WO2013039177A1 - しゅう動部材及びしゅう動材料組成物 - Google Patents
しゅう動部材及びしゅう動材料組成物 Download PDFInfo
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- WO2013039177A1 WO2013039177A1 PCT/JP2012/073525 JP2012073525W WO2013039177A1 WO 2013039177 A1 WO2013039177 A1 WO 2013039177A1 JP 2012073525 W JP2012073525 W JP 2012073525W WO 2013039177 A1 WO2013039177 A1 WO 2013039177A1
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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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
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/043—Sliding surface consisting mainly of ceramics, cermets or hard carbon, e.g. diamond like carbon [DLC]
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/06—Sliding surface mainly made of metal
- F16C33/12—Structural composition; Use of special materials or surface treatments, e.g. for rust-proofing
- F16C33/121—Use of special 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
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/20—Sliding surface consisting mainly of plastics
- F16C33/203—Multilayer structures, e.g. sleeves comprising a plastic lining
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/061—Carbides; Hydrides; Nitrides
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/044—Polyamides
- C10M2217/0443—Polyamides used as base material
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C2202/00—Solid materials defined by their properties
- F16C2202/50—Lubricating properties
- F16C2202/54—Molybdenum disulfide
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- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C2208/00—Plastics; Synthetic resins, e.g. rubbers
- F16C2208/02—Plastics; Synthetic resins, e.g. rubbers comprising fillers, fibres
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- F16C2223/00—Surface treatments; Hardening; Coating
- F16C2223/02—Mechanical treatment, e.g. finishing
- F16C2223/08—Mechanical treatment, e.g. finishing shot-peening, blasting
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- F16C2223/00—Surface treatments; Hardening; Coating
- F16C2223/30—Coating surfaces
- F16C2223/42—Coating surfaces by spraying the coating material, e.g. plasma spraying
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- F16C2240/00—Specified values or numerical ranges of parameters; Relations between them
- F16C2240/40—Linear dimensions, e.g. length, radius, thickness, gap
- F16C2240/54—Surface roughness
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- F16C2240/00—Specified values or numerical ranges of parameters; Relations between them
- F16C2240/40—Linear dimensions, e.g. length, radius, thickness, gap
- F16C2240/60—Thickness, e.g. thickness of coatings
Definitions
- the present invention relates to a sliding member and a sliding material composition suitable for a soft counterpart material.
- Patent Documents 1 to 3 As a conventional sliding material composition, a composition containing an antiwear agent, a solid lubricant, and a resin binder is known (see Patent Documents 1 to 3).
- Japanese Patent No. 4004631 Japanese Unexamined Patent Publication No. 10-37962 Japanese Unexamined Patent Publication No. 2002-53883
- the counterpart material of the sliding member is a high hardness material that has been subjected to heat treatment such as chilling treatment or quenching, and the conventional sliding material composition is configured to assume a counterpart material having high hardness. Limited.
- shafts that do not undergo hardening treatment have been developed due to low cost, and therefore, there is an increasing demand for suitable sliding members for counterpart materials having low hardness. It is an object of the present invention to provide a sliding member that satisfies this requirement.
- the present invention relates to the following sliding member and sliding material composition.
- a sliding material composition and a sliding member exhibiting excellent wear resistance and seizure resistance can be provided by lapping the roughened portion of the counterpart material having a ferrite phase by sliding.
- FIG. 1 is a graph showing the relationship between the particle size of hard particles and the surface roughness of the mating shaft after the wear test.
- FIG. 2 is a graph showing the relationship between the particle size of the hard particles and the wear depth of the specimen (bearing) after the wear test.
- the sliding material composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes a binder resin, molybdenum disulfide, and hard particles.
- the binder resin is a material that collects the composition of the present invention, and is at least one selected from the group consisting of a polyamideimide (PAI) resin, a polyimide resin, a phenol resin, a polyacetal resin, a polyether ether ketone resin, and a polyphenylene sulfide resin.
- PAI polyamideimide
- PAI polyamideimide
- the composition of the present invention contains hard particles.
- Ferrite phases exist in mating materials (also called “mating members”) such as forged shafts and cast shafts that are not subjected to hardening treatment such as quenching.
- the hardness of the counterpart material having the ferrite phase is as low as about HV 200 to 300 in terms of Vickers hardness, and burrs are likely to occur after polishing finish.
- the surface of the sliding bearing, that is, the sliding surface of the sliding member is softer than the ferrite phase and is subject to abrasive wear against burrs.
- the hard particles contained in the sliding material composition give a so-called lapping action in which the burr generated in the ferrite phase is scraped off and the mating material surface is smoothed, thereby providing wear resistance and seizure resistance. It has improved.
- the average particle diameter (mode diameter) of the hard particles is preferably 0.5 to 10 times, more preferably 2 to 5 times the arithmetic average roughness (Ra) of the sliding surface of the counterpart material.
- Ra arithmetic average roughness
- the shape of the hard particles is preferably a lump or a sphere, and the lump is more preferable because the lapping effect is higher than the sphere.
- the lump means an irregular shape that substantially does not include protrusions of 90 ° or less, and shapes that can be formed by processing such as a spherical shape and an acute angle shape are excluded.
- an acute-angle shape is not preferable because there is a possibility of attacking the counterpart material.
- the hardness of the hard particles is not limited as long as the hard particles have sufficient hardness with respect to the counterpart material having a ferrite phase. However, since the hardness of the counterpart material is HV200 to 300, it is more than twice that hardness.
- the hardness is preferably HV600 or more, and more preferably HV800 or more.
- the hardness means Vickers hardness (the same applies hereinafter).
- the kind of hard particles is not particularly limited, but from the viewpoint of satisfying the above hardness, Fe 3 P (HV about 800), Al 2 O 3 (HV 1500 or more), SiC (HV 2000 or more), AlN (HV 1000 or more), etc. It can be preferably used.
- the content of hard particles in the composition of the present invention is preferably 0.1 to 5% by volume, more preferably 1 to 4% by volume. If the content is within the above range, there is a wrapping effect and the aggressiveness to the counterpart material is low.
- molybdenum disulfide functions as a solid lubricant that imparts wear resistance.
- a solid lubricant By adding a solid lubricant, lapping by hard particles becomes fine.
- molybdenum disulfide exhibits a lubricating action superior to other solid lubricants in oil, and thus this effect in oil is particularly exerted.
- the content of molybdenum disulfide in the composition of the present invention is 30 to 70% by volume, preferably 35 to 60% by volume. A sufficient lubricating action can be obtained when the content of molybdenum disulfide is within the above range.
- Molybdenum disulfide preferably has an average particle size of 5 ⁇ m or less, more preferably 3 ⁇ m or less.
- the composition of the present invention may contain other solid lubricant other than molybdenum disulfide.
- the other solid lubricant is preferably at least one selected from the group consisting of graphite, polytetrafluoroethylene (PTFE), tungsten disulfide, mica, boron nitride, graphite fluoride, and fullerene. These contents are preferably 5 to 35% by volume as an auxiliary function of molybdenum disulfide, particularly from the viewpoint of obtaining a lubricating action when the lubricating oil runs out.
- PTFE polytetrafluoroethylene
- the composition of the present invention may further contain an inorganic additive, and is preferably at least one selected from the group consisting of calcium carbonate, barium sulfate, and calcium phosphate. From the viewpoint of wear resistance, the content of the inorganic additive in the composition is preferably 5 to 10% by volume.
- the sliding material composition according to the present invention can be used as a coating layer on the surface of the base material of the sliding member.
- it is suitable for coating the sliding surface when the counterpart sliding material has a ferrite phase at least on the surface.
- Specific examples of such a counterpart material include a forged shaft that has not been quenched, a spheroidal graphite cast iron shaft that has not been quenched, a forged shaft that has not been nitrided, and the like.
- the sliding member according to the present invention includes a base material and a coating layer provided on the base material, and the coating layer is formed from the sliding material composition of the present invention.
- the material of the base material of the sliding member according to the present invention is not particularly limited, but is a material selected from the group consisting of steel, stainless steel, cast iron, copper, copper alloy, aluminum, aluminum alloy, rubber, plastics and ceramics. Is preferred.
- the shape of the substrate is not particularly limited, and may be plate-shaped or tubular.
- a base material has back metal steel, such as steel or stainless steel, and the alloy layer which is arrange
- the coating layer is formed by, for example, mixing the composition of the present invention together with a binder resin solvent, forming a film on the substrate surface by a known method such as air spray coating, and then baking at the baking temperature of the binder resin. Is applicable.
- a roughening treatment may be performed before the surface of the substrate is coated, or an adhesive layer may be provided between the substrate and the coating layer.
- the thickness of the coating layer is preferably 5 to 30 ⁇ m.
- the surface roughness of the coating layer is not particularly limited, but is preferably 0.3 to 3 ⁇ mRa.
- the lubrication conditions of the sliding member according to the present invention are not particularly limited, and can be used for any of oil lubrication, grease lubrication, and no lubrication.
- the composition shown in Table 1 is spray-coated at a thickness of about 10 ⁇ m to form a coating layer Formed.
- firing was performed at 200 ° C. to prepare a test material.
- the materials used are as follows. The remainder other than the solid lubricant and the hard material was adjusted with a binder resin so that the total composition was 100% by volume.
- Binder resin Polyamideimide (PAI) resin manufactured by Hitachi Chemical Co., Ltd.
- Example 1 For the specimens (bearings) of each Example and Comparative Example, a wear test was performed using a cast shaft or a forged shaft having a ferrite phase on the sliding surface as the mating material, and the surface of the mating shaft sliding surface before and after the test. The roughness and the wear depth of the specimen sliding surface after the test were measured. The results are shown in Table 1. Moreover, about an Example, the relationship between the particle size of a hard material particle and the surface roughness of the other party shaft after a test is shown in FIG. The relationship is shown in FIG. Each counterpart material has not been subjected to an effect treatment such as quenching and has a hardness of HV200 to 300.
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Abstract
Description
〔1〕 少なくとも表面にフェライト相を有する相手部材としゅう動するしゅう動部材であって、バインダー樹脂、二硫化モリブデン、及び硬質物粒子を含む被覆層を有するしゅう動部材。
〔2〕 前記硬質物粒子の平均粒径が、前記相手部材のしゅう動面の表面算術平均粗さRaの0.5~10倍である上記〔1〕に記載のしゅう動部材。
〔3〕 前記硬質物粒子の形状が塊状である上記〔1〕又は〔2〕に記載のしゅう動部材。
〔4〕 前記硬質物粒子の硬度が、相手部材の硬度の2倍以上である上記〔1〕から〔3〕の何れか1に記載のしゅう動部材。
〔5〕 少なくとも表面にフェライト相を有する相手部材としゅう動するしゅう動部材に用いられるしゅう動材料組成物であって、バインダー樹脂、二硫化モリブデン、及び硬質物粒子を含むしゅう動材料組成物。
なお、表面粗さを十点平均粗さ(Rz)で規定する場合は下記関係式に従う。
算術平均粗さ(Ra)=1/2~1/3×十点平均粗さ(Rz)
なお、二硫化モリブデンは平均粒径が5μm以下であることが好ましく、3μm以下がより好ましい。
その他の固体潤滑剤としてはグラファイト、ポリテトラフルオロエチレン(PTFE)、二硫化タングステン、雲母、窒化ほう素、フッ化黒鉛、及びフラーレンからなる群より選ばれる少なくとも1種であることが好ましい。これらの含有量は二硫化モリブデンの補助的な働きとして、特に潤滑油が切れた際の潤滑作用を得る観点から5~35体積%が好ましい。
本発明に係るしゅう動部材の基材の材質は特に制限されないが、鉄鋼、ステンレス、鋳鉄、銅、銅合金、アルミニウム、アルミニウム合金、ゴム、プラスチックス及びセラミックスからなる群より選ばれる材料であることが好ましい。また、基材の形状は特に制限されず、板状でも管状でもよい。また、基材は、鉄鋼又はステンレス等の裏金鋼と、裏金鋼の上に配置されアルミニウム合金又は銅合金等を含む合金層とを有することが好ましい。
・バインダー樹脂
ポリアミドイミド(PAI)樹脂:日立化成工業株式会社製
・固体潤滑剤
二硫化モリブデン:住鋼潤滑剤株式会社製、平均粒径2μm
グラファイト:住鋼潤滑剤株式会社製、平均粒径2μm
二硫化タングステン:住鋼潤滑剤株式会社製、平均粒径2μm
・硬質物粒子
Al2O3:株式会社フジミインコーポレーテッド製、全て塊状
SiC:株式会社フジミインコーポレーテッド製、全て塊状
Fe3P:福田金属箔粉工業株式会社製、全て塊状
AlN:東洋アルミニウム株式会社製、全て塊状
摩耗試験は片当たり摩耗試験機を用いて以下の条件で行った。
回転数:0rpm(1分保持)→1200rpm(1分保持)→0rpm(1分保持)のサイクル試験
潤滑油:0W-20
給油温度:100℃
荷重:4.41kN
試験時間:100時間
JIS B 061(2001)に準拠し、算術平均粗さRaを測定した。
供試材(軸受)の被覆層の厚さを試験前後で測定し、その値から摩耗深さを算出した。
また、比較例5と実施例7、比較例6と実施例5との対比から、二硫化モリブデンを含むが硬質物粒子を含まないことにより軸受摩耗深さが大きくなる結果が明らかとなった。
Claims (5)
- 少なくとも表面にフェライト相を有する相手部材としゅう動するしゅう動部材であって、バインダー樹脂、二硫化モリブデン、及び硬質物粒子を含む被覆層を有するしゅう動部材。
- 前記硬質物粒子の平均粒径が、前記相手部材のしゅう動面の表面算術平均粗さRaの0.5~10倍である請求項1に記載のしゅう動部材。
- 前記硬質物粒子の形状が塊状である請求項1又は2に記載のしゅう動部材。
- 前記硬質物粒子の硬度が、相手部材の硬度の2倍以上である請求項1から3の何れか1項に記載のしゅう動部材。
- 少なくとも表面にフェライト相を有する相手部材としゅう動するしゅう動部材に用いられるしゅう動材料組成物であって、
バインダー樹脂、二硫化モリブデン、及び硬質物粒子を含むしゅう動材料組成物。
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KR1020157035060A KR101639549B1 (ko) | 2011-09-13 | 2012-09-13 | 미끄럼 부재 및 미끄럼 재료 조성물 |
EP12831115.6A EP2757277B1 (en) | 2011-09-13 | 2012-09-13 | Sliding member and sliding material composition |
JP2013533721A JP5941472B2 (ja) | 2011-09-13 | 2012-09-13 | しゅう動部材及びしゅう動材料組成物 |
BR112014005643-9A BR112014005643B1 (pt) | 2011-09-13 | 2012-09-13 | elemento deslizante e composição de material deslizante |
US14/344,358 US9303230B2 (en) | 2011-09-13 | 2012-09-13 | Sliding member and sliding material composition |
CN201280044676.XA CN103797256B (zh) | 2011-09-13 | 2012-09-13 | 滑动构件和滑动材料组合物 |
KR1020147006327A KR20140045586A (ko) | 2011-09-13 | 2012-09-13 | 미끄럼 부재 및 미끄럼 재료 조성물 |
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EP3051158A4 (en) * | 2013-09-27 | 2017-05-31 | Senju Metal Industry Co., Ltd | Sliding member and method for producing sliding member |
EP3051157A4 (en) * | 2013-09-27 | 2017-05-31 | Senju Metal Industry Co., Ltd | Sliding member |
JP2017115135A (ja) * | 2015-12-11 | 2017-06-29 | 株式会社リコー | 摺動部材、部品、および機械装置の騒音低減方法 |
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- 2012-09-13 US US14/344,358 patent/US9303230B2/en not_active Expired - Fee Related
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Also Published As
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JP5941472B2 (ja) | 2016-06-29 |
BR112014005643A2 (pt) | 2017-03-28 |
US9303230B2 (en) | 2016-04-05 |
KR101639549B1 (ko) | 2016-07-13 |
EP2757277A1 (en) | 2014-07-23 |
EP2757277A4 (en) | 2015-06-03 |
JPWO2013039177A1 (ja) | 2015-03-26 |
CN103797256B (zh) | 2017-05-31 |
KR20150144821A (ko) | 2015-12-28 |
CN103797256A (zh) | 2014-05-14 |
KR20140045586A (ko) | 2014-04-16 |
US20150018255A1 (en) | 2015-01-15 |
EP2757277B1 (en) | 2018-06-06 |
BR112014005643B1 (pt) | 2021-05-25 |
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