+

WO2018190061A1 - Élément coulissant et procédé pour le produire - Google Patents

Élément coulissant et procédé pour le produire Download PDF

Info

Publication number
WO2018190061A1
WO2018190061A1 PCT/JP2018/009886 JP2018009886W WO2018190061A1 WO 2018190061 A1 WO2018190061 A1 WO 2018190061A1 JP 2018009886 W JP2018009886 W JP 2018009886W WO 2018190061 A1 WO2018190061 A1 WO 2018190061A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
sliding member
smooth sliding
smooth
concavo
Prior art date
Application number
PCT/JP2018/009886
Other languages
English (en)
Japanese (ja)
Inventor
豊 磯部
清治 水元
Original Assignee
株式会社ダイセル
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 株式会社ダイセル filed Critical 株式会社ダイセル
Publication of WO2018190061A1 publication Critical patent/WO2018190061A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/18—Ethers, e.g. epoxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • 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
    • 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

Definitions

  • the present invention relates to a sliding member such as a piston and a manufacturing method thereof.
  • the piston in the internal combustion engine is made of an aluminum alloy and has a skirt for sliding contact with the inner wall of the cylinder. On the surface of the skirt portion, streaks extending spirally along the axial direction are formed in order to prevent seizure and retain oil. Resin coated film containing solid lubricant etc. on the surface with streaks to reduce fuel consumption, reduce frictional force due to skirt surface, and improve wear resistance of skirt surface Is formed. However, since there is an uneven shape due to the streak, the slidability is not sufficient, and further improvement in slidability is required due to the recent increase in awareness of environmental problems.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2010-216362 (Patent Document 1) includes a lower layer coating composition formed on the surface of a piston substrate and an upper layer coating composition formed on the upper surface of the lower layer coating composition.
  • a piston of an internal combustion engine in which a multilayer lubricating film is formed wherein both the lower layer coating composition and the upper layer coating composition include at least one of a polyamideimide resin, a polyimide resin, or an epoxy resin that is a binding resin
  • the lower layer coating composition has a solid lubricant content of at least 50 wt% or less of either graphite or molybdenum disulfide, while the upper layer coating composition contains at least graphite or molybdenum disulfide.
  • Either 50% or 95% solid lubricant containing both graphite and molybdenum disulfide Piston is set to t% is disclosed.
  • a multilayer lubricating film having a shape following the striation is formed on the surface of the skirt portion having the striation, and the upper layer film is worn by sliding. Lubricated.
  • this piston forms a smooth sliding surface in a relatively short time due to the softness of the upper layer coating, it requires an initial familiarization period, and the clearance between the piston and cylinder is wide due to wear. Therefore, there is a concern that the energy transfer efficiency is lowered.
  • Patent Document 2 Japanese Patent Laid-Open No. 2016-180331
  • Patent Document 2 has at least one layer of coating on the outer peripheral surface of a skirt that slides against the inner wall of a cylinder and has streak, and at least one of the coatings.
  • An internal combustion engine piston is disclosed in which the layer is an electrodeposited film.
  • the electrodeposition film is a film formed by electrodeposition of an electrodeposition paint containing a binder resin such as a polyamide-imide resin, a polyimide resin, or an epoxy resin, and improves the smoothness of the skirt portion. It is described as functioning as a decorative layer.
  • an electrodeposition film is formed on the lubricating coating to improve the smoothness of the outer peripheral surface of the skirt portion.
  • Patent Document 3 discloses that fine particles of metal or ceramic having an average particle size of 20 to 400 ⁇ m are compressed air or compressed with respect to a piston skirt portion for an internal combustion engine made of an aluminum alloy. Uniform structure of the piston base material in the range of 1 to 15 ⁇ m deep from the surface of the skirt by injecting and colliding as a mixed fluid with nitrogen at an injection speed of 80 m / sec or more or an injection pressure of 0.2 MPa or more. And a surface treatment for forming a modified layer having a surface activated, and after the foundation treatment, a new surface is exposed on the surface of the modified layer and activated while the surface of the skirt is low.
  • a surface treatment method of a piston skirt portion for an internal combustion engine that forms a lubricating layer made of a resin film having a friction coefficient is disclosed.
  • This document describes an epoxy-based resin and a polyamide-imide resin as a low-friction coefficient resin constituting the lubricating layer, and in the examples, polyamide-imide is used.
  • the center line average roughness Ra of the modified layer is 0.5 to 2.5 ⁇ m, and that the center line average roughness Ra of the lubricating layer can be 1 ⁇ m or less.
  • the roughness Ra is 0.6 ⁇ m.
  • Patent Documents 1 to 3 exemplify an epoxy resin as a binder, details of the epoxy resin are not described, and general-purpose epoxy resins have low slidability and rigidity (hardness).
  • Patent Document 4 describes light that can be suitably used for automobile clear paints, topcoat agents for plastic films, coating agents for protecting plastic parts, coating agents for forming color filter protective films, and the like.
  • the curable resin composition includes an alicyclic diepoxy compound containing a 3,4,3′4′-diepoxybicyclohexyl compound, an epoxy compound other than the alicyclic diepoxy compound, an oxetane compound, a vinyl ether compound, an acrylic polymer A combination with a combination and at least one compound selected from the group consisting of bi- to hexafunctional polyol compounds is disclosed.
  • JP-A-2016-180331 (Claims 1 and 2, paragraphs [0012] [0043] [0045], FIGS. 3 and 10) JP 2010-90812 A (Claim 1, paragraphs [0080] [0082], Examples) JP 2008-189853 A (claim 1, paragraph [0014], example)
  • an object of the present invention is to provide a sliding member having a smooth surface and high productivity even in a member having a concavo-convex structure such as a streak (particularly an artificially processed concavo-convex structure) and a method for manufacturing the same. Is to provide.
  • Another object of the present invention is to provide a sliding member having high slidability, heat resistance and chemical resistance and a method for producing the same.
  • Still another object of the present invention is to provide a sliding member having excellent wear resistance and capable of maintaining an initial clearance between a piston and a cylinder, and a method for manufacturing the same.
  • Another object of the present invention is to provide a sliding member capable of preventing seizure even when worn due to long-term use or the like, and a method for manufacturing the same.
  • the present inventors have found that a curable liquid containing a specific alicyclic epoxy compound on the surface of a sliding member formed of metal and having an uneven structure such as a streak.
  • a curable liquid containing a specific alicyclic epoxy compound on the surface of a sliding member formed of metal and having an uneven structure such as a streak.
  • the smooth sliding member of the present invention is a smooth sliding member comprising a sliding member formed of metal and having a concavo-convex structure on the surface, and a smooth coat layer covering the surface of the sliding member.
  • the coating layer has the formula (1)
  • R 1 to R 18 are the same or different and each represents a hydrogen atom, a halogen atom, an oxo group, a hydroxy group, a hydroperoxy group, an amino group, a sulfo group or an organic group, and X is a direct bond or Indicates a linking group
  • a primer layer following the concavo-convex shape of the concavo-convex structure may be interposed between the surface of the sliding member and the coat layer.
  • the primer layer may contain a polyamideimide resin.
  • the primer layer may further include at least one solid lubricant selected from the group consisting of fluorine compounds, metal sulfides, and carbon materials.
  • the uneven structure may have an uneven shape with an average height of protrusions of 0.5 to 30 ⁇ m.
  • the average height of the projections of the concavo-convex structure is h
  • the difference in height between the highest surface and the lowest surface in the region 50 times longer than h is h / 10 or less on the surface of the coat layer. May be.
  • the maximum thickness d of the coat layer may be 1.1 times or more the average height h of the protrusions of the concavo-convex structure.
  • R 1 to R 18 may be a hydrogen atom, and X may be a direct bond.
  • the curable liquid composition may further contain a curing agent.
  • the curable liquid composition may further contain a leveling agent.
  • the metal may be an aluminum simple substance, an iron simple substance, a nickel simple substance, a copper simple substance, a chromium simple substance, or an alloy containing any of these simple substances.
  • the sliding member may be a piston having a skirt portion, and a concavo-convex structure may be formed on a surface of the skirt portion.
  • the present invention also includes a method for producing the smooth sliding member including a coating layer forming step of coating and curing a curable liquid composition on the surface of the sliding member having a concavo-convex structure.
  • the smooth sliding member includes a primer layer
  • a method for producing the smooth sliding member including a coating layer forming step of coating and curing the curable liquid composition is also included.
  • the curable liquid composition may be coated by a spray method.
  • the surface of the sliding member formed of metal and having a concavo-convex structure is coated with a curable liquid composition containing a specific alicyclic epoxy compound and cured.
  • a sliding member having a smooth surface at a site having a concavo-convex structure such as streak is obtained.
  • the resulting sliding member is excellent in slidability, heat resistance and chemical resistance. Moreover, it is excellent in wear resistance and can maintain the initial clearance between the piston and the cylinder. Moreover, since it has uneven structures, such as a streak, in the lower layer of a smooth coating layer, even if a surface layer wears out by long-term use etc., baking can be prevented.
  • FIG. 1 is a schematic diagram showing the relationship between the average height h of convex portions of the concavo-convex structure, the maximum thickness d of the coat layer, and the surface height difference ⁇ H.
  • FIG. 2 is a scanning electron microscope (SEM) photograph of a cross section of the smooth sliding member obtained in Example 1 (and Comparative Example 1).
  • FIG. 3 is a cross-sectional CCD (charge coupled device) photograph of the smooth sliding member obtained in Example 2.
  • FIG. 4 is a CCD (charge coupled device) photograph of a cross section of the smooth sliding member obtained in Example 3 (and Comparative Example 2).
  • FIG. 5 is a CCD (charge coupled device) photograph of a cross section of the sliding member obtained in Example 4.
  • 6 is a scanning electron microscope (SEM) photograph of a cross section of the sliding member obtained in Example 5.
  • FIG. FIG. 7 is a scanning electron microscope (SEM) photograph of a cross section of the smooth sliding member obtained in Comparative Example 3.
  • the smooth sliding member of the present invention includes a sliding member formed of metal and having a concavo-convex structure such as a streak on the surface, and a smooth coat layer (surface layer) covering the surface of the sliding member.
  • the sliding member is not particularly limited as long as the sliding member is made of metal and has a concavo-convex structure such as a streak (artificially processed concavo-convex structure) on the surface (sliding surface). Also, sliding members (for example, cylinders, pistons, bearings, etc.) used in transportation equipment such as automobiles and airplanes, electronic and electrical equipment, and the like may be used.
  • sliding members used in transportation equipment such as automobiles, for example, pistons that are engine parts; sliding members such as cam bearings, crank bearings, connecting rod bearings; shaft members such as cam shafts and crank shafts; rollers Valve-operated sliding members such as rockers, rocker arms, lash adjusters, and valve lifters; Chain-driven sliding members such as chain guides, chain dampers, and chain slippers; Bearing members for vane and trochoidal oil pumps; Alternators An auxiliary engine member such as a bearing member; a bearing member of a transmission is preferable, and a piston having a skirt portion is particularly preferable.
  • the metal constituting the sliding member is not particularly limited as long as it is a conventionally used metal depending on the type of the sliding member.
  • the metal include aluminum, iron, nickel, copper, and chromium.
  • the metal may be the single metal or an alloy of the metal (for example, stainless steel or steel).
  • the metal surface may be subjected to plating treatment such as galvanization for rust prevention treatment.
  • metals including aluminum and iron are widely used, and in the case of a piston having a skirt portion used for an internal combustion engine of an automobile, it is usually formed of a metal including aluminum (aluminum alone or an aluminum alloy).
  • the alloy containing aluminum may be, for example, an alloy of aluminum and a metal such as silicon, copper, or magnesium.
  • the shape of the concavo-convex structure (particularly the concavo-convex structure) formed on the surface (sliding surface) of the sliding member is not particularly limited as long as it is an concavo-convex shape, and is conventionally used depending on the type of the sliding member. As long as the irregular shape is formed, the irregular shape formed regularly may be used, or the irregular shape formed irregularly or randomly may be used.
  • a concavo-convex structure having a regular concavo-convex shape for example, in the case of a columnar shape such as a piston, even if it is a streak formed with a convex portion that continuously spirals in the axial direction on the peripheral surface, It is also possible that the protrusions extending in the circumferential direction are regularly formed at intervals.
  • the streak may be formed on the sliding surface according to the type of the sliding member, but in the case of a piston having a skirt part, the streak is formed on the skirt part.
  • the concavo-convex structure having a random concavo-convex shape may be, for example, a randomly concavo-convex shape.
  • Such an uneven shape may be formed by, for example, a processing method in which particles described in Patent Document 3 collide.
  • the shape of the convex portion forming the concavo-convex structure is not particularly limited as long as it is a shape extending linearly, and the cross-sectional shape perpendicular to the longitudinal direction is, for example, a substantially semicircular shape, a mountain shape or a wave shape, a triangle Examples include a shape and a square shape. Of these, the semi-circular shape, the mountain shape, or the wave shape is usually used.
  • the average height h of the convex portion (the height at the top of the convex portion or the average value of the maximum height of each convex portion) can be selected from a range of about 0.5 to 100 ⁇ m (for example, 0.5 to 30 ⁇ m). It is about 30 to 30 ⁇ m, preferably 2 to 25 ⁇ m, more preferably about 3 to 20 ⁇ m (especially 5 to 15 ⁇ m). If the average height is too small, there is a possibility that seizure will occur when the coat layer is worn, and if it is too large, the uneven structure (or the primer layer formed on the uneven structure) may be exposed.
  • the average pitch of the protrusions can be selected from a range of about 1 to 1000 ⁇ m, for example, 10 to 500 ⁇ m, preferably 50 to 400 ⁇ m, more preferably 100 to 350 ⁇ m (particularly 150 to 300 ⁇ m). If the average pitch is too small, it may be difficult to form the concavo-convex structure, and if it is too large, there is a possibility that seizure will occur during wear.
  • the coat layer covers the surface of a sliding member having a concavo-convex structure such as the streaks (or a concavo-convex structure coated with a primer layer formed following the concavo-convex structure on the concavo-convex structure) to provide a smooth surface
  • a coating layer having high slidability, wear resistance, heat resistance, and chemical resistance is formed by coating, the coating layer is formed in the same manner as the primer layer described later.
  • a smooth coat layer can be formed by a simple method by coating and curing a curable liquid composition containing a specific alicyclic epoxy compound.
  • the smoothness of the coating layer (that is, that the sliding member does not follow the concavo-convex structure) can be evaluated by the difference in surface height [surface deviation ( ⁇ H value)]. Specifically, when the average height of the protrusions of the concavo-convex processed structure is h, the height of the highest surface and the lowest surface in the 50-fold length region (reference length) on the surface of the coat layer.
  • the difference ( ⁇ H value) is h / 10 or less, preferably h / 12 or less, more preferably h / 15 or less (particularly h / 20 or less). If the height difference is too large, the smoothness is lowered and the slidability may be lowered.
  • region 50 times long is a direction substantially perpendicular
  • the height difference ( ⁇ H value) can be measured, for example, by a method such as microscopic measurement, SEM observation, or surface roughness measurement of a cross section obtained by cutting the sliding member.
  • the maximum thickness d of the coat layer only needs to be higher than the average height h of the convex portions of the concavo-convex structure, and may be 1.1 times or more (particularly 1.3 times or more) of the average height h, for example. 1.5 times or more, for example, 1.5 to 5 times, preferably 1.6 to 4 times, and more preferably about 1.8 to 3 times. If the maximum thickness d is too small, the concavo-convex structure or the primer layer formed on the concavo-convex structure may be exposed.
  • the maximum thickness d of a coating layer can be measured as an average value of arbitrary 10 places, for example using an optical film thickness meter. In FIG. 1, the relationship between the average height h of the convex part 1 of the concavo-convex structure, the maximum thickness d of the coat layer 2, and the surface height difference ⁇ H value is schematically shown.
  • the maximum thickness d of the coat layer can be selected according to the size of the convex portion of the concavo-convex structure.
  • it may be, for example, 12 ⁇ m or more (particularly 15 ⁇ m or more).
  • the thickness is about 12 to 100 ⁇ m, preferably about 15 to 50 ⁇ m, more preferably about 20 to 40 ⁇ m (particularly about 25 to 35 ⁇ m).
  • the average height h of the convex portion of the concavo-convex structure for obtaining the height difference ⁇ value and the maximum thickness d is, when a primer layer is formed on the concavo-convex structure, It is set as the average height of the convex part of the primer layer (the convex part having a shape following the convex part of the concave-convex structure).
  • the arithmetic average roughness Ra of the coat layer may be 100 nm or less (for example, 1 to 100 nm), for example, 2 to 50 nm, preferably 3 to 30 nm (for example, 4 to 20 nm), more preferably 5 to 15 nm (particularly 7 to 10 nm). 10 nm).
  • an arithmetic operation is performed by combining a coat layer containing an alicyclic epoxy compound represented by the formula (1) (particularly an alicyclic epoxy compound in which X is a direct bond) and a primer layer containing a polyamideimide resin.
  • High surface smoothness with an average roughness Ra of 20 nm or less (particularly 10 nm or less) can also be realized. If the arithmetic average roughness Ra is too large, the surface smoothness may be reduced, leading to a decrease in slidability.
  • the average roughness can be measured by a method based on JIS B0601 (2001).
  • the coat layer has a high hardness and may have an indentation hardness of 300 N / mm 2 or more (for example, 300 to 1000 N / mm 2 ), preferably 450 N / mm 2 or more (for example, 450 to 800 N / mm). 2 ), more preferably 550 N / mm 2 or more (for example, about 550 to 700 N / mm 2 ). If the indentation hardness is too small, it may be difficult to maintain the wear resistance of the coat layer for a long period of time. In the present specification and claims, the indentation hardness can be measured using, for example, a micro hardness tester (“ENT-2100” manufactured by Elionix Co., Ltd.).
  • Such a coating layer is a cured product of a curable liquid composition containing the alicyclic epoxy compound represented by the formula (1).
  • Alicyclic epoxy compound The alicyclic epoxy compound is represented by the formula (1).
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the organic group is not particularly limited as long as it contains a carbon atom, for example, a hydrocarbon group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyl group, an acyloxy group, an alkylthio group, an alkenylthio group, Arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, epoxy-containing group, oxetanyl group, oxetanyl-containing group, cyano group, isocyanate group, carbamoyl group, isothiocyanate Examples thereof include a narate group and a substituted amino group.
  • hydrocarbon group examples include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • Examples of the alkyl group include C 1-20 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group (preferably C 1-1 10 alkyl group, more preferably C 1-4 alkyl group).
  • alkenyl group examples include C 2-20 alkenyl groups such as vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group (preferably C 2-10 alkenyl group). And more preferably a C 2-4 alkenyl group).
  • alkynyl group examples include C 2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C 2-10 alkynyl group, more preferably C 2-4 alkynyl group).
  • Examples of the alicyclic hydrocarbon group include a C 3-12 cycloalkyl group (particularly a C 5-8 cycloalkyl group) such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group; a cyclohexenyl group And C 3-12 cycloalkenyl groups such as C 4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl group and bicycloheptenyl group.
  • a C 3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group
  • C 3-12 cycloalkenyl groups such as C 4-15 bridged cyclic hydrocarbon groups such as bicycloh
  • aromatic hydrocarbon group examples include C 6-14 aryl groups (particularly C 6-10 aryl groups) such as a phenyl group and a naphthyl group.
  • alkoxy group examples include C 1-10 alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group (preferably C 1-6 alkoxy group, more preferably C 1-4 alkoxy group).
  • alkenyloxy group examples include a C 2-10 alkenyloxy group such as an allyloxy group (preferably a C 2-6 alkenyloxy group, more preferably a C 2-4 alkenyloxy group).
  • aryloxy group examples include a C 6-20 aryloxy group (particularly a C 6-14 aryloxy group) such as a phenoxy group, a tolyloxy group, and a naphthyloxy group.
  • aralkyloxy group examples include a C 7-20 aralkyloxy group (particularly a C 7-18 aralkyloxy group) such as a benzyloxy group and a phenethyloxy group.
  • acyl group examples include C 1-20 acyl groups such as acetyl group, propionyl group, (meth) acryloyl group, and benzoyl group (particularly, C 1-12 acyl group).
  • acyloxy group examples include C 1-20 acyloxy groups such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group, and benzoyloxy group (particularly, C 1-12 acyloxy group).
  • alkylthio group examples include a C 1-6 alkylthio group such as a methylthio group and an ethylthio group (particularly a C 1-4 alkylthio group).
  • alkenylthio group examples include a C 2-6 alkenylthio group such as an allylthio group (particularly a C 2-4 alkenylthio group).
  • arylthio group examples include 6-20 arylthio groups (particularly C 6-14 arylthio groups) such as a phenylthio group, a tolylthio group, and a naphthylthio group.
  • aralkylthio group examples include a C 6-20 aralkylthio group (particularly a C 7-18 aralkylthio group) such as a benzylthio group and a phenethylthio group.
  • alkoxycarbonyl group examples include a C 1-10 alkoxy-carbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group (particularly a C 1-6 alkoxy-carbonyl group).
  • aryloxycarbonyl group examples include a C 6-20 aryloxy-carbonyl group such as a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group (particularly a C 6-14 aryloxy-carbonyl group).
  • aralkyloxycarbonyl group examples include a C 7-20 aralkyloxy-carbonyl group such as a benzyloxycarbonyl group (particularly a C 7-18 aralkyloxy-carbonyl group).
  • Examples of the epoxy-containing group include a glycidyl group and a glycidyloxy group.
  • Examples of the oxetanyl-containing group include a C 1-10 alkyl oxetanyloxy group such as an ethyl oxetanyloxy group.
  • substituted amino group examples include mono- or dialkylamino groups (particularly mono- or di-C 1-6 alkylamino groups) such as methylamino group, ethylamino group, dimethylamino group, and diethylamino group, acetylamino group, and propionylamino.
  • acylamino groups such as benzoylamino group (particularly C 1-11 acylamino group).
  • organic groups may be groups in which two or more organic groups are combined (bonded).
  • combinations of two or more organic groups include a combination of an aliphatic hydrocarbon group and an alicyclic hydrocarbon group (such as a cyclohexylmethyl group or a methylcyclohexyl group), an aliphatic hydrocarbon group, and an aromatic hydrocarbon.
  • groups such as C 7-18 aralkyl groups such as benzyl and phenethyl groups (especially C 7-10 aralkyl groups), C 6-10 aryl-C 2-6 alkenyl groups such as cinnamyl groups, tolyl groups, etc.
  • a combination with a group such as a methylphenoxy group
  • the organic group may further have a substituent.
  • substituents include a halogen atom, an oxo group, a hydroxyl group, a hydroperoxy group, an amino group, and a sulfo group.
  • R 1 to R 18 a hydrogen atom, a linear or branched C 1-6 alkyl group (particularly, a linear C 1-3 alkyl group such as a methyl group), etc. are widely used and rigid
  • at least one of R 1 to R 18 is preferably a hydrogen atom, and all of them are particularly preferably hydrogen atoms.
  • examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, and a group in which a plurality of these linking groups are connected.
  • the divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.
  • divalent aliphatic hydrocarbon group examples include an alkylene group, an alkenylene group, and an alkynylene group.
  • alkylene group examples include C 1 such as methylene group, ethylene group, propylene group, trimethylene group, butylene group, tetramethylene group, hexamethylene group, isohexylene group, octamethylene group, isooctylene group, decamethylene group, and dodecamethylene group. And a -20 alkylene group.
  • alkenylene group examples include C such as vinylene group, arylene group, metalrylene group, 1-propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, and octenylene group. And a 2-20 alkenylene group.
  • the alkenylene group may be an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized.
  • alkynylene group examples include C 2-20 alkynylene groups such as ethynylene group and propynylene group.
  • divalent alicyclic hydrocarbon group examples include a cyclopropylene group, a cyclobutylene group, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, and a 1,3-cyclohexene group.
  • cyclohexylene 1,4-cyclohexylene group, cyclohexylidene group, cyclododecane - C 3-12 cycloalkylene groups (especially C 5-8 cycloalkylene group), such diyl group; C, such as cyclohexylene group 3 12 cycloalkenylene group; C 4-15 bridged cyclic hydrocarbon linking group such as bicycloheptanylene group and bicycloheptenylene group.
  • the divalent alicyclic hydrocarbon group may have an epoxy group, and may be, for example, an epoxy C 5-12 cycloalkylene group such as an epoxycyclohexylene group.
  • divalent aromatic hydrocarbon group examples include a C 6-14 arylene group such as a phenylene group and a naphthylene group.
  • These divalent hydrocarbon groups may have a substituent.
  • substituents include C 1-4 alkyl groups such as a methyl group and an ethyl group, C groups such as a methoxy group and an ethoxy group, in addition to the substituents exemplified as the substituents of the organic group in R 1 to R 18.
  • substituents include 1-4 alkoxy groups and carbonyl groups.
  • linking groups may be groups in which two or more linking groups are combined (bonded or connected).
  • a combination of two or more kinds of linking groups for example, a combination of a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group (for example, cyclohexylene methylene group, methylene cyclohexylene group, dicyclohexyl methane).
  • a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group eg, a tolylene group, a xylylene group) , Diphenylmethane-4,4′-diyl group, diphenylpropane-4,4′-diyl group, etc.
  • a combination of an ester bond and a divalent hydrocarbon group for example, carbonyloxymethylene group, carbonyloxyhydrogenated xylylene Oxycarbonyl group
  • a combination of a carbonate bond and a divalent hydrocarbon group for example, methyleneoxycarboni) Oxymethylene group, methyleneoxycarbonyloxy hydrogenated xylyleneoxycarbonyloxymethylene group, etc.
  • a combination of a plurality of ester bonds for example, a polyester bond such as polycaprolact
  • X a direct bond, an alkylene group (C 1-4 alkylene group which may have a C 1-4 alkyl group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, etc.)
  • An ether bond-containing group for example, C 1-4 alkyleneoxy C 1-4 alkylene group such as methyleneoxymethylene group
  • a combination of an ester bond and an alkylene group for example, carbonyloxy C 1 such as carbonyloxymethylene group
  • alkylene group a combination of a carbonate bond and an alkylene group (e.g., a C 1-4 alkylene oxy carbonyloxy C 1-4 alkylene group such as methylene oxycarbonyl oxymethylene group) are preferred, such as sliding property ( Direct bonding is particularly preferred because of its excellent surface smoothness and rigidity. Yes.
  • the alicyclic epoxy compound represented by the formula (1) may be composed of only a single type of alicyclic epoxy compound, and the substituents R 1 to R 18 and / or the group X may be different from each other. It may be a combination of various alicyclic epoxy compounds.
  • Preferred alicyclic epoxy compounds include, for example, methyl groups such as 3,4,3 ′, 4′-diepoxybicyclohexyl and (3,4,3 ′, 4′-diepoxy-6-methyl) bicyclohexyl.
  • Diepoxybi C 5-8 cycloalkyl optionally having a C 1-4 alkyl group; 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl
  • Examples include alkane carboxylates. These alicyclic epoxy compounds can be used alone or in combination of two or more.
  • Curing agent The curable liquid composition preferably further contains a curing agent.
  • Curing agents include cationic polymerization initiators (acid generators) and conventional curing agents [for example, acid and acid anhydride curing agents, amine curing agents, polyaminoamide curing agents, imidazole curing agents, organic acid hydrazides. -Based curing agents, latent curing agents (such as dicyandiamides), polymercaptan-based curing agents, phenol-based curing agents, etc.].
  • cationic polymerization initiators (acid generators) and amine curing agents are widely used.
  • the cationic polymerization initiator includes a photoacid generator and a thermal acid generator depending on the type of polymerization.
  • the photoacid generator examples include a sulfonium salt (a salt of sulfonium ion and anion), an iodonium salt (a salt of iodonium ion and anion), a selenium salt (a salt of selenium ion and anion), and an ammonium salt (ammonium ion). And a phosphonium salt (a salt of a phosphonium ion and an anion), a salt of a transition metal complex ion and an anion, and the like.
  • These photoacid generators can be used alone or in combination of two or more.
  • an acid generator having a high acidity for example, a sulfonium salt is preferable from the viewpoint that the reactivity can be improved and the hardness of the cured product can be improved.
  • sulfonium salt examples include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenylsulfonium salt.
  • Tris (4-fluorophenyl) sulfonium salt tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium salts, triarylsulfonium salts such as 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salts; Diarylsulfonium salts such as nium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; phenylmethylbenzylsulfonium salt, 4-
  • anion (counter ion) for forming a salt with the cation examples include SbF 6 ⁇ , PF 6 ⁇ , BF 4 ⁇ , fluorinated alkyl fluorophosphate ion [(CF 3 CF 2 ) 3 PF 3 ⁇ , ( CF 3 CF 2 CF 2 ) 3 PF 3- etc.], (C 6 F 5 ) 4 B ⁇ , (C 6 F 5 ) 4 Ga ⁇ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion Nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), (CF 3 SO 2 ) 3 C ⁇ , (CF 3 SO 2 ) 2 N ⁇ , perhalogen acid Ion, halogenated sulf
  • a commercially available photoacid generator can be used as the photoacid generator.
  • Examples of commercially available photoacid generators include “CPI-101A”, “CPI-110A”, “CPI-100P”, “CPI-110P”, “CPI-210S”, “CPI-200K” manufactured by San Apro Co., Ltd. Can be used.
  • thermal acid generator examples include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes. These thermal acid generators can be used alone or in combination of two or more. Of these thermal acid generators, an acid generator having a high acidity, for example, an arylsulfonium salt, is preferable from the viewpoint that the reactivity can be improved and the hardness of the cured product can be improved.
  • the anion include the same anions as those of the photoacid generator, and may be an antimony fluoride ion such as SbF 6- .
  • thermal acid generator can also be used as the thermal acid generator.
  • thermal acid generators include “Sun-Aid SI-60L”, “Sun-Aid SI-60S”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L” manufactured by Sanshin Chemical Industry Co., Ltd. ) "SP-66", “SP-77” manufactured by ADEKA can be used.
  • amine curing agent examples include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetra Cycloaliphatic polyamines such as oxaspiro [5.5] undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene 2,4-d
  • amine curing agents can be used alone or in combination of two or more.
  • aliphatic polyamines ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, etc.
  • alicyclic polyamines mensendiamine, isophoronediamine, etc.
  • aromatic polyamines xylenediamine
  • Metaphenylenediamine etc.
  • cationic polymerization initiators are preferred because they can promote polymerization and improve the hardness of the cured product.
  • the proportion of the curing agent can be selected from a range of about 0.01 to 200 parts by weight (for example, 0.1 to 150 parts by weight) with respect to 100 parts by weight of the alicyclic epoxy compound depending on the type of the curing agent.
  • the proportion of the cationic polymerization initiator can be selected from the range of about 0.01 to 10 parts by weight, for example 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the alicyclic epoxy compound. Part, more preferably about 0.3 to 2 parts by weight (particularly 0.5 to 1.5 parts by weight). If the proportion of the cationic polymerization initiator is too small, the progress of the curing reaction may be reduced and the hardness of the cured product may be lowered. If the proportion is too large, the storage stability of the composition may be reduced, or the cured product may be colored. There is a fear.
  • the proportion of a conventional curing agent such as an amine-based curing agent may be, for example, about 50 to 200 parts by weight, preferably about 80 to 150 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound.
  • the curable liquid composition further contains a leveling agent.
  • a leveling agent any conventional leveling agent (such as an ethylene oxide adduct of acetylene glycol) may be used as long as it has the ability to lower the surface tension. From the viewpoint of excellent surface tension reducing ability, a silicone leveling agent, Fluorine leveling agents are preferred.
  • surface smoothness can be improved and slidability can be improved by combining the alicyclic epoxy compound and the leveling agent.
  • the hardness can be improved by controlling the blending ratio.
  • the silicone leveling agent may be a leveling agent having a polyorganosiloxane skeleton.
  • the polyorganosiloxane skeleton includes a monofunctional M unit (generally represented by R 3 SiO 1/2 ) and a bifunctional D unit (generally represented by R 2 SiO 2/2 ). Unit), trifunctional T unit (generally expressed as RSiO 3/2 ), tetrafunctional Q unit (generally expressed as SiO 4/2 ), polyorgano Siloxane may be used, but polyorganosiloxane formed with D units is usually used.
  • the organic group (R) of the polyorganosiloxane can be selected from the hydrocarbon groups exemplified as R 1 to R 18 in the formula (1) of the alicyclic epoxy compound, and is usually C 1-4 alkyl. Groups and aryl groups are used, and methyl groups and phenyl groups (particularly methyl groups) are widely used.
  • the number of repeating siloxane units (degree of polymerization) is, for example, about 2 to 3000, preferably about 3 to 2000, and more preferably about 5 to 1000.
  • the fluorine-based leveling agent may be any leveling agent having a fluoroaliphatic hydrocarbon skeleton.
  • the fluoroaliphatic hydrocarbon skeleton include fluoroC 1-10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluoro t-butane, fluoropentane, and fluorohexane. Can be mentioned.
  • fluoroaliphatic hydrocarbon skeletons it is sufficient that at least some of the hydrogen atoms are substituted with fluorine atoms, but from the viewpoint of improving slidability and rigidity, all of the hydrogen atoms are substituted with fluorine atoms.
  • a perfluoroaliphatic hydrocarbon skeleton is preferred.
  • the fluoroaliphatic hydrocarbon skeleton may form a polyfluoroalkylene ether skeleton that is a repeating unit via an ether bond.
  • the fluoroaliphatic hydrocarbon group as the repeating unit is at least one selected from the group consisting of fluoro C 1-4 alkylene groups such as a fluoromethylene group, a fluoroethylene group, a fluoropropylene group, and a fluoroisopropylene group. Also good.
  • These fluoroaliphatic hydrocarbon groups may be the same or a combination of plural kinds.
  • the number of repeating fluoroalkylene ether units (degree of polymerization) may be, for example, about 10 to 3000, preferably 30 to 1000, and more preferably about 50 to 500.
  • a polyorganosiloxane skeleton is preferable because of its excellent affinity with the cationic curable silicone resin.
  • the leveling agent having such a skeleton has various functionalities such as a hydrolytic condensable group, a functional group such as a reactive group with respect to an epoxy group, a radical polymerizable group, a polyether group, a polyester group, It may have a polyurethane group or the like. Further, the silicone leveling agent may have a fluoroaliphatic hydrocarbon group, and the fluorine leveling agent may have a polyorganosiloxane group.
  • hydrolyzable groups include hydroxysilyl groups; trihalosilyl groups such as trichlorosilyl groups; dihaloC 1-4 alkylsilyl groups such as dichloromethylsilyl groups; dihaloarylsilyl groups such as dichlorophenylsilyl groups; Kuroroji C 1-4 Haroji C 1-4 alkylsilyl group such as an alkyl silyl group and the like; trimethoxysilyl group, tri C 1-4 alkoxysilyl group such as triethoxysilyl group; dimethoxymethylsilyl group, diethoxymethylsilyl di C 1-4 alkoxy C 1-4 alkylsilyl group such as group; dimethoxyphenyl silyl group, di-C 1-4 alkoxyaryl silyl group such as diethoxyphenylsilyl group; methoxydimethylsilyl groups, such as ethoxy dimethylsilyl group C 1-4 alkoxydi C -4 alky
  • Examples of the reactive group for the epoxy group include a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group (such as a maleic anhydride group), and an isocyanate group.
  • a hydroxyl group, an amino group, an acid anhydride group, an isocyanate group and the like are widely used from the viewpoint of reactivity and the like, and a hydroxyl group is preferable from the viewpoint of handleability and availability.
  • radical polymerizable group examples include a (meth) acryloyloxy group and a vinyl group. Of these, (meth) acryloyloxy groups are widely used.
  • polyether group examples include polyoxy C 2-4 alkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and a polyoxyethylene-polyoxypropylene group.
  • the number of repeating oxyalkylene groups is, for example, about 2 to 1000, preferably 3 to 100, and more preferably about 5 to 50.
  • polyoxyC 2-3 alkylene groups such as polyoxyethylene groups and polyoxypropylene groups (particularly polyoxyethylene groups) are preferred.
  • polyester group examples include a polyester group formed by a reaction between a dicarboxylic acid (an aromatic carboxylic acid such as terephthalic acid or an aliphatic carboxylic acid such as adipic acid) and a diol (an aliphatic diol such as ethylene glycol).
  • polyester groups formed by ring-opening polymerization of cyclic esters for example, lactones such as caprolactone).
  • polyurethane group examples include a conventional polyester type polyurethane group and a polyether type polyurethane group.
  • These functional groups may be directly bonded to the polyorganosiloxane skeleton or fluoroaliphatic hydrocarbon skeleton, and may be a linking group (for example, an alkylene group, a cycloalkylene group, an ether bond, an ester bond, An amide bond, a urethane bond, a linking group combining these, or the like).
  • a linking group for example, an alkylene group, a cycloalkylene group, an ether bond, an ester bond, An amide bond, a urethane bond, a linking group combining these, or the like.
  • a hydrolytic condensable group and a reactive group with respect to the epoxy group are preferred from the viewpoint of reacting with the alicyclic epoxy compound to improve the hardness of the cured product, and a reactive group with respect to the epoxy group ( Particularly preferred is a hydroxyl group.
  • the hydroxyl group may be a terminal hydroxyl group of a (poly) oxyalkylene group [(poly) oxyethylene group or the like].
  • a leveling agent for example, a silicone leveling agent in which a (poly) oxy C 2-3 alkylene group such as a (poly) oxyethylene group is introduced into a side chain of a polyorganosiloxane skeleton such as polydimethylsiloxane ( Fluorine leveling agents in which a fluoroaliphatic hydrocarbon group is introduced into the side chain of a (poly) oxy C 2-3 alkylene skeleton such as (polydimethylsiloxane polyoxyethylene) and (poly) oxyethylene (fluoroalkyl polyoxyethylene) Etc.).
  • a commercially available silicone leveling agent can be used as the silicone leveling agent.
  • examples of commercially available silicone leveling agents include BYK series leveling agents (“BYK-300”, “BYK-301 / 302”, “BYK-306”, “BYK-307”, manufactured by BYK Japan KK), “BYK-310”, “BYK-315”, “BYK-313”, “BYK-320”, “BYK-322”, “BYK-323”, “BYK-325”, “BYK-330”, “BYK” -331 ",” BYK-333 “,” BYK-337 “,” BYK-341 ",” BYK-344 “,” BYK-345 / 346 ",” BYK-347 “,” BYK-348 “,” BYK -349 ",” BYK-370 “,” BYK-375 “,” BYK-377 “,” BYK-378 “,” BYK-UV3500 “,” BYK-UV3 " 10 ”,“ B
  • KP series leveling agents KP-323 “,” KP-326 “,” KP-341 “,” KP-104 “, “KP-110”, “KP-112”, etc.
  • Toray Da Leveling agents LP-7001”, “LP-7002”, “8032ADDITIVE”, “57ADDITIVE”, “L-7604”, “FZ-2110”, “FZ-2105”, “67ADDITIVE”, manufactured by Corning Corp., "8618ADDITIVE”, “3ADDITIVE”, “56ADDITIVE”, etc.).
  • a commercially available fluorine leveling agent can be used as the fluorine leveling agent.
  • commercially available fluorine-based leveling agents include leveling agents ("DSX” and “DAC-HP”) manufactured by Daikin Industries, Ltd., and Surflon series leveling agents (“DSX” and “DAC-HP") manufactured by AGC Seimi Chemical Co., Ltd. S-242 ",” S-243 “,” S-420 “,” S-611 “,” S-651 “,” S-386 “, etc.), BYK series leveling agents manufactured by Big Chemie Japan K.K.
  • PF series leveling agents (“ PF-136A “,” PF-156A “,” PF-151N ”,“ PF-636 ”,“ PF-6320 ”,“ PF-656 ”,“ PF-6520 ”,“ PF-651 ”,“ PF-652 ”,“ PF-3320 ”, etc.) Can be mentioned.
  • leveling agents can be used alone or in combination of two or more.
  • a plurality of types of silicone leveling agents and a plurality of types of fluorine leveling agents may be combined. Silicone leveling agents and fluorine leveling agents And may be used in combination.
  • a silicone-based leveling agent having a hydroxyl group is preferable because it has excellent affinity with an alicyclic epoxy compound, can react with an epoxy group, and can improve the hardness and appearance of a cured product.
  • silicone-based leveling agent having a hydroxyl group examples include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane) or the main chain of a polyorganosiloxane skeleton.
  • a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton such as polydimethylsiloxane
  • transduced the polyorganosiloxane to the (meth) acrylic resin, etc. are mentioned.
  • the hydroxyl group may have a polyorganosiloxane skeleton, or a polyether group, a polyester group, or a (meth) acryloyl group.
  • a leveling agent for example, “BYK-370”, “BYK-SILCLEAN3700”, “BYK-SILCLEAN3720” manufactured by Big Chemie Japan Co., Ltd. can be used.
  • the ratio of the leveling agent can be selected from the range of about 0.01 to 20 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound, for example, 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, More preferably, it is about 0.2 to 5 parts by weight. If the ratio of the leveling agent is too small, the slidability of the cured product may be reduced, and if too high, the hardness of the cured product may be reduced.
  • the ratio of the silicone leveling agent is, for example, 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound. Part (especially 0.5 to 2 parts by weight).
  • the ratio of the fluorine leveling agent is, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.2 to 1 part by weight (100 parts by weight based on 100 parts by weight of the alicyclic epoxy compound. In particular, it may be about 0.3 to 0.8 part by weight).
  • the curable liquid composition may contain other curable resins.
  • other curable resins include other epoxy resins (epoxy resins other than alicyclic epoxy compounds), oxetane resins, vinyl ether resins, and the like. These curable resins can be used alone or in combination of two or more. Among these curable resins, other epoxy resins are preferable in terms of reactivity and miscibility. Examples of the other epoxy resins include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and long chain aliphatic epoxy resins.
  • the ratio of the other curable resin is about 100 parts by weight or less with respect to 100 parts by weight of the alicyclic epoxy compound, for example, 50 parts by weight or less (for example, 1 to 50 parts by weight), preferably 30 parts by weight or less (for example, 5 to 30 parts by weight).
  • the curable liquid composition may contain a conventional additive as long as the slidability and rigidity are not impaired.
  • conventional additives include curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organometallic compounds, etc.) Fillers (inorganic fillers such as titanium oxide and alumina), stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.), plasticizers, lubricants, antifoaming agents, antistatic agents, It may contain a flame retardant. These additives can be used alone or in combination of two or more.
  • the total proportion of these additives is about 100 parts by weight or less with respect to 100 parts by weight of the alicyclic epoxy compound, for example, 30 parts by weight or less (eg, 0.01 to 30 parts by weight), preferably 10 parts by weight or less. (For example, 0.1 to 10 parts by weight).
  • the curable liquid composition may contain an organic solvent and water.
  • the organic solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.) ), Aromatic hydrocarbons (benzene, toluene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, etc.), alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), Examples include cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amides (dimethylform
  • the solid content weight of the curable liquid composition can be arbitrarily selected according to the process of the molding process, and is not particularly limited, in order to adjust the viscosity of the liquid composition suitable for the process.
  • a primer layer following the uneven shape of the uneven structure is preferably interposed between the surface of the sliding member and the coat layer.
  • the primer layer is interposed, not only the adhesion between the sliding member and the coating layer can be improved, but also the heat resistance can be improved.
  • the primer layer only needs to contain a conventional binder resin that can improve the adhesion between the sliding member and the coat layer, but from the viewpoint of heat resistance, it preferably contains a polyamideimide resin.
  • the polyamideimide resin is a polymer having an imide bond and an amide bond in the main chain, and a polyamideimide obtained by reacting a tricarboxylic acid anhydride (or a reactive derivative such as a halide or a lower alkyl ester thereof) with a polyvalent isocyanate, It may be a polyamideimide formed by reacting a tricarboxylic acid anhydride with a polyvalent amine to form an imide bond and then amidating with a polyisocyanate.
  • Polyamideimide resin is usually a resin obtained by using trimellitic anhydride as the tricarboxylic acid anhydride, for example, the formula (2)
  • Y represents a group containing a divalent hydrocarbon group
  • the resin which has a repeating unit represented by these may be sufficient.
  • examples of the divalent hydrocarbon group include the divalent hydrocarbon groups exemplified as X in the formula (1).
  • the divalent hydrocarbon group may be a C 1-10 alkylene group such as an ethylene group or a C 5-8 cycloalkylene group such as a cyclohexylene group, but from the viewpoint of heat resistance, a phenylene group or a naphthylene group.
  • a group containing a divalent aromatic hydrocarbon group is a direct bond; an alkylene group (for example, a C 1-4 alkylene group such as a methylene group, an ethylene group, a dimethylmethylene group (propane-2,2-diyl group), etc.)
  • a divalent aromatic hydrocarbon group and an alkylene group are substituted (for example, a C 1-4 alkyl group such as a methyl group or an ethyl group, a C 1-4 alkoxy group such as a methoxy group or an ethoxy group, A halogen atom such as a chlorine atom or a fluorine atom, or a hydroxyl group).
  • Examples of Y include a phenylene group (1,4-phenylene group, 1,3-phenylene group, etc.), a naphthylene group (1,5-naphthylene group, 2,6-naphthylene group, etc.), a biphenylene group (4,4 '-Biphenylene group, 3,3'-biphenylene group, etc.), bisphenol residue [diphenylmethane-4,4'-diyl group (bisphenol F residue), dimethyldiphenylmethane-4,4'-diyl group (bisphenol A residue) ), Diphenylcarbonyl-4,4′-diyl group, diphenylsulfonyl-4,4′-diyl group (bisphenol S residue), diphenylthio-4,4′-diyl group, diphenyloxy-4,4′-diyl Group, etc.], or these groups are further directly bonded or linking groups (carbonyl group,
  • phenylene groups, biphenylene groups, bisphenol residues, etc. are widely used, and substituents (halogen atoms such as fluorine atoms and chlorine atoms, C 1-3 alkyl groups such as methyl groups, C groups such as methoxy groups, etc.) are added to the benzene ring.
  • substituents halogen atoms such as fluorine atoms and chlorine atoms, C 1-3 alkyl groups such as methyl groups, C groups such as methoxy groups, etc.
  • a biphenylene group or a diphenylmethane-4,4′-diyl group (bisphenol F residue) which may have a 1-3 alkoxy group or the like is preferable.
  • the number average molecular weight of the polyamideimide resin is 1,000 or more in terms of polystyrene in gel permeation chromatography (GPC), for example, 3,000 to 500,000, preferably 5,000 to 300,000, more preferably. It is about 8,000 to 100,000 (particularly 10,000 to 50,000). If the molecular weight is too small, heat resistance and mechanical properties may be reduced.
  • GPC gel permeation chromatography
  • the glass transition temperature of the polyamide-imide resin may be 150 ° C. or higher, for example, 180 to 400 ° C., preferably 200 to 380 ° C., more preferably 250 to 350 ° C. (especially 280 to 330 ° C.). If the glass transition temperature is too low, the heat resistance may be reduced. In the present invention, the glass transition temperature of the polyamideimide resin can be measured using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the primer layer may contain a solid lubricant in addition to the polyamideimide resin.
  • the solid lubricant include conventional solid lubricants such as fluorine compounds (fluorine resins such as polytetrafluoroethylene, fluorinated graphite), boron compounds (such as boron nitride), and sulfides such as metal sulfides (such as molybdenum disulfide). Examples thereof include molybdenum, tungsten sulfide such as tungsten disulfide), carbon materials (such as graphite and carbon black), simple metals (such as silver, lead, and nickel), mica, organic molybdenum compounds, and melamine cyanurate.
  • fluorine compounds fluorine resins such as polytetrafluoroethylene, fluorinated graphite
  • boron compounds such as boron nitride
  • sulfides such as metal sulfides (such as molybdenum disulfide
  • solid lubricants can be used alone or in combination of two or more.
  • fluorine compounds particularly polytetrafluoroethylene
  • metal sulfides particularly molybdenum disulfide
  • carbon materials particularly graphite
  • the ratio of the solid lubricant is about 500 parts by weight or less (for example, 0.1 to 500 parts by weight, preferably 10 to 200 parts by weight) with respect to 100 parts by weight of the polyamideimide resin. If the ratio of the solid lubricant is too large, the mechanical properties of the solidified coating film may be deteriorated.
  • the primer layer may contain a solid lubricant at the above ratio depending on the application, but it is preferable that the primer layer does not contain a solid lubricant from the viewpoint of adhesion to the substrate.
  • the primer layer may also contain other additives as long as the heat resistance and slidability are not impaired.
  • additives include curing agents (such as epoxy resins), fillers (such as inorganic fillers such as titanium oxide and alumina), stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.) ), Plasticizers, antifoaming agents, antistatic agents, flame retardants, and the like. These additives can be used alone or in combination of two or more.
  • the ratio of these additives is about 100 parts by weight or less with respect to 100 parts by weight of the polyamideimide resin, for example, 30 parts by weight or less (for example, 0.01 to 30 parts by weight), preferably 10 parts by weight or less (for example, 0.1 to 10 parts by weight).
  • the average thickness of the primer layer may be 0.5 ⁇ m or more, for example, 0.5 to 30 ⁇ m, preferably 0.8 to 10 ⁇ m, more preferably about 1 to 5 ⁇ m (particularly 1.5 to 3 ⁇ m). If the average thickness is too thin, the heat resistance and the adhesion between the sliding member and the coat layer may be reduced.
  • the average thickness of a primer layer can be measured as an average value of arbitrary 10 places using an optical film thickness meter, for example.
  • the smooth sliding member of the present invention is obtained by a production method including a coating layer forming step of coating and curing a curable liquid composition on the surface of the sliding member having an uneven structure. Specifically, when the primer layer is not formed, the curable liquid composition for forming the coat layer is directly coated on the surface (sliding surface) having an uneven structure of the sliding member. On the other hand, when the primer layer is formed, after the primer layer forming step of coating and solidifying the liquid composition on the sliding surface, the curability for forming a coat layer on the surface of the obtained primer layer A liquid composition is coated.
  • the liquid composition may contain an organic solvent or water.
  • organic solvent include amides (for example, N-mono or diC 1-4 alkylformamide such as N-methylformamide and N, N-dimethylformamide; N-methylacetamide and N, N-dimethylacetamide and the like.
  • the solid content weight of the liquid composition can be arbitrarily selected according to the process of the molding step to adjust the viscosity of the liquid composition suitable for the step, and is not particularly limited. For example, about 1 to 80% by weight You can choose from a range of
  • a coating method of the liquid composition conventional methods such as roll coating, air knife coating, blade coating, rod coating, reverse coating, bar coating, comma coating, die coating, gravure coating, screen coating method, spray method, spinner Law.
  • a blade coating method, a bar coating method, a gravure coating method, a spray method and the like are widely used.
  • the method for solidifying the liquid composition is not particularly limited, and may be natural drying or heat drying. However, firing treatment is preferable from the viewpoint of improving the strength of the primer layer and the adhesion to the sliding member.
  • the calcination temperature may be 120 ° C. or higher, for example, 120 to 300 ° C., preferably 150 to 280 ° C., more preferably 160 to 250 ° C. (especially 180 to 230 ° C.). If the firing temperature is too low, the strength of the primer layer and the adhesion to the sliding member may be reduced.
  • the firing time is 1 minute or longer (for example, 1 minute to 3 hours), preferably 10 minutes or longer (for example, 10 minutes to 2 hours), and more preferably 30 minutes or longer (for example, 30 minutes to 1.5 hours).
  • the baking treatment for forming the primer layer may be a heat treatment (for example, an aging treatment in a coat layer forming step described later) for forming a coat layer in the coat layer forming step.
  • the aging treatment for forming the layer also serves as the firing treatment for the primer layer. From the viewpoint of improving the surface smoothness of the coat layer, the firing treatment for forming the primer layer is preferably performed in the primer layer forming step, not the coat layer forming step.
  • the same coating method as in the primer layer forming step can be used as a coating method for the curable liquid composition.
  • even a simple coating method can form a coat layer having a smooth surface, and for example, a spray method may be used.
  • the curable liquid composition may be heated and dried (preliminary heating) before the curing treatment.
  • the preheating temperature is, for example, about 40 to 150 ° C., preferably 50 to 120 ° C., more preferably 60 to 100 ° C. (especially 70 to 90 ° C.).
  • the preheating time may be 10 seconds or longer (for example, 10 seconds to 10 minutes), preferably 20 seconds or longer (for example, 20 seconds to 5 minutes), and more preferably 30 seconds or longer (for example, 30 seconds to 2 minutes). Good.
  • the curable liquid composition may be cured by irradiating an active energy ray depending on the type of the curing agent, or may be cured by heating. Among these, it can be usually cured by irradiating with active energy rays.
  • Heat and / or light energy rays can be used as the active energy rays, and it is particularly useful to irradiate light using the light energy rays.
  • As light energy rays radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, electron beams (EB), etc. can be used, and usually ultraviolet rays and electron beams are often used.
  • irradiation with an electron beam may be performed.
  • a Deep UV lamp for example, in the case of ultraviolet rays, a Deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. may be used. it can.
  • Irradiation light amount varies depending on the thickness of the coating film, for example, 50 ⁇ 10000mJ / cm 2, preferably 70 ⁇ 5000mJ / cm 2, more preferably may be 100 ⁇ 1000mJ / cm 2 approximately.
  • the light amount and the irradiation time may be increased.
  • the irradiation light amount is, for example, 300 to 10,000 mJ / cm 2 (particularly 400 to 3000 mJ / cm 2 ). It may be a degree.
  • a method of irradiating an electron beam with an exposure source such as an electron beam irradiation apparatus can be used.
  • the irradiation amount (dose) varies depending on the thickness of the coating film, but is, for example, about 1 to 200 kGy (gray), preferably 5 to 150 kGy, more preferably 10 to 100 kGy (particularly 20 to 80 kGy).
  • the acceleration voltage is, for example, about 10 to 1000 kV, preferably about 50 to 500 kV, and more preferably about 100 to 300 kV.
  • Irradiation with active energy rays may be performed in an inert gas (for example, nitrogen gas, argon gas, helium gas, etc.) atmosphere if necessary.
  • an inert gas for example, nitrogen gas, argon gas, helium gas, etc.
  • the heating temperature is, for example, about 30 to 250 ° C., preferably 50 to 220 ° C., more preferably 60 to 200 ° C. (particularly 120 to 160 ° C.).
  • the heating time is, for example, about 10 minutes to 10 hours, preferably about 30 minutes to 5 hours, and more preferably about 45 minutes to 3 hours.
  • the heating temperature is, for example, about 30 to 200 ° C, preferably about 50 to 190 ° C, and more preferably about 60 to 180 ° C.
  • a curing treatment using active energy rays such as ultraviolet rays is preferable because it can be used for a wide range of sliding members.
  • Polyamideimide A “Dry coat 3500” manufactured by Sumiko Lubricant Co., Ltd.
  • Polyamideimide B “Viromax HR-11NN” manufactured by Toyobo Co., Ltd.
  • Alicyclic epoxy compound 3,4,3 ′, 4′-diepoxybicyclohexyl Curing agent: [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate Leveling Agent: Polyether-modified polydimethylsiloxane solution having a hydroxyl group, “BYK-SILCLEAN3720” manufactured by Big Chemie Japan Co., Ltd.
  • ⁇ H value is h / 10 or less
  • ⁇ H value is larger than h / 10.
  • Example 1 Using a hand spray gun (“W-101” manufactured by Anest Iwata Co., Ltd.) on the sliding surface of the skirt portion of the sliding member, polyamide is used as a primer layer so that the maximum thickness is 11 ⁇ m with compressed air. After the imide A was applied, it was baked at 200 ° C. for 60 minutes.
  • W-101 manufactured by Anest Iwata Co., Ltd.
  • a compressed layer of alicyclic epoxy is used as a coating layer so that the maximum thickness is 25 ⁇ m.
  • Example 2 A smooth sliding member was produced in the same manner as in Example 1 except that the maximum thickness of the primer layer was changed to 12 ⁇ m and the maximum thickness of the coat layer was changed to 29 ⁇ m. A CCD photograph of the cross section is shown in FIG.
  • Example 3 A smooth sliding member was produced in the same manner as in Example 1 except that the maximum thickness of the primer layer was changed to 32 ⁇ m and the maximum thickness of the coat layer was changed to 23 ⁇ m. A CCD photograph of the cross section is shown in FIG.
  • Example 4 A smooth sliding member is produced in the same manner as in Example 1 except that the coat layer is formed on the sliding surface of the skirt portion of the sliding member without forming the primer layer, and the maximum thickness of the coating layer is changed to 20 ⁇ m. did.
  • a CCD photograph of the cross section is shown in FIG.
  • Example 5 A smooth sliding member was produced in the same manner as in Example 4 except that the maximum thickness of the coat layer was changed to 28 ⁇ m. A cross-sectional SEM photograph is shown in FIG.
  • Example 6 A smooth sliding member was produced in the same manner as in Example 1 except that polyamideimide B was used instead of polyamideimide A, the maximum thickness of the primer layer was changed to 10 ⁇ m, and the maximum thickness of the coat layer was changed to 20 ⁇ m.
  • Comparative Example 1 In Example 1, the coating layer was not applied and formed as Comparative Example 1 and evaluated in the same manner as in Example 1.
  • Comparative Example 2 In Example 3, the coating layer was not applied and formed as Comparative Example 2.
  • Comparative Example 3 A smooth sliding member was prepared in the same manner as in Example 1 except that the maximum thickness of the primer layer was changed to 1 ⁇ m and the maximum thickness of the coat layer was changed to 10 ⁇ m. evaluated. A cross-sectional SEM photograph is shown in FIG.
  • Comparative Example 4 In Example 6, the coating layer was not applied and formed as Comparative Example 4, and as in Example 1, the surface state was evaluated from the cross section.
  • Table 1 shows the evaluation results of the smooth sliding members obtained in Examples and Comparative Examples.
  • the surface of the smooth sliding member obtained in the example was smooth. Furthermore, the SEM photograph of the cross section in the smooth sliding member obtained in Example 1 is shown in FIG. When the coating layer surface of FIG. 2 is seen, the surface of the coating layer is formed smoothly with respect to the streak having an uneven shape. On the other hand, when the cross section of the primer layer (corresponding to Comparative Example 1) in FIG. 2 is also seen, a polyamideimide layer is formed following the protrusions of the stripes. Also in FIG. 4, the coat layer (Example 3) is formed smoothly, but the cross section of the primer layer (corresponding to Comparative Example 2) is a polyamide that is a primer layer with respect to the protrusions of the streaks.
  • the sliding member of the present invention can be used as sliding members (for example, cylinders, pistons, bearings, etc.) for various industrial equipment, transportation equipment such as automobiles and airplanes, electronic and electrical equipment.
  • sliding parts for automobile parts such as pistons that are engine parts; sliding members such as cam bearings, crank bearings and connecting rod bearings; shaft members such as cam shafts and crank shafts; roller rockers, rocker arms, lash adjusters, Valve drive sliding members such as valve lifters; Chain drive sliding members such as chain guides, chain dampers, and chain slippers; Vane and trochoidal oil pump bearing members; Alternator bearings and other engine accessories Member: It can be effectively used as a bearing member of a transmission, and is particularly effective as a piston having a skirt portion.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Metallurgy (AREA)
  • Emergency Medicine (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Lubricants (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Sliding-Contact Bearings (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un élément coulissant lisse comprenant : un élément coulissant en métal et ayant une structure irrégulière en surface ; et une couche de revêtement lisse qui recouvre la surface dudit élément coulissant. La couche de revêtement est formée du produit durci à partir d'une composition liquide durcissable contenant un composé époxy alicyclique représenté par la formule (1) (dans la formule, R1 à R18 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, un groupe oxo, un groupe hydroxyle, un groupe hydropéroxy, un groupe amino, un groupe sulfo, ou un groupe organique, et X est une liaison directe ou un groupe de liaison). Cet élément coulissant lisse possède une surface lisse et également prend en charge une productivité élevée.
PCT/JP2018/009886 2017-04-11 2018-03-14 Élément coulissant et procédé pour le produire WO2018190061A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-077976 2017-04-11
JP2017077976A JP2018177928A (ja) 2017-04-11 2017-04-11 摺動部材及びその製造方法

Publications (1)

Publication Number Publication Date
WO2018190061A1 true WO2018190061A1 (fr) 2018-10-18

Family

ID=63793261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/009886 WO2018190061A1 (fr) 2017-04-11 2018-03-14 Élément coulissant et procédé pour le produire

Country Status (2)

Country Link
JP (1) JP2018177928A (fr)
WO (1) WO2018190061A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07189804A (ja) * 1993-12-27 1995-07-28 Toyota Motor Corp 内燃機関のピストンおよびその製造方法
JP2005330941A (ja) * 2004-05-21 2005-12-02 Toyota Motor Corp ピストンおよびその製造方法
JP2008056750A (ja) * 2006-08-30 2008-03-13 Sumikou Junkatsuzai Kk 複層潤滑被膜用組成物と複層潤滑被膜及び該被膜を有するピストン
JP2010127142A (ja) * 2008-11-26 2010-06-10 Isuzu Motors Ltd 内燃機関のピストン
JP2010216362A (ja) * 2009-03-17 2010-09-30 Hitachi Automotive Systems Ltd 複層被膜組成物が施された内燃機関のピストン及び該ピストンの表面処理方法
JP2016120476A (ja) * 2014-12-25 2016-07-07 トヨタ自動車株式会社 摺動部材およびその製造方法
JP2016121314A (ja) * 2014-12-25 2016-07-07 株式会社ダイセル 耐摩耗剤
JP2017089494A (ja) * 2015-11-10 2017-05-25 株式会社ダイセル 自動車部品及びその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07189804A (ja) * 1993-12-27 1995-07-28 Toyota Motor Corp 内燃機関のピストンおよびその製造方法
JP2005330941A (ja) * 2004-05-21 2005-12-02 Toyota Motor Corp ピストンおよびその製造方法
JP2008056750A (ja) * 2006-08-30 2008-03-13 Sumikou Junkatsuzai Kk 複層潤滑被膜用組成物と複層潤滑被膜及び該被膜を有するピストン
JP2010127142A (ja) * 2008-11-26 2010-06-10 Isuzu Motors Ltd 内燃機関のピストン
JP2010216362A (ja) * 2009-03-17 2010-09-30 Hitachi Automotive Systems Ltd 複層被膜組成物が施された内燃機関のピストン及び該ピストンの表面処理方法
JP2016120476A (ja) * 2014-12-25 2016-07-07 トヨタ自動車株式会社 摺動部材およびその製造方法
JP2016121314A (ja) * 2014-12-25 2016-07-07 株式会社ダイセル 耐摩耗剤
JP2017089494A (ja) * 2015-11-10 2017-05-25 株式会社ダイセル 自動車部品及びその製造方法

Also Published As

Publication number Publication date
JP2018177928A (ja) 2018-11-15

Similar Documents

Publication Publication Date Title
US20170130091A1 (en) Automotive parts and processes for producing the same
TWI803470B (zh) 硬塗膜
US10563091B2 (en) Curable composition, and moulded body
US20180346759A1 (en) Curable composition and shaped product
CN102471639B (zh) 表面处理方法和经处理的制品
JP5272338B2 (ja) フッ素系重合体および樹脂組成物
KR102561501B1 (ko) 플라스틱 렌즈
JP2017514928A (ja) 潤滑被膜用塗料組成物
WO2018193979A1 (fr) Silsesquioxane fluoré modifié par un époxy et composition durcissable comprenant ce dernier
US20210189173A1 (en) Thoroughly modified, functionalized polymeric hard coating material for coatings, methods for synthesizing the same and applications thereof
KR20210008809A (ko) 광학 적층체 및 이를 포함하는 플렉서블 디스플레이 장치
WO2018190061A1 (fr) Élément coulissant et procédé pour le produire
JP2017218545A (ja) 硬化性組成物、硬化物、硬化物の製造方法、及び成形体
CN112135731B (zh) 层叠膜及可折叠设备
WO2017081963A1 (fr) Kit de traitement de surface et article moulé composite et procédé pour les produire
JP2018176516A (ja) 積層体並びに複合成形体及びその製造方法
JP2020041059A (ja) 硬化性組成物及びその硬化物並びにその用途
KR102484993B1 (ko) 광학 다층 구조체, 이의 제조방법 및 이를 포함하는 윈도우 커버 필름
US20200079972A1 (en) Automotive parts and processes for producing the same
CN113956791A (zh) 一种硬涂层形成用组合物、硬涂膜及其制备方法
JP6281863B2 (ja) ゴム用コーティング剤およびそれから形成された塗膜を備えたシール
JPS58136663A (ja) 被覆組成物
US11866608B2 (en) Weather-resistant hard coat composition for metal, cured product, and coated metal substrate
WO2022044967A1 (fr) Polyorganosilsesquioxane, composition durcissable, objet durci, film de revêtement dur, feuille adhésive, et stratifié
KR20220166445A (ko) 윈도우 커버 필름, 이의 제조방법 및 이를 포함하는 플렉서블 디스플레이 패널.

Legal Events

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

Ref document number: 18783825

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18783825

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载