WO2018092856A1 - 樹脂組成物および摺動部材 - Google Patents

樹脂組成物および摺動部材 Download PDF

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Publication number
WO2018092856A1
WO2018092856A1 PCT/JP2017/041336 JP2017041336W WO2018092856A1 WO 2018092856 A1 WO2018092856 A1 WO 2018092856A1 JP 2017041336 W JP2017041336 W JP 2017041336W WO 2018092856 A1 WO2018092856 A1 WO 2018092856A1
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Prior art keywords
resin composition
mos
ptfe
average particle
binder resin
Prior art date
Application number
PCT/JP2017/041336
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English (en)
French (fr)
Inventor
恭平 山根
政憲 秋月
Original Assignee
大豊工業株式会社
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Filing date
Publication date
Application filed by 大豊工業株式会社 filed Critical 大豊工業株式会社
Priority to US16/461,054 priority Critical patent/US11352581B2/en
Priority to KR1020197014779A priority patent/KR102373093B1/ko
Priority to EP17872673.3A priority patent/EP3543295B1/en
Priority to CN201780069675.3A priority patent/CN110072945A/zh
Publication of WO2018092856A1 publication Critical patent/WO2018092856A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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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
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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
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/06—Metal compounds
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
    • C10M107/44—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • 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
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • 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
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    • C08K3/02—Elements
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    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
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    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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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
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    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0413—Carbon; Graphite; Carbon black used as base material
    • 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
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    • C10M2201/066—Molybdenum sulfide
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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
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    • C10M2201/066—Molybdenum sulfide
    • C10M2201/0663—Molybdenum sulfide used as base material
    • 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
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    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • 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
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    • C10M2213/0623—Polytetrafluoroethylene [PTFE] used as base material
    • 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
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    • C10M2217/044—Polyamides
    • C10M2217/0443—Polyamides used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Definitions

  • the present invention relates to a sliding member.
  • a sliding member in which a resin coating layer in which PTFE, graphite and MoS 2 are added as a solid lubricant to a binder resin is formed (Patent Documents 1 and 2).
  • the present invention provides a technique for improving seizure resistance and wear resistance under conditions of high load load in an environment where the supply of lubricating oil is not sufficient.
  • the present invention has a binder resin formed of a thermosetting resin and an additive dispersed in the binder resin, and the additive includes PTFE (polytetrafluoroethylene), at least one of graphite and MoS 2.
  • PTFE polytetrafluoroethylene
  • the average particle size of each of the additives is less than 10 ⁇ m, and the average particle size of the PTFE is larger than the average particle size of graphite and MoS 2 .
  • the binder resin may contain at least one of polyamideimide and polyimide.
  • the binder resin may be a polyamideimide.
  • the content of the binder resin may be 50 to 80% by volume.
  • the PTFE content may be larger than the MoS 2 content.
  • the MoS 2 content may be 0 to 10% by volume.
  • the additive may contain hard particles.
  • this invention provides the sliding member which has a base material and the coating layer formed with the resin composition as described in any one of Claims 1 thru
  • seizure resistance and wear resistance can be improved under conditions of high load load in an environment where the supply of lubricating oil is not sufficient.
  • FIG. 1 The figure which illustrates the positional relationship of the swash plate 3 and the shoes 5.
  • FIG. The figure which illustrates the cross-sectional structure of the swash plate.
  • FIG. 1 is a schematic cross-sectional view showing a structure of a compressor 1 according to an embodiment.
  • the compressor 1 is a so-called swash plate compressor.
  • the compressor 1 has a shaft 2, a swash plate 3, a piston 4, and a shoe 5.
  • the shaft 2 is rotatably supported with respect to a housing (not shown).
  • the swash plate 3 is fixed obliquely with respect to the rotation axis of the shaft 2.
  • the swash plate 3 is an example of a sliding member according to the present invention.
  • the piston 4 reciprocates in a cylinder bore (not shown) provided in the housing.
  • the shoe 5 is provided between the swash plate 3 and the piston 4, and slides with the swash plate 3 and the piston 4, respectively.
  • the surface that slides with the swash plate 3 is substantially flat, and the surface that slides with the piston 4 has a dome-like (hemispherical) shape.
  • the shoe 5 is an example of a counterpart material that slides with the sliding member according to the present invention.
  • the rotation of the shaft 2 is converted into a reciprocating motion of the piston 4 by the swash plate 3.
  • FIG. 2 is a diagram illustrating the positional relationship between the swash plate 3 and the shoe 5.
  • FIG. 2 is a diagram viewed from a direction perpendicular to the sliding surface.
  • the swash plate 3 has a disk shape having a hole in the center as a whole.
  • the rotational movement refers to a movement in which the shoe 5 draws a circular locus with respect to the swash plate 3.
  • FIG. 3 is a diagram illustrating a cross-sectional structure of the swash plate 3.
  • FIG. 3 is a schematic diagram showing a structure in a cross section perpendicular to the sliding surface with the shoe 5.
  • the swash plate 3 has a base material 31, a coating layer 32, and a coating layer 33. Both the coating layer 32 and the coating layer 33 slide with the shoe 5.
  • the coating layer 32 and the coating layer 33 are both examples of the coating layer according to the present invention.
  • the base material 31 has a disk shape with a hole in the center, and is formed of a metal that satisfies the required characteristics, for example, an iron-based, copper-based, or aluminum-based alloy. From the viewpoint of preventing adhesion with the shoe 5, the swash plate 3 is preferably formed of a material different from that of the shoe 5.
  • the coating layer 32 is formed to improve the characteristics of the sliding surface of the swash plate 3.
  • the coating layer 32 is formed of a resin composition.
  • This resin composition contains a binder resin and an additive dispersed in the binder resin.
  • the binder resin is formed of, for example, a thermosetting resin.
  • the thermosetting resin for example, at least one of polyamideimide (PAI), polyamide (PA), polyimide (PI), epoxy, and phenol is used.
  • the binder resin preferably contains at least one of PAI and PI.
  • the content of the binder resin in this resin composition is preferably 50 to 80% by volume. The content is more preferably more than 60% by volume, and the upper limit is more preferably 75% by volume.
  • a solid lubricant is used as the additive. Solid lubricants are added to improve lubrication properties, i.e. to reduce the coefficient of friction.
  • the resin composition includes a total amount of 20 to 50% by volume of a solid lubricant.
  • PTFE polytetrafluoroethylene
  • this resin composition contains at least one of graphite (Gr) and MoS 2 in addition to PTFE.
  • the content of MoS 2 is preferably smaller than the content of PTFE.
  • the PTFE content is 10 to 30% by volume, and more preferably 15 to 25% by volume.
  • the content of MoS 2 is 0 to 10% by volume, preferably 0 to 4% by volume (that is, MoS 2 may not be contained).
  • the content of graphite is preferably 0 to 20% by volume, more preferably 10 to 20% by volume. Further, the MoS 2 content is preferably smaller than the graphite content.
  • the average particle size of the additive added to the binder resin is preferably less than 10 ⁇ m, and more preferably 5 ⁇ m or less.
  • the average particle diameter means a 50% diameter (median diameter) in the distribution of equivalent sphere diameters obtained by a laser diffraction method in the state of the raw material before mixing with the binder resin.
  • the average particle diameter of PTFE is preferably larger than both the average particle diameter of graphite and the average particle diameter of MoS 2 . According to the hypothesis of the present inventors, by using PTFE having an average particle diameter larger than that of graphite and MoS 2 , the PTFE is stretched on the sliding surface to cover the graphite or MoS 2 , and the sliding surface is smooth. It becomes easy to keep the sex.
  • This resin composition may further contain hard particles as an additive.
  • hard particles for example, at least one of oxide, nitride, carbide, and sulfide is used.
  • the average particle size of the hard particles is preferably less than 10 ⁇ m, and more preferably smaller than the average particle size of PTFE.
  • the coating layer 33 is also formed using the same resin composition as the coating layer 32.
  • the surface used as a sliding surface ie, the surface in which the coating layer 32 is formed, and the surface in which the coating layer 33 is formed are both substantially flat.
  • the surface of the base material 31 may be roughened.
  • An intermediate layer may be formed between the base material 31 and the coating layer 32.
  • the sliding member having a coating layer formed using the resin composition according to the present embodiment is not limited to a swash plate for a compressor, for example, a shoe for a compressor, a half bearing used in an engine, a bush, Alternatively, it may be a thrust washer.
  • Experimental Example Test pieces of sliding members were prepared under various conditions, and their characteristics were evaluated. Cast iron was used as the base material of the sliding member, and this was processed into the shape of a swash plate as shown in FIG. On this base material, the coating layer was formed with the resin composition described in Table 1. PAI was used as the binder resin.
  • Experimental example 3 can be said to be an example in which the average particle size of MoS 2 is larger than the average particle size of PTFE.
  • test device High-pressure atmosphere friction and wear tester Peripheral speed: 40 m / sec Surface pressure: 4-12 MPa (gradual increase: 2 MPa / 3 minutes) Time: Hold for 1 hour at maximum surface pressure Atmosphere: Refrigerant poor lubrication atmosphere Counterpart: Bearing steel
  • test equipment Oil spray type poor lubrication tester Peripheral speed: 6.3 m / sec Surface pressure: 2 to 20 MPa (gradual increase: 2 MPa / 1 min) Time: Up to 10 minutes
  • Lubrication method Spray Lubricating oil: Refrigeration machine Partner material: Bearing steel
  • FIG. 4 is a diagram showing the seizing surface pressure obtained in the seizure resistance test.
  • the test piece of Experimental Example 3 was seized at a surface pressure of 10 MPa, the test pieces of Experimental Examples 1 and 2 were not seized even at the maximum surface pressure of 20 MPa of the test apparatus.
  • Experimental Examples 1 and 2 have improved seizure resistance.
  • the inventors of the present application conduct a sliding test on the test pieces of Experimental Examples 1 and 2, and measure the surface roughness of the sliding surface before and after the test with a surface roughness meter (SP81B manufactured by Kosaka Laboratory). The surface was observed with an electron microscope.
  • the test conditions of the sliding test are the same as in the above-mentioned seizure resistance test.
  • FIG. 5 is a diagram showing the state of the sliding surface before and after the sliding test.
  • 5A shows Experimental Example 1
  • FIG. 5B shows Experimental Example 2
  • FIG. 5C shows Experimental Example 3.
  • FIG. The surface roughness represents the ten-point average roughness RzJIS in JIS B 0601: 2001.
  • the surface roughness was increased by the sliding test, but in Experimental Examples 1 and 2, the surface roughness was decreased in the sliding test. That is, in Experimental Example 3, the surface is rough due to use, but in Experimental Examples 1 and 2, the surface is smoother due to use.

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Abstract

本発明に係る樹脂組成物は、熱硬化性樹脂で形成されたバインダー樹脂と、前記バインダー樹脂中に分散された添加剤とを有し、前記添加剤が、ＰＴＦＥ（polytetrafluoroethylene）と、グラファイトおよびＭｏＳ2の少なくとも一方とを含み、前記添加剤の各々の平均粒径が、いずれも１０μｍ未満であり、前記ＰＴＦＥの平均粒径が、グラファイトおよびＭｏＳ2の平均粒径よりも大きい。

Description

樹脂組成物および摺動部材
　本発明は、摺動部材に関する。
　摺動面の特性を改善するため、バインダー樹脂に、固体潤滑剤としてＰＴＦＥ、グラファイトおよびＭｏＳ2を添加した樹脂コーティング層を形成した摺動部材が知られている（特許文献１および２）。
特開２００２－３１０３４５号公報 特開２００８－５６７５０号公報
　特許文献１または２に記載の技術においては、高負荷荷重の条件で固体潤滑剤の脱落または劈開が起こり、摺動面が荒れるという問題があった。摺動面が荒れると、特に潤滑油の供給が十分でない低油量またはドライの環境で油膜の形成が困難になり、耐焼付性および耐摩耗性が十分でない場合があった。
　これに対し本発明は、潤滑油の供給が十分でない環境において高負荷荷重の条件で耐焼付性および耐摩耗性を向上させる技術を提供する。
　本発明は、熱硬化性樹脂で形成されたバインダー樹脂と、前記バインダー樹脂中に分散された添加剤とを有し、前記添加剤が、ＰＴＦＥ（polytetrafluoroethylene）と、グラファイトおよびＭｏＳ2の少なくとも一方とを含み、前記添加剤の各々の平均粒径が、いずれも１０μｍ未満であり、前記ＰＴＦＥの平均粒径が、グラファイトおよびＭｏＳ2の平均粒径よりも大きい樹脂組成物を提供する。
　前記バインダー樹脂が、ポリアミドイミドおよびポリイミドの少なくとも一方を含んでもよい。
　前記バインダー樹脂が、ポリアミドイミドであってもよい。
　前記バインダー樹脂の含有量が、５０～８０体積％であってもよい。
　前記ＰＴＦＥの含有量が、前記ＭｏＳ2の含有量よりも多くてもよい。
　前記ＭｏＳ2の含有量が、０～１０体積％であってもよい。
　前記添加剤が、硬質粒子を含んでもよい。
　また、本発明は、基材と、前記基材の上に、請求項１ないし７のいずれか一項に記載の樹脂組成物で形成されたコーティング層とを有する摺動部材を提供する。
　本発明によれば、潤滑油の供給が十分でない環境において高負荷荷重の条件で耐焼付性および耐摩耗性を向上させることができる。
一実施形態に係るコンプレッサー１の構造を示す断面模式図。 斜板３とシュー５との位置関係を例示する図。 斜板３の断面構造を例示する図。 耐焼付性試験において得られた焼付面圧を示す図。 摺動試験前後の摺動面の状態を示す図。
１…コンプレッサー
２…シャフト
３…斜板
　３１…基材
　３２…コーティング層
　３３…コーティング層
４…ピストン
１．構造
　図１は、一実施形態に係るコンプレッサー１の構造を示す断面模式図である。コンプレッサー１は、いわゆる斜板式コンプレッサーである。コンプレッサー１は、シャフト２、斜板３、ピストン４、およびシュー５を有する。シャフト２は、ハウジング（図示略）に対して回転可能に支持されている。斜板３は、シャフト２の回転軸に対して斜めに固定されている。斜板３は、本発明に係る摺動部材の一例である。ピストン４は、ハウジングに設けられたシリンダボア（図示略）内を往復運動する。シュー５は、斜板３とピストン４との間に設けられており、斜板３およびピストン４とそれぞれ摺動する。シュー５において、斜板３と摺動する面はほぼ平坦であり、ピストン４と摺動する面はドーム状（半球状）の形状を有している。シュー５は、本発明に係る摺動部材と摺動する相手材の一例である。シャフト２の回転は、斜板３によりピストン４の往復運動に変換される。
　図２は、斜板３とシュー５との位置関係を例示する図である。図２は、摺動面に垂直な方向から見た図である。斜板３は、全体として中央部に孔を有する円板形状を有する。斜板３から見ると、シュー５は、摺動面上を回転運動している。ここで回転運動とは、斜板３に対してシュー５が円状の軌跡を描く運動をいう。
　図３は、斜板３の断面構造を例示する図である。図３は、シュー５との摺動面に垂直な断面における構造を示す模式図である。斜板３は、基材３１、コーティング層３２、およびコーティング層３３を有する。コーティング層３２およびコーティング層３３はいずれもシュー５と摺動する。コーティング層３２およびコーティング層３３は、いずれも、本発明に係るコーティング層の一例である。基材３１は、中央部に孔を有する円板形状を有しており、要求される特性を満たす金属、例えば、鉄系、銅系、またはアルミニウム系の合金により形成される。シュー５との凝着を防ぐ観点から、斜板３はシュー５とは異なる材料で形成されることが好ましい。
　コーティング層３２は、斜板３の摺動面の特性を改善するために形成されている。コーティング層３２は、樹脂組成物で形成される。この樹脂組成物は、バインダー樹脂およびバインダー樹脂中に分散された添加剤を含む。バインダー樹脂は、例えば熱硬化性樹脂により形成される。熱硬化性樹脂としては、例えば、ポリアミドイミド（ＰＡＩ）、ポリアミド（ＰＡ）、およびポリイミド（ＰＩ）、エポキシ、およびフェノールの少なくとも１種が用いられる。バインダー樹脂は、このうち特に、ＰＡＩおよびＰＩの少なくとも一方を含むことが好ましい。一例として、この樹脂組成物におけるバインダー樹脂の含有量は５０～８０体積％であることが好ましい。含有量は６０体積％を超えることがより好ましく、上限は７５体積％であることがより好ましい。
　添加剤としては、固体潤滑剤が用いられる。固体潤滑剤は、潤滑特性を改善するため、すなわち摩擦係数を低減するために添加される。一例として、この樹脂組成物は、総量で２０～５０体積％の固体潤滑剤を含む。固体潤滑剤としては、ＰＴＦＥ（polytetrafluoroethylene、ポリテトラフルオロエチレン）が用いられる。さらに、この樹脂組成物は、ＰＴＦＥに加え、グラファイト（Ｇｒ）およびＭｏＳ2の少なくとも一方を含む。ＭｏＳ2の含有量は、ＰＴＦＥの含有量よりも少ないことが好ましい。一例として、ＰＴＦＥの含有量は、１０～３０体積％であり、１５～２５体積％であることがより好ましい。ＭｏＳ2の含有量は、０～１０体積％であり、０～４体積％であることが好ましい（すなわちＭｏＳ2は含有されていなくてもよい）。グラファイトの含有量は、０～２０体積％であることが好ましく、１０～２０体積％であることがより好ましい。また、ＭｏＳ2の含有量は、グラファイトの含有量よりも少ないことが好ましい。
　摺動面の平滑性を高め、油膜形成を助けるため、バインダー樹脂に添加される添加剤の平均粒径は１０μｍ未満であることが好ましく、５μｍ以下であることがより好ましい。ここで、平均粒径とは、バインダー樹脂と混合する前の原料の状態において、レーザー回折法により得られる球相当径の分布における５０％径（メディアン径）をいう。添加剤の平均粒径を１０μｍ未満とすることで、摺動面において添加剤の脱落または劈開が生じても、添加剤の平均粒径が１０μｍ以上である場合と比較して摺動面が滑らかなままであり油膜の形成が助けられる。そのため、境界潤滑から混合～流体潤滑へ遷移しやすく、低油量かつ高負荷荷重という過酷な条件でも良好な潤滑状態が得られやすい。
　ＰＴＦＥの平均粒径は、グラファイトの平均粒径およびＭｏＳ2の平均粒径のいずれよりも大きいことが好ましい。本願発明者らの仮説によれば、平均粒径がグラファイトおよびＭｏＳ2よりも大きいＰＴＦＥを用いることで、摺動面においてＰＴＦＥが引き延ばされてグラファイトまたはＭｏＳ2を覆い、摺動面の平滑性が保たれやすくなる。
　この樹脂組成物は、添加剤としてさらに、硬質粒子を含んでもよい。硬質粒子としては、例えば、酸化物、窒化物、炭化物、および硫化物の少なくとも１種が用いられる。硬質粒子の平均粒径は１０μｍ未満であることが好ましく、さらにＰＴＦＥの平均粒径よりも小さいことがより好ましい。
　コーティング層３３も、コーティング層３２と同じ樹脂組成物を用いて形成される。なお、基材３１において、摺動面となる面、すなわちコーティング層３２が形成される面およびコーティング層３３が形成される面はいずれもほぼ平坦である。コーティング層３２との接着力を強化するため、基材３１の表面は粗面化されていてもよい。また、基材３１とコーティング層３２との間に中間層が形成されてもよい。
　なお、本発明は上述の実施形態に限定されるものではなく、種々の変形実施が可能である。例えば、本実施形態に係る樹脂組成物を用いて形成されたコーティング層を有する摺動部材はコンプレッサー用の斜板に限られず、例えば、コンプレッサー用のシュー、エンジンにおいて用いられる半割軸受、ブシュ、またはスラストワッシャであってもよい。
２．実験例
　種々の条件で摺動部材の試験片を作製し、これらの特性を評価した。摺動部材の基材としては鋳鉄を用い、これを図１のような斜板の形状に加工した。この基材の上に、表１に記載される樹脂組成物でコーティング層を形成した。バインダー樹脂としてはＰＡＩを用いた。なお、実験例３は、ＭｏＳ2の平均粒径がＰＴＦＥの平均粒径よりも大きい例であると言える。
Figure JPOXMLDOC01-appb-T000001
　上記の３つの実験例の試験片に対し、まず耐摩耗性試験を行った。耐摩耗性試験の試験条件は以下のとおりである。
　試験装置：高圧雰囲気摩擦摩耗試験機
　周速：４０ｍ／ｓｅｃ
　面圧：４～１２ＭＰａ（漸増：２ＭＰａ／３分）
　時間：最大面圧時に１時間保持
　雰囲気：冷媒貧潤滑雰囲気
　相手材：軸受鋼
　試験後の試験片の摺動面を目視で観察し、コーティング層の摩耗の有無を調べた。その結果、実験例３においては摩耗が発生していたが、実験例１および２においては摩耗が確認できなかった。すなわち、実験例３と比較して、実験例１および２は耐摩耗性が向上している。
　さらに、本願の発明者らは、実験例１および２の試験片に対し、耐焼付性試験を行った。耐焼付性試験の試験条件は以下のとおりである。
　試験装置：油噴霧式貧潤滑試験機
　周速：６．３ｍ／ｓｅｃ
　面圧：２～２０ＭＰａ（漸増：２ＭＰａ／１分）
　時間：最大１０分間
　潤滑方法：噴霧
　潤滑油：冷凍機油
　相手材：軸受鋼
　図４は、耐焼付性試験において得られた焼付面圧を示す図である。実験例３の試験片では１０ＭＰａの面圧で焼付が発生したところ、実験例１および２の試験片では、試験装置の最大面圧２０ＭＰａでも焼付が発生しなかった。このように、実験例３と比較して、実験例１および２は耐焼付性が向上している。
　さらに、本願の発明者らは、実験例１および２の試験片に対し摺動試験を行い、試験前後の摺動面の表面粗さを表面粗さ計（小坂研究所製ＳＰ８１Ｂ）で測定し、表面を電子顕微鏡で観察した。摺動試験の試験条件は前述の耐焼付性試験と同様である。
　図５は、摺動試験前後の摺動面の状態を示す図である。図５（Ａ）は実験例１を、（Ｂ）は実験例２を、（Ｃ）は実験例３を示す。なお表面粗さは、ＪＩＳ　Ｂ　０６０１：２００１における十点平均粗さＲｚＪＩＳを表している。実験例３においては、摺動試験により表面粗さが増加しているものの、実験例１および２においては、摺動試験において表面粗さが減少している。すなわち、実験例３では使用により表面が荒れているところ、実験例１および２では使用により表面がより滑らかになっている。

Claims (8)

  1. 　熱硬化性樹脂で形成されたバインダー樹脂と、
    　前記バインダー樹脂中に分散された添加剤と
    　を有し、
    　前記添加剤が、
    　　ＰＴＦＥ（polytetrafluoroethylene）と、
    　　グラファイトおよびＭｏＳ2の少なくとも一方と
    　を含み、
    　前記添加剤の各々の平均粒径が、いずれも１０μｍ未満であり、
    　前記ＰＴＦＥの平均粒径が、グラファイトおよびＭｏＳ2の平均粒径よりも大きい
    　樹脂組成物。
  2. 　前記バインダー樹脂が、ポリアミドイミドおよびポリイミドの少なくとも一方を含む
    　請求項１に記載の樹脂組成物。
  3. 　前記バインダー樹脂が、ポリアミドイミドである
    　請求項２に記載の樹脂組成物。
  4. 　前記バインダー樹脂の含有量が、５０～８０体積％である
    　請求項１ないし３のいずれか一項に記載の樹脂組成物。
  5. 　前記ＰＴＦＥの含有量が、前記ＭｏＳ2の含有量よりも多い
    　請求項１ないし４のいずれか一項に記載の樹脂組成物。
  6. 　前記ＭｏＳ2の含有量が、０～１０体積％である
    　請求項５に記載の樹脂組成物。
  7. 　前記添加剤が、硬質粒子を含む
    　請求項１ないし６のいずれか一項に記載の樹脂組成物。
  8. 　基材と、
    　前記基材の上に、請求項１ないし７のいずれか一項に記載の樹脂組成物で形成されたコーティング層と
    　を有する摺動部材。
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US16/461,054 US11352581B2 (en) 2016-11-17 2017-11-16 Resin composition and sliding member
KR1020197014779A KR102373093B1 (ko) 2016-11-17 2017-11-16 수지 조성물 및 미끄럼 부재
EP17872673.3A EP3543295B1 (en) 2016-11-17 2017-11-16 Resin composition and sliding member
CN201780069675.3A CN110072945A (zh) 2016-11-17 2017-11-16 树脂组合物和滑动部件

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CN110072945A (zh) 2019-07-30
EP3543295B1 (en) 2022-02-16
US20190309235A1 (en) 2019-10-10
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US11352581B2 (en) 2022-06-07
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