JP2006016561A - Polyamideimide resin composition for sliding member and sliding member using the same - Google Patents
Polyamideimide resin composition for sliding member and sliding member using the same Download PDFInfo
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本発明は摺動部材用ポリアミドイミド樹脂組成物及びそれを用いた摺動部材に関する。本発明は、優れた低摩擦係数、耐摩耗性、耐焼き付け性を付与しその効果が長期間持続するという効果を奏するものである。 The present invention relates to a polyamideimide resin composition for a sliding member and a sliding member using the same. The present invention provides an excellent low friction coefficient, wear resistance, and seizure resistance, and the effect is sustained for a long time.
従来、エポキシ樹脂やフッ素樹脂、ポリアミドイミド樹脂に固体潤滑剤を配合した組成物をコーティングした摺動部材は知られており、例えば特許文献１には固体潤滑剤を含むフッ素樹脂をコーティングしたピストンスカートが開示されている。また、特許文献２にはポリアミドイミド又はポリイミド樹脂と固体潤滑剤を含有する潤滑被覆用組成物が開示されている。このように摺動部材の表面に潤滑被膜をコーティングすることで摺動部のなじみやスカッフィングを防止し、摩擦係数を低減している。 Conventionally, a sliding member obtained by coating a composition in which a solid lubricant is blended with an epoxy resin, a fluororesin, or a polyamideimide resin is known. For example, Patent Document 1 discloses a piston skirt coated with a fluororesin containing a solid lubricant. Is disclosed. Patent Document 2 discloses a lubricating coating composition containing a polyamideimide or polyimide resin and a solid lubricant. Thus, the lubrication film is coated on the surface of the sliding member to prevent the familiarity and scuffing of the sliding portion and reduce the friction coefficient.
摩擦係数の低減には固体潤滑剤の比率を増やすことが有効であるが固体潤滑剤が多い為に被膜自体が軟らかくなり過ぎて被膜の摩耗が多くなる問題が生じる。この問題を解決するために特許文献３では摩擦係数低減と耐摩耗性両立のためバインダーにも潤滑性を有するシリコーン変成ポリアミドイミド樹脂をバインダーにした摺動部材用樹脂組成物も開示されている。また、特許文献４にはｏ−トリジン構造を含有することで耐磨耗性、摩擦特性、耐焼き付け性を付与した摺動部材用ポリアミドイミド樹脂組成物が開示されている。しかし、近年の自動車用摺動部材において、低燃費化を図る観点から潤滑膜の摩擦係数の低減、耐摩耗性の向上、及びこれら効果の長期持続性の要求を十分に満足するとはいえない。 Increasing the ratio of the solid lubricant is effective for reducing the friction coefficient. However, since there are many solid lubricants, the coating itself becomes too soft, and there is a problem that the wear of the coating increases. In order to solve this problem, Patent Document 3 discloses a resin composition for a sliding member in which a binder is a silicone-modified polyamideimide resin having lubricity in order to reduce friction coefficient and wear resistance. Patent Document 4 discloses a polyamide-imide resin composition for a sliding member which has an o-tolidine structure and is given wear resistance, friction characteristics, and seizure resistance. However, in recent automobile sliding members, from the viewpoint of reducing fuel consumption, it cannot be said that the requirements for reduction of the friction coefficient of the lubricating film, improvement of wear resistance, and long-term sustainability of these effects are sufficiently satisfied.
本発明の課題は、低摩擦係数、耐摩耗性、耐焼き付け性を付与しその効果が長期間持続するような摺動部材用組成物及びこれを用いた摺動部材を提供することにある。 An object of the present invention is to provide a composition for a sliding member that imparts a low coefficient of friction, wear resistance, and seizure resistance, and the effect lasts for a long period of time, and a sliding member using the same.
本発明は上記目的を達成するために、鋭意検討を重ねた結果、本発明に到達した。即ち本発明は、以下の摺動部材用ポリアミドイミド樹脂組成物及びそれを用いた摺動部材である。 The present invention has reached the present invention as a result of intensive studies to achieve the above object. That is, this invention is the following polyamideimide resin compositions for sliding members, and a sliding member using the same.
（１）式１及び／又は式２で示される化合物を共重合したポリアミドイミド樹脂に固体潤滑剤を含有されてなることを特徴とする摺動部材用ポリアミドイミド樹脂組成物。
（２）式１及び／又は式２で表される化合物の共重合量がポリアミドイミド樹脂１００重量％のうち、０．１重量％以上３０重量％以下であることを特徴とする（１）に記載の摺動部材用ポリアミドイミド樹脂組成物。 (2) The amount of copolymerization of the compound represented by Formula 1 and / or Formula 2 is 0.1 wt% or more and 30 wt% or less in 100 wt% of the polyamideimide resin. The polyamideimide resin composition for sliding members as described.
（３）式１及び／又は式２で表される化合物の分子量が１０００以上１３０００以下であることを特徴とする（１）または（２）に記載の摺動部材用ポリアミドイミド樹脂組成物。 (3) The polyamideimide resin composition for a sliding member according to (1) or (2), wherein the molecular weight of the compound represented by Formula 1 and / or Formula 2 is 1000 or more and 13000 or less.
（４）ポリアミドイミド樹脂の対数粘度が０．３ｄｌ／ｇ以上２．０ｄｌ／ｇ以下であり、ガラス転移温度が２００℃以上４００℃以下であることを特徴とする（１）〜（３）のいずれかに記載の摺動部材用ポリアミドイミド樹脂組成物。 (4) The logarithmic viscosity of the polyamideimide resin is 0.3 dl / g or more and 2.0 dl / g or less, and the glass transition temperature is 200 ° C. or more and 400 ° C. or less. (1) to (3) The polyamideimide resin composition for sliding members according to any one of the above.
（５）固体潤滑剤が金属硫化物、フッ素化合物、及びグラファイトから選ばれる少なくとも１種以上であり、且つポリアミドイミド１００重量部に対し５重量部以上５００重量部以下含むことを特徴とする（１）〜（４）のいずれかに記載の摺動部材用ポリアミドイミド樹脂組成物。 (5) The solid lubricant is at least one selected from metal sulfides, fluorine compounds, and graphite, and includes 5 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of polyamideimide (1 The polyamideimide resin composition for sliding members according to any one of (1) to (4).
（６）固体潤滑剤が二硫化モリブデン及び／又は二硫化タングステンであり、且つポリアミドイミド１００重量部に対し５重量部以上５００重量部以下含むことを特徴とする（１）〜（４）のいずれかに記載の摺動部材用ポリアミドイミド樹脂組成物。 (6) Any of (1) to (4), wherein the solid lubricant is molybdenum disulfide and / or tungsten disulfide and contains 5 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of polyamideimide. The polyamideimide resin composition for sliding members according to claim 1.
（７）フッ素化合物がポリテロラフルオロエチレン、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トリクロロトリフルオロエチレンの群から選ばれる少なくとも１種以上であることを特徴とする（５）に記載の摺動部材用ポリアミドイミド樹脂組成物。 (7) The fluorine compound is polyterolafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and trichlorotri The polyamideimide resin composition for sliding members according to (5), which is at least one selected from the group of fluoroethylene.
（８）ポリアミドイミド樹脂１００重量部に対して、さらに粒子径が０．１μｍ〜１０μｍの窒化珪素、アルミナ、炭化珪素、窒化ホウ素、ダイヤモンド、およびシリカからなる群から選ばれる少なくとも１種以上を、５〜２００重量部含有することを特徴とする（１）〜（７）のいずれかに記載の摺動部材用ポリアミドミド樹脂組成物。 (8) With respect to 100 parts by weight of the polyamideimide resin, at least one selected from the group consisting of silicon nitride, alumina, silicon carbide, boron nitride, diamond, and silica having a particle size of 0.1 μm to 10 μm, The polyamideimide resin composition for sliding members according to any one of (1) to (7), which is contained in an amount of 5 to 200 parts by weight.
（９）ポリアミドイミド樹脂１００重量部に対して、さらに多官能のエポキシ化合物、イソシアネート化合物及びメラミン化合物の群から選ばれる少なくとも１種以上を１〜３０重量部含有することを特徴とする（１）〜（８）のいずれかに記載の摺動部材用ポリアミドイミド樹脂組成物。 (9) 1 to 30 parts by weight of at least one selected from the group of polyfunctional epoxy compounds, isocyanate compounds and melamine compounds is further contained with respect to 100 parts by weight of the polyamideimide resin (1) The polyamideimide resin composition for sliding members according to any one of to (8).
（１０）（１）〜（９）のいずれかに記載のポリアミドイミド樹脂組成物を用いた摺動部材。 (10) A sliding member using the polyamideimide resin composition according to any one of (1) to (9).
本発明の摺動部材用ポリアミドイミド樹脂組成物を塗布した摺動部材は摩擦係数の低減、耐摩耗性に優れ、且つ十分な耐久性を有するため家電製品や自動車エンジンのピストンスカート等に有用である。 The sliding member coated with the polyamideimide resin composition for sliding member of the present invention is useful for home appliances and piston skirts of automobile engines because it has a reduced coefficient of friction, excellent wear resistance, and sufficient durability. is there.
以下本発明を詳細に説明する。本発明に用いるポリアミドイミド樹脂は式１及び／又は式２で示される化合物を共重合することを特徴とする。
ここで特許文献３には式３の化合物を変性又は共重合することが開示されている。
式３の化合物は側鎖に長鎖のポリエステルを有しておりポリアミドイミド樹脂と混ざりやすく樹脂単体のフイルムは透明である。このため潤滑性を有する式３の成分が樹脂表面に現れにくく更に摩擦係数を低下させることは困難であった。これに対し式１及び式２の化合物はポリアミドイミド樹脂と混ざりにくく、樹脂単体のフイルムは不透明になる。その結果潤滑性を有する式１及び式２の成分が樹脂表面に現れやすく更に摩擦係数を低下させることが可能である。この式１または式２の化合物をポリアミドイミド樹脂に共重合するとき、２種の併用、単独のどちらで使用しても良い。共重合量はポリアミドイミド樹脂１００重量％中、０．１重量％以上３０重量％以下であるが、好ましくは０．５重量％以上２０重量％以下、更に好ましくは１重量％以上１０重量％以下である。３０重量％を超えると耐摩耗性が悪くなる問題が生じ、０．１重量％未満の場合摩擦係数が高くなる問題が生じるおそれがある。また、式１及び式２の分子量は１０００以上１３０００以下が望ましく、好ましくは２０００以上１００００以下が、更に好ましくは３０００以上８０００以下である。分子量１０００未満ではポリアミドイミドに共重合しても相分離しないため摩擦係数が低下しないことがある。また、１３０００を超えるとポリアミドイミドに共重合することが困難になる場合がある。
Here, Patent Document 3 discloses that a compound of Formula 3 is modified or copolymerized.
The compound of Formula 3 has a long-chain polyester in the side chain, and is easily mixed with the polyamide-imide resin, and the film of the resin itself is transparent. For this reason, it is difficult for the component of Formula 3 having lubricity to appear on the resin surface and to further reduce the friction coefficient. On the other hand, the compound of Formula 1 and Formula 2 is difficult to mix with the polyamide-imide resin, and the film of the resin alone becomes opaque. As a result, the components of Formula 1 and Formula 2 having lubricity are likely to appear on the resin surface, and the friction coefficient can be further reduced. When the compound of Formula 1 or Formula 2 is copolymerized with a polyamideimide resin, it may be used either in combination of two or alone. The amount of copolymerization is from 0.1% by weight to 30% by weight in 100% by weight of the polyamideimide resin, preferably from 0.5% by weight to 20% by weight, more preferably from 1% by weight to 10% by weight. It is. If it exceeds 30% by weight, there is a problem that the wear resistance is deteriorated, and if it is less than 0.1% by weight, there is a possibility that the coefficient of friction becomes high. Moreover, the molecular weight of Formula 1 and Formula 2 is desirably 1000 or more and 13000 or less, preferably 2000 or more and 10,000 or less, and more preferably 3000 or more and 8000 or less. If the molecular weight is less than 1,000, the friction coefficient may not decrease because phase separation does not occur even when copolymerized with polyamideimide. Moreover, when it exceeds 13000, it may become difficult to copolymerize with polyamideimide.
式１の具体例としては信越化学社製のＸ−２２−１６１Ａ、Ｘ−２２−１６１Ｂ、ＫＦ−８０１２、ＫＦ−８００８等の両末端ジアミンタイプ、Ｘ−２２−１６３Ａ、Ｘ−２２−１６３Ｂ、Ｘ−２２−１６３Ｃ等の両末端エポキシタイプ、Ｘ−２２−１６２Ｃ、Ｘ−２２−３７０１Ｅ、Ｘ−２２−３７１０等の両末端カルボキシル基タイプ、ＫＦ−６００１、ＫＦ−６００２、ＫＦ−６００３等の両末端水酸基タイプが挙げられる。また式２の具体例としてはＸ−２２−１７６Ｂ、Ｘ−２２−１７６Ｄ、Ｘ−２２−１７６ＤＸ等の片末端２官能水酸基タイプが挙げられる。上記以外に末端官能基がチオール基、メタクリル基、フェノール性水酸基等が挙げられるが、反応性の点からアミノ基、水酸基、カルボキシル基が好ましい。また、式１と式２を比較すると式２を用いる方が摩擦係数低下の面から好ましい。 Specific examples of Formula 1 include Shin-Etsu Chemical X-22-161A, X-22-161B, KF-8012, KF-8008 and other terminal diamine types, X-22-163A, X-22-163B, Both terminal epoxy types such as X-22-163C, Carboxyl group types such as X-22-162C, X-22-3701E, X-22-3710, KF-6001, KF-6002, KF-6003, etc. A hydroxyl group type at both ends can be mentioned. Specific examples of Formula 2 include one-terminal bifunctional hydroxyl group types such as X-22-176B, X-22-176D, and X-22-176DX. In addition to the above, examples of the terminal functional group include a thiol group, a methacryl group, a phenolic hydroxyl group, and the like. From the viewpoint of reactivity, an amino group, a hydroxyl group, and a carboxyl group are preferable. Further, when Expression 1 is compared with Expression 2, it is preferable to use Expression 2 from the viewpoint of lowering the friction coefficient.
式１及び／又式２を共重合したポリアミドイミド樹脂の製造方法は酸成分とイソシアネート成分から製造するイソシアネート法、或は酸クロリドとアミンから製造する酸クロリド法、酸成分とアミン成分から製造する直接法などの公知の方法で製造されが、製造コストの点からイソシアネート法が好ましい。 Polyamideimide resin obtained by copolymerizing Formula 1 and / or Formula 2 is produced from an isocyanate method produced from an acid component and an isocyanate component, an acid chloride method produced from an acid chloride and an amine, or an acid component and an amine component. Although it is produced by a known method such as a direct method, the isocyanate method is preferred from the viewpoint of production cost.
本発明のポリアミドイミド樹脂の合成に用いられる酸成分としてトリメリット酸無水物を用いることが望ましいが、その一部を他の多塩基酸またはその無水物に置き換えることができる。例えば、ピロメリット酸、ビフェニルテトラカルボン酸、ビフェニルスルホンテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ビフェニルエーテルテトラカルボン酸、エチレングリコールビストリメリテート、プロピレングリコールビストリメリテート等のテトラカルボン酸及びこれらの無水物、シュウ酸、アジピン酸、マロン酸、セバシン酸、アゼライン酸、ドデカンジカルボン酸、ジカルボキシポリブタジエン、ジカルボキシポリ（アクリロニトリル−ブタジエン）、ジカルボキシポリ（スチレン−ブタジエン）等の脂肪族ジカルボン酸。１，４−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、４，４’−ジシクロヘキシルメタンジカルボン酸、ダイマー酸等の脂環族ジカルボン酸。テレフタル酸、イソフタル酸、ジフェニルスルホンジカルボン酸、ジフェニルエーテルジカルボン酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸が挙げられる。これらの中ではトリメリット酸無水物、ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、エチレングリコールビストリメテートが好ましい。 Although it is desirable to use trimellitic anhydride as the acid component used in the synthesis of the polyamideimide resin of the present invention, a part of it can be replaced with another polybasic acid or its anhydride. For example, tetracarboxylic acids such as pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, ethylene glycol bistrimellitate, propylene glycol bistrimellitate and their anhydrides, Aliphatic dicarboxylic acids such as oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene) and dicarboxypoly (styrene-butadiene). Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-dicyclohexylmethane dicarboxylic acid, and dimer acid. Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid and the like can be mentioned. Among these, trimellitic anhydride, pyromellitic acid, benzophenone tetracarboxylic anhydride, and ethylene glycol bistrimethate are preferable.
また、トリメリット酸化合物の一部をグリコールに置き換えてウレタン基を分子内に導入することもできる。グリコールとしてはエチレングリコール、プロピレングリコール、テトラメチレングリコール、ネオペンチルグリコール、ヘキサンジオール等のアルキレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリアルキレングリコールや上記ジカルボン酸の１種又は２種以上と上記グリコールの１種又は２種以上とから合成される末端水酸基のポリエステル等が挙げられる。 In addition, a urethane group can be introduced into the molecule by replacing part of the trimellitic acid compound with glycol. Examples of glycols include alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, and hexanediol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and one or more of the above dicarboxylic acids. And polyesters having terminal hydroxyl groups synthesized from one or more of the above glycols.
本発明のポリアミドイミド樹脂の合成に用いられるジアミン（ジイソシアネート）成分としては、フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、ベンジジン、キシリレンジアミン、トリレンジアミン、トリジン等の芳香族ジアミン及びこれらのジイソシアネート、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン及びこれらのジイソシアネート、１，４−シクロヘキサンジアミン、１，３−シクロヘキサンジアミン、イソホロンジアミン、４，４’−ジシクロヘキシルメタンジアミン等の脂環族ジアミン及びこれらのジイソシアネート、が挙げられ、これらの中では反応性、耐摩耗性の点からフェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、ベンジジン、キシリレンジアミン、トリレンジアミン、トリジン等の芳香族ジアミン及びこれらのジイソシアネートが好ましく、更に好ましくはフェニレンジアミン、４，４’−ジアミノジフェニルメタン、トリレンジアミン、トリジン及びこれらのジイソシアネートである。 Examples of the diamine (diisocyanate) component used in the synthesis of the polyamideimide resin of the present invention include phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, benzidine, and xylidine. Aromatic diamines such as range amine, tolylenediamine and tolidine, and diisocyanates thereof, aliphatic diamines such as ethylene diamine, propylene diamine and hexamethylene diamine, and diisocyanates thereof, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, Examples thereof include alicyclic diamines such as isophorone diamine and 4,4′-dicyclohexylmethane diamine, and diisocyanates thereof. Among these, phenylene is used in terms of reactivity and wear resistance. Preferred are aromatic diamines such as amines, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, benzidine, xylylenediamine, tolylenediamine, tolidine, and their diisocyanates, More preferred are phenylenediamine, 4,4′-diaminodiphenylmethane, tolylenediamine, tolidine and their diisocyanates.
本発明に用いるポリアミドイミド樹脂はＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン等の極性溶剤中、６０〜２００℃に加熱しながら攪拌することで容易に製造することができる。この場合、必要に応じてトリエチルアミン、ジエチレントリアミン、トリエチレンジアミン、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン等のアミン類、フッ化ナトリウム、フッ化カリウム、フッ化セシウム等のハロゲン化金属、ナトリウムメトキシド、ナトリウムエトキシド等の有機塩基、水酸化ナトリウム、水酸化カリウムの無機塩基を触媒として用いることもできる。触媒量は酸成分に対して０．１モル％以上１０モル％以下が好ましく、更に好ましくは０．５モル％以上５モル％以下である。 The polyamideimide resin used in the present invention is stirred in a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone while heating to 60 to 200 ° C. Can be manufactured easily. In this case, amines such as triethylamine, diethylenetriamine, triethylenediamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and halogenated sodium fluoride, potassium fluoride, cesium fluoride, etc. Metals, organic bases such as sodium methoxide and sodium ethoxide, and inorganic bases such as sodium hydroxide and potassium hydroxide can also be used as catalysts. The catalyst amount is preferably from 0.1 mol% to 10 mol%, more preferably from 0.5 mol% to 5 mol%, based on the acid component.
シリコーンの共重合の方法に特に制限は無いが、シリコーンを他原料と一括で仕込む方法、シリコーンを後から添加する方法、反応完了後にシリコーンを添加して共重合する方法が挙げられる。 The method for copolymerizing silicone is not particularly limited, and examples thereof include a method in which silicone is added together with other raw materials, a method in which silicone is added later, and a method in which silicone is added and copolymerized after completion of the reaction.
本発明に用いるポリアミドイミド樹脂はガラス転移温度が２００℃以上４００℃以下であることが望ましい。２００℃以下では自動車の摺動部材に応用するには耐熱性に問題があることがある。また、４００℃以上ではポリアミドイミドの溶解性が低くなり取扱が困難になる場合がある。また、対数粘度は０．３ｄｌ／ｇ以上２．０ｄｌ／ｇが望ましく、好ましくは０．３ｄｌ／ｇ以上１．５ｄｌ／ｇである。０．３ｄｌ／ｇ未満では脆くなり耐摩耗性に問題が生じる場合がある。また２．０ｄｌ／ｇを超えるとポリアミドイミド樹脂溶液の粘度が高くなりハンドリングが困難になるおそれがある。 The polyamide-imide resin used in the present invention preferably has a glass transition temperature of 200 ° C. or higher and 400 ° C. or lower. Below 200 ° C., there may be a problem in heat resistance when applied to a sliding member of an automobile. Moreover, if it is 400 degreeC or more, the solubility of a polyamideimide will become low and handling may become difficult. The logarithmic viscosity is desirably 0.3 dl / g or more and 2.0 dl / g, preferably 0.3 dl / g or more and 1.5 dl / g. If it is less than 0.3 dl / g, it becomes brittle and may cause a problem in wear resistance. Moreover, when it exceeds 2.0 dl / g, there exists a possibility that the viscosity of a polyamidoimide resin solution may become high, and handling may become difficult.
本発明に用いられる固体潤滑剤としては二硫化モリブデンや二硫化タングステンなどの硫化物、ポリテトラフルオロエチレン、テトラフルオロエチレン−パーフルオロアルキルブニルエーテル、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、ポリブニリデンフルオライド、トリクロロトリフルオロエチレン等のフッ化物及びグラファイトであり、その配合量はポリアミドイミド樹脂１００重量部に対して５〜５００重量部、好ましくは１０〜２００重量部である。固体潤滑剤が５重量部未満では摩擦係数の低減効果及び耐焼き付け特性が十分発揮されないことがある。一方、５００重量部を越えるとバインダー成分が少なくなりその結果耐摩耗性が不十分になる場合がある。 Solid lubricants used in the present invention include sulfides such as molybdenum disulfide and tungsten disulfide, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl butyl ether, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoro Fluorides such as ethylene-ethylene copolymer, polyvinylidene fluoride, trichlorotrifluoroethylene, and graphite, and the blending amount thereof is 5 to 500 parts by weight, preferably 10 to 200 parts per 100 parts by weight of the polyamideimide resin. Parts by weight. If the solid lubricant is less than 5 parts by weight, the effect of reducing the friction coefficient and the anti-seizure property may not be sufficiently exhibited. On the other hand, if it exceeds 500 parts by weight, the binder component is decreased, and as a result, the wear resistance may be insufficient.
本発明ではさらに耐磨耗剤を併用しても良い。耐摩耗剤としては、窒化珪素、窒化ホウ素、ダイヤモンド、シリカ等の１種又は２種以上であるが、その粒子径は０．１μｍ〜１０μｍでその配合量は５〜２００重量部が好ましい。粒子径が０．１μｍ以下では耐摩耗性の向上効果が小さく、１０μｍ以上では潤滑皮膜から固体潤滑剤が脱落しやすくなる。配合量が５重量部以下では耐摩耗剤の効果が十分発揮されず、２００重量部を越えると摺動相手へのダメージが大きくなり、摩擦係数も大きくなる。 In the present invention, an antiwear agent may be used in combination. The antiwear agent is one or more of silicon nitride, boron nitride, diamond, silica and the like, and the particle diameter is preferably 0.1 μm to 10 μm and the blending amount is preferably 5 to 200 parts by weight. When the particle size is 0.1 μm or less, the effect of improving the wear resistance is small, and when the particle size is 10 μm or more, the solid lubricant is easily dropped from the lubricating film. When the blending amount is 5 parts by weight or less, the effect of the antiwear agent is not sufficiently exhibited, and when it exceeds 200 parts by weight, damage to the sliding partner increases and the friction coefficient also increases.
また本発明の摺動部材用組成物の耐摩耗性を更に改良するためにポリアミドイミド樹脂を架橋、硬化させることができる。この硬化剤としては多官能エポキシ化合物、イソシアネート化合物、メラミン化合物等が挙げられ、これらの中では特に硬化性、得られた塗膜の摺動特性から多官能エポキシ化合物が好ましくビスフェノールＡ型、ビスフェノールＦ型フェノールノボラック型、フェノキシ型、ビフェノール型等が挙げられ、その中でもビスフェノールＡ型、フェノールノボラック型、ビフェノール型が硬化性、耐摩耗性から好ましい。これらの硬化剤の配合量は硬化剤にもよるが、ポリアミドイミド樹脂固形物１００部に対して１〜３０部、好ましくは３〜２０部である。硬化剤の量が１部以下ではポリアミドイミド樹脂を硬化させるのに十分で無いため耐磨耗性を良くする効果が発揮されない。また、３０部以上では塗膜が脆くなり逆に耐摩耗性が低下することがある。 Moreover, in order to further improve the abrasion resistance of the composition for a sliding member of the present invention, the polyamide-imide resin can be crosslinked and cured. Examples of the curing agent include polyfunctional epoxy compounds, isocyanate compounds, and melamine compounds. Of these, polyfunctional epoxy compounds are preferred because of their curability and sliding properties of the resulting coating film. Bisphenol A type, bisphenol F Type phenol novolac type, phenoxy type, biphenol type, and the like. Among them, bisphenol A type, phenol novolac type, and biphenol type are preferable from the viewpoint of curability and wear resistance. Although the compounding quantity of these hardening | curing agents is based also on a hardening | curing agent, it is 1-30 parts with respect to 100 parts of polyamideimide resin solids, Preferably it is 3-20 parts. If the amount of the curing agent is 1 part or less, it is not sufficient to cure the polyamideimide resin, so that the effect of improving the wear resistance is not exhibited. On the other hand, if it is 30 parts or more, the coating film becomes brittle and, conversely, the wear resistance may decrease.
次に本発明の摺動部材用組成物の製造方法について説明する。本発明の摺動部材用組成物を調整するために用いられる溶剤は前記ポリアミドイミド樹脂の合成に用いられるアミド系溶剤の他、概アミド系溶剤の４０％以下をトルエン、キシレン、ソルベッソ等の芳香族炭化水素、メチルエチルケトン、シクロヘキサノン等のケトンで置き換えることができる。 Next, the manufacturing method of the composition for sliding members of this invention is demonstrated. In addition to the amide solvent used for the synthesis of the polyamideimide resin, the solvent used for adjusting the composition for a sliding member of the present invention is 40% or less of the amide solvent, and the fragrance such as toluene, xylene, or solvesso. It can be replaced with a ketone such as a group hydrocarbon, methyl ethyl ketone, or cyclohexanone.
ポリアミドイミド樹脂、固体潤滑剤の他にレベリング剤、消泡材、カップリング材等の添加剤を加えてもよい。添加剤の量は全組成の５重量％以下が好ましい。 In addition to the polyamideimide resin and the solid lubricant, additives such as a leveling agent, an antifoaming material, and a coupling material may be added. The amount of additive is preferably 5% by weight or less of the total composition.
ポリアミドイミド樹脂を溶解した溶液に固体潤滑剤及び耐摩耗剤を加え、ボールミルや３本ロールミル、サンドミル等を用いて分散させる。硬化剤の添加時期について特に制限は無いが、好ましくは最後に配合し攪拌する事で摺動部材用組成物を調整することができる。 A solid lubricant and an antiwear agent are added to the solution in which the polyamideimide resin is dissolved, and the mixture is dispersed using a ball mill, a three-roll mill, a sand mill, or the like. Although there is no restriction | limiting in particular about the addition time of a hardening | curing agent, Preferably the composition for sliding members can be adjusted by mix | blending and stirring at the end.
以下に本発明の摺動部材用組成物を用いて潤滑膜を形成させる方法について説明する。本発明の組成物を摺動部材に塗布する方法としてはスプレー法、ロールコート法デイップ法、スクリーン印刷法等が挙げられ、摺動部材の形状や潤滑皮膜の厚みによって選択することができる。塗布された摺動部材は乾燥及び硬化のため熱処理される。この熱処理は１８０〜２００℃で２０分〜１００分の範囲が好ましい。熱処理が１８０℃で２０分以下では塗膜に溶剤が残って摺動特性を発揮させないことがあり、２００℃で１００分以上ではそれ以上の効果が期待できないし、場合によっては固体潤滑剤の劣化を招きむしろ摺動特性を低下させることがある。 The method for forming a lubricating film using the composition for sliding member of the present invention will be described below. Examples of a method for applying the composition of the present invention to the sliding member include a spray method, a roll coating method, a dip method, a screen printing method, and the like, which can be selected depending on the shape of the sliding member and the thickness of the lubricating film. The applied sliding member is heat treated for drying and curing. This heat treatment is preferably performed at 180 to 200 ° C. for 20 to 100 minutes. When heat treatment is performed at 180 ° C. for 20 minutes or less, the solvent may remain in the coating film and the sliding characteristics may not be exhibited. When the heat treatment is performed at 200 ° C. for 100 minutes or more, no further effect can be expected. Rather, the sliding characteristics may be deteriorated.
以下、実施例で本発明を更に詳細に説明するが、本発明はこれらの実施例で制限されるものではない。実施例で示される評価は以下の方法で測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples. The evaluation shown in the examples was measured by the following method.
１．対数粘度
ポリアミドイミド重合溶液からメタノールを用いて再沈殿、濾別、乾燥したポリアミドイミド樹脂０．５ｇを１００ｍｌのＮ−メチル−２−ピロリドンに溶解した溶液を用いて、ウベローデ粘度管で２５℃において測定した。
1. Reprecipitate, filter, and dry polyamideimide resin from logarithmic viscosity polyamideimide polymerization solution using a solution of 0.5 g of polyamideimide resin dissolved in 100 ml of N-methyl-2-pyrrolidone at 25 ° C. in an Ubbelohde viscosity tube. It was measured.
２．ガラス転移温度
ポリアミドイミド樹脂溶液をポリエステルフイルムに流延して半乾燥してフイルムを得た。そのフイルムを３００ｍｍ×２００ｍｍの金枠に張付け２００℃８時間乾燥し３０μｍのポリアミドイミド樹脂フイルムを得た。このフイルムを測定幅５ｍｍ、長さ１５ｍｍのポリアミドイミドフィルムをリガク製熱機械分析装置（ＰＴＣ１０Ａ）を用い、引張り荷重法で重り２ｇ、１０℃／分の条件で測定した時のサンプル長変曲点をガラス転移温度とした。
2. A glass transition temperature polyamideimide resin solution was cast on a polyester film and semi-dried to obtain a film. The film was attached to a 300 mm × 200 mm metal frame and dried at 200 ° C. for 8 hours to obtain a 30 μm polyamideimide resin film. Sample length inflection point when this film was measured on a polyamideimide film with a measurement width of 5 mm and a length of 15 mm using a Rigaku thermomechanical analyzer (PTC10A) under the conditions of a weight of 2 g and 10 ° C./min. Was the glass transition temperature.
３．摩擦係数の測定
摺動部材用組成物を約２０μｍの厚みに塗布した焼き入れ鋼からなる平板状に粗さ約１μｍＲＺの焼き入れ鋼からなる円筒材（外径２５ｍｍ、内径２０ｍｍ）の下端面を押し当て、油浴条件で平板を荷重９８Ｎ、１０００ｒｐｍで回転させながら測定した。
3. Measurement of coefficient of friction The lower end surface of a cylindrical material (outer diameter 25 mm, inner diameter 20 mm) made of hardened steel having a roughness of about 1 μm RZ is formed into a flat plate made of hardened steel coated with a composition for sliding member to a thickness of about 20 μm. The measurement was performed while rotating the plate at a load of 98 N and 1000 rpm under the pressure and oil bath conditions.
４．摩耗量の測定
ファレックス社製のリングオンリング試験器を用い、摺動部材用組成物を塗布したブロックに粗さ約１μｍＲＺの焼き入れ鋼からなる直径３５ｍｍの円筒を９８Ｎの荷重で押しつけ、油浴下室温で３０ｒｐｍ、１０分間摺動させた後皮膜の表面粗さを測定した結果から摩耗量を求めた。
4). Wear amount measurement Using a ring-on-ring tester manufactured by Falex, a cylinder with a diameter of 35 mm made of hardened steel with a roughness of about 1 μm RZ was pressed against a block coated with the sliding member composition with a load of 98 N to obtain oil. The amount of wear was determined from the result of measuring the surface roughness of the coating after sliding at 30 rpm for 10 minutes in a bath at room temperature.
＜ポリアミドイミド樹脂の合成例１＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート１モル、ＫＦ６００３（信越化学社製両末端水酸基ポリジメチルシロキサン、分子量５１００）２０ｇ（０．００４モル）、触媒としてフッ化カリウム０．０１モル、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより５％、対数粘度は０．６２ｄｌ／ｇ、ガラス転移温度は２７０℃であった。
<Synthesis example 1 of polyamideimide resin>
In a four-necked flask equipped with a nitrogen introduction tube and a cooling device, 1 mol of trimellitic anhydride, 1 mol of diphenylmethane diisocyanate, 20 g (0.004 mol) of KF6003 (both terminal hydroxyl group polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 5100), 0.01 mol of potassium fluoride as a catalyst and N-methyl-2-pyrrolidone as a solvent were added and reacted at a solid content concentration of 30% at 100 ° C. for 2 hours, and then reacted at 150 ° C. for 3 hours. Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 5% from the preparation, the logarithmic viscosity was 0.62 dl / g, and the glass transition temperature was 270 ° C.
＜ポリアミドイミド樹脂の合成例２＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート１モル、Ｘ−２２−１７６ＤＸ（信越化学社製片末端水酸基二官能ポリジメチルシロキサン、分子量３５００）２０ｇ（０．００６モル）、触媒としてフッ化カリウム０．０１モル、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより５％、対数粘度は０．６０ｄｌ／ｇ、ガラス転移温度は２７０℃であった。
<Synthesis example 2 of polyamideimide resin>
20 grams of trimellitic anhydride 1 mol, diphenylmethane diisocyanate 1 mol, X-22-176DX (single-end hydroxyl group bifunctional polydimethylsiloxane, molecular weight 3500) manufactured by Shin-Etsu Chemical Co., Ltd. 0.006 mol), 0.01 mol of potassium fluoride as a catalyst, and N-methyl-2-pyrrolidone as a solvent were charged and reacted at a solid content concentration of 30% at 100 ° C. for 2 hours, and then reacted at 150 ° C. for 3 hours. . Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 5% from the preparation, the logarithmic viscosity was 0.60 dl / g, and the glass transition temperature was 270 ° C.
＜ポリアミドイミド樹脂の合成例３＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート１モル、ＫＦ６００３（信越化学社製両末端水酸基ポリジメチルシロキサン、分子量５１００）１０ｇ（０．００２モル）、触媒として１，８−ジアザビシクロ［５．４．０］−７−ウンデセン０．０１モル、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより３％、対数粘度は０．６４ｄｌ／ｇ、ガラス転移温度は２７５℃であった。
<Synthesis example 3 of polyamideimide resin>
In a four-necked flask equipped with a nitrogen inlet tube and a cooling device, 1 mol of trimellitic anhydride, 1 mol of diphenylmethane diisocyanate, 10 g (0.002 mol) of KF6003 (both terminal hydroxyl group polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 5100), After 0.01 mol of 1,8-diazabicyclo [5.4.0] -7-undecene as a catalyst and N-methyl-2-pyrrolidone as a solvent were reacted at 100 ° C. for 2 hours at a solid content concentration of 30%, 150 The reaction was carried out at 0 ° C. for 3 hours. Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 3% from the preparation, the logarithmic viscosity was 0.64 dl / g, and the glass transition temperature was 275 ° C.
＜ポリアミドイミド樹脂の合成例４＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート１モル、Ｘ−２２−１７６ＤＸ（信越化学社製片末端水酸基二官能ポリジメチルシロキサン、分子量３５００）４０ｇ（０．０１１モル）、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより１０％、対数粘度は０．５３ｄｌ／ｇ、ガラス転移温度は２６５℃であった。
<Synthesis example 4 of polyamideimide resin>
In a four-necked flask equipped with a nitrogen inlet tube and a cooling device, 1 g of trimellitic anhydride, 1 mol of diphenylmethane diisocyanate, X-22-176DX (single-end hydroxyl group bifunctional polydimethylsiloxane, molecular weight 3500, manufactured by Shin-Etsu Chemical Co., Ltd.) 40 g ( 0.011 mol), and N-methyl-2-pyrrolidone as a solvent was added and reacted at a solid content concentration of 30% at 100 ° C. for 2 hours and then at 150 ° C. for 3 hours. Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 10% from the preparation, the logarithmic viscosity was 0.53 dl / g, and the glass transition temperature was 265 ° C.
＜ポリアミドイミド樹脂の合成例５＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ｏ−トリジンジイソシアネート０．５モル、ジフェニルメタンジイソシアネート０．５モル、Ｘ−２２−１７６ＤＸ（信越化学社製片末端水酸基二官能ポリジメチルシロキサン、分子量３５００）４０ｇ（０．０１１モル）、触媒としてフッ化カリウム０．０１モル、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより１０％、対数粘度は０．８３ｄｌ／ｇ、ガラス転移温度は３００℃であった。
<Synthesis example 5 of polyamideimide resin>
In a four-necked flask equipped with a nitrogen inlet tube and a cooling device, 1 mol of trimellitic anhydride, 0.5 mol of o-tolidine diisocyanate, 0.5 mol of diphenylmethane diisocyanate, X-22-176DX (one end hydroxyl group manufactured by Shin-Etsu Chemical Co., Ltd.) 40 g (0.011 mol) of bifunctional polydimethylsiloxane, molecular weight 3500), 0.01 mol of potassium fluoride as a catalyst, N-methyl-2-pyrrolidone as a solvent, and reaction at 100 ° C. for 2 hours at a solid content concentration of 30% And then reacted at 150 ° C. for 3 hours. Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 10% from the preparation, the logarithmic viscosity was 0.83 dl / g, and the glass transition temperature was 300 ° C.
＜ポリアミドイミド樹脂の合成例６（特開平８−９２５２８合成例１）＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート１モル、Ｂｙｋ−３７０（ＢＹＫ−ｃｈｅｍｉｅ社：ＯＨ基含有ポリエステル変性ポリシロキサン固形分濃度２５％）を７１ｇ、Ｎ−メチル−２−ピロリドン８３０ｇを仕込み、攪拌しながら約３０分で１２０℃に昇温し、５時間反応を行った後冷却して反応停止した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより５％、対数粘度は０．５７ｄｌ／ｇ、ガラス転移温度は２８０℃であった。
<Synthesis Example 6 of Polyamideimide Resin (Synthesis Example 1 of JP-A-8-92528)>
71 g of trimellitic anhydride 1 mol, diphenylmethane diisocyanate 1 mol, BYK-370 (BYK-chemie: OH group-containing polyester-modified polysiloxane solid content concentration 25%) in a four-necked flask equipped with a nitrogen inlet tube and a cooling device , 830 g of N-methyl-2-pyrrolidone was added, the temperature was raised to 120 ° C. in about 30 minutes with stirring, the reaction was performed for 5 hours, and then cooled to stop the reaction. The amount of silicone copolymerization of the obtained polyamideimide resin was 5% from the preparation, the logarithmic viscosity was 0.57 dl / g, and the glass transition temperature was 280 ° C.
＜ポリアミドイミド樹脂の合成例７＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート０．９３モル、Ｘ−２２−１７６ＤＸ（信越化学社製片末端水酸基二官能ポリジメチルシロキサン、分子量３５００）１０ｇ（０．０１１モル）、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより３％、対数粘度は０．２３ｄｌ／ｇ、ガラス転移温度はフイルムが脆く測定できなかった。
<Synthesis example 7 of polyamideimide resin>
In a four-necked flask equipped with a nitrogen inlet tube and a cooling device, 1 mol of trimellitic anhydride, 0.93 mol of diphenylmethane diisocyanate, X-22-176DX (single-end hydroxyl group bifunctional polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 3500) 10 g (0.011 mol) of N-methyl-2-pyrrolidone as a solvent was added and reacted at a solid content concentration of 30% at 100 ° C. for 2 hours, and then reacted at 150 ° C. for 3 hours. Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 3% from the preparation, the logarithmic viscosity was 0.23 dl / g, and the glass transition temperature could not be measured because the film was brittle.
＜ポリアミドイミド樹脂の合成例８＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート１．０４モル、Ｘ−２２−１７６ＤＸ（信越化学社製片末端水酸基二官能ポリジメチルシロキサン、分子量３５００）１８０ｇ（０．０５１モル）、触媒としてフッ化カリウム０．０１モル、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより３４％、対数粘度は０．５８ｄｌ／ｇ、ガラス転移温度は２４０℃であった。
<Synthesis example 8 of polyamideimide resin>
In a four-necked flask equipped with a nitrogen inlet tube and a cooling device, 1 mol of trimellitic anhydride, 1.04 mol of diphenylmethane diisocyanate, X-22-176DX (single-end hydroxyl group bifunctional polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 3500) 180 g (0.051 mol), 0.01 mol of potassium fluoride as a catalyst, and N-methyl-2-pyrrolidone as a solvent were added and reacted at 100 ° C. for 2 hours at a solid concentration of 30%, and then reacted at 150 ° C. for 3 hours. I let you. Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 34% from the preparation, the logarithmic viscosity was 0.58 dl / g, and the glass transition temperature was 240 ° C.
＜ポリアミドイミド樹脂の合成例９＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート０．９８モル、溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させた。冷却し、固形分濃度が２０％となるようＮ−メチル−２−ピロリドンで希釈した。得られたポリアミドイミド樹脂のシリコーン共重合量は仕込みより０％、対数粘度は０．５８ｄｌ／ｇ、ガラス転移温度は２９０℃であった。
<Synthesis example 9 of polyamideimide resin>
A 4-necked flask equipped with a nitrogen inlet tube and a cooling device was charged with 1 mol of trimellitic anhydride, 0.98 mol of diphenylmethane diisocyanate and N-methyl-2-pyrrolidone as a solvent, and reacted at 100 ° C. for 2 hours at a solid content concentration of 30%. And allowed to react at 150 ° C. for 3 hours. Cooled and diluted with N-methyl-2-pyrrolidone to a solid content concentration of 20%. The amount of silicone copolymerization of the obtained polyamideimide resin was 0% from the preparation, the logarithmic viscosity was 0.58 dl / g, and the glass transition temperature was 290 ° C.
＜ポリアミドイミド樹脂の合成例１０＞
窒素導入管と冷却装置の付いた４ツ口フラスコに無水トリメリット酸１モル、ジフェニルメタンジイソシアネート０．９９モル、Ｘ−２２−１７６Ｆ（信越化学社製片末端水酸基二官能ポリジメチルシロキサン、分子量１４０００）２０ｇ（０．００１モル）溶剤としてＮ−メチル−２−ピロリドンを仕込み固形分濃度３０％で１００℃２時間反応させた後、１５０℃で３時間反応させたがシリコーン成分が分離してフラスコの壁に付着しており、共重合が困難であった。
<Synthesis Example 10 of Polyamideimide Resin>
In a four-necked flask equipped with a nitrogen inlet tube and a cooling device, 1 mol of trimellitic anhydride, 0.99 mol of diphenylmethane diisocyanate, X-22-176F (single-end hydroxyl group bifunctional polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 14000) 20 g (0.001 mol) of N-methyl-2-pyrrolidone as a solvent was added and reacted at a solid content of 30% at 100 ° C. for 2 hours and then at 150 ° C. for 3 hours. It was attached to the wall and copolymerization was difficult.
＜摺動部材用組成物の調整及び摺動特性の評価＞
合成例１〜８のポリアミドイミド樹脂を表２に示す割合で配合し、ディゾルバーで３０分分散を行なった後、３本ロールミルで分散を行った。摩擦、摩耗性を測定するテストピースの摺動面を脱脂して表面の汚れ、油分を除いた後、表２の組成物を乾燥後で約２０μｍの厚みになるよう塗布し、熱風オーブン中２００℃で１００分間焼き付けを行った。摩耗量と摩擦係数の値を表２に示す。
<Adjustment of composition for sliding member and evaluation of sliding characteristics>
The polyamide imide resins of Synthesis Examples 1 to 8 were blended in the proportions shown in Table 2, and dispersed with a dissolver for 30 minutes, and then dispersed with a three roll mill. The sliding surface of the test piece for measuring the friction and wear properties was degreased to remove dirt and oil on the surface, and then the composition shown in Table 2 was applied to a thickness of about 20 μm after drying, and then heated in a hot air oven. Baking was performed at 100 ° C. for 100 minutes. Table 2 shows the values of the wear amount and the friction coefficient.
表２より明らかなように、実施例１〜５は、比較例１〜５に比べて、摩耗量や摩耗係数が優れていることがわかる。 As is apparent from Table 2, Examples 1 to 5 are superior to Comparative Examples 1 to 5 in the amount of wear and the wear coefficient.
本発明の摺動部材用ポリアミドイミド樹脂組成物を塗布した摺動部材は摩擦係数の低減、耐摩耗性に優れ、且つ十分な耐久性を有するため家電製品や自動車エンジンのピストンスカート等に有用である。 The sliding member coated with the polyamideimide resin composition for sliding member of the present invention is useful for home appliances and piston skirts of automobile engines because it has a reduced coefficient of friction, excellent wear resistance, and sufficient durability. is there.
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| US9777241B2 (en) | 2012-05-07 | 2017-10-03 | Nok Klueber Co., Ltd. | Composition for sliding member |
| JP2014012803A (en) * | 2012-07-03 | 2014-01-23 | Vision Development Co Ltd | Sliding resin member having excellent mold releasability and containing diamond fine particle having silicon and/or fluorine |
| CN104073156A (en) * | 2014-07-03 | 2014-10-01 | 东莞市垠星科技发展有限公司 | Self-lubricating polyamideimide insulation varnish and preparation method thereof |
| JP2016074892A (en) * | 2014-10-02 | 2016-05-12 | マーレ インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツングＭＡＨＬＥ Ｉｎｔｅｒｎａｔｉｏｎａｌ ＧｍｂＨ | Bearing material |
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