JP2004051725A - Coating composition, method for forming coating film, and material having coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a self-deposit type coating composition which has a low frictional coefficient, can be maintained in a stable state, can correspond to sliding members having excellent abrasion resistance, and can further correspond to complicated shaped articles in simple processes. <P>SOLUTION: This self-deposit type coating composition is characterized by comprising one or more resins (for example, an anionic polyester resin obtained by the condensation reaction of a polyhydric alcohol with an acid) selected from the group of water-dispersible or soluble organic resins, an acid component (for example, hydrogen fluoride), a metal ion (for example, iron ion), and a lubricant component (for example, polytetrafluoroethylene). <P>COPYRIGHT: (C)2004,JPO

Description

［但し、Ｒ_１はアルキレン基である。中でも、炭素数が１〜１０の直鎖または分岐鎖のアルキレン基、炭素数が１〜１０の不飽和のアルキレン基、ヒドロキシル基及び／又はハロゲン元素を含む前記アルキレン基である。］
一般式［ＩＩ］

［但し、Ｒ_２，Ｒ_３，Ｒ_４，Ｒ_５は、互いに、独立して、水素及びアルキル基の群の中から選ばれる何れかである。特に、水素またはメチル基である。ｍ，ｎは、１以上の整数で、かつ、２≦ｍ＋ｎ≦６である。］
又、アニオン性のポリエステル樹脂であり、前記ポリエステル樹脂を構成する酸成分が下記の一般式［ＩＩＩ］で表される脂肪族カルボン酸及びその誘導体、下記の一般式［ＩＶ］で表される芳香族カルボン酸及びその誘導体、下記の一般式［Ｖ］で表される芳香族酸無水物及びその誘導体、下記の一般式［ＶＩ］で表されるピロメリット酸の無水物及びその誘導体、及び下記の一般式［ＶＩＩ］で表されるナフタレン誘導体の群の中から選ばれる１種又は２種以上のものであるポリエステル樹脂は好ましい。
【００１８】
一般式［ＩＩＩ］

［但し、Ｒ_６はアルキレン基である。中でも、炭素数が１〜３０の直鎖または分岐鎖のアルキレン基、炭素数が１〜３０の不飽和のアルキレン基、−ＣＯＯＸ_３（Ｘ_３は水素または炭素数が１〜１０の直鎖または分岐鎖のアルキレン基）を含むアルキレン基あるいは不飽和のアルキレン基である。Ｘ_１，Ｘ_２は、互いに、独立して、水素又はアルキル基である。中でも、水素または炭素数が１〜１０のアルキル基である。］
一般式［ＩＶ］

［但し、Ｘ_４，Ｘ_５は、互いに、独立して、水素又はアルキル基である。中でも、水素又は炭素数が１〜３のアルキル基である。Ｙ_１，Ｙ_２，Ｙ_３，Ｙ_４は、互いに、独立して、水素、−ＣＯＯＸ_６（Ｘ_６は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）、−ＳＯ_３Ｚ_１（Ｚ_１は、水素、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）の群の中から選ばれる何れかである。中でも、水素、−ＣＯＯＸ_６（Ｘ_６は炭素数１〜３のアルキル基、Ｈ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）、−ＳＯ_３Ｚ_１（Ｚ_１はＨ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）である。］
一般式［Ｖ］

［但し、Ｙ_５，Ｙ_６は、互いに、独立して、水素、−ＣＯＯＸ_７（Ｘ_７は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）、−ＳＯ_３Ｚ_２（Ｚ_２は、水素、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）の群の中から選ばれる何れかである。中でも、水素、−ＣＯＯＸ_７（Ｘ_７は炭素数１〜３のアルキル基、Ｈ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）、−ＳＯ_３Ｚ_２（Ｚ_２はＨ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）である。］
一般式［ＶＩ］

一般式［ＶＩＩ］

［但し、Ｘ_８，Ｘ_９は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。中でも、水素、炭素数１〜３のアルキル基、Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４である。Ｙ_７，Ｙ_８，Ｙ_９，Ｙ_１０は、互いに、独立して、水素、−ＣＯＯＸ_８（Ｘ_８は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）、−ＳＯ_３Ｚ_３（Ｚ_３は、水素、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）の群の中から選ばれる何れかである。中でも、水素、−ＣＯＯＸ_８（Ｘ_８は炭素数１〜３のアルキル基、Ｈ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）、−ＳＯ_３Ｚ_３（Ｚ_３はＨ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）である。］
本発明で用いられる酸化剤は酸化作用を有するものであれば良い。例えば、過酸化水素、過マンガン酸カリウム、亜硝酸ナトリウム等を使用できる。中でも過酸化水素は好ましい。
【００１９】
又、前記の課題は、上記の塗料組成物に材料を接触させ、前記材料の表面に塗膜を析出させた後、乾燥することを特徴とする塗膜形成方法によつて解決される。
【００２０】
又、前記の課題は、上記の塗料組成物による塗膜を有することを特徴とする塗膜を有する材料によって解決される。
【００２１】
【発明の実施の形態】
本発明になる塗料組成物、特に自己析出型塗料組成物は、水分散性および水溶性の有機樹脂の群の中から選ばれる１種又は２種以上の樹脂（ａ）と、酸成分（ｂ）と、金属イオン（ｃ）と、潤滑剤成分（ｄ）とを含有する。特に、水分散性および水溶性の有機樹脂の群の中から選ばれる１種又は２種以上の樹脂（ａ）と、酸成分（ｂ）と、金属イオン（ｃ）と、潤滑剤成分（ｄ）と、酸化剤（ｅ）とを含有する。更に水を含有する。成分（ａ），（ｂ），（ｃ），（ｄ）の好ましい配合割合（重量比）は、（ａ）：（ｂ）：（ｃ）：（ｄ）＝１００：２〜１００（特に、１０〜６０）：４〜１０００（特に、２０〜１００）：１０〜２０００（特に、２０〜１０００）である。酸化剤（ｅ）の好ましい配合割合（重量比）は、（ａ）：（ｅ）＝１００：０．２〜６０（特に、０．６〜２０）である。又、（ａ）の濃度が、樹脂固形分濃度として、５〜５５０ｇ／Ｌ（特に、４０〜２００ｇ／Ｌ）である。（ｂ）の濃度が、０．１〜５ｇ／Ｌ（特に、０．５〜３ｇ／Ｌ）である。（ｃ）の濃度が、不揮発分として、０．５〜５ｇ／Ｌ（特に、０．７５〜３ｇ／Ｌ）である。（ｄ）の濃度が、不揮発分として、０．５〜１００ｇ／Ｌ（特に、１〜５０ｇ／Ｌ）である。
【００２２】
本発明の塗料組成物で用いられる酸成分（ｂ）は酸であれば良い。好ましい酸は有機酸よりも無機酸である。中でも、ジルコニウムフッ化水素（酸）、チタンフッ化水素（酸）、ケイフッ化水素（酸）、ホウフッ化水素（酸）、フッ化水素（酸）、リン酸、硝酸などが挙げられる。特に、フッ化水素（酸）が好ましい。
【００２３】
本発明の塗料組成物で用いられる金属イオン（ｃ）は金属イオンであれば良い。好ましい金属イオンとしては、例えば鉄イオン、コバルトイオン、ジルコニウムイオンである。このような金属イオンを供給できる物質は液中で安定しているものであれば良い。例えば、硝酸第二鉄、フッ化第二鉄、燐酸第一鉄、硝酸第一コバルト、ジルコニウムフッ化水素酸等が挙げられる。ジルコニウムフッ化水素酸やフッ化第二鉄は特に好ましい。
【００２４】
本発明の塗料組成物で用いられる潤滑剤成分（ｄ）は潤滑作用を有するものであれば良い。しかしながら、特に好ましいものは、例えばポリテトラフルオロエチレンやポリトリフルオルクロロエチレン等のフッ素系樹脂、ポリエチレンワックスやポリプロピレンワックス等のポリオレフィン系ワックス、メラミンシアヌレート、及び二硫化モリブデンの群の中から選ばれる１種又は２種以上の潤滑剤である。潤滑剤成分は水系分散性のものである。
【００２５】
本発明の塗料組成物で用いられる酸化剤（ｅ）は酸化作用を有するものであれば良い。酸化剤（ｅ）は、本発明の塗料組成物を安定的に使用できるようにさせる。すなわち、本発明の塗料組成物を用いて鉄系素材を処理すると、処理液中に２価の鉄イオンが溶出し、処理液を不安定化する。このような場合、酸化剤が含まれていると、生成した２価の鉄イオンを速やかに３価のものに酸化してしまうので、処理液は安定化する。従って、アルミニウムなどの如く、価数の変化を伴わない金属しか溶出しない場合には、酸化剤は必ずしも必要としない。酸化剤（ｅ）としては、過マンガン酸カリウム、過酸化水素、亜硝酸ナトリウム等を使用できる。中でも過酸化水素は好ましい。
【００２６】
本発明において（ａ）は水分散性または水溶性の有機樹脂であれば良い。しかしながら、好ましい樹脂としてアクリル樹脂、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、及びポリアミド樹脂の群の中から選ばれる１種又は２種以上のものが挙げられる。特に、界面活性剤などの乳化剤を用いて水系化した強制乳化型有機高分子樹脂、若しくはその構造の一部がカルボキシル基、スルホン酸基、リン酸基、ホスホン酸基等のアニオン性官能基で変性された水溶性、又は自己乳化性の有機高分子樹脂である。これらの中でもポリエステル樹脂、特にアニオン性のポリエステル樹脂は好ましい。更には、ポリエステル樹脂の中でも、多価アルコールと酸との縮合反応により得られたアニオン性のポリエステル樹脂である。
【００２７】
特に、アニオン性のポリエステル樹脂であり、前記ポリエステル樹脂を構成するアルコール成分が上記の一般式［Ｉ］で表される脂肪族多価アルコール及びその誘導体、上記の一般式［ＩＩ］で表される芳香族多価アルコール及びその誘導体の群の中から選ばれる１種又は２種以上のものであるポリエステル樹脂は好ましいものである。尚、一般式［Ｉ］におけるＲ_１はアルキレン基である。中でも、炭素数が１〜１０の直鎖または分岐鎖のアルキレン基、炭素数が１〜１０の不飽和のアルキレン基、ヒドロキシル基及び／又はハロゲン元素を含む前記アルキレン基である。一般式［Ｉ］のものとしては、例えばエチレングリコール、ネオペンチルグリコール、ジブロムネオペンチルグリコール、１，２−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、３−メチルペンタンジオール、１，４−シクロヘキサンジメタノール、３−メチル−１，５−ペンタンジオール、２−メチル−１，３−プロパンジオール、２，２−ジエチル−１，　　３−プロパンジオール、グリセリン、ペンタエリスリトール、トリメチロールプロパン等が挙げられる。一般式［ＩＩ］におけるＲ_２，Ｒ_３，Ｒ_４，Ｒ_５は、互いに、独立して、水素及びアルキル基の群の中から選ばれる何れかである。特に、水素またはメチル基である。ｍ，ｎは、１以上の整数で、かつ、２≦ｍ＋ｎ≦６である。一般式［ＩＩ］のものとしては、例えばビスフェノールＡエチレンオキサイド付加物、ビスフェノールＡプロピレンオキサイド付加物、ビスフェノールＦエチレンオキサイド付加物、ビスフェノールＦプロピレンオキサイド付加物などが挙げられる。
【００２８】
又、アニオン性のポリエステル樹脂であり、上記ポリエステル樹脂を構成する酸成分が上記の一般式［ＩＩＩ］で表される脂肪族カルボン酸及びその誘導体、上記の一般式［ＩＶ］で表される芳香族カルボン酸及びその誘導体、上記の一般式［Ｖ］で表される芳香族酸無水物及びその誘導体、上記の一般式［ＶＩ］で表されるピロメリット酸の無水物及びその誘導体、及び上記の一般式［ＶＩＩ］で表されるナフタレン誘導体の群の中から選ばれる１種又は２種以上のものであるポリエステル樹脂は好ましいものである。一般式［ＩＩＩ］におけるＲ_６はアルキレン基である。中でも、炭素数が１〜３０の直鎖または分岐鎖のアルキレン基、炭素数が１〜３０の不飽和のアルキレン基、−ＣＯＯＸ_３（Ｘ_３は水素または炭素数が１〜１０の直鎖または分岐鎖のアルキレン基）を含むアルキレン基あるいは不飽和のアルキレン基である。Ｘ_１，Ｘ_２は、互いに、独立して、水素又はアルキル基である。中でも、水素または炭素数が１〜１０のアルキル基である。一般式［ＩＩＩ］のものとしては、例えばコハク酸、メチルコハク酸、エチルコハク酸、ブチルコハク酸、コハク酸モノエチルエステル、コハク酸ジエチルエステル、コハク酸モノブチルエステル、コハク酸ジブチルエステル、グルタル酸、メチルグルタル酸、エチルグルタル酸、ブチルグルタル酸、グルタル酸モノメチルエステル、グルタル酸ジメチルエステル、グルタル酸モノエチルエステル、グルタル酸ジエチルエステル、グルタル酸モノブチルエステル、グルタル酸ジブチルエステル、アジピン酸、アジピン酸モノメチルエステル、アジピン酸ジメチルエステル、アジピン酸モノエチルエステル、アジピン酸ジオクチルエステル、セバシン酸、セバシン酸ジエチルエステル、セバシン酸ジブチルエステル、セバシン酸ジオクチルエステル、トリカルバリル酸、ブテンテトラカルボン酸などが挙げられる。一般式［ＩＶ］におけるＸ_４，Ｘ_５は、互いに、独立して、水素又はアルキル基である。中でも、水素又は炭素数が１〜３のアルキル基である。Ｙ_１，Ｙ_２，Ｙ_３，Ｙ_４は、互いに、独立して、水素、−ＣＯＯＸ_６（Ｘ_６は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）、−ＳＯ_３Ｚ_１（Ｚ_１は、水素、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）の群の中から選ばれる何れかである。中でも、水素、−ＣＯＯＸ_６（Ｘ_６は炭素数１〜３のアルキル基、Ｈ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）、−ＳＯ_３Ｚ_１（Ｚ_１はＨ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）である。］。一般式［ＩＶ］のものとしては、例えばテレフタル酸、テレフタル酸モノメチルエステル、テレフタル酸ジメチルエステル、テレフタル酸モノエチルエステル、テレフタル酸ジエチルエステル、イソフタル酸、イソフタル酸モノメチルエステル、イソフタル酸ジメチルエステル、イソフタル酸ジメチル−５−スルホン酸ナトリウム塩、トリメリット酸、トリメリット酸１，４−ジメチルエステル、ピロメリット酸テトラメチルエステル、ピロメリット酸テトラエチルエステル等が挙げられる。一般式［Ｖ］におけるＹ_５，Ｙ_６は、互いに、独立して、水素、−ＣＯＯＸ_７（Ｘ_７は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）、−ＳＯ_３Ｚ_２（Ｚ_２は、水素、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）の群の中から選ばれる何れかである。中でも、水素、−ＣＯＯＸ_７（Ｘ_７は炭素数１〜３のアルキル基、Ｈ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）、−ＳＯ_３Ｚ_２（Ｚ_２はＨ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）である。一般式［Ｖ］のものとしては、例えば無水フタル酸、無水トリメリット酸、無水トリメリット酸エチルエステル等が挙げられる。一般式［ＶＩ］のものとしては、ピロメリット酸無水物がある。一般式［ＶＩＩ］におけるＸ_８，Ｘ_９は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。中でも、水素、炭素数１〜３のアルキル基、Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４である。Ｙ_７，Ｙ_８，Ｙ_９，Ｙ_１０は、互いに、独立して、水素、−ＣＯＯＸ_８（Ｘ_８は、水素、アルキル基、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）、−ＳＯ_３Ｚ_３（Ｚ_３は、水素、アルカリ金属、アルカリ土類金属、アンモニウム基の群の中から選ばれる何れかである。）の群の中から選ばれる何れかである。中でも、水素、−ＣＯＯＸ_８（Ｘ_８は炭素数１〜３のアルキル基、Ｈ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）、−ＳＯ_３Ｚ_３（Ｚ_３はＨ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ又はＮＨ_４）である。一般式［ＶＩＩ］のものとしては、例えば１，２−ナフタレンジカルボン酸、１，２−ナフタレンジカルボン酸ジメチルエステル、１，３−ナフタレンジカルボン酸、１，３−ナフタレンジカルボン酸ジメチルエステル、１，４−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸ジメチルエステル、１，５−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸ジメチルエステル、１，６−ナフタレンジカルボン酸、１，６−ナフタレンジカルボン酸ジメチルエステル、１，７−ナフタレンジカルボン酸、１，７−ナフタレンジカルボン酸ジメチルエステル、２，３−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸ジメチルエステル、２，６−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸ジメチルエステル、２，７−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸ジメチルエステル等が挙げられる。
【００２９】
上記ポリエステル樹脂は、その酸成分として、一般式［ＩＶ］，［Ｖ］，［ＶＩＩ］の群の中から選ばれる１種または２種以上のものが用いられるのが好ましい。このようなポリエステル樹脂を用いることによって、耐食性、密着性および耐熱性が一段と向上する。特に、前記酸成分が全酸成分中の６０〜１００ｍｏｌ％である場合、その効果が著しい。
【００３０】
前記一般式［ＩＶ］，［Ｖ］，［ＶＩＩ］において、Ｙ_１〜Ｙ_１０の少なくとも一つはカルボキシル基またはスルホン酸基、即ち、−ＣＯＯＸ_６，−ＳＯ_３Ｚ_１，−ＣＯＯＸ_７，−ＳＯ_３Ｚ_２，−ＣＯＯＸ_８，−ＳＯ_３Ｚ_３から選ばれる少なくとも１種を全酸成分中に１〜４０ｍｏｌ％（特に、２〜３０ｍｏｌ％）含有することが好ましい。
【００３１】
本発明の水分散性または水溶性の有機樹脂（ａ）の分子量は如何なるものでも良いが、本発明の効果を特に奏するのは、数平均分子量で２０００〜５００００のものである。
【００３２】
本発明で使用されるポリエステル樹脂は、その合成方法が特に限定されるものでは無いが、例えば前記の多価アルコールと酸とを用い、更に必要に応じてジブチル錫オキシド、酢酸鉛、酢酸カルシウム、Ｎ−ブチルチタネート等の触媒を用いて、１０ｍｍＨｇ以下の減圧状態で１４０〜３００℃の条件下で、エステル化またはエステル交換反応を行って重縮合させることにより得られたものが好ましい。
【００３３】
本発明の塗料組成物は、上記成分の他にも任意成分として、例えばトリアルキルペンタンジオールイソブチレートやアルキルカルビトール等の造膜助剤、例えばカーボンブラック、フタロシアニンブルーやハンザイエロー等の着色剤を、本発明の目的を損なわない程度で含有することが出来る。
【００３４】
本発明の塗膜形成方法は、上記の塗料組成物に材料を接触させ、前記材料の表面に塗膜を析出させた後、乾燥する方法である。接触方法としては各種の手法を採用できる。複雑な表面に均一な塗膜を形成するには浸漬が好ましい。処理温度は、好ましくは５〜５０℃、特に１０〜４０℃である。これは、処理温度が５℃を下回ると、析出効率が悪くなる傾向があり、十分な塗膜量を得難い。逆に、５０℃を越えると、反応過多の傾向があり、塗膜の表面外観性が低下する傾向がある。処理時間は、好ましくは１０〜５００秒、特に２０〜３００秒である。処理時間が短すぎると、析出反応不足の傾向となる。処理時間が長すぎると、被処理物の溶解が進み、塗膜中の金属イオン濃度が高くなる傾向に有り、外観不良となり易い。又、耐食性も低下する傾向が有る。塗布量（塗膜厚）については特に制限はないが、好ましくは、乾燥後の膜厚で５〜４０μｍ、特に１０〜２５μｍの範囲である。膜厚が薄すぎると本発明の目的が達成でき難い。逆に、厚すぎると塗膜にフクレが生じる傾向が有り、外観性が低下する傾向にある。乾燥は如何なる手法を用いても良い。例えば、電気やガスを熱源とした熱風循環式乾燥炉、遠赤外線を利用した加熱炉、高周波加熱、誘導加熱などが使用できる。乾燥温度は、好ましくは６０〜３００℃、特に８０〜２５０℃である。乾燥温度が低すぎると、効率が悪いのみならず、造膜不良となる傾向がある。そして、耐食性、摺動性が低下する。逆に、乾燥温度が高くなり過ぎると、塗膜を構成する樹脂が熱分解する恐れが有る。尚、塗膜外観を一層向上させる為には、先ず、６０〜１００℃の温度で付着水分を十分に乾燥し、その後で前記工程での温度以上の温度で加熱することが効果的である。
【００３５】
そして、本発明の塗膜を有する材料は、上記のような膜を有するものである。
【００３６】
以下、具体的な実施例および比較例を挙げて説明する。
【００３７】
【実施例および比較例】
［被処理材料］
実施例および比較例で用いた被処理材料（厚さ０．８ｍｍで７０ｍｍ×１５０ｍｍの板材）Ｈ，Ｉ，Ｊは以下の通りである。
Ｈ　　ＳＰＣＣ　　冷延鋼板
Ｉ　　ＡＤ４Ｃ　　アルミ鋳物
Ｊ　　ＳＣ５５　　鉄鋳物
［塗料組成物における樹脂（ａ）］
（Ａ１）　エチレングリコール（９０ｍｏｌ％）とトリメチロールプロパン（１０ｍｏｌ％）とからなるアルコール成分と、イソフタル酸（４０ｍｏｌ％）とテレフタル酸（４１ｍｏｌ％）とイソフタル酸ジメチル−５−スルホン酸ナトリウム（２ｍｏｌ％）と無水トリメリット酸（１７ｍｏｌ％）とからなる酸成分との縮合反応によるアニオン性のポリエステル樹脂（固形分（ＮＶＣ．）３０％）
（Ａ２）　エチレングリコール（７０ｍｏｌ％）と１，４−ブタンジオール（３０ｍｏｌ％）とからなるアルコール成分と、イソフタル酸（４５ｍｏｌ％）とテレフタル酸（４５ｍｏｌ％）とイソフタル酸ジメチル−５−スルホン酸ナトリウム（３ｍｏｌ％）と無水ピロメリット酸（７ｍｏｌ％）とからなる酸成分との縮合反応によるアニオン性のポリエステル樹脂（ＮＶＣ．３０％）
（Ａ３）　ネオペンチルグリコール（３０ｍｏｌ％）とエチレングリコール（７０ｍｏｌ％）とからなるアルコール成分と、テレフタル酸（８１ｍｏｌ％）とイソフタル酸ジメチル−５−スルホン酸ナトリウム（２ｍｏｌ％）とトリメリット酸（１７ｍｏｌ％）とからなる酸成分との縮合反応によるアニオン性のポリエステル樹脂（ＮＶＣ．３０％）
（Ａ４）　ネオペンチルグリコール（３３ｍｏｌ％）とエチレングリコール（４４ｍｏｌ％）と１，４−ブタンジオール（２３ｍｏｌ％）とからなるアルコール成分と、セバシン酸（６ｍｏｌ％）とテレフタル酸（６６ｍｏｌ％）とトリメリット酸（２２ｍｏｌ％）と無水ピロメリット酸（６ｍｏｌ％）とからなる酸成分との縮合反応によるポリエステル樹脂（ＮＶＣ．３０％）
（Ａ５）　ネオペンチルグリコール（２０ｍｏｌ％）とエチレングリコール（７０ｍｏｌ％）とビスフェノールＡプロピレンオキサイド付加物（１０ｍｏｌ％）とからなるアルコール成分と、イソフタル酸（５３ｍｏｌ％）とテレフタル酸（３０ｍｏｌ％）とイソフタル酸ジメチル−５−スルホン酸ナトリウム（２ｍｏｌ％）と無水トリメリット酸（５ｍｏｌ％）と２，６−ナフタレンジカルボン酸（１０ｍｏｌ％）とからなる酸成分との縮合反応によるアニオン性のポリエステル樹脂（ＮＶＣ．３０％）
（Ａ６）　エチレングリコール（７０ｍｏｌ％）と１，４−ブタンジオール（３０ｍｏｌ％）とからなるアルコール成分と、イソフタル酸（４１ｍｏｌ％）とテレフタル酸（４０ｍｏｌ％）とイソフタル酸ジメチル−５−スルホン酸ナトリウム（２ｍｏｌ％）とトリメリット酸（１７ｍｏｌ％）とからなる酸成分との縮合反応によるアニオン性のポリエステル樹脂（ＮＶＣ．３０％）
（Ａ７）　エポキシ樹脂（油化シェルエポキシ社のエピレッツ３５２２Ｗ６０（ＮＶＣ．６０％））
（Ａ８）　アクリル樹脂（Ｒｏｈｍ＆Ｈａｓｓ社のロープレックスＷＬ−９１（ＮＶＣ．４１．５％））
（Ａ９）　ウレタン樹脂
（Ａ１０）　ポリアミド樹脂
（Ａ１１）　塩化ビニリデン樹脂（Ｗ．Ｒ．Ｇｒａｃｅ社のＤａｒａｎ　ＳＬ１４３（ＮＶｃ．５５％））
尚、上記組成のポリエステル樹脂は、次の方法で合成した。クライゼン管および空気冷却器を取り付けた１０００ｍＬの丸底フラスコに、１ｍｏｌの全酸成分と２ｍｏｌの全アルコール成分と触媒（酢酸カルシウム０．２５ｇ、Ｎ−ブチルチタネート０．１ｇ）とを入れ、系内を窒素置換し、１８０℃に加熱して内容物を融解させた。そして、浴温を２００℃に上げ、約２時間加熱撹拌し、エステル化もしくはエステル交換反応を行わせた。次に、浴温を２６０℃に上げ、約１５分後に系内を０．５ｍｍＨｇまで減圧し、約３時間反応（重縮合反応）させた。反応終了後、窒素導入下で放冷し、内容物を取り出した。取り出した樹脂に最終ｐＨが６〜７になる適当量のアンモニア水（水は固形分２５％になる量）を加え、オートクレーブ中で１００℃、２時間加熱撹拌し、水系エマルジョン樹脂とした。
【００３８】
［塗料組成物における酸成分（ｂ）］
（Ｂ１）　ＨＦ
（Ｂ２）　Ｈ_２ＺｒＦ_６
（Ｂ３）　Ｈ_３ＰＯ_４
［塗料組成物における金属イオン（ｃ）供給物質］
（Ｃ１）　フッ化第二鉄
（Ｃ２）　硝酸第二鉄
（Ｃ３）　フッ化ジルコニウム
［塗料組成物における潤滑剤成分（ｄ）］
（Ｄ１）　フッ素系潤滑剤（住友３Ｍ社のダイニオンＰＴＦＥ５０３５（ＮＶＣ．６０％））
（Ｄ２）　二硫化モリブデン
（Ｄ３）　ポリオレフィン系ワックス（三井化学社のケミパールＷ９００（ＮＶＣ．４０％）
［塗料組成物における酸化剤（ｅ）］
（Ｅ１）　過酸化水素
上記各成分を下記の通り配合し、下記の実施例１〜１０及び比較例１〜５の塗料を作成した。
【００３９】
［実施例１の塗料］
上記（Ａ１）が１６７ｇ／Ｌ、上記（Ｂ１）が１ｇ／Ｌ、上記（Ｃ１）が３ｇ／Ｌ、上記（Ｄ２）が０．１５ｇ／Ｌ、上記（Ｅ１）が０．１ｇ／Ｌの水溶液
［実施例２の塗料］
上記（Ａ２）が１３３ｇ／Ｌ、上記（Ｂ１）が１ｇ／Ｌ、上記（Ｃ２）が３ｇ／Ｌ、上記（Ｄ１）が０．１ｇ／Ｌ、上記（Ｅ１）が０．１ｇ／Ｌの水溶液
［実施例３の塗料］
上記（Ａ３）が２００ｇ／Ｌ、上記（Ｂ２）が１ｇ／Ｌ、上記（Ｃ３）が２．５ｇ／Ｌ、上記（Ｄ３）が０．１ｇ／Ｌ、上記（Ｅ１）が０．１ｇ／Ｌの水溶液
［実施例４の塗料］
上記（Ａ４）が１００ｇ／Ｌ、上記（Ａ５）が１００ｇ／Ｌ、上記（Ｂ３）が２ｇ／Ｌ、上記（Ｃ２）が４ｇ／Ｌ、上記（Ｄ３）が０．２ｇ／Ｌの水溶液
［実施例５の塗料］
上記（Ａ６）が１６７ｇ／Ｌ、上記（Ｂ２）が１．５ｇ／Ｌ、上記（Ｃ１）が１．５ｇ／Ｌ、上記（Ｄ２）が０．２ｇ／Ｌ、上記（Ｅ１）が０．１ｇ／Ｌの水溶液
［実施例６の塗料］
上記（Ａ７）が１５０ｇ／Ｌ、上記（Ｂ１）が１ｇ／Ｌ、上記（Ｃ１）が３ｇ／Ｌ、上記（Ｄ１）が０．２ｇ／Ｌの水溶液
［実施例７の塗料］
上記（Ａ８）が１６７ｇ／Ｌ、上記（Ｂ１）が１ｇ／Ｌ、上記（Ｃ１）が０．１ｇ／Ｌ、上記（Ｄ２）が０．１５ｇ／Ｌ、上記（Ｅ１）が０．１ｇ／Ｌの水溶液
［実施例８の塗料］
上記（Ａ１１）が１１０ｇ／Ｌ、上記（Ｂ１）が１ｇ／Ｌ、上記（Ｃ１）が０．１ｇ／Ｌ、上記（Ｄ２）が０．１５ｇ／Ｌ、上記（Ｅ１）が０．１ｇ／Ｌの水溶液
［比較例１の塗料］
実施例１の塗料において（Ｂ１）を０ｇ／Ｌとした以外は同じ水溶液
［比較例２塗料］
実施例１の塗料において（Ｃ１）を０ｇ／Ｌとした以外は同じ水溶液
［比較例３塗料］
実施例１の塗料において（Ｄ２）を０ｇ／Ｌとした以外は同じ水溶液
［比較例４の塗料］
上記（Ａ３）が２００ｇ／Ｌ、上記（Ｃ１）が０．１ｇ／Ｌ、上記（Ｄ３）が０．２ｇ／Ｌの水溶液
［比較例５の塗料］
上記（Ａ３）が２００ｇ／Ｌ、上記（Ｃ３）が２．５ｇ／Ｌの水溶液
上記の塗料を用いて、次の脱脂、水洗１、水洗２、膜析出、水洗３、加熱乾燥の工程を順に経て膜を形成した。
【００４０】
［脱脂］
被処理材料がＨ，Ｊの場合には、日本パー力ライジング社のアルカリ脱脂剤ファインクリーナー４３６０（２０ｇ／Ｌ建浴）を用いて、６０℃の条件下で５分間浸漬する。
【００４１】
被処理材料がＩの場合には、日本パー力ライジング社の酸性脱脂パルクリーン５００（Ａ剤：４０ｇ／Ｌ，Ｂ剤：４０ｇ／Ｌ，Ｃ剤：０．５ｇ／Ｌ）を用いて、７５℃の条件下で１分間浸漬する。
【００４２】
［水洗１］
水道水を３０秒間スプレーした。
【００４３】
［水洗２］
純水を３０秒間スプレーした。
【００４４】
［膜析出］
実施例１〜１０および比較例１〜５の塗料（自己析出型表面処理液）に浸漬して皮膜を析出させた。
【００４５】
条件Ｍ：処理液温度が２２±２℃で、１８０秒間浸漬。処理液中で被処理物を上下に静かに揺動（１回／秒）した。
【００４６】
条件Ｎ：処理液温度が３０±２℃で、１２０秒間浸漬。１Ｌポリビーカー中の処理液（ＩＬ）をマグネチックスターラーで攪拌（チップ３０ｍｍ、速度２００ｒｐｍ）した。
【００４７】
［水洗３］
１０Ｌのステンレス容器に水道水を貯め、２Ｌ／分の流量補給でオーバーフローさせた水洗浴中に２分間浸漬し、被処理物を上下に静かに揺動（１回／秒）した。
【００４８】
［加熱乾燥］
熱風循環式乾燥炉（（株）タバイ製　パーフェクトオーブンＰＳ１１２）を用いて下記条件で行った。
【００４９】
条件Ｘ：８０℃で５分間加熱乾燥した後、炉内の温度を１０分間で１８０℃まで昇温させ、１８０℃に昇温してから更に５分間炉内（風速：２ｍ／分）に放置した。
【００５０】
条件Ｙ：１００℃で５分間加熱乾燥した後、炉内の温度を１０分間で２００℃まで昇温させ、２００℃に昇温してから更に５分間炉内（風速：２ｍ／分）に放置した。
【００５１】
条件Ｚ：１１０℃で２０分間加熱乾燥（風速：２ｍ／分）した。
【００５２】
処理条件の組み合わせを下記の表−１に示す。
【００５３】

上記のようにして得られた膜の特性を調べたので、その結果を表−２に示す。
【００５４】
［膜厚］
接触型電磁式膜厚計を用いて測定した。単位はμｍで表示した。
【００５５】
［耐蝕性］
塩水噴霧試験（ＪＩＳ−Ｚ２３７１）を５００ｈｒ行い、発錆面積を見積もって評価した。
【００５６】
◎：錆０％
○：錆５％未満
△：錆５％以上、２０％未満
×：錆２０％以上
［塗膜硬度］
鉛筆ひっかき試験方法（ＪＩＳ−Ｋ５４００）で評価し、鉛筆硬度で表示した。
【００５７】
［耐熱性］
２２０℃で３０分間放置し、前後の重量減少率で評価した。
【００５８】
○：重量減少１％未満
△：重量減少１％以上、５％未満
×：重量減少５％以上
又、耐熱試験（２２０℃，３０分間放置）後の供試材について、碁盤目テープ剥離試験（ｌｍｍマス、１００個）を行い、テープ剥離後の皮膜残存数を調べた。
【００５９】
◎：１００個
○：９０〜９９個
△：８０〜８９個
×：７９個以下
［潤滑性］
市販の潤滑試験機（新東科学製　トライボギア　ＨＥＩＤＯＮ−１４ＤＲ）を用いて評価を行った。処理した試験片と無処理の硬球（ＳＵＪ２　直径５ｍｍ）を組み合わせ、非潤滑条件にて焼き付けに至る荷重（表−２に表示した単位はｋｇｆ／２ｃｍ^２）を測定した。又、一定荷動５ｋｇｆ／２ｃｍ^２で焼き付けに至る摺動距離（表−２に表示した単位はｍ）を調べた。
【００６０】

【発明の効果】
鉄、亜鉛めっき、アルミニウム等の金属表面上に、簡易なプロセスで、摩擦係数が低く、耐摩耗性に優れ、安定した状態に維持できる水系の自己析出型塗料組成物が得られる。
この自己析出型塗料組成物は、複雑な形状物にも対応でき、特に摺動部材に対して適用された場合、このものは極めて優れた特長が奏される。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coating composition, a coating film forming method, and a material having a coating film. In particular, the present invention relates to a self-deposition paint composition having lubricity, a method for forming a coating film using the self-deposition paint composition having lubricity, and a material having a coating film formed from the self-deposition paint composition having lubricity. More specifically, lubrication applied to metals such as cold-rolled steel sheets, carbon steel sheets, silicon steel sheets, galvanized steel sheets, tin-plated steel sheets, castings, aluminum, and other sintered materials such as ferrite-based and Nb / Fe / B-based materials. The present invention relates to a self-precipitating coating composition having lubricity, a method for forming a coating film using a self-precipitating coating composition having lubricity, and a material having a coating film using the self-precipitating coating composition having lubricity. Although the shape of the target product may be any shape, the present invention can be applied to a complicated shape such as an automobile part such as a buckle base or a sliding part of a seat belt, or a home appliance part such as a compressor. Then, the self-deposition coating composition according to the present invention is brought into contact with the surface of a molded article to form a uniform coating film having excellent lubricity on the surface, a self-deposition coating composition, a coating film forming method, and a coating film And a material having:
[0002]
[Problems to be solved by the invention]
Sliding members used under non-lubricated conditions particularly require a reduction in the coefficient of friction on the sliding surface and an improvement in wear resistance. Conventionally, as a sliding member that performs sliding contact without lubrication, a sliding member coated with a resin in order to reduce a friction coefficient has been used.
[0003]
However, the conventional sliding members have not been sufficient in terms of reducing the coefficient of friction and improving the wear resistance.
[0004]
Therefore, a sliding member having a eutectoid plating in which a solid lubricant is dispersed on a sliding surface, for example, a Ni-P composite plating layer in which PTFE (polytetrafluoroethylene) particles are dispersed is used. Most of these are fired for the purpose of increasing the hardness of the plating layer. However, since calcination is usually performed in the atmosphere, there is a problem that a hard oxide layer is formed on the surface layer and the surface is discolored. Further, when the oxide layer is worn by initial wear due to sliding, hard wear powder is generated, and the wear powder (hard particles) generated with the increase in the number of sliding causes abrasive wear. Therefore, abrasion of the non-oxidized layer having a lower hardness than the oxidized layer is promoted, and the durability of the sliding member is deteriorated. In many cases, the partner metal is a soft alloy such as an aluminum alloy or a soft metal, and in such a case, there is a particularly serious problem.
[0005]
There is a solvent-based lubricating coating in which PTFE is blended with a binder resin called defric coating. However, this technique is difficult to apply to complicated shapes and small items, and is troublesome. Furthermore, since an organic solvent is used, it is not preferable from an environmental point of view.
[0006]
Therefore, the problem to be solved by the present invention is to solve the above problem. Among them, a water-based self-precipitating coating composition which has a low coefficient of friction, can be maintained in a stable state, can be used for sliding members having excellent wear resistance, and can be used for complicated shapes by a simple process. To provide.
[0007]
Another object of the present invention is to provide a method for forming a coating film using the above self-precipitating coating composition and a material having a coating film.
[0008]
[Means for Solving the Problems]
As a result of intensive studies by the present inventor to solve the above problems, a self-precipitating coating composition containing a water-dispersible or water-soluble organic resin, an acid component, a metal ion and a lubricant component When the metal surface was coated with an object, it was found that the object could be solved, and the present invention was completed.
[0009]
That is, the object is to provide one or more resins (a) selected from the group of water-dispersible and water-soluble organic resins,
An acid component (b);
A metal ion (c);
Lubricant component (d)
And a coating composition characterized by containing:
[0010]
Even if only one of the above components (a), (b), (c), and (d) is missing, the features of the present invention cannot be achieved. That is, as can be seen from the comparison between the examples and the comparative examples described later, all of the above (a), (b), (c), and (d) act synergistically, and for the first time, the unique features of the present invention. Is played. For example, even if the component (b) is simply missing, the sliding characteristics are significantly reduced. In addition, even if the component (d) is missing, the sliding characteristics are remarkably reduced. In addition, if the component (d) is lacking, scratches are likely to occur, and the water resistance of the coating film also decreases.
[0011]
Those containing an oxidizing agent (e) in addition to the components (a), (b), (c), and (d) further improve the sliding characteristics.
[0012]
The mixing ratio (weight ratio) of the components (a), (b), (c), and (d) is (a) :( b) :( c) :( d) = 100: 2 to 100: 4. ~ 1000: 10 ~ 2000 is preferred. A particularly desirable ratio is from 100: 10 to 60:20 to 100: 20 to 1000. When the oxidizing agent (e) is contained, the mixing ratio (weight ratio) of the oxidizing agent (e) is preferably (a) :( e) = 100: 0.2 to 60. A particularly desirable ratio is 100: 0.6 to 20.
[0013]
In the present invention, (d) may be any as long as it has a lubricating action. However, particularly preferred are one or more lubricants selected from the group consisting of fluororesins, polyolefin waxes, melamine cyanurate, and molybdenum disulfide.
[0014]
In the present invention, (a) may be any water-dispersible or water-soluble organic resin. However, preferred resins include one or more selected from the group consisting of acrylic resins, epoxy resins, urethane resins, polyester resins, and polyamide resins. Among them, a polyester resin is preferable.
[0015]
Among the above polyester resins, an anionic polyester resin obtained by a condensation reaction between a polyhydric alcohol and an acid is preferable.
[0016]
In particular, it is an anionic polyester resin, and the alcohol component constituting the polyester resin is an aliphatic polyhydric alcohol represented by the following general formula [I] and its derivative, and represented by the following general formula [II]. Polyester resins that are one or more selected from the group of aromatic polyhydric alcohols and derivatives thereof are preferred.
[0017]
General formula [I]

[However, R₁Is an alkylene group. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, the above-mentioned alkylene group containing a hydroxyl group and / or a halogen element. ]
General formula [II]

[However, R₂, R₃, R₄, R₅Are each independently selected from the group consisting of hydrogen and an alkyl group. In particular, hydrogen or a methyl group. m and n are integers of 1 or more, and 2 ≦ m + n ≦ 6. ]
Further, the polyester resin is an anionic polyester resin, wherein the acid component constituting the polyester resin is an aliphatic carboxylic acid or a derivative thereof represented by the following general formula [III], or an aromatic compound represented by the following general formula [IV]. Aromatic carboxylic acids and derivatives thereof, aromatic acid anhydrides and derivatives thereof represented by the following general formula [V], anhydrides of pyromellitic acid represented by the following general formula [VI] and derivatives thereof, and Polyester resins which are one or more selected from the group of naphthalene derivatives represented by the general formula [VII] are preferred.
[0018]
General formula [III]

[However, R₆Is an alkylene group. Among them, a linear or branched alkylene group having 1 to 30 carbon atoms, an unsaturated alkylene group having 1 to 30 carbon atoms, -COOX₃(X₃Is an alkylene group containing hydrogen or a linear or branched alkylene group having 1 to 10 carbon atoms) or an unsaturated alkylene group. X₁, X₂Are, independently of one another, a hydrogen or an alkyl group. Among them, it is hydrogen or an alkyl group having 1 to 10 carbon atoms. ]
General formula [IV]

[However, X₄, X₅Are, independently of one another, a hydrogen or an alkyl group. Among them, it is hydrogen or an alkyl group having 1 to 3 carbon atoms. Y₁, Y₂, Y₃, Y₄Are, independently of one another, hydrogen, -COOX₆(X₆Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. ), -SO₃Z₁(Z₁Is any one selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, and an ammonium group. ) Is any one selected from the group. Among them, hydrogen, -COOX₆(X₆Is an alkyl group having 1 to 3 carbon atoms, H, Li, Na, K, Ca, Ba or NH₄), -SO₃Z₁(Z₁Is H, Li, Na, K, Ca, Ba or NH₄). ]
General formula [V]

[However, Y₅, Y₆Are, independently of one another, hydrogen, -COOX₇(X₇Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. ), -SO₃Z₂(Z₂Is any one selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, and an ammonium group. ) Is any one selected from the group. Among them, hydrogen, -COOX₇(X₇Is an alkyl group having 1 to 3 carbon atoms, H, Li, Na, K, Ca, Ba or NH₄), -SO₃Z₂(Z₂Is H, Li, Na, K, Ca, Ba or NH₄). ]
General formula [VI]

General formula [VII]

[However, X₈, X₉Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. Among them, hydrogen, an alkyl group having 1 to 3 carbon atoms, Li, Na, K, Ca, Ba or NH₄It is. Y₇, Y₈, Y₉, Y₁₀Are, independently of one another, hydrogen, -COOX₈(X₈Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. ), -SO₃Z₃(Z₃Is any one selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, and an ammonium group. ) Is any one selected from the group. Among them, hydrogen, -COOX₈(X₈Is an alkyl group having 1 to 3 carbon atoms, H, Li, Na, K, Ca, Ba or NH₄), -SO₃Z₃(Z₃Is H, Li, Na, K, Ca, Ba or NH₄). ]
The oxidizing agent used in the present invention only needs to have an oxidizing action. For example, hydrogen peroxide, potassium permanganate, sodium nitrite and the like can be used. Among them, hydrogen peroxide is preferable.
[0019]
Further, the above-mentioned problem is solved by a method for forming a coating film, which comprises bringing a material into contact with the above-mentioned coating composition, depositing a coating film on the surface of the material, and then drying.
[0020]
Further, the above-mentioned object is achieved by a material having a coating film characterized by having a coating film of the above-mentioned coating composition.
[0021]
BEST MODE FOR CARRYING OUT THE INVENTION
The coating composition according to the present invention, particularly the self-deposition coating composition, comprises one or more resins (a) selected from the group of water-dispersible and water-soluble organic resins, and an acid component (b). ), A metal ion (c), and a lubricant component (d). In particular, one or more resins (a) selected from the group of water-dispersible and water-soluble organic resins, an acid component (b), a metal ion (c), and a lubricant component (d ) And an oxidizing agent (e). Further contains water. The preferred mixing ratio (weight ratio) of the components (a), (b), (c), and (d) is (a) :( b) :( c) :( d) = 100: 2-100 (particularly, 10 to 60): 4 to 1000 (particularly 20 to 100): 10 to 2000 (particularly 20 to 1000). A preferred compounding ratio (weight ratio) of the oxidizing agent (e) is (a) :( e) = 100: 0.2 to 60 (particularly, 0.6 to 20). The concentration of (a) is 5 to 550 g / L (particularly, 40 to 200 g / L) as a resin solid content concentration. The concentration of (b) is 0.1 to 5 g / L (particularly, 0.5 to 3 g / L). The concentration of (c) is 0.5 to 5 g / L (particularly, 0.75 to 3 g / L) as a nonvolatile component. The concentration of (d) is 0.5 to 100 g / L (particularly, 1 to 50 g / L) as a nonvolatile component.
[0022]
The acid component (b) used in the coating composition of the present invention may be an acid. Preferred acids are inorganic acids over organic acids. Among them, zirconium hydrogen fluoride (acid), titanium hydrogen fluoride (acid), hydrogen silicofluoride (acid), hydrogen borofluoride (acid), hydrogen fluoride (acid), phosphoric acid, nitric acid and the like can be mentioned. Particularly, hydrogen fluoride (acid) is preferable.
[0023]
The metal ion (c) used in the coating composition of the present invention may be a metal ion. Preferred metal ions are, for example, iron ions, cobalt ions, and zirconium ions. Any substance that can supply such metal ions may be used as long as it is stable in the liquid. Examples include ferric nitrate, ferric fluoride, ferrous phosphate, cobaltous nitrate, zirconium hydrofluoric acid, and the like. Zirconium hydrofluoric acid and ferric fluoride are particularly preferred.
[0024]
The lubricant component (d) used in the coating composition of the present invention may have any lubricating action. However, particularly preferred ones are selected from the group of fluorine resins such as polytetrafluoroethylene and polytrifluorochloroethylene, polyolefin waxes such as polyethylene wax and polypropylene wax, melamine cyanurate, and molybdenum disulfide. One or more lubricants. The lubricant component is water-dispersible.
[0025]
The oxidizing agent (e) used in the coating composition of the present invention only needs to have an oxidizing action. The oxidizing agent (e) enables the coating composition of the present invention to be used stably. That is, when an iron-based material is treated with the coating composition of the present invention, divalent iron ions are eluted in the treatment liquid, and the treatment liquid is destabilized. In such a case, if an oxidizing agent is contained, the generated divalent iron ions are quickly oxidized to trivalent ones, so that the treatment liquid is stabilized. Therefore, when only a metal such as aluminum which does not change its valence elutes, an oxidizing agent is not necessarily required. As the oxidizing agent (e), potassium permanganate, hydrogen peroxide, sodium nitrite and the like can be used. Among them, hydrogen peroxide is preferable.
[0026]
In the present invention, (a) may be any water-dispersible or water-soluble organic resin. However, preferred resins include one or more selected from the group consisting of acrylic resins, epoxy resins, urethane resins, polyester resins, and polyamide resins. In particular, a forced emulsification type organic polymer resin which is water-based using an emulsifier such as a surfactant, or a part of the structure is an anionic functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group. It is a modified water-soluble or self-emulsifying organic polymer resin. Of these, polyester resins, particularly anionic polyester resins, are preferred. Further, among the polyester resins, an anionic polyester resin obtained by a condensation reaction between a polyhydric alcohol and an acid.
[0027]
In particular, it is an anionic polyester resin, and the alcohol component constituting the polyester resin is an aliphatic polyhydric alcohol represented by the general formula [I] and a derivative thereof, and represented by the general formula [II]. Polyester resins that are one or more selected from the group of aromatic polyhydric alcohols and derivatives thereof are preferred. Incidentally, R in the general formula [I]₁Is an alkylene group. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, the above-mentioned alkylene group containing a hydroxyl group and / or a halogen element. Examples of the compound represented by the general formula [I] include ethylene glycol, neopentyl glycol, dibromoneopentyl glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, 3-methylpentanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl -1, 3-propanediol, glycerin, pentaerythritol, trimethylolpropane and the like. R in the general formula [II]₂, R₃, R₄, R₅Are each independently selected from the group consisting of hydrogen and an alkyl group. In particular, hydrogen or a methyl group. m and n are integers of 1 or more, and 2 ≦ m + n ≦ 6. Examples of the compound of the general formula [II] include bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct, and bisphenol F propylene oxide adduct.
[0028]
Further, the polyester resin is an anionic polyester resin, and the acid component constituting the polyester resin is an aliphatic carboxylic acid represented by the above general formula [III] and a derivative thereof; Aromatic carboxylic acids and derivatives thereof, aromatic acid anhydrides and derivatives thereof represented by the above general formula [V], anhydrides of pyromellitic acid represented by the above general formula [VI] and derivatives thereof, and Polyester resins which are one or more selected from the group of naphthalene derivatives represented by the general formula [VII] are preferred. R in the general formula [III]₆Is an alkylene group. Among them, a linear or branched alkylene group having 1 to 30 carbon atoms, an unsaturated alkylene group having 1 to 30 carbon atoms, -COOX₃(X₃Is an alkylene group containing hydrogen or a linear or branched alkylene group having 1 to 10 carbon atoms) or an unsaturated alkylene group. X₁, X₂Are, independently of one another, a hydrogen or an alkyl group. Among them, it is hydrogen or an alkyl group having 1 to 10 carbon atoms. Examples of the compound represented by the general formula [III] include succinic acid, methyl succinic acid, ethyl succinic acid, butyl succinic acid, monoethyl succinate, diethyl succinate, monobutyl succinate, dibutyl succinate, glutaric acid, and methyl glutarate. Acid, ethyl glutaric acid, butyl glutaric acid, glutaric acid monomethyl ester, glutaric acid dimethyl ester, glutaric acid monoethyl ester, glutaric acid diethyl ester, glutaric acid monobutyl ester, glutaric acid dibutyl ester, adipic acid, adipic acid monomethyl ester, Adipic acid dimethyl ester, adipic acid monoethyl ester, adipic acid dioctyl ester, sebacic acid, sebacic acid diethyl ester, sebacic acid dibutyl ester, sebacic acid dioctyles Le, tricarballylic acid, butene-tetracarboxylic acid. X in the general formula [IV]₄, X₅Are, independently of one another, a hydrogen or an alkyl group. Among them, it is hydrogen or an alkyl group having 1 to 3 carbon atoms. Y₁, Y₂, Y₃, Y₄Are, independently of one another, hydrogen, -COOX₆(X₆Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. ), -SO₃Z₁(Z₁Is any one selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, and an ammonium group. ) Is any one selected from the group. Among them, hydrogen, -COOX₆(X₆Is an alkyl group having 1 to 3 carbon atoms, H, Li, Na, K, Ca, Ba or NH₄), -SO₃Z₁(Z₁Is H, Li, Na, K, Ca, Ba or NH₄). ]. Examples of the compound of the general formula [IV] include terephthalic acid, monomethyl terephthalate, dimethyl terephthalate, monoethyl terephthalate, diethyl terephthalate, isophthalic acid, monomethyl isophthalate, dimethyl isophthalate, and isophthalic acid Examples include dimethyl-5-sulfonic acid sodium salt, trimellitic acid, trimellitic acid 1,4-dimethyl ester, pyromellitic acid tetramethyl ester, and pyromellitic acid tetraethyl ester. Y in general formula [V]₅, Y₆Are, independently of one another, hydrogen, -COOX₇(X₇Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. ), -SO₃Z₂(Z₂Is any one selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, and an ammonium group. ) Is any one selected from the group. Among them, hydrogen, -COOX₇(X₇Is an alkyl group having 1 to 3 carbon atoms, H, Li, Na, K, Ca, Ba or NH₄), -SO₃Z₂(Z₂Is H, Li, Na, K, Ca, Ba or NH₄). Examples of the compound of the general formula [V] include phthalic anhydride, trimellitic anhydride, and ethyl trimellitic anhydride. Examples of the compound of the general formula [VI] include pyromellitic anhydride. X in the general formula [VII]₈, X₉Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. Among them, hydrogen, an alkyl group having 1 to 3 carbon atoms, Li, Na, K, Ca, Ba or NH₄It is. Y₇, Y₈, Y₉, Y₁₀Are, independently of one another, hydrogen, -COOX₈(X₈Is any selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. ), -SO₃Z₃(Z₃Is any one selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, and an ammonium group. ) Is any one selected from the group. Among them, hydrogen, -COOX₈(X₈Is an alkyl group having 1 to 3 carbon atoms, H, Li, Na, K, Ca, Ba or NH₄), -SO₃Z₃(Z₃Is H, Li, Na, K, Ca, Ba or NH₄). Examples of the compound of the general formula [VII] include 1,2-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid dimethyl ester, 1,3-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid dimethyl ester, 1,4 -Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid dimethyl ester, 1,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid dimethyl ester, 1,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid dimethyl ester 1,7-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid dimethyl ester, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid dimethyl ester, 2,6-naphthalenedicarboxylic acid, 2,6-naphthalene Dicarboxylate Ester, 2,7-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid dimethyl ester.
[0029]
As the above-mentioned polyester resin, it is preferable to use, as an acid component thereof, one or more kinds selected from the group represented by the general formulas [IV], [V], and [VII]. By using such a polyester resin, corrosion resistance, adhesion and heat resistance are further improved. In particular, when the acid component accounts for 60 to 100 mol% of the total acid component, the effect is remarkable.
[0030]
In the general formulas [IV], [V] and [VII], Y₁~ Y₁₀At least one is a carboxyl group or a sulfonic group, that is, -COOX₆, -SO₃Z₁, -COOX₇, -SO₃Z₂, -COOX₈, -SO₃Z₃It is preferable that at least one selected from the group consisting of 1 to 40 mol% (particularly 2 to 30 mol%) is contained in all the acid components.
[0031]
The molecular weight of the water-dispersible or water-soluble organic resin (a) of the present invention may be any, but the effect of the present invention is particularly exhibited when the number average molecular weight is 2,000 to 50,000.
[0032]
Polyester resin used in the present invention, the synthesis method is not particularly limited, for example, using the above polyhydric alcohol and acid, further dibutyltin oxide, lead acetate, calcium acetate, if necessary, It is preferably obtained by performing an esterification or transesterification reaction and performing a polycondensation under a reduced pressure of 10 mmHg or less at 140 to 300 ° C. using a catalyst such as N-butyl titanate.
[0033]
The coating composition of the present invention may contain, as optional components other than the above components, for example, a film-forming aid such as trialkylpentanediol isobutyrate or an alkyl carbitol, for example, a colorant such as carbon black, phthalocyanine blue or Hansa Yellow. Can be contained to such an extent that the object of the present invention is not impaired.
[0034]
The coating film forming method of the present invention is a method in which a material is brought into contact with the above-mentioned coating composition, a coating film is deposited on the surface of the material, and then dried. Various methods can be adopted as the contact method. Immersion is preferred to form a uniform coating on a complex surface. The treatment temperature is preferably 5 to 50C, particularly 10 to 40C. If the treatment temperature is lower than 5 ° C., the deposition efficiency tends to be poor, and it is difficult to obtain a sufficient amount of coating film. Conversely, if the temperature exceeds 50 ° C., the reaction tends to be excessive, and the surface appearance of the coating film tends to decrease. The processing time is preferably from 10 to 500 seconds, especially from 20 to 300 seconds. If the treatment time is too short, the precipitation reaction tends to be insufficient. If the treatment time is too long, the dissolution of the object to be treated proceeds, and the metal ion concentration in the coating film tends to increase, which tends to cause poor appearance. Also, the corrosion resistance tends to decrease. The coating amount (coating film thickness) is not particularly limited, but is preferably in the range of 5 to 40 μm, particularly 10 to 25 μm in terms of film thickness after drying. If the thickness is too small, it is difficult to achieve the object of the present invention. Conversely, if the thickness is too large, blisters tend to occur in the coating film, and the appearance tends to decrease. For drying, any method may be used. For example, a hot-air circulating drying furnace using electricity or gas as a heat source, a heating furnace using far-infrared rays, high-frequency heating, induction heating, or the like can be used. The drying temperature is preferably from 60 to 300C, especially from 80 to 250C. If the drying temperature is too low, not only efficiency is poor but also film formation tends to be poor. And corrosion resistance and slidability deteriorate. Conversely, if the drying temperature is too high, the resin constituting the coating film may be thermally decomposed. In order to further improve the appearance of the coating film, it is effective to first dry the adhered water sufficiently at a temperature of 60 to 100 ° C., and then to heat the film at a temperature higher than the temperature in the above-mentioned step.
[0035]
The material having the coating film of the present invention has the above-mentioned film.
[0036]
Hereinafter, the present invention will be described with reference to specific examples and comparative examples.
[0037]
[Examples and Comparative Examples]
[Material to be treated]
The materials to be processed (plate materials of thickness 0.8 mm and 70 mm × 150 mm) H, I, and J used in Examples and Comparative Examples are as follows.
H SPCC cold rolled steel sheet
I AD4C aluminum casting
J {SC55} Iron casting
[Resin (a) in coating composition]
(A1) {Alcohol component composed of ethylene glycol (90 mol%) and trimethylolpropane (10 mol%), isophthalic acid (40 mol%), terephthalic acid (41 mol%), and sodium isophthalate dimethyl-5-sulfonate (2 mol%) ) And an anionic polyester resin obtained by a condensation reaction with an acid component composed of trimellitic anhydride (17 mol%) (solid content (NVC.) 30%)
(A2) {Alcohol component composed of ethylene glycol (70 mol%) and 1,4-butanediol (30 mol%), isophthalic acid (45 mol%), terephthalic acid (45 mol%), and sodium dimethyl-5-sulfonate isophthalate (3 mol%) and an anionic polyester resin (NVC. 30%) by a condensation reaction with an acid component composed of pyromellitic anhydride (7 mol%)
(A3) @Alcohol component composed of neopentyl glycol (30 mol%) and ethylene glycol (70 mol%), terephthalic acid (81 mol%), sodium dimethyl-5-isophthalate-5-sulfonate (2 mol%) and trimellitic acid (17 mol) %) And an anionic polyester resin (NVC. 30%) by a condensation reaction with an acid component consisting of
(A4) {Alcohol component composed of neopentyl glycol (33 mol%), ethylene glycol (44 mol%), 1,4-butanediol (23 mol%), sebacic acid (6 mol%), terephthalic acid (66 mol%) and tri Polyester resin (NVC. 30%) by condensation reaction of acid component consisting of melitic acid (22 mol%) and pyromellitic anhydride (6 mol%)
(A5) {Alcohol component composed of neopentyl glycol (20 mol%), ethylene glycol (70 mol%) and bisphenol A propylene oxide adduct (10 mol%), isophthalic acid (53 mol%), terephthalic acid (30 mol%), and isophthalic acid Polyester resin (NVC) by a condensation reaction of an acid component consisting of sodium dimethyl-5-sulfonate (2 mol%), trimellitic anhydride (5 mol%) and 2,6-naphthalenedicarboxylic acid (10 mol%) .30%)
(A6) {Alcohol component composed of ethylene glycol (70 mol%) and 1,4-butanediol (30 mol%), isophthalic acid (41 mol%), terephthalic acid (40 mol%), and sodium dimethyl-5-sulfonate isophthalate Anionic polyester resin (NVC. 30%) by condensation reaction of an acid component consisting of (2 mol%) and trimellitic acid (17 mol%)
(A7) Epoxy resin (Epilets 3522W60 (NVC. 60%) from Yuka Shell Epoxy)
(A8) Acrylic resin (Rohm & Hass Rhoplex WL-91 (NVC.41.5%))
(A9) Urethane resin
(A10) Polyamide resin
(A11) Vinylidene chloride resin (Daran SL143 (NVc. 55%) from WR Grace)
The polyester resin having the above composition was synthesized by the following method. In a 1000 mL round-bottom flask equipped with a Claisen tube and an air cooler, 1 mol of all acid components, 2 mol of all alcohol components, and a catalyst (0.25 g of calcium acetate, 0.1 g of N-butyl titanate) were placed. Was replaced with nitrogen and heated to 180 ° C. to melt the contents. Then, the bath temperature was raised to 200 ° C., and the mixture was heated and stirred for about 2 hours to carry out esterification or transesterification. Next, the bath temperature was raised to 260 ° C., and after about 15 minutes, the pressure in the system was reduced to 0.5 mmHg, and the reaction (polycondensation reaction) was performed for about 3 hours. After completion of the reaction, the mixture was allowed to cool under nitrogen introduction, and the contents were taken out. A suitable amount of aqueous ammonia (the amount of water becomes 25% of solid content) to give a final pH of 6 to 7 was added to the resin taken out, and the mixture was heated and stirred in an autoclave at 100 ° C for 2 hours to obtain an aqueous emulsion resin.
[0038]
[Acid component (b) in coating composition]
(B1) @HF
(B2) @H₂ZrF₆
(B3) @H₃PO₄
[Metal ion (c) supply substance in coating composition]
(C1) Ferric fluoride
(C2) Ferric nitrate
(C3) zirconium fluoride
[Lubricant component (d) in coating composition]
(D1) Fluorine-based lubricant (Dynion PTFE 5035 (NVC. 60%) from Sumitomo 3M)
(D2) Molybdenum disulfide
(D3) Polyolefin wax (Chemipearl W900 from Mitsui Chemicals, Inc. (NVC. 40%)
[Oxidizing agent (e) in coating composition]
(E1) Hydrogen peroxide
The above components were blended as described below to prepare coatings of Examples 1 to 10 and Comparative Examples 1 to 5 described below.
[0039]
[Paint of Example 1]
(A1) is an aqueous solution of 167 g / L, (B1) is 1 g / L, (C1) is 3 g / L, (D2) is 0.15 g / L, and (E1) is 0.1 g / L.
[Paint of Example 2]
(A2) 133 g / L, (B1) 1 g / L, (C2) 3 g / L, (D1) 0.1 g / L, (E1) 0.1 g / L
[Paint of Example 3]
(A3) is 200 g / L, (B2) is 1 g / L, (C3) is 2.5 g / L, (D3) is 0.1 g / L, and (E1) is 0.1 g / L. Aqueous solution
[Paint of Example 4]
(A4) 100 g / L, (A5) 100 g / L, (B3) 2 g / L, (C2) 4 g / L, (D3) 0.2 g / L
[Paint of Example 5]
(A6) is 167 g / L, (B2) is 1.5 g / L, (C1) is 1.5 g / L, (D2) is 0.2 g / L, and (E1) is 0.1 g. / L aqueous solution
[Paint of Example 6]
(A7) 150 g / L, (B1) 1 g / L, (C1) 3 g / L, (D1) 0.2 g / L aqueous solution
[Paint of Example 7]
(A8) is 167 g / L, (B1) is 1 g / L, (C1) is 0.1 g / L, (D2) is 0.15 g / L, and (E1) is 0.1 g / L. Aqueous solution
[Coating of Example 8]
(A11) is 110 g / L, (B1) is 1 g / L, (C1) is 0.1 g / L, (D2) is 0.15 g / L, and (E1) is 0.1 g / L. Aqueous solution
[Paint of Comparative Example 1]
Same aqueous solution except that (B1) was changed to 0 g / L in the paint of Example 1.
[Comparative Example 2 paint]
Same aqueous solution except that (C1) was 0 g / L in the paint of Example 1.
[Comparative Example 3 paint]
Same aqueous solution except that (D2) was set to 0 g / L in the paint of Example 1.
[Paint of Comparative Example 4]
(A3) 200 g / L, (C1) 0.1 g / L, (D3) 0.2 g / L aqueous solution
[Paint of Comparative Example 5]
(A3) 200 g / L, (C3) 2.5 g / L aqueous solution
Using the above paint, a film was formed through the following steps of degreasing, water washing 1, water washing 2, film deposition, water washing 3, and heat drying.
[0040]
[Degrease]
When the material to be treated is H or J, the material is immersed for 5 minutes at 60 ° C. using an alkaline degreaser Fine Cleaner 4360 (20 g / L bath) manufactured by Nippon Puriki Rising Co., Ltd.
[0041]
When the material to be treated is I, 75 g of acid defatted Pulclean 500 (A agent: 40 g / L, B agent: 40 g / L, C agent: 0.5 g / L) manufactured by Nippon Puriki Rising Co., Ltd. Immerse for 1 minute under the condition of ° C.
[0042]
[Washing 1]
Tap water was sprayed for 30 seconds.
[0043]
[Washing 2]
Pure water was sprayed for 30 seconds.
[0044]
[Film deposition]
The films were immersed in the coating materials of Examples 1 to 10 and Comparative Examples 1 to 5 (autodeposition type surface treatment liquids) to deposit films.
[0045]
Condition M: immersion for 180 seconds at a treatment liquid temperature of 22 ± 2 ° C. The object to be processed was gently rocked up and down (once / second) in the processing solution.
[0046]
Condition N: immersion for 120 seconds at a treatment liquid temperature of 30 ± 2 ° C. The treatment liquid (IL) in the 1 L polybeaker was stirred with a magnetic stirrer (tip 30 mm, speed 200 rpm).
[0047]
[Wash 3]
Tap water was stored in a 10 L stainless steel container, immersed for 2 minutes in a flushing bath overflowed at a flow rate of 2 L / min, and the object was gently rocked up and down (once / second).
[0048]
[Heat drying]
The drying was performed under the following conditions using a hot air circulation type drying furnace (Perfect Oven PS112 manufactured by Tabai Co., Ltd.).
[0049]
Condition X: After heating and drying at 80 ° C. for 5 minutes, the temperature in the furnace is raised to 180 ° C. in 10 minutes, and then raised to 180 ° C., and then left in the furnace (wind speed: 2 m / min) for another 5 minutes. did.
[0050]
Condition Y: After heating and drying at 100 ° C. for 5 minutes, the temperature in the furnace is raised to 200 ° C. in 10 minutes, and then raised to 200 ° C., and left in the furnace (wind speed: 2 m / min) for another 5 minutes. did.
[0051]
Condition Z: Heat drying at 110 ° C. for 20 minutes (wind speed: 2 m / min).
[0052]
Table 1 below shows combinations of the processing conditions.
[0053]

The characteristics of the film obtained as described above were examined, and the results are shown in Table-2.
[0054]
[Thickness]
It measured using the contact-type electromagnetic film thickness meter. The unit is expressed in μm.
[0055]
[Corrosion resistance]
The salt spray test (JIS-Z2371) was performed for 500 hours, and the rusting area was estimated and evaluated.
[0056]
：: 0% rust
：: less than 5% rust
△: 5% or more of rust, less than 20%
×: Rust 20% or more
[Coating film hardness]
It was evaluated by the pencil scratch test method (JIS-K5400) and indicated by pencil hardness.
[0057]
[Heat-resistant]
It was left at 220 ° C. for 30 minutes and evaluated by the weight loss rate before and after.
[0058]
：: less than 1% weight loss
Δ: Weight loss 1% or more and less than 5%
×: 5% or more weight loss
In addition, the test material after the heat resistance test (leaving at 220 ° C. for 30 minutes) was subjected to a cross-cut tape peel test (100 mm), and the number of remaining films after peeling the tape was examined.
[0059]
◎: 100 pieces
○: 90 to 99
Δ: 80 to 89
×: 79 or less
[Lubricity]
The evaluation was performed using a commercially available lubrication tester (Tribogear @ HEIDON-14DR manufactured by Shinto Kagaku). Combination of a treated test piece and an untreated hard sphere (SUJ2 5 mm in diameter), the load to bake under non-lubricated conditions (unit shown in Table-2 is kgf / 2cm²) Was measured. In addition, constant load 5kgf / 2cm²Then, the sliding distance (unit shown in Table 2 is m) until burning was examined.
[0060]

【The invention's effect】
An aqueous self-precipitating coating composition having a low friction coefficient, excellent abrasion resistance, and capable of maintaining a stable state can be obtained on a metal surface such as iron, zinc plating, and aluminum by a simple process.
This self-precipitating coating composition can cope with complicated shapes, and especially when applied to sliding members, it exhibits extremely excellent features.

Claims (11)

One or more resins (a) selected from the group of water-dispersible and water-soluble organic resins;
An acid component (b);
A metal ion (c);
Lubricant component (d)
And a coating composition comprising: The coating composition according to claim 1, further comprising an oxidizing agent (e). The resin (a): acid component (b): metal ion (c): lubricant component (d) = 100: 2 to 100: 4 to 1000: 10 to 2000 (weight ratio). 1 paint composition. 3. The coating composition according to claim 2, wherein the ratio of resin (a): oxidizing agent (e) = 100: 0.2 to 60 (weight ratio). The lubricant component (d) is one or more selected from the group consisting of a fluororesin, a polyolefin wax, melamine cyanurate, and molybdenum disulfide. The coating composition according to claim 4. The resin (a) is one or two or more resins selected from the group consisting of an acrylic resin, an epoxy resin, a urethane resin, a polyester resin, and a polyamide resin. Any coating composition. The coating composition according to any one of claims 1 to 6, wherein the resin (a) is an anionic polyester resin obtained by a condensation reaction between a polyhydric alcohol component and an acid component. The resin (a) is an anionic polyester resin, and the alcohol component constituting the polyester resin is an aliphatic polyhydric alcohol represented by the following general formula [I] and a derivative thereof; The coating composition according to any one of claims 1 to 7, wherein the coating composition is one or more selected from the group consisting of an aromatic polyhydric alcohol and a derivative thereof.
General formula [I]

[However, R ₁ is an alkylene group. ]
General formula [II]

[However, R ₂ , R ₃ , R ₄ , and R ₅ are each independently any one selected from the group consisting of hydrogen and an alkyl group, m and n are integers of 1 or more, and 2 ≦ m + n ≦ 6. ] The resin (a) is an anionic polyester resin, and the acid component constituting the polyester resin is an aliphatic carboxylic acid represented by the following general formula [III] and a derivative thereof, and a resin represented by the following general formula [IV]. Aromatic carboxylic acids and derivatives thereof, aromatic anhydrides and derivatives thereof represented by the following general formula [V], and pyromellitic anhydrides and derivatives thereof represented by the following general formula [VI] And one or more selected from the group of naphthalene derivatives represented by the following general formula [VII]: 9. .
General formula [III]

[However, R ₆ is an alkylene group, and X ₁ and X ₂ are each independently a hydrogen or an alkyl group. ]
General formula [IV]

[However, X ₄ and X ₅ are each independently hydrogen or an alkyl group, and Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently hydrogen or —COOX ₆ (X ₆ Is any one selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group.), -SO ₃ Z ₁ (Z ₁ is hydrogen, an alkali metal, an alkaline earth metal) , Or any one selected from the group of ammonium groups.). ]
General formula [V]

[However, Y ₅ and Y ₆ are each independently hydrogen, —COOX ₇ (X ₇ is any one selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. Or —SO ₃ Z ₂ (Z ₂ is any one selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, and an ammonium group). is there. ]
General formula [VI]

General formula [VII]

[However, X ₈ and X ₉ are any one selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. Y ₇ , Y ₈ , Y ₉ , and Y ₁₀ are each independently hydrogen, —COOX ₈ (X ₈ is selected from the group consisting of hydrogen, an alkyl group, an alkali metal, an alkaline earth metal, and an ammonium group. are _{either), -. SO 3 Z 3} (Z 3 is hydrogen, chosen from the group of alkali metals, alkaline earth metals, is either selected from the group of ammonium groups). Either. ] A method for forming a coating film, comprising bringing a material into contact with the coating composition according to any one of claims 1 to 9, depositing a coating film on the surface of the material, and then drying. A material having a coating film, characterized by having a coating film of the coating composition according to any one of claims 1 to 9.