JP3963683B2 - Aqueous surface treatment agent for plated metal plate, surface treated metal plate and method for producing the same - Google Patents
Aqueous surface treatment agent for plated metal plate, surface treated metal plate and method for producing the same Download PDFInfo
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- JP3963683B2 JP3963683B2 JP2001283822A JP2001283822A JP3963683B2 JP 3963683 B2 JP3963683 B2 JP 3963683B2 JP 2001283822 A JP2001283822 A JP 2001283822A JP 2001283822 A JP2001283822 A JP 2001283822A JP 3963683 B2 JP3963683 B2 JP 3963683B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Description
【０００１】
【発明の属する技術分野】
本発明は平面部耐食性、加工部耐食性、耐溶剤性、塗装密着性および溶接性のみならず耐傷つき性に優れた表面処理金属板と、それを得ることができる水系表面処理剤とその製造方法に関する。
【０００２】
【従来の技術】
従来から、家庭電化製品や建材等には、亜鉛や亜鉛系めっき鋼板が広く用いられている。これらの鋼板は、そのままでは、耐食性や上塗り塗装性が不十分であるために、クロメート化成処理やリン酸塩化成処理が施される。その後、プレス加工や折り曲げ加工等の成形加工や塗装等が施されることが多いが、使用される用途によっては、塗装を行わないでそのまま用いられる場合も少なくない。塗装を行わないで用いる場合には、クロメート化成処理鋼板と呼ばれる表面処理鋼板が多く適用されてきたが、成形加工や組み立ての際の指紋の付着や傷が付きやすい等の問題を有している。そこで、これらの問題点を解決するために、亜鉛系めっき鋼板の表面にクロメート処理後、厚さ１μｍ前後の有機樹脂層を形成させた有機複合鋼板が用いられる様になってきた。
【０００３】
この有機複合鋼板は、耐指紋性以外に、耐食性、耐溶剤性、上塗り塗装性など様々な皮膜性能が要求される。これらの性能のうち、近年、特に耐傷付き性等、表面外観品位に対する要求レベルが高くなってきている。これは家電業界において省工程、省コストの観点からプレス成形後塗装せずにそのまま適用されることに加えて、最近では無塗油あるいは速乾油でのプレス成形が行われるものが増えてきたためである。このようなプレス成形加工条件では鋼板の表面に金型との摺動によって傷が発生しやすくなる他、成形加工後の製品を運搬する際に、成形物どうし、あるいは成形物とそれを納めている容器（段ボール箱など）とが擦れあい、成形物の表面に傷が生じる。この様な傷付き部は、通常の有機被覆鋼板表面より耐食性が劣り、外観上傷が目立つため、品質の低下は免れない。
【０００４】
このため、耐食性、上塗り塗装性の他に耐傷付き性も考慮した表面処理鋼板に関する技術がいくつか提案されている。この様な技術としては、特開平３−１７１８９号公報、特公平６−１０４７９９号公報、特開平６−２９２８５９号公報に記載されている方法がある。
【０００５】
特開平３−１７１８９号公報には、ウレタン変性ポリオレフィン樹脂にフッ素系樹脂粒子およびシリカ粒子を配合した樹脂皮膜に関する方法が開示されている。この方法の特徴は、フッ素系樹脂粒子を使用することで傷付き部を保護するところにあるが、フッ素系樹脂粒子を水溶液中で均一に分散するためには、界面活性剤の使用が必要不可欠であり、この界面活性剤を使用しているために耐食性のレベルが全体的に低く、満足できる耐食性を得ることはできなかった。
【０００６】
特公平６−１０４７９９号公報には、ポリエステル系樹脂と架橋剤と平均分子量２０００〜８０００のポリエチレン系ワックスを含有する皮膜に関する方法が開示されている。この方法では、ベース樹脂にポリエステル樹脂を使用しているため、皮膜自体の耐加水分解性が不十分であり、満足できる耐食性を得ることができなかった。
【０００７】
特開平６−２９２８５９号公報には、分子内に活性水素を有するウレタン樹脂に常温架橋型エポキシ樹脂を含有させた樹脂に、球形ポリエチレンワックス粒子と鎖状コロイダルシリカを含有させた皮膜に関する方法が開示されている。コロイダルシリカは、固体表面に付着して摩擦係数を高くする増摩性と呼ばれる性質を有しており、この方法のような鎖状コロイダルシリカを使用した場合、コロイダルシリカ自体の構造性により耐傷付き性が低下する。このため、この方法では球状ポリエチレンワックスを配合しているが、乾燥温度が１００℃よりも低い温度であるため、ポリエチレンワックスが樹脂皮膜中に埋没してしまい、潤滑性が不十分となり、満足できる耐傷つき性を得ることができない。
【０００８】
【発明が解決しようとする課題】
本発明は、前記従来技術が抱える問題点を解決するためのものであり、平面部耐食性、耐溶剤性、上塗り塗装性および溶接性のみならず、加工部耐食性、耐傷つき性に優れた表面処理金属材とそれを得ることができる水系表面処理剤とその製造方法を提供する。
【０００９】
【課題を解決するための手段】
本発明者らは、前記従来技術が抱える課題を解決するための手段について鋭意検討を重ねた結果、特定モノマーから重合されるアクリル系樹脂、シリカを含有する水系表面処理剤を用いることによって、前記課題を解決できることを新たに見出し、本発明を完成するに至った。
【００１０】
即ち、本発明の要旨とするところは、
（１）アクリル系樹脂、水および固形分質量換算で５〜３５質量％のコロイダルシリカを含有し、前記アクリル系樹脂が、固形分質量換算で（ａ）下記一般式（１）で示される１５〜７６質量％の（メタ）アクリル酸エステル不飽和単量体と、（ｂ）分子内にカルボキシル基を有する２〜１０質量％のα，β−エチレン性不飽和単量体と、（ｃ）分子内に水酸基を有する２〜１０質量％のα，β−エチレン性不飽和単量体と、（ｄ）１０〜３０質量％のスチレンと、（ｅ）１０〜３０質量％のアクリロニトリルと、（ｆ）これら単量体と共重合可能である０〜１０質量％の不飽和単量体との重合反応により得られる重合体であって、かつガラス転移温度が０〜３０℃であることを特徴とする水系表面処理剤、
【００１１】
【化３】
（式中、Ｒ1は水素またはメチル基、Ｒ2は炭素数１〜８の直鎖もしくは分岐アルキル基）
（２）前記アクリル系樹脂中の（ｆ）が、グリシジル基、アジリジニル基、メチロール基及びシラノール基から選ばれる１種類以上の官能基を分子内に持つ不飽和単量体を含むものであることを特徴とする前記（１）に記載の水系表面処理剤、
（３）水系表面処理剤中にさらに固形分質量換算で３５質量％以下のポリオレフィンワックスディスパージョンを含有することを特徴とする前記（１）または（２）に記載の水系表面処理剤、
（４）めっき金属板上に、アクリル系樹脂と固形分換算で５〜３５質量％のコロイダルシリカを含有する有機無機複合皮膜を０．３〜５．０ｇ／ｍ2有し、前記アクリル系樹脂が固形分質量換算で（ａ）上記一般式（１）で示される１５〜７６質量％の（メタ）アクリル酸エステル不飽和単量体と、（ｂ）分子内にカルボキシル基を有する２〜１０質量％のα，β−エチレン性不飽和単量体と、（ｃ）分子内に水酸基を有する２〜１０質量％のα，β−エチレン性不飽和単量体と、（ｄ）１０〜３０質量％のスチレンと、（ｅ）１０〜３０質量％のアクリロニトリルと、（ｆ）これら単量体と共重合可能である０〜１０質量％の不飽和単量体によって構成された重合体で、かつガラス転移温度が０〜３０℃であることを特徴とする表面処理金属材、
（５）アクリル系樹脂を構成する（ｆ）が、グリシジル基、アジリジニル基、メチロール基及びシラノール基からなる群から選ばれる少なくとも１種の官能基を分子内に持つ不飽和単量体を含むものであることを特徴とする前記（４）に記載の表面処理金属材、
（６）有機無機複合皮膜中にさらに固形分質量換算で３５質量％以下のポリオレフィンワックスディスパージョンを含有することを特徴とする前記（４）または（５）に記載の表面処理金属材、
（７）めっき金属板もしくは下地処理を施しためっき金属板上に、前記（１）〜（３）のいずれか一つに記載の水系表面処理剤を、乾燥固形分質量換算で０．３〜５．０ｇ／ｍ2塗布した後、乾燥して有機無機複合皮膜を形成することを特徴とする表面処理金属材の製造方法、である。
【００１３】
【発明の実施の形態】
以下に本発明の構成を詳細に説明する。
本発明の第一の特徴は、ベースとなるアクリル樹脂が、エチレン性二重結合を有する数種類の単量体を共重合させて得られる共重合体であって、かつ適切なモノマー種および量から重合されて得られるものを使用することにある。なお、本発明に用いられる重合体の重合方法は特に限定するものではないが、懸濁重合及び乳化重合による方法が好ましい。
【００１４】
かかる単量体としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、桂皮酸、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アリルエーテル、３−ヒドロキシプロピル（メタ）アリルエーテル、４−ヒドロキシブチル（メタ）アリルエーテル、アリルアルコール、グリシジル（メタ）アクリレート、２−（１−アジリジニル）エチルアクリレート、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルグリシジルエーテル、イミノールメタクリレート、アクリロイルモルホリン、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−エトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、蟻酸ビニル、酢酸ビニル、酪酸ビニル、アクリル酸ビニル、スチレン、α−メチルスチレン、ｔ−ブチルスチレン、ビニルトルエン、（メタ）アクリロニトリル、ケイ皮酸ニトリル、（メタ）アクリロキシエチルフォスフェート、ビス−（メタ）アクリロキシエチルフォスフェート、（メタ）アクリロキシエチルフェニールアシッドフォスフェート、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル及びその異性体、（メタ）アクリル酸ブチル及びその異性体、（メタ）アクリル酸ペンチル及びその異性体、（メタ）アクリル酸ヘキシル及びその異性体など挙げられる。なお、ここで用いる「（メタ）アクリル」、「（メタ）アクリレート」、「（メタ）アリル」、および「（メタ）アクリロキシ」なる記載は、それぞれ、「アクリル」もしくは「メタクリル」、「アクリレート」もしくは「メタクリレート」、「アリル」もしくは「メタリル」、および「アクリロキシ」もしくは「メタクリロキシ」を意味するものであり、その他の同様の表記において同様である。
【００１５】
前記アクリル系樹脂は、固形分質量換算で（ａ）下記一般式（１）で示される１５〜７６質量％の（メタ）アクリル酸エステル不飽和単量体と、（ｂ）分子内にカルボキシル基を有する２〜１０質量％のα，β−エチレン性不飽和単量体と、（ｃ）分子内に水酸基を有する２〜１０質量％のα，β−エチレン性不飽和単量体と、（ｄ）１０〜３０質量％のスチレンと、（ｅ）１０〜３０質量％のアクリロニトリルと、（ｆ）これら単量体と共重合可能である０〜１０質量％の不飽和単量体との重合反応により得られる重合体を用いる必要がある。
【００１６】
【化４】
（式中、Ｒ1は水素またはメチル基、Ｒ2は炭素数１〜８の直鎖もしくは分岐アルキル基）
【００１８】
本発明に使用される（メタ）アクリル酸エステル不飽和単量体（ａ）は一般式（１）で表される。例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレートおよびその異性体、ｎ−ブチル（メタ）アクリレートおよびその異性体、ｎ−ペンチル（メタ）アクリレートおよびその異性体、ｎ−ヘキシル（メタ）アクリレートおよびその異性体、ｎ−ヘプチル（メタ）アクリレートおよびその異性体、ｎ−オクチル（メタ）アクリレートおよびその異性体、が挙げられ、その構造は一般式（１）で示される。
【００１９】
この様な不飽和単量体（ａ）の配合量は、アクリル系樹脂を構成する不飽和単量体（ａ）〜（ｆ）の合計１００質量％に対して、１５〜７６質量％、好ましくは３０〜７０質量％である。不飽和単量体（ａ）の配合量が１５質量％未満では得られる重合体皮膜の柔軟性が欠如するため、成膜時に皮膜にクラックが入り、十分な耐食性を得ることができない。一方、配合量が７６質量％を超える場合は耐溶剤性が劣るため好ましくない。
【００２０】
本発明に使用される分子内にカルボキシル基を有するα，β−エチレン性不飽和単量体（ｂ）としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、桂皮酸等が挙げられる。この様な不飽和単量体（ｂ）の配合量は、アクリル系樹脂を構成する不飽和単量体（ａ）〜（ｆ）の合計１００質量％に対して２〜１０質量％であり、より好ましくは２．５〜８質量％である。２質量％未満の場合鋼板に対する皮膜の密着性に劣り、１０質量％を超える場合は耐食性、耐水性に劣るため好ましくない。
【００２１】
本発明に使用される分子内に水酸基を有するα，β−エチレン性不飽和単量体（ｃ）としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アリルエーテル、３−ヒドロキシプロピル（メタ）アリルエーテル、４−ヒドロキシブチル（メタ）アリルエーテル、アリルアルコール、などが挙げられる。この様な不飽和単量体（ｃ）の配合量は、アクリル系樹脂を構成する不飽和単量体（ａ）〜（ｆ）の合計１００質量％に対して２〜１０質量％であり、より好ましくは２．５〜８質量％である。２質量％未満の場合鋼板に対する密着性に劣り、１０質量％を超える場合は耐食性、耐水性に劣るため好ましくない。
【００２２】
本発明で使用されるスチレン（ｄ）の配合量はアクリル系樹脂を構成する不飽和単量体（ａ）〜（ｆ）の合計１００質量％に対して１０〜３０質量％であり、より好ましくは１２〜２５質量％である。１０質量％未満の場合耐傷つき性に劣り、３０質量％を超える場合は加工部耐食性に劣るため好ましくない。
【００２３】
本発明で使用されるアクリロニトリル（ｅ）の配合量はアクリル系樹脂を構成する不飽和単量体（ａ）〜（ｆ）の合計１００質量％に対して１０〜３０質量％であり、より好ましくは１５〜２８質量％である。１０質量％未満の場合耐溶剤性に劣り、３０質量％を超える場合は耐水性、耐食性に劣るため好ましくない。
【００２４】
不飽和単量体（ｆ）は（ａ）〜（ｅ）と共重合可能な（ａ）〜（ｅ）以外の不飽和単量体であり、形成した皮膜の耐溶剤性、密着性、耐傷つき性等をさらに向上させる目的で、本発明の効果を損なわない限り使用しても構わない。
【００２５】
不飽和単量体（ｆ）としては、例えば、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、などのアミド基含有不飽和単量体、蟻酸ビニル、酢酸ビニル、酪酸ビニル、アクリル酸ビニル、などのエステル化不飽和単量体、スチレン、α−メチルスチレン、ｔ−ブチルスチレン、ビニルトルエン、などの芳香族不飽和単量体、（メタ）アクリロニトリル、ケイ皮酸ニトリル、などのシアノ化不飽和単量体、（メタ）アクリロキシエチルフォスフェート、ビス−（メタ）アクリロキシエチルフォスフェート、（メタ）アクリロキシエチルフェニールアシッドフォスフェート、などのリン酸基含有不飽和単量体、グリシジル（メタ）アクリレート、２−（１−アジリジニル）エチルアクリレート、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルグリシジルエーテル、イミノールメタクリレート、アクリロイルモルホリン、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−エトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、などの水酸基やカルボキシル基と反応しえる官能基を有する不飽和単量体などが挙げられる。この中の少なくとも１種は、水酸基やカルボキシル基と反応しえる官能基を有する不飽和単量体が好ましく、より好ましくは、グリシジル基、アジリジニル基、メチロール基、シラノール基を含有する不飽和単量体である。このような化合物としては、例えば、グリシジル（メタ）アクリレート、２−（１−アジリジニル）エチルアクリレート、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルグリシジルエーテル、イミノールメタクリレート、アクリロイルモルホリン、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−エトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミドがあげられる。不飽和単量体（ｆ）の配合量がアクリル系樹脂を構成する不飽和単量体（ａ）〜（ｆ）の合計１００質量％に対して１０質量％を越えた場合は重合体が増粘しやすくなり、水系表面処理剤の可使時間が短くなる他、均一な膜を形成することができず耐食性が劣化するため好ましくない。
【００２６】
本発明に使用されるアクリル系樹脂のガラス転移温度は０〜３０℃とするのが好ましい。アクリル系樹脂のガラス転移温度０℃未満では、耐ブロッキング性が劣るため好ましくない。一方、３０℃を超える場合は造膜性が低下し、加工部耐食性に劣るため好ましくない。
【００２７】
なお、本発明におけるガラス転移温度（Ｔｇ）とは、単量体成分の単独重合体のＴｇを用いて計算される値のことであり、次式によって求めることができる。
【００２８】
【数１】
ここで、Ｔｇは重合体のガラス転移温度、Ｔｇ1 、Ｔｇ2 、・・・Ｔｇn は各単量体成分の単独重合体のガラス転移温度、ｗ1 、ｗ2 、・・・ｗn は各単量体の質量分率を表し、ｗ1 ＋ｗ2 ＋・・・＋ｗn ＝１である。なお、各単量体の単独重合体のガラス転移温度はＪＩＳ Ｋ ７１２１による。
【００３０】
本発明の水系表面処理剤および表面処理金属材中のコロイダルシリカの配合量は固形分質量換算で５〜３５質量％である。コロイダルシリカの配合量が５質量％未満では耐食性に劣るため好ましくない。また、３５質量％を超える場合は、樹脂のバインダー効果が小さく、耐食性が低下するため好ましくない。なお、コロイダルシリカの粒径および種類については、本発明では特に限定するものではなく、例えば、日産化学工業（株）製スノーテックスＯ、Ｎ、Ｃや旭電化工業（株）製アデライトＡＴ−２０Ｎ、Ａ、Ｑなどの市販品が適用できる。
【００３１】
また、本発明では表面処理金属材の耐傷つき性を向上させるためにポリオレフィンワックスディスパージョンを水系表面処理剤および有機無機複合皮膜中に配合することができる。
【００３２】
ポリオレフィンワックスディスパージョンとしては、ポリエチレンワックス、ポリプロピレンワックス、ポリブチレンワックスあるいはこれらのワックスに極性基を付与した変性ポリオレフィンワックスを乳化剤濃度５％以下、好ましくは乳化剤を用いることなく水または水溶液に分散させたものを用いる。極性基は、触媒存在下で、ポリオレフィンワックスを酸素、オゾンあるいは硝酸等の酸化剤で酸化処理することによって得られる酸化ポリオレフィンワックス、あるいはアクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマール酸、イタコン酸等のエチレン性不飽和カルボン酸モノマーとポリオレフィンワックスとをベンゾール等で溶解し、重合開始剤（パーオキサイド、レドックス、重金属触媒等）と共に窒素気流中で加熱してグラフト化して得る。
【００３３】
ポリオレフィンワックスディスパージョンの質量平均粒径は０．１〜５．０μｍが好ましく、さらに好ましくは１．０〜４．０μｍのものが使用される。質量平均粒径が０．１μｍ未満の場合、凝集しやすく安定性に劣るため好ましくない。また、質量平均粒径が５．０μｍを越えると分散安定性に劣るため好ましくない。また、質量平均粒径と数平均粒径の比率としては、質量平均粒径／数平均粒径＜３の範囲内であることが好ましい。
【００３４】
これらのポリオレフィンワックスディスパージョンは、水系表面処理剤および有機無機複合皮膜中に固形分換算で３５質量％以下の範囲で配合させることが好ましい。３５質量％を越えると塗料密着性が劣化するため好ましくない。
【００３５】
本発明では金属板上に付着量として固形分質量換算で０．３〜５．０ｇ／ｍ2の有機無機複合皮膜を形成する。０．３ｍｇ／ｍ2未満の場合は耐傷つき性に劣り、加工部耐食性も良好でないため好ましくない。一方、５．０ｇ／ｍ2を超える場合は溶接性に劣るため好ましくない。
【００３６】
また、本発明で用いる水系表面処理剤は、被塗面に均一な皮膜を得るための濡れ性向上剤と呼ばれる界面活性剤や増粘剤、溶接性向上のための導電性物質、意匠性向上のための着色顔料や艶消し材料、造膜性向上のための溶剤等を、本発明の効果を損なわない限り添加しても構わない。
【００３７】
本発明において適用可能な下地めっき金属板としては、亜鉛めっき金属板、亜鉛−ニッケルめっき金属板、亜鉛−鉄めっき金属板、亜鉛−クロムめっき金属板、亜鉛−アルミニウムめっき金属板、亜鉛−チタンめっき金属板、亜鉛−マグネシウムめっき金属板、亜鉛−マンガンめっき金属板等の亜鉛系の電気めっき、溶融めっき、蒸着めっき鋼板、アルミニウムまたはアルミニウム合金めっき金属板、鉛または鉛合金めっき金属板、錫または錫合金めっき金属板、さらにはこれらのめっき層に少量の異種金属元素あるいは不純物としてコバルト、モリブデン、タングステン、ニッケル、チタン、クロム、アルミニウム、マンガン、鉄、マグネシウム、鉛、アンチモン、錫、銅、カドミウム、ヒ素等を含有したもの、または／およびシリカ、アルミナ、チタニア等の無機物を分散させたものが含まれる。さらには、以上のめっきと他の種類のめっき、例えば鉄めっき、鉄−りんめっき等と組み合わせた複層めっきにも適用可能である。
【００３８】
本発明で用いる水系表面処理剤は、かかるめっき金属板上に直接塗布することもできるが、本発明の効果を十分発揮させるためには、まず常法によるクロメート処理またはノンクロメート処理により下地皮膜を形成し、その上に、本発明の水系表面処理剤を塗布し樹脂皮膜を形成させるのが好ましい。
【００３９】
クロメート処理には、電解によってクロメート皮膜を形成する電解クロメート、素材との反応を利用して皮膜を形成させ、その後余分な処理液を洗い流す反応型クロメート、処理液を被塗物に塗布し水洗することなく乾燥して皮膜を形成させる塗布型クロメートがあり、本発明ではいずれの処理も採用することができる。
【００４０】
ノンクロメート処理には、電解によってノンクロメート皮膜を形成する電解型ノンクロメート、素材との反応を利用して皮膜を形成させ、その後、余分な処理液を洗い流す反応型ノンクロメート、処理液を被塗物に塗布し水洗することなく乾燥して皮膜を形成させる塗布型ノンクロメートがあり、本発明ではいずれの処理も採用することができる。
【００４１】
前記クロメート処理によって形成された下地めっき金属板上に本発明で用いる水系表面処理剤を塗布して、到達板温度６０〜２００℃で乾燥させることにより、有機無機複合皮膜を形成させる。塗布方法としては、常法、例えばロールコート法、浸漬法、静電塗布法等を用いることができる。
【００４２】
【実施例】
以下に本発明を、製造例、実施例及び比較例を用いて、具体的に説明する。これらの実施例は本発明の説明のために記載するものであり、本発明を何ら限定するものではない。
【００４３】
（１）金属材料
下記に示した市販の素材を供試材として使用した。
金属板は表１に示すものを用いた。
【００４４】
【表１】
（２）脱脂処理
上記の各金属板をシリケート系アルカリ脱脂剤のファインクリーナー４３３６（登録商標：日本パーカライジング（株）製）で脱脂処理した。なお、濃度２０ｇ／ｌ、温度６０℃にてスプレーで２分間処理した後、水道水で３０秒間スプレー洗浄した。
【００４６】
（３）下地処理
１）反応型クロメート処理（素材：ＥＧ、ＺＮ、ＧＩ）
ジンクロム３５７（登録商標：日本パーカライジング（株）製）を用い、液温度５０℃で５秒間スプレー処理を行い、水道水で洗浄後風乾して試験板を作製した。なお、目標クロム付着量は２０ｍｇ／ｍ2 である。
【００４７】
２）塗布型クロメート化成処理（素材：ＥＧ、ＺＮ、ＧＩ）
ジンクロム１３００ＡＮ（登録商標：日本パーカライジング（株）製）を用い、ロールコート法で塗布し、水洗することなく直ちに２００℃の雰囲気温度で１０秒間乾燥して試験板を作製した。なお、この際の到達板温度は１００℃、目標クロム付着量は４０ｍｇ／ｍ2 である。
【００４８】
３）電解型クロメート処理（素材：ＥＧ、ＺＮ、ＧＩ）
クロム酸５０ｇ／ｌ、硫酸０．３ｇ／ｌの浴中で電流密度１０Ａ／ｄｍ2で所定の電気量を通電して電解型クロメート処理を施し、水洗した後２００℃の雰囲気温度で８秒間乾燥して試験板を作製した。なお、この際の到達板温度は８０℃、目標クロム付着量は４０ｍｇ／ｍ2 である。
【００４９】
（４）水系表面処理剤の調製
表２に略号を示した、（ａ）（メタ）アクリル酸エステル不飽和単量体、（ｂ）分子内にカルボキシル基をもつα，β−エチレン性不飽和単量体、（ｃ）分子内に水酸基をもつα，β−エチレン性不飽和単量体、（ｄ）スチレン、（ｅ）アクリロニトリル、（ｆ）これらの単量体と共重合可能である不飽和単量体を、表３に示す比率で使用して、表３に示すＡ１〜Ａ３７の重合体を得た。表２の各単量体の名称の後のかっこ内の数値はそれらの単量体成分の単独重合体の℃を単位とするガラス転移温度（Ｔｇ）を示しており、表３の右端のＴｇは各重合体のガラス転移温度である。
室温にて、表３の重合体の水分散液、並びに表４および表５に示すコロイダルシリカおよびポリオレフィンワックスディスパージョンを表７〜１２に示す組成比率でプロペラ攪拌機を用いて攪拌しながら混合し、蒸留水を加えて固形分濃度を調整した。なお、表７〜１２に示した皮膜中固形分組成は、重合体とシリカとワックスの合計量が１００質量％であり、またこれらの表中のシリカとワックスの量は質量％で表したものである。
【００５０】
【表２】
【表３】
【表４】
【表５】
（５）水系表面処理剤の試験板への塗布方法
上記にて調製された各水系表面処理剤をバーコーターを用いて、上記各試験板に塗布し、２８０℃の雰囲気温度で１２秒間乾燥した。この際の到達板温は１３０℃、目標付着量は１．０ｍｇ／ｍ2 である。なお、付着量の調整は該組成物の固形分濃度およびバーコーターの種類を適宜変更することで行った。
【００５５】
（６）表面処理金属板の性能試験
１）平面部耐食性
JIS Z 2371に記載されている塩水噴霧試験方法に準じて、雰囲気温度35℃で、5％のNaCl水溶液を表面処理金属板試料に吹き付け、７２時間後の白錆発生率を測定した。以下の評価で、◎および○を良好と判定した。結果を表７〜１２に示す。
＜評価基準＞
◎：白錆発生面積率が全面積の ５％未満
○：白錆発生面積率が全面積の ５％以上１０％未満
△：白錆発生面積率が全面積の１０％以上３０％未満
×：白錆発生面積率が全面積の３０％以上
【００５６】
２）加工部耐食性
表面処理金属板試料に６ｍｍのエリクセン加工を施し、JIS Z 2371に記載されている塩水噴霧試験方法に準じて、雰囲気温度35℃で、5％のNaCl水溶液を塗装鋼板試料に吹き付け、４８時間後の加工部における白錆発生率を測定した。以下の評価で、◎および○を良好と判定した。結果を表７〜１２に示す。
＜評価基準＞
◎：白錆発生面積率 加工部面積の５％未満
○：白錆発生面積率 加工部面積の５％以上１０％未満
△：白錆発生面積率 加工部面積の１０％以上３０％未満
×：白錆発生面積率 加工部面積の３０％以上
【００５７】
３）耐溶剤性
表面処理金属板試料の表面を、ガーゼに溶剤（エタノールまたはＭＥＫ）を染み込ませて荷重５００ｇで往復１０回摺動させる。摺動後の外観を観察し、以下の評価で、◎および○を良好と判定した。結果を表７〜１２に示す。
＜評価基準＞
◎：皮膜の膨潤面積 摺動部全体の３０％未満
○：皮膜の膨潤面積 摺動部全体の３０％以上
△：皮膜の溶解面積 摺動部全体の３０％未満
×：皮膜の溶解面積 摺動部全体の３０％以上
【００５８】
４）塗装密着性
表面処理金属板試料に、バーコータを用いて、メラミンアルキッド樹脂塗料（関西ぺイント（株）製、アミラック＃1000）を、乾燥膜厚が２５μｍとなるように塗布し、炉温130℃で20分間焼き付けた。次に、１晩放置した後、沸騰水に３０分浸漬したものとそうでないものについて、７ｍｍエリクセン加工を施し、粘着テープ（ニチバン（株）：商品名セロテープ）を試験片のエリクセン加工部に張り付けた。粘着テープを速やかに斜め４５゜の方向に引っ張り、エリクセン加工部の外観を目視で評価した。以下の評価で、◎および○を良好と判定した。結果を表７〜１２に示す。
＜評価基準＞
◎ ： 剥離なし
○ ： 剥離面積率 ５％未満
△ ： 剥離面積率 ５％以上、５０％未満
× ： 剥離面積率 ５０％以上
【００５９】
５）耐プレスかじり性
表面処理金属板試料について角筒クランクプレス試験を行った。角筒クランクプレス試験の条件は、しわ押さえ圧６トンでサンプル（０．８×２２０×１８０ｍｍ）を６５×１１５ｍｍ、高さ５０ｍｍに成形して、成形後の摺動面を目視にて評価した。以下の評価で◎および○を良好と判定した。結果を表７〜１２に示す。
◎ ： 黒化なし
○ ： 摺動部の５０％未満の面積が黒化、摺動疵あり
△ ： 摺動部の５０％以上の面積が黒化、摺動疵あり
× ： 下地金属が露出、かじりあり
【００６０】
６）溶接性
表面処理金属板試料を表６に示す条件で連続スポット溶接試験を行い、安定してナゲット径が３ｍｍφ以上形成できる打点数を求めた。結果を表７〜１２に示す。
【００６１】
【表６】
＜評価基準＞
以下の評価で◎および○を良好と判定した。
◎ ： 打点数５０００以上
○ ： 打点数２５００以上 ５０００未満
△ ： 打点数１０００以上 ２５００未満
× ： 打点数１０００未満
【００６３】
【表７】
【表８】
【表９】
【表１０】
【表１１】
【表１２】
表７〜１２からも明らかなように、本発明の表面処理法によって得られる表面処理金属板はいずれも平面部耐食性、耐溶剤性、上塗り塗装性、溶接性のみならず、加工部耐食性、耐傷つき性に優れることが明らかである。
【００７０】
【発明の効果】
本発明の表面処理金属板は、平面部耐食性、耐溶剤性、上塗り塗装性、溶接性のみならず、加工部耐食性、耐傷つき性に優れたものであるため、家電、建材および自動車分野向け材料として好適で産業上の利用価値が極めて高い。また、かかる水系表面処理剤と製造方法により、平面部耐食性、耐溶剤性、上塗り塗装性、溶接性、加工部耐食性、耐傷つき性に優れた表面処理金属板を市場に提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a surface-treated metal plate excellent in scratch resistance as well as flat part corrosion resistance, processed part corrosion resistance, solvent resistance, paint adhesion and weldability, an aqueous surface treatment agent capable of obtaining the same, and a method for producing the same. About.
[0002]
[Prior art]
Conventionally, zinc and zinc-based plated steel sheets have been widely used for home appliances and building materials. These steel sheets are subjected to chromate chemical conversion treatment and phosphate chemical conversion treatment because of their insufficient corrosion resistance and top coatability. After that, molding processing such as press processing and bending processing, painting, and the like are often performed. However, depending on the application to be used, it is often used as it is without coating. When used without coating, a surface-treated steel sheet called a chromate conversion-treated steel sheet has been applied in many cases, but it has problems such as being susceptible to fingerprint attachment and scratches during molding and assembly. . Accordingly, in order to solve these problems, an organic composite steel sheet in which an organic resin layer having a thickness of about 1 μm is formed on the surface of a zinc-based plated steel sheet after the chromate treatment has been used.
[0003]
This organic composite steel sheet is required to have various film properties such as corrosion resistance, solvent resistance, and top coatability in addition to fingerprint resistance. Among these performances, in recent years, the required level of surface appearance quality such as scratch resistance has been increasing. In the home appliance industry, in addition to being applied as it is without coating after press molding from the viewpoint of process and cost savings, recently there has been an increase in press molding with no coating or quick-drying oil. It is. Under such press forming conditions, the surface of the steel sheet is likely to be damaged by sliding with the mold, and when carrying the product after forming, The container (such as a cardboard box) rubs against each other, and the surface of the molded product is damaged. Such a scratched part is inferior in corrosion resistance to the surface of a normal organic coated steel sheet, and scratches are conspicuous in appearance.
[0004]
For this reason, several techniques relating to surface-treated steel sheets that take into consideration scratch resistance in addition to corrosion resistance and top coatability have been proposed. As such a technique, there are methods described in JP-A-3-17189, JP-B-6-104799, and JP-A-6-292859.
[0005]
Japanese Patent Application Laid-Open No. 3-17189 discloses a method relating to a resin film in which fluorine-modified resin particles and silica particles are blended with urethane-modified polyolefin resin. The feature of this method is that the scratched part is protected by using fluorine resin particles, but in order to disperse the fluorine resin particles uniformly in an aqueous solution, the use of a surfactant is indispensable. Since this surfactant was used, the level of corrosion resistance was low overall, and satisfactory corrosion resistance could not be obtained.
[0006]
Japanese Patent Publication No. 6-104799 discloses a method relating to a film containing a polyester resin, a crosslinking agent, and a polyethylene wax having an average molecular weight of 2000 to 8000. In this method, since a polyester resin is used as the base resin, the hydrolysis resistance of the coating itself is insufficient and satisfactory corrosion resistance cannot be obtained.
[0007]
Japanese Patent Application Laid-Open No. Hei 6-292859 discloses a method relating to a film in which spherical polyethylene wax particles and chain colloidal silica are contained in a resin in which a room temperature crosslinking epoxy resin is contained in a urethane resin having active hydrogen in the molecule. Has been. Colloidal silica has a property called lubricity that adheres to a solid surface and increases the coefficient of friction. When chain colloidal silica is used like this method, it is scratched by the structure of colloidal silica itself. Sexuality decreases. For this reason, spherical polyethylene wax is blended in this method, but since the drying temperature is lower than 100 ° C., the polyethylene wax is buried in the resin film, resulting in insufficient lubricity and satisfactory. Scratch resistance cannot be obtained.
[0008]
[Problems to be solved by the invention]
The present invention is for solving the problems of the prior art described above, and is a surface treatment excellent in not only flat part corrosion resistance, solvent resistance, top coatability and weldability, but also processed part corrosion resistance and scratch resistance. Provided are a metal material, an aqueous surface treatment agent capable of obtaining the metal material, and a method for producing the same.
[0009]
[Means for Solving the Problems]
As a result of intensive studies on the means for solving the problems of the conventional techniques, the present inventors have used an acrylic resin polymerized from a specific monomer, and an aqueous surface treatment agent containing silica. The inventors have newly found that the problem can be solved, and have completed the present invention.
[0010]
That is, the gist of the present invention is that
(1) It contains 15 to 35 mass% colloidal silica in terms of acrylic resin, water and solid content, and the acrylic resin is represented by (a) the following general formula (1) in terms of solid content: 15 -76 mass% (meth) acrylic acid ester unsaturated monomer, (b) 2-10 mass% α, β-ethylenically unsaturated monomer having a carboxyl group in the molecule, (c) 2 to 10% by mass of an α, β-ethylenically unsaturated monomer having a hydroxyl group in the molecule, (d) 10 to 30% by mass of styrene, (e) 10 to 30% by mass of acrylonitrile, f) A polymer obtained by a polymerization reaction with 0 to 10% by weight of an unsaturated monomer copolymerizable with these monomers, and having a glass transition temperature of 0 to 30 ° C. An aqueous surface treatment agent,
[0011]
[Chemical 3]
(Wherein R 1 Is hydrogen or methyl group, R 2 Is a linear or branched alkyl group having 1 to 8 carbon atoms)
(2) The (f) in the acrylic resin contains an unsaturated monomer having in the molecule one or more functional groups selected from a glycidyl group, an aziridinyl group, a methylol group, and a silanol group. The aqueous surface treating agent according to (1),
(3) The aqueous surface treatment agent according to (1) or (2) above, wherein the aqueous surface treatment agent further contains a polyolefin wax dispersion of 35% by mass or less in terms of solid content.
(4) 0.3-5.0 g / m of an organic-inorganic composite film containing 5-35% by mass of colloidal silica in terms of solid content and an acrylic resin on the plated metal plate. 2 And (a) 15 to 76% by mass of (meth) acrylate unsaturated monomer represented by the above general formula (1) in terms of solid content, and (b) in the molecule 2 to 10% by mass of an α, β-ethylenically unsaturated monomer having a carboxyl group, and (c) 2 to 10% by mass of an α, β-ethylenically unsaturated monomer having a hydroxyl group in the molecule; (D) 10-30% by weight of styrene, (e) 10-30% by weight of acrylonitrile, and (f) 0-10% by weight of unsaturated monomer copolymerizable with these monomers. A surface-treated metal material characterized in that it is a composed polymer and has a glass transition temperature of 0 to 30 ° C.,
(5) (f) constituting the acrylic resin contains an unsaturated monomer having at least one functional group selected from the group consisting of a glycidyl group, an aziridinyl group, a methylol group, and a silanol group in the molecule. The surface-treated metal material as described in (4) above,
(6) The surface-treated metal material according to (4) or (5) above, wherein the organic-inorganic composite film further contains a polyolefin wax dispersion of 35% by mass or less in terms of solid content.
(7) The aqueous surface treatment agent according to any one of (1) to (3) above is 0.3 to 0.3 in terms of dry solid content on the plated metal plate or the plated metal plate subjected to the base treatment. 5.0 g / m 2 A method for producing a surface-treated metal material, which is characterized by forming an organic-inorganic composite film after coating and drying.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The configuration of the present invention will be described in detail below.
The first feature of the present invention is that the base acrylic resin is a copolymer obtained by copolymerizing several types of monomers having an ethylenic double bond, and from an appropriate monomer species and amount. It is to use what is obtained by polymerization. In addition, the polymerization method of the polymer used in the present invention is not particularly limited, but a suspension polymerization method and an emulsion polymerization method are preferable.
[0014]
Examples of such monomers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl. (Meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) allyl ether , 3-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, allyl alcohol, glycidyl (meth) acrylate, 2- (1-aziridinyl) ethyl acrylate, vinyltrimethoxysilane, vinyltriethoxy Silane, allyl glycidyl ether, iminol methacrylate, acryloylmorpholine, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, (meta ) Acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, vinyl formate, vinyl acetate, vinyl butyrate, vinyl acrylate, styrene, α-methylstyrene , T-butylstyrene, vinyltoluene, (meth) acrylonitrile, cinnamate nitrile, (meth) acryloxyethyl phosphate, bis- (meth) acryloxyethyl phosphate, (meth) acrylo Xylethyl phenyl acid phosphate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and its isomer, butyl (meth) acrylate and its isomer, pentyl (meth) acrylate and Examples thereof include hexyl (meth) acrylate and isomers thereof. As used herein, “(meth) acryl”, “(meth) acrylate”, “(meth) allyl”, and “(meth) acryloxy” are “acryl”, “methacryl”, and “acrylate”, respectively. Alternatively, it means “methacrylate”, “allyl” or “methallyl”, and “acryloxy” or “methacryloxy”, and the same applies to other similar notations.
[0015]
The acrylic resin comprises (a) 15 to 76% by mass of a (meth) acrylate unsaturated monomer represented by the following general formula (1) in terms of solid content, and (b) a carboxyl group in the molecule. 2 to 10% by mass of an α, β-ethylenically unsaturated monomer having (c) 2-10% by mass of an α, β-ethylenically unsaturated monomer having a hydroxyl group in the molecule; d) Polymerization of 10-30% by weight of styrene, (e) 10-30% by weight of acrylonitrile, and (f) 0-10% by weight of unsaturated monomer copolymerizable with these monomers. It is necessary to use a polymer obtained by the reaction.
[0016]
[Formula 4]
(Wherein R 1 Is hydrogen or methyl group, R 2 Is a linear or branched alkyl group having 1 to 8 carbon atoms)
[0018]
The (meth) acrylate unsaturated monomer (a) used in the present invention is represented by the general formula (1). For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and its isomer, n-butyl (meth) acrylate and its isomer, n-pentyl (meth) acrylate and its isomer, n-hexyl (meth) acrylate and its isomer, n-heptyl (meth) acrylate and its isomer, n-octyl (meth) acrylate and its isomer, and the structure thereof is represented by the general formula (1). It is.
[0019]
The blending amount of such unsaturated monomer (a) is 15 to 76% by mass, preferably 100% by mass of the total of unsaturated monomers (a) to (f) constituting the acrylic resin. Is 30-70 mass%. If the blending amount of the unsaturated monomer (a) is less than 15% by mass, the resulting polymer film lacks flexibility, so that the film is cracked during film formation and sufficient corrosion resistance cannot be obtained. On the other hand, when the blending amount exceeds 76% by mass, the solvent resistance is poor, which is not preferable.
[0020]
Examples of the α, β-ethylenically unsaturated monomer (b) having a carboxyl group in the molecule used in the present invention include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and crotonic acid. , Itaconic acid, citraconic acid, cinnamic acid and the like. The blending amount of such an unsaturated monomer (b) is 2 to 10% by mass with respect to a total of 100% by mass of the unsaturated monomers (a) to (f) constituting the acrylic resin, More preferably, it is 2.5-8 mass%. If it is less than 2% by mass, the adhesion of the film to the steel sheet is inferior. If it exceeds 10% by mass, the corrosion resistance and water resistance are inferior.
[0021]
Examples of the α, β-ethylenically unsaturated monomer (c) having a hydroxyl group in the molecule used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl ( (Meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, allyl alcohol, etc. are mentioned. The blending amount of such an unsaturated monomer (c) is 2 to 10% by mass with respect to a total of 100% by mass of the unsaturated monomers (a) to (f) constituting the acrylic resin, More preferably, it is 2.5-8 mass%. When the amount is less than 2% by mass, the adhesion to the steel sheet is inferior, and when it exceeds 10% by mass, the corrosion resistance and water resistance are inferior.
[0022]
The blending amount of styrene (d) used in the present invention is 10-30% by mass, more preferably 10% by mass to 100% by mass of the unsaturated monomers (a)-(f) constituting the acrylic resin. Is 12 to 25% by mass. If it is less than 10% by mass, the scratch resistance is poor, and if it exceeds 30% by mass, the corrosion resistance of the processed part is inferior.
[0023]
The amount of acrylonitrile (e) used in the present invention is 10 to 30% by mass, more preferably 10% to 30% by mass with respect to 100% by mass of the unsaturated monomers (a) to (f) constituting the acrylic resin. Is 15 to 28% by mass. If it is less than 10% by mass, the solvent resistance is inferior, and if it exceeds 30% by mass, the water resistance and corrosion resistance are inferior.
[0024]
The unsaturated monomer (f) is an unsaturated monomer other than (a) to (e) copolymerizable with (a) to (e), and the solvent resistance, adhesion, and resistance of the formed film. For the purpose of further improving scratchability and the like, it may be used as long as the effects of the present invention are not impaired.
[0025]
Examples of the unsaturated monomer (f) include amide groups such as (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-dimethylaminopropyl (meth) acrylamide. Contained unsaturated monomer, esterified unsaturated monomer such as vinyl formate, vinyl acetate, vinyl butyrate, vinyl acrylate, aromatic aromatics such as styrene, α-methylstyrene, t-butylstyrene, vinyltoluene Saturated monomers, cyanated unsaturated monomers such as (meth) acrylonitrile, cinnamic nitrile, (meth) acryloxyethyl phosphate, bis- (meth) acryloxyethyl phosphate, (meth) acryloxy Phosphoric acid group-containing unsaturated monomers such as ethyl phenyl acid phosphate, glycidyl (meth) a Lilate, 2- (1-aziridinyl) ethyl acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, allyl glycidyl ether, iminol methacrylate, acryloylmorpholine, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, Examples thereof include unsaturated monomers having a functional group capable of reacting with a hydroxyl group or a carboxyl group such as N-ethoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide. At least one of these is preferably an unsaturated monomer having a functional group capable of reacting with a hydroxyl group or a carboxyl group, and more preferably an unsaturated monomer containing a glycidyl group, an aziridinyl group, a methylol group, or a silanol group. Is the body. Examples of such compounds include glycidyl (meth) acrylate, 2- (1-aziridinyl) ethyl acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, allylglycidyl ether, iminol methacrylate, acryloylmorpholine, N-methylol ( Examples include meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. When the blending amount of the unsaturated monomer (f) exceeds 10% by mass with respect to the total of 100% by mass of the unsaturated monomers (a) to (f) constituting the acrylic resin, the polymer increases. This is not preferable because it tends to be viscous and the pot life of the water-based surface treatment agent is shortened, and a uniform film cannot be formed and the corrosion resistance deteriorates.
[0026]
The glass transition temperature of the acrylic resin used in the present invention is preferably 0 to 30 ° C. If the glass transition temperature of the acrylic resin is less than 0 ° C., the blocking resistance is inferior, which is not preferable. On the other hand, when it exceeds 30 ° C., the film forming property is lowered, and the corrosion resistance of the processed part is inferior.
[0027]
In addition, the glass transition temperature (Tg) in this invention is a value calculated using Tg of the homopolymer of a monomer component, and can be calculated | required by following Formula.
[0028]
[Expression 1]
Where Tg is the glass transition temperature of the polymer, Tg 1 , Tg 2 ... Tg n Is the glass transition temperature of the homopolymer of each monomer component, w 1 , W 2 ... w n Represents the mass fraction of each monomer and w 1 + W 2 + ... + w n = 1. In addition, the glass transition temperature of the homopolymer of each monomer is based on JISK7121.
[0030]
The compounding amount of the colloidal silica in the aqueous surface treatment agent and the surface-treated metal material of the present invention is 5 to 35% by mass in terms of solid content. If the amount of colloidal silica is less than 5% by mass, the corrosion resistance is poor, which is not preferable. Moreover, when it exceeds 35 mass%, since the binder effect of resin is small and corrosion resistance falls, it is unpreferable. The particle size and type of colloidal silica are not particularly limited in the present invention. For example, SNOWTEX O, N, C manufactured by Nissan Chemical Industries, Ltd. or Adelite AT-20N manufactured by Asahi Denka Kogyo Co., Ltd. Commercial products such as A, Q, etc. are applicable.
[0031]
In the present invention, in order to improve the scratch resistance of the surface-treated metal material, a polyolefin wax dispersion can be blended in the aqueous surface treatment agent and the organic-inorganic composite film.
[0032]
As the polyolefin wax dispersion, polyethylene wax, polypropylene wax, polybutylene wax, or modified polyolefin wax having polar groups added to these waxes was dispersed in water or an aqueous solution without using an emulsifier, preferably without using an emulsifier. Use things. The polar group is an oxidized polyolefin wax obtained by oxidizing a polyolefin wax with an oxidizing agent such as oxygen, ozone or nitric acid in the presence of a catalyst, or acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itacone. An ethylenically unsaturated carboxylic acid monomer such as an acid and a polyolefin wax are dissolved in benzol or the like and grafted by heating in a nitrogen stream together with a polymerization initiator (peroxide, redox, heavy metal catalyst, etc.).
[0033]
The polyolefin wax dispersion preferably has a mass average particle size of 0.1 to 5.0 μm, more preferably 1.0 to 4.0 μm. A mass average particle size of less than 0.1 μm is not preferred because it tends to aggregate and is inferior in stability. Further, if the mass average particle diameter exceeds 5.0 μm, it is not preferable because the dispersion stability is poor. The ratio of the mass average particle size to the number average particle size is preferably in the range of mass average particle size / number average particle size <3.
[0034]
These polyolefin wax dispersions are preferably blended in the water-based surface treatment agent and the organic-inorganic composite film in a range of 35% by mass or less in terms of solid content. If it exceeds 35% by mass, the paint adhesion deteriorates, which is not preferable.
[0035]
In the present invention, the amount of adhesion on the metal plate is 0.3 to 5.0 g / m in terms of solid mass. 2 An organic-inorganic composite film is formed. 0.3 mg / m 2 If it is less than 1, the scratch resistance is inferior, and the corrosion resistance of the processed part is not good. On the other hand, 5.0 g / m 2 If the ratio exceeds 1, the weldability is inferior.
[0036]
In addition, the water-based surface treatment agent used in the present invention is a surfactant or thickener called a wettability improver for obtaining a uniform film on the surface to be coated, a conductive material for improving weldability, and a design improvement Coloring pigments, matting materials, solvents for improving film-forming properties, etc. may be added as long as the effects of the present invention are not impaired.
[0037]
As the base plating metal plate applicable in the present invention, zinc plating metal plate, zinc-nickel plating metal plate, zinc-iron plating metal plate, zinc-chromium plating metal plate, zinc-aluminum plating metal plate, zinc-titanium plating Zinc-based electroplating such as metal plate, zinc-magnesium plating metal plate, zinc-manganese plating metal plate, hot dipping, vapor deposition plating steel plate, aluminum or aluminum alloy plating metal plate, lead or lead alloy plating metal plate, tin or tin Alloy plating metal plates, and also in these plating layers as a small amount of different metal elements or impurities cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, antimony, tin, copper, cadmium, Containing arsenic, etc., and / or silica, Mina, include those obtained by dispersing an inorganic material titania. Furthermore, the present invention can also be applied to multilayer plating in combination with the above plating and other types of plating such as iron plating and iron-phosphorus plating.
[0038]
The water-based surface treatment agent used in the present invention can be directly applied onto such a plated metal plate. However, in order to fully demonstrate the effects of the present invention, first, a base film is formed by a chromate treatment or a non-chromate treatment by a conventional method. It is preferable to form and form the resin film by applying the aqueous surface treating agent of the present invention thereon.
[0039]
For chromate treatment, electrolytic chromate that forms a chromate film by electrolysis, a film is formed by utilizing the reaction with the material, and then the reactive chromate that rinses away the excess treatment liquid, and then the treatment liquid is applied to the substrate and washed with water. There is a coating type chromate that forms a film without drying, and any treatment can be employed in the present invention.
[0040]
For non-chromate treatment, electrolytic non-chromate that forms a non-chromate film by electrolysis, a film is formed by utilizing the reaction with the material, and then reactive non-chromate that rinses off the excess treatment liquid and treatment liquid is applied. There is a coating type non-chromate which is applied to an object and dried to form a film without washing, and any treatment can be employed in the present invention.
[0041]
The organic-inorganic composite film is formed by applying the aqueous surface treatment agent used in the present invention on the base plating metal plate formed by the chromate treatment and drying it at a reaching plate temperature of 60 to 200 ° C. As a coating method, a conventional method such as a roll coating method, a dipping method, an electrostatic coating method, or the like can be used.
[0042]
【Example】
Hereinafter, the present invention will be specifically described using production examples, examples, and comparative examples. These examples are described for the purpose of illustrating the present invention and are not intended to limit the present invention in any way.
[0043]
(1) Metal material
The commercially available materials shown below were used as test materials.
The metal plate shown in Table 1 was used.
[0044]
[Table 1]
(2) Degreasing treatment
Each of the metal plates was degreased with a fine cleaner 4336 (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.), a silicate alkaline degreasing agent. In addition, after processing for 2 minutes by spraying at the density | concentration of 20 g / l and the temperature of 60 degreeC, it spray-washed for 30 seconds with tap water.
[0046]
(3) Surface treatment
1) Reactive chromate treatment (Material: EG, ZN, GI)
Using Ginchrome 357 (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.), spray treatment was performed at a liquid temperature of 50 ° C. for 5 seconds, washed with tap water, and then air-dried to prepare a test plate. The target chromium adhesion amount is 20 mg / m. 2 It is.
[0047]
2) Coating type chromate conversion treatment (Material: EG, ZN, GI)
A test plate was prepared by applying a roll coating method using Ginchrome 1300AN (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.) and immediately drying at 200 ° C. for 10 seconds without washing with water. At this time, the ultimate plate temperature is 100 ° C., and the target chromium adhesion amount is 40 mg / m. 2 It is.
[0048]
3) Electrolytic chromate treatment (Material: EG, ZN, GI)
Current density 10 A / dm in a bath of 50 g / l chromic acid and 0.3 g / l sulfuric acid 2 Then, an electrolytic chromate treatment was performed by energizing a predetermined amount of electricity, washed with water, and then dried at 200 ° C. for 8 seconds to prepare a test plate. In this case, the ultimate plate temperature is 80 ° C., and the target chromium adhesion amount is 40 mg / m. 2 It is.
[0049]
(4) Preparation of aqueous surface treatment agent
(A) (meth) acrylate unsaturated monomer, (b) α, β-ethylenically unsaturated monomer having a carboxyl group in the molecule, (c) intramolecular Table 3 shows α, β-ethylenically unsaturated monomers having a hydroxyl group, (d) styrene, (e) acrylonitrile, and (f) unsaturated monomers copolymerizable with these monomers. Polymers of A1 to A37 shown in Table 3 were obtained using the ratios shown. The numerical value in parentheses after the name of each monomer in Table 2 indicates the glass transition temperature (Tg) in units of ° C of homopolymers of those monomer components. Is the glass transition temperature of each polymer.
At room temperature, the aqueous dispersions of the polymers in Table 3 and the colloidal silica and polyolefin wax dispersions shown in Tables 4 and 5 were mixed with stirring at a composition ratio shown in Tables 7 to 12 using a propeller stirrer. Distilled water was added to adjust the solid content concentration. In addition, the solid content composition in the film shown in Tables 7 to 12 is that the total amount of the polymer, silica and wax is 100% by mass, and the amount of silica and wax in these tables is expressed by mass%. It is.
[0050]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
(5) Application method of aqueous surface treatment agent to test plate
Each aqueous surface treatment agent prepared above was applied to each test plate using a bar coater, and dried at an ambient temperature of 280 ° C. for 12 seconds. The ultimate plate temperature at this time is 130 ° C., and the target adhesion amount is 1.0 mg / m. 2 It is. The amount of adhesion was adjusted by appropriately changing the solid content concentration of the composition and the type of bar coater.
[0055]
(6) Performance test of surface-treated metal sheet
1) Flat surface corrosion resistance
In accordance with the salt spray test method described in JIS Z 2371, a 5% NaCl aqueous solution was sprayed onto the surface-treated metal plate sample at an atmospheric temperature of 35 ° C., and the white rust generation rate after 72 hours was measured. In the following evaluations, ◎ and ○ were judged as good. The results are shown in Tables 7-12.
<Evaluation criteria>
A: White rust generation area ratio is less than 5% of the total area
○: White rust generation area ratio is 5% or more and less than 10% of the total area
Δ: White rust generation area ratio is 10% or more and less than 30% of the total area
×: White rust generation area ratio is 30% or more of the total area
[0056]
2) Processed part corrosion resistance
The surface-treated metal plate sample was subjected to 6 mm Erichsen processing, and in accordance with the salt spray test method described in JIS Z 2371, 5% NaCl aqueous solution was sprayed on the coated steel plate sample at an ambient temperature of 35 ° C, and after 48 hours. The white rust occurrence rate in the processed part was measured. In the following evaluations, ◎ and ○ were judged as good. The results are shown in Tables 7-12.
<Evaluation criteria>
◎: White rust generation area ratio Less than 5% of the processing area
○: White rust generation area ratio 5% or more and less than 10% of the processed area
Δ: White rust generation area ratio 10% or more and less than 30% of the processed area
×: White rust generation area ratio 30% or more of the processing area
[0057]
3) Solvent resistance
The surface of the surface-treated metal plate sample is slid back and forth 10 times with a load of 500 g by impregnating gauze with a solvent (ethanol or MEK). The appearance after sliding was observed, and ◎ and ○ were determined to be good in the following evaluation. The results are shown in Tables 7-12.
<Evaluation criteria>
A: Swelling area of the film Less than 30% of the entire sliding part
○: Swelled area of film 30% or more of entire sliding part
Δ: Dissolved area of film Less than 30% of entire sliding part
X: Melting area of film 30% or more of entire sliding part
[0058]
4) Paint adhesion
A melamine alkyd resin paint (Amirac # 1000, manufactured by Kansai Paint Co., Ltd.) was applied to the surface-treated metal plate sample using a bar coater so that the dry film thickness was 25 μm, and the furnace temperature was 130 ° C. for 20 minutes. I baked it. Next, after being left overnight, 7 mm Erichsen processing was applied to those immersed in boiling water for 30 minutes and those that were not so, and adhesive tape (Nichiban Co., Ltd .: trade name cello tape) was attached to the Eriksen processed portion of the test piece. It was. The adhesive tape was quickly pulled obliquely at 45 °, and the appearance of the Erichsen processed part was visually evaluated. In the following evaluations, ◎ and ○ were judged as good. The results are shown in Tables 7-12.
<Evaluation criteria>
◎: No peeling
○: Peeling area ratio less than 5%
Δ: Peel area ratio 5% or more and less than 50%
×: Peeling area ratio 50% or more
[0059]
5) Press galling resistance
A square cylinder crank press test was performed on the surface-treated metal plate sample. The condition of the square cylinder crank press test was that a sample (0.8 × 220 × 180 mm) was molded to 65 × 115 mm and a height of 50 mm with a wrinkle holding pressure of 6 tons, and the sliding surface after molding was visually evaluated. . In the following evaluation, ◎ and ○ were judged as good. The results are shown in Tables 7-12.
◎: No blackening
○: Less than 50% of the sliding area is blackened and has sliding wrinkles
△: Area of 50% or more of the sliding part is blackened and there is sliding wrinkles
×: The underlying metal is exposed and galling occurs
[0060]
6) Weldability
The surface-treated metal plate sample was subjected to a continuous spot welding test under the conditions shown in Table 6, and the number of hitting points capable of stably forming a nugget diameter of 3 mmφ or more was determined. The results are shown in Tables 7-12.
[0061]
[Table 6]
<Evaluation criteria>
In the following evaluation, ◎ and ○ were judged as good.
◎: More than 5,000 hits
○: Number of RBIs 2500 or more and less than 5000
Δ: Number of RBIs 1000 or more and less than 2500
×: Less than 1000 batting points
[0063]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
As is clear from Tables 7 to 12, all of the surface-treated metal plates obtained by the surface treatment method of the present invention are not only flat part corrosion resistance, solvent resistance, top coatability and weldability, but also processed part corrosion resistance, It is clear that it has excellent scratch resistance.
[0070]
【The invention's effect】
The surface-treated metal plate of the present invention is excellent in not only flat part corrosion resistance, solvent resistance, top coatability and weldability, but also processed part corrosion resistance and scratch resistance. As such, the industrial utility value is extremely high. Moreover, the surface-treated metal plate excellent in flat part corrosion resistance, solvent resistance, top coatability, weldability, processed part corrosion resistance, and scratch resistance can be provided to the market by the aqueous surface treatment agent and the production method.
Claims (7)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001283822A JP3963683B2 (en) | 2001-02-22 | 2001-09-18 | Aqueous surface treatment agent for plated metal plate, surface treated metal plate and method for producing the same |
| TW091103018A TW539768B (en) | 2001-02-22 | 2002-02-21 | Aqueous surface treatment agent for plated metal sheet, surface treated metal sheet and process for production thereof |
| PCT/JP2002/001632 WO2002066703A1 (en) | 2001-02-22 | 2002-02-22 | Water-based surface-treating agent for plated metal sheet, surface-treated metal sheet, and process for producing the same |
| MYPI20020614A MY148699A (en) | 2001-02-22 | 2002-02-22 | Aqueous surface treatment agent for plated metal sheet, surface treated metal sheet and process for production thereof. |
| CNB028053974A CN100510183C (en) | 2001-02-22 | 2002-02-22 | Water-based surface-treating agent for plated metal sheet, surface-treated metal sheet, and process for producing the same |
| KR1020037010948A KR100626417B1 (en) | 2001-02-22 | 2002-02-22 | Water-based surface-treating agent for plated metal sheet, surface-treated metal sheet, and process for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-47214 | 2001-02-22 | ||
| JP2001047214 | 2001-02-22 | ||
| JP2001283822A JP3963683B2 (en) | 2001-02-22 | 2001-09-18 | Aqueous surface treatment agent for plated metal plate, surface treated metal plate and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002322409A JP2002322409A (en) | 2002-11-08 |
| JP3963683B2 true JP3963683B2 (en) | 2007-08-22 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001283822A Expired - Fee Related JP3963683B2 (en) | 2001-02-22 | 2001-09-18 | Aqueous surface treatment agent for plated metal plate, surface treated metal plate and method for producing the same |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3963683B2 (en) |
| KR (1) | KR100626417B1 (en) |
| CN (1) | CN100510183C (en) |
| MY (1) | MY148699A (en) |
| TW (1) | TW539768B (en) |
| WO (1) | WO2002066703A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10149148B4 (en) * | 2000-10-11 | 2006-06-14 | Chemetall Gmbh | A method of coating metallic surfaces with an aqueous polymer-containing composition, the aqueous composition, and the use of the coated substrates |
| JP4573586B2 (en) * | 2004-07-07 | 2010-11-04 | 関西ペイント株式会社 | Surface-treated steel sheet |
| EP2072542B1 (en) | 2007-12-20 | 2014-05-07 | Rohm and Haas Company | Core-shell polymers suitable for use in organic media |
| KR101918879B1 (en) | 2014-12-10 | 2018-11-14 | 신닛테츠스미킨 카부시키카이샤 | Surface treatment agent for zinc-plated steel sheets |
| WO2016136834A1 (en) * | 2015-02-26 | 2016-09-01 | 新日鐵住金株式会社 | Metal-surface treatment agent for zinc-coated steel or zinc-based-alloy-coated steel, coating method, and coated steel |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0427538A (en) * | 1990-05-23 | 1992-01-30 | Kawasaki Steel Corp | Surface-treated steel sheet excellent in low temperature chipping resistance and film peeling resistance |
| KR100195757B1 (en) * | 1996-12-10 | 1999-06-15 | 한영재 | Organic-inorganic composite metal surface coating composition |
| JP2000073180A (en) * | 1998-08-31 | 2000-03-07 | Nippon Parkerizing Co Ltd | Water-based surface treating agent for metal material and surface treated metal material |
-
2001
- 2001-09-18 JP JP2001283822A patent/JP3963683B2/en not_active Expired - Fee Related
-
2002
- 2002-02-21 TW TW091103018A patent/TW539768B/en not_active IP Right Cessation
- 2002-02-22 KR KR1020037010948A patent/KR100626417B1/en not_active IP Right Cessation
- 2002-02-22 WO PCT/JP2002/001632 patent/WO2002066703A1/en not_active Application Discontinuation
- 2002-02-22 CN CNB028053974A patent/CN100510183C/en not_active Expired - Fee Related
- 2002-02-22 MY MYPI20020614A patent/MY148699A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030077637A (en) | 2003-10-01 |
| CN1492945A (en) | 2004-04-28 |
| KR100626417B1 (en) | 2006-09-20 |
| CN100510183C (en) | 2009-07-08 |
| TW539768B (en) | 2003-07-01 |
| WO2002066703A1 (en) | 2002-08-29 |
| MY148699A (en) | 2013-05-31 |
| JP2002322409A (en) | 2002-11-08 |
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