WO2023008405A1 - Coating composition for sliding member, and sliding member - Google Patents

Coating composition for sliding member, and sliding member Download PDF

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Publication number
WO2023008405A1
WO2023008405A1 PCT/JP2022/028704 JP2022028704W WO2023008405A1 WO 2023008405 A1 WO2023008405 A1 WO 2023008405A1 JP 2022028704 W JP2022028704 W JP 2022028704W WO 2023008405 A1 WO2023008405 A1 WO 2023008405A1
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WIPO (PCT)
Prior art keywords
sliding member
coating
wear
coating composition
silica
Prior art date
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PCT/JP2022/028704
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French (fr)
Japanese (ja)
Inventor
真 牧野
圭資 宮本
恭平 藤井
直樹 山川
貴晴 宮下
弘樹 宮坂
Original Assignee
アクロス株式会社
アート金属工業株式会社
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Publication of WO2023008405A1 publication Critical patent/WO2023008405A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present disclosure relates to a sliding member coating composition for forming a coating on the surface of a sliding member, and a sliding member having a coating formed from the sliding member coating composition on its surface.
  • sliding members examples include bearings and pistons of automobile engines, and swash plates of swash plate compressors.
  • a piston has a piston skirt in sliding contact with a cylinder bore, which is a mating sliding member.
  • lubricity between the piston skirt and the cylinder bore is important. If the lubricity between the piston skirt and the cylinder bore is low, seizure will occur and the engine will stop. Therefore, the surface (sliding surface) of the piston skirt, which is in sliding contact with the cylinder bore, has conventionally been provided with a coating.
  • Coatings for such sliding members are required not only to have a low friction coefficient and seizure resistance, which directly contribute to lubricity, but also to have wear resistance and low mating aggression. If the wear resistance is low, repeated sliding contact with the mating material will cause the coating to deteriorate early, and the function will not be maintained. If the mating aggressiveness is high, the mating material is likely to be damaged due to sliding contact with the film.
  • Patent Documents 1 to 6 disclose techniques for improving the various physical properties required for such coatings.
  • the coating compositions for sliding members described in Patent Documents 1 to 6 generally contain a binder resin, a solid lubricant, and a wear suppressing material that is an inorganic filler. Moreover, other additives are also contained as needed.
  • adjusting the blending amount of each component, adjusting the surface roughness of the coating, adjusting the particle size of each component, using special materials, etc. any one of the various physical properties required for this type of coating is specialized.
  • Patent Documents 1 to 6 specialize in one of the physical properties of low friction coefficient, seizure resistance, wear resistance, and low mating aggression. However, other physical properties are sacrificed to achieve that goal. That is, Patent Documents 1 to 6 cannot satisfy all of low friction coefficient, seizure resistance, wear resistance, and low mating aggression. Moreover, when a special material is used, it is difficult to obtain and manufacture, or the material cost increases.
  • the present disclosure is a sliding coating capable of forming a coating that simultaneously satisfies all of the physical properties of low friction coefficient, seizure resistance, wear resistance, and low mating aggression with a simple formulation using conventionally known materials. It is an object of the present invention to provide a coating composition for moving members and a sliding member having a coating formed thereon on its surface.
  • the present disclosure is a coating composition for sliding members for forming a coating on the surface of the sliding member. It contains a binder resin, a solid lubricant, and a wear inhibitor. 0.5 to 6 parts by weight of the solid lubricant and 5 to 30 parts by weight of the wear inhibitor are blended with 100 parts by weight of the binder resin. At least polytetrafluoroethylene (PTFE) is used as the solid lubricant, and at least silica is used as the wear suppressing material. In addition, the particle size ratio between the PTFE and the silica calculated as (PTFE/silica) is 0.8-80.
  • PTFE polytetrafluoroethylene
  • a sliding member having a coating formed from the coating composition for a sliding member on its surface.
  • the coating composition for sliding members of the present disclosure contains, in addition to the binder resin, PTFE and silica, which are known materials generally used in this type of coating composition for sliding members, as essential components. It is a simple combination. In addition, by adjusting the content and particle size ratio, it is possible to form a film that simultaneously satisfies all of the physical properties of a low coefficient of friction, seizure resistance, wear resistance, and low mating aggression.
  • the coating composition for sliding member of the present disclosure is a composition for forming a coating for coating at least the sliding surface of the sliding member.
  • the coating composition for sliding members of the present disclosure contains a binder resin, a solid lubricant, and a wear inhibitor.
  • the binder resin is a base component of the film.
  • the binder resin is not particularly limited as long as it can form a film while containing additional components.
  • known organic binders conventionally used in coating compositions for sliding members of this type can be used.
  • Specific examples include thermoplastic resins such as polyamideimide resin, polyvinyl butyral resin, chlorinated polyolefin resin, nylon, polyetherimide resin, polyethersulfone resin, and thermoplastic polyimide resin.
  • Alkyd resin, epoxy resin, amino resin, acrylic resin, polyaminoamide resin, polyurethane resin, unsaturated polyester resin, phenol resin, xylene resin, vinyl ester resin, furan resin, silicone resin, polyimide resin, wholly aromatic polyester, etc. can be exemplified by thermosetting resins.
  • thermoplastic resins polyamideimide resins, polyvinyl butyral resins, polyethersulfone resins, and thermoplastic polyimides are preferred.
  • thermosetting resins epoxy resins, amino resins, acrylic resins, polyaminoamide resins, polyurethane resins, unsaturated polyester resins, phenol resins, xylene resins, silicone resins, and polyimide resins are preferred.
  • polyamideimide resin polyethersulfone resin, thermoplastic polyimide resin, epoxy resin, or polyimide resin is more preferable from the viewpoint of adhesiveness, chemical resistance, strength, and the like.
  • binder resins may be used alone or in combination of two or more.
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • the average particle size of PTFE should be 0.1 to 50 ⁇ m, preferably 0.2 to 40 ⁇ m.
  • the term "average particle size” as used herein means a volume cumulative average particle size ( D50 ) measured by a laser diffraction/scattering particle size distribution measurement method.
  • the blending amount of PTFE is 0.5 to 6 parts by weight, preferably 1 to 4 parts by weight, per 100 parts by weight of the binder resin. If the blending amount of PTFE is less than 0.5 parts by weight with respect to 100 parts by weight of the binder resin, the lubricating property is insufficient, so that the wear suppressing material tends to aggressively attack the mating material. On the other hand, when it is more than 6 parts by weight, the content of the binder resin is relatively decreased, resulting in deterioration of wear resistance and seizure resistance.
  • solid lubricants include, for example, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and polychlorotri Fluorine compounds such as fluoroethylene, sulfides such as molybdenum disulfide (MoS 2 ) and tungsten disulfide, graphite (GP), graphite fluoride, boron nitride, lamellar flake substances such as mica, lead, zinc, copper, etc.
  • MoS 2 molybdenum disulfide
  • GP graphite
  • graphite fluoride boron nitride
  • lamellar flake substances such as mica, lead, zinc, copper, etc.
  • Examples include particles of soft metals, melamine cyanurate, and the like.
  • One or two or more of these other solid lubricants may be added within a range that does not inhibit the effects of the present disclosure (the amount of PTFE blended or less), but it is preferable to blend only PTFE.
  • At least silica particles are used as an essential component of the wear suppressing material.
  • silica has good compatibility with PTFE, mainly improves the wear resistance of the coating, and has low attacking property.
  • the average particle size of silica should be 0.001 to 20 ⁇ m, preferably 0.015 to 10 ⁇ m.
  • the amount of silica compounded is 5 to 30 parts by weight, preferably 10 to 25 parts by weight, per 100 parts by weight of the binder resin. If the amount of PTFE to be blended is less than 5 parts by weight per 100 parts by weight of the binder resin, the wear resistance is lowered, and accordingly the seizure resistance is also lowered. On the other hand, if it is more than 30 parts by weight, the aggressiveness to the mating member increases and the seizure resistance also decreases.
  • wear inhibitors include aluminas such as aluminum oxide, aluminum hydroxide, alumina white, silica alumina, barium sulfate, zirconia, tungsten carbide, titanium carbide, silicon carbide, titanium dioxide, iron oxide, feldspar, pumice, orthoclase, iridium, quartz, beryllium oxide, zirconium oxide, chromium, boron carbide, tungsten carbide, metallic tungsten, silicone carbide, and the like.
  • aluminas such as aluminum oxide, aluminum hydroxide, alumina white, silica alumina, barium sulfate, zirconia, tungsten carbide, titanium carbide, silicon carbide, titanium dioxide, iron oxide, feldspar, pumice, orthoclase, iridium, quartz, beryllium oxide, zirconium oxide, chromium, boron carbide, tungsten carbide, metallic tungsten, silicone carbide, and the like.
  • the particle size ratio (average particle size ratio) between PTFE and silica calculated by (PTFE/silica) is set to 0.8 to 80. If the particle size ratio of (PTFE/silica) is less than 0.8, silica is too large relative to PTFE, resulting in increased attacking property. On the other hand, if the particle size ratio of (PTFE/silica) exceeds 80, the silica is too small relative to PTFE, resulting in a decrease in wear resistance.
  • additives can be added to the film composition for sliding members within a range that does not impair the effects of the present disclosure.
  • examples include dispersants such as PTFE that improve dispersibility, silane coupling agents that improve adhesion, leveling agents and surfactants that control surface tension, and thickeners that control thixotropy. .
  • the sliding member it can be applied not only to a member that slides with a mating member in a lubricated state using a lubricant such as lubricating oil or grease, but also to a member that slides in a non-lubricated state without using a lubricant.
  • a lubricant such as lubricating oil or grease
  • the material of the sliding member is not particularly limited, and typically includes metals or alloys such as aluminum and iron, but rubber, plastic, ceramics, etc. may also be used.
  • the sliding coating composition may be applied to at least the sliding surface of the sliding member, but may be applied to the entire surface.
  • any organic solvent can be used without particular limitation as long as it can dissolve the binder resin.
  • a typical resin in the case of an epoxy resin, a ketone solvent such as methyl ethyl ketone, an ester solvent such as ethyl acetate, or an aromatic solvent such as xylene or toluene can be used.
  • NMP N-methyl-2-pyrrolidone
  • NMP includes aromatic solvents such as xylene, ketone solvents such as methyl ethyl ketone, and ester solvents such as ethyl acetate.
  • the coating method of the sliding coating composition conventionally known general coating methods can be adopted. Specific examples include brush, roller, roll coater, air spray, airless spray, dip coating, screen printing, pad printing and gravure coating.
  • the sliding surface of the sliding member may be subjected to pretreatment such as alkali degreasing, solvent degreasing, etching, chemical conversion treatment, etc., if necessary.
  • the coating After applying the sliding coating composition, the coating can be formed by drying and curing.
  • the film thickness of the coating may be about 5 to 50 ⁇ m, preferably about 10 to 45 ⁇ m, which is conventionally common.
  • Tables 1 and 2 The materials shown in Tables 1 and 2 were mixed in the proportions shown in Tables 1 and 2, and a coating composition for sliding members was prepared by adjusting the viscosity with an organic solvent as necessary. The amount of each material shown in Tables 1 and 2 is in parts by weight. Using the coating composition for sliding members of each example and comparative example, the following tests were conducted to evaluate each physical property of the coating.
  • a seizure load was measured using a thrust tester 1 (manufactured by A&D Co., Ltd.) shown in FIG.
  • the sliding surface 11 of the test plate 10 was subjected to solvent degreasing as a pretreatment.
  • Each composition was applied to the sliding surface 11 by spraying, dried and cured to form a film having a thickness of 15 ⁇ m.
  • the drying and curing conditions for the composition with the binder resin as polyamideimide resin (PAI) and phenol resin (PF) are 180 ° C. and 90 minutes, and the composition with polyimide resin (PI) is 350 ° C. and 10 minutes. and the epoxy resin composition was heated at 200° C. for 30 minutes. The same applies to other tests described later.
  • This mating member 12 was placed on the sliding surface 11 coated with the film.
  • the test plate 10 was rotated in the direction of arrow 15 in FIG. 1 at a rotation speed of 1000 rpm. After a break-in rotation (a pressing load of 245 N was applied for 10 minutes), a pressing load was applied from the direction of arrow 16 in FIG.
  • the test was performed under lubrication with lubricating oil (mineral oil; 0W-20) at 80°C.
  • the load (N) at which the film was removed and seizure was measured and evaluated according to the following criteria. The results are also shown in Tables 1 and 2.
  • Seizure load is 3920 N or more ⁇ : Seizure load is 3500 N or more and less than 3920 N ⁇ : Seizure load is 3200 N or more and less than 3500 N ⁇ : Seizure load is less than 3200 N
  • Abrasion resistance test The abrasion resistance of the film was evaluated using a block-on-ring tester 2 (“FALEX LFW-1” manufactured by FALEX CORPORATION) shown in FIG.
  • Solvent degreasing was applied to the sliding surface 21 of the test material 20 in FIG. 2 as a pretreatment.
  • Each test composition was applied to the sliding surface 21 by spraying, dried and cured to form a film having a thickness of 15 ⁇ m.
  • This mating member 22 was brought into contact with the sliding surface 21 .
  • the mating material 22 was rotated at a rotational speed of 20 rpm in the direction of arrow 25 in FIG.
  • the test was performed under lubrication with lubricating oil (mineral oil; 0W-20) at a lubricating oil temperature of 80°C. After 15 minutes from the start of the test, the wear amount ( ⁇ m) of the coating was measured with a laser microscope (“VK-X100”, manufactured by Keyence Corporation) and evaluated according to the following criteria. The results are also shown in Tables 1 and 2.
  • the amount of abrasion of the coating is less than 3 ⁇ m ⁇ : The amount of abrasion of the coating is 3 ⁇ m or more and less than 4 ⁇ m ⁇ : The amount of abrasion of the coating is 4 ⁇ m or more and less than 6 ⁇ m ⁇ : The amount of abrasion of the coating is 6 ⁇ m or more
  • Partner Aggression Test Using a friction wear tester 3 (HEIDON TYPE 20, manufactured by Shinto Kagaku Co., Ltd.) shown in FIG. A plate-shaped test material 30 (t0.5 ⁇ 35 ⁇ 70 mm, material SPCC (cold-rolled steel plate)) was used as a sliding member to be coated. Solvent degreasing was applied to the sliding surface 31 of the test material 30 as a pretreatment. After each composition was applied to the sliding surface 31 by spraying, it was dried and cured to form a film having a thickness of 15 ⁇ m.
  • a ball-shaped member (outer diameter ⁇ 3/8 inch, material SUJ2 (high carbon chromium bearing steel)) was used as the mating member 32. This mating member was brought into contact with the sliding surface 31. The mating material 32 was rotated in the direction of arrow 35 at a rotation speed of 200 rpm, and a pressing load (0.98 N) was applied to the test material 30 from the direction of arrow 36. The test was performed without lubrication at room temperature. The wear amount ( ⁇ m 2 ) of the mating member 32 after 10 minutes from the start of the test was measured with a laser microscope (“VK-X100” manufactured by Keyence Corporation) and evaluated according to the following criteria.The results are also shown in Table 1. , 2.
  • ⁇ The amount of wear of the mating material is less than 8 ⁇ m 2 (the amount of wear cannot be determined)
  • Wear amount of mating material is 8 ⁇ m 2 or more and less than 20 ⁇ m 2
  • Wear amount of mating material is 20 ⁇ m 2 or more and less than 30 ⁇ m 2
  • Wear amount of mating material is 30 ⁇ m 2 or more
  • the coefficient of friction of the film was evaluated using a friction wear tester 4 (HEIDON TYPE 14, manufactured by Shinto Kagaku Co., Ltd.) shown in FIG.
  • a plate-shaped test material 40 (t0.5 ⁇ 35 ⁇ 70 mm, material SPCC (cold-rolled steel plate)) was used as a sliding member to be coated.
  • Solvent degreasing was applied to the sliding surface 41 of the test material 40 as a pretreatment.
  • Each test composition was applied to the sliding surface 41 by spraying, dried and cured to form a film having a thickness of 15 ⁇ m.
  • a ball-shaped member (outer diameter ⁇ 3/8 inch, material SUJ2 (high carbon chromium bearing steel) was used. This mating member 42 was brought into contact with the sliding surface 41. In this state, 4, and a pressing load (0.98 N) was applied to the test material 40 from the direction of the arrow 46 in Fig. 4. The test was performed at room temperature without lubrication. The static friction coefficient ( ⁇ s) and dynamic friction coefficient ( ⁇ k) at that time were measured and evaluated according to the following criteria.
  • Example 1 to 15 shown in Table 1 and Comparative Examples 1 to 9 shown in Table 2 used in the above tests the average particle size of PTFE was 3.5 ⁇ m, and the average particle size of silica was 0.3 ⁇ m. .
  • the wear resistance (wear depth), mating aggressiveness (mating material wear amount), and friction coefficient are as low as possible, and the seizure resistance (seizure load) is as high as possible. is preferred.
  • Examples 1 to 15 had good results in all of the coefficient of friction, seizure resistance, wear resistance, and low mating aggression.
  • Comparative Examples 1 to 4 have too little or too much PTFE or silica content, so that any one of low friction coefficient, seizure resistance, wear resistance, or low mating attack There was a problem with physical properties.
  • Comparative Examples 5 to 9 if PTFE as a solid lubricant and silica as a wear suppressing material are not contained as essential components, the coefficient of friction, seizure resistance, wear resistance, and It was confirmed that it is not possible to satisfy all of low opponent aggression.
  • Examples 16 and 17 in which the PTFE/silica particle size ratio is in the range of 0.8 to 80, have good coefficient of friction, seizure resistance, wear resistance, and low mating attack. It was a good result. On the other hand, in Comparative Examples 10 and 11, the balance of the PTFE/silica particle size ratio is poor, so there is a problem in any of the physical properties of low friction coefficient, seizure resistance, wear resistance, and low mating attack. rice field.

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  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
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Abstract

Provided is a coating composition for a sliding member, the coating composition being used for forming a coating on the surface of a sliding member. The coating composition contains a binder resin, a solid lubricant, and a wear-suppressing material. The coating composition contains 0.5-6 parts by weight of the solid lubricant and 5-30 parts by weight of the wear-suppressing material per 100 parts by weight of the binder resin. The solid lubricant is at least polytetrafluoroethylene. The wear-suppressing material is at least silica. The grain diameter ratio of the polytetrafluoroethylene and the silica, as calculated using (polytetrafluoroethylene/silica), is 0.8-80. The coating composition according to the present disclosure makes it possible to form a coating that can simultaneously fulfill all of low friction coefficient, high scorch resistance, high wear resistance, and low counterpart aggression while being a simple blend.

Description

摺動部材用被膜組成物及び摺動部材Coating composition for sliding member and sliding member
　本開示は、摺動部材の表面に被膜を形成するための摺動部材用被膜組成物と、この摺動部材用被膜組成物により形成された被膜を表面に備える摺動部材に関する。 The present disclosure relates to a sliding member coating composition for forming a coating on the surface of a sliding member, and a sliding member having a coating formed from the sliding member coating composition on its surface.
　摺動部材の一例としては、例えば自動車エンジンの軸受けやピストン、及び斜板式コンプレッサーの斜板などが挙げられる。例えばピストンは、ピストンスカートが摺動相手材であるシリンダボアと摺接する。このとき、ピストンスカートとシリンダボアとの間の潤滑性が重要となる。ピストンスカートとシリンダボア間での潤滑性が低いと、焼付き現象が生じてエンジンが停止してしまう。そのため、シリンダボアと摺接するピストンスカートの表面（摺動面）には、被膜を付与することが従来から行われている。 Examples of sliding members include bearings and pistons of automobile engines, and swash plates of swash plate compressors. For example, a piston has a piston skirt in sliding contact with a cylinder bore, which is a mating sliding member. At this time, lubricity between the piston skirt and the cylinder bore is important. If the lubricity between the piston skirt and the cylinder bore is low, seizure will occur and the engine will stop. Therefore, the surface (sliding surface) of the piston skirt, which is in sliding contact with the cylinder bore, has conventionally been provided with a coating.
　このような摺動部材用の被膜には、潤滑性に直接寄与する低摩擦係数や耐焼付き性のみならず、耐摩耗性及び低相手攻撃性が求められる。耐摩耗性が低いと、相手材と繰り返し摺接することで早期に被膜が劣化し、その機能を維持できなくなる。相手攻撃性が高いと、被膜との摺接により相手材が損傷し易くなってしまう。 Coatings for such sliding members are required not only to have a low friction coefficient and seizure resistance, which directly contribute to lubricity, but also to have wear resistance and low mating aggression. If the wear resistance is low, repeated sliding contact with the mating material will cause the coating to deteriorate early, and the function will not be maintained. If the mating aggressiveness is high, the mating material is likely to be damaged due to sliding contact with the film.
　そこで、このような被膜に要求される各種物性を向上する技術として、例えば下記特許文献１～特許文献６が開示されている。特許文献１～特許文献６に記載の摺動部材用被膜組成物は、一般的にバインダー樹脂と、固体潤滑剤と、無機充填材（フィラー）である摩耗抑制材とを含有する。また、必要に応じてその他の添加剤も含有する。特許文献１～特許文献６では、各成分の配合量を調整したり、被膜の表面粗さを調整したり、各成分の粒径を調整したり、特殊な材料を使用したりするなどして、この種の被膜に要求される各種物性のうち、いずれかの物性を特化させている。 Therefore, Patent Documents 1 to 6 below, for example, disclose techniques for improving the various physical properties required for such coatings. The coating compositions for sliding members described in Patent Documents 1 to 6 generally contain a binder resin, a solid lubricant, and a wear suppressing material that is an inorganic filler. Moreover, other additives are also contained as needed. In Patent Documents 1 to 6, adjusting the blending amount of each component, adjusting the surface roughness of the coating, adjusting the particle size of each component, using special materials, etc. , any one of the various physical properties required for this type of coating is specialized.
特開平７－９７５１７号公報JP-A-7-97517 特開２００４－１４９６２２号公報JP-A-2004-149622 特開２０１８－２１６７３号公報JP 2018-21673 A 特開２０１５－１２４３３８号公報JP 2015-124338 A 再表２０１２－１１１７７４号公報Retable 2012-111774 特開２０１８－１８８６２１号公報JP 2018-188621 A
　特許文献１～特許文献６では、低摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性のうち、いずれかの物性を特化させている。しかし、その目的達成のためにその他の物性を犠牲にしている。すなわち、特許文献１～特許文献６は、低摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性の全てを満足できるものではない。また、特殊な材料を使用する場合は、入手や製造が困難であったり、材料コストが嵩んでしまう。 Patent Documents 1 to 6 specialize in one of the physical properties of low friction coefficient, seizure resistance, wear resistance, and low mating aggression. However, other physical properties are sacrificed to achieve that goal. That is, Patent Documents 1 to 6 cannot satisfy all of low friction coefficient, seizure resistance, wear resistance, and low mating aggression. Moreover, when a special material is used, it is difficult to obtain and manufacture, or the material cost increases.
　そこで、本開示は上記課題を解決するものである。本開示は、従来から公知の材料を使用したシンプルな配合でありながら、低摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性の全ての物性を同時に満足できる被膜を形成可能な摺動部材用被膜組成物と、これにより形成された被膜を表面に備える摺動部材を提供することを目的とする。 Therefore, the present disclosure solves the above problems. The present disclosure is a sliding coating capable of forming a coating that simultaneously satisfies all of the physical properties of low friction coefficient, seizure resistance, wear resistance, and low mating aggression with a simple formulation using conventionally known materials. It is an object of the present invention to provide a coating composition for moving members and a sliding member having a coating formed thereon on its surface.
　本開示は、摺動部材の表面に被膜を形成するための摺動部材用被膜組成物である。バインダー樹脂と、固体潤滑剤と、摩耗抑制材とを含有する。前記バインダー樹脂１００重量部に対して、前記固体潤滑剤を０．５～６重量部、摩耗抑制材を５～３０重量部配合する。前記固体潤滑剤としては少なくともポリテトラフルオロエチレン（ＰＴＦＥ）を使用し、前記摩耗抑制材としては少なくともシリカを使用する。そのうえで、（ＰＴＦＥ／シリカ）で計算される前記ＰＴＦＥと前記シリカとの粒径比が、０．８～８０である。 The present disclosure is a coating composition for sliding members for forming a coating on the surface of the sliding member. It contains a binder resin, a solid lubricant, and a wear inhibitor. 0.5 to 6 parts by weight of the solid lubricant and 5 to 30 parts by weight of the wear inhibitor are blended with 100 parts by weight of the binder resin. At least polytetrafluoroethylene (PTFE) is used as the solid lubricant, and at least silica is used as the wear suppressing material. In addition, the particle size ratio between the PTFE and the silica calculated as (PTFE/silica) is 0.8-80.
　また、本開示によれば、上記摺動部材用被膜組成物により形成された被膜を表面に備える、摺動部材を提供することもできる。 Further, according to the present disclosure, it is also possible to provide a sliding member having a coating formed from the coating composition for a sliding member on its surface.
　本開示の摺動部材用被膜組成物は、バインダー樹脂に対して、この種の摺動部材用被膜組成物において従来から一般的に使用されている公知の材料であるＰＴＦＥとシリカを必須成分としたシンプルな配合である。そのうえで、その含有量と粒径比を調整することで、低摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性の全ての物性を同時に満足できる被膜を形成できる。 The coating composition for sliding members of the present disclosure contains, in addition to the binder resin, PTFE and silica, which are known materials generally used in this type of coating composition for sliding members, as essential components. It is a simple combination. In addition, by adjusting the content and particle size ratio, it is possible to form a film that simultaneously satisfies all of the physical properties of a low coefficient of friction, seizure resistance, wear resistance, and low mating aggression.
耐焼付き性試験の模式図である。It is a schematic diagram of a seizure resistance test. 耐摩耗性試験の模式図である。It is a schematic diagram of an abrasion resistance test. 相手攻撃性試験の模式図である。It is a schematic diagram of an opponent aggression test. 摩擦係数試験の模式図である。It is a schematic diagram of a friction coefficient test.
《摺動部材用被膜組成物》
　本開示の摺動部材用被膜組成物は、摺動部材の少なくとも摺動面を被覆するための被膜を形成するための組成物である。本開示の摺動部材用被膜組成物は、バインダー樹脂と、固体潤滑剤と、摩耗抑制材とを含有する。 <<Coating composition for sliding member>>
The coating composition for sliding member of the present disclosure is a composition for forming a coating for coating at least the sliding surface of the sliding member. The coating composition for sliding members of the present disclosure contains a binder resin, a solid lubricant, and a wear inhibitor.
＜バインダー樹脂＞
　バインダー樹脂は、被膜のベースとなる成分である。バインダー樹脂は、添加成分を含んだ状態で被膜を形成できるものであれば特に限定されない。例えば、従来からこの種の摺動部材用被膜組成物において使用されている公知の有機系バインダーを使用できる。具体的には、ポリアミドイミド樹脂、ポリビニルブチラール樹脂、塩素化ポリオレフィン樹脂、ナイロン、ポリエーテルイミド樹脂、ポリエーテルサルホン樹脂、熱可塑性ポリイミド樹脂などの熱可塑性樹脂を例示できる。また、アルキド樹脂、エポキシ樹脂、アミノ樹脂、アクリル樹脂、ポリアミノアミド樹脂、ポリウレタン樹脂、不飽和ポリエステル樹脂、フェノール樹脂、キシレン樹脂、ビニルエステル樹脂、フラン樹脂、シリコーン樹脂、ポリイミド樹脂、全芳香族ポリエステルなどの熱硬化性樹脂を例示できる。熱可塑性樹脂の中では、ポリアミドイミド樹脂、ポリビニルブチラール樹脂、ポリエーテルサルホン樹脂、熱可塑性ポリイミドが好ましい。熱硬化性樹脂の中では、エポキシ樹脂、アミノ樹脂、アクリル樹脂、ポリアミノアミド樹脂、ポリウレタン樹脂、不飽和ポリエステル樹脂、フェノール樹脂、キシレン樹脂、シリコーン樹脂、ポリイミド樹脂が好ましい。これらは取り扱いが容易で、後述のＰＴＦＥを良好に分散させながら塗料状態で被膜を形成できるからである。さらには、接着性、耐薬品性、強度などの点から、ポリアミドイミド樹脂、ポリエーテルサルホン樹脂、熱可塑性ポリイミド樹脂、エポキシ樹脂、又はポリイミド樹脂がより好ましい。これらのバインダー樹脂は、１種のみを単独で使用してもよく、２種以上を混合使用してもよい。 <Binder resin>
The binder resin is a base component of the film. The binder resin is not particularly limited as long as it can form a film while containing additional components. For example, known organic binders conventionally used in coating compositions for sliding members of this type can be used. Specific examples include thermoplastic resins such as polyamideimide resin, polyvinyl butyral resin, chlorinated polyolefin resin, nylon, polyetherimide resin, polyethersulfone resin, and thermoplastic polyimide resin. Alkyd resin, epoxy resin, amino resin, acrylic resin, polyaminoamide resin, polyurethane resin, unsaturated polyester resin, phenol resin, xylene resin, vinyl ester resin, furan resin, silicone resin, polyimide resin, wholly aromatic polyester, etc. can be exemplified by thermosetting resins. Among thermoplastic resins, polyamideimide resins, polyvinyl butyral resins, polyethersulfone resins, and thermoplastic polyimides are preferred. Among thermosetting resins, epoxy resins, amino resins, acrylic resins, polyaminoamide resins, polyurethane resins, unsaturated polyester resins, phenol resins, xylene resins, silicone resins, and polyimide resins are preferred. This is because they are easy to handle and can form a film in the form of a paint while dispersing PTFE, which will be described later, well. Furthermore, polyamideimide resin, polyethersulfone resin, thermoplastic polyimide resin, epoxy resin, or polyimide resin is more preferable from the viewpoint of adhesiveness, chemical resistance, strength, and the like. These binder resins may be used alone or in combination of two or more.
＜固体潤滑剤＞
　固体潤滑剤としては、少なくともポリテトラフルオロチエチレン（ＰＴＦＥ）粒子を必須成分として使用する。固体潤滑剤の中でもＰＴＦＥは潤滑性に優れており、被膜の潤滑性能を主体的に発揮する。ＰＴＦＥの平均粒子径は、０．１～５０μｍ、好ましくは０．２～４０μｍであればよい。なお、本明細書でいう「平均粒子径」とは、レーザー回折散乱式粒度分布測定法により測定した体積累積平均粒子径（Ｄ５０）を意味する。 <Solid lubricant>
At least polytetrafluoroethylene (PTFE) particles are used as an essential component of the solid lubricant. Among solid lubricants, PTFE has excellent lubricating properties, and mainly exerts the lubricating performance of the coating. The average particle size of PTFE should be 0.1 to 50 μm, preferably 0.2 to 40 μm. The term "average particle size" as used herein means a volume cumulative average particle size ( D50 ) measured by a laser diffraction/scattering particle size distribution measurement method.
　ＰＴＦＥの配合量は、バインダー樹脂１００重量部に対して０．５～６重量部、好ましくは１～４重量部とする。ＰＴＦＥの配合量がバインダー樹脂１００重量部に対して０．５重量部より少ないと、潤滑性不足から摩耗抑制材による相手材への攻撃性が高くなってしまう。一方、６重量部より多いと、相対的にバインダー樹脂の含有量が低下して、耐摩耗性や耐焼付き性が低下する。 The blending amount of PTFE is 0.5 to 6 parts by weight, preferably 1 to 4 parts by weight, per 100 parts by weight of the binder resin. If the blending amount of PTFE is less than 0.5 parts by weight with respect to 100 parts by weight of the binder resin, the lubricating property is insufficient, so that the wear suppressing material tends to aggressively attack the mating material. On the other hand, when it is more than 6 parts by weight, the content of the binder resin is relatively decreased, resulting in deterioration of wear resistance and seizure resistance.
　その他の固体潤滑剤としては、例えばテトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン－エチレン共重合体、ポリビニリデンフルオライド、及びポリクロロトリフルオロエチレンなどのフッ素化合物、二硫化モリブデン（ＭｏＳ２）及び二硫化タングステンなどの硫化物、グラファイト（ＧＰ）、フッ化グラファイト、窒化硼素、マイカなどの層状鱗片状物質、鉛、亜鉛、銅などの軟質金属、メラミンシアヌレートなどの粒子が挙げられる。これらその他の固体潤滑剤は、本開示の効果を阻害しない範囲（ＰＴＦＥの配合量以下）で１種又は２種以上を添加してもよいが、ＰＴＦＥのみを配合することが好ましい。 Other solid lubricants include, for example, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and polychlorotri Fluorine compounds such as fluoroethylene, sulfides such as molybdenum disulfide (MoS 2 ) and tungsten disulfide, graphite (GP), graphite fluoride, boron nitride, lamellar flake substances such as mica, lead, zinc, copper, etc. Examples include particles of soft metals, melamine cyanurate, and the like. One or two or more of these other solid lubricants may be added within a range that does not inhibit the effects of the present disclosure (the amount of PTFE blended or less), but it is preferable to blend only PTFE.
＜摩耗抑制材＞
　摩耗抑制材としては、少なくともシリカ粒子を必須成分として使用する。摩耗抑制材の中でも、シリカはＰＴＦＥとの相性が良く、主として被膜の耐摩耗性を向上すると共に、相手攻撃性も低い。シリカの平均粒子径は、０．００１～２０μｍ、好ましくは０．０１５～１０μｍであればよい。 <Wear suppressing material>
At least silica particles are used as an essential component of the wear suppressing material. Among wear-suppressing materials, silica has good compatibility with PTFE, mainly improves the wear resistance of the coating, and has low attacking property. The average particle size of silica should be 0.001 to 20 μm, preferably 0.015 to 10 μm.
　シリカの配合量は、バインダー樹脂１００重量部に対して５～３０重量部、好ましくは１０～２５重量部とする。ＰＴＦＥの配合量がバインダー樹脂１００重量部に対して５重量部より少ないと耐摩耗性が低下し、これに基づき耐焼付き性も低下する。一方、３０重量部より多いと、相手材への攻撃性が高くなると共に、耐焼付き性も低下する。 The amount of silica compounded is 5 to 30 parts by weight, preferably 10 to 25 parts by weight, per 100 parts by weight of the binder resin. If the amount of PTFE to be blended is less than 5 parts by weight per 100 parts by weight of the binder resin, the wear resistance is lowered, and accordingly the seizure resistance is also lowered. On the other hand, if it is more than 30 parts by weight, the aggressiveness to the mating member increases and the seizure resistance also decreases.
　その他の摩耗抑制材としては、例えば酸化アルミニウム、水酸化アルミニウム、アルミナホワイト、シリカアルミナなどのアルミナ類のほか、硫酸バリウム、ジルコニア、炭化タングステン、炭化チタン、炭化ケイ素、二酸化チタン、酸化鉄、長石、軽石、正長石、イリジウム、石英、酸化ベリリウム、酸化ジルコニウム、クロム、ボロンカーバイト、タングステンカーバイト、金属タングステン、シリコーンカーバイト等が挙げられる。これらその他の摩耗抑制材は、本開示の効果を阻害しない範囲（シリカの配合量以下）で１種又は２種以上を添加してもよいが、シリカのみを配合することが好ましい。 Other wear inhibitors include aluminas such as aluminum oxide, aluminum hydroxide, alumina white, silica alumina, barium sulfate, zirconia, tungsten carbide, titanium carbide, silicon carbide, titanium dioxide, iron oxide, feldspar, pumice, orthoclase, iridium, quartz, beryllium oxide, zirconium oxide, chromium, boron carbide, tungsten carbide, metallic tungsten, silicone carbide, and the like. One or two or more of these other wear inhibitors may be added within a range that does not impair the effects of the present disclosure (the amount of silica to be blended or less), but it is preferable to blend only silica.
　そのうえで、（ＰＴＦＥ／シリカ）で計算されるＰＴＦＥとシリカとの粒径比（平均粒子径の比）は０．８～８０とする。（ＰＴＦＥ／シリカ）の粒径比が０．８より小さいと、ＰＴＦＥに対してシリカが大きすぎて、相手攻撃性が高くなってしまう。一方、（ＰＴＦＥ／シリカ）の粒径比が８０を超えると、ＰＴＦＥに対してシリカが小さすぎて、耐摩耗性が低下してしまう。 In addition, the particle size ratio (average particle size ratio) between PTFE and silica calculated by (PTFE/silica) is set to 0.8 to 80. If the particle size ratio of (PTFE/silica) is less than 0.8, silica is too large relative to PTFE, resulting in increased attacking property. On the other hand, if the particle size ratio of (PTFE/silica) exceeds 80, the silica is too small relative to PTFE, resulting in a decrease in wear resistance.
　また、摺動部材用被膜組成物には、本開示の効果を阻害しない範囲で、その他の一般的な添加剤を配合することもできる。例えば、ＰＴＦＥ等の分散性を向上する分散剤、接着性を向上させるシランカップリング剤、表面張力をコントロールするレベリング剤や界面活性剤、及びチキソトロピー性をコントロールする増粘剤などを挙げることができる。 In addition, other general additives can be added to the film composition for sliding members within a range that does not impair the effects of the present disclosure. Examples include dispersants such as PTFE that improve dispersibility, silane coupling agents that improve adhesion, leveling agents and surfactants that control surface tension, and thickeners that control thixotropy. .
《摺動部材》
　このような摺動部材用被膜組成物を摺動部材の表面（摺動面）へ塗布し、硬化させることで、表面に被膜を有する摺動部材が得られる。 《Sliding member》
By applying such a film composition for a sliding member to the surface (sliding surface) of the sliding member and curing it, a sliding member having a film on the surface can be obtained.
　摺動部材としては、潤滑油やグリース等の潤滑剤を使用した潤滑状態で相手材と摺接する部材のほか、潤滑剤を使用しない無潤滑状態で相手材と摺接する部材にも適用できる。具体的には、自動車エンジンのピストン、湿式クラッチ、ギヤ、スプライン、ワッシャー、動弁系部品、斜板式コンプレッサーの斜板、半球シュー、摺動式スプラインシャフト、すべり軸受用オーバーレイ、転がり軸受用保持器などが挙げられる。 As the sliding member, it can be applied not only to a member that slides with a mating member in a lubricated state using a lubricant such as lubricating oil or grease, but also to a member that slides in a non-lubricated state without using a lubricant. Specifically, automobile engine pistons, wet clutches, gears, splines, washers, valve train parts, swash plate compressor swash plates, hemispherical shoes, sliding spline shafts, slide bearing overlays, rolling bearing retainers etc.
　摺動部材の材質は特に限定されず、典型的にはアルミニウムや鉄などの金属ないし合金が挙げられるが、他にもゴム、プラスチック、セラミックなどでもよい。摺動被膜組成物は、摺動部材の少なくとも摺動面に塗布すればよいが、全体的に塗布してもよい。 The material of the sliding member is not particularly limited, and typically includes metals or alloys such as aluminum and iron, but rubber, plastic, ceramics, etc. may also be used. The sliding coating composition may be applied to at least the sliding surface of the sliding member, but may be applied to the entire surface.
　摺動被膜組成物を塗布する際は、必要に応じて有機溶剤によって粘度を調整しておく。有機溶剤は、バインダー樹脂を溶解することができる有機溶媒であれば特に制限なく用いることができる。代表的な樹脂で例示すると、エポキシ樹脂の場合、メチルエチルケトン等のケトン系溶剤、酢酸エチル等のエステル系溶剤、キシレン、トルエン等の芳香族系の溶剤などを用いることができる。ポリアミドイミド樹脂の場合、ＮＭＰ（Ｎ－メチル－２－ピロリドン）を用いることができ、また、ＮＭＰにキシレン等の芳香族系溶剤や、メチルエチルケトン等のケトン系溶剤、酢酸エチル等のエステル系溶剤などを加えた混合溶剤を用いることができる。 When applying the sliding coating composition, adjust the viscosity with an organic solvent as necessary. Any organic solvent can be used without particular limitation as long as it can dissolve the binder resin. As an example of a typical resin, in the case of an epoxy resin, a ketone solvent such as methyl ethyl ketone, an ester solvent such as ethyl acetate, or an aromatic solvent such as xylene or toluene can be used. In the case of polyamide-imide resin, NMP (N-methyl-2-pyrrolidone) can be used, and NMP includes aromatic solvents such as xylene, ketone solvents such as methyl ethyl ketone, and ester solvents such as ethyl acetate. can be used.
　摺動被膜組成物の塗装方法は、従来から公知の一般的な塗装方法を採用できる。具体的には刷毛、ローラー、ロールコーター、エアスプレー、エアレススプレー、浸漬塗装、スクリーン印刷、パット印刷、グラビアコートなどが挙げられる。摺動部材の摺動面には、必要に応じてアルカリ脱脂や溶剤脱脂、エッチング、化成処理等の前処理を施しておいてもよい。 As for the coating method of the sliding coating composition, conventionally known general coating methods can be adopted. Specific examples include brush, roller, roll coater, air spray, airless spray, dip coating, screen printing, pad printing and gravure coating. The sliding surface of the sliding member may be subjected to pretreatment such as alkali degreasing, solvent degreasing, etching, chemical conversion treatment, etc., if necessary.
　摺動被膜組成物を塗布した後は、乾燥・硬化させることで被膜を形成できる。被膜の膜厚は、従来から一般的な５～５０μｍ、好ましくは１０～４５μｍ程度とすればよい。 After applying the sliding coating composition, the coating can be formed by drying and curing. The film thickness of the coating may be about 5 to 50 μm, preferably about 10 to 45 μm, which is conventionally common.
　表１，２に記載の材料を表１，２に示す割合で混合し、必要に応じて有機溶剤で粘度を調整した摺動部材用被膜組成物を調製した。なお、表１，２に示す各材料の配合量は重量部である。各実施例及び比較例の摺動部材用被膜組成物を用いて下記試験を行い、被膜の各物性を評価した。 The materials shown in Tables 1 and 2 were mixed in the proportions shown in Tables 1 and 2, and a coating composition for sliding members was prepared by adjusting the viscosity with an organic solvent as necessary. The amount of each material shown in Tables 1 and 2 is in parts by weight. Using the coating composition for sliding members of each example and comparative example, the following tests were conducted to evaluate each physical property of the coating.
（耐焼付き性試験）
　図１に示すスラスト試験機１（エーアンドデイ社製）を用いて焼付き荷重を測定した。被膜形成対象である摺動部材として、板形状の試験板１０（ｔ５×３０×３０ｍｍ，材質ＡＣ８Ａ，粗さＲｚ＝０．５μｍ）を用いた。試験板１０の摺動面１１には、前処理として溶剤脱脂を施した。この摺動面１１に、各組成物をスプレーで塗付し、乾燥・硬化させて膜厚１５μｍの被膜を形成した。なお、バインダー樹脂をポリアミドイミド樹脂（ＰＡＩ）及びフェノール樹脂（ＰＦ）とした組成物の乾燥・硬化条件は１８０℃、９０分であり、ポリイミド樹脂（ＰＩ）とした組成物は３５０℃、１０分であり、エポキシ樹脂とした組成物は２００℃、３０分である。後述する他の試験でも同様である。 (Seizure resistance test)
A seizure load was measured using a thrust tester 1 (manufactured by A&D Co., Ltd.) shown in FIG. A plate-shaped test plate 10 (t5×30×30 mm, material AC8A, roughness Rz=0.5 μm) was used as a sliding member to be coated. The sliding surface 11 of the test plate 10 was subjected to solvent degreasing as a pretreatment. Each composition was applied to the sliding surface 11 by spraying, dried and cured to form a film having a thickness of 15 μm. The drying and curing conditions for the composition with the binder resin as polyamideimide resin (PAI) and phenol resin (PF) are 180 ° C. and 90 minutes, and the composition with polyimide resin (PI) is 350 ° C. and 10 minutes. and the epoxy resin composition was heated at 200° C. for 30 minutes. The same applies to other tests described later.
　相手材１２として、中空円筒形状の部材（外径φ２５．６ｍｍ，内径φ２０ｍｍ，材質ＦＣ２５０，粗さＲｚ＝１μｍ）を用いた。この相手材１２を、被膜が塗付された摺動面１１上に配置した。この状態で、図１の矢印１５方向に試験板１０を回転数１０００ｒｐｍにて回転させた。そして、馴らし回転（２４５Ｎの押付け荷重を１０分間かける）の後、図１の矢印１６方向から押付け荷重を相手材１２にかけて、一定の周期（２４５Ｎ／２ｍｉｎ）で押し付け荷重を上昇させていった。試験は、潤滑油（鉱油；０Ｗ－２０）の潤滑下で行い、潤滑油は８０℃とした。被膜がなくなり焼付く荷重（Ｎ）を測定し、次の基準で評価した。その結果も表１，２に示す。 A hollow cylindrical member (outer diameter φ25.6 mm, inner diameter φ20 mm, material FC250, roughness Rz=1 μm) was used as the mating member 12 . This mating member 12 was placed on the sliding surface 11 coated with the film. In this state, the test plate 10 was rotated in the direction of arrow 15 in FIG. 1 at a rotation speed of 1000 rpm. After a break-in rotation (a pressing load of 245 N was applied for 10 minutes), a pressing load was applied from the direction of arrow 16 in FIG. The test was performed under lubrication with lubricating oil (mineral oil; 0W-20) at 80°C. The load (N) at which the film was removed and seizure was measured and evaluated according to the following criteria. The results are also shown in Tables 1 and 2.
◎：焼付き荷重が３９２０Ｎ以上
○：焼付き荷重が３５００Ｎ以上３９２０Ｎ未満
△：焼付き荷重が３２００Ｎ以上３５００Ｎ未満
×：焼付き荷重が３２００Ｎ未満 ◎: Seizure load is 3920 N or more ○: Seizure load is 3500 N or more and less than 3920 N △: Seizure load is 3200 N or more and less than 3500 N ×: Seizure load is less than 3200 N
（耐摩耗性試験）
　図２に示すブロックオンリング試験機２（「ＦＡＬＥＸ ＬＦＷ－１」　ＦＡＬＥＸ ＣＯＲＰＯＲＡＴＩＯＮ社製）を用いて、被膜の耐摩耗性を評価した。被膜形成対象である摺動部材として、ブロック状の試験材２０（６×１６×１０ｍｍ、材質ＡＣ８Ａ、表面粗さＲｚ＝１μｍ）を用いた。図２で見て試験材２０の摺動面２１には、前処理として溶剤脱脂を施した。この摺動面２１に、各試験用組成物をスプレーで塗付したのち、乾燥・硬化させて膜厚１５μｍの被膜を形成した。 (Abrasion resistance test)
The abrasion resistance of the film was evaluated using a block-on-ring tester 2 (“FALEX LFW-1” manufactured by FALEX CORPORATION) shown in FIG. A block-shaped test material 20 (6×16×10 mm, material AC8A, surface roughness Rz=1 μm) was used as a sliding member to be coated. Solvent degreasing was applied to the sliding surface 21 of the test material 20 in FIG. 2 as a pretreatment. Each test composition was applied to the sliding surface 21 by spraying, dried and cured to form a film having a thickness of 15 μm.
　相手材２２として、リング形状の部材（外径φ３５ｍｍ、厚み８ｍｍ、材質ＦＣ２５０（ねずみ鋳鉄）、表面粗さＲｚ＝１μｍ）を用いた。この相手材２２を摺動面２１に当接させた。この状態で、図２の矢印２５方向に相手材２２を回転速度２０ｒｐｍで回転させていき、図２の矢印２６方向から押付け荷重４５Ｎを試験材２０にかけた。試験は、潤滑油（鉱油；０Ｗ－２０）の潤滑下で行い、潤滑油の油温は８０℃とした。試験開始から１５分経過した時の被膜の摩耗量（μｍ）をレーザー顕微鏡（「ＶＫ－Ｘ１００」、キーエンス社製）にて測定し、次の基準で評価した。その結果も表１，２に示す。 A ring-shaped member (outer diameter φ35 mm, thickness 8 mm, material FC250 (gray cast iron), surface roughness Rz=1 μm) was used as the mating member 22 . This mating member 22 was brought into contact with the sliding surface 21 . In this state, the mating material 22 was rotated at a rotational speed of 20 rpm in the direction of arrow 25 in FIG. The test was performed under lubrication with lubricating oil (mineral oil; 0W-20) at a lubricating oil temperature of 80°C. After 15 minutes from the start of the test, the wear amount (μm) of the coating was measured with a laser microscope (“VK-X100”, manufactured by Keyence Corporation) and evaluated according to the following criteria. The results are also shown in Tables 1 and 2.
◎：被膜の摩耗量が３μｍ未満
○：被膜の摩耗量が３μｍ以上４μｍ未満
△：被膜の摩耗量が４μｍ以上６μｍ未満
×：被膜の摩耗量が６μｍ以上 ◎: The amount of abrasion of the coating is less than 3 μm ○: The amount of abrasion of the coating is 3 μm or more and less than 4 μm △: The amount of abrasion of the coating is 4 μm or more and less than 6 μm ×: The amount of abrasion of the coating is 6 μm or more
（相手攻撃性試験）
　図３に示す摩擦摩耗試験機３（ＨＥＩＤＯＮ ＴＹＰＥ２０，新東科学社製）を用いて、被膜の相手攻撃性を評価した。被膜形成対象である摺動部材として、板形状の試験材３０（ｔ０．５×３５×７０ｍｍ，材質ＳＰＣＣ（冷間圧延鋼板））を用いた。試験材３０の摺動面３１には、前処理として溶剤脱脂を施した。この摺動面３１に、各組成物をスプレーで塗付したのち、乾燥・硬化させて膜厚１５μｍの被膜を形成した。 (Partner Aggression Test)
Using a friction wear tester 3 (HEIDON TYPE 20, manufactured by Shinto Kagaku Co., Ltd.) shown in FIG. A plate-shaped test material 30 (t0.5×35×70 mm, material SPCC (cold-rolled steel plate)) was used as a sliding member to be coated. Solvent degreasing was applied to the sliding surface 31 of the test material 30 as a pretreatment. After each composition was applied to the sliding surface 31 by spraying, it was dried and cured to form a film having a thickness of 15 μm.
　相手材３２として、ボール形状の部材（外径φ３／８in，材質ＳＵＪ２（高炭素クロム軸受鋼鋼材）を用いた。この相手材を摺動面３１に当接させた。この状態で、図の矢印３５方向に相手材３２を回転速度２００ｒｐｍにて回転させていき、図の矢印３６方向から押付け荷重（０．９８Ｎ）を試験材３０にかけた。試験は、無潤滑・室温下で行った。試験開始から１０分経過した時の相手材３２の摩耗量（μｍ２）をレーザー顕微鏡（「ＶＫ－Ｘ１００」、キーエンス社製）にて測定し、次の基準で評価した。その結果も表１，２に示す。 A ball-shaped member (outer diameter φ3/8 inch, material SUJ2 (high carbon chromium bearing steel)) was used as the mating member 32. This mating member was brought into contact with the sliding surface 31. The mating material 32 was rotated in the direction of arrow 35 at a rotation speed of 200 rpm, and a pressing load (0.98 N) was applied to the test material 30 from the direction of arrow 36. The test was performed without lubrication at room temperature. The wear amount (μm 2 ) of the mating member 32 after 10 minutes from the start of the test was measured with a laser microscope (“VK-X100” manufactured by Keyence Corporation) and evaluated according to the following criteria.The results are also shown in Table 1. , 2.
◎：相手材の摩耗量が８μｍ２未満（摩耗量が判断できない）
○：相手材の摩耗量が８μｍ２以上２０μｍ２未満
△：相手材の摩耗量が２０μｍ２以上３０μｍ２未満
×：相手材の摩耗量が３０μｍ２以上 ◎: The amount of wear of the mating material is less than 8 μm 2 (the amount of wear cannot be determined)
○: Wear amount of mating material is 8 μm 2 or more and less than 20 μm 2 △: Wear amount of mating material is 20 μm 2 or more and less than 30 μm 2 ×: Wear amount of mating material is 30 μm 2 or more
（摩擦係数試験）
　図４に示す摩擦摩耗試験機４（ＨＥＩＤＯＮ ＴＹＰＥ１４，新東科学社製）を用いて、被膜の摩擦係数を評価した。被膜形成対象である摺動部材として、板形状の試験材４０（ｔ０．５×３５×７０ｍｍ，材質ＳＰＣＣ（冷間圧延鋼板））を用いた。試験材４０の摺動面４１には、前処理として溶剤脱脂を施した。この摺動面４１に、各試験用組成物をスプレーで塗付したのち、乾燥・硬化させて膜厚１５μｍの被膜を形成した。 (Friction coefficient test)
The coefficient of friction of the film was evaluated using a friction wear tester 4 (HEIDON TYPE 14, manufactured by Shinto Kagaku Co., Ltd.) shown in FIG. A plate-shaped test material 40 (t0.5×35×70 mm, material SPCC (cold-rolled steel plate)) was used as a sliding member to be coated. Solvent degreasing was applied to the sliding surface 41 of the test material 40 as a pretreatment. Each test composition was applied to the sliding surface 41 by spraying, dried and cured to form a film having a thickness of 15 μm.
　相手材４２として、ボール形状の部材（外径φ３／８in，材質ＳＵＪ２（高炭素クロム軸受鋼鋼材）を用いた。この相手材４２を摺動面４１に当接させた。この状態で、図４の矢印４５方向に相手材４２を摺動（１ｍｍ／ｓ）させ、図４の矢印４６方向から押付け荷重（０．９８Ｎ）を試験材４０にかけた。試験は、無潤滑・室温下で行った。その際の静止摩擦係数（μｓ）および動摩擦係数（μｋ）を測定し、次の基準で評価した。その結果も表１，２に示す。 As the mating member 42, a ball-shaped member (outer diameter φ3/8 inch, material SUJ2 (high carbon chromium bearing steel) was used. This mating member 42 was brought into contact with the sliding surface 41. In this state, 4, and a pressing load (0.98 N) was applied to the test material 40 from the direction of the arrow 46 in Fig. 4. The test was performed at room temperature without lubrication. The static friction coefficient (μs) and dynamic friction coefficient (μk) at that time were measured and evaluated according to the following criteria.
（静止摩擦係数 μｓ）
◎：０．２０未満
○：０．２０以上０．２５未満
×：０．２５以上 (Static friction coefficient μs)
◎: less than 0.20 ○: 0.20 or more and less than 0.25 ×: 0.25 or more
（動摩擦係数 μｋ）
◎：０．１５未満
○：０．１５以上０．２０未満
×：０．２０以上 (Dynamic friction coefficient μk)
◎: less than 0.15 ○: 0.15 or more and less than 0.20 ×: 0.20 or more
　上記各試験に用いた表１に示す実施例１～１５、及び表２に示す比較例１～９におけるＰＴＦＥの平均粒子径は３．５μｍであり、シリカの平均粒子径は０．３μｍである。表１及び表２に示す試験結果において、耐摩耗性（摩耗深さ）、相手攻撃性（相手材摩耗量）、及び摩擦係数はできるだけ低いことが好ましく、耐焼付き性（焼き付き荷重）はできるだけ高いことが好ましい。 In Examples 1 to 15 shown in Table 1 and Comparative Examples 1 to 9 shown in Table 2 used in the above tests, the average particle size of PTFE was 3.5 μm, and the average particle size of silica was 0.3 μm. . In the test results shown in Tables 1 and 2, it is preferable that the wear resistance (wear depth), mating aggressiveness (mating material wear amount), and friction coefficient are as low as possible, and the seizure resistance (seizure load) is as high as possible. is preferred.
　表１に示す各材料の含有量は重量部である。
Figure JPOXMLDOC01-appb-T000001
 The content of each material shown in Table 1 is in parts by weight.
Figure JPOXMLDOC01-appb-T000001
　表２に示す各材料の含有量は重量部である。
Figure JPOXMLDOC01-appb-T000002
 The content of each material shown in Table 2 is in parts by weight.
Figure JPOXMLDOC01-appb-T000002
　表１の結果から、実施例１～１５は、摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性の全てが良好な結果となっていた。一方、表２の結果から、比較例１～４はＰＴＦＥやシリカの含有量が過小又は過多のため、低摩擦係数、耐焼付き性、耐摩耗性、又は低相手攻撃性のうち、いずれかの物性に問題があった。また、比較例５～９の結果から明らかなように、固体潤滑剤としてＰＴＦＥを、摩耗抑制材としてシリカをそれぞれ必須成分として含有していなければ、摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性の全てを満足することはできないことが確認された。 From the results in Table 1, Examples 1 to 15 had good results in all of the coefficient of friction, seizure resistance, wear resistance, and low mating aggression. On the other hand, from the results in Table 2, Comparative Examples 1 to 4 have too little or too much PTFE or silica content, so that any one of low friction coefficient, seizure resistance, wear resistance, or low mating attack There was a problem with physical properties. Further, as is clear from the results of Comparative Examples 5 to 9, if PTFE as a solid lubricant and silica as a wear suppressing material are not contained as essential components, the coefficient of friction, seizure resistance, wear resistance, and It was confirmed that it is not possible to satisfy all of low opponent aggression.
（粒径比試験）
　上記試験から、固体潤滑剤としてＰＴＦＥを、摩耗抑制材としてシリカをそれぞれ必須成分とすべきことが確認されたことに続いて、ＰＴＦＦとシリカとの平均粒子径の粒径比について検討した。具体的には、被膜組成物中の各材料の含有量は、実施例１のバインダー樹脂１００重量部に対してＰＴＦＥ３重量部、シリカ１８重量部で固定し、ＰＴＦＥとシリカの平均粒子径を種々変更した場合について、上記各試験と同じ方法で摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性について測定した。その結果を表３に示す。 (Particle size ratio test)
From the above test, it was confirmed that PTFE should be used as the solid lubricant, and silica should be used as the wear suppressing material. Subsequently, the particle size ratio of the average particle size of PTFE and silica was investigated. Specifically, the content of each material in the coating composition was fixed at 3 parts by weight of PTFE and 18 parts by weight of silica with respect to 100 parts by weight of the binder resin of Example 1, and the average particle size of PTFE and silica was varied. For the changed cases, the coefficient of friction, seizure resistance, wear resistance, and low mating aggression were measured in the same manner as in the above tests. Table 3 shows the results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３の結果から、ＰＴＦＥ／シリカの粒径比が０．８～８０の範囲にある実施例１６～１７は、摩擦係数、耐焼付き性、耐摩耗性、及び低相手攻撃性の全てが良好な結果となっていた。これに対し比較例１０～１１は、ＰＴＦＥ／シリカ粒径比のバランスが悪いため、低摩擦係数、耐焼付き性、耐摩耗性、又は低相手攻撃性のうち、いずれかの物性に問題があった。 From the results in Table 3, Examples 16 and 17, in which the PTFE/silica particle size ratio is in the range of 0.8 to 80, have good coefficient of friction, seizure resistance, wear resistance, and low mating attack. It was a good result. On the other hand, in Comparative Examples 10 and 11, the balance of the PTFE/silica particle size ratio is poor, so there is a problem in any of the physical properties of low friction coefficient, seizure resistance, wear resistance, and low mating attack. rice field.
１・２・３・４　試験機
１０・２０・３０・４０　試験材
１１・２１・３１・４１　摺動面
１２・２２・３２・４２　相手材
 
 
 
 

  1, 2, 3, 4 Testing machine 10, 20, 30, 40 Test material 11, 21, 31, 41 Sliding surface 12, 22, 32, 42 Mating material

Claims (2)

  1. 　摺動部材用被膜組成物であって、
    　摺動部材の表面に被膜を形成するためのものであり、
    　バインダー樹脂と、固体潤滑剤と、摩耗抑制材とを含有し、
    　前記バインダー樹脂１００重量部に対して、前記固体潤滑剤を０．５～６重量部、前記摩耗抑制材を５～３０重量部含有し、
    　前記固体潤滑剤が少なくともポリテトラフルオロエチレンであり、
    　前記摩耗抑制材が少なくともシリカであり、
    　（ポリテトラフルオロエチレン／シリカ）で計算される前記ポリテトラフルオロエチレンと前記シリカとの粒径比が０．８～８０である、摺動部材用被膜組成物。     A coating composition for a sliding member,
    It is for forming a coating on the surface of the sliding member,
    containing a binder resin, a solid lubricant, and a wear inhibitor,
    Containing 0.5 to 6 parts by weight of the solid lubricant and 5 to 30 parts by weight of the wear suppressing material with respect to 100 parts by weight of the binder resin,
    The solid lubricant is at least polytetrafluoroethylene,
    The wear suppressing material is at least silica,
    A coating composition for a sliding member, wherein the particle size ratio of said polytetrafluoroethylene and said silica calculated by (polytetrafluoroethylene/silica) is 0.8 to 80.
  2. 　請求項１に記載の摺動部材用被膜組成物により形成された被膜を表面に備える、摺動部材。 A sliding member having a coating film formed from the coating composition for sliding member according to claim 1 on its surface.
PCT/JP2022/028704 2021-07-28 2022-07-26 Coating composition for sliding member, and sliding member WO2023008405A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0565666A (en) * 1991-09-06 1993-03-19 Nippon Steel Corp Production of lubricative plated steel sheet excellent in sliding property and press-workability
JP2004084656A (en) * 2002-06-24 2004-03-18 Toyota Industries Corp Sliding parts
JP2015124311A (en) * 2013-12-26 2015-07-06 トヨタ自動車株式会社 Sliding resin composition
WO2018074150A1 (en) * 2016-10-18 2018-04-26 株式会社村田製作所 Rotating encoder
WO2021014901A1 (en) * 2019-07-25 2021-01-28 Nok株式会社 Coating agent for oil seal

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0565666A (en) * 1991-09-06 1993-03-19 Nippon Steel Corp Production of lubricative plated steel sheet excellent in sliding property and press-workability
JP2004084656A (en) * 2002-06-24 2004-03-18 Toyota Industries Corp Sliding parts
JP2015124311A (en) * 2013-12-26 2015-07-06 トヨタ自動車株式会社 Sliding resin composition
WO2018074150A1 (en) * 2016-10-18 2018-04-26 株式会社村田製作所 Rotating encoder
WO2021014901A1 (en) * 2019-07-25 2021-01-28 Nok株式会社 Coating agent for oil seal

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