WO2015133131A1 - Coating composition for lubricating coating film - Google Patents

Coating composition for lubricating coating film Download PDF

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Publication number
WO2015133131A1
WO2015133131A1 PCT/JP2015/001128 JP2015001128W WO2015133131A1 WO 2015133131 A1 WO2015133131 A1 WO 2015133131A1 JP 2015001128 W JP2015001128 W JP 2015001128W WO 2015133131 A1 WO2015133131 A1 WO 2015133131A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating film
component
lubricating coating
weight
composition
Prior art date
Application number
PCT/JP2015/001128
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.
Priority to CN201580012055.7A priority Critical patent/CN106062105B/en
Priority to KR1020167027502A priority patent/KR20160141744A/en
Priority to JP2016555634A priority patent/JP2017514928A/en
Priority to EP15757740.4A priority patent/EP3114182B1/en
Priority to US15/123,266 priority patent/US10294441B2/en
Publication of WO2015133131A1 publication Critical patent/WO2015133131A1/en

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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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/20—Condensation polymers of aldehydes or ketones
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic 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
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/02—Carbon; Graphite
    • 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
    • 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
    • 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
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • 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
    • 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
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/28—Polyoxyalkylenes of alkylene oxides containing 2 carbon atoms only
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B35/00—Piston pumps specially adapted for elastic fluids and characterised by the driving means to their working members, or by combination with, or adaptation to, specific driving engines or motors, not otherwise provided for
    • 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
    • F16C33/201—Composition of the plastic
    • 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
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D3/00—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive
    • F16D3/02—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive adapted to specific functions
    • F16D3/06—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive adapted to specific functions specially adapted to allow axial displacement
    • 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
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
    • 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
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
    • F16D69/02—Compositions of linings; Methods of manufacturing
    • F16D69/025—Compositions based on an organic binder
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J1/00—Pistons; Trunk pistons; Plungers
    • F16J1/01—Pistons; Trunk pistons; Plungers characterised by the use of particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/44—Free-space packings
    • F16J15/447—Labyrinth packings
    • F16J15/4472—Labyrinth packings with axial path
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
    • 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
    • F16N—LUBRICATING
    • F16N15/00—Lubrication with substances other than oil or grease; Lubrication characterised by the use of particular lubricants in particular apparatus or conditions
    • 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
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    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/04—Polyethene
    • 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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    • C10M107/44—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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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    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0413—Carbon; Graphite; Carbon black used as base material
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    • C10M2201/061—Carbides; Hydrides; Nitrides
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    • C—CHEMISTRY; METALLURGY
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    • C10M2201/0623—Oxides; Hydroxides; Carbonates or bicarbonates 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
    • 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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    • C10M2201/1006—Compounds containing silicon 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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    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C10M2205/0225—Ethene 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/1003—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • C10M2209/1013—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/003—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • 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
    • 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
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • 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
    • 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
    • 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
    • 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
    • F16C2208/00—Plastics; Synthetic resins, e.g. rubbers
    • F16C2208/80—Thermosetting resins
    • 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
    • F16C33/208—Methods of manufacture, e.g. shaping, applying coatings
    • 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
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D2200/00—Materials; Production methods therefor
    • F16D2200/006—Materials; Production methods therefor containing fibres or particles
    • F16D2200/0073—Materials; Production methods therefor containing fibres or particles having lubricating properties

Definitions

  • the present invention relates to a coating composition for a lubricating coating film. Moreover, the present invention relates to a lubricating coating film obtained by curing the coating composition for a lubricating coating film, a sliding member provided with a lubricating coating film, and a method for manufacturing the sliding member.
  • a sliding member provided with a binder including a phenolic resin and an epoxy resin and with a coating film including a solid lubricant is known.
  • the abovementioned coating film lacks flexibility, and in such cases, adhesion between a base material and the coating film may be impaired.
  • the flexibility of the coating film is meagre, and therefore cracks can occur in the coating film during bending or such when processing the base material.
  • the ability of the coating film to follow deformation of the base material is meagre, when a location of a bend is scratched, the coating film may peel away.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2013-189569
  • An object of the present invention is to provide a coating composition for a lubricating coating film capable of forming a lubricating coating film having a high level of flexibility on surfaces of various base materials.
  • an object of the present invention is to provide a coating composition for a lubricating coating film capable of forming a lubricating coating film having a high level of adhesion with the surfaces of various types of base materials, and particularly with the surfaces of base materials made of metal, and also having an excellent following capability, and capable of providing a sliding member that can maintain an excellent sliding characteristic for a long period of time through the lubricating coating film.
  • another object of the present invention is to use the coating composition for a lubricating coating film to provide a lubricating coating film, a sliding member provided with the lubricating coating film, and a method for manufacturing the sliding member.
  • the inventors of the present invention discovered that by controlling: (i) the blending ratio of phenolic resin, which is a binder, and epoxy resin, and (ii) the epoxy equivalent weight of the epoxy resin (defined by the number average molecular weight per the number of epoxy groups in a single molecule), in a lubricating coating film including phenolic resin, epoxy resin, and a solid lubricant, a lubricating coating film having a high level of flexibility and exhibiting excellent adhesion with a base material and an excellent ability to follow the deformation of a base material can be formed, and thereby arrived at the present invention.
  • a first object of the present invention is achieved by a coating composition for a lubricating coating film including: (A) a phenolic resin, (B) an epoxy resin having an epoxy equivalent weight of 600 to 4000, and (C) at least one type of solid lubricant; and a weight ratio of component (A) per the total weight of component (A) and component (B) is at least 50 weight %.
  • the epoxy equivalent weight of component (B) is alternatively 600 to 3300 or preferably 800 to 1200.
  • the weight ratio of component (A) per the total weight of component (A) and component (B) is preferably at least 60 weight % and not more than 80 weight %.
  • Component (C) may contain at least one or more types of substances selected from fluororesin, polyethylene resin, polyamide resin, and mixtures thereof.
  • Component (C) preferably contains one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof.
  • component (C) includes (C1) a fluororesin and (C2) one or more types of a metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof, and the weight ratio of component (C1) to component (C2) is preferably in a range of from 50:50 to 90:10.
  • the coating composition for a lubricating coating film of the present invention can contain 1 to 200 parts by weight of component (C) per 100 parts by weight of the total weight of component (A) and component (B).
  • the coating composition for a lubricating coating film of the present invention is used for forming a coating film.
  • the present invention also relates to a lubricating coating film obtained by curing the coating composition for a lubricating coating film.
  • the lubricating coating film of the present invention is obtained by curing the coating composition for a lubricating coating film, and the Erichsen value (JIS Z 2247) when the coating composition for a lubricating coating film is cured at a film thickness of 10 to 20 micro-meters is preferably 8.0 mm or greater.
  • the present invention also relates to a sliding member provided with the lubricating coating film.
  • the sliding member can be a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
  • the present invention also relates to a method for manufacturing a sliding member provided with a base material having the lubricating coating film formed on a surface, the method thereof including: - a step of applying the coating composition for a lubricating coating film onto a surface of the base material, and - a step of heating the coating composition for a lubricating coating film to form a lubricating coating film on the surface of the base material.
  • the base material preferably contains metal.
  • the method for manufacturing a sliding member of the present invention may further include a step of pressing or punching the base material having the lubricating coating film formed on a surface thereof.
  • the sliding member can be a crankshaft, compressor shaft, a slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
  • the present invention also relates to formation of a lubricating coating film by curing the coating composition for a lubricating coating film on a sliding member.
  • Specific examples of the sliding member are preferably those described above.
  • the coating composition for a lubricating coating film according to the present invention can form a lubricating coating film having a high level of flexibility on surfaces of various types of base materials.
  • the coating composition for a lubricating coating film of the present invention can form a lubricating coating film having a high level of adhesion even with a base material made from a deformable substance such as metal, and because the following capability of the lubricating coating film is high, the generation of cracking in the lubricating coating film and/or peeling of the lubricating coating film from the base material can be avoided or reduced.
  • the lubricating coating film obtained through the coating composition for a lubricating coating film of the present invention contains a solid lubricant, and therefore the lubricating coating film is provided with an excellent sliding characteristic. Moreover, the lubricating coating film obtained through the coating composition for a lubricating coating film of the present invention exhibits a high level of flexibility, and therefore it functions as a lubricating coating film with superior sliding durability. Accordingly, a lubricating coating film formed on a surface of a base material through the coating composition for a lubricating coating film according to the present invention can maintain an excellent sliding characteristic for a long period of time.
  • the lubricating coating film of the present invention is highly flexible and exhibits excellent adhesion and following capability, and therefore, for example, if the above-described coating film is formed on the surface of a base material having a sheet, film, or plate form, even if the base material is bent or the like, cracking of the coating film and peeling of the coating film from the base material will not occur or the extent thereof will be minimal. Accordingly, after a lubricating coating film is formed on a surface of a base material according to the present invention, the base material can be moulded to manufacture a sliding member, and a sliding member can be efficiently manufactured.
  • a sliding member having a lubricating coating film with a high level of flexibility and with excellent adhesion and following capability can be easily produced, and the productivity of a sliding member can be improved.
  • a sliding member can be manufactured by pressing, punching, or the like the base material, and the sliding member can be efficiently manufactured.
  • this type of sliding member include a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
  • the coating composition for a lubricating coating film of the present invention preferably contains, as component (C), fluororesin and microparticles including one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof, the coefficient of friction of the resulting lubricating coating film can be further reduced, and the wear resistance of the lubricating coating film under high load conditions can be further increased.
  • component (C) fluororesin and microparticles including one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof
  • a first embodiment of the present invention is a coating composition for lubricating coating film including: (A) a phenolic resin, (B) an epoxy resin having an epoxy equivalent weight of 600 to 4000 (defined by the number average molecular weight per the number of epoxy groups in a single molecule), and (C) at least one type of solid lubricant; and a ratio of the weight % of component (A) per the total weight % of component (A) and component (B) is at least 50 weight %.
  • composition of the present invention contains phenolic resin as component (A).
  • Component (A) may be a single type of phenolic resin, or may be a mixture of two or more types thereof.
  • the phenolic resin is a resin obtained by a condensation reaction of phenol, cresol, bisphenol A, or other phenolic compounds and formaldehyde or another aldehyde in the presence of an acidic catalyst or a basic catalyst, and of these, phenolic resins condensed with an acidic catalyst are called novolac-type phenolic resins, and those condensed with a basic catalyst are called resol-type phenolic resins.
  • the phenolic resin as component (A) is not particularly limited, and either a novolac-type phenolic resin or a resol-type phenolic resin may be used, but a resol-type phenolic resin is preferred. Moreover, a resin in which methylol groups are introduced is included, and a phenolic resin having a portion or all of the introduced methylol groups alkyl-etherified with an alcohol having 6 or fewer carbon atoms can be used.
  • a commercially available phenolic resin can be used as the phenolic resin.
  • examples of commercially available phenolic resins include Sumilite Resin PR-HF-3, Sumilite Resin PR-HF-6, Sumilite Resin PR-53194, Sumilite Resin PR-53195, Sumilite Resin PR-54869, Sumilite Resin PR-16382, Sumilite Resin PR-51939, Sumilite Resin PR-53153, Sumilite Resin PR-53364, Sumilite Resin PR-53365, and Sumilite Resin PR-50702 (all produced by Sumitomo Bakelite Co., Ltd.); Phenolite TD-2131, Phenolite TD-2106, Phenolite TD-2093, Phenolite TD-2091, Phenolite TD-2090, Phenolite VH-4150, Phenolite VH-4170, Phenolite VH-4240, Phenolite KH-1160, Phenolite KH-1163, Phenolite KH
  • a preferable phenolic resin is a resol-type phenolic resin having a hydroxyl group equivalent in a range of 80 to 200 g/eq, and a resol-type phenolic resin having a hydroxyl group equivalent in a range of 100 to 130 g/eq is particularly preferred.
  • the amount of component (A) in the composition of the present invention is 50 weight % or greater based on the total weight % of components (A) and (B) in the composition, but 55 weight % or greater is preferable, 60 weight % or greater is more preferable, and 65 weight % or greater is even more preferable. If the amount of component (A) in the composition of the present invention is less than the abovementioned lower limit based on the total weight % of components (A) and (B) in the composition, even if the below-described component (B) is used, for example, the flexibility of the obtained lubricating coating film will be insufficient (Erichsen value of less than 8.0 mm).
  • a high level of flexibility can be imparted to the lubricating coating film obtained from the composition of the present invention by setting the amount of component (A) in the composition of the present invention to be 50 weight % or greater based on the total weight % of components (A) and (B) in the composition, and combining this with other conditions.
  • the amount of component (A) in the composition of the present invention is preferably not more than 85 weight %, more preferably not more than 80 weight %, even more preferably not more than 75 weight %, and particularly preferably not more than 70 weight % based on the total weight % of components (A) and (B) in the composition.
  • the amount of component (A) in the composition of the present invention can be, for example, 50 to 85 weight %, 50 to 80 weight %, 50 to 75 weight %, or 50 to 70 weight % based on the total weight % of components (A) and (B) in the composition. More particularly, the amount thereof is preferably in a range of not less than 60 weight % to not more than 80 weight %.
  • composition of the present invention contains epoxy resin having an epoxy equivalent weight of 600 to 4000 as component (B).
  • Component (B) may be a single type of epoxy resin, or a mixture of two or more types thereof.
  • the epoxy equivalent weight is defined by the number average molecular weight per the number of epoxy groups in a single molecule. If the number of epoxy groups in a single molecule of epoxy resin is one, the value of that number average molecular weight is the epoxy equivalent weight. If the number of epoxy groups in a single molecule of epoxy resin is two or more, the number average molecular weight of the epoxy resin divided by the number of epoxy groups is the epoxy equivalent weight. Note that the epoxy equivalent weight of epoxy resin can also be determined by the method described by JIS K 7236.
  • the epoxy resin of component (B) has an epoxy equivalent weight of 600 to 4000, but an epoxy equivalent weight of 600 to 3300 is preferable, an epoxy equivalent weight of 800 to 1200 is more preferable, and from the perspective of improving flexibility, an epoxy equivalent weight of 850 to 1100 is most preferable.
  • a high level of flexibility with an Erichsen value of 8.0 mm or greater can be imparted to the lubricating coating film resulting from the cure of the composition of the present invention by setting the epoxy equivalent weight of component (B) in the composition of the present invention to be in a range of 600 to 4000, and combining this with other conditions.
  • the epoxy equivalent weight of component (B) is the summation of M x X (A x /A).
  • an epoxy resin by itself does not have an epoxy equivalent weight that corresponds to a range of 600 to 4000
  • the epoxy resin is mixed and used with another epoxy resin, resulting in an overall epoxy equivalent weight of 600 to 4000
  • the epoxy resin thereof can be used as a structural component of component (B).
  • use of a mixture of epoxy resins for which the epoxy equivalent weights of the single epoxy resins correspond to a range of 600 to 4000 as component (B) is preferred.
  • the epoxy resin is not particularly limited, and one or more types may be selected and used including bisphenol based epoxy resin, amine based epoxy resin, phenol novolac based epoxy resin, cresol novolac based epoxy resin, resorcinol based epoxy resin, phenol aralkyl based epoxy resin, naphthol aralkyl based epoxy resin, dicyclopentadiene based epoxy resin, epoxy resin having a biphenyl backbone, isocyanate modified epoxy resin, tetraphenyl ethane based epoxy resin, triphenyl methane based epoxy resin, fluorene based epoxy resin, and the like.
  • bisphenol based epoxy resin is an epoxy resin for which two phenolic hydroxyl groups of a bisphenol compound have been glycidylated, and examples include a bisphenol A type, a bisphenol F type, a bisphenol AD type, a bisphenol S type, or halogen or alkyl substitutes, hydrogenated products, dimer acid-modified products, or the like of these bisphenols.
  • the bisphenol based epoxy resin is not limited to monomers, and polymers having a plurality of repeating units can also be favourably used.
  • Examples of commercially available bisphenol A type epoxy resin include “jER (registered trademark)” 825, 828, 834, 1001, 1002, 1003, 1003F, 1004, 1004AF, 1005F, 1006FS, 1007, 1009, and 1010 (the above-described are products of Mitsubishi Chemical Corporation), and the like.
  • Examples of brominated bisphenol A type epoxy resin include “jER (registered trademark)” 505, 5050, 5051, 5054, and 5057 (the above-described are products of Mitsubishi Chemical Corporation), and the like.
  • Examples of commercially available hydrogenated bisphenol A type epoxy resin include ST5080, ST4000D, ST4100D, and ST5100 (the above-described are products of the Nippon Steel Chemical Co., Ltd.).
  • Examples of commercially available bisphenol F type epoxy resin products include "jER (registered trademark)” 806, 807, 4002P, 4004P, 4005P, 4007P, 4009P, and 4010P (the above-described are products of Mitsubishi Chemical Corporation), “Epototo (registered trademark)” YDF2001 and YDF2004 (the above-described are products of the Nippon Steel Chemical Co., Ltd.), and the like.
  • Examples of tetramethyl bisphenol F type epoxy resin include YSLV-80XY (product of the Nippon Steel Chemical Co., Ltd.), and the like.
  • bisphenol S type epoxy resin examples include "Epiclon (registered trademark)" EXA-154 (from DIC Corporation), and the like.
  • amine based epoxy resin examples include tetraglycidyl diaminodiphenyl methane, triglycidyl aminophenol, triglycidyl aminocresol, tetraglycidyl xylylene diamine, and halogen or alkynol substitutes, hydrogenated products, or the like of these.
  • Examples of the tetraglycidyl diaminodiphenyl methane include "Sumi-Epoxy (registered trademark)” ELM434 (from Sumitomo Chemical Co., Ltd.), YH434L (from Nippon Steel Chemical Co., Ltd.), “jER (registered trademark)” 604 (from Mitsubishi Chemical Corporation), “Araldite (registered trademark)” MY720 and MY721 (the above-described are products of Huntsman Advanced Materials), and the like.
  • triglycidyl aminophenol and triglycidyl aminocresol examples include "Sumi-Epoxy (registered trademark)” ELM100 and ELM120 (the above-described are products of Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY0500, MY0510, and MY0600 (the above-described are products of Huntsman Advanced Materials), “jER (registered trademark)” 630 (Mitsubishi Chemical Corporation), and the like.
  • tetraglycidyl xylylene diamine and hydrogenated products thereof examples include TETRAD-X and TETRAD-C (the above-described are products of the Mitsubishi Gas Chemical Company, Inc.), and the like.
  • Examples of commercially available products of phenol novolac based epoxy resin include "jER (registered trademark)” 152 and 154 (the above-described are products of Mitsubishi Chemical Corporation), “Epiclon (registered trademark)” N-740, N-770, and N-775 (the above-described are products of DIC Corporation), and the like.
  • cresol novolac based epoxy resin examples include "Epiclon (registered trademark)" N-660, N-665, N-670, N-673, and N-695 (the above-described are products of DIC Corporation), EOCN-1020, EOCN-102S, and EOCN-104S (the above-described are products of Nippon Kayaku Co., Ltd.), and the like.
  • resorcinol based epoxy resin examples include "Denacol (registered trademark)" EX-201 (from Nagase ChemteX Corporation), and the like.
  • Examples of commercially available products of dicyclopentadiene based epoxy resin include "Epiclon (registered trademark)” HP-7200, HP-7200L, HP-7200H, HP-7200HH, and HP-7200HHH (the above-described are products of DIC Corporation), “Tactix (registered trademark)” 558 (from Huntsman Advanced Materials), XD-1000-1L and XD-1000-2L (the above-described are products of Nippon Kayaku Co., Ltd.), and the like.
  • Examples of commercially available products of epoxy resin having a biphenyl backbone include "jER (registered trademark)" YX4000H, YX4000, and YL6616 (the above-described are products of Mitsubishi Chemical Corporation), NC-3000 (from Nippon Kayaku Co., Ltd.), and the like.
  • Examples of commercially available products of isocyanate modified epoxy resin include AER4152 and XAC4151 with an oxazolidone ring (from Asahi Kasei Epoxy Co., Ltd.) and ACR1348 (from ADEKA Corporation), and the like.
  • Examples of commercially available tetraphenyl ethane based epoxy resin products include the tetrakis(glycidyl oxyphenyl)ethane based epoxy resin "jER (registered trademark)" 1031 (from Mitsubishi Chemical Corporation), and the like.
  • triphenyl methane based epoxy resin examples include "jER (registered trademark)” 1032S50 (from Mitsubishi Chemical Corporation), “Tactix (registered trademark)” 742 (from Huntsman Advanced Materials), and the like.
  • fluorene based epoxy resin products examples include "OGSOL (registered trademark)” (from Osaka Gas Chemicals Co., Ltd.), LME10169 (from Huntsman Advanced Materials), and the like.
  • the epoxy resin may also be an epoxy resin containing an epoxy resin having a functionality of 3 or higher.
  • epoxy resins having a functionality of 3 or higher include tetraglycidyl diaminodiphenyl methane, triglycidyl aminophenol, triglycidyl aminocresol, tetraglycidyl xylylene diamine, and halogen or alkynol substitutes and hydrogenated products thereof, phenol novolac based epoxy resin, cresol novolac based epoxy resin, dicyclopentadiene based epoxy resin with a functionality of 3 or higher, tetraphenyl ethane based epoxy resin, triphenyl methane based epoxy resin, and the like.
  • Component (B) is preferably an epoxy resin having an epoxy equivalent weight in a range of 600 to 4000 on an independent basis, and examples of such epoxy resins include the commercially available bisphenol A epoxy resin products of "jER (registered trademark)" 872, 1001, 1002, 1003, 1003F, 1004, 1004AF, 1005F, 1006FS, 1007, and 1007FS (the above-described are products of Mitsubishi Chemical Corporation), "Epiclon (registered trademark)” 1050, 1055, 2050, 3050, 4050, and 7050 (the above-described are products of DIC Corporation), brominated bisphenol A type epoxy resins of "jER (registered trademark)” 153, 153-60T, 153-60M, 1121N-80M, and 1123P-75M (the above-described are products of Mitsubishi Chemical Corporation), the commercially available bisphenol F epoxy resin products of "jER (registered trademark)” 4004P, 4005P, 4007P, and 4010P (the above-described are
  • the epoxy resin may also be a rubber-modified epoxy resin.
  • a rubber-modified epoxy resin includes CTBN (carboxy-terminated butadiene-nitrile rubber) modified epoxy resin.
  • CTBN-modified epoxy resin having an epoxy equivalent weight in a range of 600 to 4000 on an independent basis includes Epiclon TSR-601 (from DIC Corporation) and the like.
  • the amount of component (B) in the composition of the present invention is 50 weight % or less based on the total weight % of components (A) and (B) in the composition, but 45 weight % or less is preferable, 40 weight % or less is more preferable, and 35 weight % or less is even more preferable.
  • the amount of component (B) in the composition of the present invention is preferably at least 15 weight % based on the total weight % of components (A) and (B) in the composition, more preferably at least 20 weight %, even more preferably at least 25 weight %, and particularly preferably at least 30 weight %.
  • the amount of component (B) in the composition of the present invention can be, for example, 15 to 50 weight %, 20 to 45 weight %, 25 to 40 weight %, or 30 to 40 weight % based on the total weight % of components (A) and (B) in the composition.
  • the amount thereof is preferably at least 20 weight % and not more than 40 weight % based on the total weight % of components (A) and (B) in the composition.
  • components (A) and (B) are thermosetting resin components that become a binder for the hereinafter described component (C), and the thermosetting resin component substantially preferably includes only component (A) and component (B).
  • composition of the present invention contains at least one type of solid lubricant as component (C).
  • component (C) By containing a solid lubricant in this manner, the composition of the present invention can form a highly lubricative coating film on a base material surface, and the lubricating coating film can maintain an excellent sliding characteristic for a long period of time. Accordingly, as a coating composition for a lubricating coating film, the composition of the present invention containing component (C) can impart a lubricating coating film exhibiting a high level of adhesion and excellent sliding durability.
  • the solid lubricant is not particularly limited, and a single type of solid lubricant may be used, or two or more types thereof may be used in combination.
  • the solid lubricant is in a particle form, and the average (median) particle size thereof is preferably not more than 15 micro-meters, and is more preferably from 0.2 to 12 micro-meters.
  • the average particle size referred to herein means the volume average particle size measured using a laser diffraction type particle size distribution measuring apparatus.
  • solid lubricant examples include microparticles of organic compounds including fluororesin (particularly polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, and the like), polyethylene resin, polyamide resin, and the like, microparticles of inorganic compounds including titanium nitride, titanium oxide, molybdenum disulfide, graphite, aluminum oxide, silicon nitride, boron nitride, silicon dioxide, zinc oxide, and the like, microparticles of metals such as lead, and mixtures thereof.
  • organic compounds including fluororesin (particularly polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, and the like), polyethylene resin, polyamide resin, and the like
  • microparticles of inorganic compounds including titanium nitride, titanium oxide, molybdenum disulfide, graphite, aluminum oxide, silicon nitride, boro
  • the composition of the present invention preferably contains, as a solid lubricant, one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof, and more preferably contains a fluororesin as a component (C1), and one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof as a component (C2).
  • the coefficient of friction of the lubricating coating film obtained by the composition of the present invention can be further reduced, and the wear resistance of the lubricating coating film under high load conditions can be further increased particularly by using microparticles of a fluororesin, which is component (C1), in conjunction with a specific metal oxide or metal nitride that is component (C2).
  • the weight % ratio of component (C1) and component (C2) is not particularly limited, but is preferably in a range of 50:50 to 90:10, and particularly preferably in a range of 60:40 to 85:15.
  • microparticles of the (C1) fluororesin are preferably used in combination with microparticles of metal oxide or metal nitride of the (C2) component at the abovementioned weight ratio.
  • composition of the present invention contains a combination of microparticles including the above-described specific solid lubricant, the coefficient of friction of the lubricating coating film obtained through the composition of the present invention can be further reduced, and the wear resistance of the lubricating coating film under high load conditions can be further increased.
  • composition of the present invention can be particularly favourably cured through heating.
  • composition of the present invention can contain component (C) at an amount of 1 to 200 parts by weight per 100 parts by weight of the total weight of components (A) and (B).
  • component (C) is an organic solid lubricant
  • the composition of the present invention preferably contains component (C) at an amount of 1 to 100 parts by weight, and more preferably 10 to 50 parts by weight per 100 parts by weight of the total weight of components (A) and (B).
  • component (C) is an inorganic solid lubricant
  • the composition of the present invention preferably contains component (C) at an amount of 1 to 50 parts by weight, and more preferably 2 to 20 parts by weight per 100 parts by weight of the total weight of components (A) and (B).
  • composition of the present invention may also contain, as appropriate, various other components according to the application within a scope that does not hinder the technical effects of the present invention.
  • the composition of the present invention can contain a thermosetting resin including an organic resin curable by heat other than components (A) and (B) or mixtures thereof.
  • the chemical reaction involved in the curing is not particularly limited, and the thermosetting resin thereof may be one cured by condensation polymerization, one cured by radical addition polymerization, or a mixture thereof.
  • thermosetting resin may be curable at normal temperature (approximately 25 C), or may be curable by heating (approximately 30 C or greater). Furthermore, a plurality of thermosetting resins may be mixed and used.
  • thermosetting resin examples include urethane resin, urea resin, melamine resin, unsaturated polyester resin, polyimide resin, polyamide-imide resin, diallyl phthalate resin, silicone resin, and the like, and mixtures thereof. From the perspective of being able to further improve the heat resistance of the lubricating coating film, use of a polyamide-imide resin or the like as the thermosetting resin is more preferable. Furthermore, from the perspective of being able to further improve adhesiveness with a base material, the use of urethane resin or the like is preferred. Adhesiveness with the base material and flexibility can be further improved by using urethane resin.
  • the type of urethane resin is not particularly limited, but a urethane resin obtained by reacting (c1) at least one type of polyol and (c2) at least 1 type of isocyanate is preferred.
  • the (c1) polyol is not particularly limited as long as it has two or more hydroxyl groups in a single molecule, and a conventionally known polyol can be used. Examples include polyester polyol, polycarbonate polyol, polyether polyol, poly caprolactone polyol, polyalkylene polyol, and the like. The polyol may be used singularly, or two or more types may be used in combination.
  • polyester polyol examples include polyester polyol obtained through a condensation polymerization reaction of polyvalent carboxylic acid and polyol.
  • polyvalent carboxylic acid examples include succinic acid, terephthalic acid, isophthalic acid, dodecanedioc acid, 1,5-naphthalate, 2,6-naphthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacylic acid, dodecamethylene dicarboxylate, and other dicarboxylic acids, and the like.
  • straight-chain dicarboxylic acids are preferred, and the number of carbon atoms of the straight-chain dicarboxylic acid is preferably 4 or more, and 4 to 12 carbon atoms is more preferable. Moreover, the number of carbon atoms of the straight-chain dicarboxylic acid is most preferably an even number.
  • this type of straight-chain dicarboxlyic acid include succinic acid, adipic acid, suberic acid, sebacylic acid, dodecanedioic acid, and the like.
  • examples of the polyol include propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, cyclohexanediol, and the like.
  • the polyvalent carboxylic acid and the polyol may each be used singularly, or two or more types thereof may be used in combination.
  • the hydroxyl value of the polyester polyol is preferably 2 to 160 mgKOH/g.
  • Polycarbonate diol is a compound having the abovementioned repeating units and two hydroxyl groups in a molecule.
  • Polycarbonate diol can be synthesized from aliphatic and/or alicyclic diol through the various methods described in Polymer Review Vol. 9 (1964), pages 9 to 20 by Schell.
  • preferable diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, 2,5-hexane diol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, and the like.
  • the range of the average molecular weight of the polycarbonate diol is ordinarily 500 to 5000 in terms of the number average molecular weight, and a polycarbonate diol having an average molecular weight of 1000 to 3000 is preferably used, and preferably, the polymer ends thereof are substantially all hydroxyl groups.
  • a polycarbonate that has been polyfunctionalized by using a small amount of a compound having 3 or more hydroxyl groups in a single molecule for example, trimethylol ethane, trimethylol propane, hexanetriol, pentaerythritol, and the like, may also be used.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers or block copolymers thereof, and a polyoxyalkylene modified form of bisphenol A.
  • polycaprolactone polyol is a polycaprolactone polyol obtained by ring-opening addition polymerization of a lactone compound to a polyol.
  • the polyol the same polyols as those described above with the polyester polyol may be used.
  • the lactone compound include beta-propiolactone, pivalolactone, delta-valerolactone, epsilon-caprolactone, methyl-epsilon-caprolactone, dimethyl-epsilon-caprolactone, trimethyl-epsilon-caprolactone, and the like.
  • polyalkylene polyol examples include polybutadiene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and the like.
  • polyester polyol or polycarbonate polyol is preferable, polycarbonate polyol is more preferable, and polycarbonate diol is even more preferable.
  • the (c2) isocyanate is not particularly limited as long as it has an isocyanate group in a single molecule, and a conventionally known isocyanate can be used.
  • a conventionally known isocyanate can be used as the isocyanate.
  • polyisocyanate having two or more isocyanate groups in a single molecule is preferable.
  • a single type of isocyanate may be used, or two or more types may be used in combination.
  • polyisocyanate examples include 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4-diphenylmethane diisocyanate (2,4-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, tolylene diisocyanate (TDI, 2,4-TDI, 2,6-TDI, or mixtures thereof), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diis
  • diisocyanate or triisocyanate are preferred.
  • diisocyanate and triisocyanate include isophorone diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3'-dichloro-4,4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, and the like.
  • the urethane resin is more preferably a polycarbonate based urethane resin obtained by reacting (c1-1) polycarbonate polyol and (c2-1) diisocyanate.
  • the amount of the thermosetting resin in the composition of the present invention may be, for example, 1 to 50 weight %, 2 to 45 weight %, or 3 to 30 weight % based on the total weight % of the composition including the solvent, pigment, and the like.
  • thermosetting resin in the composition of the present invention substantially includes only component (A) and component (B), and thus the amount of the thermosetting resin is preferably 3 to 30 weight %, and preferably 5 to 20 weight % based on the total weight % of the composition.
  • thermosetting resin component that become a binder for component (C) and the like, and from the perspective of the technical effects of the present invention, the thermosetting resin component preferably includes substantially only component (A) and component (B). If other thermosetting resin components are contained at an amount of 10 weight % or more with respect to the sum of component (A) and (B), the technical effects of the present invention could be lost in some cases.
  • composition of the present invention contains a radical-polymerizable thermosetting resin
  • the composition of the present invention is preferably further blended with a radical thermal polymerization initiator.
  • a radical polymerization initiator curing can be achieved in a short period of time, the generation of heat at the time of curing can be suppressed, and the impact on the base material can be reduced.
  • radical thermal polymerization initiators examples include ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile, dibutyl peroxide, benzoyl peroxide, 1,1'-azobis(1-acetoxy-1-phenyl ethane), and the like.
  • the radical thermal polymerization initiator may be used singularly, or as a combination of two or more types.
  • the blending amount of the radical polymerization initiator may be, for example, 0.1 to 5 weight % based on the total weight % of the composition of the present invention.
  • the composition of the present invention can also contain, for example, at least one type of film-forming auxiliary agent.
  • a film-forming auxiliary agent includes epoxy silane or the like.
  • a single film-forming auxiliary agent may be used independently, or a plurality of film-forming auxiliary agents may be used in combination.
  • epoxy silane is used as a film-forming auxiliary agent, it can be used, for example, in a range of 0.1 to 5 weight % based on the total weight % of the composition of the present invention.
  • the composition of the present invention can contain at least one type of solvent.
  • a single type of solvent may be used independently, or a plurality of solvents may be used in combination.
  • the solvent is not particularly limited, but organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), chloroform, dichloromethane, chlorobenzene, dichlorobenzene, N-methylpyrrolidone (NMP), toluene, dioxane, propanol, gamma--picoline, acetonitrile, dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), and the like are preferred, methylethylketone, methyl isobutyl ketone, cyclohexanone, and other ketone based organic solvents are more preferred.
  • the solvent can be appropriately used, for example, in a range of 10 to 800 parts by weight, preferably 20 to 600 parts by weight, and more preferably 30 to 500 parts by weight based on 100 parts by weight of the total weight of components (A) and (B) of the composition of the present invention.
  • the composition of the present invention can contain at least one type of silicone rubber.
  • a single type of silicone rubber may be used independently, or a plurality of silicone rubbers may be used in combination.
  • the temperature dependency of the viscosity of the composition of the present invention can be reduced by blending silicone rubber with the composition thereof.
  • a conventionally known silicone rubber can be appropriately used as the silicone rubber, and for example, the silicone rubber can be used in a range of 0.001 to 3 weight % based on the total weight % of the composition of the present invention.
  • the composition of the present invention can contain at least one type of antifoaming agent.
  • a single type of antifoaming agent may be used independently, or a plurality of antifoaming agents may be used in combination. Foaming during application of the composition of the present invention can be suppressed by blending the composition thereof with an antifoaming agent, thereby facilitating application work.
  • an antifoaming agent a conventionally known agent can be appropriately used, and for example, the antifoaming agent can be used in a range of 0.00001 to 1 weight% based on the total weight % of the composition of the present invention.
  • the composition of the present invention can contain at least one type of thickening agent.
  • a single type of thickening agent may be used independently, or a plurality of thickening agents may be used in combination.
  • the viscosity of the composition can be increased to thereby reduce dripping during application by blending the composition thereof with a thickening agent, thereby facilitating application work.
  • a conventionally known agent can be appropriately used, and for example, the thickening agent can be used in a range of 0.001 to 1 weight % based on the total weight % of the composition of the present invention.
  • composition of the present invention may also contain other components within a range that does not hinder the effect of the present invention.
  • other components include a release agent, surface treatment agent, fire retardant, levelling agent, antifoaming agent, thixotropic agent, thermal stabilizer, light stabilizer, ultraviolet absorbing agent, colouring agent, coupling agent, metal alkoxide, and the like.
  • the composition of the present invention can contain carbon black or another pigment as a colouring agent in a range of 0.1 to 5 weight % based on the total weight % of the composition (100%).
  • composition of the present invention can be produced by appropriately mixing components (A) to (C) and the various other abovementioned optional components.
  • composition of the present invention can be favourably used as a coating composition for a lubricating coating film in the formation of a lubricating coating film and can form a lubricating coating film having a high level of flexibility on the surfaces of various base materials.
  • the material of the base material is not particularly limited, and for example, iron, aluminum, copper, or another metal, rubber, resin, and the like, and combinations thereof can be used.
  • the base material preferably contains metal, and is more preferably made of metal.
  • the surface of the base material may be subjected to a surface roughening treatment through electrolytic etching, chemical etching, shot blast, or the like, or may be subjected to a chemical treatment through phosphate or the like in order to improve adhesiveness as needed.
  • a coating film can be formed on a surface of a base material by applying the already-described coating composition for a lubricating coating film onto a surface of the base material, and then curing the composition by heating.
  • the method for applying the coating composition for lubricating coating film onto a surface of a base material is not particularly limited, and for example, conventionally known application methods can be used such as roll coating, coil coating, screen printing, spraying, tumbling, immersing, brush coating, and the like.
  • levelling is preferably implemented by leaving the coating to sit for a certain amount of time.
  • the lubricating property of the obtained coating film can be improved through levelling.
  • the base material may be preheated, but from the perspective of operation ease, the coating composition is preferably applied at room temperature (approximately 25 C).
  • the coating composition for a lubricating coating film contains a solvent
  • the coating composition is left, for example, for 1 to 60 minutes at room temperature, or for example, it is preferably heated for 1 to 60 minutes at 40 to 80 C to remove the solvent.
  • the composition film coated onto the surface of the base material is heated, and a cured coating film can be obtained.
  • the heating conditions can be appropriately adjusted, and for example, heating can be implemented for 5 to 90 minutes at 170 to 200 C. If necessary, heating for the abovementioned solvent removal and resin curing can be performed simultaneously.
  • the present invention also relates to a lubricating coating film obtained in this manner.
  • the thickness of the coating film of the present invention may be appropriately selected, and for example, can be 1 to 50 micro-meters, preferably 2 to 25 micro-meters, and more preferably 3 to 15 micro-meters.
  • the lubricating coating film of the present invention exhibits a high level of flexibility in particular, and if a lubricating coating film having a film thickness of 10 to 20 micro-meters is formed in particular, a lubricating coating film can be imparted having an Erichsen value (in accordance with JIS Z 2247 issued in 2006) of 8.0 mm or greater, and favourably 8.5 mm or greater.
  • a film thickness of 10 to 20 micro-meters is a condition for specifying a lubricating coating film obtained by the coating composition for a lubricating coating film with that physical property value (Erichsen value), and it goes without saying that lubricating coating films having film thicknesses outside of this range are also included in the subject of protection of the present invention.
  • the definition of the Erichsen value in the present invention is a measurement value based on JIS Z 2247.
  • the coating composition for a lubricating coating film contains component (C), and therefore, the coating film of the present invention can be used as a superior lubricating coating film.
  • the lubricating coating film of the present invention can be favourably used on the surface of a sliding member.
  • the type of sliding member is not particularly limited, and examples include sliding members made of rubber, plastic, or metal.
  • Example of sliding members made of metal include a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, and pressurization pad.
  • sliding members made of rubber include a timing belt, conveyor belt, body seal for a sunroof, glass run, weather stripping, oil seal, packing, wiper blade, doctor blade, charging roller, developing roller, toner supply roller, transfer roller, heat roller, pressurization roller, cleaning blade, paper feed roller, transport roller, doctor blade, intermediate transfer belt, intermediate transfer drum, heat belt, and the like.
  • sliding members made of plastic include gears, door panels, instrument panels, door locks, bearings, and pads.
  • the form of the sliding member is also not particularly limited, and for example, the sliding member may have a fibrous form or may contain fibres.
  • the sliding member may have a fibrous form or may contain fibres.
  • Examples of sliding members having a fibrous form and of sliding members containing fibres include vehicle seats, carpet, tire cord, seatbelts, and the like.
  • the sliding member of the present invention is provided with a base material having a lubricating coating film formed on the surface thereof, and for example, can be produced through a step of applying the coating composition for a lubricating coating film onto a surface of a base material, and a step of heating the coating composition for a lubricating coating film to form a lubricating coating film on a surface of the base material.
  • the base material preferably contains metal, and more preferably is made of metal.
  • the method of producing the sliding member of the present invention may further include a step of pressing or punching the base material having the lubricating coating film formed on a surface thereof.
  • the sliding member can be produced by pressing, punching, or the like the base material, and the sliding member can be efficiently produced.
  • sliding member examples include a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad, but a brake pad, brake pad clip, brake shim, and a brake insulator are preferable, a brake pad and brake pad clip are more preferable, and a brake pad clip is even more preferable.
  • the present invention can be used in various types of products provided with a lubricating coating film, and in particular, can be favourably used in the production of a sliding member provided with a lubricating coating film.
  • Coating compositions for lubricating coating films for Examples 1 to 13 and Comparative Examples 1 to 5 were obtained by mixing each component shown in Table 1-1, 1-2 and Table 2 at the ratios shown in Table 1-1, 1-2 and Table 2. Note that the numeric figures shown in Table 1-1, 1-2 and Table 2 represent parts by weight. Also, the solid lubricants used in the tables are as follows.
  • -Fluororesin microparticles Polytetrafluoroethylene powder (dry solid content of 100 weight%) having a median diameter of 2 to 7 micro-meters as measured by laser diffraction scattering type particle size distribution method.
  • -Titanium nitride microparticles Black titanium nitride powder (dry solid content of 100 weight%) having a median diameter of 0.8 to 1.0 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
  • -Titanium oxide microparticles White rutile type titanium oxide powder (dry solid content of 100 weight%) having a median diameter of 0.3 to 0.5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
  • -Boron nitride particles White boron nitride powder (dry solid content of 100 weight%) having a median diameter of 5 to 11 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
  • -Alumina particles White alumina powder (dry solid content of 100 weight%) having a median diameter of 0.3 to 0.5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
  • -Silicon nitride microparticles White silicon nitride powder (dry solid content of 100 weight%) having a median diameter of 1 to 5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
  • -Silicon dioxide microparticles White silicon dioxide powder (dry solid content of 100 weight%) having a particle diameter of the primary particles of 5 to 50 nm as observed with a scanning electron microscope.
  • -Molybdenum disulfide microparticles Molybdenum disulfide powder (dry solid content of 100 weight%) having a median diameter of 1 to 6 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
  • -Graphite microparticles Graphite powder (dry solid content of 100 weight%) having a median diameter of 3 to 5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
  • -Carbon black Black carbon black powder (dry solid content of 100 weight%) having a particle diameter of the primary particles of 20 to 40 nm as observed with a scanning electron microscope.
  • Phenolic resin Resol type phenolic resin (hydroxyl group equivalent 111 g/eq, cured color: gold)
  • Epoxy resin 1 jER (registered trademark) 1004 (from Mitsubishi Chemical Corporation)
  • Epoxy resin 2 jER (registered trademark) 872 (from Mitsubishi Chemical Corporation)
  • Epoxy resin 3 jER (registered trademark) 1009 (from Mitsubishi Chemical Corporation)
  • Epoxy resin 4 Epiclon TSR-960 (from DIC Corporation)
  • Epoxy resin 5 Epiclon TSR-601 (from DIC Corporation)
  • Epoxy resin 6 jER (registered trademark) 1256 (from Mitsubishi Chemical Corporation)
  • a bar coater (#44) was used to apply each coating composition for a lubricating coating film onto a surface of a stainless steel plate (SUS301) that had been solvent degreased, and the coating composition was then heated for 20 minutes at a temperature of 200 C to prepare a cured coating film having a thickness of 15 to 20 micro-meters.
  • test pieces obtained as described above were secured to an Erichsen tester (COTES from Coating Tester KK), and subjected to punch pressing at a speed of 5 to 10 mm/minute, and the pressing distances at which cracking and peeling were first generated in the coating were measured. Testing was conducted at least three times, and the measured values of each of the tests were averaged to obtain the Erichsen value.
  • the measured Erichsen values (mm) are shown in Tables 1 and 2. Note that an Erichsen value of 8.0 mm or greater indicates a coating film with good flexibility.
  • a surface roughness gage (SURFCOM 1400D from Tokyo Seimitsu Co., Ltd.) was used to measure the difference in surface levels of the stainless steel plate between the sliding locations and non-sliding locations, and the difference thereof was recorded as the wear depth (units: micro-meters).
  • A Less than 5micro-meters
  • B 5 to 10 micro-meters
  • C 11 to 19 micro-meters
  • D (20 micro-meters or greater, or the base material is exposed)
  • the coating compositions for lubricating coating films of Examples 1 to 13 can form a lubricating coating film having excellent flexibility with an Erichsen value of 8 mm or greater.
  • the coating composition contains fluororesin microparticles and a prescribed metal oxide or metal nitride in particular, the lubricating coating film can be provided with not only excellent flexibility, but also with a low frictional property and high wear resistance.
  • the lubricating coating films formed from the coating compositions for lubricating coating films of Comparative Examples 1 to 5 exhibit little flexibility.
  • the results for Comparative Examples 2 to 5 in particular indicated inferior wear resistance regardless of compositions containing titanium nitride and titanium oxide, and thus in addition to the specification of components (A) and (B), which are characteristics of the invention of the present application, if the ratio of component (A) to component (B) is not within the prescribed range, it is difficult to realize the technical effects of the invention of the present application regardless of the type of solid lubricant that is used.

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Abstract

To provide a coating composition for a lubricating coating film capable of forming a lubricating coating film having a high level of flexibility on surfaces of various base materials. <Resolution Means> A coating composition for a lubricating coating film including: (A) a phenolic resin, (B) an epoxy resin having an epoxy equivalent weight of 600 to 4000, and (C) at least one type of solid lubricant; and having a weight ratio of component (A) to the total weight of component (A) and component (B) of at least 50 weight %.

Description

COATING COMPOSITION FOR LUBRICATING COATING FILM
The present invention relates to a coating composition for a lubricating coating film. Moreover, the present invention relates to a lubricating coating film obtained by curing the coating composition for a lubricating coating film, a sliding member provided with a lubricating coating film, and a method for manufacturing the sliding member.
As described in, for example, Japanese Unexamined Patent Application Publication No. 2013-189569, a sliding member provided with a binder including a phenolic resin and an epoxy resin and with a coating film including a solid lubricant is known.
However, in some cases, the abovementioned coating film lacks flexibility, and in such cases, adhesion between a base material and the coating film may be impaired. For example, if the abovementioned coating film is formed on a surface of a sheet shaped based material made of metal, the flexibility of the coating film is meagre, and therefore cracks can occur in the coating film during bending or such when processing the base material. Moreover, because the ability of the coating film to follow deformation of the base material is meagre, when a location of a bend is scratched, the coating film may peel away.
The various disadvantages attributable to the low flexibility of the coating film with respect to this type of base material are particularly problematic with lubricating coating films that are formed for the purpose of lubrication on a surface of a sliding member that contacts another member for a long period of time.
Patent Document 1: Japanese Unexamined Patent Application Publication No. 2013-189569
An object of the present invention is to provide a coating composition for a lubricating coating film capable of forming a lubricating coating film having a high level of flexibility on surfaces of various base materials.
More specifically, an object of the present invention is to provide a coating composition for a lubricating coating film capable of forming a lubricating coating film having a high level of adhesion with the surfaces of various types of base materials, and particularly with the surfaces of base materials made of metal, and also having an excellent following capability, and capable of providing a sliding member that can maintain an excellent sliding characteristic for a long period of time through the lubricating coating film.
Moreover, another object of the present invention is to use the coating composition for a lubricating coating film to provide a lubricating coating film, a sliding member provided with the lubricating coating film, and a method for manufacturing the sliding member.
As a result of a detailed investigation to solve the abovementioned problems, the inventors of the present invention discovered that by controlling:
(i) the blending ratio of phenolic resin, which is a binder, and epoxy resin, and
(ii) the epoxy equivalent weight of the epoxy resin (defined by the number average molecular weight per the number of epoxy groups in a single molecule),
in a lubricating coating film including phenolic resin, epoxy resin, and a solid lubricant, a lubricating coating film having a high level of flexibility and exhibiting excellent adhesion with a base material and an excellent ability to follow the deformation of a base material can be formed, and thereby arrived at the present invention.
Namely, a first object of the present invention is achieved by a coating composition for a lubricating coating film including:
(A) a phenolic resin,
(B) an epoxy resin having an epoxy equivalent weight of 600 to 4000, and
(C) at least one type of solid lubricant; and
a weight ratio of component (A) per the total weight of component (A) and component (B) is at least 50 weight %.
The epoxy equivalent weight of component (B) is alternatively 600 to 3300 or preferably 800 to 1200.
The weight ratio of component (A) per the total weight of component (A) and component (B) is preferably at least 60 weight % and not more than 80 weight %.
Component (C) may contain at least one or more types of substances selected from fluororesin, polyethylene resin, polyamide resin, and mixtures thereof.
Component (C) preferably contains one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof.
Moreover, component (C) includes (C1) a fluororesin and (C2) one or more types of a metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof, and the weight ratio of component (C1) to component (C2) is preferably in a range of from 50:50 to 90:10.
The coating composition for a lubricating coating film of the present invention can contain 1 to 200 parts by weight of component (C) per 100 parts by weight of the total weight of component (A) and component (B).
The coating composition for a lubricating coating film of the present invention is used for forming a coating film.
The present invention also relates to a lubricating coating film obtained by curing the coating composition for a lubricating coating film.
The lubricating coating film of the present invention is obtained by curing the coating composition for a lubricating coating film, and the Erichsen value (JIS Z 2247) when the coating composition for a lubricating coating film is cured at a film thickness of 10 to 20 micro-meters is preferably 8.0 mm or greater.
The present invention also relates to a sliding member provided with the lubricating coating film.
The sliding member can be a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
The present invention also relates to a method for manufacturing a sliding member provided with a base material having the lubricating coating film formed on a surface, the method thereof including:
- a step of applying the coating composition for a lubricating coating film onto a surface of the base material, and
- a step of heating the coating composition for a lubricating coating film to form a lubricating coating film on the surface of the base material.
The base material preferably contains metal.
The method for manufacturing a sliding member of the present invention may further include a step of pressing or punching the base material having the lubricating coating film formed on a surface thereof.
The sliding member can be a crankshaft, compressor shaft, a slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
The present invention also relates to formation of a lubricating coating film by curing the coating composition for a lubricating coating film on a sliding member. Specific examples of the sliding member are preferably those described above.
The coating composition for a lubricating coating film according to the present invention can form a lubricating coating film having a high level of flexibility on surfaces of various types of base materials.
In particular, the coating composition for a lubricating coating film of the present invention can form a lubricating coating film having a high level of adhesion even with a base material made from a deformable substance such as metal, and because the following capability of the lubricating coating film is high, the generation of cracking in the lubricating coating film and/or peeling of the lubricating coating film from the base material can be avoided or reduced.
The lubricating coating film obtained through the coating composition for a lubricating coating film of the present invention contains a solid lubricant, and therefore the lubricating coating film is provided with an excellent sliding characteristic. Moreover, the lubricating coating film obtained through the coating composition for a lubricating coating film of the present invention exhibits a high level of flexibility, and therefore it functions as a lubricating coating film with superior sliding durability. Accordingly, a lubricating coating film formed on a surface of a base material through the coating composition for a lubricating coating film according to the present invention can maintain an excellent sliding characteristic for a long period of time.
The lubricating coating film of the present invention is highly flexible and exhibits excellent adhesion and following capability, and therefore, for example, if the above-described coating film is formed on the surface of a base material having a sheet, film, or plate form, even if the base material is bent or the like, cracking of the coating film and peeling of the coating film from the base material will not occur or the extent thereof will be minimal. Accordingly, after a lubricating coating film is formed on a surface of a base material according to the present invention, the base material can be moulded to manufacture a sliding member, and a sliding member can be efficiently manufactured.
Hence, with the method for manufacturing a sliding member of the present invention, a sliding member having a lubricating coating film with a high level of flexibility and with excellent adhesion and following capability can be easily produced, and the productivity of a sliding member can be improved.
In particular, if a base material is made of metal, after a lubricating coating film has been formed on the surface of the base material, a sliding member can be manufactured by pressing, punching, or the like the base material, and the sliding member can be efficiently manufactured. Examples of this type of sliding member include a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
Moreover, if the coating composition for a lubricating coating film of the present invention preferably contains, as component (C), fluororesin and microparticles including one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof, the coefficient of friction of the resulting lubricating coating film can be further reduced, and the wear resistance of the lubricating coating film under high load conditions can be further increased.
A first embodiment of the present invention is a coating composition for lubricating coating film including:
(A) a phenolic resin,
(B) an epoxy resin having an epoxy equivalent weight of 600 to 4000 (defined by the number average molecular weight per the number of epoxy groups in a single molecule), and
(C) at least one type of solid lubricant; and
a ratio of the weight % of component (A) per the total weight % of component (A) and component (B) is at least 50 weight %.
<Component (A)>
The composition of the present invention contains phenolic resin as component (A). Component (A) may be a single type of phenolic resin, or may be a mixture of two or more types thereof.
The phenolic resin is a resin obtained by a condensation reaction of phenol, cresol, bisphenol A, or other phenolic compounds and formaldehyde or another aldehyde in the presence of an acidic catalyst or a basic catalyst, and of these, phenolic resins condensed with an acidic catalyst are called novolac-type phenolic resins, and those condensed with a basic catalyst are called resol-type phenolic resins.
The phenolic resin as component (A) is not particularly limited, and either a novolac-type phenolic resin or a resol-type phenolic resin may be used, but a resol-type phenolic resin is preferred. Moreover, a resin in which methylol groups are introduced is included, and a phenolic resin having a portion or all of the introduced methylol groups alkyl-etherified with an alcohol having 6 or fewer carbon atoms can be used.
A commercially available phenolic resin can be used as the phenolic resin. Examples of commercially available phenolic resins include Sumilite Resin PR-HF-3, Sumilite Resin PR-HF-6, Sumilite Resin PR-53194, Sumilite Resin PR-53195, Sumilite Resin PR-54869, Sumilite Resin PR-16382, Sumilite Resin PR-51939, Sumilite Resin PR-53153, Sumilite Resin PR-53364, Sumilite Resin PR-53365, and Sumilite Resin PR-50702 (all produced by Sumitomo Bakelite Co., Ltd.); Phenolite TD-2131, Phenolite TD-2106, Phenolite TD-2093, Phenolite TD-2091, Phenolite TD-2090, Phenolite VH-4150, Phenolite VH-4170, Phenolite VH-4240, Phenolite KH-1160, Phenolite KH-1163, Phenolite KH-1165, Phenolite TD-2093-60M, Phenolite TD-2090-60M, Phenolite LF-4711, Phenolite LF-6161, Phenolite LF-4871, Phenolite LA-7052, Phenolite LA-7054, Phenolite LA-7751, Phenolite LA-1356, and Phenolite LA-3018-50P (the above are produced by DIC Corporation); Shonol BRG-555, Shonol BRG-556, Shonol BRG-558, Shonol CKM-923, Shonol CKM-983, Shonol BKM-2620, Shonol BRL-2854, Shonol BRG-5590M, Shonol CKS-3898, Shonol CKS-3877A, Shonol CKM-908, and Shonol CKM-937 (the above are produced by "Showa Highpolymer Co., Ltd").
In the present invention, a preferable phenolic resin is a resol-type phenolic resin having a hydroxyl group equivalent in a range of 80 to 200 g/eq, and a resol-type phenolic resin having a hydroxyl group equivalent in a range of 100 to 130 g/eq is particularly preferred.
The amount of component (A) in the composition of the present invention is 50 weight % or greater based on the total weight % of components (A) and (B) in the composition, but 55 weight % or greater is preferable, 60 weight % or greater is more preferable, and 65 weight % or greater is even more preferable. If the amount of component (A) in the composition of the present invention is less than the abovementioned lower limit based on the total weight % of components (A) and (B) in the composition, even if the below-described component (B) is used, for example, the flexibility of the obtained lubricating coating film will be insufficient (Erichsen value of less than 8.0 mm).
A high level of flexibility can be imparted to the lubricating coating film obtained from the composition of the present invention by setting the amount of component (A) in the composition of the present invention to be 50 weight % or greater based on the total weight % of components (A) and (B) in the composition, and combining this with other conditions.
On the other hand, the amount of component (A) in the composition of the present invention is preferably not more than 85 weight %, more preferably not more than 80 weight %, even more preferably not more than 75 weight %, and particularly preferably not more than 70 weight % based on the total weight % of components (A) and (B) in the composition.
Accordingly, the amount of component (A) in the composition of the present invention can be, for example, 50 to 85 weight %, 50 to 80 weight %, 50 to 75 weight %, or 50 to 70 weight % based on the total weight % of components (A) and (B) in the composition. More particularly, the amount thereof is preferably in a range of not less than 60 weight % to not more than 80 weight %.
< Component (B)>
The composition of the present invention contains epoxy resin having an epoxy equivalent weight of 600 to 4000 as component (B). Component (B) may be a single type of epoxy resin, or a mixture of two or more types thereof.
The epoxy equivalent weight is defined by the number average molecular weight per the number of epoxy groups in a single molecule. If the number of epoxy groups in a single molecule of epoxy resin is one, the value of that number average molecular weight is the epoxy equivalent weight. If the number of epoxy groups in a single molecule of epoxy resin is two or more, the number average molecular weight of the epoxy resin divided by the number of epoxy groups is the epoxy equivalent weight. Note that the epoxy equivalent weight of epoxy resin can also be determined by the method described by JIS K 7236.
The epoxy resin of component (B) has an epoxy equivalent weight of 600 to 4000, but an epoxy equivalent weight of 600 to 3300 is preferable, an epoxy equivalent weight of 800 to 1200 is more preferable, and from the perspective of improving flexibility, an epoxy equivalent weight of 850 to 1100 is most preferable. A high level of flexibility with an Erichsen value of 8.0 mm or greater can be imparted to the lubricating coating film resulting from the cure of the composition of the present invention by setting the epoxy equivalent weight of component (B) in the composition of the present invention to be in a range of 600 to 4000, and combining this with other conditions. However, if the epoxy equivalent weight of component (B) is less than the abovementioned lower limit or exceeds the abovementioned upper limit, the flexibility of the obtained lubricating coating film will be insufficient (Erichsen value of less than 8.0 mm)
If a plurality of epoxy resins are used as component (B), and if the total amount of each epoxy resin is designated by A (parts by weight), the amount of each epoxy resin is designated by Ax (parts by weight), and the epoxy equivalent weight of each epoxy resin is designated by Mx, then in this case, the epoxy equivalent weight of component (B) is the summation of Mx X (Ax/A).
Accordingly, even if an epoxy resin by itself does not have an epoxy equivalent weight that corresponds to a range of 600 to 4000, if the epoxy resin is mixed and used with another epoxy resin, resulting in an overall epoxy equivalent weight of 600 to 4000, the epoxy resin thereof can be used as a structural component of component (B). However, use of a mixture of epoxy resins for which the epoxy equivalent weights of the single epoxy resins correspond to a range of 600 to 4000 as component (B) is preferred.
The epoxy resin is not particularly limited, and one or more types may be selected and used including bisphenol based epoxy resin, amine based epoxy resin, phenol novolac based epoxy resin, cresol novolac based epoxy resin, resorcinol based epoxy resin, phenol aralkyl based epoxy resin, naphthol aralkyl based epoxy resin, dicyclopentadiene based epoxy resin, epoxy resin having a biphenyl backbone, isocyanate modified epoxy resin, tetraphenyl ethane based epoxy resin, triphenyl methane based epoxy resin, fluorene based epoxy resin, and the like.
Generally, bisphenol based epoxy resin is an epoxy resin for which two phenolic hydroxyl groups of a bisphenol compound have been glycidylated, and examples include a bisphenol A type, a bisphenol F type, a bisphenol AD type, a bisphenol S type, or halogen or alkyl substitutes, hydrogenated products, dimer acid-modified products, or the like of these bisphenols. Moreover, the bisphenol based epoxy resin is not limited to monomers, and polymers having a plurality of repeating units can also be favourably used.
Examples of commercially available bisphenol A type epoxy resin include "jER (registered trademark)" 825, 828, 834, 1001, 1002, 1003, 1003F, 1004, 1004AF, 1005F, 1006FS, 1007, 1009, and 1010 (the above-described are products of Mitsubishi Chemical Corporation), and the like. Examples of brominated bisphenol A type epoxy resin include "jER (registered trademark)" 505, 5050, 5051, 5054, and 5057 (the above-described are products of Mitsubishi Chemical Corporation), and the like. Examples of commercially available hydrogenated bisphenol A type epoxy resin include ST5080, ST4000D, ST4100D, and ST5100 (the above-described are products of the Nippon Steel Chemical Co., Ltd.).
Examples of commercially available bisphenol F type epoxy resin products include "jER (registered trademark)" 806, 807, 4002P, 4004P, 4005P, 4007P, 4009P, and 4010P (the above-described are products of Mitsubishi Chemical Corporation), "Epototo (registered trademark)" YDF2001 and YDF2004 (the above-described are products of the Nippon Steel Chemical Co., Ltd.), and the like. Examples of tetramethyl bisphenol F type epoxy resin include YSLV-80XY (product of the Nippon Steel Chemical Co., Ltd.), and the like.
Examples of bisphenol S type epoxy resin include "Epiclon (registered trademark)" EXA-154 (from DIC Corporation), and the like.
Examples of amine based epoxy resin include tetraglycidyl diaminodiphenyl methane, triglycidyl aminophenol, triglycidyl aminocresol, tetraglycidyl xylylene diamine, and halogen or alkynol substitutes, hydrogenated products, or the like of these.
Examples of the tetraglycidyl diaminodiphenyl methane include "Sumi-Epoxy (registered trademark)" ELM434 (from Sumitomo Chemical Co., Ltd.), YH434L (from Nippon Steel Chemical Co., Ltd.), "jER (registered trademark)" 604 (from Mitsubishi Chemical Corporation), "Araldite (registered trademark)" MY720 and MY721 (the above-described are products of Huntsman Advanced Materials), and the like. Examples of triglycidyl aminophenol and triglycidyl aminocresol include "Sumi-Epoxy (registered trademark)" ELM100 and ELM120 (the above-described are products of Sumitomo Chemical Co., Ltd.), "Araldite (registered trademark)" MY0500, MY0510, and MY0600 (the above-described are products of Huntsman Advanced Materials), "jER (registered trademark)" 630 (Mitsubishi Chemical Corporation), and the like. Examples of tetraglycidyl xylylene diamine and hydrogenated products thereof include TETRAD-X and TETRAD-C (the above-described are products of the Mitsubishi Gas Chemical Company, Inc.), and the like.
Examples of commercially available products of phenol novolac based epoxy resin include "jER (registered trademark)" 152 and 154 (the above-described are products of Mitsubishi Chemical Corporation), "Epiclon (registered trademark)" N-740, N-770, and N-775 (the above-described are products of DIC Corporation), and the like.
Examples of commercially available products of cresol novolac based epoxy resin include "Epiclon (registered trademark)" N-660, N-665, N-670, N-673, and N-695 (the above-described are products of DIC Corporation), EOCN-1020, EOCN-102S, and EOCN-104S (the above-described are products of Nippon Kayaku Co., Ltd.), and the like.
Specific examples of resorcinol based epoxy resin include "Denacol (registered trademark)" EX-201 (from Nagase ChemteX Corporation), and the like.
Examples of commercially available products of dicyclopentadiene based epoxy resin include "Epiclon (registered trademark)" HP-7200, HP-7200L, HP-7200H, HP-7200HH, and HP-7200HHH (the above-described are products of DIC Corporation), "Tactix (registered trademark)" 558 (from Huntsman Advanced Materials), XD-1000-1L and XD-1000-2L (the above-described are products of Nippon Kayaku Co., Ltd.), and the like.
Examples of commercially available products of epoxy resin having a biphenyl backbone include "jER (registered trademark)" YX4000H, YX4000, and YL6616 (the above-described are products of Mitsubishi Chemical Corporation), NC-3000 (from Nippon Kayaku Co., Ltd.), and the like.
Examples of commercially available products of isocyanate modified epoxy resin include AER4152 and XAC4151 with an oxazolidone ring (from Asahi Kasei Epoxy Co., Ltd.) and ACR1348 (from ADEKA Corporation), and the like.
Examples of commercially available tetraphenyl ethane based epoxy resin products include the tetrakis(glycidyl oxyphenyl)ethane based epoxy resin "jER (registered trademark)" 1031 (from Mitsubishi Chemical Corporation), and the like.
Examples of commercially available products of triphenyl methane based epoxy resin include "jER (registered trademark)" 1032S50 (from Mitsubishi Chemical Corporation), "Tactix (registered trademark)" 742 (from Huntsman Advanced Materials), and the like.
Examples of commercially available fluorene based epoxy resin products include "OGSOL (registered trademark)" (from Osaka Gas Chemicals Co., Ltd.), LME10169 (from Huntsman Advanced Materials), and the like.
From the viewpoint of heat resistance, modulus of elasticity, and other dynamic properties, the epoxy resin may also be an epoxy resin containing an epoxy resin having a functionality of 3 or higher.
Examples of epoxy resins having a functionality of 3 or higher include tetraglycidyl diaminodiphenyl methane, triglycidyl aminophenol, triglycidyl aminocresol, tetraglycidyl xylylene diamine, and halogen or alkynol substitutes and hydrogenated products thereof, phenol novolac based epoxy resin, cresol novolac based epoxy resin, dicyclopentadiene based epoxy resin with a functionality of 3 or higher, tetraphenyl ethane based epoxy resin, triphenyl methane based epoxy resin, and the like.
Component (B) is preferably an epoxy resin having an epoxy equivalent weight in a range of 600 to 4000 on an independent basis, and examples of such epoxy resins include the commercially available bisphenol A epoxy resin products of "jER (registered trademark)" 872, 1001, 1002, 1003, 1003F, 1004, 1004AF, 1005F, 1006FS, 1007, and 1007FS (the above-described are products of Mitsubishi Chemical Corporation), "Epiclon (registered trademark)" 1050, 1055, 2050, 3050, 4050, and 7050 (the above-described are products of DIC Corporation), brominated bisphenol A type epoxy resins of "jER (registered trademark)" 153, 153-60T, 153-60M, 1121N-80M, and 1123P-75M (the above-described are products of Mitsubishi Chemical Corporation), the commercially available bisphenol F epoxy resin products of "jER (registered trademark)" 4004P, 4005P, 4007P, and 4010P (the above-described are products of Mitsubishi Chemical Corporation), and the like.
The epoxy resin may also be a rubber-modified epoxy resin. An example of a rubber-modified epoxy resin includes CTBN (carboxy-terminated butadiene-nitrile rubber) modified epoxy resin. An example of a commercially available CTBN-modified epoxy resin having an epoxy equivalent weight in a range of 600 to 4000 on an independent basis includes Epiclon TSR-601 (from DIC Corporation) and the like.
The amount of component (B) in the composition of the present invention is 50 weight % or less based on the total weight % of components (A) and (B) in the composition, but 45 weight % or less is preferable, 40 weight % or less is more preferable, and 35 weight % or less is even more preferable.
On the other hand, the amount of component (B) in the composition of the present invention is preferably at least 15 weight % based on the total weight % of components (A) and (B) in the composition, more preferably at least 20 weight %, even more preferably at least 25 weight %, and particularly preferably at least 30 weight %.
Accordingly, the amount of component (B) in the composition of the present invention can be, for example, 15 to 50 weight %, 20 to 45 weight %, 25 to 40 weight %, or 30 to 40 weight % based on the total weight % of components (A) and (B) in the composition. In particular, the amount thereof is preferably at least 20 weight % and not more than 40 weight % based on the total weight % of components (A) and (B) in the composition.
Note that components (A) and (B) are thermosetting resin components that become a binder for the hereinafter described component (C), and the thermosetting resin component substantially preferably includes only component (A) and component (B).
<Component (C)>
The composition of the present invention contains at least one type of solid lubricant as component (C). By containing a solid lubricant in this manner, the composition of the present invention can form a highly lubricative coating film on a base material surface, and the lubricating coating film can maintain an excellent sliding characteristic for a long period of time. Accordingly, as a coating composition for a lubricating coating film, the composition of the present invention containing component (C) can impart a lubricating coating film exhibiting a high level of adhesion and excellent sliding durability.
The solid lubricant is not particularly limited, and a single type of solid lubricant may be used, or two or more types thereof may be used in combination.
The solid lubricant is in a particle form, and the average (median) particle size thereof is preferably not more than 15 micro-meters, and is more preferably from 0.2 to 12 micro-meters. Note that the average particle size referred to herein means the volume average particle size measured using a laser diffraction type particle size distribution measuring apparatus.
Examples of the solid lubricant include microparticles of organic compounds including fluororesin (particularly polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, and the like), polyethylene resin, polyamide resin, and the like, microparticles of inorganic compounds including titanium nitride, titanium oxide, molybdenum disulfide, graphite, aluminum oxide, silicon nitride, boron nitride, silicon dioxide, zinc oxide, and the like, microparticles of metals such as lead, and mixtures thereof.
From the perspective of improving wear resistance of the lubricating coating film under high load conditions, the composition of the present invention preferably contains, as a solid lubricant, one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof, and more preferably contains a fluororesin as a component (C1), and one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof as a component (C2). The coefficient of friction of the lubricating coating film obtained by the composition of the present invention can be further reduced, and the wear resistance of the lubricating coating film under high load conditions can be further increased particularly by using microparticles of a fluororesin, which is component (C1), in conjunction with a specific metal oxide or metal nitride that is component (C2).
When the solid lubricant includes the (C1) component of fluororesin and the (C2) component including one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof, the weight % ratio of component (C1) and component (C2) is not particularly limited, but is preferably in a range of 50:50 to 90:10, and particularly preferably in a range of 60:40 to 85:15.
From the perspective of improving wear resistance, microparticles of the (C1) fluororesin are preferably used in combination with microparticles of metal oxide or metal nitride of the (C2) component at the abovementioned weight ratio.
If the composition of the present invention contains a combination of microparticles including the above-described specific solid lubricant, the coefficient of friction of the lubricating coating film obtained through the composition of the present invention can be further reduced, and the wear resistance of the lubricating coating film under high load conditions can be further increased.
Note that if a black coloured to coloured solid lubricant such as molybdenum disulfide, graphite, or titanium nitride is blended in the composition of the present invention, the composition can be particularly favourably cured through heating.
The composition of the present invention can contain component (C) at an amount of 1 to 200 parts by weight per 100 parts by weight of the total weight of components (A) and (B).
If component (C) is an organic solid lubricant, the composition of the present invention preferably contains component (C) at an amount of 1 to 100 parts by weight, and more preferably 10 to 50 parts by weight per 100 parts by weight of the total weight of components (A) and (B).
If component (C) is an inorganic solid lubricant, the composition of the present invention preferably contains component (C) at an amount of 1 to 50 parts by weight, and more preferably 2 to 20 parts by weight per 100 parts by weight of the total weight of components (A) and (B).
In addition to components (A) to (C), the composition of the present invention may also contain, as appropriate, various other components according to the application within a scope that does not hinder the technical effects of the present invention.
For example, the composition of the present invention can contain a thermosetting resin including an organic resin curable by heat other than components (A) and (B) or mixtures thereof. The chemical reaction involved in the curing is not particularly limited, and the thermosetting resin thereof may be one cured by condensation polymerization, one cured by radical addition polymerization, or a mixture thereof.
The thermosetting resin may be curable at normal temperature (approximately 25 C), or may be curable by heating (approximately 30 C or greater). Furthermore, a plurality of thermosetting resins may be mixed and used.
Examples of the thermosetting resin include urethane resin, urea resin, melamine resin, unsaturated polyester resin, polyimide resin, polyamide-imide resin, diallyl phthalate resin, silicone resin, and the like, and mixtures thereof. From the perspective of being able to further improve the heat resistance of the lubricating coating film, use of a polyamide-imide resin or the like as the thermosetting resin is more preferable. Furthermore, from the perspective of being able to further improve adhesiveness with a base material, the use of urethane resin or the like is preferred. Adhesiveness with the base material and flexibility can be further improved by using urethane resin.
The type of urethane resin is not particularly limited, but a urethane resin obtained by reacting (c1) at least one type of polyol and (c2) at least 1 type of isocyanate is preferred.
The (c1) polyol is not particularly limited as long as it has two or more hydroxyl groups in a single molecule, and a conventionally known polyol can be used. Examples include polyester polyol, polycarbonate polyol, polyether polyol, poly caprolactone polyol, polyalkylene polyol, and the like. The polyol may be used singularly, or two or more types may be used in combination.
Examples of the polyester polyol include polyester polyol obtained through a condensation polymerization reaction of polyvalent carboxylic acid and polyol. Examples of the polyvalent carboxylic acid include succinic acid, terephthalic acid, isophthalic acid, dodecanedioc acid, 1,5-naphthalate, 2,6-naphthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacylic acid, dodecamethylene dicarboxylate, and other dicarboxylic acids, and the like. As the polyvalent carboxylic acid, straight-chain dicarboxylic acids are preferred, and the number of carbon atoms of the straight-chain dicarboxylic acid is preferably 4 or more, and 4 to 12 carbon atoms is more preferable. Moreover, the number of carbon atoms of the straight-chain dicarboxylic acid is most preferably an even number. Specific examples of this type of straight-chain dicarboxlyic acid include succinic acid, adipic acid, suberic acid, sebacylic acid, dodecanedioic acid, and the like. Moreover, examples of the polyol include propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, cyclohexanediol, and the like. The polyvalent carboxylic acid and the polyol may each be used singularly, or two or more types thereof may be used in combination. The hydroxyl value of the polyester polyol is preferably 2 to 160 mgKOH/g.
The polycarbonate polyol is a compound having repeating units expressed by the formula -R-O(C=O)O- (wherein, R represents a divalent aliphatic or alicyclic hydrocarbon group having 2 to 5 carbon atoms) and two or more hydroxyl groups, and examples include polyhexamethylene carbonate polyol, polycyclohexane dimethylene carbonate polyol, and the like.
Polycarbonate diol is a compound having the abovementioned repeating units and two hydroxyl groups in a molecule. Polycarbonate diol can be synthesized from aliphatic and/or alicyclic diol through the various methods described in Polymer Review Vol. 9 (1964), pages 9 to 20 by Schell. Examples of preferable diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, 2,5-hexane diol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, and the like.
The range of the average molecular weight of the polycarbonate diol is ordinarily 500 to 5000 in terms of the number average molecular weight, and a polycarbonate diol having an average molecular weight of 1000 to 3000 is preferably used, and preferably, the polymer ends thereof are substantially all hydroxyl groups. In the present invention, in addition to the diol presented above, a polycarbonate that has been polyfunctionalized by using a small amount of a compound having 3 or more hydroxyl groups in a single molecule, for example, trimethylol ethane, trimethylol propane, hexanetriol, pentaerythritol, and the like, may also be used.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers or block copolymers thereof, and a polyoxyalkylene modified form of bisphenol A.
An example of a polycaprolactone polyol is a polycaprolactone polyol obtained by ring-opening addition polymerization of a lactone compound to a polyol. As the polyol, the same polyols as those described above with the polyester polyol may be used. Furthermore, examples of the lactone compound include beta-propiolactone, pivalolactone, delta-valerolactone, epsilon-caprolactone, methyl-epsilon-caprolactone, dimethyl-epsilon-caprolactone, trimethyl-epsilon-caprolactone, and the like.
Examples of polyalkylene polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and the like.
As the (c1) polyol, polyester polyol or polycarbonate polyol is preferable, polycarbonate polyol is more preferable, and polycarbonate diol is even more preferable.
The (c2) isocyanate is not particularly limited as long as it has an isocyanate group in a single molecule, and a conventionally known isocyanate can be used. However, as the isocyanate, polyisocyanate having two or more isocyanate groups in a single molecule is preferable. A single type of isocyanate may be used, or two or more types may be used in combination.
Examples of the polyisocyanate include 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4-diphenylmethane diisocyanate (2,4-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, tolylene diisocyanate (TDI, 2,4-TDI, 2,6-TDI, or mixtures thereof), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like.
As the polyisocyanate, diisocyanate or triisocyanate are preferred. Examples of diisocyanate and triisocyanate include isophorone diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3'-dichloro-4,4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, and the like.
The urethane resin is more preferably a polycarbonate based urethane resin obtained by reacting (c1-1) polycarbonate polyol and (c2-1) diisocyanate.
The amount of the thermosetting resin in the composition of the present invention may be, for example, 1 to 50 weight %, 2 to 45 weight %, or 3 to 30 weight % based on the total weight % of the composition including the solvent, pigment, and the like.
However, the thermosetting resin in the composition of the present invention substantially includes only component (A) and component (B), and thus the amount of the thermosetting resin is preferably 3 to 30 weight %, and preferably 5 to 20 weight % based on the total weight % of the composition.
Components (A) and (B) are thermosetting resin components that become a binder for component (C) and the like, and from the perspective of the technical effects of the present invention, the thermosetting resin component preferably includes substantially only component (A) and component (B). If other thermosetting resin components are contained at an amount of 10 weight % or more with respect to the sum of component (A) and (B), the technical effects of the present invention could be lost in some cases.
If the composition of the present invention contains a radical-polymerizable thermosetting resin, the composition of the present invention is preferably further blended with a radical thermal polymerization initiator. By including a radical polymerization initiator, curing can be achieved in a short period of time, the generation of heat at the time of curing can be suppressed, and the impact on the base material can be reduced.
Examples of radical thermal polymerization initiators include ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile, dibutyl peroxide, benzoyl peroxide, 1,1'-azobis(1-acetoxy-1-phenyl ethane), and the like. The radical thermal polymerization initiator may be used singularly, or as a combination of two or more types.
The blending amount of the radical polymerization initiator may be, for example, 0.1 to 5 weight % based on the total weight % of the composition of the present invention.
Moreover, the composition of the present invention can also contain, for example, at least one type of film-forming auxiliary agent. An example of a film-forming auxiliary agent includes epoxy silane or the like. With the present invention, a single film-forming auxiliary agent may be used independently, or a plurality of film-forming auxiliary agents may be used in combination. When epoxy silane is used as a film-forming auxiliary agent, it can be used, for example, in a range of 0.1 to 5 weight % based on the total weight % of the composition of the present invention.
Moreover, the composition of the present invention can contain at least one type of solvent. With the present invention, a single type of solvent may be used independently, or a plurality of solvents may be used in combination. The solvent is not particularly limited, but organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), chloroform, dichloromethane, chlorobenzene, dichlorobenzene, N-methylpyrrolidone (NMP), toluene, dioxane, propanol, gamma--picoline, acetonitrile, dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), and the like are preferred, methylethylketone, methyl isobutyl ketone, cyclohexanone, and other ketone based organic solvents are more preferred. The solvent can be appropriately used, for example, in a range of 10 to 800 parts by weight, preferably 20 to 600 parts by weight, and more preferably 30 to 500 parts by weight based on 100 parts by weight of the total weight of components (A) and (B) of the composition of the present invention.
Moreover, the composition of the present invention can contain at least one type of silicone rubber. With the present invention, a single type of silicone rubber may be used independently, or a plurality of silicone rubbers may be used in combination. The temperature dependency of the viscosity of the composition of the present invention can be reduced by blending silicone rubber with the composition thereof. A conventionally known silicone rubber can be appropriately used as the silicone rubber, and for example, the silicone rubber can be used in a range of 0.001 to 3 weight % based on the total weight % of the composition of the present invention.
Moreover, the composition of the present invention can contain at least one type of antifoaming agent. With the present invention, a single type of antifoaming agent may be used independently, or a plurality of antifoaming agents may be used in combination. Foaming during application of the composition of the present invention can be suppressed by blending the composition thereof with an antifoaming agent, thereby facilitating application work. As the antifoaming agent, a conventionally known agent can be appropriately used, and for example, the antifoaming agent can be used in a range of 0.00001 to 1 weight% based on the total weight % of the composition of the present invention.
Moreover, the composition of the present invention can contain at least one type of thickening agent. With the present invention, a single type of thickening agent may be used independently, or a plurality of thickening agents may be used in combination. The viscosity of the composition can be increased to thereby reduce dripping during application by blending the composition thereof with a thickening agent, thereby facilitating application work. As the thickening agent, a conventionally known agent can be appropriately used, and for example, the thickening agent can be used in a range of 0.001 to 1 weight % based on the total weight % of the composition of the present invention.
Furthermore, the composition of the present invention may also contain other components within a range that does not hinder the effect of the present invention. Examples of other components include a release agent, surface treatment agent, fire retardant, levelling agent, antifoaming agent, thixotropic agent, thermal stabilizer, light stabilizer, ultraviolet absorbing agent, colouring agent, coupling agent, metal alkoxide, and the like. For example, the composition of the present invention can contain carbon black or another pigment as a colouring agent in a range of 0.1 to 5 weight % based on the total weight % of the composition (100%).
The composition of the present invention can be produced by appropriately mixing components (A) to (C) and the various other abovementioned optional components.
The composition of the present invention can be favourably used as a coating composition for a lubricating coating film in the formation of a lubricating coating film and can form a lubricating coating film having a high level of flexibility on the surfaces of various base materials.
The material of the base material is not particularly limited, and for example, iron, aluminum, copper, or another metal, rubber, resin, and the like, and combinations thereof can be used. The base material preferably contains metal, and is more preferably made of metal. The surface of the base material may be subjected to a surface roughening treatment through electrolytic etching, chemical etching, shot blast, or the like, or may be subjected to a chemical treatment through phosphate or the like in order to improve adhesiveness as needed.
With the present invention, a coating film can be formed on a surface of a base material by applying the already-described coating composition for a lubricating coating film onto a surface of the base material, and then curing the composition by heating.
The method for applying the coating composition for lubricating coating film onto a surface of a base material is not particularly limited, and for example, conventionally known application methods can be used such as roll coating, coil coating, screen printing, spraying, tumbling, immersing, brush coating, and the like. After the application of the coating composition, levelling is preferably implemented by leaving the coating to sit for a certain amount of time. The lubricating property of the obtained coating film can be improved through levelling. Note that when applying the coating composition, the base material may be preheated, but from the perspective of operation ease, the coating composition is preferably applied at room temperature (approximately 25 C).
Next, if the coating composition for a lubricating coating film contains a solvent, the coating composition is left, for example, for 1 to 60 minutes at room temperature, or for example, it is preferably heated for 1 to 60 minutes at 40 to 80 C to remove the solvent.
After the solvent is removed, the composition film coated onto the surface of the base material is heated, and a cured coating film can be obtained. The heating conditions can be appropriately adjusted, and for example, heating can be implemented for 5 to 90 minutes at 170 to 200 C. If necessary, heating for the abovementioned solvent removal and resin curing can be performed simultaneously.
The present invention also relates to a lubricating coating film obtained in this manner. The thickness of the coating film of the present invention may be appropriately selected, and for example, can be 1 to 50 micro-meters, preferably 2 to 25 micro-meters, and more preferably 3 to 15 micro-meters.
The lubricating coating film of the present invention exhibits a high level of flexibility in particular, and if a lubricating coating film having a film thickness of 10 to 20 micro-meters is formed in particular, a lubricating coating film can be imparted having an Erichsen value (in accordance with JIS Z 2247 issued in 2006) of 8.0 mm or greater, and favourably 8.5 mm or greater. Note that a film thickness of 10 to 20 micro-meters is a condition for specifying a lubricating coating film obtained by the coating composition for a lubricating coating film with that physical property value (Erichsen value), and it goes without saying that lubricating coating films having film thicknesses outside of this range are also included in the subject of protection of the present invention. Moreover, as other bend related standards corresponding to the Erichsen value defined by the abovementioned JIS Z 2247 (2006) standard, the "Metallic materials - Sheet and strip - Erichsen cupping test" defined by the ISO 20482 (2013) standard, and other standards exist. However, as described previously, the definition of the Erichsen value in the present invention is a measurement value based on JIS Z 2247.
The coating composition for a lubricating coating film contains component (C), and therefore, the coating film of the present invention can be used as a superior lubricating coating film.
The lubricating coating film of the present invention can be favourably used on the surface of a sliding member. The type of sliding member is not particularly limited, and examples include sliding members made of rubber, plastic, or metal.
Example of sliding members made of metal include a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, and pressurization pad.
Examples of sliding members made of rubber include a timing belt, conveyor belt, body seal for a sunroof, glass run, weather stripping, oil seal, packing, wiper blade, doctor blade, charging roller, developing roller, toner supply roller, transfer roller, heat roller, pressurization roller, cleaning blade, paper feed roller, transport roller, doctor blade, intermediate transfer belt, intermediate transfer drum, heat belt, and the like.
Examples of sliding members made of plastic include gears, door panels, instrument panels, door locks, bearings, and pads.
The form of the sliding member is also not particularly limited, and for example, the sliding member may have a fibrous form or may contain fibres. Examples of sliding members having a fibrous form and of sliding members containing fibres include vehicle seats, carpet, tire cord, seatbelts, and the like.
The sliding member of the present invention is provided with a base material having a lubricating coating film formed on the surface thereof, and for example, can be produced through a step of applying the coating composition for a lubricating coating film onto a surface of a base material, and a step of heating the coating composition for a lubricating coating film to form a lubricating coating film on a surface of the base material.
The base material preferably contains metal, and more preferably is made of metal.
The method of producing the sliding member of the present invention may further include a step of pressing or punching the base material having the lubricating coating film formed on a surface thereof.
If the base material is made of metal in particular, after the lubricating coating film is formed on the surface of the base material, the sliding member can be produced by pressing, punching, or the like the base material, and the sliding member can be efficiently produced.
Examples of this type of sliding member include a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad, but a brake pad, brake pad clip, brake shim, and a brake insulator are preferable, a brake pad and brake pad clip are more preferable, and a brake pad clip is even more preferable.
The present invention can be used in various types of products provided with a lubricating coating film, and in particular, can be favourably used in the production of a sliding member provided with a lubricating coating film.
Examples
The present invention is described below with reference to examples, but the present invention is in no way limited thereby.
< Examples 1 to 13 and Comparative Examples 1 to 5>
Coating compositions for lubricating coating films for Examples 1 to 13 and Comparative Examples 1 to 5 were obtained by mixing each component shown in Table 1-1, 1-2 and Table 2 at the ratios shown in Table 1-1, 1-2 and Table 2. Note that the numeric figures shown in Table 1-1, 1-2 and Table 2 represent parts by weight. Also, the solid lubricants used in the tables are as follows.
-Fluororesin microparticles: Polytetrafluoroethylene powder (dry solid content of 100 weight%) having a median diameter of 2 to 7 micro-meters as measured by laser diffraction scattering type particle size distribution method.
-Titanium nitride microparticles: Black titanium nitride powder (dry solid content of 100 weight%) having a median diameter of 0.8 to 1.0 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
-Titanium oxide microparticles: White rutile type titanium oxide powder (dry solid content of 100 weight%) having a median diameter of 0.3 to 0.5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
-Boron nitride particles: White boron nitride powder (dry solid content of 100 weight%) having a median diameter of 5 to 11 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
-Alumina particles: White alumina powder (dry solid content of 100 weight%) having a median diameter of 0.3 to 0.5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
-Silicon nitride microparticles: White silicon nitride powder (dry solid content of 100 weight%) having a median diameter of 1 to 5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
-Silicon dioxide microparticles: White silicon dioxide powder (dry solid content of 100 weight%) having a particle diameter of the primary particles of 5 to 50 nm as observed with a scanning electron microscope.
-Molybdenum disulfide microparticles: Molybdenum disulfide powder (dry solid content of 100 weight%) having a median diameter of 1 to 6 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
-Graphite microparticles: Graphite powder (dry solid content of 100 weight%) having a median diameter of 3 to 5 micro-meters as measured by a laser diffraction scattering type particle size distribution method.
-Carbon black: Black carbon black powder (dry solid content of 100 weight%) having a particle diameter of the primary particles of 20 to 40 nm as observed with a scanning electron microscope.
Table 1-1
Figure JPOXMLDOC01-appb-I000001
Table 1-2
Figure JPOXMLDOC01-appb-I000002
Phenolic resin: Resol type phenolic resin (hydroxyl group equivalent 111 g/eq, cured color: gold)
Epoxy resin 1: jER (registered trademark) 1004 (from Mitsubishi Chemical Corporation)
Epoxy resin 2: jER (registered trademark) 872 (from Mitsubishi Chemical Corporation)
Epoxy resin 3: jER (registered trademark) 1009 (from Mitsubishi Chemical Corporation)
Table 2
Figure JPOXMLDOC01-appb-I000003
Epoxy resin 4: Epiclon TSR-960 (from DIC Corporation)
Epoxy resin 5: Epiclon TSR-601 (from DIC Corporation)
Epoxy resin 6: jER (registered trademark) 1256 (from Mitsubishi Chemical Corporation)
< Lubricating Coating Film Formation >
A bar coater (#44) was used to apply each coating composition for a lubricating coating film onto a surface of a stainless steel plate (SUS301) that had been solvent degreased, and the coating composition was then heated for 20 minutes at a temperature of 200 C to prepare a cured coating film having a thickness of 15 to 20 micro-meters.
The below-described measurements and tests were performed on the lubricating coating films prepared from each of the coating compositions for lubricating coating films for Examples 1 to 13 and Comparative Examples 1 to 5, and the lubricating coating films were evaluated. The results are shown in Tables 1 and 2.
<Erichsen Test in Conformance with JIS Z 2247 (2006): Erichsen Value (mm) Measurements>
Erichsen tests were conducted in conformance with JIS Z 2247 (2006). The test pieces were 0.6 mm thick and 70 mm wide by 150 mm long. A bar coater (#44) was used to apply each coating composition for a lubricating coating film onto the surface of steel plates (SPCC-SB) that had been solvent degreased, and the coating compositions were heated for 20 minutes at a temperature of 200 C to fabricate test pieces for Erichsen testing having a coating thickness of 12 to 17 micro-meters. Next, the test pieces obtained as described above were secured to an Erichsen tester (COTES from Coating Tester KK), and subjected to punch pressing at a speed of 5 to 10 mm/minute, and the pressing distances at which cracking and peeling were first generated in the coating were measured. Testing was conducted at least three times, and the measured values of each of the tests were averaged to obtain the Erichsen value. The measured Erichsen values (mm) are shown in Tables 1 and 2. Note that an Erichsen value of 8.0 mm or greater indicates a coating film with good flexibility.
<Flexibility>
Pressure was applied at an angle of 90 to each of the stainless steel test pieces on which a lubricating coating film was formed to thereby bend the test pieces, after which the bend locations were scratched with an acrylic resin plate, and the number of times that the bend locations had to be scratched until the lubricating coating film peeled was recorded.
A (30 or more times), B (15 to 29 times), C (6 to 10 times), D (5 or fewer times)
<Coefficient of Friction>
A reciprocal motion frictional abrasion testing machine that caused the stainless steel test pieces on which lubricating coating films were formed to reciprocate by causing 1/2 inch steel balls having a vertical load applied to slide and move was used, and the coefficient of dynamic friction (units: micro) during sliding after 5000 times of sliding of the steel balls was measured under conditions that included a sliding speed of 100 cpm, a weight of 1 kg, and a sliding distance (stroke) of 50 mm.
<Wear Depth>
After the measurements, a surface roughness gage (SURFCOM 1400D from Tokyo Seimitsu Co., Ltd.) was used to measure the difference in surface levels of the stainless steel plate between the sliding locations and non-sliding locations, and the difference thereof was recorded as the wear depth (units: micro-meters).
A (Less than 5micro-meters), B (5 to 10 micro-meters), C (11 to 19 micro-meters), D (20 micro-meters or greater, or the base material is exposed)
As is clear from Table 1, the coating compositions for lubricating coating films of Examples 1 to 13 can form a lubricating coating film having excellent flexibility with an Erichsen value of 8 mm or greater. When the coating composition contains fluororesin microparticles and a prescribed metal oxide or metal nitride in particular, the lubricating coating film can be provided with not only excellent flexibility, but also with a low frictional property and high wear resistance.
On the other hand, as is clear from Table 2, the lubricating coating films formed from the coating compositions for lubricating coating films of Comparative Examples 1 to 5 exhibit little flexibility. The results for Comparative Examples 2 to 5 in particular indicated inferior wear resistance regardless of compositions containing titanium nitride and titanium oxide, and thus in addition to the specification of components (A) and (B), which are characteristics of the invention of the present application, if the ratio of component (A) to component (B) is not within the prescribed range, it is difficult to realize the technical effects of the invention of the present application regardless of the type of solid lubricant that is used.

Claims (16)

  1. A coating composition for a lubricating coating film comprising:
    (A) a phenolic resin,
    (B) an epoxy resin having an epoxy equivalent weight of 600 to 4000, and
    (C) at least one type of solid lubricant; and
    a weight ratio of component (A) per the total weight of component (A) and component (B) is at least 50 weight %.
  2. The coating composition for a lubricating coating film according to claim 1, wherein the epoxy equivalent weight of component (B) is 800 to 1200.
  3. The coating composition for a lubricating coating film according to claim 1 or claim 2, wherein the weight ratio of component (A) per the total weight of component (A) and component (B) is at least 60 weight % and not more than 80 weight %.
  4. The coating composition for a lubricating coating film according to claims 1 to 3, wherein component (C) comprises at least one or more types of substances selected from fluororesin, polyethylene resin, polyamide resin, and mixtures thereof.
  5. The coating composition for a lubricating film according to any one of claims 1 to 4, wherein component (C) comprises one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide, and mixtures thereof.
  6. The coating composition for a lubricating film according to any one of claims 1 to 5, wherein component (C) comprises (C1) fluororesin, and (C2) one or more types of metal oxide or metal nitride selected from titanium nitride, titanium oxide, aluminum oxide, silicon nitride, silicon dioxide and mixtures thereof, and a weight ratio of component (C1) and component (C2) is in a range of 50:50 to 90:10.
  7. The coating composition for a lubricating coating film according to any one of claims 1 to 6, wherein component (C) is contained at an amount of 1 to 200 parts by weight per 100 parts by weight of the total weight of components (A) and (B).
  8. A lubricating coating film obtained by curing the coating composition for a lubricating coating film as per any one of claims 1 to 7.
  9. A lubricating coating film obtained by curing the coating composition for a lubricating coating film as per any one of claims 1 to 8, and having an Erichsen value (JIS Z 2247) of 8.0 mm or greater when the coating composition for a lubricating coating film is cured with a film thickness of 10 to 20 micro-meters.
  10. A sliding member provided with a lubricating coating film as per claim 8 or claim 9.
  11. The sliding member according to claim 10, wherein the sliding member is a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door lock, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
  12. A method for manufacturing a sliding member provided with a base material having the lubricating coating film formed on a surface, the method thereof comprising:
    a step of applying the coating composition for a lubricating coating film according to any one of claims 1 to 7 onto a surface of the base material, and
    a step of heating the coating composition for a lubricating coating film to form a lubricating coating film on the surface of the base material.
  13. The method for manufacturing according to claim 12, wherein the base material comprises metal.
  14. The method for manufacturing according to claim 12 or claim 13, further comprising a step of pressing or punching the base material having a lubricating coating film formed on a surface.
  15. The method for manufacturing according to any one of claims 12 to 14, wherein the sliding member is a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door look, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
  16. Use of a composition in accordance any one of claims 1 to 7 to provide a lubricating coating film on a sliding member selected from a crankshaft, compressor shaft, slide bearing, gear, oil pump gear, piston, piston ring, piston pin, gasket, door look, guide rail, seatbelt buckle, brake pad, brake pad clip, brake shim, brake insulator, hinge, screw, or pressurization pad.
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US20170073605A1 (en) 2017-03-16
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EP3114182A1 (en) 2017-01-11
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EP3114182B1 (en) 2019-01-30
CN106062105B (en) 2019-03-01

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