JP2007145894A - Multi-layer sliding member - Google Patents

Multi-layer sliding member Download PDF

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JP2007145894A
JP2007145894A JP2005338535A JP2005338535A JP2007145894A JP 2007145894 A JP2007145894 A JP 2007145894A JP 2005338535 A JP2005338535 A JP 2005338535A JP 2005338535 A JP2005338535 A JP 2005338535A JP 2007145894 A JP2007145894 A JP 2007145894A
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fullerene
layer
sliding member
resin
sliding
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Akio Niuchi
昭夫 似内
Tomoya Kudo
朋也 工藤
Masahiro Sato
雅洋 佐藤
Jun Sato
佐藤  淳
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Oiles Industry Co Ltd
Tamagawa Gakuen
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Oiles Industry Co Ltd
Tamagawa Gakuen
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a multi-layer sliding member having low friction properties and excellent abrasion resistance. <P>SOLUTION: The multi-layer sliding member is obtained by integrating a platy back plate made of a metal with a sliding layer. In the multi-layer sliding member, the sliding layer is composed of a polyimide resin and fullerene. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、複層摺動部材に関し、詳しくは、フラーレンを分散含有したポリイミド系樹脂組成物のすべり層を金属製の板状裏金の表面に被着形成した複層摺動部材に関する。   The present invention relates to a multilayer sliding member, and more particularly to a multilayer sliding member in which a sliding layer of a polyimide resin composition containing a fullerene in a dispersed manner is formed on the surface of a metal plate-like backing metal.

すべり層を有する軸受などの複層摺動部材として、合成樹脂組成物から成るすべり層を金属製の裏金の表面に一体成形した複層摺動部材が知られている。例えば、ポリイミド樹脂と四ふっ化エチレン樹脂と固体潤滑成分として鉛、一酸化鉛、酸化カドミウム、窒化ホウ素、黒鉛、二硫化モリブデン、二硫化タングステンとから成る合成樹脂被膜を有するすべり軸受が知られており(特許文献1参照)。また、合成樹脂組成物として、ポリイミド系樹脂と、必要に応じて四ふっ化エチレン樹脂、二硫化モリブデン及び/又はグラファイトとから成る組成物を使用する摺動部材が提案されている(特許文献2参照)。
特開昭52−44871号公報 特開昭55−106230号公報
As a multilayer sliding member such as a bearing having a sliding layer, a multilayer sliding member in which a sliding layer made of a synthetic resin composition is integrally formed on the surface of a metal back metal is known. For example, a plain bearing having a synthetic resin film composed of polyimide resin, ethylene tetrafluoride resin, and lead, lead monoxide, cadmium oxide, boron nitride, graphite, molybdenum disulfide, and tungsten disulfide as solid lubricant components is known. (Refer to Patent Document 1). Further, as a synthetic resin composition, there has been proposed a sliding member using a composition comprising a polyimide resin and, if necessary, a tetrafluoroethylene resin, molybdenum disulfide and / or graphite (Patent Document 2). reference).
JP 52-44871 A JP 55-106230 A

しかしながら、特許文献1に記載された合成樹脂被膜を有するすべり軸受は、摩耗量が比較的大きく、耐摩耗性が不十分である。また、特許文献2に記載された合成樹脂組成物から成る摺動部材は、摩擦係数が十分低く、且つ、摩耗量も十分小さいものではない。   However, the plain bearing having the synthetic resin coating described in Patent Document 1 has a relatively large wear amount and insufficient wear resistance. Further, the sliding member made of the synthetic resin composition described in Patent Document 2 has a sufficiently low coefficient of friction and a wear amount that is not sufficiently small.

本発明は上記実情に鑑みてなされたものであり、その目的は、低摩擦性と優れた耐摩耗性を有する複層摺動部材を提供することにある。   The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a multilayer sliding member having low friction and excellent wear resistance.

本発明者らは、種々検討を重ねた結果、次の様な知見を得た。すなわち、ポリイミド系樹脂にフラーレンを含有させることにより、すべり軸受などに使用される複層摺動部材として低摩擦性と優れた耐摩耗性を発揮することを見出した。   As a result of various studies, the present inventors have obtained the following knowledge. That is, it has been found that inclusion of fullerene in a polyimide resin exhibits low friction and excellent wear resistance as a multi-layer sliding member used in a sliding bearing or the like.

すなわち、本発明の要旨は、金属製の板状の裏金とすべり層とを一体化して成る複層摺動部材において、前記すべり層がポリイミド系樹脂とフラーレンとから成ることを特徴とする複層摺動部材に存する。   That is, the gist of the present invention is a multilayer sliding member in which a metal plate-like back metal and a sliding layer are integrated, wherein the sliding layer is composed of a polyimide resin and fullerene. It exists in the sliding member.

本発明によれば、低摩擦性を発揮すると共に優れた耐摩耗性を発揮する複層摺動部材が提供され、本発明の工業的価値は顕著である。   ADVANTAGE OF THE INVENTION According to this invention, the multilayer sliding member which exhibits the low abrasion property and outstanding abrasion resistance is provided, The industrial value of this invention is remarkable.

以下、本発明を詳細に説明する。本発明の複層摺動部材における金属製の板状裏金の表面に一体に被着形成されたすべり層は、ポリイミド系樹脂とフラーレンとから成る。   Hereinafter, the present invention will be described in detail. The sliding layer integrally formed on the surface of the metal plate-like backing metal in the multilayer sliding member of the present invention is composed of polyimide resin and fullerene.

金属製の板状の裏金としては、冷間圧延鋼板(SPCC)、無酸素銅(JIS−H−2123で規定されている無酸素形銅の1種又は2種)、タフピッチ銅(JIS−H−2123で規定されているタフピッチ形銅)等から成る純銅板、リン青銅などから成る銅合金板、アルミニウム板、アルミニウム合金板などが用途によって適宜選択される。   As the metal plate-shaped backing metal, cold rolled steel plate (SPCC), oxygen-free copper (one or two types of oxygen-free copper specified in JIS-H-2123), tough pitch copper (JIS-H) -Pure copper plate defined by -2123), a copper alloy plate made of phosphor bronze, an aluminum plate, an aluminum alloy plate, or the like is selected as appropriate.

ポリイミド系樹脂としては、分子内に少なくともイミド結合を有する樹脂であって、摺動部材の使用時に熱劣化することなく、板状の裏金の表面との接着性に優れた樹脂が使用出来る。具体的には、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエステルイミド樹脂、ポリエステルアミドイミド樹脂などが挙げられる。これらポリイミド系樹脂の中で、ポリイミド樹脂(以下、「PI」と略称することがある)及びポリアミドイミド樹脂(以下、「PAI」と略称することがある)が好適である。   As the polyimide-based resin, a resin having at least an imide bond in the molecule and having excellent adhesion to the surface of the plate-shaped backing metal can be used without causing thermal degradation when the sliding member is used. Specific examples include polyimide resins, polyamideimide resins, polyesterimide resins, and polyesteramideimide resins. Among these polyimide resins, a polyimide resin (hereinafter sometimes abbreviated as “PI”) and a polyamideimide resin (hereinafter sometimes abbreviated as “PAI”) are preferable.

ポリイミド樹脂は、例えば、N−メチル−2−ピロリドン(NMP)、ジメチルアセトアミド(DMAC)等の非プロトン系極性溶媒中で酸二無水物とジアミンとの開環重付加反応により得られるポリイミド前駆体のポリアミドカルボン酸を加熱脱水閉環することにより得られる樹脂であって、その樹脂成分がポリアミドカルボン酸の状態、ポリイミドの状態またはそれらが混在している状態で存在する樹脂である。   The polyimide resin is, for example, a polyimide precursor obtained by a ring-opening polyaddition reaction between an acid dianhydride and a diamine in an aprotic polar solvent such as N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC). It is a resin obtained by heat-dehydrating and ring-closing the polyamide carboxylic acid, and the resin component is a resin existing in a polyamide carboxylic acid state, a polyimide state or a mixture thereof.

ポリアミドイミド樹脂は、例えば、無水トリメリット酸と芳香族ジアミンとの反応によって得られる樹脂であって、分子内にイミド結合とアミド結合とを有する樹脂である。   Polyamideimide resin is a resin obtained by reaction of trimellitic anhydride and aromatic diamine, for example, and is a resin having an imide bond and an amide bond in the molecule.

フラーレンとしては、C60フラーレン、C70フラーレン、高次フラーレン及びそれらの混合物が挙げられる。 Fullerenes include C 60 fullerene, C 70 fullerene, higher order fullerene and mixtures thereof.

フラーレンは、グラファイトや炭化水素を原料とし、レーザー気化法、アーク放電法、燃焼法などによって製造される炭素6員環および5員環から構成される球殻状の炭素クラスターである。通常、60個の炭素原子からなるサッカーボール状のC60フラーレン、70個の炭素原子からなるラグビーボール状のC70フラーレン及びさらに多くの炭素原子からなる高次フラーレンの混合物として得られ、この混合物を精製することにより、C60フラーレン及びC70フラーレンが単離される。 Fullerene is a spherical shell-like carbon cluster composed of carbon 6-membered ring and 5-membered ring produced from graphite or hydrocarbon as a raw material by laser vaporization method, arc discharge method, combustion method or the like. Usually, it is obtained as a mixture of a soccer ball-like C60 fullerene consisting of 60 carbon atoms, a rugby ball-like C70 fullerene consisting of 70 carbon atoms, and a higher order fullerene consisting of more carbon atoms. by purifying, C 60 fullerene, and C 70 fullerenes are isolated.

フラーレンは、その球殻状分子構造により潤滑性を発揮し、且つ、その結晶構造が約1500℃まで壊れないことから、300℃以上の高温使用条件下で優れた潤滑特性を発揮する。特に、C60フラーレン及びC70フラーレンは、その直径が小さく、例えば、約0.7nmであるため、樹脂に対する均一分散性に優れている。 Fullerene exhibits lubricity due to its spherical shell molecular structure, and its crystal structure does not break up to about 1500 ° C., and therefore exhibits excellent lubrication characteristics under high temperature use conditions of 300 ° C. or higher. In particular, since C 60 fullerene and C 70 fullerene have small diameters, for example, about 0.7 nm, they are excellent in uniform dispersibility with respect to the resin.

すべり層中のフラーレンの量は、通常0.1〜1重量%、好ましくは0.3〜0.7重量%である。フラーレンの量が0.1重量%未満の場合は、フラーレンの潤滑性が発揮されないことがある。また、フラーレンの量が1重量%を超える場合は、すべり層の低摩擦性が劣化することがある。   The amount of fullerene in the sliding layer is usually 0.1 to 1% by weight, preferably 0.3 to 0.7% by weight. When the amount of fullerene is less than 0.1% by weight, the lubricity of fullerene may not be exhibited. When the amount of fullerene exceeds 1% by weight, the low friction property of the sliding layer may be deteriorated.

60フラーレンとC70フラーレンとを併用する場合、C60フラーレン100重量部に対するC70フラーレンの配合量は、通常5〜100重量部、好ましくは7〜90重量部、さらに好ましくは10〜70重量部である。C60フラーレンとC70フラーレンとを上記の配合割合で使用すると、樹脂におけるC60フラーレン及びC70フラーレンの分散安定性が向上する。 When C 60 fullerene and C 70 fullerene are used in combination, the blending amount of C 70 fullerene with respect to 100 parts by weight of C 60 fullerene is usually 5 to 100 parts by weight, preferably 7 to 90 parts by weight, more preferably 10 to 70 parts by weight. Part. When a C 60 fullerene and C 70 fullerene used in the blend ratio of the above, improved dispersion stability of C 60 fullerene and C 70 fullerene in resin.

次に、本発明の複層摺動部材の製造方法の一例について説明する。   Next, an example of the manufacturing method of the multilayer sliding member of this invention is demonstrated.

複層摺動部材のすべり層は、金属製の板状の裏金の表面に上述の摺動部材組成物を公知の方法で被着することにより得られる。被着の方法としては、電着塗装法、ディッピング法(浸漬塗装法)、スプレーコート法(霧化塗装法)、刷毛塗り法、ロールコーター法などが挙げられる。   The sliding layer of the multi-layer sliding member can be obtained by depositing the above-mentioned sliding member composition on the surface of a metal plate-like backing metal by a known method. Examples of the deposition method include an electrodeposition coating method, a dipping method (dip coating method), a spray coating method (atomization coating method), a brush coating method, and a roll coater method.

電着塗装法としては、例えば、ポリイミド系樹脂とフラーレンとから成る摺動部材組成物を含有する電着塗装溶液にイオン交換水を1:1の割合(重量比)で添加して希釈し、得られた溶液を電着塗装槽に導入し、陰極側に板状の裏金を貼付してカチオン電着塗装を行い、裏金の表面に摺動部材組成物を成膜する。成膜後、乾燥し、次いで、加熱処理して板状の裏金の表面にすべり層を一体に被着形成する方法が例示される。   As an electrodeposition coating method, for example, ion-exchanged water is added at a ratio (weight ratio) of 1: 1 to an electrodeposition coating solution containing a sliding member composition composed of a polyimide resin and fullerene, and diluted. The obtained solution is introduced into an electrodeposition coating tank, a plate-like backing metal is attached to the cathode side, and cationic electrodeposition coating is performed, and a sliding member composition is formed on the surface of the backing metal. An example is a method in which after the film formation, the film is dried and then subjected to heat treatment to integrally form a slipping layer on the surface of the plate-like backing metal.

ディッピング法、スプレーコーティング法、刷毛塗り法およびロールコーター法としては、例えば、ポリイミド系樹脂とフラーレンとから成る摺動部材組成物を溶剤に分散し、得られた分散液を板状の裏金の表面にディッピング法、スプレーコート法、刷毛塗り法またはロールコーター法で塗布・被覆し、得られた被覆層を乾燥した後、加熱処理する方法が例示される。   As the dipping method, spray coating method, brush coating method and roll coater method, for example, a sliding member composition comprising a polyimide resin and fullerene is dispersed in a solvent, and the resulting dispersion is applied to the surface of a plate-like backing metal. Examples thereof include a method of coating and coating by the dipping method, spray coating method, brush coating method or roll coater method, and drying the resulting coating layer, followed by heat treatment.

板状の裏金の表面に形成された層の乾燥は、通常50℃〜100℃の範囲に加熱された乾燥炉内に通常10〜120分間に保持させて行う。乾燥処理により、形成された層の発泡などを抑制することが出来る。   Drying of the layer formed on the surface of the plate-shaped backing metal is usually carried out for 10 to 120 minutes in a drying furnace heated to a range of 50 ° C to 100 ° C. By the drying treatment, foaming of the formed layer can be suppressed.

ポリイミド樹脂の場合、加熱処理温度は、通常200〜350℃、好ましくは210〜300℃で、加熱処理時間は、通常20〜120分間である。加熱処理温度が200℃未満の場合は、ポリイミド樹脂の硬化反応が進行せず、形成された層の裏金の表面に対する密着性が劣ることがある。また、形成された層の裏金の表面に対する密着性は、350℃付近で平衡となるので、昇温に要するエネルギー消費量を考慮すると350℃以下で加熱処理することが好適である。   In the case of a polyimide resin, the heat treatment temperature is usually 200 to 350 ° C., preferably 210 to 300 ° C., and the heat treatment time is usually 20 to 120 minutes. When the heat treatment temperature is less than 200 ° C., the curing reaction of the polyimide resin does not proceed, and the adhesion of the formed layer to the back metal surface may be inferior. Further, since the adhesion of the formed layer to the surface of the back metal is balanced at around 350 ° C., it is preferable to perform the heat treatment at 350 ° C. or lower in consideration of the energy consumption required for raising the temperature.

また、ポリアミドイミド樹脂の場合、加熱処理温度は、通常170〜280℃、好ましくは180〜260℃で、加熱処理時間は、通常20〜120分間である。加熱処理温度が170℃未満の場合は、ポリアミドイミド樹脂の硬化反応が進行せず、形成された層の裏金の表面に対する密着性が劣ることがある。また、形成された層の裏金の表面に対する密着性は、280℃付近で平衡となるので、昇温に要するエネルギー消費量を考慮すると280℃以下で加熱処理することが好適である。   In the case of polyamideimide resin, the heat treatment temperature is usually 170 to 280 ° C, preferably 180 to 260 ° C, and the heat treatment time is usually 20 to 120 minutes. When the heat treatment temperature is less than 170 ° C., the curing reaction of the polyamideimide resin does not proceed, and the adhesion of the formed layer to the back metal surface may be inferior. In addition, since the adhesion of the formed layer to the back metal surface is in the vicinity of 280 ° C., it is preferable to perform the heat treatment at 280 ° C. or lower in consideration of the energy consumption required for temperature increase.

加熱処理した後、常温まで冷却する。冷却の方法としては、例えば、通常60〜180分程度の時間をかけて徐冷する方法が挙げられる。徐冷することにより、すべり層と裏金の表面とが互いに均一に精度よく収縮し、精度の高い複層摺動部材を得ることが出来る。   After heat treatment, cool to room temperature. As a cooling method, for example, a method of slowly cooling usually over about 60 to 180 minutes can be mentioned. By slowly cooling, the sliding layer and the surface of the back metal contract with each other uniformly and accurately, and a highly accurate multilayer sliding member can be obtained.

使用する溶剤としては、アセトン、メチルエチルケトン等のケトン類、酢酸メチル、酢酸エチル等のエステル類、トルエン、キシレン等の芳香族炭化水素類、メチルクロロホルム、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化合物類、N−メチル−2−ピロリドン(NMP)、メチルイソピロリドン(MIP)、ジメチルホルムアミド(DMF)、ジメチルアセトアミド(DMAC)等の非プロトン系極性溶剤類などが挙げられる。これらの溶剤類は、単独または混合物として使用する。   Solvents used include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, and organic halogenated compounds such as methyl chloroform, trichloroethylene, and trichlorotrifluoroethane. And aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP), methylisopyrrolidone (MIP), dimethylformamide (DMF), and dimethylacetamide (DMAC). These solvents are used alone or as a mixture.

電着塗装法おける希釈液中のポリイミド系樹脂とフラーレンの固形分濃度は、摺動部材組成物溶液中のポリイミド系樹脂とフラーレンの固形分濃度として、通常5〜25重量%、好ましくは5〜15重量%である。   The solid content concentration of the polyimide resin and fullerene in the diluent in the electrodeposition coating method is usually 5 to 25% by weight, preferably 5 to 5% as the solid content concentration of the polyimide resin and fullerene in the sliding member composition solution. 15% by weight.

ディッピング法、スプレーコーティング法、刷毛塗り法およびロールコーター法における分散液中のポリイミド系樹脂とフラーレンの固形分濃度は、溶剤100重量部に対して通常5〜100重量部(摺動部材組成物溶液中のポリイミド系樹脂とフラーレンの固形分濃度として、通常4.8〜50重量%)、好ましくは25〜50重量部(摺動部材組成物溶液中のポリイミド系樹脂とフラーレンの固形分濃度として、好ましくは20〜33重量%)である。   The solid content concentration of the polyimide resin and fullerene in the dispersion in the dipping method, spray coating method, brush coating method and roll coater method is usually 5 to 100 parts by weight (sliding member composition solution) with respect to 100 parts by weight of the solvent. The solid content concentration of the polyimide resin and fullerene in the resin is usually 4.8 to 50% by weight), preferably 25 to 50 parts by weight (as the solid content concentration of the polyimide resin and fullerene in the sliding member composition solution, Preferably, it is 20 to 33% by weight.

電着塗装法により形成された被覆層は、加熱処理後のすべり層の厚さが通常5〜100μm、好ましくは10〜70μmとなる様に形成される。すべり層の厚さが5μm未満の場合は、すべり層に片当たり等が生じることがあり、その結果、局部的な摩耗が発生する虞がある。また、すべり層の厚さが100μmを超える場合は、すべり層の剥離が発生することがある。   The coating layer formed by the electrodeposition coating method is formed so that the thickness of the sliding layer after the heat treatment is usually 5 to 100 μm, preferably 10 to 70 μm. When the thickness of the sliding layer is less than 5 μm, the sliding layer may be partly contacted, and as a result, local wear may occur. Moreover, when the thickness of the slip layer exceeds 100 μm, the slip layer may be peeled off.

ディッピング法、スプレーコーティング法、刷毛塗り法またはロールコーター法の方法により塗布された被覆層は、加熱処理後のすべり層の厚さが通常10〜150μm、好ましくは20〜100μmとなる様に形成される。すべり層の厚さが10μm未満の場合は、すべり層に片当たり等が生じることがあり、その結果、局部的な摩耗が発生する虞がある。また、すべり層の厚さが150μmを超える場合は、すべり層の剥離が発生することがある。   The coating layer applied by the dipping method, spray coating method, brush coating method or roll coater method is formed so that the thickness of the sliding layer after heat treatment is usually 10 to 150 μm, preferably 20 to 100 μm. The When the thickness of the slip layer is less than 10 μm, the slip layer may come into contact with each other, and as a result, local wear may occur. Further, when the thickness of the slip layer exceeds 150 μm, the slip layer may be peeled off.

スプレーコート法による塗装被覆方法では、塗布液が微小な粒子体となって裏金の表面に付着されるため、被覆層の厚みを精度よく形成することが出来る。   In the coating and coating method by the spray coating method, the coating liquid is formed as fine particles and adhered to the surface of the back metal, so that the thickness of the coating layer can be formed with high accuracy.

以下、実施例により本発明を詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded.

実施例1:
板状の裏金として、一辺が30mm、厚さが3.2mmの冷間圧延鋼板(SPCC)を準備した。ポリイミド系樹脂としてPI電着塗装溶液(シミズ社製)を使用し、C60フラーレン、C70フラーレン、高次フラーレン混合物(フロンティアカーボン社製「ナノムミックス(商品名))をすべり層のフラーレン量が0.5重量%となる様に配合したイオン交換水と前記PI電着塗装溶液とを1対1(重量比)の割合で混合・希釈し、得られた希釈液(固形分濃度:5重量%)を電着塗装槽としてのビーカーに投入した。電極にカーボンを使用し、その陰極側に冷間圧延鋼板を貼付して、電圧60V、成膜時間5.5分間、電極間距離30mmの条件でカチオン型電着塗装を行い、フラーレン0.5重量%含有したポリイミド樹脂組成物を冷間圧延鋼板の表面に成膜した。電着塗装後、乾燥炉にて100℃の温度で10分間乾燥し、次いで、210℃の温度で30分間加熱処理して該冷間圧延鋼板の表面に厚さ65μmのすべり層を形成し、複層摺動部材を作製した。
Example 1:
A cold rolled steel plate (SPCC) having a side of 30 mm and a thickness of 3.2 mm was prepared as a plate-shaped backing metal. PI electrodeposition coating solution (manufactured by Shimizu Co., Ltd.) is used as the polyimide resin, and C 60 fullerene, C 70 fullerene, and higher fullerene mixture (“Nanomumix (trade name) manufactured by Frontier Carbon Co., Ltd.) are included in the sliding layer. Mixing and diluting the ion-exchanged water and the PI electrodeposition coating solution blended so as to be 0.5% by weight in a ratio of 1: 1 (weight ratio), the resulting diluted solution (solid content concentration: 5% by weight) %) Was put into a beaker as an electrodeposition coating tank, carbon was used for the electrode, a cold rolled steel sheet was attached to the cathode side, the voltage was 60 V, the film formation time was 5.5 minutes, and the distance between the electrodes was 30 mm. Cation type electrodeposition coating was performed under the conditions, and a polyimide resin composition containing 0.5% by weight of fullerene was formed on the surface of the cold-rolled steel sheet.After electrodeposition coating, 10 minutes at a temperature of 100 ° C. in a drying furnace. Dried and next In, and heated at a temperature of 210 ° C. 30 minutes to form a sliding layer having a thickness of 65μm on the surface of the rolled steel plate between cold, to prepare a multi-layer slide member.

実施例2〜3:
板状の裏金として、一辺が30mm、厚さが3.2mmの冷間圧延鋼板(SPCC)を準備した。ポリイミド系樹脂としてポリアミドイミド樹脂(トーロン社製、「トーロンAI−10」(商品名))を使用し、このポリアミドイミド樹脂をN−メチル−2−ピロリドン(NMP)に溶解し、得られた樹脂溶液にC60フラーレン、C70フラーレン、高次フラーレン混合物(フロンティアカーボン社製「ナノムミックス(商品名))をすべり層のフラーレン量が0.5重量%(実施例2)、1重量%(実施例3)となる様に配合して均一な組成物を得、ポリアミドイミド樹脂とフラーレンの固形分濃度が約25重量%となる様に、N−メチル−2−ピロリドン(NMP)、ジメチルホルムアミド(DMF)、キシレン及び酢酸エチルの混合溶媒を加えて希釈し、被覆溶液(固形分濃度(実施例2):25重量%および固形分濃度(実施例3):25重量%)を得た。この被覆溶液を冷間圧延鋼板の表面にスプレーコート法で吹き付け、被覆層を被着形成した。この被覆層を乾燥炉内で80℃で15分間乾燥させ、次いで、240℃の温度で30分間加熱処理して該冷間圧延鋼板の表面に厚さ50μmのすべり層を形成し、複層摺動部材を作製した。
Examples 2-3:
A cold rolled steel plate (SPCC) having a side of 30 mm and a thickness of 3.2 mm was prepared as a plate-shaped backing metal. Polyamideimide resin (“Torlon AI-10” (trade name) manufactured by Torlon Co., Ltd.) is used as the polyimide resin, and this polyamideimide resin is dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a resin. C 60 fullerene, C 70 fullerene, high-order fullerene mixture (“Nanomumix (trade name) manufactured by Frontier Carbon Co., Ltd.)” was added to the solution. Example 3) is mixed to obtain a uniform composition, and N-methyl-2-pyrrolidone (NMP), dimethylformamide (NMP) so that the solid content concentration of the polyamideimide resin and fullerene is about 25% by weight. DMF), xylene and ethyl acetate mixed solvent to dilute, coating solution (solid content concentration (Example 2): 25 wt% and solid content concentration (implementation) 3): 25 wt%) This coating solution was sprayed onto the surface of the cold-rolled steel sheet by spray coating to form a coating layer, which was dried in a drying oven at 80 ° C. for 15 minutes. Then, heat treatment was performed at a temperature of 240 ° C. for 30 minutes to form a 50 μm-thick slip layer on the surface of the cold-rolled steel sheet, and a multilayer sliding member was produced.

比較例1:
実施例1において、PI単体の電着塗装溶液(シミズ社製)にイオン交換水を1対1(重量比)の割合で添加した液(固形分濃度:5重量%)でカチオン型電着塗装を行うことを除いて、実施例1と同様の方法により、厚さ39μmのすべり層を有する複層摺動部材を作製した。
Comparative Example 1:
In Example 1, a cation-type electrodeposition coating with a solution (solid content concentration: 5% by weight) in which ion-exchanged water is added in a ratio of 1: 1 (weight ratio) to an electrodeposition coating solution of PI alone (manufactured by Shimizu). A multilayer sliding member having a sliding layer with a thickness of 39 μm was produced in the same manner as in Example 1 except that

比較例2:
実施例1において、PI単体の電着塗装溶液(シミズ社製)に粒径5μmの黒鉛をすべり層の黒鉛量が0.5重量となる様に配合したイオン交換水を1対1(重量比)の割合で添加した液(固形分濃度:5重量%)でカチオン型電着塗装を行うことを除いて、実施例1と同様の方法により、厚さ33μmの黒鉛0.5重量%含有したすべり層を有する複層摺動部材を作製した。
Comparative Example 2:
In Example 1, ion-exchanged water prepared by blending graphite with a particle size of 5 μm into an electrodeposition coating solution of PI alone (manufactured by Shimizu Co., Ltd.) so that the amount of graphite in the sliding layer is 0.5 wt. ) In the same manner as in Example 1 except that the cationic electrodeposition coating is performed with the liquid added at a ratio of (solid content concentration: 5% by weight), and 0.5% by weight of graphite having a thickness of 33 μm is contained. A multilayer sliding member having a sliding layer was produced.

次に、上記実施例1〜3で得た複層摺動部材と比較例1及び2で得た複層摺動部材の摩擦摩耗特性を表1に示す試験条件の往復動摩擦摩耗試験方法により評価した。   Next, the frictional wear characteristics of the multilayer sliding members obtained in Examples 1 to 3 and the multilayer sliding members obtained in Comparative Examples 1 and 2 were evaluated by the reciprocating frictional wear test method under the test conditions shown in Table 1. did.

Figure 2007145894
Figure 2007145894

<試験方法>
図1に示す試験装置により、上側試験片1としてSUS440Cの直径3mmの鋼球を使用し、下側試験片2として該鋼板21の表面に各すべり層22を一体に被着形成した複層摺動部材を使用し、複層摺動部材のすべり層22を上向きにして可動テーブル3に固定した。鋼球に荷重Pを負荷して該鋼球を複層摺動部材のすべり層22に押し付け、その状態で可動テーブル3をX、Y方向に往復運動させる。上側試験片(鋼球)1に変位センサー(図示せず)を取付け、往復摺動によりすべり層22に摩耗が発生すると上側試験片(鋼球)1が下方に変位し、その変位量が出力される。この上側試験片1の変位量を摩耗量とした。また、摩擦力測定用のロードセル(図示せず)を取付け、摩擦力を計測して、その値から摩擦係数を算出した。
<Test method>
With the test apparatus shown in FIG. 1, a multi-layer slide in which a SUS440C steel ball having a diameter of 3 mm is used as the upper test piece 1 and each slide layer 22 is integrally formed on the surface of the steel plate 21 as the lower test piece 2. The moving member was used and fixed to the movable table 3 with the sliding layer 22 of the multilayer sliding member facing upward. A load P is applied to the steel ball, the steel ball is pressed against the sliding layer 22 of the multilayer sliding member, and in this state, the movable table 3 is reciprocated in the X and Y directions. When a displacement sensor (not shown) is attached to the upper test piece (steel ball) 1 and wear occurs in the sliding layer 22 by reciprocating sliding, the upper test piece (steel ball) 1 is displaced downward, and the amount of displacement is output. Is done. The amount of displacement of the upper test piece 1 was defined as the amount of wear. In addition, a load cell (not shown) for measuring the frictional force was attached, the frictional force was measured, and the friction coefficient was calculated from the value.

実施例1〜3で得た複層摺動部材と比較例1及び2で得た複層摺動部材の各すべり層の成分組成と上記往復動摩擦摩耗試験により得た摩擦摩耗特性の結果を表2示す。   Table 2 shows the component composition of each sliding layer of the multilayer sliding member obtained in Examples 1 to 3 and the multilayer sliding member obtained in Comparative Examples 1 and 2 and the results of the frictional wear characteristics obtained by the reciprocating frictional wear test. 2 is shown.

Figure 2007145894
Figure 2007145894

上記した試験結果から、本発明の実施例の複層摺動部材は、試験時間中を通して低い摩擦係数で安定した摺動性能を発揮し、摩耗量も極めて低い値を示した。一方、比較例の複層摺動部材は、摩擦係数が高く、摩耗量も多く、摩擦摩耗特性に劣るものであった。従って、本発明の複層摺動部材は、優れた摩擦摩耗特性を発揮するものである。   From the test results described above, the multilayer sliding member of the example of the present invention exhibited stable sliding performance with a low coefficient of friction throughout the test time, and the wear amount was extremely low. On the other hand, the multilayer sliding member of the comparative example had a high friction coefficient, a large amount of wear, and was inferior in friction and wear characteristics. Therefore, the multilayer sliding member of the present invention exhibits excellent frictional wear characteristics.

本発明で使用した試験装置の説明図である。It is explanatory drawing of the test apparatus used by this invention.

符号の説明Explanation of symbols

1:上側試験片(鋼球)
2:下側試験片(複層摺動部材)
3:可動テーブル
1: Upper specimen (steel ball)
2: Lower test piece (multi-layer sliding member)
3: Movable table

Claims (4)

金属製の板状の裏金とすべり層とを一体化して成る複層摺動部材において、前記すべり層がポリイミド系樹脂とフラーレンとから成ることを特徴とする複層摺動部材。   A multilayer sliding member formed by integrating a metal plate-like backing metal and a sliding layer, wherein the sliding layer is composed of a polyimide resin and fullerene. すべり層中のフラーレン量が0.1〜1重量%である請求項1に記載の複層摺動部材。   The multilayer sliding member according to claim 1, wherein the amount of fullerene in the sliding layer is 0.1 to 1% by weight. フラーレンがC60フラーレン、C70フラーレン、高次フラーレン又はその混合物である請求項1又は2に記載の複層摺動部材。 Fullerene C 60 fullerene, C 70 fullerene, multilayer sliding member according to claim 1 or 2 is higher fullerenes or mixtures thereof. ポリイミド系樹脂がポリイミド樹脂、ポリアミドイミド樹脂又はその混合物である請求項1〜3の何れかに記載の複層摺動部材。   The multilayer sliding member according to claim 1, wherein the polyimide resin is a polyimide resin, a polyamideimide resin, or a mixture thereof.
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