | 2017-03-02 |
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