WO2022024984A1 - Molded rubber object - Google Patents

Molded rubber object Download PDF

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Publication number
WO2022024984A1
WO2022024984A1 PCT/JP2021/027521 JP2021027521W WO2022024984A1 WO 2022024984 A1 WO2022024984 A1 WO 2022024984A1 JP 2021027521 W JP2021027521 W JP 2021027521W WO 2022024984 A1 WO2022024984 A1 WO 2022024984A1
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Prior art keywords
rubber
oil
parts
molded product
weight
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PCT/JP2021/027521
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French (fr)
Japanese (ja)
Inventor
貴寛 安斎
敦 横田
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Nok株式会社
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Publication of WO2022024984A1 publication Critical patent/WO2022024984A1/en

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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing

Definitions

  • the present invention relates to a rubber molded product. More specifically, the present invention relates to a rubber molded product used as an oil seal or the like.
  • Oil seals are widely used as important machine parts in fields such as automobiles and industrial machinery. Of these, double-rotation oil seals, which aim to keep the fluid sealed even during both forward and reverse rotation of various parts, are used as parts for parts such as pumps, automobile differentials, agricultural machinery, and railroad vehicles. It is used in a wide range of fields.
  • the conventionally used oil seal may cause leakage of the sealed fluid when the member in contact with the oil seal is rotated in the forward rotation direction and then reversed.
  • the applicant first used fluororubber which has excellent oil resistance and fuel oil resistance and is used as a sealing material for O-rings, packings, etc. in a wide range of fields such as automobiles and industrial machinery, as a rubber material, and weighs 100 rubber.
  • a fluororubber composition prepared by adding 1 to 100 parts by weight of wollastonite with an aspect ratio of 8 or more per part and kneading it is vulcanized to form a sliding surface.
  • Patent Document 2 as a molding material for an oil seal which is excellent in durability such as heat resistance and wear resistance and can sufficiently satisfy lubrication oil resistance and sealing property, an average per 100 parts by weight of fluororubber is used.
  • a fluororubber composition containing 3 to 60 parts by weight of at least one of diatomaceous earth, wollastonite, talc, graphite and carbon fiber having a particle size of 6 to 35 ⁇ m has been proposed.
  • the sliding surface of the shaft may be damaged by the metal foreign matter contained in the oil in the oil seal for both forward and reverse rotation, and in this case, it becomes necessary to replace the shaft.
  • the metal foreign matter contained in the oil intervenes in the sliding surface of the lip and the shaft as a factor of damaging the shaft, that is, the foreign matter bites into the sliding surface. , It is estimated that the shaft will be damaged.
  • An object of the present invention is to provide a rubber molded product that can be suitably used as a sealing material for an oil seal or the like, which can suppress the biting of a metallic foreign substance into the oil seal for both forward and reverse rotation.
  • An object of the present invention is to contain 10 to 50 parts by weight of a filler having an average particle size of 0.2 to 5.0 ⁇ m per 100 parts by weight of rubber, and the arithmetic average height Sa of the cross-sectional roughness of the vulcanized molded product is 0.1 to 1.0. Achieved by a rubber molded product of ⁇ m.
  • the rubber molded product according to the present invention contains a filler having an average particle size of 0.2 to 5.0 ⁇ m, and the vulcanized molded product has an arithmetic average height of Sa 0.1 to 1.0 ⁇ m.
  • the rubber molded product of the present invention contains a filler having an average particle size of 0.2 to 5.0 ⁇ m per 100 parts by weight of rubber, and the arithmetic mean height of the cross-sectional roughness of the obtained vulcanized molded product is Sa 0.1 to 1.0. It is ⁇ m.
  • Examples of rubber include fluororubber, nitrile rubber, acrylic rubber, etc., but fluororubber is used from the viewpoint of excellent heat resistance and oil resistance.
  • fluororubber a copolymerized rubber of vinylidene fluoride or tetrafluoroethylene and another fluorine-containing olefin or olefin is used, for example, vinylidene fluoride [VdF] -hexafluoropropylene [HFP] copolymer, fluoride.
  • VdF vinylidene fluoride
  • HFP hexafluoropropylene
  • Examples include former copolymers, and those in which crosslinkable groups such as bromine and / or iodine-containing compounds, nitrile groups, glycidyl groups, hydroxyalkyl groups, and perfluorophenyl groups are introduced into these various cop
  • Fluorine rubber contains a filler having an average particle size (measured by the laser diffraction / scattering method) of 0.2 to 5.0 ⁇ m, preferably 0.2 to 3.0 ⁇ m, and is 10 to 50 parts by weight, preferably 10 to 50 parts by weight per 100 parts by weight of the fluorine rubber. It is blended in a proportion of 40 parts by weight.
  • the arithmetic average height Sa of the cross-sectional roughness which is the object of the present invention, cannot be imparted to the vulcanized molded product, and the sealing performance is inferior. Will come to be.
  • the average particle size means the average fiber length.
  • the filler is used in a smaller proportion than this, the arithmetic average height Sa of the cross-sectional roughness, which is the object of the present invention, cannot be imparted to the vulcanized molded product, and the sealing performance is deteriorated.
  • it is used in a larger proportion than this, it tends to become sandy at the time of kneading, and kneading becomes impossible.
  • diatomaceous earth polytetrafluoroethylene [PTFE] resin, wollastonite, graphite and the like are preferably used, and diatomaceous earth and PTFE resin are preferably used.
  • PTFE polytetrafluoroethylene
  • a polyol-based or organic peroxide-based compound used for fluororubber vulcanization a polyol-based or organic peroxide-based compound used for fluororubber vulcanization.
  • Vulcanizing agents, vulcanization aids such as quaternary onium salts, phosphate-based vulcanization accelerators, polyfunctional unsaturated compound co-crosslinking agents, reinforcing agents or fillers such as carbon black, oxides of divalent metals
  • the composition is prepared by any kneading means using an open roll, a kneader, etc.
  • an acid receiving agent such as hydroxide and hydrotalcite, and other necessary compounding agents
  • the composition is about 160 to 200.
  • an acid receiving agent such as hydroxide and hydrotalcite, and other necessary compounding agents
  • vulcanization is performed on sealing materials such as oil seals. It is molded.
  • the obtained vulcanized molded product is selected so that the arithmetic average height Sa of the cross-sectional roughness is about 0.1 to 1.0 ⁇ m.
  • the maximum height Sz of the cross-sectional roughness is about 10 to 20 ⁇ m.
  • Example 1 VdF-HFP copolymer (DuPont product Byton A500) 100 parts by weight carbon black (CANCARB product THERMAX N990 LSR) 2 ⁇ Diatomaceous earth (Central silica product Oplite W3005K; 20 ⁇ Average particle size 2.7 ⁇ m) Magnesium Oxide (Kyowa Chemical Industry Product Star Mug CX-150) 5 ⁇ Calcium hydroxide (Omi Chemical Industry product CALDIC # 1000) 5 ⁇ Bisphenol AF 50% by weight Fluororubber diluted product 2.3 ⁇ (Unimatec product CHEMINOX AF-50) 35% by weight phosphate-based vulcanization accelerator diluted product (the company's product B-35F) 1 ⁇
  • Each of the above components is kneaded using a closed kneader and an open roll, and using a 2RT-35t press machine, press vulcanization at 180 ° C for 4 minutes and oven vulcanization at 200 ° C for 15 hours (second
  • Example 2 In Example 1, the amount of carbon black was changed to 13.5 parts by weight and the amount of diatomaceous earth was changed to 14.1 parts by weight.
  • Example 3 In Example 1, the amount of carbon black was changed to 18 parts by weight, and the same amount (20 parts by weight) of PTFE resin (AGC product FLUON PTFE L-172JE; average particle size 0.24 ⁇ m) was used instead of diatomaceous earth. ..
  • Example 4 In Example 3, the amount of carbon black was changed to 30 parts by weight and used.
  • Example 1 Comparative Example 1 In Example 1, the same amount (20 parts by weight) of the central chemical product SILIKA # 6B (average particle diameter 12.6 ⁇ m) was used as diatomaceous earth.
  • Example 3 carbon beads (Gun Ei Chemical Industry Co., Ltd. Marilin GC-025; average particle diameter 25 ⁇ m) were used in the same amount (20 parts by weight) instead of diatomaceous earth.
  • Comparative Example 4 In Comparative Example 1, the amount of diatomaceous earth was changed to 70 parts by weight.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A molded rubber object which contains a filler having an average particle diameter of 0.2-5.0 μm incorporated in an amount of 10-50 parts by weight per 100 parts by weight of the rubber to enable the vulcanized molded object to have a cross-sectional roughness of 0.1-1.0 μm in terms of arithmetic average height Sa. This molded rubber object exhibits a prominent effect wherein, when the molded resin object is used as, for example, an oil seal for rotation in both directions, normal and reverse, an oil film on the sliding surface of the seal has a reduced thickness to inhibit metallic foreign matter from being trapped between the seal and the sliding surface of the shaft, because of the selection of the incorporated filler, which has a specific average particle diameter and enables the vulcanized molded object to have a cross-sectional roughness of 0.1-1.0 μm in terms of arithmetic average height Sa. The molded rubber object is hence suitable for use as oil seals, etc.

Description

ゴム成形物Rubber molded product
　本発明は、ゴム成形物に関する。さらに詳しくは、オイルシール等として用いられるゴム成形物に関する。 The present invention relates to a rubber molded product. More specifically, the present invention relates to a rubber molded product used as an oil seal or the like.
　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、鉄道車両等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. Of these, double-rotation oil seals, which aim to keep the fluid sealed even during both forward and reverse rotation of various parts, are used as parts for parts such as pumps, automobile differentials, agricultural machinery, and railroad vehicles. It is 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。 The conventionally used oil seal may cause leakage of the sealed fluid when the member in contact with the oil seal is rotated in the forward rotation direction and then reversed.
　本出願人は先に、耐油性、耐燃料油性にすぐれ、自動車、産業機械等の幅広い分野で、Ｏリング、パッキン等のシール材料として用いられているフッ素ゴムをゴム材料として用い、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１)。 The applicant first used fluororubber, which has excellent oil resistance and fuel oil resistance and is used as a sealing material for O-rings, packings, etc. in a wide range of fields such as automobiles and industrial machinery, as a rubber material, and weighs 100 rubber. For railway vehicles, a fluororubber composition prepared by adding 1 to 100 parts by weight of wollastonite with an aspect ratio of 8 or more per part and kneading it is vulcanized to form a sliding surface. We have proposed an oil seal for both forward and reverse rotation (Patent Document 1).
　また、特許文献２では、耐熱性、耐摩耗性などの耐久性にすぐれるとともに、耐潤滑油性、シール性をも十分に満足し得るオイルシールの成形材料として、フッ素ゴム100重量部当り平均粒子径が6～35μmの珪藻土、ウォラストナイト、タルク、グラファイトおよび炭素繊維の少なくとも一種を3～60重量部含有せしめたフッ素ゴム組成物が提案されている。 Further, in Patent Document 2, as a molding material for an oil seal which is excellent in durability such as heat resistance and wear resistance and can sufficiently satisfy lubrication oil resistance and sealing property, an average per 100 parts by weight of fluororubber is used. A fluororubber composition containing 3 to 60 parts by weight of at least one of diatomaceous earth, wollastonite, talc, graphite and carbon fiber having a particle size of 6 to 35 μm has been proposed.
　しかしながら、市場において、正・逆両回転用オイルシールではオイル中に含まれる金属異物によって軸の摺動面が傷つく場合があり、この場合には軸を交換する必要が生じてしまう。かかる現象を回避するためには、軸の傷つきを抑制し、軸の使用期間延長を図ることが望まれる。 However, in the market, the sliding surface of the shaft may be damaged by the metal foreign matter contained in the oil in the oil seal for both forward and reverse rotation, and in this case, it becomes necessary to replace the shaft. In order to avoid such a phenomenon, it is desired to suppress damage to the shaft and extend the period of use of the shaft.
　ここで、市場回収品の分析結果から、軸が傷つく要因としてオイル中に含有されている金属の異物がリップと軸の摺動面に介在すること、すなわち異物が摺動面に噛み込むことで、軸の傷つきが発生すると推定されている。 Here, from the analysis results of the products collected on the market, the metal foreign matter contained in the oil intervenes in the sliding surface of the lip and the shaft as a factor of damaging the shaft, that is, the foreign matter bites into the sliding surface. , It is estimated that the shaft will be damaged.
特開２００８－６４２０１号公報Japanese Unexamined Patent Publication No. 2008-64201 特許第６，４３５，６６６号公報Japanese Patent No. 6,435,666
　本発明の目的は、正・逆両回転用オイルシール等への金属異物の噛み込み抑制を可能とする、オイルシール等のシール材料として好適に用いられるゴム成形物を提供することにある。 An object of the present invention is to provide a rubber molded product that can be suitably used as a sealing material for an oil seal or the like, which can suppress the biting of a metallic foreign substance into the oil seal for both forward and reverse rotation.
　かかる本発明の目的は、ゴム100重量部当り平均粒子径が0.2～5.0μmの充填剤を10～50重量部含有せしめ、加硫成形物の断面粗さの算術平均高さSaが0.1～1.0μmとなるゴム成形物によって達成される。 An object of the present invention is to contain 10 to 50 parts by weight of a filler having an average particle size of 0.2 to 5.0 μm per 100 parts by weight of rubber, and the arithmetic average height Sa of the cross-sectional roughness of the vulcanized molded product is 0.1 to 1.0. Achieved by a rubber molded product of μm.
　本発明に係るゴム成形物は、平均粒子径が0.2～5.0μmの充填剤含有せしめ、加硫成形物の断面粗さの算術平均高さがSa 0.1～1.0μmとなるものを選択することにより、正・逆両回転用オイルシール等のシール摺動面の油膜厚さを減少させることで、シールと軸の摺動面への金属異物の噛み込みが抑制されるといったすぐれた効果を奏する。そのため、オイルシールなどのシール材料などとして好適に用いられる。 The rubber molded product according to the present invention contains a filler having an average particle size of 0.2 to 5.0 μm, and the vulcanized molded product has an arithmetic average height of Sa 0.1 to 1.0 μm. By reducing the oil film thickness on the sliding surface of the seal such as the oil seal for both forward and reverse rotation, it has an excellent effect of suppressing the biting of metal foreign matter into the sliding surface of the seal and the shaft. Therefore, it is suitably used as a sealing material such as an oil seal.
　本発明のゴム成形物は、ゴム100重量部当り平均粒子径が0.2～5.0μmの充填剤を含有してなり、得られる加硫成形物の断面粗さの算術平均高さがSa 0.1～1.0μmである。 The rubber molded product of the present invention contains a filler having an average particle size of 0.2 to 5.0 μm per 100 parts by weight of rubber, and the arithmetic mean height of the cross-sectional roughness of the obtained vulcanized molded product is Sa 0.1 to 1.0. It is μm.
　ゴムとしては、フッ素ゴム、ニトリルゴム、アクリルゴム等が挙げられるが、耐熱性、耐油性などにすぐれているといった観点からは、フッ素ゴムが用いられる。 Examples of rubber include fluororubber, nitrile rubber, acrylic rubber, etc., but fluororubber is used from the viewpoint of excellent heat resistance and oil resistance.
　フッ素ゴムとしては、フッ化ビニリデンまたはテトラフルオロエチレンと他の含フッ素オレフィンまたはオレフィンとの共重合ゴム等が用いられ、例えばフッ化ビニリデン〔VdF〕-ヘキサフルオロプロピレン〔HFP〕共重合体、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3元共重合体、フッ化ビニリデン-テトラフルオロエチレン-プロピレン3元共重合体、フッ化ビニリデン-パーフルオロ(メチルビニルエーテル)共重合体、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、テトラフルオロエチレン-プロピレン共重合体、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)共重合体、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)-エチレン3元共重合体等が挙げられ、これらの各種共重合フッ素ゴム中に、臭素および/またはヨウ素含有化合物、ニトリル基、グリシジル基、ヒドロキシアルキル基、パーフルオロフェニル基等の架橋性基を導入したものも用いることができる。 As the fluororubber, a copolymerized rubber of vinylidene fluoride or tetrafluoroethylene and another fluorine-containing olefin or olefin is used, for example, vinylidene fluoride [VdF] -hexafluoropropylene [HFP] copolymer, fluoride. Vinylidene-hexafluoropropylene-tetrafluoroethylene ternary copolymer, vinylidene fluoride-tetrafluoroethylene-propylene ternary copolymer, vinylidene fluoride-perfluoro (methyl vinyl ether) copolymer, vinylidene fluoride-tetrafluoropolymer Ethylene-perfluoro (methyl vinyl ether) ternary copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-perfluoro (methyl vinyl ether) copolymer, tetrafluoroethylene-perfluoro (methyl vinyl ether) -ethylene 3 Examples include former copolymers, and those in which crosslinkable groups such as bromine and / or iodine-containing compounds, nitrile groups, glycidyl groups, hydroxyalkyl groups, and perfluorophenyl groups are introduced into these various copolymer fluororubbers. Can also be used.
　フッ素ゴムには、平均粒子径(レーザー回析散乱法により測定)が0.2～5.0μm、好ましくは0.2～3.0μmの充填剤が、フッ素ゴム100重量部当り10～50重量部、好ましくは10～40重量部の割合で配合される。 Fluorine rubber contains a filler having an average particle size (measured by the laser diffraction / scattering method) of 0.2 to 5.0 μm, preferably 0.2 to 3.0 μm, and is 10 to 50 parts by weight, preferably 10 to 50 parts by weight per 100 parts by weight of the fluorine rubber. It is blended in a proportion of 40 parts by weight.
　オイル中に存在する異物のシール材と軸の摺動面への噛み込みは、ゴムの粗さが粗いほど摺動面の油膜が厚くなって、生じ易くなるものと考えられる。従って、充填剤の平均粒子径がこれより大きいものが用いられると、正・逆両回転シールでは、オイル中に存在する異物がリップと軸の摺動面に介在し、異物の噛み込みによる軸の傷つきが発生してしまう。 It is considered that the coarser the roughness of the rubber, the thicker the oil film on the sliding surface, and the more likely it is that foreign matter present in the oil will get caught in the sealing material and the sliding surface of the shaft. Therefore, if a filler having an average particle size larger than this is used, in the forward / reverse rotation seal, foreign matter existing in the oil intervenes in the sliding surface of the lip and the shaft, and the shaft due to the foreign matter being caught. Will be scratched.
　一方、充填剤の平均粒子径がこれより小さいものが用いられると、加硫成形物に本発明の目的とする断面粗さの算術平均高さSaを付与することができず、シール性能が劣ってしまうようになる。ここで、充填剤が繊維状の場合には、平均粒子径とはその平均繊維長を意味している。 On the other hand, if an filler having an average particle size smaller than this is used, the arithmetic average height Sa of the cross-sectional roughness, which is the object of the present invention, cannot be imparted to the vulcanized molded product, and the sealing performance is inferior. Will come to be. Here, when the filler is fibrous, the average particle size means the average fiber length.
　また、充填剤がこれより少ない割合で用いられると、加硫成形物に本発明の目的とする断面粗さの算術平均高さSaを付与することができず、シール性能が劣ってしまうようになり、一方これより多い割合で用いられると、混練時に砂状になりやすくなり、混練ができなくなってしまう。 Further, if the filler is used in a smaller proportion than this, the arithmetic average height Sa of the cross-sectional roughness, which is the object of the present invention, cannot be imparted to the vulcanized molded product, and the sealing performance is deteriorated. On the other hand, if it is used in a larger proportion than this, it tends to become sandy at the time of kneading, and kneading becomes impossible.
　充填剤としては、珪藻土、ポリテトラフルオロエチレン〔PTFE〕樹脂、ウォラストナイト、グラファイト等が、好ましくは珪藻土、PTFE樹脂が用いられる。 As the filler, diatomaceous earth, polytetrafluoroethylene [PTFE] resin, wollastonite, graphite and the like are preferably used, and diatomaceous earth and PTFE resin are preferably used.
　以上の必須成分よりなるゴム組成物には、加硫操作上、物性上、機能上などから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、リン酸塩系加硫促進剤、多官能性不飽和化合物共架橋剤、カーボンブラック等の補強剤または充填剤、2価金属の酸化物または水酸化物、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、ニーダ等を用いる任意の混練手段により組成物の調製が行われ、約160～200℃、約3～30分間のヒートプレスによる一次加硫および必要に応じて約150～250℃、約0.5～24時間の二次加硫を行うことにより、オイルシール等のシール材へと加硫成形される。 Various compounding agents required for vulcanization operation, physical properties, function, etc. are added to the rubber composition composed of the above essential components. For example, a polyol-based or organic peroxide-based compound used for fluororubber vulcanization. Vulcanizing agents, vulcanization aids such as quaternary onium salts, phosphate-based vulcanization accelerators, polyfunctional unsaturated compound co-crosslinking agents, reinforcing agents or fillers such as carbon black, oxides of divalent metals Alternatively, the composition is prepared by any kneading means using an open roll, a kneader, etc. after blending an acid receiving agent such as hydroxide and hydrotalcite, and other necessary compounding agents, and the composition is about 160 to 200. By performing primary vulcanization by heat pressing at ℃ for about 3 to 30 minutes and secondary vulcanization at about 150 to 250 ° C for about 0.5 to 24 hours as needed, vulcanization is performed on sealing materials such as oil seals. It is molded.
　得られる加硫成形物は、断面粗さの算術平均高さSaが約0.1～1.0μmとなるものが選択される。また、その断面粗さの最大高さSzは約10～20μmである。 The obtained vulcanized molded product is selected so that the arithmetic average height Sa of the cross-sectional roughness is about 0.1 to 1.0 μm. The maximum height Sz of the cross-sectional roughness is about 10 to 20 μm.
　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 respect to Examples.
　実施例１
　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(CANCARB社製品THERMAX N990 LSR)　　　　　　2　〃
　珪藻土(中央シリカ製品オプライトW3005K；　　　　　　 　　  20　〃
　　　　　平均粒子径 2.7μm) 
　酸化マグネシウム(協和化学工業製品スターマグ CX-150)　　　　5　〃
　水酸化カルシウム(近江化学工業製品CALDIC#1000)　　　　　　　5　〃
　ビスフェノールAF 50重量％フッ素ゴム希釈品 　　　　　　　 2.3　〃
　　　　　(ユニマテック製品CHEMINOX AF-50)
　35重量％リン酸塩系加硫促進剤希釈品(同社製品B-35F)　　　　　1　〃
以上の各成分を密閉式混練機およびオープンロールを用いて混練し、2RT-35tプレス機を用いて、180℃、4分間のプレス加硫および200℃、15時間のオーブン加硫(二次加硫)を行って、厚さ2mmの粗さ測定用試験片およびオイルシールを加硫成形した。 Example 1
VdF-HFP copolymer (DuPont product Byton A500) 100 parts by weight carbon black (CANCARB product THERMAX N990 LSR) 2 〃
Diatomaceous earth (Central silica product Oplite W3005K; 20 〃
Average particle size 2.7 μm)
Magnesium Oxide (Kyowa Chemical Industry Product Star Mug CX-150) 5 〃
Calcium hydroxide (Omi Chemical Industry product CALDIC # 1000) 5 〃
Bisphenol AF 50% by weight Fluororubber diluted product 2.3 〃
(Unimatec product CHEMINOX AF-50)
35% by weight phosphate-based vulcanization accelerator diluted product (the company's product B-35F) 1 〃
Each of the above components is kneaded using a closed kneader and an open roll, and using a 2RT-35t press machine, press vulcanization at 180 ° C for 4 minutes and oven vulcanization at 200 ° C for 15 hours (secondary addition). Sulfurization) was performed, and a test piece for roughness measurement having a thickness of 2 mm and an oil seal were vulcanized and molded.
　実施例２
　実施例１において、カーボンブラック量が13.5重量部に、また珪藻土量が14.1重量部にそれぞれ変更されて用いられた。 Example 2
In Example 1, the amount of carbon black was changed to 13.5 parts by weight and the amount of diatomaceous earth was changed to 14.1 parts by weight.
　実施例３
　実施例１において、カーボンブラック量が18重量部に変更され、また珪藻土の代わりにPTFE樹脂(AGC社製品FLUON PTFE L-172JE；平均粒子径0.24μm)が同量(20重量部)用いられた。 Example 3
In Example 1, the amount of carbon black was changed to 18 parts by weight, and the same amount (20 parts by weight) of PTFE resin (AGC product FLUON PTFE L-172JE; average particle size 0.24 μm) was used instead of diatomaceous earth. ..
　実施例４
　実施例３において、カーボンブラック量が30重量部に変更されて用いられた。 Example 4
In Example 3, the amount of carbon black was changed to 30 parts by weight and used.
　比較例１
　実施例１において、珪藻土として中央化成製品SILIKA ♯6B(平均粒子径12.6μm)が同量(20重量部)用いられた。 Comparative Example 1
In Example 1, the same amount (20 parts by weight) of the central chemical product SILIKA # 6B (average particle diameter 12.6 μm) was used as diatomaceous earth.
　比較例２
　実施例１において、珪藻土が用いられなかった。 Comparative Example 2
In Example 1, diatomaceous earth was not used.
　比較例３
　実施例１において、珪藻土の代わりにカーボンビーズ(群栄化学工業製品Marilin GC-025；平均粒子径25μm)が同量(20重量部)用いられた。 Comparative Example 3
In Example 1, carbon beads (Gun Ei Chemical Industry Co., Ltd. Marilin GC-025; average particle diameter 25 μm) were used in the same amount (20 parts by weight) instead of diatomaceous earth.
　比較例４
　比較例１において、珪藻土量が70重量部に変更して用いられた。 Comparative Example 4
In Comparative Example 1, the amount of diatomaceous earth was changed to 70 parts by weight.
　以上の各実施例および比較例で得られたテストピースを用いて粗さ測定が、またオイルシールを用いて軸耐久性およびシール性の評価を行った。
　　メスカット面粗さ：JIS B0601、ISO 4287準拠、
　　　　　　　　　　　カットオフ；λs 2.5μm、λc 0.8mm
　　　　　　　　　　　ゴム組成物の加硫成型品をスライサー等を用いて
　　　　　　　　　　　カットし、その平滑な断面をレーザー顕微鏡を用い
　　　　　　　　　　　て非接触法により観察算術平均高さの算出および
　　　　　　　　　　　最大高さの計測を行った
　　軸耐久性試験：オイルシールを回転試験機にセットし、粒径 2.0μmの
　　　　　　　　　アルミナ(市場回収油の金属異物を想定)含有タービン油
　　　　　　　　　を回転軸を中心とした状態で密封し、試験油温度 120℃
　　　　　　　　　、回転数 1500rpmの条件下で、正転1時間および
　　　　　　　　　休止5分間を1サイクルとして120時間の運転を行い、
　　　　　　　　　軸の摩耗深さを測定
　　　　　　　　　軸の摩耗深さが20μm未満のものを○、
　　　　　　　　　　20μm以上のものを×と評価
　　シール性：オイルシールを回転試験機にセットし、タービン油を回転
　　　　　　　軸を中心とした状態で密封し、試験油温度100℃、
　　　　　　　回転数2000rpmの条件下で、逆転で15分間ならし運転をした
　　　　　　　後にオイルシールのリップ部大気側からシリンジで一定量
　　　　　　　注油して油側への油送り込み量を測定、続けて正転で15分
　　　　　　　間ならし運転をした後に油送り込み量を測定
　　　　　　　　下記式によりK値を算出することでシール性の評価とした
　　　　　　　　　　　　　　Q=KUD2G1/2
　　　　　　　　　Q：単位時間当たりの流体送り込み量、U：軸周速、
　　　　　　　　　D：軸径、G：無次元特性数(＝μub/Pr、
　　　　　　　　　　　　　　　μ：流体の粘度、u：軸周速、b：シール
　　　　　　　　　　　　　　　の接触幅、Pr：緊迫力）
　　　　　　　　　　K値が1.0×10-5以上のものを〇、
　　　　　　　　　　0.5×10-5以上1.0×10-5未満のものを△、
　　　　　　　　　　0.5×10-5未満のものを×と評価 Roughness measurement was performed using the test pieces obtained in each of the above Examples and Comparative Examples, and shaft durability and sealing property were evaluated using an oil seal.
Female cut surface roughness: JIS B0601, ISO 4287 compliant,
Cutoff; λs 2.5 μm, λc 0.8 mm
A vulfurized molded product of the rubber composition was cut using a slicer or the like, and the smooth cross section was observed by a non-contact method using a laser microscope. Arithmetic average height was calculated and maximum height was measured. Shaft durability Test: Set the oil seal on the rotary tester, seal the turbine oil containing alumina (assuming metallic foreign matter of market-recovered oil) with a particle size of 2.0 μm around the rotary shaft, and test oil temperature 120 ° C.
Under the condition of a rotation speed of 1500 rpm, it was operated for 120 hours with 1 hour of normal rotation and 5 minutes of rest as one cycle.
Measure the wear depth of the shaft ○, if the wear depth of the shaft is less than 20 μm
Evaluation of 20 μm or more as × Sealing property: Set the oil seal on the rotary tester, seal the turbine oil around the rotary shaft, and test oil temperature 100 ° C.
Under the condition of rotation speed 2000 rpm, after running for 15 minutes in reverse rotation, lubricate a certain amount from the atmosphere side of the lip part of the oil seal with a syringe and measure the amount of oil sent to the oil side, and then continue for 15 minutes in normal rotation. Measure the amount of oil sent after the break-in operation Q = KUD 2 G 1/2 was used to evaluate the sealing performance by calculating the K value using the following formula.
Q: Fluid feed amount per unit time, U: Shaft peripheral speed,
D: Shaft diameter, G: Dimensionless characteristic number (= μub / Pr,
μ: Fluid viscosity, u: Axial peripheral speed, b: Seal contact width, Pr: Tension force)
If the K value is 1.0 x 10 -5 or more, 〇,
Those with 0.5 × 10 -5 or more and less than 1.0 × 10 -5 are △,
Those less than 0.5 × 10 -5 are evaluated as ×
　以上の各実施例および比較例で得られた結果は、次の表に示される。
Figure JPOXMLDOC01-appb-I000001
The results obtained in each of the above Examples and Comparative Examples are shown in the following table.
Figure JPOXMLDOC01-appb-I000001
　以上の結果より、次のことがいえる。
　(1) 各実施例では、微細な充填剤を使用し、材料表面の粗さを小さくすることにより、リップシール摺動面に異物が噛み込み難くなり、軸耐久性が向上している。
　(2) 充填剤の平均粒子径が大きい場合、異物が噛み込み易く、所望の軸耐久性を担保することができない(比較例１、３)。
　(3) 充填剤を配合しない場合には、オイルのポンプ機能が低下してしまい、十分なシール性を得ることができない(比較例２)。
　(4) 充填剤の配合量が多すぎると、混練時に砂状になりやすく、混練ができなくなってしまう(比較例４)。 From the above results, the following can be said.
(1) In each embodiment, by using a fine filler and reducing the roughness of the material surface, it becomes difficult for foreign matter to get caught in the sliding surface of the lip seal, and the shaft durability is improved.
(2) When the average particle size of the filler is large, foreign matter is easily caught and the desired shaft durability cannot be guaranteed (Comparative Examples 1 and 3).
(3) If the filler is not blended, the pump function of the oil is deteriorated and sufficient sealing property cannot be obtained (Comparative Example 2).
(4) If the amount of the filler compounded is too large, it tends to become sandy during kneading, and kneading becomes impossible (Comparative Example 4).

Claims (6)

  1. 　ゴム100重量部当り平均粒子径が0.2～5.0μmの充填剤を10～50重量部含有せしめ、加硫成形物の断面粗さの算術平均高さSaが0.1～1.0μmとなるゴム成形物。 A rubber molded product containing 10 to 50 parts by weight of a filler having an average particle size of 0.2 to 5.0 μm per 100 parts by weight of rubber, and an arithmetic average height Sa of the cross-sectional roughness of the vulcanized molded product is 0.1 to 1.0 μm.
  2. 　ゴムがフッ素ゴムである請求項１記載のゴム成形物。 The rubber molded product according to claim 1, wherein the rubber is fluororubber.
  3. 　充填剤が珪藻土またはポリテトラフルオロエチレン樹脂の粉末である請求項１記載のゴム成形物。 The rubber molded product according to claim 1, wherein the filler is a powder of diatomaceous earth or polytetrafluoroethylene resin.
  4. 　加硫成形物の断面粗さの最大高さSz が10～20μmである請求項１記載のゴム成形物。 The rubber molded product according to claim 1, wherein the maximum height Sz of the cross-sectional roughness of the vulcanized molded product is 10 to 20 μm.
  5. 　請求項１記載のゴム成形物からなるシール材。 A sealing material made of the rubber molded product according to claim 1.
  6. 　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.
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08190270A (en) * 1994-08-12 1996-07-23 Ntn Corp Fitting structure of roller axis in developing device
JPH08193197A (en) * 1994-08-12 1996-07-30 Ntn Corp V ring
JP2002338808A (en) * 2001-05-15 2002-11-27 Shin Etsu Chem Co Ltd Conductive silicone rubber composition for electrophotographic image formation apparatus
WO2006006468A1 (en) * 2004-07-08 2006-01-19 Uchiyama Manufacturing Corp. Fluororubber composition
JP2006117745A (en) * 2004-10-20 2006-05-11 Three M Innovative Properties Co Sealing material comprising fluoroelastomer-containing composition
JP2008064201A (en) * 2006-09-07 2008-03-21 Nok Corp Normal/reverse rotation oil seal
US20100018778A1 (en) * 2008-07-23 2010-01-28 Smith International, Inc. Seal comprising elastomeric composition with nanoparticles
JP2010084049A (en) * 2008-10-01 2010-04-15 Kyoritsu Sangyo Kk Diaphragm
WO2014126240A1 (en) * 2013-02-18 2014-08-21 イーグル工業株式会社 Lip seal for water pump
JP2016014092A (en) * 2014-07-01 2016-01-28 Nok株式会社 Fluororubber composition
JP2016156404A (en) * 2015-02-23 2016-09-01 光洋シーリングテクノ株式会社 Rubber composition, and oil seal
WO2017150192A1 (en) * 2016-03-01 2017-09-08 Nok株式会社 Fluororubber composition and crosslinked fluororubber
WO2019070040A1 (en) * 2017-10-06 2019-04-11 Ａｇｃ株式会社 Fluorine-containing copolymer composition and metal-rubber layered body

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08190270A (en) * 1994-08-12 1996-07-23 Ntn Corp Fitting structure of roller axis in developing device
JPH08193197A (en) * 1994-08-12 1996-07-30 Ntn Corp V ring
JP2002338808A (en) * 2001-05-15 2002-11-27 Shin Etsu Chem Co Ltd Conductive silicone rubber composition for electrophotographic image formation apparatus
WO2006006468A1 (en) * 2004-07-08 2006-01-19 Uchiyama Manufacturing Corp. Fluororubber composition
JP2006117745A (en) * 2004-10-20 2006-05-11 Three M Innovative Properties Co Sealing material comprising fluoroelastomer-containing composition
JP2008064201A (en) * 2006-09-07 2008-03-21 Nok Corp Normal/reverse rotation oil seal
US20100018778A1 (en) * 2008-07-23 2010-01-28 Smith International, Inc. Seal comprising elastomeric composition with nanoparticles
JP2010084049A (en) * 2008-10-01 2010-04-15 Kyoritsu Sangyo Kk Diaphragm
WO2014126240A1 (en) * 2013-02-18 2014-08-21 イーグル工業株式会社 Lip seal for water pump
JP2016014092A (en) * 2014-07-01 2016-01-28 Nok株式会社 Fluororubber composition
JP2016156404A (en) * 2015-02-23 2016-09-01 光洋シーリングテクノ株式会社 Rubber composition, and oil seal
WO2017150192A1 (en) * 2016-03-01 2017-09-08 Nok株式会社 Fluororubber composition and crosslinked fluororubber
WO2019070040A1 (en) * 2017-10-06 2019-04-11 Ａｇｃ株式会社 Fluorine-containing copolymer composition and metal-rubber layered body

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