JP2018177928A - Sliding member and method of manufacturing the same - Google Patents

Abstract

Provided is a sliding member having a concavo-convex structure with a smooth surface and high productivity. In a smooth sliding member including a sliding member formed of metal and having a concavo-convex structure on a surface thereof and a smooth coating layer covering the surface of the sliding member, the coat layer is represented by the formula ( 1) (wherein R1 to R18 are the same or different and each represents a hydrogen atom, a halogen atom, an oxo group, a hydroxyl group, a hydroperoxy group, an amino group, a sulfo group or an organic group, and X is a direct bond or A curable liquid composition containing a cycloaliphatic epoxy compound represented by a linking group). [Selection figure] None

Description

  The present invention relates to a sliding member such as a piston and a method of manufacturing the same.

  The piston in the internal combustion engine is formed of an aluminum alloy and has a skirt portion for sliding contact with the inner wall of the cylinder. On the surface of the skirt portion, streaks extending in a spiral along the axial direction are formed to prevent burning and to retain the oil. Resin coated film containing solid lubricant etc. on the surface with streaks to realize low fuel consumption, to reduce the friction force by the surface of the skirt, and to improve the wear resistance of the surface of the skirt. Is formed. However, due to the uneven shape due to the streaks, the slidability is not sufficient, and further improvement in the slidability is required from the recent increase in awareness of environmental problems.

  In JP 2010-216362 A (Patent Document 1), an underlayer coating composition coated on the surface of a piston substrate and an upper layer coating composition coated on the upper surface of the underlayer coating composition A piston of an internal combustion engine having a multi-layered lubricating film formed thereon, wherein the lower layer coating composition and the upper layer coating composition both include at least one of a polyamideimide resin, a polyimide resin or an epoxy resin which is a binding resin, The underlayer coating composition has a solid lubricant content of at least either graphite or molybdenum disulfide set at 50 wt% or less, while the upper layer coating composition comprises at least graphite or molybdenum disulfide. Content of solid lubricant containing either one or both of graphite and molybdenum disulfide is 50 to 95 w % Pistons set in is disclosed. In the example of this document, a multi-layered lubricating film having a shape following the streaks is formed on the surface of the skirt portion having the streaks, and the multi-layered lubricating film wears the upper layer coating by sliding. It is lubricating.

  However, although this piston forms a smooth sliding surface in a relatively short time due to the softness of the upper layer coating, an initial familiarization period is required, and the clearance between the piston and the cylinder is wide depending on the amount of wear. And there is a concern that energy transfer efficiency will decline.

  In JP-A-2016-180331 (Patent Document 2), at least one layer of a coating is provided on the outer peripheral surface of a skirt portion which slides on the inner wall of a cylinder and has streaks, The piston of an internal combustion engine is disclosed in which the layer is an electrodeposited film. In this document, the electrodeposition film is a film formed by electrodeposition of an electrodeposition paint containing a binder resin such as a polyamideimide resin, a polyimide resin, an epoxy resin, etc., for improving the smoothness of the skirt portion. It is stated to function as a cosmetic layer. Moreover, after forming a lubricating film in the outer peripheral surface of a skirt part, the aspect which forms the electrodeposition film on a lubricating film, and improves the smoothness of a skirt part outer peripheral surface is also described.

  However, in this piston, since the skirt portion is smoothed by electrodeposition coating, the smoothness is not sufficient, the production of a smooth film is complicated, and the productivity is low.

  JP-A-2010-90812 (Patent Document 3) discloses that aluminum or aluminum alloy piston skirts for internal combustion engines are made of compressed metal or ceramic fine particles having an average particle diameter of 20 to 400 μm. The structure of the piston base material is uniformed in a depth range of 1 to 15 μm from the surface of the skirt portion by injecting and colliding at a jet velocity of 80 m / sec or more or a jet pressure of 0.2 MPa or more as a mixed fluid with nitrogen. Surface treatment to form a modified layer with activated surface, and after the surface treatment, the surface of the modified layer is exposed and activated while the new surface is exposed and activated. A surface treatment method of a piston skirt portion for an internal combustion engine is disclosed which forms a lubricating layer made of a resin coating having a coefficient of friction. In this document, an epoxy resin and a polyamideimide resin are described as a resin having a low friction coefficient that constitutes a lubricating layer, and in the examples, a polyamideimide is used. Furthermore, it is described that the centerline average roughness Ra of the modified layer is 0.5 to 2.5 μm and the centerline average roughness Ra of the lubricating layer can be 1 μm or less, and the centerline average of the lubricating layer in the examples is described. The roughness Ra is 0.6 μm.

  However, even with this surface treatment method, the smoothness of the surface by the lubricating layer is not sufficient.

  Furthermore, although an epoxy resin is illustrated as a binder by patent documents 1-3, the detail of the epoxy resin is not described and sliding property and rigidity (hardness) are low in the general purpose epoxy resin.

  On the other hand, Japanese Patent Application Laid-Open No. 2008-189853 (Patent Document 4) is a light that can be suitably used as an automotive clear paint, top coat agent for plastic film, coat agent for protecting plastic parts, coat agent for forming color filter protective film, etc. An alicyclic diepoxy compound containing a 3,4,3′4′-diepoxybicyclohexyl compound as a curable resin composition, an epoxy compound other than this alicyclic diepoxy compound, an oxetane compound, a vinyl ether compound, an acrylic weight Disclosed is a combination with at least one compound selected from the group consisting of combined and 2 to 6 functional polyol compounds.

  However, this document does not describe sliding members having streaks. Furthermore, compared with epoxy resins such as bisphenol A epoxy compounds used as general-purpose adhesives, alicyclic epoxy compounds are generally excellent in slidability and rigidity, but have low adhesion and adhesiveness. . Furthermore, the slidability and the adhesion are contradictory characteristics, and it was difficult to make both characteristics compatible.

Unexamined-Japanese-Patent No. 2010-216362 (Claim 1, Example, FIG. 4 (A)) JP, 2016-180331, A (claims 1 and 2, paragraph [0012] [0043] [0045], Drawing 3 and 10) JP, 2010-90812, A (claim 1, paragraph [0080] [0082], an example) JP 2008-189853 A (claim 1, paragraph [0014], an embodiment)

  Therefore, an object of the present invention is a sliding member having a smooth surface and high productivity even with a member having a concavo-convex structure (in particular, a concavo-convex processed structure artificially processed) such as streaks and a method of manufacturing the same 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 of manufacturing the same.

  Still another object of the present invention is to provide a sliding member which has excellent wear resistance and can maintain an initial clearance between a piston and a cylinder, and a method of manufacturing the same.

  Another object of the present invention is to provide a sliding member and a method of manufacturing the same, which can prevent baking even when worn due to long-term use and the like.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors formed a metal, and a curable liquid containing a specific alicyclic epoxy compound on the surface of a sliding member having a concavo-convex structure such as streaks. By coating and curing the composition, it has been found that the surface of a portion having a concavo-convex structure such as streaks is smooth, and a sliding member having high productivity can be provided, thereby completing the present invention.

  That is, the smooth sliding member of the present invention is a smooth sliding member including a sliding member formed of metal and having a concavo-convex structure on the surface, and a smooth coating layer covering the surface of the sliding member. And the coat layer has the formula (1)

(Wherein, 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)
It is a hardened | cured material of the curable liquid composition containing the alicyclic epoxy compound represented by these. A primer layer following the uneven shape of the uneven 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 contain at least one solid lubricant selected from the group consisting of a fluorine compound, a metal sulfide and a carbon material. The uneven structure may have an uneven shape with an average height of 0.5 to 30 μm of the convex portion. When the average height of the projections of the uneven structure is h, the height difference between the highest surface and the lowest surface in the 50-fold length region of h is h / 10 or less on the surface of the coating layer May be The maximum thickness d of the coating layer may be at least 1.1 times the average height h of the projections of the concavo-convex structure. In the above formula (1), at least one of 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 alone, an iron alone, a nickel alone, a copper alone, a chromium alone, or an alloy including any one of these alone. The sliding member may be a piston having a skirt portion, and an uneven structure may be formed on the surface of the skirt portion.

  The present invention also includes the method for producing the smooth sliding member, which includes a coating layer forming step of coating and curing the curable liquid composition on the surface of the sliding member having the uneven structure. Further, in the present invention, when the smooth sliding member includes a primer layer, a primer layer forming step of coating and solidifying a liquid composition on the surface having a concavo-convex structure of the sliding member, the surface of the obtained primer layer In addition, the method for producing the smooth sliding member, which includes a coating layer forming step of coating and curing the curable liquid composition is also included. In the coating layer forming step, the curable liquid composition may be coated by a spray method.

  In the present invention, since the curable liquid composition containing the specific alicyclic epoxy compound is coated on the surface of the sliding member formed of metal and having the concavo-convex structure and hardened, the productivity is high. The sliding member in which the surface of the site | part which has uneven structures, such as a streak, is smooth is obtained. The resulting sliding member is excellent in slidability, heat resistance and chemical resistance. Moreover, it is excellent in abrasion resistance, and can maintain the initial clearance between a piston and a cylinder. In addition, since the uneven layer structure such as streaks is provided in the lower layer of the smooth coat layer, the baking can be prevented even if the surface layer is worn by long-term use or the like.

FIG. 1 is a schematic view showing the relationship between the average height h of the projections of the concavo-convex structure, the maximum thickness d of the coating layer, and the surface height difference ΔH. 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 CCD (charge coupled device) photograph of a cross section 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 scanning electron microscope (CCD (charge coupled device)) photograph of the cross section of the sliding member obtained in Example 4. FIG. 6 is a scanning electron microscope (SEM) photograph of the cross section of the sliding member obtained in Example 5. FIG. 7 is a scanning electron microscope (SEM) photograph of the cross section of the smooth sliding member obtained in Comparative Example 3.

[Smooth sliding member]
The smooth sliding member of the present invention includes a sliding member formed of metal and having a concavo-convex structure such as streaks on the surface, and a smooth coat layer (surface layer) covering the surface of the sliding member.

(Sliding member)
The sliding member is not particularly limited as long as it is formed of metal and has a concavo-convex structure (concretely processed concavo-convex processing) such as streaks on the surface (sliding surface), and various industrial devices It may be a sliding member (for example, a cylinder, a piston, a bearing, etc.) used for transport machines such as automobiles and aircrafts, and electronic and electric devices, etc. Among them, sliding members used in transport machines such as automobiles, for example, pistons which are engine parts; sliding members such as cam bearings, crank bearings, connecting rod bearings, etc .; shaft members such as camshafts, crankshafts; Sliding members for valve systems such as rockers, rocker arms, lash adjusters, valve lifters, etc. Engine accessory components such as bearing members; bearing members for transmissions, etc. are preferable, and pistons having a skirt portion are particularly preferable.

  It does not specifically limit as a metal which comprises a sliding member, According to the kind of sliding member, what is necessary is just the metal utilized conventionally. As a metal, aluminum, iron, nickel, copper, chromium etc. are mentioned, for example. The metal may be the metal alone or an alloy of the metal (for example, stainless steel, steel, etc.). Furthermore, the metal surface may be subjected to plating treatment such as zinc plating for anti-corrosion treatment. Among these, metals including aluminum and iron are generally used, and in the case of a piston having a skirt portion used for an internal combustion engine of a car, it is usually formed of a metal including aluminum (aluminum alone or 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 (in particular, the concavo-convex processed structure) formed on the surface (sliding surface) of the sliding member is not particularly limited as long as it is a concavo-convex shape, and is conventionally used according to the type of sliding member. The uneven shape may be any as long as it is uneven, or may be irregularly formed regularly, or irregularly or randomly formed irregularly.

  The uneven structure having a regular uneven shape is, for example, in the case of a cylindrical shape such as a piston, even in the circumferential surface, a streak having a convex portion continuously extending in a spiral direction toward the axial center direction. Alternatively, the circumferentially extending projections may be regularly formed spaced apart streaks. The streaks 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 portion, the streaks are formed on the skirt portion.

  The uneven structure having a random uneven shape may be, for example, a randomly subdivided uneven shape or the like. Such a concavo-convex shape may be formed by, for example, a processing method for causing particles to collide as described in Patent Document 3 or the like.

  The shape of the convex portion forming the concavo-convex processed structure is not particularly limited as long as it is a shape extending linearly, and the shape of the cross section perpendicular to the longitudinal direction is, for example, substantially semicircular shape, mountain shape or wave shape, triangular Shape, square shape etc. are mentioned. Among these, generally, it has a substantially semicircular shape, a mountain shape or a wave shape.

  The average height h of the protrusions (the height at the top of the protrusions or the average value of the maximum height of the protrusions) can be selected from the range of about 0.5 to 100 μm (for example, 0.5 to 30 μm), for example 1 It is about 30 to 30 μm, preferably about 2 to 25 μm, and more preferably about 3 to 20 μm (particularly about 5 to 15 μm). If the average height is too small, baking may occur when the coating layer is worn, and if too large, the asperity processed structure (or the primer layer formed on the asperity processed structure) may be exposed.

  When forming a regular uneven structure such as streaks, the average pitch of the convex portions can be selected from the range of about 1 to 1000 μm, for example 10 to 500 μm, preferably 50 to 400 μm, more preferably 100 to 350 μm (in particular 150 to 300 μm). If the average pitch is too small, it may be difficult to form a concavo-convex structure, and if it is too large, baking may occur at the time of wear.

(Coat layer)
The coating layer covers the surface of the sliding member having a concavo-convex structure (or a concavo-convex structure covered with a primer layer formed on the concavo-convex structure following the concavo-convex structure) to form a smooth surface. In the prior art, when the coating layer having high slidability, wear resistance, heat resistance and chemical resistance is formed by coating, the coating layer is formed like a primer layer described later. In order to follow the shape of the uneven structure such as a mark, it was difficult to form a smooth coat layer. On the other hand, in the present invention, by coating and curing a curable liquid composition containing a specific alicyclic epoxy compound, a smooth coated layer can be formed by a simple method.

  The smoothness of the coating layer (that is, the inability to follow the uneven structure of the sliding member) can be evaluated by the surface level difference [surface deviation (ΔH value)]. Specifically, when the average height of the convex portions 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) of h on the surface of the coating layer The difference (ΔH value) is h / 10 or less, preferably h / 12 or less, and more preferably h / 15 or less (particularly h / 20 or less). If the height difference is too large, the smoothness may be reduced and the slidability may be reduced. In the present specification and claims, in the 50-fold length region of h, when the concavo-convex processed structure is a streak, the direction substantially perpendicular to the lengthwise direction of the convex portion of the streak is It means an extended length area. Further, in the present specification and claims, the height difference (ΔH value) can be measured, for example, by a method such as microscopic measurement or SEM observation of the cross section of the sliding member or surface roughness measurement.

  The maximum thickness d of the coating layer may be higher than the average height h of the projections of the concavo-convex structure, and may be, for example, 1.1 times or more (in particular 1.3 times or more) the average height h 1.5 times or more is preferable, 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 asperity structure or the primer layer formed on the asperity structure may be exposed. In the present specification and the claims, the maximum thickness d of the coating layer can be measured, for example, as an average value at any 10 points using an optical film thickness meter. FIG. 1 is a schematic view showing the relationship between the average height h of the projections 1 of the concavo-convex structure, the maximum thickness d of the coating layer 2 and the surface height difference ΔH value.

  As described above, the maximum thickness d of the coat layer can be selected according to the size of the convex portion of the concavo-convex structure, but in the case of a piston having a skirt, for example, 12 μm or more (particularly 15 μm or more) may be used. For example, it is about 12 to 100 μm, preferably about 15 to 50 μm, and more preferably about 20 to 40 μm (particularly about 25 to 35 μm).

  In the present specification and claims, when the primer layer is formed on the concavo-convex structure, the average height h of the projections of the concavo-convex structure for obtaining the height difference Δ value and the maximum thickness d is as follows: The average height of the protrusions of the primer layer (the protrusions having a shape that follows the protrusions of the uneven structure) is used.

  The arithmetic average roughness Ra of the coating 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 7) 10 nm). In the present invention, the arithmetic average is obtained by the combination of the coating layer containing the alicyclic epoxy compound (especially an alicyclic epoxy compound in which X is a direct bond) represented by the above (1) and the primer layer containing a polyamideimide resin. High surface smoothness with a roughness Ra of 20 nm or less (particularly 10 nm or less) can also be realized. If the arithmetic mean roughness Ra is too large, the surface smoothness may be reduced, which may lead to a decrease in the slidability. In the present specification and claims, the average roughness can be measured by a method in accordance with JIS B0601 (2001).

The coat layer has high hardness, and the indentation hardness by a microhardness tester may be 300 N / mm ² or more (eg 300 to 1000 N / mm ² ), preferably 450 N / mm ² or more (eg 450 to 800 N / mm) ^2), it is more preferably 550 N / mm ² or more (e.g. 550~700N / mm ² approximately). If the indentation hardness is too small, it may be difficult to maintain the abrasion resistance of the coating layer for a long time. In the present specification and claims, the indentation hardness can be measured, for example, using a microhardness 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).

(1) Alicyclic epoxy compound An alicyclic epoxy compound is represented by said Formula (1). In R ^{1 to} R ¹⁸ of 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, and examples thereof include 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 And the like.

  The hydrocarbon group includes, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

As an aliphatic hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group is mentioned, for example. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, isooctyl group, decyl group, the C _1-20 alkyl group (preferably a dodecyl group C _{1- 10} alkyl group, more preferably a C _1-4 alkyl group) and the like. As the alkenyl group, for example, a C _2-20 alkenyl group such as a vinyl group, an allyl group, a methallyl group, a 1-propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group (preferably a C _2-10 alkenyl group More preferably, a _C2-4 alkenyl group etc. are mentioned. As an alkynyl group, _C2-20 alkynyl groups (Preferably _C2-10 alkynyl group, More preferably _C2-4 alkynyl group), such as an ethynyl group and propynyl group, etc. are mentioned, for example.

As the alicyclic hydrocarbon group, for example, a C _3-12 cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, _cyclododecyl group (especially C _5-8 cycloalkyl group); cyclohexenyl group C _3-12 cycloalkenyl group such as, bicycloheptadiene group, such as C _4-15 bridged cyclic hydrocarbon group such as bicyclo heptenyl group.

As an aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned, for example.

The alkoxy group is a C _1-10 alkoxy group 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 Group) and the like. The alkenyloxy group includes, for example, 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). The aryloxy group include a phenoxy group, tolyloxy group, _{C 6-20} aryloxy group (in particular _{C 6-14} aryloxy group), such as naphthyloxy group and the like. As an aralkyloxy group, _C7-20 aralkyloxy groups (especially _C7-18 aralkyloxy group), such as a benzyloxy group and a phenethyl oxy group, etc. are mentioned, for example.

As an acyl group, _C1-20 acyl groups (especially _C1-12 acyl group), such as an acetyl group, a propionyl group, a (meth) acryloyl group, a benzoyl group, etc. are mentioned, for example. As an acyloxy group, _C1-20 acyloxy groups (especially _C1-12 acyloxy group), such as an acetyloxy group, a propionyloxy group, a (meth) acryloyloxy group, a benzoyloxy group, etc. are mentioned, for example.

The alkylthio group include a methylthio group, _{C 1-6} alkylthio groups such as ethylthio group (especially _{C 1-4} alkylthio group). The alkenylthio group, for example, _{C 2-6} alkenylthio group (especially _{C 2-4} alkenylthio group) such as allyl group and the like. As an arylthio group, _6-20 arylthio groups (especially _C6-14 arylthio group), such as a phenylthio group, a tolylthio group, a naphthylthio group, etc. are mentioned, for example. The aralkylthio group, for example, benzylthio group, _{C 6-20} aralkylthio group (especially _{C 7-18} aralkylthio group) such as phenethylthio group, and the like.

As the alkoxycarbonyl group, for example, a C _1-10 alkoxy-carbonyl group (in particular, a C _1-6 alkoxy-carbonyl group) such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and the like can be mentioned. The aryloxycarbonyl group, for example, a phenoxycarbonyl group, tolyloxycarbonyl group, C _6-20 aryloxy such as naphthyloxycarbonyl group - carbonyl group (especially C _6-14 aryloxy - carbonyl group). As the aralkyloxycarbonyl group, for example, a C _7-20 aralkyloxy-carbonyl group such as a benzyloxycarbonyl group (in particular, a C _7-18 aralkyloxy-carbonyl group) and the like can be mentioned.

As an epoxy containing group, a glycidyl group, glycidyl oxy group, etc. are mentioned, for example. The oxetanyl-containing radical, such as C _1-10 alkyl oxetanyl group such as ethyloxetanyl oxy group.

Examples of the substituted amino group include mono- or dialkylamino groups such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (especially mono- or di-C _1-6 alkylamino group), acetylamino group, propionylamino And an acylamino group such as benzoylamino group (in particular, a C _1-11 acylamino group).

These organic groups may be groups in which two or more types of organic groups are combined (bonded). As a combination of two or more organic groups, for example, a combination of an aliphatic hydrocarbon group and an alicyclic hydrocarbon group (such as cyclohexyl methyl group and methyl cyclohexyl group), an aliphatic hydrocarbon group and an aromatic hydrocarbon Combination with a group [C _7-18 aralkyl group such as benzyl group, phenethyl group (especially, C _7-10 aralkyl group), C _6-10 aryl-C _2-6 alkenyl group such as cinnamyl group, tolyl group, etc. C _1-4 alkyl-substituted aryl group, C _2-4 alkenyl-substituted aryl group such as styryl group], a combination of an alkoxy group and an aliphatic hydrocarbon group (such as methoxyethyl group), an aliphatic hydrocarbon group and an aryloxy Combinations with groups (such as methyl phenoxy group) and the like can be mentioned.

  The organic group may further have a substituent. As a substituent, a halogen atom, an oxo group, a hydroxyl group, a hydroperoxy group, an amino group, a sulfo group etc. are mentioned, for example.

Among them, as R ^{1 to} R ¹⁸ , a hydrogen atom, a linear or branched C _1-6 alkyl group (in particular, a linear C _1-3 alkyl group such as a methyl group) and the like are widely used, and rigidity From the point of point of view, it is preferable that at least one of R ^{1 to} R ¹⁸ be a hydrogen atom, and it is particularly preferable that all of them be a hydrogen atom.

  In X, 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 these linking groups are connected in plural. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

  As a bivalent aliphatic hydrocarbon group, an alkylene group, an alkenylene group, an alkynylene group etc. are mentioned, for example.

As the alkylene group, for example, 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, dodecamethylene group and the like _{And -20} alkylene group and the like.

Examples of the alkenylene group include vinylene group, allylene group, methallyl group, 1-propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, octenylene group and the like C _2-20 alkenylene group etc. are mentioned. The alkenylene group may be an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized.

As an alkynylene group, _C2-20 alkynylene groups, such as an ethynylene group and a propynylene group, etc. are mentioned, for example.

Examples of the divalent alicyclic hydrocarbon group 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, bicycloheptenylene group, etc. may be mentioned. 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 epoxy cyclohexylene group.

As a bivalent aromatic hydrocarbon group, _C6-14 arylene groups, such as a phenylene group and a naphthylene group, etc. are mentioned, for example.

These divalent hydrocarbon groups may have a substituent. As the substituent, for example, in addition to the substituents exemplified as the substituents of the organic group in R ^{1 to} R ¹⁸ , C _1-4 alkyl groups such as methyl group and ethyl group, C such as methoxy group and ethoxy group _{A 1-4} alkoxy group, a carbonyl group, etc. are mentioned.

  These linking groups may be (combined or linked) groups combining two or more linking groups. As a combination of two or more types of linking groups, for example, a combination of a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group (eg, cyclohexylmethylene group, methylenecyclohexylene group, dicyclohexylmethane) -4,4'-diyl group, dicyclohexylpropane-4,4'-diyl group etc., a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (eg, tolylene group, xylylene group) , A diphenylmethane-4,4'-diyl group, a diphenylpropane-4,4'-diyl group, etc., a combination of an ester bond and a divalent hydrocarbon group (eg, a carbonyloxy methylene group, a carbonyloxy hydrogenated xylylene group) (Eg, an oxycarbonyl group), a combination of a carbonate bond and a divalent hydrocarbon group (eg, methylene oxycarbony) A combination of multiple ester bonds (eg, a polyester bond such as polycaprolactone etc.), a combination of a plurality of ether bonds (eg, polyoxyethylene ethylene glycol, methylene oxy carbonyl oxyhydrogenated xylylene oxy carbonyl oxy methylene group, etc.) Groups, etc.), combinations of plural ether bonds and plural ester bonds (polyether ester bonds), combinations of plural urethane bonds (polyurethane bonds), a combination of epoxy cycloalkylene groups and polyester bonds, etc. Can be mentioned.

Among these, as X, a direct bond, an alkylene group (a 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 (eg, a C _1-4 alkyleneoxy C _1-4 alkylene group such as a methylene oxymethylene group), a combination of an ester bond and an alkylene group (eg, a carbonyloxy C ₁ such as a carbonyloxy methylene group) _-4 etc. 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.

Multiple The alicyclic epoxy compound represented by the formula (1) may include only the alicyclic epoxy compound of a single species, the type of the substituents R ¹ to R ¹⁸ and / or group X are different It may be a combination of various cycloaliphatic epoxy compounds.

Preferred alicyclic epoxy compounds include, for example, methyl groups such as 3,4,3 ′, 4′-diepoxybicyclohexyl, (3,4,3 ′, 4′-diepoxy-6-methyl) bicyclohexyl, etc. Diepoxybi C _5-8 cycloalkyl optionally having C _1-4 alkyl group; 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl Epoxy C _5-8 cycloalkyl C _1-4 alkyl (epoxy) C _5-8 cyclo _optionally having a C _1-4 alkyl group such as methyl (3,4-epoxy-6-methyl) cyclohexanecarboxylate Alkane carboxylate etc. are mentioned. These alicyclic epoxy compounds can be used alone or in combination of two or more.

(2) Curing Agent The curable liquid composition preferably further contains a curing agent. As a curing agent, a cationic polymerization initiator (acid generator) or a conventional curing agent [eg, acid and acid anhydride curing agents, amine curing agents, polyaminoamide curing agents, imidazole curing agents, organic acid hydrazides Curing agents, latent curing agents (such as dicyandiamides), polymercaptan curing agents, phenolic curing agents and the like] and the like.

  Among these, 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.

  Examples of the photoacid generator include sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (ammonium ions) And salts of phosphonium ions (salts of phosphonium ions and anions), salts of transition metal complex ions and anions, and the like. These photoacid generators can be used alone or in combination of two or more. Among these photoacid generators, an acid generator having a high acidity, for example, a sulfonium salt is preferable in that the reactivity can be improved and the hardness of the cured product can be improved.

  As the sulfonium salt, for example, triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium Salts, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, Triarylsulfonium salts such as [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium salt, 4- (p-tolylthio) phenyl di- (p-phenyl) sulfonium salt; diphenylphenacylsulfo Diarylsulfonium salts such as sodium salts, diphenyl 4-nitrophenacylsulfonium salts, diphenylbenzylsulfonium salts, diphenylmethylsulfonium salts; phenylmethylbenzylsulfonium salts, 4-hydroxyphenylmethylbenzylsulfonium salts, 4-methoxyphenylmethylbenzylsulfonium salts And monoarylsulfonium salts such as; dimethylphenacylsulfonium salts, phenacyltetrahydrothiophenium salts, and trialkylsulfonium salts such as dimethylbenzylsulfonium salts. These sulfonium salts can be used alone or in combination of two or more. Of these sulfonium salts, triarylsulfonium salts are preferred.

As an anion (counter ion) for forming a salt with a cation, for example, 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- and the} like], (C ₆ F ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion) Nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, etc., (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenated acid Ion, halogenated sulfonate ion, sulfate ion, carbonate ion, aluminate ion, hexafluorobisma Examples thereof include a sulfate ion, a carboxylate ion, an aryl borate ion, a thiocyanate ion, and a nitrate ion. Among these anions, fluorinated alkyl fluorophosphate ions are preferred from the viewpoint of solubility and the like.

  A photo-acid generator can use a commercially available photo-acid generator. Examples of commercially available photoacid generators include “CPI-101A”, “CPI-110A”, “CPI-100P”, “CPI-110P”, “CPI-210S”, and “CPI-200K” manufactured by San-Apro Co., Ltd. Can be used.

Examples of the thermal acid generator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes and the like. These thermal acid generators can be used alone or in combination of two or more. Among these thermal acid generators, acid generators having high acidity, such as arylsulfonium salts, are preferable in that they can improve the reactivity and the hardness of the cured product. As an anion, the anion similar to a photo-acid generator etc. is mentioned, The fluoride ion of antimony, such as SbF ^6- etc., may be sufficient.

  A thermal acid generator can also use a commercially available thermal acid generator. Examples of commercially available thermal acid generators include “San Aid SI-60L”, “San Aid SI-60 S”, “San Aid SI-80 L”, “San Aid SI-100 L”, manufactured by Sanshin Chemical Industry Co., Ltd. ) "SP-66" and "SP-77" manufactured by ADEKA can be used.

  Examples of amine-based curing agents include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, polypropylenetriamine, and the like; mensenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetra Alicyclic polyamines such as oxaspiro [5.5] undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene- 2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6-diamine, biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine And aromatic polyamines such as 2,6-naphthylenedamine. These amine curing agents can be used alone or in combination of two or more. Among these, aliphatic polyamines (ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, etc.), alicyclic polyamines (mensenediamine, isophorone diamine, etc.), aromatic polyamines (xylenediamine) And metaphenylene diamine etc.).

  Among these, cationic polymerization initiators (acid generators) are preferable from the viewpoint of promoting polymerization and improving the hardness of the cured product.

  The proportion of the curing agent can be selected from the 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 according to 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 with respect to 100 parts by weight of the alicyclic epoxy compound, and for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight Part, more preferably about 0.3 to 2 parts by weight (especially 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 reduced. If it is too large, the storage stability of the composition may be reduced or the cured product may be colored. There is a risk.

  The proportion of a conventional curing agent such as an amine 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.

(3) Leveling Agent The curable liquid composition preferably further contains a leveling agent. Any leveling agent may be used as long as it has a surface tension reducing ability, and a conventional leveling agent (such as ethylene oxide adduct of acetylene glycol) can be used, but from the viewpoint of excellent surface tension reducing ability, a silicone based leveling agent Fluorine-based leveling agents are preferred. In the present invention, by combining the alicyclic epoxy compound and the leveling agent, the surface smoothness can be improved and the slidability can be improved. Furthermore, by using a specific leveling agent, not only the hardness can be maintained, but also the hardness can be improved by controlling the blending ratio.

The silicone-based leveling agent may be any leveling agent having a polyorganosiloxane skeleton. As a polyorganosiloxane skeleton, a monofunctional M unit (generally represented by R ₃ SiO _1/2 ), a difunctional D unit (generally represented by R ₂ SiO _2/2 ) Units), trifunctional T units (generally represented by RSiO _3/2 ), and tetrafunctional Q units (generally represented by SiO _4/2 ) Any siloxane may be used, but usually a polyorganosiloxane formed of D units is used. The organic group (R) of the polyorganosiloxane can be selected from the hydrocarbon groups exemplified as R ^{1 to} R ¹⁸ of the formula (1) of the alicyclic epoxy compound, but usually a C _1-4 alkyl. A group or an aryl group is used, and a methyl group or a phenyl group (especially a methyl group) is generally used. The repeating number (degree of polymerization) of the siloxane unit is, for example, about 2 to 3,000, preferably about 3 to 2,000, and more preferably about 5 to 1,000.

The fluorine-based leveling agent may be any leveling agent having a fluoroaliphatic hydrocarbon skeleton. As a fluoro aliphatic hydrocarbon skeleton, for example, fluoro C _1-10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluoro t-butane, fluoropentane, fluorohexane and the like It can be mentioned.

  In these fluoroaliphatic hydrocarbon backbones, at least a part of hydrogen atoms may be substituted with fluorine atoms, but all hydrogen atoms are substituted with fluorine atoms in terms of improving the slidability and rigidity. Perfluoroaliphatic hydrocarbon backbones are preferred.

Furthermore, the fluoroaliphatic hydrocarbon backbone may form a polyfluoroalkylene ether backbone which 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 _{fluoroC 1-4} alkylene groups such as fluoromethylene group, fluoroethylene group, fluoropropylene group and fluoroisopropylene group, It is also good. These fluoroaliphatic hydrocarbon groups may be the same or may be a combination of two or more. The repeating number (degree of polymerization) of the fluoroalkylene ether unit may be, for example, about 10 to 3,000, preferably about 30 to 1,000, and more preferably about 50 to 500.

  Among these skeletons, a polyorganosiloxane skeleton is preferable from the viewpoint of being excellent in affinity with the cation curable silicone resin.

  A leveling agent having such a skeleton has a hydrolytic condensation group, a functional group such as a reactive group to an epoxy group, a radical polymerizable group, a polyether group, a polyester group, etc., to impart various functionalities. It may have a polyurethane group or the like. Further, the silicone-based leveling agent may have a fluoroaliphatic hydrocarbon group, and the fluorine-based leveling agent may have a polyorganosiloxane group.

As the hydrolyzable group, for example, a hydroxysilyl group; a trihalosilyl group such as a trichlorosilyl group; a dihalo C _1-4 alkylsilyl group such as a dichloromethylsilyl group; a dihaloarylsilyl group such as a dichlorophenylsilyl group; 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 Groups such as di C _1-4 alkoxy C _1-4 alkylsilyl groups; dimethoxyphenylsilyl groups, diethoxyphenylsilyl groups such as di C _1-4 alkoxyarylsilyl groups; methoxydimethylsilyl groups, ethoxydimethylsilyl groups etc. C _1-4 alkoxydi C _-4 alkylsilyl group; methoxymethylphenyl silyl group, C _1-4 alkoxy C _1-4 alkyl aryl silyl groups such as ethoxymethyl triphenylsilyl group; methoxydiphenylsilyl, C _1-4 alkoxy diarylsilyl group such as ethoxy butyldiphenylsilyl Etc. Among these, tri-C _1-4 alkoxysilyl groups such as trimethoxysilyl group are preferable in terms of reactivity and the like.

  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. Among these, from the viewpoint of reactivity and the like, a hydroxyl group, an amino group, an acid anhydride group, an isocyanate group and the like are widely used, and a hydroxyl group is preferable from the viewpoint of handleability and availability.

  As a radically polymerizable group, a (meth) acryloyloxy group, a vinyl group etc. are mentioned, for example. Among these, (meth) acryloyloxy group is widely used.

As a polyether group, polyoxy _C2-4 alkylene groups, such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a polyoxyethylene polyoxypropylene group, etc. are mentioned, for example. In the polyether group, the repeating number (additional mole number) of the oxyalkylene group is, for example, about 2 to 1000, preferably about 3 to 100, and more preferably about 5 to 50. Of these, polyoxy C _2-3 alkylene group such as a polyoxyethylene group or a polyoxypropylene group (especially polyoxyethylene group) are preferred.

  As a polyester group, for example, a polyester group formed by the reaction of a dicarboxylic acid (an aromatic carboxylic acid such as terephthalic acid or an aliphatic carboxylic acid such as adipic acid) with a diol (an aliphatic diol such as ethylene glycol) And polyester groups formed by ring-opening polymerization of cyclic esters (eg, lactones such as caprolactone).

  As a polyurethane group, a conventional polyester type polyurethane group, a polyether type polyurethane group etc. are mentioned, for example.

  These functional groups may be introduced as a direct bond to the polyorganosiloxane skeleton or fluoroaliphatic hydrocarbon skeleton, and a linking group (eg, an alkylene group, a cycloalkylene group, an ether bond, an ester bond, It may be introduced via an amide bond, a urethane bond, or a linking group combining these.

  Among these functional groups, from the viewpoint of being able to react with an alicyclic epoxy compound and improve the hardness of a cured product, a reactive group for a hydrolytic condensation group or an epoxy group is preferable, and a reactive group for an epoxy group ( Particularly preferred is a hydroxyl group).

The hydroxyl group may be a terminal hydroxyl group of a (poly) oxyalkylene group [such as (poly) oxyethylene group]. As such a leveling agent, for example, a silicone-based 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 Fluorinated leveling agent (fluoroalkylpolyoxyethylene) 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 Etc.).

  A commercially available silicone type leveling agent can be used as a silicone type leveling agent. As a commercially available silicone type | system | group leveling agent, the leveling agent ("BYK-300", "BYK-301 / 302", "BYK-306", "BYK-307", the BYK series made by BIC Chemie Japan KK), for example, "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-UV 3500 "," BYK-UV3 10 "," BYK-UV 3570 "," BYK-3550 "," BYK-SILCLEAN 3700 "," BYK-SILCLEAN 3720 ", etc., Algin Chemie AC series leveling agent (" AC FS 180 "," AC FS 360 "," AC S20 ", etc.), Kyoeisha Chemical Co., Ltd. Polyflow series leveling agent (" Polyflow KL-400X "," Polyflow KL-400HF "," Polyflow KL-401 "," Polyflow KL-402 "," Polyflow KL " -403 "," Polyflow KL-404 ", etc., Shin-Etsu Chemical Co., Ltd. KP series leveling agent (" KP-323 "," KP-326 "," KP-341 "," KP-104 ", "KP-110", "KP-112", etc.) Leveling agent ("LP-7001", "LP-7002", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE", Examples include "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE", and the like.

  A commercially available fluorine-type leveling agent can be used as a fluorine-type leveling agent. As commercially available fluorine-based leveling agents, for example, leveling agents ("DSX", "DAC-HP") manufactured by Daikin Industries, Ltd. manufactured by Daikin Industries, Ltd., and leveling agents manufactured by AGC Seimi Chemical Co., Ltd. manufactured by Surfron series (" "S-242", "S-243", "S-420", "S-611", "S-651", "S-386", etc., BYK series BYK series leveling agent "BYK-340", etc.) Algin Chemie AC series leveling agent ("AC 110a", "AC 100a" etc.), DIC Corporation's Megafuck series leveling agent ("Megafuck F-114", "Megafuck F-410", "Megafuck F-444", "Megafuck EXP TP 2066", "MegaFat F-430 "," Megafuck F-472SF "," Megafuck F-477 "," Megafuck F-552 "," Megafuck F-553 "," Megafuck F-554 "," Megafuck F- " 555 "," Megafuck R-94 "," Megafuck RS-72-K "," Megafuck RS-75 "," Megafuck F-556 "," Megafuck EXP TF-1367 "," Megafuck EXP " TF-1437 "," Megafuck F-558 "," Megafuck EXP TF-1537 ", etc., Sumitomo 3M Co., Ltd. FC series leveling agent (" FC-4430 "," FC-4432 ", etc.), Ltd. NEOS HOTTERgent Series Leveling Agents ("FURTAGENT 100", "FURTAGENT 100C", "FURTAGE" 110, "Futagent 150", "Futagent 150 CH", "Futagent A-K", "Futagent 501", "Futagent 250", "Futagent 251", "Futagent 222F", "Futagent" GENT 208 G "," FURTAGENT 300 "," FURTAGENT 310 "," FURTgent 400 SW, etc. ", Kitamura Chemical Industries, Ltd. PF series leveling agent (" PF-136A "," PF-156A "," PF-Series ") PF-151N "," PF-636 "," PF-6320 "," PF-656 "," PF-6520 "," PF-651 "," PF-652 "," PF-3320 ", etc. It can be mentioned.

  These leveling agents can be used alone or in combination of two or more kinds. For example, plural kinds of silicone type leveling agents and plural kinds of fluorine type leveling agents may be respectively combined, and the silicone type leveling agent and the fluorine type leveling agent And may be used in combination. Among these leveling agents, a silicone-based leveling agent having a hydroxyl group is preferable from the viewpoint of being excellent in affinity with the alicyclic epoxy compound, capable of reacting with the epoxy group, and improving the hardness and appearance of the cured product.

  As a silicone type leveling agent which has a hydroxyl group, for example, polyether modified polyorganosiloxane which introduce | transduced the polyether group into the principal chain or side chain of polyorganosiloxane frame | skeleton (polydimethylsiloxane etc.), the principal chain of polyorganosiloxane frame | skeleton Or polyester modified polyorganosiloxane which introduce | transduced polyester group into the side chain, silicone modified (meth) acrylic resin which introduce | transduced polyorganosiloxane into (meth) acrylic resin, etc. are mentioned. In these leveling agents, the hydroxyl group may have a polyorganosiloxane skeleton, or may have a polyether group, a polyester group, or a (meth) acryloyl group. As such a leveling agent, "BYK-370", "BYK-SILCLEAN 3700", "BYK-SILCLEAN 3720" etc. made by Big Chemie Japan KK can be used, for example.

  The proportion 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 proportion of the leveling agent is too small, the slidability of the cured product may be reduced, and if too large, the hardness of the cured product may be reduced.

  In particular, the proportion of the silicone-based 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. It may be about part (especially 0.5 to 2 parts by weight). The proportion of the fluorine-based leveling agent is, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.2 to 1 parts by weight, per 100 parts by weight of the alicyclic epoxy compound. In particular, it may be about 0.3 to 0.8 parts by weight. When the proportion of the leveling agent is adjusted to these ranges, not only the slidability of the cured product can be improved, but also the hardness of the cured product, which has not been conventionally considered as a function of the leveling agent, can be improved.

(4) Other Additives The curable liquid composition may contain other curable resin. Examples of 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 from the viewpoint of reactivity and miscibility. As another epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a long chain aliphatic epoxy resin etc. can be illustrated, for example. The proportion of the other curable resin is about 100 parts by weight or less, for example 50 parts by weight or less (eg, 1 to 50 parts by weight), preferably 30 parts by weight or less (eg, 30 parts by weight or less). 5 to 30 parts by weight).

  The curable liquid composition may contain conventional additives as long as the slidability and rigidity are not impaired. Conventional additives include, for example, curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organic metal compounds, etc.) Fillers (Inorganic fillers such as titanium oxide and alumina), Stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers etc), plasticizers, lubricants, antifoams, antistatic agents, You may contain a flame retardant, an ultraviolet absorber, etc. These additives may be used alone or in combination of two or more. The total proportion of these additives is about 100 parts by weight or less, for example, 30 parts by weight or less (eg, 0.01 to 30 parts by weight), preferably 10 parts by weight or less, per 100 parts by weight of the alicyclic epoxy compound. (For example, 0.1 to 10 parts by weight) or so.

  Furthermore, the curable liquid composition may contain an organic solvent or water. Examples of 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.), Cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amides (dimethylformamide, dimethylacetamide, etc.) and the like can be mentioned. These solvents can be used alone or in combination of two or more.

  The solid content weight of the curable liquid composition can be optionally selected and not particularly limited in order to adjust to the viscosity of the liquid composition suitable for the process depending on the process of the molding process.

(Primer layer)
In the smooth sliding member of the present invention, it is preferable that a primer layer following the uneven shape of the uneven structure be interposed between the surface of the sliding member and the coating layer. When 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 may contain a conventional binder resin or the like that can improve the adhesion between the sliding member and the coat layer, but it is preferable to contain a polyamideimide resin in terms of heat resistance and the like.

  The polyamideimide resin is a polymer having an imide bond and an amide bond in the main chain, and is a polyamideimide obtained by reacting a tricarboxylic acid anhydride (or a reactive derivative such as a halide or lower alkyl ester thereof) with a polyvalent isocyanate, The tricarboxylic acid anhydride and the polyvalent amine may be reacted to form an imide bond, and then the polyvalent isocyanate may be reacted to form an amidated polyamideimide or the like.

  The polyamideimide resin is usually a resin obtained by using trimellitic anhydride as the tricarboxylic acid anhydride, for example, a compound of the formula (2)

(Wherein, Y represents a group containing a divalent hydrocarbon group)
It may be a resin having a repeating unit represented by

In Y of said Formula (2), the bivalent hydrocarbon group etc. which were illustrated as X of said Formula (1) etc. are mentioned as a bivalent hydrocarbon group. The divalent hydrocarbon group may be a C _1-10 alkylene group such as ethylene group, a C _5-8 cycloalkylene group such as cyclohexylene group, etc., but from the viewpoint of heat resistance, a phenylene group or a naphthylene group And the like, preferably containing a divalent aromatic hydrocarbon group such as The 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 carbonyl group; a sulfonyl group; an ether bond; a group in which a plurality of divalent aromatic hydrocarbon groups (eg, 1,4-phenylene group etc.) are linked via a linking group such as a thioether (sulfide) bond May be In this group, the divalent aromatic hydrocarbon group and the alkylene group are substituents (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, It may have a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group or the like.

  As Y, for example, phenylene group (1,4-phenylene group, 1,3-phenylene group etc.), naphthylene group (1,5-naphthylene group, 2,6-naphthylene group etc.), 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 Group, etc.] or these groups are further directly bonded or the above linking group (carbonyl group, sulfonyl group, ether bond, thioether bond, etc. ) And attached group through, the substituent on the benzene ring of these groups include groups in substituted. These groups can be used alone or in combination of two or more.

Among them, phenylene group, biphenylene group, bisphenol residue and the like are widely used, and a benzene ring (substituent group (halogen atom such as fluorine atom or chlorine atom, C _1-3 alkyl group such as methyl group, C group such as methoxy group) _The biphenylene group which may have a _1-3 alkoxy group etc. and diphenylmethane 4,4'- diyl group (bisphenol F residue) are 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 (especially 10,000 to 50,000). If the molecular weight is too small, the heat resistance and mechanical properties may be reduced.

  The glass transition temperature of the polyamideimide resin may be 150 ° C. or higher, and is, for example, about 180 to 400 ° C., preferably 200 to 380 ° C., and more preferably about 250 to 350 ° C. (particularly about 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).

  The primer layer may contain a solid lubricant in addition to the polyamideimide resin. As solid lubricants, commonly used solid lubricants, for example, fluorine compounds (fluororesins such as polytetrafluoroethylene, fluorinated graphite etc.), boron compounds (boron nitride etc.), metal sulfides (eg sulfurized molybdenum disulfide etc.) Molybdenum, tungsten sulfide such as tungsten disulfide), carbon materials such as graphite (graphite, carbon black, etc.), simple metals (silver, lead, nickel, etc.), mica, organic molybdenum compounds, melamine cyanurate, etc. may be mentioned. These solid lubricants can be used alone or in combination of two or more. Among these solid lubricants, fluorine compounds (especially polytetrafluoroethylene), metal sulfides (especially molybdenum disulfide), and carbon materials (especially graphite) are preferable.

  The proportion of the solid lubricant is about 500 parts by weight or less (eg, 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 proportion of the solid lubricant is too large, the mechanical properties of the solidified coating may be degraded.

  The primer layer may contain the solid lubricant in the above proportion, depending on the application, but it is preferable not to include the 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 the slidability are not impaired. Commonly used additives include curing agents (such as epoxy resins), fillers (such as inorganic fillers such as titanium oxide and alumina), stabilizers (such as antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.) ), Plasticizers, antifoaming agents, antistatic agents, flame retardants, UV absorbers, etc. may be contained. These additives may be used alone or in combination of two or more. The proportion 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 (eg, 0.01 to 30 parts by weight), preferably 10 parts by weight or less (eg, 0.1 to 10 parts by weight).

  The average thickness of the primer layer may be 0.5 μm or more, and is, for example, about 0.5 to 30 μm, preferably about 0.8 to 10 μm, and more preferably about 1 to 5 μm (particularly about 1.5 to 3 μm). If the average thickness is too thin, the heat resistance and the adhesion between the sliding member and the coating layer may be reduced. In the present specification and claims, the average thickness of the primer layer can be measured, for example, as an average value at any 10 points using an optical film thickness meter.

[Method of manufacturing smooth sliding member]
The smooth sliding member of the present invention is obtained by a manufacturing method including a coating layer forming step of coating and curing a curable liquid composition on the surface of the sliding member having the uneven structure. Specifically, when the primer layer is not formed, the curable liquid composition for forming the coating layer is directly coated on the surface (sliding surface) of the sliding member having the uneven structure. On the other hand, when forming a primer layer, after passing through a primer layer forming step of coating and solidifying a liquid composition on the sliding surface, a hardenability for forming a coat layer on the surface of the obtained primer layer The liquid composition is coated.

In the primer layer formation step, the liquid composition may contain an organic solvent or water. As the organic solvent, for example, amides (eg, N-mono or di C _1-4 alkylformamide such as N-methylformamide, N, N-dimethylformamide, etc .; N-methylacetamide, N, N-dimethylacetamide etc. N-mono or di C _1-4 alkyl acetamide; N-methyl pyrrolidone etc., ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), ethers (dioxane, tetrahydrofuran etc.), aliphatic hydrocarbons (hexane Etc.), alicyclic hydrocarbons (eg cyclohexane), aromatic hydrocarbons (eg benzene, toluene), halogenated carbons (eg dichloromethane, dichloroethane etc.), esters (eg methyl acetate, ethyl acetate), alcohols (Methanol, Ethane , Isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), may contain such cellosolve acetates. These solvents can be used alone or in combination of two or more. Among these solvents, preferred solvents for polyamideimide resins such as N-methylpyrrolidone are preferred.

  The solid content weight of the liquid composition can be optionally selected in order to adjust the viscosity of the liquid composition suitable for the process according to the process of the molding process, and is not particularly limited. You can choose from the range of

  As a method of coating a 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 etc. Among these methods, blade coating method, bar coating method, gravure coating method, 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, but firing treatment is preferable from the viewpoint of improving the strength of the primer layer and the adhesion to the sliding member.

  The firing temperature may be 120 ° C. or higher, and is, for example, about 120 to 300 ° C., preferably about 150 to 280 ° C., and more preferably about 160 to 250 ° C. (particularly about 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 baking time is about 1 minute or more (eg, 1 minute to 3 hours), preferably about 10 minutes or more (eg, 10 minutes to 2 hours), and more preferably about 30 minutes or more (eg, 30 minutes to 1.5 hours).

  The baking treatment for forming the primer layer may be heat treatment for forming the coating layer in the coating layer forming step (for example, aging treatment in the coating layer forming step described later), in which case the coating is Aging treatment for forming a layer also serves as firing treatment of the primer layer. From the viewpoint of being able to improve the surface smoothness of the coat layer, the baking treatment for forming the primer layer is preferably performed not in the coat layer forming step but in the primer layer forming step.

  In the coating layer forming step, as the coating method of the curable liquid composition, the same coating method as the primer layer forming step can be used. In particular, in the present invention, a coating layer having a smooth surface can be formed even by a simple coating method, and for example, a spray method may be used.

  In the coating layer forming step, the curable liquid composition may be heated and dried (preheated) before the curing treatment. The preheating temperature is, for example, about 40 to 150 ° C., preferably about 50 to 120 ° C., and more preferably about 60 to 100 ° C. (particularly about 70 to 90 ° C.). The preheating time is about 10 seconds or more (eg, 10 seconds to 10 minutes), preferably 20 seconds or more (eg, 20 seconds to 5 minutes), and more preferably 30 seconds or more (eg, 30 seconds to 2 minutes). Good.

  In the curing treatment, the curable liquid composition may be cured by irradiation with active energy rays or may be cured by heating, depending on the type of the curing agent. Of these, in general, curing can be performed by irradiation with active energy rays.

  As active energy rays, heat and / or light energy rays can be used, and in particular, light irradiation using light energy rays is useful. As the light energy ray, radiation (gamma ray, X-ray, etc.), ultraviolet ray, visible ray, electron beam (EB), etc. can be used, and usually, ultraviolet ray, electron beam is often used. In particular, in applications where polymerization can be performed without using a curing agent and high weather resistance is required, electron beam irradiation may be performed.

As a light source, for example, in the case of ultraviolet light, a Deep UV lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser, excimer laser) etc. may be used it can. Irradiation light amount (irradiation energy) varies depending on the thickness of the coating film, for example 50~10000mJ / cm ^2, preferably 70~5000mJ / cm ^2, more preferably about 100~1000mJ / cm ^2. Furthermore, in order to improve the adhesion to the two-dimensional or three-dimensional shaped body, it may be increased the amount of light and irradiation time, the irradiation amount of light, for example 300~10000mJ / cm ² (particularly 400~3000mJ / ^cm 2) It may be an extent.

  In the case of the electron beam, a method of irradiating the electron beam by an exposure source such as an electron beam irradiation device can be used. The irradiation dose (dose) varies depending on the thickness of the coating, but is, for example, about 1 to 200 kGy (gray), preferably about 5 to 150 kGy, and more preferably about 10 to 100 kGy (especially 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 of active energy rays (in particular, electron beams) may be performed in an inert gas (for example, nitrogen gas, argon gas, helium gas, etc.) atmosphere, if necessary.

  In addition, after curing by active energy rays, the primer layer after curing may be heat-treated (annealing treatment or aging treatment). In the aging treatment, the heating temperature is, for example, about 30 to 250 ° C, preferably about 50 to 220 ° C, and more preferably about 60 to 200 ° C (particularly about 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.

  On the other hand, in the case of heat curing using a thermal cationic polymerization initiator, 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.

  As the curing treatment, a curing treatment using active energy rays such as ultraviolet rays is preferable in that it can be used for a wide range of sliding members.

  The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. In addition, the detail of the raw material and sliding member which were used by the Example and the comparative example is as follows, and the smooth sliding member obtained by the Example and the comparative example was evaluated by the following items.

[material]
(Raw material for primer layer)
Polyamide imide A: "Dry Coat 3500" manufactured by Sumi Mining Co., Ltd.
Polyamide imide B: “Viromax HR-11NN” manufactured by Toyobo Co., Ltd.
(Raw material for coat layer)
Alicyclic epoxy compound: 3,4,3 ′, 4′-diepoxybicyclohexyl curing agent: [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate leveling Agent: Polyether modified polydimethyl siloxane solution having a hydroxyl group, "BYK-SILCLEAN 3720" manufactured by Big Chemie Japan Co., Ltd.

[Sliding member]
Aluminum alloy piston which has a skirt part in which convex parts with an average height of 10 micrometers and an average pitch of 200 micrometers were formed in parallel.

[Film thickness]
The thickness of the primer layer and the coat layer was measured using a dual type film thickness meter ("LZ-990" manufactured by Ketto Scientific Research Institute, Ltd.).

[Surface smoothness]
Regarding the smoothness of the surface of the obtained coat layer, the sliding member is cut, and after embedding in acrylic resin so that the cut surface comes out, the sample whose cross section is precisely polished is observed by SEM or CCD, and streaks are observed. The height difference (ΔH value) in a 50-fold length region of the average height h of the convex portions of the (primer layer) was measured, and the measured ΔH value was evaluated based on the following criteria.

〇: ΔH value is h / 10 or less. ×: ΔH 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 of the sliding member, use polyamide as a primer layer so that the maximum thickness is 11 μm with compressed air After the imide A was applied, it was baked at 200 ° C. for 60 minutes.

On the obtained primer layer, using a hand spray gun ("W-101" manufactured by Anest Iwata Co., Ltd.), a cycloaliphatic epoxy as a coating layer so that the maximum thickness is 25 μm with compressed air. 100 parts by weight of a compound, 0.25 parts by weight of a curing agent and 1 part by weight of a leveling agent are applied, followed by prebaking at 80 ° C. for 1 minute, followed by a conveyor type ultraviolet curing device ("Aicure" manufactured by Panasonic Corporation) It was irradiated with ultraviolet light at a conveyor speed of 1.0 m / min and treated with a metal halide lamp (output 70%, illuminance 50 mW / cm ² ) and ultraviolet light with an integrated light amount of 400 mJ / cm ² . Finally, the coated film of the coating layer was cured by heat treatment (aging treatment) at 150 ° C. for 1 hour to produce a smooth sliding member having a primer layer and a coating layer. An SEM photograph of the cross section is shown in FIG.

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 μm and the maximum thickness of the coating layer to 29 μm. 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 μm and the maximum thickness of the coating layer to 23 μm. 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 a coat layer is formed on the sliding surface of the skirt portion of the sliding member without forming a primer layer, and the maximum thickness of the coat layer is changed to 20 μm. 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 coating layer was changed to 28 μm. The SEM photograph of the cross section 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 μm, and the maximum thickness of the coating layer was changed to 20 μm.

Comparative Example 1
In the same manner as in Example 1, evaluation was made in the same manner as in Example 1 except that the coating layer was not formed by coating in Example 1.

Comparative example 2
A comparative example 2 was obtained in which the coating layer was not formed by coating in Example 3.

Comparative example 3
A smooth sliding member is produced in the same manner as in Example 1 except that the maximum thickness of the primer layer is changed to 1 μm and the maximum thickness of the coat layer is changed to 10 μm. evaluated. The SEM photograph of the cross section is shown in FIG.

Comparative example 4
The surface state was evaluated from the cross section in the same manner as in Example 1 except that the coating layer was not formed by coating in Example 6 as Comparative Example 4.

  Table 1 shows the evaluation results of the smooth sliding member obtained in Examples and Comparative Examples.

  As apparent from the results in Table 1, 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 coat layer surface of FIG. 2 is seen, the surface of the coat layer is formed smooth with respect to the streaks having the uneven shape. On the other hand, similarly, looking at the primer layer cross section (corresponding to Comparative Example 1) in FIG. 2, the polyamideimide layer is formed to follow the convex portion of the streak. Also in FIG. 4, although the coat layer (Example 3) is formed to be smooth, the cross section of the primer layer (corresponding to Comparative Example 2) is a polyamide which is the primer layer with respect to the convex portion of the streaks. Even when the film thickness of imide was increased, the polyamideimide layer was formed following (without smoothness), and ΔH was 3 μm, and ΔH> d / 10. However, in the coat layers of Examples 4 and 5 shown in FIGS. 5 and 6, the surface of the coat layer is formed smooth even when the streaks having the uneven shape are directly applied.

  The sliding member of the present invention can be used as sliding members (for example, cylinders, pistons, bearings, etc.) of various industrial devices, transport machines such as automobiles and aircrafts, and electronic and electrical devices. In particular, sliding members of automobile parts, for example, pistons which are engine parts; sliding members such as cam bearings, crank bearings, connecting rod bearings, etc .; shaft members such as camshafts, crankshafts; roller lockers, rocker arms, lash adjusters, Sliding members for valve lifters and other valve trains; Chain-driven sliding members such as chain guides, chain dampers, and chain slippers; Bearing members for vane-type and turquoid-type oil pumps; Engine auxiliary equipment such as bearing members for alternators It can be effectively used as a member; a bearing member of a transmission, etc., and is particularly effective as a piston having a skirt portion.

1 ... coat layer 2, 3 ... convex portion of streaks 4 ... polyamide imide layer

Claims (15)

A smooth sliding member comprising a sliding member formed of metal and having a concavo-convex structure on the surface, and a smooth coating layer covering the surface of the sliding member, wherein the coating layer is represented by the formula (1)
(Wherein, R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxo group, a hydroxyl 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)
The smooth sliding member which is a hardened | cured material of the curable liquid composition containing the alicyclic epoxy compound represented by these.   The smooth sliding member according to claim 1, wherein a primer layer following the uneven shape of the uneven structure is interposed between the surface of the sliding member and the coating layer.   The smooth sliding member according to claim 2, wherein the primer layer contains a polyamideimide resin.   The smooth sliding member according to claim 2 or 3, wherein the primer layer further comprises at least one solid lubricant selected from the group consisting of a fluorine compound, a metal sulfide and a carbon material.   The smooth sliding member according to any one of claims 1 to 4, wherein the concavo-convex structure has a concavo-convex shape having an average height of 0.5 to 30 μm of the convex portions.   When the average height of the convex portions of the concavo-convex structure is h, the height difference between the highest surface and the lowest surface in the 50-fold length region of h is h / 10 or less on the surface of the coating layer. The smooth sliding member according to any one of Items 1 to 5.   The smooth sliding member according to any one of claims 1 to 6, wherein the maximum thickness d of the coating layer is 1.1 times or more the average height h of the convex portions of the concavo-convex structure. The smooth sliding member according to any one of claims 1 to 7, wherein in the formula (1), at least one of R ^{1 to} R ¹⁸ is a hydrogen atom, and X is a direct bond.   The smooth sliding member according to any one of claims 1 to 8, wherein the curable liquid composition further comprises a curing agent.   The smooth sliding member according to any one of claims 1 to 9, wherein the curable liquid composition further comprises a leveling agent.   The smooth sliding member according to any one of claims 1 to 10, wherein the metal is an aluminum alone, an iron alone, a nickel alone, a copper alone, a chromium alone, or an alloy comprising any one of these alone.   The smooth sliding member according to any one of claims 1 to 11, wherein the sliding member is a piston having a skirt portion, and an uneven structure is formed on a surface of the skirt portion.   The method for producing a smooth sliding member according to claim 1, further comprising a coating layer forming step of coating and curing the curable liquid composition on the surface of the sliding member having the concavo-convex structure.   A primer layer forming step of coating and solidifying the liquid composition on the surface having the uneven structure of the sliding member, and a coating layer forming step of coating and curing the curable liquid composition on the surface of the obtained primer layer The method for producing a smooth sliding member according to claim 2, further comprising:   The method according to claim 13 or 14, wherein the curable liquid composition is coated by a spray method in the coating layer forming step.