WO2014175079A1 - Fluorine-containing rubber composition - Google Patents
Fluorine-containing rubber composition Download PDFInfo
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- WO2014175079A1 WO2014175079A1 PCT/JP2014/060488 JP2014060488W WO2014175079A1 WO 2014175079 A1 WO2014175079 A1 WO 2014175079A1 JP 2014060488 W JP2014060488 W JP 2014060488W WO 2014175079 A1 WO2014175079 A1 WO 2014175079A1
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- fluororubber
- oil seal
- fluorine
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Classifications
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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
- F16J15/18—Sealings between relatively-moving surfaces with stuffing-boxes for elastic or plastic packings
- F16J15/20—Packing materials therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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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
Definitions
- the present invention relates to a fluororubber composition. More specifically, the present invention relates to a fluororubber composition used as a molding material for a rotary sliding seal product such as an oil seal.
- Oil seals are widely used as important machine parts in fields such as automobiles and industrial machinery. Among these, oil seals for both rotations aiming to keep the fluid sealed even during forward and reverse rotation of various members are used as parts for parts such as pumps, automobile differentials, agricultural machinery, and railway vehicles. Used in a wide range of fields.
- the oil seal that has been used in the past may cause leakage of the sealed fluid when the member in contact with the oil seal is rotated in the forward direction and then rotated in the reverse direction.
- the anti-sealing target side inclined surface of the oil seal lip that adheres to the first annular member fitted to one member and slides closely with the other member.
- a rotation direction in which the respective screw portions are provided There has been proposed an oil seal in which auxiliary screw portions having a specific inclination angle with respect to the opposite rotation direction are provided so as to be paired with the respective screw portions.
- Patent Document 2 discloses a rubber material composition having 100 parts by weight of raw rubber and 20 to 90 parts by weight of a fluororesin, and giving a rubber material having a spring hardness of 60 to 90.
- No. 3 proposes rubber compositions each having 100 parts by weight of carboxylated acrylonitrile butadiene rubber and 20 to 90 parts by weight of carbon black.
- none of the materials are sufficient for seal leakage due to forward / reverse rotation, and improvements are desired.
- the applicant first vulcanized and molded a fluororubber composition prepared by adding 1 to 100 parts by weight of wollastonite having an aspect ratio of 8 or more to fluororubber per 100 parts by weight of rubber and kneading it.
- An oil seal for forward / reverse rotation for railway vehicles is proposed in which a sliding surface is formed (Patent Document 4).
- oil seals are also required to have durability performance under severe conditions such as high temperature and high speed.
- An object of the present invention is to provide a fluororubber composition that can be suitably used as an oil seal molding material for both rotations and the like that can keep a fluid well sealed even in both forward and reverse rotation operations. .
- the object of the present invention is to have an average fiber diameter of 5 ⁇ m or less and an average fiber diameter per 100 parts by weight of a fluororubber composed of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-ethylene-perfluoro (methyl vinyl ether) ternary copolymer. This is achieved by a fluororubber composition containing 1 to 100 parts by weight of a needle-like or fibrous filler having a fiber length of 40 to 80 ⁇ m.
- the fluorororubber vulcanized molded product obtained from the fluororubber composition according to the present invention has resistance to deformation due to the shape effect of the filler, and thereby, for example, the sliding direction of the oil seal sliding surface It is possible to suppress the deformation to, and to produce a good lubrication state on the sliding surface, it has an excellent effect such as showing a good torque value while maintaining the sealing performance from the initial use to the long period after wear by use. Play.
- the sealing material vulcanized and molded from the fluororubber composition according to the present invention is operated in both forward and reverse rotations, and is used under a relatively high temperature condition such as 100 to 200 ° C.
- a relatively high temperature condition such as 100 to 200 ° C.
- it can be used effectively as a sealing material for railway vehicles, a sealing material for servo motors, etc. in order to keep the fluid sealed well.
- vinylidene fluoride [VdF] -hexafluoropropylene [HFP] -tetrafluoroethylene [TFE] -ethylene [E] -perfluoro (methyl vinyl ether) [FMVE] terpolymer is used.
- a commercially available Solvey product Thecnoflon BR9151 can be used as it is.
- a fluoro rubber not copolymerized with ethylene or perfluoro (methyl vinyl ether) is used, the sealing material that is a vulcanized molded product cannot achieve the intended durability of the present invention.
- Such a ternary copolymer is preferably crosslinked by a crosslinking system comprising an organic peroxide crosslinking agent-polyfunctional unsaturated compound co-crosslinking agent.
- Fluorororubber has an average particle diameter (measured by laser scattering method) of 5 ⁇ m or less, preferably 3 to 5 ⁇ m, and an average particle length (measured with an optical microscope) of 40 to 80 ⁇ m, preferably 40 to 60 ⁇ m.
- the filler in the form of 1 to 100 parts by weight, preferably 10 to 50 parts by weight, and more preferably 20 to 40 parts by weight per 100 parts by weight of the fluororubber. If the amount of these fillers is less than this, the sealability after wear due to the intended use of the present invention cannot be maintained. On the other hand, if it is used in a larger proportion, the rubber hardness increases and the seal This is not preferable because the followability is impaired.
- needle-like or fibrous filler examples include wollastonite, carbon fiber, glass fiber, potassium titanate whisker, basic magnesium sulfate, sepiolite, alumina fiber, silicon carbide whisker, silicon nitride whisker, etc. Does not belong to this category.
- fluororubber composition comprising the above essential components, various compounding agents required in terms of vulcanization operation, physical properties and functions are added.
- the composition is prepared by any kneading means using an open roll, kneader, etc. after mixing the acid acceptor such as sight and other necessary compounding agents, and heat at 160 to 200 ° C. for 3 to 30 minutes It is vulcanized and molded into an oil seal by pressing and, if necessary, secondary vulcanization at 150 to 250 ° C. for 0.5 to 24 hours.
- Example Fluoro rubber VdF-HFP-TFE-E-FMVE ternary copolymer: 100 parts by weight Solvey product Tecnoflon BR9151) MT carbon black (CANCARB LIMITED product THERMAX N-990LSR) 2 ⁇ Wollastonite (NYCO Minerals product NYGLOS4W: 25 ⁇ Average fiber diameter 4.5 ⁇ m, average fiber length 50 ⁇ m, (Aspect ratio 11) Bengala (Resino Color Industrial Product Brown No.601) 5 ⁇ Carnauba wax 1.5 ⁇ (DuPont Dow Elastomer Product VPA No.2) Hydrotalcite (Kyowa Chemical Product DHT-4A) 6 ⁇ Triallyl isocyanurate (Nippon Kasei product Thaik WH-60) 2 ⁇ Organic peroxides (NIPPON YILLOW PRODUCT PERHEXA 25B-40) 2 ⁇
- the above components are kneaded using a kneader and an open roll, subjected to primary vul
- Fluoro rubber VdF-HFP-TFE terpolymer; 60 parts by weight Daikin product DAIEL G-912) Fluoro rubber (VdF-HFP-TFE terpolymer; 40 ⁇ Daikin product DAIEL G-902) MT carbon black 2 ⁇ Wollastonite (NYGLOS4W) 20 ⁇ Bengala (Brown No.601) 5 ⁇ Magnesium oxide (# 150) 3 Aliphatic sodium monocarboxylate (Kao NS-SOAP) 1 ⁇ Organic peroxide (Perhexa 25B-40) 2 ⁇ Triallyl isocyanurate (Nippon Kasei products TAIC M-60S) 2 ⁇
- Fluoro rubber (Tecnoflon BR9151; 100 parts by weight VdF-HFP-TFE-E-FMVE ternary copolymer) MT carbon black 2 ⁇ Diatomaceous earth (central silica product silica 6B) 20 ⁇ Graphite (Nidec carbon product graphite C-1) 5 ⁇ Bengala (Brown No.601) 5 ⁇ Carnauba wax (VPA No.2) 1.5 ⁇ Hydrotalcite (DHT-4A) 6 ⁇ Triallyl isocyanurate (Tyke WH-60) 2 ⁇ Organic peroxide (Perhexa 25B-40) 2 ⁇
- Fluoro rubber VdF-HFP binary copolymer; 100 parts by weight DuPont Dow Elastomer Japan product Viton A-500
- MT carbon black 2 ⁇ Diatomaceous earth (silica 6B) 20 ⁇ Graphite (graphite C-1) 5 ⁇ Bengala (Brown No.601) 5 ⁇ Magnesium oxide (# 150) 6 ⁇ Carnauba wax (VPA No.2) 1.5 ⁇ Calcium hydroxide (Omi Chemical Co., Ltd.CALDIC 2000) 3 ⁇ Bisphenol AF 50 wt% fluororubber diluted product 2.5 ⁇ (Unimatec product CHEMINOX AF-50) Diluted 35% by weight phosphate crosslinking accelerator 1.4 ⁇ (Unimatec product CHEMINOX B-35F)
- Comparative Example 4 In Comparative Example 2, the same amount (100 parts by weight) of Solvey product Tecnoflon P757 (VdF-HFP-TFE terpolymer) was used as the fluororubber.
- Comparative Example 5 In Comparative Example 1, 40 parts by weight of NYCO Minerals product NYAD 1250 (average fiber diameter 3 ⁇ m, average fiber length 9 ⁇ m, aspect ratio 3) was used as wollastonite.
- Comparative Example 6 In Comparative Example 1, 40 parts by weight of NYCO Minerals product NYAD 400 (average fiber diameter 7 ⁇ m, average fiber length 35 ⁇ m, aspect ratio 5) was used as wollastonite.
- Comparative Example 7 In Comparative Example 1, 20 parts by weight of diatomaceous earth (silica 6B) was used instead of wollastonite.
- Comparative Example 8 In Comparative Example 1, 50 parts by weight of talc (Asada Milled Product Talc H) was used instead of wollastonite.
Abstract
A fluorine-containing rubber composition comprising: 100 parts by weight of a fluorine-containing rubber comprising a (vinylidene fluoride)-hexafluoropropylene- tetrafluoroethylene-ethylene-perfluoro(methyl vinyl ether) five-component polymer; and 1 to 100 parts by weight of a needle-shaped or fibrous filler having an average fiber diameter of 5 μm or less and an average fiber length of 40 to 80 μm. The fluorine-containing rubber composition can be used suitably as, for example, a material for molding a bi-directional-rotation-type oil seal which enables a fluid to be sealed continuously and satisfactorily in both a normal-direction rotational operation and a reverse-direction rotational operation.
Description
本発明は、フッ素ゴム組成物に関する。さらに詳しくは、オイルシール等の回転摺動用シール製品の成形材料などとして用いられるフッ素ゴム組成物に関する。
The present invention relates to a fluororubber composition. More specifically, the present invention relates to a fluororubber composition used as a molding material for a rotary sliding seal product such as an oil seal.
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。このうち各種部材の正・逆両回転の作動においても流体を密封し続けることを目的とする両回転用オイルシールは、例えばポンプ、自動車のデフ、農業用機械、鉄道車両などの部材用部品として幅広い分野で用いられている。
Oil seals are widely used as important machine parts in fields such as automobiles and industrial machinery. Among these, oil seals for both rotations aiming to keep the fluid sealed even during forward and reverse rotation of various members are used as parts for parts such as pumps, automobile differentials, agricultural machinery, and railway vehicles. Used in a wide range of fields.
従来用いられていたオイルシールは、オイルシールと接触している部材を正転方向に回転させた後逆転方向に回転させた場合に、密封していた流体の漏れを生ずる場合がある。かかる不具合を回避するために、例えば特許文献１では、一の部材に嵌合する第一環状部材に接着し他の部材と密接に摺動するオイルシールリップの反密封対象側傾斜面に、前記他の部材の正回転時および逆回転時における回転方向に対し特定の傾斜角を有するねじ部をそれぞれ複数本づつ群として交互に設けたオイルシールにおいて、前記各ねじ部が設けられた回転方向と反対回転方向に対し特定の傾斜角を有する補助ねじ部を前記各ねじ部と対になるように設けたオイルシールが提案されている。しかるに、このような補助ねじをねじ部と対になるように設けた構造のみでは、正転・逆転が繰り返された場合に、摩耗によるシール面の状態に何らかの不具合が生じ、逆回転時にシール漏れを生ずる可能性があり得る。
The oil seal that has been used in the past may cause leakage of the sealed fluid when the member in contact with the oil seal is rotated in the forward direction and then rotated in the reverse direction. In order to avoid such a problem, for example, in Patent Document 1, the anti-sealing target side inclined surface of the oil seal lip that adheres to the first annular member fitted to one member and slides closely with the other member, In the oil seal in which a plurality of screw portions each having a specific inclination angle with respect to the rotation direction at the time of forward rotation and reverse rotation of other members are provided alternately as a group, a rotation direction in which the respective screw portions are provided There has been proposed an oil seal in which auxiliary screw portions having a specific inclination angle with respect to the opposite rotation direction are provided so as to be paired with the respective screw portions. However, with such a structure in which such auxiliary screws are provided so as to be paired with the threaded portion, when the forward rotation and reverse rotation are repeated, some trouble occurs in the state of the seal surface due to wear, and seal leakage occurs during reverse rotation. May occur.
一方、鉄道車両用部材などに用いられる正・逆両回転用オイルシールの耐摩耗材料としては、従来ポリオール架橋系２元系フッ素ゴムに珪藻土を主とする充填剤を配合せしめたフッ素ゴム組成物が用いられている。また、特許文献２には原料ゴム100重量部とフッ素樹脂20～90重量部とを有するゴム材料組成物であって、スプリング硬度が60～90のゴム材料を与えるゴム組成物が、また特許文献３にはカルボキシル化アクリロニトリルブタジエンゴム100重量部とカーボンブラック20～90重量部とを有するゴム組成物がそれぞれ提案されている。しかるに、いずれの材料も正・逆回転によるシール漏れについては十分ではなく、その改良が望まれている。
On the other hand, as a wear resistant material for oil seals for both forward and reverse rotations used for rolling stock members, a conventional fluororubber composition in which a filler mainly composed of diatomaceous earth is blended with a polyol-crosslinked binary fluororubber. Is used. Patent Document 2 discloses a rubber material composition having 100 parts by weight of raw rubber and 20 to 90 parts by weight of a fluororesin, and giving a rubber material having a spring hardness of 60 to 90. No. 3 proposes rubber compositions each having 100 parts by weight of carboxylated acrylonitrile butadiene rubber and 20 to 90 parts by weight of carbon black. However, none of the materials are sufficient for seal leakage due to forward / reverse rotation, and improvements are desired.
本出願人は先に、ゴム100重量部当り、アスペクト比8以上のウォラストナイト1～100重量部をフッ素ゴムに添加し、それを混練して調製されたフッ素ゴム組成物を加硫成形して摺動面を形成させてなる、鉄道車両用の正・逆両回転用オイルシールを提案している(特許文献４)。しかるに、新幹線など鉄道の高速化に伴って、オイルシールに対しても高温、高速などといった過酷な条件下における耐久性能が求められている。
The applicant first vulcanized and molded a fluororubber composition prepared by adding 1 to 100 parts by weight of wollastonite having an aspect ratio of 8 or more to fluororubber per 100 parts by weight of rubber and kneading it. An oil seal for forward / reverse rotation for railway vehicles is proposed in which a sliding surface is formed (Patent Document 4). However, with the speeding up of railways such as the Shinkansen, oil seals are also required to have durability performance under severe conditions such as high temperature and high speed.
本発明の目的は、正・逆両回転の作動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両回転用オイルシール成形材料などとして好適に用いられるフッ素ゴム組成物を提供することにある。
An object of the present invention is to provide a fluororubber composition that can be suitably used as an oil seal molding material for both rotations and the like that can keep a fluid well sealed even in both forward and reverse rotation operations. .
かかる本発明の目的は、フッ化ビニリデン-ヘキサフルオロプロピレン-テトラフルオロエチレン-エチレン-パーフルオロ(メチルビニルエーテル)5元共重合体よりなるフッ素ゴム100重量部当り、平均繊維径が5μm以下でかつ平均繊維長が40～80μmの針状または繊維状の充填剤を1～100重量部含有せしめたフッ素ゴム組成物によって達成される。
The object of the present invention is to have an average fiber diameter of 5 μm or less and an average fiber diameter per 100 parts by weight of a fluororubber composed of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-ethylene-perfluoro (methyl vinyl ether) ternary copolymer. This is achieved by a fluororubber composition containing 1 to 100 parts by weight of a needle-like or fibrous filler having a fiber length of 40 to 80 μm.
本発明に係るフッ素ゴム組成物より得られるフッ素ゴム加硫成形品は、充填剤の形状効果により、変形に対して抵抗力を有するようになり、これによって例えばオイルシール摺動面の摺動方向への変形を抑制でき、また摺動面に良好な潤滑状態を生み出すことで、使用初期から使用による摩耗後の長期間にわたって、シール性を維持しつつ良好なトルク値を示すといったすぐれた効果を奏する。
The fluororubber vulcanized molded product obtained from the fluororubber composition according to the present invention has resistance to deformation due to the shape effect of the filler, and thereby, for example, the sliding direction of the oil seal sliding surface It is possible to suppress the deformation to, and to produce a good lubrication state on the sliding surface, it has an excellent effect such as showing a good torque value while maintaining the sealing performance from the initial use to the long period after wear by use. Play.
従って、本発明に係るフッ素ゴム組成物から加硫成形されたシール材は、正・逆両回転の作動であって、使用環境温度が例えば100～200℃といった比較的高温度条件下にあっても、良好に流体を密封し続けることを可能とするため、鉄道車両用シール材、サーボモータ用シール材などとして有効に用いられる。
Therefore, the sealing material vulcanized and molded from the fluororubber composition according to the present invention is operated in both forward and reverse rotations, and is used under a relatively high temperature condition such as 100 to 200 ° C. However, it can be used effectively as a sealing material for railway vehicles, a sealing material for servo motors, etc. in order to keep the fluid sealed well.
フッ素ゴムとしては、フッ化ビニリデン〔VdF〕-ヘキサフルオロプロピレン〔HFP〕-テトラフルオロエチレン〔TFE〕-エチレン〔E〕-パーフルオロ(メチルビニルエーテル)〔FMVE〕5元共重合体が用いられ、これは例えば市販品であるSolvey製品Thecnoflon BR9151などをそのまま用いることができる。ここで、エチレンあるいはパーフルオロ(メチルビニルエーテル)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耐久性を達成することができない。かかる5元共重合体は、好ましくは有機過酸化物架橋剤-多官能性不飽和化合物共架橋剤よりなる架橋系によって架橋される。
As the fluororubber, vinylidene fluoride [VdF] -hexafluoropropylene [HFP] -tetrafluoroethylene [TFE] -ethylene [E] -perfluoro (methyl vinyl ether) [FMVE] terpolymer is used. For example, a commercially available Solvey product Thecnoflon BR9151 can be used as it is. Here, when a fluoro rubber not copolymerized with ethylene or perfluoro (methyl vinyl ether) is used, the sealing material that is a vulcanized molded product cannot achieve the intended durability of the present invention. . Such a ternary copolymer is preferably crosslinked by a crosslinking system comprising an organic peroxide crosslinking agent-polyfunctional unsaturated compound co-crosslinking agent.
フッ素ゴムには、平均粒子径(レーザー散乱法により測定)が5μm以下、好ましくは3～5μmでかつ平均粒子長(光学顕微鏡で測定)が40～80μm、好ましくは40～60μmの針状または繊維状の充填剤が、フッ素ゴム100重量部当り1～100重量部、好ましくは10～50重量部、さらに好ましくは20～40重量部の割合で配合される。これらの充填剤の量がこれより少ないと本発明の目的とする使用による摩耗後のシール性を維持することができず、一方これより多い割合で用いられると、ゴム硬度が上昇し、シールの追随性を損なうようになるため好ましくない。また、平均粒子径がこれ以上のものを用いると、摺動面からの充填剤の脱落により隙間漏れが生じるおそれがあり、その結果使用による摩耗後のトルク値は維持できるものの、シール性が低下することがあり、平均粒子長がこれ以外のものを用いると、摩耗後のトルク値が悪化するようになる。
Fluororubber has an average particle diameter (measured by laser scattering method) of 5 μm or less, preferably 3 to 5 μm, and an average particle length (measured with an optical microscope) of 40 to 80 μm, preferably 40 to 60 μm. The filler in the form of 1 to 100 parts by weight, preferably 10 to 50 parts by weight, and more preferably 20 to 40 parts by weight per 100 parts by weight of the fluororubber. If the amount of these fillers is less than this, the sealability after wear due to the intended use of the present invention cannot be maintained. On the other hand, if it is used in a larger proportion, the rubber hardness increases and the seal This is not preferable because the followability is impaired. In addition, if an average particle size larger than this is used, gap leakage may occur due to the falling off of the filler from the sliding surface. As a result, the torque value after wear due to use can be maintained, but the sealing performance is reduced. If a particle having an average particle length other than this is used, the torque value after wear will deteriorate.
針状または繊維状の充填剤としては、ウォラストナイト、炭素繊維、ガラス繊維、チタン酸カリウムウィスカー、塩基性硫酸マグネシウム、セピオライト、アルミナ繊維、炭化ケイ素ウィスカー、窒化ケイ素ウィスカー等が用いられ、珪藻土等はこの範疇に属さない。
Examples of the needle-like or fibrous filler include wollastonite, carbon fiber, glass fiber, potassium titanate whisker, basic magnesium sulfate, sepiolite, alumina fiber, silicon carbide whisker, silicon nitride whisker, etc. Does not belong to this category.
なお、特許文献４には、鉄道車両用正・逆両回転用オイルシールの成形材料として、フッ素ゴム(VdF-HFP共重合体)100重量部当り、アスペクト比8以上のウォラストナイト1～100重量部を添加し、それを混練して調製されたフッ素ゴム組成物が開示されているが、本発明の５元共重合体ではなく、２元または３元共重合体を用いた場合には、例えば1000時間以上といった耐久時間を達成することは難しくなる。
In Patent Document 4, wollastonite 1 to 100 having an aspect ratio of 8 or more per 100 parts by weight of fluororubber (VdF-HFP copolymer) is used as a molding material for forward and reverse rotation oil seals for railway vehicles. Although a fluororubber composition prepared by adding parts by weight and kneading it is disclosed, when a binary or ternary copolymer is used instead of the quinary copolymer of the present invention, For example, it is difficult to achieve a durability time of 1000 hours or more.
以上の必須成分よりなるフッ素ゴム組成物には、加硫操作上、物性上、機能上要求される各種配合剤が添加され、例えば、フッ素ゴム加硫に用いられるポリオール系または有機過酸化物系加硫剤、4級オニウム塩等の加硫助剤、多官能性不飽和化合物共架橋剤、カーボンブラック、シリカ等の補強剤または充填剤、2価金属の酸化物、水酸化物またはハイドロタルサイト等の受酸剤、その他必要な配合剤が配合された上で、オープンロール、ニーダなどを用いる任意の混練手段により組成物の調製が行われ、160～200℃、3～30分間のヒートプレスおよび必要に応じて150～250℃、0.5～24時間の二次加硫を行うことにより、オイルシールへと加硫成形される。
To the fluororubber composition comprising the above essential components, various compounding agents required in terms of vulcanization operation, physical properties and functions are added. For example, polyol-based or organic peroxide-based used for fluororubber vulcanization Vulcanizing agents, vulcanizing aids such as quaternary onium salts, polyfunctional unsaturated compound co-crosslinking agents, reinforcing agents or fillers such as carbon black and silica, bivalent metal oxides, hydroxides or hydrotals The composition is prepared by any kneading means using an open roll, kneader, etc. after mixing the acid acceptor such as sight and other necessary compounding agents, and heat at 160 to 200 ° C. for 3 to 30 minutes It is vulcanized and molded into an oil seal by pressing and, if necessary, secondary vulcanization at 150 to 250 ° C. for 0.5 to 24 hours.
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
フッ素ゴム(VdF-HFP-TFE-E-FMVE５元共重合体： 100重量部
Solvey製品Tecnoflon BR9151)
MTカーボンブラック(CANCARB LIMITED製品THERMAX N-990LSR) 2 〃
ウォラストナイト(NYCO Minerals製品NYGLOS4W： 25 〃
平均繊維径4.5μm、平均繊維長50μm、
アスペクト比11)
ベンガラ(レジノカラー工業製品ブラウンNo.601) 5 〃
カルナバワックス 1.5 〃
(デュポン・ダウ・エラストマー社製品VPA No.2)
ハイドロタルサイト(協和化学製品DHT-4A) 6 〃
トリアリルイソシアヌレート(日本化成製品タイクWH-60) 2 〃
有機過酸化物(日本油脂製品パーヘキサ25B-40) 2 〃
以上の各成分をニーダおよびオープンロールを用いて混練し、180℃、4分間の一次加硫および200℃、15時間の二次加硫を行い、内径80mm、外径105mm、幅11.5mmのオイルシールを加硫成形した。 Example Fluoro rubber (VdF-HFP-TFE-E-FMVE ternary copolymer: 100 parts by weight Solvey product Tecnoflon BR9151)
MT carbon black (CANCARB LIMITED product THERMAX N-990LSR) 2 〃
Wollastonite (NYCO Minerals product NYGLOS4W: 25 〃
Average fiber diameter 4.5μm, average fiber length 50μm,
(Aspect ratio 11)
Bengala (Resino Color Industrial Product Brown No.601) 5 〃
Carnauba wax 1.5 〃
(DuPont Dow Elastomer Product VPA No.2)
Hydrotalcite (Kyowa Chemical Product DHT-4A) 6 〃
Triallyl isocyanurate (Nippon Kasei product Thaik WH-60) 2 〃
Organic peroxides (NIPPON YILLOW PRODUCT PERHEXA 25B-40) 2 〃
The above components are kneaded using a kneader and an open roll, subjected to primary vulcanization at 180 ° C for 4 minutes and secondary vulcanization at 200 ° C for 15 hours. The seal was vulcanized.
フッ素ゴム(VdF-HFP-TFE-E-FMVE５元共重合体： 100重量部
Solvey製品Tecnoflon BR9151)
MTカーボンブラック(CANCARB LIMITED製品THERMAX N-990LSR) 2 〃
ウォラストナイト(NYCO Minerals製品NYGLOS4W： 25 〃
平均繊維径4.5μm、平均繊維長50μm、
アスペクト比11)
ベンガラ(レジノカラー工業製品ブラウンNo.601) 5 〃
カルナバワックス 1.5 〃
(デュポン・ダウ・エラストマー社製品VPA No.2)
ハイドロタルサイト(協和化学製品DHT-4A) 6 〃
トリアリルイソシアヌレート(日本化成製品タイクWH-60) 2 〃
有機過酸化物(日本油脂製品パーヘキサ25B-40) 2 〃
以上の各成分をニーダおよびオープンロールを用いて混練し、180℃、4分間の一次加硫および200℃、15時間の二次加硫を行い、内径80mm、外径105mm、幅11.5mmのオイルシールを加硫成形した。 Example Fluoro rubber (VdF-HFP-TFE-E-FMVE ternary copolymer: 100 parts by weight Solvey product Tecnoflon BR9151)
MT carbon black (CANCARB LIMITED product THERMAX N-990LSR) 2 〃
Wollastonite (NYCO Minerals product NYGLOS4W: 25 〃
Average fiber diameter 4.5μm, average fiber length 50μm,
(Aspect ratio 11)
Bengala (Resino Color Industrial Product Brown No.601) 5 〃
Carnauba wax 1.5 〃
(DuPont Dow Elastomer Product VPA No.2)
Hydrotalcite (Kyowa Chemical Product DHT-4A) 6 〃
Triallyl isocyanurate (Nippon Kasei product Thaik WH-60) 2 〃
Organic peroxides (NIPPON YILLOW PRODUCT PERHEXA 25B-40) 2 〃
The above components are kneaded using a kneader and an open roll, subjected to primary vulcanization at 180 ° C for 4 minutes and secondary vulcanization at 200 ° C for 15 hours. The seal was vulcanized.
比較例１
実施例において、フッ素ゴム組成物として下記のものが用いられた。
フッ素ゴム(VdF-HFP-TFE３元共重合体； 60重量部
ダイキン製品DAIEL G-912)
フッ素ゴム(VdF-HFP-TFE３元共重合体； 40 〃
ダイキン製品DAIEL G-902)
MTカーボンブラック 2 〃
ウォラストナイト(NYGLOS4W) 20 〃
ベンガラ(ブラウンNo.601) 5 〃
酸化マグネシウム(♯150) 3 〃
脂肪族モノカルボン酸ナトリウム(花王製品NS-SOAP) 1 〃
有機過酸化物(パーヘキサ25B-40) 2 〃
トリアリルイソシアヌレート(日本化成製品TAIC M-60S) 2 〃 Comparative Example 1
In the examples, the following were used as the fluororubber composition.
Fluoro rubber (VdF-HFP-TFE terpolymer; 60 parts by weight Daikin product DAIEL G-912)
Fluoro rubber (VdF-HFP-TFE terpolymer; 40 〃
Daikin product DAIEL G-902)
MT carbon black 2 〃
Wollastonite (NYGLOS4W) 20 〃
Bengala (Brown No.601) 5 〃
Magnesium oxide (# 150) 3
Aliphatic sodium monocarboxylate (Kao NS-SOAP) 1 〃
Organic peroxide (Perhexa 25B-40) 2 〃
Triallyl isocyanurate (Nippon Kasei products TAIC M-60S) 2 〃
実施例において、フッ素ゴム組成物として下記のものが用いられた。
フッ素ゴム(VdF-HFP-TFE３元共重合体； 60重量部
ダイキン製品DAIEL G-912)
フッ素ゴム(VdF-HFP-TFE３元共重合体； 40 〃
ダイキン製品DAIEL G-902)
MTカーボンブラック 2 〃
ウォラストナイト(NYGLOS4W) 20 〃
ベンガラ(ブラウンNo.601) 5 〃
酸化マグネシウム(♯150) 3 〃
脂肪族モノカルボン酸ナトリウム(花王製品NS-SOAP) 1 〃
有機過酸化物(パーヘキサ25B-40) 2 〃
トリアリルイソシアヌレート(日本化成製品TAIC M-60S) 2 〃 Comparative Example 1
In the examples, the following were used as the fluororubber composition.
Fluoro rubber (VdF-HFP-TFE terpolymer; 60 parts by weight Daikin product DAIEL G-912)
Fluoro rubber (VdF-HFP-TFE terpolymer; 40 〃
Daikin product DAIEL G-902)
MT carbon black 2 〃
Wollastonite (NYGLOS4W) 20 〃
Bengala (Brown No.601) 5 〃
Magnesium oxide (# 150) 3
Aliphatic sodium monocarboxylate (Kao NS-SOAP) 1 〃
Organic peroxide (Perhexa 25B-40) 2 〃
Triallyl isocyanurate (Nippon Kasei products TAIC M-60S) 2 〃
比較例２
実施例において、フッ素ゴム組成物として下記のものが用いられた。
フッ素ゴム(Tecnoflon BR9151； 100重量部
VdF-HFP-TFE-E-FMVE５元共重合体)
MTカーボンブラック 2 〃
珪藻土(中央シリカ製品シリカ 6B) 20 〃
グラファイト(日電カーボン製品グラファイトC-1) 5 〃
ベンガラ(ブラウンNo.601) 5 〃
カルナバワックス(VPA No.2) 1.5 〃
ハイドロタルサイト(DHT-4A) 6 〃
トリアリルイソシアヌレート(タイクWH-60) 2 〃
有機過酸化物(パーヘキサ25B-40) 2 〃 Comparative Example 2
In the examples, the following were used as the fluororubber composition.
Fluoro rubber (Tecnoflon BR9151; 100 parts by weight VdF-HFP-TFE-E-FMVE ternary copolymer)
MT carbon black 2 〃
Diatomaceous earth (central silica product silica 6B) 20 〃
Graphite (Nidec carbon product graphite C-1) 5 〃
Bengala (Brown No.601) 5 〃
Carnauba wax (VPA No.2) 1.5 〃
Hydrotalcite (DHT-4A) 6 〃
Triallyl isocyanurate (Tyke WH-60) 2 〃
Organic peroxide (Perhexa 25B-40) 2 〃
実施例において、フッ素ゴム組成物として下記のものが用いられた。
フッ素ゴム(Tecnoflon BR9151； 100重量部
VdF-HFP-TFE-E-FMVE５元共重合体)
MTカーボンブラック 2 〃
珪藻土(中央シリカ製品シリカ 6B) 20 〃
グラファイト(日電カーボン製品グラファイトC-1) 5 〃
ベンガラ(ブラウンNo.601) 5 〃
カルナバワックス(VPA No.2) 1.5 〃
ハイドロタルサイト(DHT-4A) 6 〃
トリアリルイソシアヌレート(タイクWH-60) 2 〃
有機過酸化物(パーヘキサ25B-40) 2 〃 Comparative Example 2
In the examples, the following were used as the fluororubber composition.
Fluoro rubber (Tecnoflon BR9151; 100 parts by weight VdF-HFP-TFE-E-FMVE ternary copolymer)
MT carbon black 2 〃
Diatomaceous earth (central silica product silica 6B) 20 〃
Graphite (Nidec carbon product graphite C-1) 5 〃
Bengala (Brown No.601) 5 〃
Carnauba wax (VPA No.2) 1.5 〃
Hydrotalcite (DHT-4A) 6 〃
Triallyl isocyanurate (Tyke WH-60) 2 〃
Organic peroxide (Perhexa 25B-40) 2 〃
比較例３
実施例において、フッ素ゴム組成物として下記のものが用いられた。
フッ素ゴム(VdF-HFP２元共重合体； 100重量部
デュポンダウエラストマージャパン製品バイトンA-500)
MTカーボンブラック 2 〃
珪藻土(シリカ 6B) 20 〃
グラファイト(グラファイトC-1) 5 〃
ベンガラ(ブラウンNo.601) 5 〃
酸化マグネシウム(♯150) 6 〃
カルナバワックス(VPA No.2) 1.5 〃
水酸化カルシウム(近江化学工業製品CALDIC 2000) 3 〃
ビスフェノールAF50重量％フッ素ゴム希釈品 2.5 〃
(ユニマテック製品CHEMINOX AF-50)
35重量％リン酸塩系架橋促進剤希釈品 1.4 〃
(ユニマテック製品CHEMINOX B-35F) Comparative Example 3
In the examples, the following were used as the fluororubber composition.
Fluoro rubber (VdF-HFP binary copolymer; 100 parts by weight DuPont Dow Elastomer Japan product Viton A-500)
MT carbon black 2 〃
Diatomaceous earth (silica 6B) 20 〃
Graphite (graphite C-1) 5 〃
Bengala (Brown No.601) 5 〃
Magnesium oxide (# 150) 6 〃
Carnauba wax (VPA No.2) 1.5 〃
Calcium hydroxide (Omi Chemical Co., Ltd.CALDIC 2000) 3 〃
Bisphenol AF 50 wt% fluororubber diluted product 2.5 〃
(Unimatec product CHEMINOX AF-50)
Diluted 35% by weight phosphate crosslinking accelerator 1.4 〃
(Unimatec product CHEMINOX B-35F)
実施例において、フッ素ゴム組成物として下記のものが用いられた。
フッ素ゴム(VdF-HFP２元共重合体； 100重量部
デュポンダウエラストマージャパン製品バイトンA-500)
MTカーボンブラック 2 〃
珪藻土(シリカ 6B) 20 〃
グラファイト(グラファイトC-1) 5 〃
ベンガラ(ブラウンNo.601) 5 〃
酸化マグネシウム(♯150) 6 〃
カルナバワックス(VPA No.2) 1.5 〃
水酸化カルシウム(近江化学工業製品CALDIC 2000) 3 〃
ビスフェノールAF50重量％フッ素ゴム希釈品 2.5 〃
(ユニマテック製品CHEMINOX AF-50)
35重量％リン酸塩系架橋促進剤希釈品 1.4 〃
(ユニマテック製品CHEMINOX B-35F) Comparative Example 3
In the examples, the following were used as the fluororubber composition.
Fluoro rubber (VdF-HFP binary copolymer; 100 parts by weight DuPont Dow Elastomer Japan product Viton A-500)
MT carbon black 2 〃
Diatomaceous earth (silica 6B) 20 〃
Graphite (graphite C-1) 5 〃
Bengala (Brown No.601) 5 〃
Magnesium oxide (# 150) 6 〃
Carnauba wax (VPA No.2) 1.5 〃
Calcium hydroxide (Omi Chemical Co., Ltd.CALDIC 2000) 3 〃
Bisphenol AF 50 wt% fluororubber diluted product 2.5 〃
(Unimatec product CHEMINOX AF-50)
Diluted 35% by weight phosphate crosslinking accelerator 1.4 〃
(Unimatec product CHEMINOX B-35F)
比較例４
比較例２において、フッ素ゴムとしてSolvey製品Tecnoflon P757(VdF-HFP-TFE３元共重合体)が同量(100重量部)用いられた。 Comparative Example 4
In Comparative Example 2, the same amount (100 parts by weight) of Solvey product Tecnoflon P757 (VdF-HFP-TFE terpolymer) was used as the fluororubber.
比較例２において、フッ素ゴムとしてSolvey製品Tecnoflon P757(VdF-HFP-TFE３元共重合体)が同量(100重量部)用いられた。 Comparative Example 4
In Comparative Example 2, the same amount (100 parts by weight) of Solvey product Tecnoflon P757 (VdF-HFP-TFE terpolymer) was used as the fluororubber.
比較例５
比較例１において、ウォラストナイトとしてNYCO Minerals製品NYAD 1250(平均繊維径 3μm、平均繊維長 9μm、アスペクト比 3)40重量部が用いられた Comparative Example 5
In Comparative Example 1, 40 parts by weight of NYCO Minerals product NYAD 1250 (average fiber diameter 3 μm, average fiber length 9 μm, aspect ratio 3) was used as wollastonite.
比較例１において、ウォラストナイトとしてNYCO Minerals製品NYAD 1250(平均繊維径 3μm、平均繊維長 9μm、アスペクト比 3)40重量部が用いられた Comparative Example 5
In Comparative Example 1, 40 parts by weight of NYCO Minerals product NYAD 1250 (average fiber diameter 3 μm, average fiber length 9 μm, aspect ratio 3) was used as wollastonite.
比較例６
比較例１において、ウォラストナイトとしてNYCO Minerals製品NYAD 400(平均繊維径 7μm、平均繊維長 35μm、アスペクト比 5)40重量部が用いられた Comparative Example 6
In Comparative Example 1, 40 parts by weight of NYCO Minerals product NYAD 400 (average fiber diameter 7 μm, average fiber length 35 μm, aspect ratio 5) was used as wollastonite.
比較例１において、ウォラストナイトとしてNYCO Minerals製品NYAD 400(平均繊維径 7μm、平均繊維長 35μm、アスペクト比 5)40重量部が用いられた Comparative Example 6
In Comparative Example 1, 40 parts by weight of NYCO Minerals product NYAD 400 (average fiber diameter 7 μm, average fiber length 35 μm, aspect ratio 5) was used as wollastonite.
比較例７
比較例１において、ウォラストナイトの代わりに珪藻土(シリカ 6B)20重量部が用いられた。 Comparative Example 7
In Comparative Example 1, 20 parts by weight of diatomaceous earth (silica 6B) was used instead of wollastonite.
比較例１において、ウォラストナイトの代わりに珪藻土(シリカ 6B)20重量部が用いられた。 Comparative Example 7
In Comparative Example 1, 20 parts by weight of diatomaceous earth (silica 6B) was used instead of wollastonite.
比較例８
比較例１において、ウォラストナイトの代わりにタルク(浅田製粉製品タルクH)50重量部が用いられた。 Comparative Example 8
In Comparative Example 1, 50 parts by weight of talc (Asada Milled Product Talc H) was used instead of wollastonite.
比較例１において、ウォラストナイトの代わりにタルク(浅田製粉製品タルクH)50重量部が用いられた。 Comparative Example 8
In Comparative Example 1, 50 parts by weight of talc (Asada Milled Product Talc H) was used instead of wollastonite.
以上の実施例および各比較例で得られたオイルシールを用いて、常態物性および耐久性の測定を行い、実施例および比較例２～４についてはさらに浸せき試験を行った。
常態物性(硬度)：ISO 7169：2004に対応するJIS K6253：1997に準拠
し、タイプAデュロメータを用いて瞬時の硬さを測
定
常態物性(引張強さ、伸び)：ISO 37：2011に対応するJIS K6251：201
0準拠
耐久性：オイルシールを回転試験機にセットし、ギア油(ジャパンエ
ナジー製品JRK-65)を回転軸を中心とした状態で密封、油温
を室温より自然上昇とし、回転数6500rpm(周速27.2m/秒)の
条件下で正回転5時間→2分間休止→逆回転5時間→2分間休止
のサイクルで漏れが生じるまでの時間を測定
浸せき試験：ギア油(JRK-65)に150℃、500時間浸せき後の硬さ、引張
強さ、伸びを測定し、各々の変化(率)を算出 Using the oil seals obtained in the above Examples and Comparative Examples, normal physical properties and durability were measured, and Examples and Comparative Examples 2 to 4 were further subjected to immersion tests.
Normal state physical properties (hardness): Conforms to JIS K6253: 1997 corresponding to ISO 7169: 2004 Measures instantaneous hardness using a type A durometer Normal state physical properties (tensile strength, elongation): Corresponds to ISO 37: 2011 JIS K6251: 201
0 compliant Durability: Set the oil seal on the rotation tester, seal the gear oil (Japan Energy product JRK-65) around the rotating shaft, let the oil temperature rise naturally from room temperature, and rotate at 6500rpm ( Measure the time until leakage occurs in a cycle of 5 hours forward rotation → 2 minutes pause → reverse rotation 5 hours → 2 minutes pause under the condition of peripheral speed 27.2 m / sec) Immersion test: gear oil (JRK-65) Measure hardness, tensile strength and elongation after immersion at 150 ° C for 500 hours and calculate each change (rate)
常態物性(硬度)：ISO 7169：2004に対応するJIS K6253：1997に準拠
し、タイプAデュロメータを用いて瞬時の硬さを測
定
常態物性(引張強さ、伸び)：ISO 37：2011に対応するJIS K6251：201
0準拠
耐久性：オイルシールを回転試験機にセットし、ギア油(ジャパンエ
ナジー製品JRK-65)を回転軸を中心とした状態で密封、油温
を室温より自然上昇とし、回転数6500rpm(周速27.2m/秒)の
条件下で正回転5時間→2分間休止→逆回転5時間→2分間休止
のサイクルで漏れが生じるまでの時間を測定
浸せき試験：ギア油(JRK-65)に150℃、500時間浸せき後の硬さ、引張
強さ、伸びを測定し、各々の変化(率)を算出 Using the oil seals obtained in the above Examples and Comparative Examples, normal physical properties and durability were measured, and Examples and Comparative Examples 2 to 4 were further subjected to immersion tests.
Normal state physical properties (hardness): Conforms to JIS K6253: 1997 corresponding to ISO 7169: 2004 Measures instantaneous hardness using a type A durometer Normal state physical properties (tensile strength, elongation): Corresponds to ISO 37: 2011 JIS K6251: 201
0 compliant Durability: Set the oil seal on the rotation tester, seal the gear oil (Japan Energy product JRK-65) around the rotating shaft, let the oil temperature rise naturally from room temperature, and rotate at 6500rpm ( Measure the time until leakage occurs in a cycle of 5 hours forward rotation → 2 minutes pause → reverse rotation 5 hours → 2 minutes pause under the condition of peripheral speed 27.2 m / sec) Immersion test: gear oil (JRK-65) Measure hardness, tensile strength and elongation after immersion at 150 ° C for 500 hours and calculate each change (rate)
試験結果は、次の表に示される。
The test results are shown in the following table.
Claims (6)
- フッ化ビニリデン-ヘキサフルオロプロピレン-テトラフルオロエチレン-エチレン-パーフルオロ(メチルビニルエーテル)5元共重合体よりなるフッ素ゴム100重量部当り、平均繊維径が5μm以下でかつ平均繊維長が40～80μmの針状または繊維状の充填剤を1～100重量部含有せしめたフッ素ゴム組成物。 An average fiber diameter of 5 μm or less and an average fiber length of 40 to 80 μm per 100 parts by weight of a fluororubber made of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-ethylene-perfluoro (methyl vinyl ether) ternary copolymer A fluororubber composition containing 1 to 100 parts by weight of a needle-like or fibrous filler.
- 針状または繊維状の充填剤が、ウォラストナイト、炭素繊維、ガラス繊維、チタン酸カリウムウィスカー、塩基性硫酸マグネシウム、セピオライト、アルミナ繊維、炭化ケイ素ウィスカーまたは窒化ケイ素ウィスカーである請求項１記載のフッ素ゴム組成物。 2. The fluorine according to claim 1, wherein the acicular or fibrous filler is wollastonite, carbon fiber, glass fiber, potassium titanate whisker, basic magnesium sulfate, sepiolite, alumina fiber, silicon carbide whisker or silicon nitride whisker. Rubber composition.
- 請求項１または２のいずれかに記載のフッ素ゴム組成物から加硫成形されたシール材。 A sealing material vulcanized and molded from the fluororubber composition according to claim 1.
- オイルシールとして用いられる請求項３記載のシール材。 The sealing material according to claim 3, which is used as an oil seal.
- 正・逆両回転用オイルシールとして用いられる請求項４記載のシール材。 The sealing material according to claim 4, which is used as an oil seal for both forward and reverse rotation.
- 鉄道車両用の正・逆両回転用オイルシールとして用いられる請求項５記載のシール材。
The sealing material according to claim 5, which is used as an oil seal for both forward and reverse rotation for a railway vehicle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015513678A JP6451626B2 (en) | 2013-04-26 | 2014-04-11 | Fluoro rubber composition |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2013093632 | 2013-04-26 | ||
| JP2013-093632 | 2013-04-26 |
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| WO2014175079A1 true WO2014175079A1 (en) | 2014-10-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2014/060488 WO2014175079A1 (en) | 2013-04-26 | 2014-04-11 | Fluorine-containing rubber composition |
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| JP (1) | JP6451626B2 (en) |
| WO (1) | WO2014175079A1 (en) |
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| JP2016014092A (en) * | 2014-07-01 | 2016-01-28 | Nok株式会社 | Fluororubber composition |
| WO2017110364A1 (en) * | 2015-12-21 | 2017-06-29 | Nok株式会社 | Fluororubber composition |
| JPWO2017150192A1 (en) * | 2016-03-01 | 2018-12-20 | Nok株式会社 | Fluororubber composition and crosslinked fluororubber |
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| JPWO2017150192A1 (en) * | 2016-03-01 | 2018-12-20 | Nok株式会社 | Fluororubber composition and crosslinked fluororubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6451626B2 (en) | 2019-01-16 |
| JPWO2014175079A1 (en) | 2017-02-23 |
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