WO2020116390A1 - Composition, film formed from the composition, sliding member having the film, and method for producing the same - Google Patents

Composition, film formed from the composition, sliding member having the film, and method for producing the same Download PDF

Info

Publication number
WO2020116390A1
WO2020116390A1 PCT/JP2019/047025 JP2019047025W WO2020116390A1 WO 2020116390 A1 WO2020116390 A1 WO 2020116390A1 JP 2019047025 W JP2019047025 W JP 2019047025W WO 2020116390 A1 WO2020116390 A1 WO 2020116390A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
film
solid lubricant
binder resin
hard particle
Prior art date
Application number
PCT/JP2019/047025
Other languages
French (fr)
Inventor
Takahiko Sasaki
Tetsuji Yamaguchi
Original Assignee
Dow Corning Toray Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Co., Ltd. filed Critical Dow Corning Toray Co., Ltd.
Publication of WO2020116390A1 publication Critical patent/WO2020116390A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/04Metals; Alloys
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/044Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/06Particles of special shape or size
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16CSHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/02Parts of sliding-contact bearings
    • F16C33/04Brasses; Bushes; Linings
    • F16C33/20Sliding surface consisting mainly of plastics
    • F16C33/201Composition of the plastic
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16CSHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C9/00Bearings for crankshafts or connecting-rods; Attachment of connecting-rods
    • F16C9/02Crankshaft bearings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0887Tungsten
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04Elements
    • C10M2201/041Carbon; Graphite; Carbon black
    • C10M2201/0413Carbon; Graphite; Carbon black used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04Elements
    • C10M2201/05Metals; Alloys
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/061Carbides; Hydrides; Nitrides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/065Sulfides; Selenides; Tellurides
    • C10M2201/066Molybdenum sulfide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/044Polyamides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04Siloxanes with specific structure
    • C10M2229/041Siloxanes with specific structure containing aliphatic substituents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/055Particles related characteristics
    • C10N2020/06Particles of special shape or size
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015Dispersions of solid lubricants
    • C10N2050/02Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023Multi-layer lubricant coatings
    • C10N2050/025Multi-layer lubricant coatings in the form of films or sheets
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16CSHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C3/00Shafts; Axles; Cranks; Eccentrics
    • F16C3/04Crankshafts, eccentric-shafts; Cranks, eccentrics
    • F16C3/06Crankshafts
    • F16C3/14Features relating to lubrication

Definitions

  • the present invention relates to a composition that provides a lubricating film having excellent sliding property. Furthermore, the present invention relates to a film formed from the composition, a sliding member having the film, and a method of manufacturing the same.
  • Film-forming compositions to improve the sliding properties of component surfaces are used in various applications such as industrial machines, construction machines and automobiles.
  • film-forming compositions contain binder and solid lubricants.
  • Film-forming compositions comprising hard particles in addition to binder and solid lubricants are also known.
  • JP2017-201165A discloses a film-forming composition comprising a thermosetting resin, a solid lubricant and/or hard particles, solvent and polyether-modified silicone.
  • metal oxides such as silicon oxide, aluminum oxide, chromium oxide, titanium oxide, zinc oxide, ferric oxide and mullite; metal carbonates such as silicon carbide and metal nitrides such as silicon nitride.
  • JP2000-265953A discloses a compressing machine coated by a film formed from a polymer composition comprising metal particles. It discloses tin, silver, aluminum, copper, zinc, nickel, titanium, tungsten, molybdenum, magnesium and iron and alloy comprising thereof as examples of metal particles. It also discloses the particle size of the metal is preferably from 10 to 100 micron.
  • a sliding member is used to slide two or more components in contact.
  • Sliding member needs to have not only the property for excellent sliding (i.e. less coefficient of friction), but also the property for wear resistance (less abrasion).
  • the present inventors have found that when a conventional film comprises metal oxides, metal carbonates or metal nitrides as hard particles, the film tends to abrade the surface of the corresponding materials.
  • An object of the present invention is to provide a composition which forms a film having excellent sliding property and the property with less abrasion for sliding member and corresponding material.
  • the present inventors have created the invention based on the finding that a film comprising metal tungsten particles within a specific average particle size can prevent the abrasion for sliding member and corresponding material in the un-expected level.
  • the first aspect of the invention relates to a composition
  • a composition comprising (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
  • the second aspect of the invention relates to a lubricating film made from the above composition.
  • the second aspect of the invention relates to a film comprising (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
  • the third aspect of the invention relates to a sliding member having the above film.
  • the forth aspect of the invention relates to a method for forming a lubricating film on surface of a member, comprising the steps of: (I) preparing a composition comprising (A) a binder resin, (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method, (II) applying the composition on surface of a member; and (III) heat-curing the applied composition, thereby forming a lubricating film on surface of the member.
  • composition of the present invention it is possible to form a film having both excellent sliding property and good wear resistances for sliding member and corresponding material.
  • the composition used in the present invention comprises (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size.
  • the average particle size of the hard particle is measured by laser diffraction scattering method.
  • the composition can further comprise (D) a solvent and/or (E) other additives.
  • Binder resin used in the present invention is a resin which forms a lubricating film as a heat resistant resin and has a function as a binder for supporting a solid lubricant described later.
  • Binder resins which can be used include, for example, polyamideimide, polyimide, epoxy resin, phenol resin, polyamide, polybenzimidazole, polyphenyl sulfonate and polyether ether ketone, and one or more of these may be contained.
  • the binder resin is thermosetting resin.
  • the binder resin contains polyamideimide or polyimide. More preferably, the binder resin contains polyamideimide.
  • the content of the binder resin is 10 to 40% by weight, preferably 20 to 30% by weight, based on the weight of the whole composition.
  • the hard particles used in the present invention comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size.
  • the average particle size can be measured by laser diffraction scattering method.
  • the average particle size of the metal tungsten particles is from 1 to 6 micrometers, more preferably from 1 to 3 micrometers.
  • the hard particles have the function of improving the load resistance of the film and improving the wear resistance. However, the hard particles sometimes abrade the member located corresponding side of the film. It is un-expected thing that when metal tungsten particles with 0.5 to 10 micrometers of average particle size are used as a hard particle, the abrasion of surface of the corresponding member is low thus the lifetime of the sliding member would be extended.
  • Preferable metal tungsten particles are monodispersed fine metal tungsten particles that almost all of the particle is existing as primary particles with less cohesion, or uniform fine metal tungsten particles that have uniform figure of tungsten particles although there are secondary particles.
  • the most preferable metal tungsten particles are monodispersed fine metal tungsten particles.
  • the hard particle of the invention can further comprise other hard particles in addition to metal tungsten particles in the amount as long as the function of the composition is not impaired.
  • Other hard particles comprise tungsten carbide, titanium carbide, zirconium carbide, zirconium oxide, tungsten disulfide, molybdenum carbide, tungsten disilicide, titanium nitride and zirconium nitride, and one or more of there.
  • the content of metal tungsten particles in the whole hard particles is preferably 50% by weight or more, more preferably 70% by weight or more based on the total weight of the hard particles.
  • the content of the hard particles depends on the compounding amount of the solid lubricant described later, but as an example, it is 70 to 140 parts by weight with respect to 100 parts by weight of the binder resin.
  • the solid lubricant used in the present invention is molybdenum disulfide or graphite.
  • the solid lubricant has a function to improve the sliding property of the film.
  • molybdenum disulfide and graphite are used in the composition of the present invention from the viewpoint of forming a film having the sliding property of good wear resistance.
  • graphite is particularly preferred in view of lowering the coefficient of friction and further imparting abrasion resistance.
  • the content of the solid lubricant depends on the blending amount of the hard particles.
  • the composition of the present invention comprises 40 to 70 parts by weight of solid lubricant with respect to 100 parts by weight of the binder resin.
  • the average particle size of the solid lubricant of the present invention can be measured by laser diffraction scattering method.
  • the average particle diameter of the solid lubricant is preferably 0.1 to 15.0 micrometers, and particularly preferably 1.0 to 10.0 micrometers.
  • the composition of the present invention can further contain a solvent for the purpose of improving coating properties and the like.
  • the solvent can be selected depending on the type of binder resin.
  • Usable solvents include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and ⁇ -butyrolactone (GBL); aromatic hydrocarbons such as toluene and xylene; organic halogen compounds such as chloroform, trichloroethylene and trichlorotrifluoroethane; amides such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), 1,3-Dimethyl-2-imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide, 1-butyl-2-pyrrolidone, N,N-d
  • the coating composition of the present invention may further contain, if necessary, one or more of other additives as long as the object of the present invention is not impaired.
  • Usable additives include, a UV absorber, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, a deformer, a thickener, an anti-settling agent, pigments (organic colored pigments, inorganic pigments), colored dyes, infrared absorbers, fluorescent whitening agents, dispersants, conductive fine particles, antistatic agents, antifogging agents and coupling agents.
  • composition of the present invention can be produced by appropriately mixing the components (A) to (C) and optionally the components (D) and (E) described above.
  • the second aspect of the present invention relates to a film comprising (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
  • the film is useful for a lubricating film of a sliding member.
  • the film is formed by the composition of the above mentioned first aspect of the invention.
  • the film of the present invention is a sliding film in which (B) hard particles and (C) a solid lubricant are dispersed in (A) a binder resin.
  • the film can further contain (E) other additives.
  • the film thickness is 1 to 50 ⁇ m, preferably 5 to 30 ⁇ m.
  • the third aspect of the present invention relates to a sliding member having a film of above mentioned the second aspect of the invention.
  • the film is formed on a sliding surface of a sliding member, and it works as a lubricating film.
  • the sliding member includes, for example, a swash plate of a compressor, an engine tappet (valve lifter), a camshaft, a crankshaft, an engine metal, an engine piston, a piston ring, a gear, a door lock, a brake shim or a brake clip.
  • the fourth aspect of the present invention is a method of forming a lubricating film on a surface of a member, and it includes the following steps (I) to (III).
  • Step (I) is a step of preparing a composition containing (A) a binder resin, (B) a hard particle, and (C) a solid lubricant, in which the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
  • the composition is as described above as the first aspect of the present invention.
  • the step can be conducted by mixing components (A) to (E).
  • Step (II) is a step of applying the composition prepared in step (I) onto the surface of a member.
  • the composition may be applied by dipping, spin coating, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, screen printing, air knife coating and so on.
  • the thickness of the coating film is not particularly limited, but a thickness of 1 to 50 ⁇ m is preferable, and a thickness of 5 to 30 ⁇ m is more preferable.
  • Step (III) is a step of forming a lubricating film on the surface of the member by heat curing the composition applied in step (II).
  • Thermal curing can be performed by heating in an oven or the like.
  • thermosetting resin is used as a binder resin
  • cross-linkage is formed by heating, and a cured film is formed on the member.
  • the solvent in the composition can be removed in the first phase of heating, and it can be cured by crosslinking reaction in the second phase of heating.
  • the first phase of heating may be performed at 60 to 100°C for 5 to 30 minutes, and then the second phase of heating may be performed at 180 to 250°C. for 20 to 120 minutes.
  • the present invention is illustrated by, but is not limited to, the following examples.
  • the “average particle diameter” in Table 1 is the average particle diameter of each particle measured by laser diffraction scattering method.
  • Example 1 A polyamideimide resin solution with about 35 wt% of solid content was obtained by dissolved 87 parts by weight of polyamideimide resin (A-1) in ⁇ -butyrolactone (GBL, D-1).
  • a binder resin solution was obtained by adding 13 parts by weight of epoxy resin (A-2) in the above mentioned polyamideimide resin solution.
  • this binder resin solution 55.7 parts by weight of graphite (C-1), which is a powdery solid lubricant, and 30.4 parts by weigh of metal tungsten particles (B-1), which are hard particles, and 0.7 parts by weight of a deformer (E-1) were added, then mixed and dispersed at room temperature.
  • C-1 graphite
  • B-1 metal tungsten particles
  • E-1 deformer
  • the mixture was diluted with GBL (D-1) and a coating composition with a solid content concentration of 47.0 wt% used for the evaluation test was formulated.
  • the total amount of GBL (D-1) was 210.9 parts by weight.
  • the coating composition was applied on the surface of a SRV cylindrical disk test piece (size: ⁇ 24 x 7.9 mm, Material: 100Cr6 (equivalent to SUJ2) Optimol Instruments Prutechnik GmbH by use of a screen printing plate (Mesh Corporation) so that the film thickness after baking was 15 ⁇ 5 ⁇ m.
  • the film was heated and the solvent was removed by heating in a circulating oven at 80°C for 20 minutes. Thereafter, baking was performed at 220°C for 20 minutes to obtain a test piece.
  • Example 2 to 3 and Comparative Examples 1 to 7 The same procedure as in Example 1 was carried out except using the components and the amount (parts by weight) shown in Table 2 or Table 3, to obtain test pieces.
  • test pieces obtained in the Examples and Comparative Examples were subjected to SRV test described later, and the results are shown in Table 2 or Table 3.
  • the test pieces according to the example of the present invention had an excellent lubricating performance (small average coefficient of dynamic friction) with less depth of wear and less width of wear of corresponding material comparing to comparative examples.
  • Evaluation method Using the SRV friction and wear tester (Optimol Instruments Prutechnik GmbH, product name: oscillation friction and wear tester Model SRV Type 5), evaluation was conducted by the method in which the SRV cylinder reciprocated on the surface of the SRV disc test piece.
  • the cylinder it is a corresponding material, was ⁇ 15 x 22 mm SRV cylinder (Optimol Instruments Prutechnik GmbH, material: 100Cr6 (equivalent to SUJ2)).
  • the SRV disk on which a film made of the composition of the present invention was formed was set on the test bed of the SRV5 tester, and 0.1 g of an engine oil (Exxon Mobil, chemically synthesized oil for gasoline and diesel engines 10W-30 SM/CF) was dropped on the film.
  • an engine oil Exxon Mobil, chemically synthesized oil for gasoline and diesel engines 10W-30 SM/CF

Abstract

A film is formed by use of a composition containing (A) a binder resin, (B) a hard particle, and (C) a solid lubricant, wherein the hard particle contains metal tungsten particle with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.

Description

COMPOSITION, FILM FORMED FROM THE COMPOSITION, SLIDING MEMBER HAVING THE FILM, AND METHOD FOR PRODUCING THE SAME
The present invention relates to a composition that provides a lubricating film having excellent sliding property. Furthermore, the present invention relates to a film formed from the composition, a sliding member having the film, and a method of manufacturing the same.
Film-forming compositions to improve the sliding properties of component surfaces are used in various applications such as industrial machines, construction machines and automobiles. Normally, film-forming compositions contain binder and solid lubricants. Film-forming compositions comprising hard particles in addition to binder and solid lubricants are also known. For example, JP2017-201165A discloses a film-forming composition comprising a thermosetting resin, a solid lubricant and/or hard particles, solvent and polyether-modified silicone. However, it discloses metal oxides such as silicon oxide, aluminum oxide, chromium oxide, titanium oxide, zinc oxide, ferric oxide and mullite; metal carbonates such as silicon carbide and metal nitrides such as silicon nitride. JP2000-265953A discloses a compressing machine coated by a film formed from a polymer composition comprising metal particles. It discloses tin, silver, aluminum, copper, zinc, nickel, titanium, tungsten, molybdenum, magnesium and iron and alloy comprising thereof as examples of metal particles. It also discloses the particle size of the metal is preferably from 10 to 100 micron.
Normally, a sliding member is used to slide two or more components in contact. Sliding member needs to have not only the property for excellent sliding (i.e. less coefficient of friction), but also the property for wear resistance (less abrasion). However, the present inventors have found that when a conventional film comprises metal oxides, metal carbonates or metal nitrides as hard particles, the film tends to abrade the surface of the corresponding materials.
[PTL1] JP2017-201165A
[PTL2] JP2000-265953A
An object of the present invention is to provide a composition which forms a film having excellent sliding property and the property with less abrasion for sliding member and corresponding material. The present inventors have created the invention based on the finding that a film comprising metal tungsten particles within a specific average particle size can prevent the abrasion for sliding member and corresponding material in the un-expected level.
The first aspect of the invention relates to a composition comprising (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
The second aspect of the invention relates to a lubricating film made from the above composition. In concretely, the second aspect of the invention relates to a film comprising (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
The third aspect of the invention relates to a sliding member having the above film.
The forth aspect of the invention relates to a method for forming a lubricating film on surface of a member, comprising the steps of: (I) preparing a composition comprising (A) a binder resin, (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method, (II) applying the composition on surface of a member; and (III) heat-curing the applied composition, thereby forming a lubricating film on surface of the member.
According to the composition of the present invention, it is possible to form a film having both excellent sliding property and good wear resistances for sliding member and corresponding material.
The composition used in the present invention comprises (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size. The average particle size of the hard particle is measured by laser diffraction scattering method. The composition can further comprise (D) a solvent and/or (E) other additives.
(A) Binder resin
The binder resin used in the present invention is a resin which forms a lubricating film as a heat resistant resin and has a function as a binder for supporting a solid lubricant described later. Binder resins which can be used include, for example, polyamideimide, polyimide, epoxy resin, phenol resin, polyamide, polybenzimidazole, polyphenyl sulfonate and polyether ether ketone, and one or more of these may be contained. Preferably, the binder resin is thermosetting resin. Preferably, the binder resin contains polyamideimide or polyimide. More preferably, the binder resin contains polyamideimide.
The content of the binder resin is 10 to 40% by weight, preferably 20 to 30% by weight, based on the weight of the whole composition.
(B) Hard particles
The hard particles used in the present invention comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size. The average particle size can be measured by laser diffraction scattering method. Preferably, the average particle size of the metal tungsten particles is from 1 to 6 micrometers, more preferably from 1 to 3 micrometers. The hard particles have the function of improving the load resistance of the film and improving the wear resistance. However, the hard particles sometimes abrade the member located corresponding side of the film. It is un-expected thing that when metal tungsten particles with 0.5 to 10 micrometers of average particle size are used as a hard particle, the abrasion of surface of the corresponding member is low thus the lifetime of the sliding member would be extended.
Preferable metal tungsten particles are monodispersed fine metal tungsten particles that almost all of the particle is existing as primary particles with less cohesion, or uniform fine metal tungsten particles that have uniform figure of tungsten particles although there are secondary particles. The most preferable metal tungsten particles are monodispersed fine metal tungsten particles.
The hard particle of the invention can further comprise other hard particles in addition to metal tungsten particles in the amount as long as the function of the composition is not impaired. Other hard particles comprise tungsten carbide, titanium carbide, zirconium carbide, zirconium oxide, tungsten disulfide, molybdenum carbide, tungsten disilicide, titanium nitride and zirconium nitride, and one or more of there. When the other hard particles are contained in addition to metal tungsten particles, the content of metal tungsten particles in the whole hard particles is preferably 50% by weight or more, more preferably 70% by weight or more based on the total weight of the hard particles.
The content of the hard particles depends on the compounding amount of the solid lubricant described later, but as an example, it is 70 to 140 parts by weight with respect to 100 parts by weight of the binder resin.
(C) Solid lubricant
The solid lubricant used in the present invention is molybdenum disulfide or graphite. The solid lubricant has a function to improve the sliding property of the film. In particular, molybdenum disulfide and graphite are used in the composition of the present invention from the viewpoint of forming a film having the sliding property of good wear resistance. Among the two, graphite is particularly preferred in view of lowering the coefficient of friction and further imparting abrasion resistance.
The content of the solid lubricant depends on the blending amount of the hard particles. Exemplarily, the composition of the present invention comprises 40 to 70 parts by weight of solid lubricant with respect to 100 parts by weight of the binder resin.
The average particle size of the solid lubricant of the present invention can be measured by laser diffraction scattering method. The average particle diameter of the solid lubricant is preferably 0.1 to 15.0 micrometers, and particularly preferably 1.0 to 10.0 micrometers.
(D) Solvent
The composition of the present invention can further contain a solvent for the purpose of improving coating properties and the like. The solvent can be selected depending on the type of binder resin. Usable solvents include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and γ-butyrolactone (GBL); aromatic hydrocarbons such as toluene and xylene; organic halogen compounds such as chloroform, trichloroethylene and trichlorotrifluoroethane; amides such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), 1,3-Dimethyl-2-imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide, 1-butyl-2-pyrrolidone, N,N-dimethylformamide (DMF) and N,N-dimethylacetoamide (DMAC). The solvent of the present invention may be one or mixed of two or more. Particularly preferred solvents contain NEP, DMI, GBL and 3-methoxy-N,N-dimethylpropanamide.
(E) Other additives
The coating composition of the present invention may further contain, if necessary, one or more of other additives as long as the object of the present invention is not impaired. Usable additives include, a UV absorber, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, a deformer, a thickener, an anti-settling agent, pigments (organic colored pigments, inorganic pigments), colored dyes, infrared absorbers, fluorescent whitening agents, dispersants, conductive fine particles, antistatic agents, antifogging agents and coupling agents.
The composition of the present invention can be produced by appropriately mixing the components (A) to (C) and optionally the components (D) and (E) described above.
The second aspect of the present invention relates to a film comprising (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method. The film is useful for a lubricating film of a sliding member. The film is formed by the composition of the above mentioned first aspect of the invention. The film of the present invention is a sliding film in which (B) hard particles and (C) a solid lubricant are dispersed in (A) a binder resin. The film can further contain (E) other additives. The film thickness is 1 to 50 μm, preferably 5 to 30 μm.
The third aspect of the present invention relates to a sliding member having a film of above mentioned the second aspect of the invention. The film is formed on a sliding surface of a sliding member, and it works as a lubricating film. The sliding member includes, for example, a swash plate of a compressor, an engine tappet (valve lifter), a camshaft, a crankshaft, an engine metal, an engine piston, a piston ring, a gear, a door lock, a brake shim or a brake clip.
The fourth aspect of the present invention is a method of forming a lubricating film on a surface of a member, and it includes the following steps (I) to (III).
Step (I)
Step (I) is a step of preparing a composition containing (A) a binder resin, (B) a hard particle, and (C) a solid lubricant, in which the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method. The composition is as described above as the first aspect of the present invention. The step can be conducted by mixing components (A) to (E).
Step (II)
Step (II) is a step of applying the composition prepared in step (I) onto the surface of a member. The composition may be applied by dipping, spin coating, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, screen printing, air knife coating and so on. The thickness of the coating film is not particularly limited, but a thickness of 1 to 50 μm is preferable, and a thickness of 5 to 30 μm is more preferable.
Step (III)
Step (III) is a step of forming a lubricating film on the surface of the member by heat curing the composition applied in step (II). Thermal curing can be performed by heating in an oven or the like. When thermosetting resin is used as a binder resin, cross-linkage is formed by heating, and a cured film is formed on the member. When heating the applied composition, the solvent in the composition can be removed in the first phase of heating, and it can be cured by crosslinking reaction in the second phase of heating. For example, the first phase of heating may be performed at 60 to 100°C for 5 to 30 minutes, and then the second phase of heating may be performed at 180 to 250°C. for 20 to 120 minutes.
The present invention is illustrated by, but is not limited to, the following examples.
The raw materials used in the examples are shown in Table 1.
The "average particle diameter" in Table 1 is the average particle diameter of each particle measured by laser diffraction scattering method.
Figure JPOXMLDOC01-appb-T000001
Example 1
A polyamideimide resin solution with about 35 wt% of solid content was obtained by dissolved 87 parts by weight of polyamideimide resin (A-1) in γ-butyrolactone (GBL, D-1). A binder resin solution was obtained by adding 13 parts by weight of epoxy resin (A-2) in the above mentioned polyamideimide resin solution. In this binder resin solution, 55.7 parts by weight of graphite (C-1), which is a powdery solid lubricant, and 30.4 parts by weigh of metal tungsten particles (B-1), which are hard particles, and 0.7 parts by weight of a deformer (E-1) were added, then mixed and dispersed at room temperature. The mixture was diluted with GBL (D-1) and a coating composition with a solid content concentration of 47.0 wt% used for the evaluation test was formulated. The total amount of GBL (D-1) was 210.9 parts by weight. The coating composition was applied on the surface of a SRV cylindrical disk test piece (size: φ24 x 7.9 mm, Material: 100Cr6 (equivalent to SUJ2) Optimol Instruments Prutechnik GmbH by use of a screen printing plate (Mesh Corporation) so that the film thickness after baking was 15±5 μm. The film was heated and the solvent was removed by heating in a circulating oven at 80°C for 20 minutes. Thereafter, baking was performed at 220°C for 20 minutes to obtain a test piece.
Examples 2 to 3 and Comparative Examples 1 to 7
The same procedure as in Example 1 was carried out except using the components and the amount (parts by weight) shown in Table 2 or Table 3, to obtain test pieces.
The test pieces obtained in the Examples and Comparative Examples were subjected to SRV test described later, and the results are shown in Table 2 or Table 3. As shown in Table 2 or Table 3, the test pieces according to the example of the present invention had an excellent lubricating performance (small average coefficient of dynamic friction) with less depth of wear and less width of wear of corresponding material comparing to comparative examples.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Evaluation method
Using the SRV friction and wear tester (Optimol Instruments Prutechnik GmbH, product name: oscillation friction and wear tester Model SRV Type 5), evaluation was conducted by the method in which the SRV cylinder reciprocated on the surface of the SRV disc test piece. The cylinder, it is a corresponding material, was φ15 x 22 mm SRV cylinder (Optimol Instruments Prutechnik GmbH, material: 100Cr6 (equivalent to SUJ2)). The SRV disk on which a film made of the composition of the present invention was formed was set on the test bed of the SRV5 tester, and 0.1 g of an engine oil (Exxon Mobil, chemically synthesized oil for gasoline and diesel engines 10W-30 SM/CF) was dropped on the film. Sliding the SRV cylinder for 12 hours under pressed with a load of 20 N, at a speed of 30 Hz and a sliding distance of 2 mm. Coefficient of friction was measured for each 1 hour. After that, engine oil was removed, the depth of wear scar was measured by surface roughness measurement equipment (SURFCOM1400D) by the comparison between the heights of sliding part and un-sliding part. The SRV cylinder, which is a corresponding material, was observed using microscope to determine the width of wear scar. The average coefficient of dynamic friction was calculated from the average of the coefficient of friction measured for each 1 hour.

Claims (10)

  1. A composition, comprising:
           (A) a binder resin;
           (B) a hard particle; and
           (C) a solid lubricant;
           wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
  2. The composition according to claim 1, wherein the solid lubricant is selected from the group consisting of molybdenum disulfide or graphite.
  3. The composition according to claim 1, wherein the binder resin is selected from the group consisting of polyamideimide, polyimide, epoxy resin, phenol resin, polyamide, polybenzimidazole, polyphenyl sulfonate and polyether ether ketone.
  4. The composition according to claim 1, further comprises (D) a solvent.
  5. A film comprising (A) a binder resin; (B) a hard particle and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method.
  6. The film according to claim 5, wherein the solid lubricant is selected from the group consisting of molybdenum disulfide or graphite.
  7. The film according to claim 5, wherein the binder resin is selected from the group consisting of polyamideimide, polyimide, epoxy resin, phenol resin, polyamide, polybenzimidazole, polyphenyl sulfonate and polyether ether ketone.
  8. A sliding member having the film any of claims 5 to 7.
  9. The sliding member according to claim 8, wherein the sliding member is a swash plate of a compressor, an engine tappet, a camshaft, a crankshaft, an engine metal, an engine piston, a piston ring, a gear, a door lock, a brake shim or a brake clip.
  10. A method for forming a lubricating film on surface of a member, comprising the steps of:
           (I) preparing a composition comprising (A) a binder resin, (B) a hard particle, and (C) a solid lubricant, wherein the hard particle comprises metal tungsten particles with 0.5 to 10 micrometers of average particle size measured by laser diffraction scattering method,
           (II) applying the composition on surface of a member; and
           (III) heat-curing the applied composition, thereby forming a lubricating film on the surface of the member.
PCT/JP2019/047025 2018-12-03 2019-12-02 Composition, film formed from the composition, sliding member having the film, and method for producing the same WO2020116390A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018226541A JP2020090562A (en) 2018-12-03 2018-12-03 Composition, coating film formed using the same, sliding member having said coating film, and manufacturing method thereof
JP2018-226541 2018-12-03

Publications (1)

Publication Number Publication Date
WO2020116390A1 true WO2020116390A1 (en) 2020-06-11

Family

ID=68887097

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/047025 WO2020116390A1 (en) 2018-12-03 2019-12-02 Composition, film formed from the composition, sliding member having the film, and method for producing the same

Country Status (2)

Country Link
JP (1) JP2020090562A (en)
WO (1) WO2020116390A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000265953A (en) 1999-03-17 2000-09-26 Toyota Autom Loom Works Ltd Compressor
EP1894987A1 (en) * 2006-08-30 2008-03-05 HONDA MOTOR CO., Ltd. Double-layer lubrication coating composition, double-layer lubrication coating and piston having same coating
EP2048392A2 (en) * 2007-10-10 2009-04-15 Daido Metal Company Ltd. Sliding bearing
EP2530317A1 (en) * 2011-06-03 2012-12-05 Perkins Engines Company Limited Bearing coating for fuel lubricated fuel pumps
JP2017201165A (en) 2016-05-03 2017-11-09 マーレ インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツングMAHLE International GmbH Piston for internal combustion engine with skirt
EP3346031A1 (en) * 2017-01-10 2018-07-11 Garware-Wall Ropes Limited Multifunctional polymer composite yarn

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000265953A (en) 1999-03-17 2000-09-26 Toyota Autom Loom Works Ltd Compressor
EP1894987A1 (en) * 2006-08-30 2008-03-05 HONDA MOTOR CO., Ltd. Double-layer lubrication coating composition, double-layer lubrication coating and piston having same coating
EP2048392A2 (en) * 2007-10-10 2009-04-15 Daido Metal Company Ltd. Sliding bearing
EP2530317A1 (en) * 2011-06-03 2012-12-05 Perkins Engines Company Limited Bearing coating for fuel lubricated fuel pumps
JP2017201165A (en) 2016-05-03 2017-11-09 マーレ インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツングMAHLE International GmbH Piston for internal combustion engine with skirt
EP3346031A1 (en) * 2017-01-10 2018-07-11 Garware-Wall Ropes Limited Multifunctional polymer composite yarn

Also Published As

Publication number Publication date
JP2020090562A (en) 2020-06-11

Similar Documents

Publication Publication Date Title
JP5060223B2 (en) Piston for internal combustion engine
EP1894987B1 (en) Double-layer lubrication coating composition, double-layer lubrication coating and piston having same coating
US7634963B2 (en) Piston ring comprising a coated running surface, and coating agent
JP4993908B2 (en) Resin composition, sliding member and sliding device
KR101771660B1 (en) sliding member sliding damper coating method using the coating composition and this
JP6133916B2 (en) Manufacturing method of sliding member and manufacturing method of piston
JP2004019759A (en) Sliding member
JP2009068584A (en) Coating structure for sliding
JP6211924B2 (en) Sliding resin composition
US20160097015A1 (en) Bearing material
WO2020116390A1 (en) Composition, film formed from the composition, sliding member having the film, and method for producing the same
US11180654B2 (en) Composition, film formed from the composition, sliding member having the film, and method for producing the same
JP6114180B2 (en) Coating composition for sliding member
JP7146833B2 (en) Coating composition for forming dry lubricating coating, dry lubricating coating, and sliding member
JP5783398B2 (en) Swing and rotary cam lifter and overhead valve engine
JP2022532146A (en) Anti-friction coating formulation composition
KR20230074142A (en) anti-friction coating composition
JPH10246149A (en) Coating material for slide part and piston ring
JP7315153B2 (en) Coating composition for sliding member and sliding member
KR101729028B1 (en) Coating compositions of sliding members for the swash plate of the swash plate type compressor

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19820896

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 24/08/2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19820896

Country of ref document: EP

Kind code of ref document: A1