JP2020090562A - Composition, coating film formed using the same, sliding member having said coating film, and manufacturing method thereof - Google Patents

Composition, coating film formed using the same, sliding member having said coating film, and manufacturing method thereof Download PDF

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JP2020090562A
JP2020090562A JP2018226541A JP2018226541A JP2020090562A JP 2020090562 A JP2020090562 A JP 2020090562A JP 2018226541 A JP2018226541 A JP 2018226541A JP 2018226541 A JP2018226541 A JP 2018226541A JP 2020090562 A JP2020090562 A JP 2020090562A
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composition
hard particles
coating
particles
solid lubricant
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佐々木　貴彦
Takahiko Sasaki
貴彦 佐々木
山口　哲司
Tetsuji Yamaguchi
哲司 山口
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DuPont Toray Specialty Materials KK
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Priority to PCT/JP2019/047025 priority patent/WO2020116390A1/en
Publication of JP2020090562A publication Critical patent/JP2020090562A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/04—Metals; Alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
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    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/06—Particles of special shape or size
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/02—Parts of sliding-contact bearings
    • F16C33/04—Brasses; Bushes; Linings
    • F16C33/20—Sliding surface consisting mainly of plastics
    • F16C33/201—Composition of the plastic
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C9/00—Bearings for crankshafts or connecting-rods; Attachment of connecting-rods
    • F16C9/02—Crankshaft bearings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0887—Tungsten
    • C—CHEMISTRY; METALLURGY
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    • C08K2201/00—Specific properties of additives
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    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0413—Carbon; Graphite; Carbon black used as base material
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/044—Polyamides
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    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings
    • C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F16C3/00—Shafts; Axles; Cranks; Eccentrics
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Abstract

To provide the composition capable of forming a sliding coating film that has an excellent sliding property, and can reduce wear of a sliding member.SOLUTION: The composition comprises: (A) a binder resin; (B) hard particles; and (C) a solid lubricant, wherein the hard particles include metallic tungsten particles having an average particle size of 0.5 to 10 μm, measured by a laser diffraction scattering method.SELECTED DRAWING: None

Description

本発明は、優れた摺動特性を有する潤滑被膜を提供する組成物に関する。さらに、本発明は、前記組成物から作成される被膜、該被膜を有する摺動部材、およびその製造方法に関する。 The present invention relates to compositions that provide lubricating coatings with excellent sliding properties. Furthermore, the present invention relates to a coating formed from the composition, a sliding member having the coating, and a method for producing the same.

部材表面の摺動特性を改善するための被膜形成性組成物は、産業機械、建設機械、自動車などの種々の用途に用いられている。通常、被膜形成性組成物は、結合基材および固体潤滑剤を含有する。また、結合基材および固体潤滑剤に加えて、硬質粒子を含有する被膜形成性組成物も知られている。例えば、特開２０１７−２０１１６５号公報は、熱硬化性樹脂、固体潤滑剤および／または硬質粒子、溶媒、ならびにポリエーテル変性シリコーンを含有する乾性潤滑被膜形成用組成物を開示している（特許文献１参照）。当該文献は、硬質粒子として、酸化ケイ素、酸化アルミニウム、酸化クロム、酸化チタン、酸化亜鉛、酸化鉄、ムライトなどの酸化物粒子、炭化ケイ素などの炭化物、および窒化ケイ素などの窒化物を開示している。 The film-forming composition for improving the sliding property of the member surface is used in various applications such as industrial machinery, construction machinery and automobiles. Typically, the film-forming composition contains a bonding substrate and a solid lubricant. Also known are film-forming compositions containing hard particles in addition to the bonding substrate and solid lubricant. For example, Japanese Patent Laid-Open No. 2017-201165 discloses a composition for forming a dry lubricating film containing a thermosetting resin, a solid lubricant and/or hard particles, a solvent, and a polyether-modified silicone (Patent Document). 1). The document discloses, as hard particles, silicon oxide, aluminum oxide, chromium oxide, titanium oxide, zinc oxide, iron oxide, oxide particles such as mullite, carbides such as silicon carbide, and nitrides such as silicon nitride. There is.

一方で、特開２０００−２６５９５３号公報には、金属粒子を含む樹脂からなるコーティング層が施された圧縮機が開示されている（特許文献２参照）。当該文献には、金属粒子の例として、錫、銀、アルミニウム、銅、亜鉛、ニッケル、チタン、タングステン、モリブデン、マグネシウム、鉄、およびこれらを含む合金が開示されている。 On the other hand, Japanese Patent Laid-Open No. 2000-265953 discloses a compressor provided with a coating layer made of a resin containing metal particles (see Patent Document 2). The document discloses tin, silver, aluminum, copper, zinc, nickel, titanium, tungsten, molybdenum, magnesium, iron, and alloys containing these as examples of metal particles.

特開２０１７−２０１１６５号公報JP, 2017-201165, A 特開２０００−２６５９５３号公報JP, 2000-265953, A

摺動部材は、通常、２または２以上の部材を接触したまま滑って動かす用途に用いられる。摺動部材には、優れた滑り特性（摩擦係数が小さいこと）のみではなく、優れた耐摩耗性（摩耗が少ないこと）も要求される。しかしながら、本発明者らの研究によれば、従来の酸化物粒子、炭化物粒子、または窒化物粒子を硬質粒子として用いる被膜を摺動部材表面に形成した場合は、接触する相手方の部材表面を摩耗する傾向が高いことがわかった。よって、本発明は、優れた滑り特性を有しながらも摺動部材および相手方部材の摩耗が少ない摺動被膜を形成し得る組成物を提供することを目的とする。 The sliding member is usually used for the purpose of sliding and moving two or two or more members in contact with each other. The sliding member is required to have not only excellent sliding characteristics (small friction coefficient) but also excellent wear resistance (low abrasion). However, according to the study by the present inventors, when a coating film using conventional oxide particles, carbide particles, or nitride particles as hard particles is formed on the sliding member surface, the contacting member surface of the other side is worn. It turns out that there is a high tendency to do. Therefore, it is an object of the present invention to provide a composition capable of forming a sliding coating that has excellent sliding characteristics and has less wear on a sliding member and a counterpart member.

特開２０００−２６５９５３号公報には、金属粒子を含む樹脂からなるコーティング層が記載されているものの、具体的にはアルミニウム合金および錫を用いた例が開示されているのみである。また、当該文献には、金属粒子の粒径は１０〜１００ミクロンの範囲内にあることが好ましい旨が記載されている。本発明者らは、バインダー樹脂、固体潤滑剤および硬質粒子を含有する被膜形成剤の組成を種々検討した結果、硬質粒子として特定の平均粒子径の金属タングステン粒子を使用することにより、従来では達成し得なかったレベルで摺動部材および相手方部材の摩耗を防ぐことができることを見出し、本発明を完成させた。 Japanese Patent Laid-Open No. 2000-265953 describes a coating layer made of a resin containing metal particles, but specifically discloses only an example using an aluminum alloy and tin. Further, the document describes that the particle size of the metal particles is preferably in the range of 10 to 100 microns. The present inventors have variously studied the composition of a film forming agent containing a binder resin, a solid lubricant and hard particles, and by using metal tungsten particles having a specific average particle diameter as the hard particles, conventionally achieved. The inventors have found that it is possible to prevent wear of the sliding member and the counterpart member at a level that could not be achieved, and have completed the present invention.

すなわち、本発明の第１の実施形態は、（Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含有する組成物であって、前記硬質粒子はレーザー回折散乱法で測定される平均粒子径が０．５〜１０μｍである金属タングステン粒子を含むことを特徴とする、組成物に関する。 That is, the first embodiment of the present invention is a composition containing (A) a binder resin, (B) hard particles, and (C) a solid lubricant, wherein the hard particles are measured by a laser diffraction scattering method. A metal tungsten particle having an average particle size of 0.5 to 10 μm.

本発明の第２の実施形態は、第１の実施形態の組成物から作成された被膜に関する。具体的には、本発明の第２の実施形態は、（Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含む被膜であって、前記硬質粒子は、レーザー回折散乱法で測定される、０．５〜１０μｍの平均粒子径を有する金属タングステン粒子を含むことを特徴とする被膜に関する。 A second embodiment of the invention relates to a coating made from the composition of the first embodiment. Specifically, the second embodiment of the present invention is a coating containing (A) binder resin, (B) hard particles, and (C) solid lubricant, wherein the hard particles are formed by a laser diffraction scattering method. And a metallic tungsten particle having an average particle diameter of 0.5 to 10 μm, as measured by 1.

本発明の第３の実施形態は、第２の実施形態の潤滑被膜を有する摺動部材に関する。 The third embodiment of the present invention relates to a sliding member having the lubricating coating of the second embodiment.

本発明の第４の実施形態は、部材表面上に潤滑被膜を形成する方法であって、（Ｉ）（Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含有し、前記硬質粒子はレーザー回折散乱法で測定される平均粒子径が０．５〜１０μｍである金属タングステン粒子を含む組成物を作成する工程と、（ＩＩ）該組成物を部材表面上に塗布する工程と、（ＩＩＩ）塗布された組成物を熱硬化させることにより部材表面に潤滑被膜を形成する工程と、を含む方法に関する。 A fourth embodiment of the present invention is a method for forming a lubricating coating on the surface of a member, which contains (I) (A) binder resin, (B) hard particles, and (C) solid lubricant, The hard particles have a step of preparing a composition containing metal tungsten particles having an average particle size of 0.5 to 10 μm measured by a laser diffraction scattering method, and (II) a step of applying the composition on the surface of a member. And (III) forming a lubricating coating on the surface of the member by thermally curing the applied composition.

本発明の組成物によれば、優れた滑り特性を有しながらも、摺動部材の摩耗および相手方部材の摩耗の両方を抑制することができる摺動被膜を形成することができる。 According to the composition of the present invention, it is possible to form a sliding coating which has excellent sliding properties, but can suppress both wear of the sliding member and wear of the mating member.

本発明の第１の実施形態は、（Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含有する組成物であって、硬質粒子は０．５〜１０μｍの平均粒子径を有する金属タングステン粒子を含む、潤滑被膜の形成に用いられる組成物に関する。本発明における硬質粒子の平均粒子径は、レーザー回折散乱法で測定される。また、本実施形態の組成物は、（Ｄ）溶媒、および／または（Ｅ）その他の添加剤をさらに含んでもよい。以下、本実施形態の組成物の各成分を説明する。 The first embodiment of the present invention is a composition containing (A) binder resin, (B) hard particles, and (C) solid lubricant, wherein the hard particles have an average particle diameter of 0.5 to 10 μm. The present invention relates to a composition used for forming a lubricating coating, the composition including metallic tungsten particles having: The average particle size of the hard particles in the present invention is measured by a laser diffraction scattering method. Further, the composition of the present embodiment may further contain (D) a solvent, and/or (E) other additives. Hereinafter, each component of the composition of the present embodiment will be described.

（Ａ）バインダー樹脂
本実施形態で用いるバインダー樹脂は、耐熱性樹脂として潤滑被膜を形成し、かつ後述する硬質粒子および固体潤滑剤を潤滑被膜中に担持する機能を有する樹脂である。バインダー樹脂は、たとえば、ポリアミドイミド、ポリイミド、エポキシ樹脂、フェノール樹脂、ポリアミド、ポリベンズイミダゾール、ポリフェニルスルフォネートおよびポリエーテルエーテルケトンからなる群から選択される１つまたは複数の樹脂を含む。バインダー樹脂として、熱硬化性樹脂を用いることが好ましい。好ましくは、バインダー樹脂は、ポリアミドイミドまたはポリイミドを含む。さらに好ましくは、バインダー樹脂はポリアミドイミドを含む。バインダー樹脂の含有量は、組成物全体の質量を基準として１０〜４０質量％であり、好ましくは２０〜３０質量％である。 (A) Binder Resin The binder resin used in the present embodiment is a resin having a function of forming a lubricating coating as a heat resistant resin and supporting hard particles and a solid lubricant described later in the lubricating coating. The binder resin includes, for example, one or more resins selected from the group consisting of polyamide-imide, polyimide, epoxy resin, phenolic resin, polyamide, polybenzimidazole, polyphenyl sulfonate and polyether ether ketone. It is preferable to use a thermosetting resin as the binder resin. Preferably, the binder resin comprises polyamide imide or polyimide. More preferably, the binder resin comprises polyamideimide. The content of the binder resin is 10 to 40% by mass, preferably 20 to 30% by mass, based on the mass of the entire composition.

（Ｂ） 硬質粒子
本実施形態の硬質粒子は、０．５〜１０μｍの平均粒子径を有する金属タングステン粒子を含む。硬質粒子の平均粒子径は、レーザー回折散乱法によって測定することができる。好ましくは、金属タングステン粒子の平均粒子径は、１〜６μｍであり、特に好ましくは１〜３μｍである。硬質粒子は、潤滑被膜の耐荷重性を向上させるとともに、耐摩耗性を向上する機能を有する。しかしながら、時として潤滑被膜が接触する相手方部材の表面を摩耗してしまう場合がある。本発明者らは、おどろくべきことには、０．５〜１０μｍの平均粒子径を有する金属タングステン粒子を硬質粒子として用いた場合には、相手方部材表面の摩耗が少なく、摺動部材の寿命を伸ばすことができることを見出した。 (B) Hard Particles The hard particles of this embodiment include metal tungsten particles having an average particle diameter of 0.5 to 10 μm. The average particle diameter of the hard particles can be measured by the laser diffraction scattering method. The average particle diameter of the metal tungsten particles is preferably 1 to 6 μm, particularly preferably 1 to 3 μm. The hard particles have the function of improving the load resistance of the lubricating coating and also improving the wear resistance. However, in some cases, the surface of the counterpart member with which the lubricating coating comes into contact may be worn away. The inventors of the present invention are surprised to find that when metal tungsten particles having an average particle diameter of 0.5 to 10 μm are used as hard particles, wear of the surface of the counterpart member is small and the life of the sliding member is reduced. I found that I can stretch.

金属タングステン粒子としては、凝集が少なくほとんどの粒子が一次粒子として存在する単分散微粒子タングステン、または二次粒子が存在するが粒子形状が均一な均一微粒子タングステンが好ましい。特に好ましい金属タングステン粒子は、単分散微粒子タングステンである。 As the metal tungsten particles, monodisperse fine particle tungsten in which most particles are present as primary particles with little aggregation, or uniform fine particle tungsten in which secondary particles are present but the particle shape is uniform is preferable. A particularly preferred metal tungsten particle is monodisperse fine particle tungsten.

本発明の組成物の有する機能を阻害しない範囲で、硬質粒子として金属タングステン粒子以外の粒子をさらに含むことができる。他の粒子としては、炭化タングステン、炭化チタン、炭化ジルコニウム、酸化ジルコニウム、二硫化タングステン、炭化モリブデン、二珪素化タングステン、窒化チタンおよび窒化ジルコニウムからなる群から選択される１種または複数種の粒子を含む。硬質粒子が前述の他の粒子を含む場合、硬質粒子は、硬質粒子全体の質量を基準として、好ましくは５０質量％以上、さらに好ましくは７０質量％以上の金属タングステン粒子を含む。 The hard particles may further include particles other than the metal tungsten particles as long as the functions of the composition of the present invention are not impaired. Other particles include one or more kinds of particles selected from the group consisting of tungsten carbide, titanium carbide, zirconium carbide, zirconium oxide, tungsten disulfide, molybdenum carbide, tungsten disilicide, titanium nitride and zirconium nitride. Including. When the hard particles include the other particles described above, the hard particles preferably include 50 mass% or more, and more preferably 70 mass% or more of the metal tungsten particles, based on the total mass of the hard particles.

硬質粒子の含有量は、後述する固体潤滑剤の配合量に依存する。一例としては、本実施形態の組成物は、バインダー樹脂１００質量部あたり７０から１４０質量部の硬質粒子を含む。 The content of the hard particles depends on the compounding amount of the solid lubricant described later. As an example, the composition of the present embodiment contains 70 to 140 parts by mass of hard particles per 100 parts by mass of the binder resin.

（Ｃ） 固体潤滑剤
本発明で用いる固体潤滑剤は、二硫化モリブデンまたはグラファイトである。固体潤滑剤は被膜の摺動特性を向上させる機能を有する。特に、良好な耐摩耗性という摺動特性を有する被膜を形成する観点から、二硫化モリブデンとグラファイトは、本発明の組成物で使用するのに好適である。両者のうちでも、摩擦係数を下げ、さらに耐摩耗性を付与する点から、グラファイトが特に好ましい。 (C) Solid Lubricant The solid lubricant used in the present invention is molybdenum disulfide or graphite. The solid lubricant has the function of improving the sliding characteristics of the coating. In particular, molybdenum disulfide and graphite are suitable for use in the composition of the present invention from the viewpoint of forming a film having a sliding property of good wear resistance. Among them, graphite is particularly preferable from the viewpoint of lowering the coefficient of friction and imparting wear resistance.

固体潤滑剤の含有量は、硬質粒子の配合量に依存する。一例としては、本実施形態の組成物は、バインダー樹脂１００質量部あたり４０から７０質量部の固体潤滑剤を含む。 The content of the solid lubricant depends on the content of the hard particles. As an example, the composition of the present embodiment includes 40 to 70 parts by mass of the solid lubricant per 100 parts by mass of the binder resin.

本発明の固体潤滑剤の平均粒子径は、レーザー回折散乱法によって測定することができる。固体潤滑剤の平均粒子径は、０．１〜１５．０μｍであることが好ましく、１．０〜１０．０μｍであることが特に好ましい。 The average particle size of the solid lubricant of the present invention can be measured by a laser diffraction scattering method. The average particle size of the solid lubricant is preferably 0.1 to 15.0 μm, and particularly preferably 1.0 to 10.0 μm.

（Ｄ） 溶媒
本発明の組成物は、塗布による被膜形成を容易にすることなどを目的として、溶媒を更に含むことができる。溶媒はバインダーレジンの種類によって選択することができる。使用することのできる溶媒の非制限的な例は、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類；酢酸メチル、酢酸エチル、γ−ブチロラクトン（ＧＢＬ）などのエステル類；トルエン、キシレンなどの芳香族炭化水素類；クロロホルム、トリクロロエチレン、トリクロロトリフルオロエタン等の有機ハロゲン化合物類；Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ−エチル−２−ピロリドン（ＮＥＰ）、１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ）、３−メトキシ−Ｎ、Ｎ−ジメチルプロパンアミド、１−ブチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）などのアミド類を含む。本実施形態における溶媒は、２種以上の前述の溶媒を含む混合溶媒であってもよい。特に好ましい溶媒は、ＮＥＰ、ＤＭＩ、ＧＢＬおよび３−メトキシ−Ｎ、Ｎ−ジメチルプロパンアミドを含む。 (D) Solvent The composition of the present invention may further contain a solvent for the purpose of facilitating film formation by coating. The solvent can be selected depending on the type of binder resin. Non-limiting examples of solvents that can be used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as methyl acetate, ethyl acetate, γ-butyrolactone (GBL); toluene, xylene and the like. Aromatic hydrocarbons; organic halogen compounds such as chloroform, trichloroethylene, trichlorotrifluoroethane; N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), 1,3-dimethyl-2 Amides such as imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide, 1-butyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC) Including types. The solvent in the present embodiment may be a mixed solvent containing two or more kinds of the above-mentioned solvents. Particularly preferred solvents include NEP, DMI, GBL and 3-methoxy-N,N-dimethylpropanamide.

（Ｅ） 添加剤
本実施形態の組成物は、本発明の目的を損なわない限り、さらに必要に応じて、１種または複数種の添加剤をさらに含んでもよい。用いることができる添加剤の非制限的な例は、紫外線吸収剤、光安定剤、酸化防止剤、熱重合防止剤、レベリング剤、消泡剤、増粘剤、沈降防止剤、顔料（有機着色顔料、無機顔料）、着色染料、赤外線吸収剤、蛍光増白剤、分散剤、導電性微粒子、帯電防止剤、防曇剤、およびカップリング剤を含む。 (E) Additive The composition of the present embodiment may further contain one or more additives, if necessary, as long as the object of the present invention is not impaired. Non-limiting examples of additives that can be used are UV absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, defoamers, thickeners, antisettling agents, pigments (organic coloring Pigments, inorganic pigments), coloring dyes, infrared absorbers, optical brighteners, dispersants, conductive fine particles, antistatic agents, antifogging agents, and coupling agents.

本発明の組成物は、成分（Ａ）、（Ｂ）および（Ｃ）、ならびに必要に応じて成分（Ｄ）および／または（Ｅ）を適宜混合することによって製造することができる。 The composition of the present invention can be produced by appropriately mixing the components (A), (B) and (C) and, if necessary, the components (D) and/or (E).

本発明の第２の実施形態は、（Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含有する被膜に関する。本実施形態の被膜は、摺動部材の潤滑被膜として有用である。本実施形態の被膜は、第１の実施形態の組成物を用いて形成することができる。本実施形態の被膜は、（Ａ）バインダー樹脂中に（Ｂ）硬質粒子および（Ｃ）固体潤滑剤が分散された潤滑被膜である。本実施形態の被膜は、（Ｅ）添加剤をさらに含んでもよい。本実施形態の被膜は、１〜５０μｍ、好ましくは５〜３０μｍの膜厚を有する。 The second embodiment of the present invention relates to a coating film containing (A) binder resin, (B) hard particles, and (C) solid lubricant. The coating of the present embodiment is useful as a lubricating coating for sliding members. The coating film of the present embodiment can be formed using the composition of the first embodiment. The coating of the present embodiment is a lubricating coating in which (B) hard particles and (C) solid lubricant are dispersed in (A) binder resin. The coating film of the present embodiment may further include (E) an additive. The coating film of the present embodiment has a film thickness of 1 to 50 μm, preferably 5 to 30 μm.

本発明の第３の実施形態は、第２の実施形態の被膜を有する摺動部材に関する。被膜は、摺動部材の摺動面に配置され、潤滑被膜として機能する。本実施形態の摺動部材の非制限的な例は、コンプレッサーの斜板、エンジンタペット（バルブリフター）、カムシャフト、クランクシャフト、エンジンメタル、エンジンピストン、ピストンリング、ギヤ、ドアロック、ブレーキシム、およびブレーキクリップを含む。 The third embodiment of the present invention relates to a sliding member having the coating film of the second embodiment. The coating is arranged on the sliding surface of the sliding member and functions as a lubricating coating. Non-limiting examples of the sliding member of this embodiment include a swash plate of a compressor, an engine tappet (valve lifter), a camshaft, a crankshaft, an engine metal, an engine piston, a piston ring, a gear, a door lock, a brake shim, And includes brake clips.

本発明の第４の実施形態は、部材表面上に潤滑被膜を形成する方法であって、以下に記載の（Ｉ）から（ＩＩＩ）の各工程を含む。 The fourth embodiment of the present invention is a method for forming a lubricating coating on the surface of a member, which includes the steps (I) to (III) described below.

工程（Ｉ）
工程（Ｉ）は、（Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含有する組成物であって、硬質粒子は０．５〜１０μｍの平均粒子径（レーザー回折散乱法により測定される）を有する金属タングステン粒子を含む組成物を作成する工程である。本工程で作製される組成物は本発明の第１の実施形態として上述したものである。本工程は、成分（Ａ）〜（Ｅ）を適宜混合することにより実施することができる。 Process (I)
Step (I) is a composition containing (A) a binder resin, (B) hard particles, and (C) a solid lubricant, wherein the hard particles have an average particle size of 0.5 to 10 μm (laser diffraction scattering). (As measured by the method). The composition produced in this step is the one described above as the first embodiment of the present invention. This step can be carried out by appropriately mixing the components (A) to (E).

工程（ＩＩ）
工程（ＩＩ）は、工程（Ｉ）にて作成された組成物を部材表面上に塗布する工程である。組成物の塗布方法の非制限的な例は、ディッピング法、スピンコート法、フローコート法、スプレー法、バーコート法、グラビアコート法、ロールコート法、ブレードコート法、スクリーン印刷法およびエアーナイフコート法を含む。塗膜は、好ましくは１〜５０μｍ、より好ましくは５〜３０μｍの膜厚を有するが、特に前述の範囲に限定されるものではない。 Process (II)
Step (II) is a step of applying the composition prepared in step (I) onto the surface of the member. Non-limiting examples of methods for applying the composition include dipping, spin coating, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, screen printing and air knife coating. Including the law. The coating film preferably has a film thickness of 1 to 50 μm, more preferably 5 to 30 μm, but is not particularly limited to the above range.

工程（ＩＩＩ）
工程（ＩＩＩ）は、工程（ＩＩ）にて塗布された組成物を加熱することにより、部材表面に潤滑被膜を形成する工程である。加熱はオーブンなどを用いて行うことができる。バインダー樹脂として熱硬化性樹脂を用いる場合には、加熱によって架橋反応が生じ、部材表面に硬化被膜を形成することができる。塗布された組成物を加熱する際には、１段目の加熱によって組成物中の溶媒を除去し、２段目の加熱によって架橋反応によって硬化させることもできる。例えば、６０〜１００℃で５〜３０分間にわたって１段目の加熱を行い、続いて１８０〜２５０℃で２０〜１２０分間にわたって２段目の加熱を行うこともできる。 Process (III)
Step (III) is a step of heating the composition applied in step (II) to form a lubricating coating on the surface of the member. The heating can be performed using an oven or the like. When a thermosetting resin is used as the binder resin, a cross-linking reaction occurs by heating and a cured coating can be formed on the surface of the member. When the applied composition is heated, the solvent in the composition may be removed by the first heating and the crosslinking reaction may be cured by the second heating. For example, the first stage heating may be performed at 60 to 100° C. for 5 to 30 minutes, and then the second stage heating may be performed at 180 to 250° C. for 20 to 120 minutes.

以下、本発明を実施例により詳細に説明するが、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

実施例にて使用した原料を第１表に示す。第１表中の「平均粒子径」はレーザー回折散乱法で測定した各粒子の平均粒子径である。 The raw materials used in the examples are shown in Table 1. The "average particle diameter" in Table 1 is the average particle diameter of each particle measured by the laser diffraction scattering method.

Figure 2020090562
Figure 2020090562

実施例１
γ−ブチロラクトン（ＧＢＬ、Ｄ−１）中に、８７質量部ポリアミドイミド樹脂（Ａ−１）を溶解させ、約３５質量％の固形分濃度を有するポリアミドイミド樹脂溶液を得た。得られたポリアミドイミド溶液に対し、１３質量部のエポキシ樹脂（Ａ−２）を加え、バインダー樹脂溶液を得た。得られたバインダー樹脂溶液に、粉末状の固体潤滑剤である５５．７質量部のグラファイト（Ｃ−１）、硬質粒子である３０．４質量部の金属タングステン粒子（Ｂ−１）、および添加剤である０．７質量部の消泡剤（Ｅ−１）を添加し、室温において混合分散した。得られた混合物をＧＢＬ（Ｄ−１）を用いて希釈し、評価用試験に用いる４７．０質量％の固形分濃度を有する塗料組成物を得た。ＧＢＬ（Ｄ−１）の総使用量は、２１０．９質量部であった。 Example 1
87 parts by mass of polyamideimide resin (A-1) was dissolved in γ-butyrolactone (GBL, D-1) to obtain a polyamideimide resin solution having a solid content concentration of about 35% by mass. 13 parts by mass of the epoxy resin (A-2) was added to the obtained polyamideimide solution to obtain a binder resin solution. To the obtained binder resin solution, 55.7 parts by mass of graphite (C-1) which is a powdery solid lubricant, 30.4 parts by mass of metal tungsten particles (B-1) which are hard particles, and addition 0.7 parts by mass of the defoaming agent (E-1), which is an agent, was added and mixed and dispersed at room temperature. The obtained mixture was diluted with GBL(D-1) to obtain a coating composition having a solid content concentration of 47.0 mass% used in the evaluation test. The total amount of GBL(D-1) used was 210.9 parts by mass.

塗料組成物を円柱状（サイズφ２４×７．９ｍｍ）のオプティモールインストルメンツブリューテクニックゲーエムベーハー製ＳＲＶディスク試験片（材質１００Ｃｒ６（ＳＵＪ２相当））の表面にスクリーン印刷版（メッシュ株式会社製）を用いて、焼成後に１５±５μｍの膜厚の被膜が得られるように塗布した。得られた塗膜を、８０℃の循環式オーブン中で２０分間にわたって加熱し溶媒を除去した。引き続いて、２２０℃で２０分間にわたる焼成を行い、試験片を得た。 The coating composition was screen-printed (made by Mesh Co., Ltd.) on the surface of a columnar (size φ24×7.9 mm) Optimol Instruments Brewtechnik SRV disc test piece manufactured by GM Behr (material 100Cr6 (equivalent to SUJ2)). Was applied so that a film having a film thickness of 15±5 μm could be obtained after firing. The obtained coating film was heated in a circulating oven at 80° C. for 20 minutes to remove the solvent. Subsequently, firing was performed at 220° C. for 20 minutes to obtain a test piece.

実施例２〜３および比較例１〜７
第２表に示す成分を用いたことを除いて、実施例１と同様の操作を行い試験片を得た。 Examples 2-3 and Comparative Examples 1-7
A test piece was obtained in the same manner as in Example 1, except that the components shown in Table 2 were used.

各実施例および比較例により得られた試験片に対し、後述するＳＲＶ試験を行った結果を合わせて、第２表に示した。第２表に示すとおり、本発明の実施例にかかる試験片は、優れた滑り特性（小さい平均動摩擦係数）を維持しながらも、比較例に対して被膜摩耗深さが少なく、かつ相手方部材の摩耗幅も少ないものであった。 The test results obtained in each of the examples and the comparative examples are shown in Table 2 together with the results of the SRV test described below. As shown in Table 2, the test pieces according to the examples of the present invention maintain excellent sliding characteristics (small average dynamic friction coefficient), but have a smaller coating wear depth than the comparative examples, and the test piece The wear width was also small.

Figure 2020090562
Figure 2020090562

評価方法
ＳＲＶ摩擦摩耗試験機（オプティモールインストルメンツブリューテクニックゲーエムベーハー製、製品名振動摩擦摩耗試験機 ＳＲＶ５型）を用い、ＳＲＶディスク試験片表面上をＳＲＶシリンダーが往復摺動する方法により、評価を行った。相手方部材であるシリンダーはφ１５×２２ｍｍのオプティモールインストルメンツブリューテクニックゲーエムベーハー製のＳＲＶシリンダー（材質１００Ｃｒ６（ＳＵＪ２相当））を用いた。本発明の組成物からなる被膜が形成されたＳＲＶディスクをＳＲＶ５型試験機の試験台に設定し、被膜上に０．１ｇのエンジン油（エクソンモービル（有）製、ガソリン・ディーゼルエンジン専用化学合成油 １０Ｗ−３０ ＳＭ／ＣＦ）を滴下した。その後、ＳＲＶシリンダーを荷重２０Ｎで押し当て、速度３０Ｈｚおよび摺動距離２ｍｍの条件下、１時間毎に摩擦係数を測定しながら、１２時間にわたって摺動した。その後、エンジン油を洗浄し、触針型の表面粗さ計（ＳＵＲＦＣＯＭ１４００Ｄ）にてＳＲＶディスクの未摺動部と摺動部の段差を測定し、被膜の摩耗深さを求めた。また、相手方部材であるＳＲＶシリンダーを実体顕微鏡により撮影し、摩耗が認められた部分の幅を測定し、相手方部材摩耗幅を求めた。さらに、１時間毎に測定した摩擦係数の算術平均値を、平均動摩擦係数とした。 Evaluation method Using an SRV friction and wear tester (manufactured by Optimall Instruments Brewtechnik GmbH, product name vibration friction and wear tester SRV5 type), the SRV cylinder slides back and forth on the surface of the SRV disk test piece. An evaluation was made. As the cylinder which is the counterpart member, an SRV cylinder (material 100Cr6 (equivalent to SUJ2)) made by Optimol Instruments Brewtechnik GmbH was used with a diameter of 15×22 mm. An SRV disk having a coating formed of the composition of the present invention was set on a test stand of an SRV5 type tester, and 0.1 g of engine oil (manufactured by ExxonMobil Corp., chemical synthesis for gasoline/diesel engine only) was set on the coating. Oil 10W-30 SM/CF) was added dropwise. Then, the SRV cylinder was pressed with a load of 20 N, and sliding was performed for 12 hours while measuring the friction coefficient every hour under the condition of the speed of 30 Hz and the sliding distance of 2 mm. Then, the engine oil was washed, and the level difference between the non-sliding part and the sliding part of the SRV disk was measured with a stylus type surface roughness meter (SURFCOM1400D) to determine the wear depth of the coating. Further, the SRV cylinder, which is the counterpart member, was photographed by a stereoscopic microscope, the width of the portion where wear was observed was measured, and the wear width of the counterpart member was obtained. Further, the arithmetic average value of the friction coefficient measured every hour was defined as the average dynamic friction coefficient.

Claims (10)

（Ａ） バインダー樹脂、
（Ｂ） 硬質粒子、および
（Ｃ） 固体潤滑剤
を含む組成物であって、前記硬質粒子は、レーザー回折散乱法で測定される、０．５〜１０μｍの平均粒子径を有する金属タングステン粒子を含むことを特徴とする組成物。 (A) Binder resin,
A composition containing (B) hard particles and (C) a solid lubricant, wherein the hard particles are metal tungsten particles having an average particle diameter of 0.5 to 10 μm measured by a laser diffraction scattering method. A composition comprising: 固体潤滑剤が二硫化モリブデンまたはグラファイトであることを特徴とする請求項１に記載の組成物。 The composition of claim 1 wherein the solid lubricant is molybdenum disulfide or graphite. バインダー樹脂が、ポリアミドイミド、ポリイミド、エポキシ樹脂、フェノール樹脂、ポリアミド、ポリベンズイミダゾール、ポリフェニルスルフォネートおよびポリエーテルエーテルケトンからなる群から選択される１種または複数種の樹脂を含むを特徴とする請求項１に記載の組成物。 The binder resin contains one or more kinds of resins selected from the group consisting of polyamideimide, polyimide, epoxy resin, phenol resin, polyamide, polybenzimidazole, polyphenyl sulfonate and polyether ether ketone. The composition of claim 1. （Ｄ）溶媒をさらに含むことを特徴とする請求項１に記載の組成物。 The composition according to claim 1, further comprising (D) a solvent. （Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含む被膜であって、前記硬質粒子は、レーザー回折散乱法で測定される、０．５〜１０μｍの平均粒子径を有する金属タングステン粒子を含むことを特徴とする被膜。 A coating film containing (A) a binder resin, (B) hard particles, and (C) a solid lubricant, wherein the hard particles have an average particle diameter of 0.5 to 10 μm measured by a laser diffraction scattering method. A coating film comprising metal tungsten particles having. 固体潤滑剤が二硫化モリブデンまたはグラファイトであることを特徴とする請求項５に記載の被膜。 The coating according to claim 5, wherein the solid lubricant is molybdenum disulfide or graphite. バインダー樹脂が、ポリアミドイミド、ポリイミド、エポキシ樹脂、フェノール樹脂、ポリアミド、ポリベンズイミダゾール、ポリフェニルスルフォネートおよびポリエーテルエーテルケトンからなる群から選択される１種または複数種の樹脂を含むを特徴とする請求項５に記載の被膜。 The binder resin contains one or more kinds of resins selected from the group consisting of polyamideimide, polyimide, epoxy resin, phenol resin, polyamide, polybenzimidazole, polyphenyl sulfonate and polyether ether ketone. The coating according to claim 5. 請求項５から７のいずれかに記載の被膜を有することを特徴とする摺動部材。 A sliding member comprising the coating according to any one of claims 5 to 7. 摺動部材がコンプレッサーの斜板、エンジンタペット、カムシャフト、クランクシャフト、エンジンメタル、エンジンピストン、ピストンリング、ギヤ、ドアロック、ブレーキシム、またはブレーキクリップからなる群から選択されることを特徴とする請求項８に記載の摺動部材。 The sliding member is selected from the group consisting of a compressor swash plate, engine tappet, camshaft, crankshaft, engine metal, engine piston, piston ring, gear, door lock, brake shim, or brake clip. The sliding member according to claim 8. 部材表面上に潤滑被膜を形成する方法であって、
（Ｉ） （Ａ）バインダー樹脂、（Ｂ）硬質粒子、および（Ｃ）固体潤滑剤を含み、前記硬質粒子は、レーザー回折散乱法で測定される、０．５〜１０μｍの平均粒子径を有する金属タングステン粒子を含む組成物を作成する工程と、
（ＩＩ） 該組成物を部材表面上に塗布する工程と、
（ＩＩＩ） 塗布された組成物を加熱することにより部材表面に潤滑被膜を形成する工程と、
を有することを特徴とする方法。 A method of forming a lubricating coating on the surface of a member,
(I) (A) Binder resin, (B) hard particles, and (C) solid lubricant are included, and the hard particles have an average particle diameter of 0.5 to 10 μm measured by a laser diffraction scattering method. Creating a composition containing metallic tungsten particles,
(II) a step of applying the composition onto the surface of the member,
(III) a step of forming a lubricating coating on the surface of the member by heating the applied composition,
A method comprising:
JP2018226541A 2018-12-03 2018-12-03 Composition, coating film formed using the same, sliding member having said coating film, and manufacturing method thereof Pending JP2020090562A (en)

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