JP3977756B2 - Surface-treated steel sheet excellent in white rust resistance and method for producing the same - Google Patents

Description

上記化学構造式中、ｑは０〜５０の整数、好ましくは１〜４０の整数、特に好ましくは２〜２０の整数である。
このようなビスフェノールＡ型エポキシ樹脂は、当業界において広く知られた製造法により得ることができる。
【００２８】
上記（Ｂ）の成分である第１級または第２級アミン化合物は、エポキシ基含有樹脂の水分散性を発現するために必須の部分である。
具体例としては、モノエチルアミン、モノｎ−またはｉｓｏ−プロピルアミン、モノｎ−またはｉｓｏ−ブチルアミン、モノエタノールアミン、ネオペンタノールアミン、２−アミノプロパノール、３−アミノプロパノール、２−ヒドロキシ−２´（アミノプロポキシ）エチルエーテル等の第１級アミン化合物；ジエチルアミン、ジブチルアミン、メチルエチルアミン、ジエタノールアミン、ジ−ｎ−または−ｉｏｓ−プロパノールアミン、Ｎ−メチルエタノールアミン、Ｎ−エチルエタノールアミン等の第２級アミン化合物等が挙げられる。これらの第１級アミン化合物、第２級アミン化合物は、１種を単独でまたは２種以上を混合して使用することができる。また、これらのなかでも特に反応のし易さや制御性、水分散性の観点からはジエタノールアミンが好適である。
【００２９】
上記（Ｃ）の成分である、一部または全部が活性水素を有するヒドラジン誘導体からなる活性水素含有化合物は、表面処理皮膜に高度の耐食性を付与するために必須の成分である。活性水素を有するヒドラジン誘導体の具体例としては、例えば以下のものを挙げることができる。
▲１▼ カルボヒドラジド、プロピオン酸ヒドラジド、サリチル酸ヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、ドデカン酸ジヒドラジド、イソフタル酸ジヒドラジド、チオカルボヒドラジド、４，４′−オキシビスベンゼンスルホニルヒドラジド、ベンゾフェノンヒドラゾン、アミノポリアクリルアミド等のヒドラジド化合物；
【００３０】
▲２▼ ピラゾール、３，５−ジメチルピラゾール、３−メチル−５−ピラゾロン、３−アミノ−５−メチルピラゾール等のピラゾール化合物；
▲３▼ １，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、４−アミノ−１，２，４−トリアゾール、３−メルカプト−１，２，４−トリアゾール、５−アミノ−３−メルカプト−１，２，４−トリアゾール、２，３−ジヒドロ−３−オキソ−１，２，４−トリアゾール、１Ｈ−ベンゾトリアゾール、１−ヒドロキシベンゾトリアゾール（１水和物）、６−メチル−８−ヒドロキシトリアゾロピリダジン、６−フェニル−８−ヒドロキシトリアゾロピリダジン、５−ヒドロキシ−７−メチル−１，３，８−トリアザインドリジン等のトリアゾール化合物；
【００３１】
▲４▼ ５−フェニル−１，２，３，４−テトラゾール、５−メルカプト−１−フェニル−１，２，３，４−テトラゾール等のテトラゾール化合物；
▲５▼ ５−アミノ−２−メルカプト−１，３，４−チアジアゾール、２，５−ジメルカプト−１，３，４−チアジアゾール等のチアジアゾール化合物；
▲６▼ マレイン酸ヒドラジド、６−メチル−３−ピリダゾン、４，５−ジクロロ−３−ピリダゾン、４，５−ジブロモ−３−ピリダゾン、６−メチル−４，５−ジヒドロ−３−ピリダゾン等のピリダジン化合物；
また、これらのなかでも、５員環または６員環の環状構造を有し、この環状構造中に窒素原子を有するピラゾール化合物、トリアゾール化合物が耐食性などの観点から特に好適である。
以上挙げたヒドラジン誘導体は１種を単独でまたは２種以上を混合して使用することができる。
【００３２】
また、本発明では活性水素含有化合物（Ｃ）の一部として、ヒドラジン誘導体以外の活性水素含有化合物を用いることができる。
ビドラジン誘導体以外の活性水素含有化合物としては、例えば、下記のものが挙げられる。
・ アンモニア、カルボン酸などの有機酸
・ 塩化水素などのハロゲン化水素類
・ アルコール類、チオール類
・ 活性水素を有しないヒドラジン誘導体または第３級アミンと酸との混合物である４級塩化剤
【００３３】
活性水素含有化合物の一部として使用できる上記４級塩化剤は、活性水素を有しないヒドラジン誘導体または第３級アミンはそれ自体ではエポキシ基と反応性を有しないので、これらをエポキシ基と反応可能とするために酸との混合物としたものである。４級塩化剤は、必要に応じて水の存在下でエポキシ基と反応し、エポキシ基含有樹脂と４級塩を形成する。４級塩化剤を得るために使用される酸は、酢酸、乳酸などの有機酸、塩酸などの無機酸のいずれでもよい。また、４級塩化剤を得るために使用される活性水素を有しないヒドラジン誘導体としては、例えば３，６−ジクロロピリダジンなどを、また、第３級アミンとしては、例えば、ジメチルエタノールアミン、トリエチルアミン、トリメチルアミン、トリイソプロピルアミン、メチルジエタノールアミンなどを挙げることができる。
【００３４】
また、活性水素含有化合物（Ｃ）中における活性水素を有するヒドラジン誘導体の割合は１０〜１００モル％、より好ましくは３０〜１００モル％、さら好ましくは４０〜１００モル％とすることが適当である。活性水素を有するヒドラジン誘導体の割合が１０モル％未満では表面処理皮膜に十分な防錆機能を付与することができず、得られる防錆効果は皮膜形成有機樹脂とヒドラジン誘導体を単に混合して使用した場合と大差なくなる。
【００３５】
本発明で用いる水性エポキシ樹脂分散液（ａ）の変性エポキシ樹脂は、エポキシ基含有樹脂（Ａ）と、第１級アミン化合物および／または第２級アミン化合物（Ｂ）と、一部または全部が活性水素を有するヒドラジン誘導体からなる活性水素含有化合物（Ｃ）とを反応させることにより得られるが、その反応は、通常１０〜３００℃、好ましくは５０〜１５０℃の温度で約１〜８時間程度行うことが望ましい。
【００３６】
この反応は有機溶剤を加えて行ってもよく、使用する有機溶剤の種類は特に限定されない。例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジブチルケトン、シクロヘキサノン等のケトン類；エタノール、ブタノール、２−エチルヘキシルアルコール、ベンジルアルコール、エチレングリコール、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル等の水酸基を含有するアルコール類やエーテル類；酢酸エチル、酢酸ブチル、エチレングリコールモノブチルエーテルアセテート等のエステル類；トルエン、キシレン等の芳香族炭化水素等を例示でき、これらの１種または２種以上を使用することができる。また、これらのなかでエポキシ樹脂との溶解性、皮膜形成性等の面からは、ケトン系またはエーテル系の溶剤が特に好ましい。
【００３７】
エポキシ基含有樹脂（Ａ）と第１級アミン化合物および／または第２級アミン化合物（Ｂ）との配合割合は、エポキシ基含有樹脂（Ａ）中のエポキシ基に対して第１級アミン化合物および／または第２級アミン化合物（Ｂ）を２０〜８０ｍｏｌ％、好ましくは３０〜７０ｍｏｌ％、より好ましくは４０〜６０ｍｏｌ％とするのが適当であり、反応後の残存エポキシ基に対してその量に相当する活性水素を有するヒドラジン誘導体を反応させることが耐食性、水分散性等の点で有利である。すなわち、活性水素を有するヒドラジン誘導体の配合量は、エポキシ基含有樹脂（Ａ）中のエポキシ基に対して８０〜２０ｍｏｌ％、好ましくは７０〜３０ｍｏｌ％、より好ましくは６０〜４０ｍｏｌ％とするのが適当である。
【００３８】
上記（Ａ）〜（Ｃ）の成分を反応させて得られた変性エポキシ樹脂を水に分散させて水性エポキシ樹脂分散液を得る方法としては、上記変性エポキシ樹脂に含まれるアミノ基に対する周知の中和剤である酢酸、蟻酸、燐酸等で中和し、水分散化する方法が有効である。その中和当量は特に制限されるものではないが、アミノ基に対して０．２〜０．８当量、好ましくは０．３〜０．７当量、より好ましくは０．４〜０．６当量が分散液性状、耐水性の点で適当である。
なお、上記成分（Ａ）〜（Ｃ）を反応させて得られた変性エポキシ樹脂またはこれを水に分散させた水性エポキシ樹脂分散液は、２種以上を混合したものを用いてもよい。
【００３９】
上記水性エポキシ樹脂分散液（ａ）は、（ｂ）〜（ｄ）の成分を加えてそのまま用いてもめっき皮膜との密着性が良好な皮膜を形成できるが、より緻密なバリア皮膜を形成するためには、水性エポキシ樹脂分散液に硬化剤を配合し、有機皮膜を加熱硬化させることが望ましい。この硬化剤としては、ポリイソシアネート化合物、アミノ樹脂化合物などを挙げることができる。
上記ポリイソシアネート化合物は、１分子中に少なくとも２個のイソシアネート基を有する化合物であり、脂肪族イソシアネート化合物、脂環族イソシアネート化合物（複素環を含む）、芳香族イソシアネート化合物；これらのイソシアネート化合物を多価アルコールで部分反応させた化合物等を挙げることができ、これらのポリイソシアネート化合物中のイソシアネート基の一部または全部がブロック剤によりブロックされていてもよい。
【００４０】
ポリイソシアネート化合物としては、例えば以下のものが例示できる。
▲１▼ ｍ−またはｐ−フェニレンジイソシアネート、２，４−または２，６−トリレンジイソシアネート、ｏ−またはｐ−キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、イソホロンジイソシアネート；
▲２▼ 上記▲１▼の化合物単独またはそれらの混合物と多価アルコール（エチレングリコール、プロピレングリコールなどの２価アルコール類；グリセリン、トリメチロールプロパンなどの３価アルコール；ペンタエリスリトールなどの４価アルコール；ソルビトール、ジペンタエリスリトールなどの６価アルコールなど）との反応生成物であって、１分子中に少なくとも２個のイソシアネートが残存する化合物；
これらのポリイソシアネート化合物は、１種を単独でまたは２種以上を混合して使用できる。
【００４１】
また、ブロック剤としては、例えば、▲１▼メタノール、エタノール、プロパノール、ブタノール、オクチルアルコール等の脂肪族モノアルコール類；▲２▼エチレングリコールおよび／またはジエチレングリコールのモノエーテル類、例えば、メチル、エチル、プロピル（ｎ−，ｉｓｏ）、ブチル（ｎ−，ｉｓｏ，ｓｅｃ）等のモノエーテル；▲３▼フェノール、クレゾール等の芳香族アルコール；▲４▼アセトオキシム、メチルエチルケトンオキシム等のオキシムなどが使用でき、これらの１種または２種以上と前記ポリイソシアネート化合物とを反応させることにより、少なくとも常温下で安定に保護されたポリイソシアネート化合物を得ることができる。
【００４２】
上記アミノ樹脂化合物としては、メラミン、尿素、ベンゾグアナミン、アセトグアナミン、ステログアナミン、スピログアナミン、ジシアンジアミド等のアミノ成分とアルデヒドとの反応によって得られるメチロール化アミノ樹脂があげられる。アルデヒドとしては、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンツアルデヒド等がある。また、このメチロール化アミノ樹脂を適当なアルコールによってエーテル化したものも使用でき、エーテル化に用いられるアルコールの例としては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、ｉ−プロピルアルコール、ｎ−ブチルアルコール、ｉ−ブチルアルコール、２−エチルブタノール、２−エチルヘキサノール等が挙げられる。また、アミノ樹脂化合物のなかでも、メチロール基の少なくとも一部をアルキルエーテル化したメチロール化メラミン樹脂が特に好適である。
水性エポキシ樹脂分散液（ａ）中における変性エポキシ樹脂（Ｄ）と硬化剤（Ｅ）との配合割合は、固形分の質量比で（Ｄ）／（Ｅ）＝９５／５〜５５／４５、好ましくは（Ｄ）／（Ｅ）＝９０／１０〜６５／３５とするのが、皮膜の密着性、上塗り適正などの観点から適当である。
【００４３】
さらに、低温架橋性を増大させるため公知の硬化促進触媒を使用することが望ましい。硬化剤としてポリイソシアネート化合物を用いる場合の硬化促進触媒としては、例えば、Ｎ−エチルモルホリン、ジブチル錫ジラウレート、ナフテン酸コバルト、塩化第１スズ、ナフテン酸亜鉛、硝酸ビスマス等が使用できる。硬化剤としてアミノ樹脂化合物を用いる場合の硬化促進触媒としては、例えば、りん酸、スルホン酸化合物またはスルホン酸化合物のアミン中和物が好適に用いられる。スルホン酸化合物の代表例としては、ｐ−トルエンスルホン酸、ドデシルベンゼンスルホン酸、ジノニルナフタレンスルホン酸、ジノニルナフタレンジスルホン酸等を挙げることができる。スルホン酸化合物のアミン中和物におけるアミンとしては、１級アミン、２級アミン、３級アミンのいずれであってもよい。
【００４４】
次に、上記（ｂ）の成分であるウレタン樹脂の水分散体について説明する。
ウレタン樹脂の水分散体は、ポリイソシアネート化合物と、ポリエーテルジオール、ポリエステルジオール等のポリヒドロキシ化合物とを反応させて得られる生成物を用いたウレタンエマルションである。
このウレタンエマルションは、例えば、分子内にイソシアネート基と反応し得る活性水素を持たない親水性有機溶剤の存在下または非存在下で、ポリイソシアネート化合物とポリヒドロキシ化合物とを、ポリヒドロキシ化合物の水酸基に対してポリイソシアネート化合物のイソシアネート基過剰で反応させることにより容易に得ることができ、必要に応じてこの反応生成物（ポリマー）とアミンと水とを混合してアミン伸長反応を行なわしめた後、ノニオン性あるいはイオン性の乳化剤と混合して水を加えることで乳化分散させ、必要により前記有機溶剤を留去することにより、得ることができる。
【００４５】
また、ウレタン樹脂骨格中に、ノニオン性、アニオン性又はカチオン性の親水性基を有するポリヒドロキシ化合物を用いることにより、乳化剤を用いずにウレタンエマルションが得られる。
上記ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート類；水素添加キシリレンジイソシアネート、イソホロンジイソシアネート等の環状脂肪族ジイソシアネート類；トリレンジイソシアネート、４，４´−ジフェニルメタンジイソシアネート等の芳香族ジイソシアネート類等の有機ジイソシアネート類、または上記有機ジイソシアネート類どうしの環化重合体、さらには上記有機ジイソシアネート類のイソシアヌレート体、ビウレット体等が挙げられ、これらの１種または２種以上を用いることができる。
また、ウレタン樹脂の水分散体（ｂ）としては、水性エポキシ樹脂分散液（ａ）との混合安定性の面から、ノニオン性またはカチオン性のポリウレタンエマルションが特に好適である。
【００４６】
表面処理組成物がウレタン樹脂の水分散体（ｂ）を含有することにより、耐白錆性を効果的に高めることができる。この理由としては、ウレタン樹脂の水分散体が適量配合されることによって表面処理組成物の造膜性が向上し、この結果、腐食因子の透過抑制作用が高まり、また皮膜中の防錆成分の流出も抑制されるためであると考えられる。
表面処理組成物中における水性エポキシ樹脂分散液（ａ）とウレタン樹脂の水分散体（ｂ）との配合割合は、固形分質量比で（ａ）／（ｂ）＝９５／５〜５／９５、好ましくは７５／２５〜２５／７５とするのが適当である。水性エポキシ樹脂分散液（ａ）に対するウレタン樹脂の水分散体（ｂ）の配合割合が上記下限を下回るとウレタン樹脂に由来する造膜性が十分ではなく、腐食因子の抑制作用が不十分となって耐白錆性が低下する傾向がある。一方、水性エポキシ樹脂分散液（ａ）に対するウレタン樹脂の水分散体（ｂ）の配合割合が上記上限を上回ると、表面処理組成物中での活性水素を有するヒドラジン誘導体からなる活性水素含有化合物の割合が低下するため、この場合も耐白錆性が低下する傾向がある。
【００４７】
また、表面処理組成物には、上述した特定の水分散性樹脂（変性エポキシ樹脂、ウレタン樹脂）以外の水分散性樹脂および／または水溶性樹脂として、例えばアクリル系樹脂、ポリエステル系樹脂、エポキシ系樹脂、エチレン系樹脂、アルキッド系樹脂、フェノール樹脂、オレフィン系樹脂の１種または２種以上を全樹脂固形分中での割合で２５質量％程度を上限として配合してもよい。
【００４８】
次に、上記（ｃ）の成分であるシランカップリング剤について説明する。
このシランカップリング剤としては、例えば、ビニルメトキシシラン、ビニルエトキシシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、β−（３，４エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメエキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、ｐ−スチリルトリメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、γ−イソシアネートプロピルトリエトキシシラン、γ−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、Ｎ−（ビニルベンジルアミン）−β−アミノエチル−γ−アミノプロピルトリメトキシシラン等を挙げることができ、これらの１種を単独でまたは２種以上を混合して使用することができる。
表面処理組成物が特定の酸成分とともにシランカップリング剤を含むことにより向上するには、先に述べたような理由が考えられる。
【００４９】
また、上記シランカップリング剤の中でも、上記水性エポキシ樹脂分散液（ａ）と反応性が高い官能基を有するという観点から、特に、反応性官能基としてアミノ基を有すシランカップリング剤が好ましい。このようなシランカップリング剤としては、例えば、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメエキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン等が挙げられ、具体的には、信越化学（株）製の「ＫＢＭ−９０３」、「ＫＢＥ−９０３」、「ＫＢＭ−６０３」、「ＫＢＥ−６０２」、「ＫＢＥ−６０３」（いずれも商品名）などを用いることができる。
【００５０】
シランカップリング剤の配合量は、表面処理組成物中の有機樹脂の固形分１００質量部に対して、１〜３００質量部、好ましくは５〜１００質量部、より好ましくは、１５〜５０質量部とするのが適当である。シランカップリング剤の配合量が１質量部未満では耐食性が劣り、一方３００質量部を超えると十分な皮膜が形成できないため、水分散性樹脂との密着性とバリア性を高める効果が発揮できず耐食性が低下する。
【００５１】
次に、上記（ｄ）の成分であるリン酸および／またはヘキサフルオロ金属酸は、不活性なめっき皮膜表面に作用して金属表面を活性化させる作用を有する。そして、このように活性化されためっき金属表面と皮膜形成樹脂との密着性がシランカップリング剤を介して著しく向上する結果、耐食性が顕著に改善される。このリン酸とヘキサフルオロ金属酸は単独で用いてもよいし、併用してもよい。
ヘキサフルオロ金属酸の種類は特に限定されないが、先に述べた擬似二層皮膜の反応層を効果的に形成させるという観点から、特に、フッ化チタン酸、フッ化ジルコン酸、ケイフッ酸等のようなＴｉ，Ｓｉ，Ｚｒの中から選ばれる１種または２種以上の元素を含むヘキサフルオロ金属酸が好ましく、これらの１種または２種以上を用いることができる。
【００５２】
リン酸および／またはヘキサフルオロ金属酸の配合量（併用する場合は合計の配合量）は、表面処理組成物中の有機樹脂の固形分１００質量部に対して、０．１〜８０質量部、好ましくは１〜６０質量部、より好ましくは５〜５０質量部とするのが適当である。リン酸および／またはヘキサフルオロ金属酸の配合量が０．１質量部未満では耐食性が劣り、一方、８０質量部超では皮膜形成後の外観ムラが生じやすい。
【００５３】
表面処理組成物には、耐食性向上を目的として、さらに水溶性無機成分を配合することが好ましい。この水溶性無機成分としては、カチオン種がＭｇ、Ｃａ、Ｙ、Ｔｉ、Ｚｒ、Ｎｂ、Ｚｎ、Ｍｎ、Ｃｏ、Ｎｉ、Ｚｎ、Ａｌ、Ｉｎ、Ｃｅ、Ｌａの中から選ばれる１種または２種以上、アニオン種が硝酸、硫酸、酢酸、炭酸、リン酸、塩化物の中から選ばれる１種または２種以上である無機成分が好ましい。具体的には、硝酸Ｍｇ、硝酸Ｃｏ、硫酸Ｔｉ、硫酸Ｎｉ、酢酸Ｚｎ、酢酸Ｃｅ、炭酸Ｍｎ等を挙げることができ、これらの１種又は２種以上を用いることができる。
【００５４】
このような水溶性無機成分を配合することにより、特にアルカリ脱脂後の耐白錆性が向上する理由は、擬似二層皮膜中の無機リッチ層の緻密性が高まり、アルカリ処理による無機リッチ層の破壊が抑制されるためであると考えられる。
また、特に優れた耐白錆性を得るという観点からは、水溶性無機成分のカチオン種としてＡｌ、Ｍｎ、Ｚｒ 、Ｃｏ、Ｍｇを有するものが特に望ましく、これらの中から選ばれる１種または２種以上の元素を含む水溶性無機成分を用いることが好ましい。
この水溶性無機成分の配合量は、表面処理組成物中の有機樹脂の固形分１００質量部に対して、固形分で０．１〜６０質量部、好ましくは０．５〜４０質量部、より好ましくは１〜３０質量部とするのが適当である。水溶性無機成分の配合量が０．１質量部未満では耐食性の向上効果が十分でなく、一方、６０質量部を超えると処理液との反応性が強くなり外観ムラを生じやすくなる。
【００５５】
表面処理組成物には、耐食性向上を目的として、必要に応じて非クロム系防錆添加剤を配合することができる。この非クロム系防錆添加剤は、特に下記（ｅ１）〜（ｅ４）の群から選ばれる１つまたは２つ以上を用いることが好ましい。
（ｅ１）酸化ケイ素
（ｅ２）カルシウムまたは／およびカルシウム化合物
（ｅ３）難溶性リン酸化合物
（ｅ４）トリアゾール類、チオール類、チアジアゾール類、チアゾール類、チウラム類の中から選ばれる１種又は２種以上のＳ原子を含有する有機化合物
これら（ｅ１）〜（ｅ４）の非クロム系防錆添加剤の詳細および防食機構は以下の通りである。
【００５６】
まず、上記（ｅ１）の成分としては微粒子シリカであるコロイダルシリカや乾式シリカを使用することができるが、耐食性の観点からは特に、カルシウムをその表面に結合させたカルシウムイオン交換シリカを使用するのが好ましい。
コロイダルシリカは、例えば、日産化学（株）製のスノーテックスＯ、20、30、40、Ｃ、Ｓ（いずれも商品名）を用いることができ、ヒュームドシリカとしては、日本アエロジル（株）製のAEROSIL R971、R812、R811、R974、R202、R805、130、200、300、300CF（いずれも商品名）を用いることができる。また、カルシウムイオン交換シリカとしてはW.R.Grace＆Co.製のSHIELDEX C303、SHIELDEX AC3、SHIELDEX AC5（いずれも商品名）、富士シリシア化学（株）製のSHIELDEX、SHIELDEX SY710（いずれも商品名）などを挙げることができる。これらシリカは、腐食環境下において緻密で安定な亜鉛の腐食生成物の生成に寄与し、この腐食生成物がめっき表面に緻密に形成されることによって、腐食の促進を抑制する。
【００５７】
上記（ｅ２）の成分であるカルシウム化合物は、カルシウム酸化物、カルシウム水酸化物、カルシウム塩のいずれでもよく、これらの１種または２種以上を使用できる。また、カルシウム塩の種類にも特に制限はなく、ケイ酸カルシウム、炭酸カルシウム、リン酸カルシウムなどのようなカチオンとしてのカルシウムのみを含む単塩のほか、リン酸カルシウム・亜鉛、リン酸カルシウム・マグネシウムなどのようなカルシウム以外のカチオンを含む複塩を使用してもよい。この（ｅ２）成分は腐食環境下においてめっき金属である亜鉛やアルミニウムよりも卑なカルシウムが優先溶解し、これがカソード反応により生成したＯＨ⁻と緻密で難溶性の生成物として欠陥部を封鎖、腐食反応を抑制する。また、上記のようなシリカとともに配合された場合には表面にカルシウムイオンが吸着し、表面電荷を電気的に中和して凝集する。その結果、緻密かつ難溶性の保護皮膜が生成して腐食起点を封鎖し、腐食反応を抑制する。
【００５８】
また、上記（ｅ３）である難溶性リン酸化合物としては、難溶性リン酸塩を用いることができる。この難溶性リン酸塩は単塩、複塩等のすべての種類の塩を含む。また、それを構成する金属カチオンに限定はなく、難溶性のリン酸亜鉛、リン酸マグネシウム、リン酸カルシウム、リン酸アルミニウム等のいずれの金属カチオンでもよい。また、リン酸イオンの骨格や縮合度などにも限定はなく、正塩、二水素塩、一水素塩または亜リン酸塩のいずれでもよく、さらに、正塩はオルトリン酸塩の他、ポリリン酸塩等の全ての縮合リン酸を含む。この難溶性リン化合物は腐食によって溶出しためっき金属の亜鉛やアルミニウムが、加水分解により解離したリン酸イオンと錯形成反応により緻密且つ難溶性の保護皮膜を生成して腐食起点を封鎖し、腐食反応を抑制する。
【００５９】
また、上記（ｅ４）のＳ原子を有する有機化合物としては、例えば、以下のようなものが挙げることができる。すなわち、トリアゾール類としては１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、３−メルカプト−１，２，４−トリアゾール、５−アミノ−３−メルカプト−１，２，４−トリアゾール、１Ｈ−ベンゾトリアゾール等が、また、チオール類としては、１，３，５−トリアジン−２，４，６−トリチオール、２−メルカプトベンツイミダゾール等が、また、チアジアゾール類としては５−アミノ−２−メルカプト−１，３，４−チアジアゾール、２，５−ジメルカプト−１，３，４−チアジアゾール、等が、また、チアゾール類としては２−Ｎ，Ｎ−ジエチルチオベンゾチアゾール、２−メルカプトベンゾチアゾール類等が、また、チウラム類としては、テトラエチルチウラムジスルフィド等が、それぞれ挙げられる。これらの有機化合物は吸着効果によって自己補修性を発現する。すなわち、腐食によって溶出した亜鉛やアルミニウムが、これらの有機化合物が有する硫黄を含む極性基に吸着して不活性皮膜を形成して腐食起点を封鎖し、腐食反応を抑制する。
【００６０】
非クロム系防錆添加剤の配合量としては、表面処理組成物中の有機樹脂の固形分１００質量部に対して、固形分で０．１〜５０質量部、好ましくは０．５〜３０質量部、より好ましくは１〜２０質量部とするのが適当である。この非クロム系防錆添加剤の配合量が０．１質量部未満では、耐アルカリ脱脂後の耐食性向上効果が十分に得られず、一方、５０質量部を超えると塗装性および加工性が低下するだけでなく、耐食性も低下するので好ましくない。
なお、上記（ｅ１）〜（ｅ４）の防錆添加剤を２種以上複合添加してもよい。
【００６１】
表面処理組成物には、皮膜の加工性（耐キズつき性）や連続磨耗性を向上させるために、必要に応じて潤滑剤を配合することができる。この潤滑剤としては、例えば、ポリオール化合物と脂肪酸とのエステル化物である脂肪酸エステルワックス、シリコン系ワックス、フッ素系ワックス、ポリエチレン等のポリオレフィンワックス、ラノリン系ワックス、モンタンワックス、マイクロクリスタリンワックス、カルナウバろう等を挙げることができるが、特に限定はされない。これらの潤滑剤は、１種を単独でまたは２種以上を混合して使用することが可能である。
【００６２】
潤滑剤の配合量は、表面処理組成物中の有機樹脂の固形分１００質量部に対して、０．１〜２０質量部、好ましくは０．３〜１０質量部とするのが適当である。上記潤滑性剤の配合量が０．１質量部未満では得られる塗膜の滑り性が低いため、厳しい加工を行った際に塗膜に傷が付きやすく、一方、２０質量部を超えると得られる塗膜の塗装性が低下すると同時に柔軟性が低下し、厳しい加工を行った際に塗膜の連続性が損なわれる。
【００６３】
また、表面処理組成物中には、腐食抑制剤として、他の酸化物微粒子（例えば、酸化アルミニウム、酸化ジルコニウム、酸化チタン、酸化セリウム、酸化アンチモン等）、リンモリブデン酸塩（例えば、リンモリブデン酸アルミニウム等）、有機リン酸およびその塩（例えば、フィチン酸、フィチン酸塩、ホスホン酸、ホスホン酸塩、およびこれらの金属塩、アルカリ金属塩、アルカリ土類金属塩等）、有機インヒビター（例えば、ヒドラジンおよびその誘導体、チオール化合物、チオカルバミン酸塩等）などの１種または２種以上を添加できる。
【００６４】
さらに必要に応じて、表面処理組成物中には添加剤として、有機着色顔料（例えば、縮合多環系有機顔料、フタロシアニン系有機顔料等）、着色染料（例えば、水溶性アゾ系金属染料等）無機顔料（例えば、酸化チタン等）、導電性顔料（例えば、亜鉛、アルミニウム、ニッケルなどの金属粉末、リン化鉄、アンチモンドープ型酸化錫等）、カップリング剤（例えば、チタンカップリング剤等）、メラミン・シアヌル酸付加物等の１種または２種以上を添加することができる。
【００６５】
以上のような表面処理組成物により形成される表面処理皮膜は、乾燥膜厚が０．０１〜５μｍ、好ましくは０．１〜３μｍ、さらに好ましくは０．３〜２μｍとする。乾燥膜厚が０．０１μｍ未満では耐食性が不十分であり、一方、５μｍを超えると導電性や加工性が低下する。
また、以上述べた表面処理皮膜の上層には、第２層皮膜として有機樹脂皮膜を形成することができる。この場合、第２層である有機樹脂皮膜の皮膜厚を０．０１μｍ以上５μｍ未満にするとともに、第１層皮膜である上記表面処理皮膜の膜厚を０．０１μｍ以上５μｍ未満とし、両皮膜の合計が５μｍを超えないようにすることが好ましい。
【００６６】
亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に上記表面処理皮膜を形成するには、上述した組成を有する表面処理組成物（処理液）を乾燥皮膜厚が上記範囲となるようにめっき鋼板に塗布し、水洗することなく加熱乾燥させる。
表面処理組成物（処理液）はｐＨ０．５〜６、好ましくは１〜４に調整することが適当である。表面処理組成物のｐＨが０．５未満では処理液の反応性が強すぎるため外観ムラが生じ、一方、ｐＨが６を超えると処理液の反応性が低くなり、めっき金属と皮膜との結合が不十分となり、耐食性が低下する。
【００６７】
表面処理組成物をめっき鋼板面に形成する方法としては塗布法、浸せき法、スプレー法のいずれでもよい。塗布処理方法としては、ロールコーター（３ロール方式、２ロール方式等）、スクイズコーター、ダイコーター等いずれの方法でもよい。また、スクイズコーター等による塗布処理、あるいは浸漬処理、スプレー処理の後に、エアナイフ法やロール絞り法により塗布量の調整、外観の均一化、膜厚の均一化を行うことも可能である。
【００６８】
表面処理組成物をコーティングした後は、水洗することなく加熱乾燥を行う。加熱乾燥手段としてはドライヤー、熱風炉、高周波誘導加熱炉、赤外線炉等を用いることができる。加熱処理は、到達板温で３０℃〜３００℃、好ましくは、４０℃〜２５０℃の範囲で行うことが適当である。この加熱温度が３０℃未満では皮膜中の水分が多量に残り、耐食性が不十分となる。また、３００℃を超えると非経済的であるばかりでなく、皮膜に欠陥が生じ耐食性が低下する。
また、上記のようにして形成された表面処理皮膜の上層に第２層皮膜として有機樹脂皮膜を形成する場合には、第２層皮膜用の処理組成物を上述した膜厚となるように上記表面処理皮膜面に塗布し、乾燥させる。処理組成物の塗布や加熱乾燥は、上述した表面処理の形成に用いた方法に準じて行えばよい。
【００６９】
したがって、本発明の製造方法およびその好ましい実施形態は以下のとおりである。
[1] 亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、
（ａ）エポキシ基含有樹脂（Ａ）と、第１級アミン化合物および／または第２級アミン化合物（Ｂ）と、一部または全部が活性水素を有するヒドラジン誘導体からなる活性水素含有化合物（Ｃ）とを反応させて得られた変性エポキシ樹脂を水に分散させた水性エポキシ樹脂分散液と、
（ｂ）ウレタン樹脂の水分散体と、
（ｃ）シランカップリング剤と、
（ｄ）リン酸および／またはヘキサフルオロ金属酸と、
を含有し、ｐＨが０．５〜６に調製された表面処理組成物を塗布し、水洗することなく５０℃〜３００℃の到達板温で加熱乾燥し、皮膜厚が０．０１〜５μｍの表面処理皮膜を形成することを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
【００７０】
[2] 上記[1]の製造方法において、活性水素を含有するヒドラジン誘導体が、５員環または６員環の環状構造を有し、該環状構造中に窒素原子を有するピラゾール化合物および／またはトリアゾール化合物であることを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
[3] 上記[1]または[2]の製造方法において、表面処理組成物が、シランカップリング剤を有機樹脂の固形分１００質量部に対して１〜３００質量部、リン酸および／またはヘキサフルオロ金属酸を有機樹脂の固形分１００質量部に対して０．１〜８０質量部含有することを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
【００７１】
[4] 上記[1]〜[3]のいずれかの製造方法において、表面処理組成物がさらに、水溶性無機成分を有機樹脂の固形分１００質量部に対して固形分で０．１〜６０質量部含有することを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
[5] 上記[4]の製造方法において、水溶性無機成分のカチオン種がＭｇ、Ｃａ、Ｙ、Ｔｉ、Ｚｒ、Ｎｂ、Ｚｎ、Ｍｎ、Ｃｏ、Ｎｉ、Ｚｎ、Ａｌ、Ｉｎ、Ｃｅ、Ｌａの中から選ばれる１種または２種以上であり、アニオン種が硝酸、硫酸、酢酸、炭酸、リン酸、塩化物の中から選ばれる１種または２種以上であることを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
[6] 上記[1]〜[5]のいずれかの製造方法において、表面処理組成物がさらに、非クロム系防錆添加剤を有機樹脂の固形分１００質量部に対して固形分で０．１〜５０質量部含有することを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
【００７２】
[7] 上記[1]〜[6]のいずれかの製造方法において、表面処理組成物が、反応性官能基としてアミノ基を有するシランカップリング剤の少なくとも１種を含有することを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
[8] 上記[1]〜[7]のいずれかの製造方法により得られた表面処理鋼板の皮膜厚を０．０１μｍ以上５μｍ未満とした表面処理皮膜の上層に、皮膜厚が０．０１μｍ以上５μｍ未満の有機樹脂皮膜を、前記表面処理皮膜厚と合計した皮膜厚が５μｍ以下となるように形成することを特徴とする耐白錆性に優れた表面処理鋼板の製造方法。
【００７３】
なお、上述した表面処理皮膜はめっき鋼板の片面、両面のいずれに形成してもよく、めっき鋼板表裏面の皮膜形成の組み合わせとしては、例えば、単層皮膜（表面処理皮膜）／無処理、二層皮膜（表面処理皮膜＋有機樹脂皮膜）／無処理、単層皮膜（表面処理皮膜）／二層皮膜（表面処理皮膜＋有機樹脂皮膜）、二層皮膜（表面処理皮膜＋有機樹脂皮膜）／二層皮膜（表面処理皮膜＋有機樹脂皮膜）など、任意の形態とすることができる。
【００７４】
【実施例】
表面処理組成物用の樹脂組成物として表２に示す水性エポキシ樹脂分散液を用い、これにウレタン樹脂水分散体（表３）、シランカップリング剤（表４）、リン酸またはヘキサフルオロ金属酸（表５）、水溶性無機成分（表６）、非クロム系防錆添加剤（表７）、固形潤滑剤（表８）を適宜配合し、さらにアンモニア水、硝酸、酢酸、硫酸、リン酸、ヘキサフルオロ金属酸等でｐＨを０．５〜６に調整した後、塗料用分散機（サンドグラインダー）を用いて所要時間攪拌し、表面処理組成物を調製した。
【００７５】
表２に示す水性エポキシ樹脂分散液の製造例１〜５を以下に示す。
・製造例１
温度計、撹拌機、冷却管を備えたガラス製４ツ口フラスコに、エピコート１００７（エポキシ樹脂，シェルジャパン（株）社製，エポキシ当量２０００） ７８７．４ｇとプロピレングリコールモノブチルエーテル４２５ｇ加え、１１０℃で撹拌混合し、均一透明になった後１００℃に冷却し、ジエタノールアミン２０．７ｇを加え、１時間反応させた後、エポキシアミン価を測定し、理論値になっていることを確認して、３−アミノ−１，２，４−トリアゾール（分子量８４）１６．５gを加えて、５時間反応させた。その後、プロピレングリコールモノブチルエーテル２５０ｇを加えて変性エポキシ樹脂を得た。この変性エポキシ樹脂にリン酸２３．３ｇを加え、水を混合・滴下し固形分濃度２０％の水性エポキシ樹脂分散液Ｅ１を得た。
【００７６】
・製造例２
温度計、撹拌機、冷却管を備えたガラス製４ツ口フラスコに、エピコート１００４（エポキシ樹脂，シェルジャパン（株）製、エポキシ当量９２５） ５４６ｇとプロピレングリコールモノブチルエーテル３１１ｇ加え、１１０℃で撹拌混合し、均一透明になった後１００℃に冷却し、ジエタノールアミン３１．５ｇを加え、１時間反応させた後、エポキシアミン価を測定し、理論値になっていることを確認して、３−アミノ−１，２，４−トリアゾール（分子量８４）２５．２ｇを加えて、５時間反応させた。その後、プロピレングリコールモノブチルエーテル１８２．６ｇを加えて変性エポキシ樹脂を得た。この変性エポキシ樹脂にリン酸３５．３ｇを加え、水を混合・滴下し固形分濃度２０％の水性エポキシ樹脂分散液Ｅ２を得た。
・製造例３
ジエタノールアミンの量を１２．４ｇ、３−アミノ−１，２，４−トリアゾールの量を２３．１ｇとした以外は製造例１と同様の条件で反応を行い、変性エポキシ樹脂を得た。この変性エポキシ樹脂に水を混合し固形分濃度２０％の水性エポキシ樹脂分散液Ｅ３を得た。
【００７７】
・製造例４（比較例）
温度計、撹拌機、冷却管を備えたガラス製４ツ口フラスコに、エピコート１００１（エポキシ樹脂，ジャパンエポキシレジン社製，エポキシ当量約４７５、数平均分子量約９００）１８６．６ｇとプロピレングリコールモノブチルエーテル１１５．２ｇを加え、１１０℃まで昇温して撹拌混合し、液が均一透明になった後１００℃に冷却し、ジエタノールアミン２５．５ｇを加えて１００℃の温度に１時間保持した。その後、プロピレングリコールモノブチルエーテル６８．０ｇを加えて変性エポキシ樹脂を得た。この変性エポキシ樹脂にリン酸２３．３ｇを加え、水を滴下しながら混合し固形分濃度２０％の水性エポキシ樹脂分散液Ｅ４を得た。
・製造例５（比較例）
製造例１で用いた３−アミノ−１，２，４−トリアゾール１６．５ｇをＮ−メチル−エタノールアミン１４．７ｇに置き換えた以外は製造例１と同様の条件で反応を行い、変性エポキシ樹脂を得た。この変性エポキシ樹脂に水を混合し固形分濃度２０％の水性エポキシ樹脂分散液Ｅ５を得た。
【００７８】
冷延鋼板をベースとした表１に示す家電、建材、自動車部品用のめっき鋼板を処理原板として用いた。なお、鋼板の板厚は、評価の目的に応じて所定の板厚を採用した。このめっき鋼板の表面をアルカリ脱脂処理、水洗乾燥した後、上記表面処理組成物をロールコーターにより塗布し、水洗することなく各種温度で加熱乾燥した。皮膜の膜厚は、表面処理組成物の固形分（加熱残分）または塗布条件（ロールの圧下力、回転速度等）により調整した。得られた表面処理鋼板の皮膜組成および品質性能（皮膜外観、耐白錆性、アルカリ脱脂後耐白錆性、導電性、塗料密着性）の各試験を行った結果を表９〜２０に示す。なお、品質性能の評価は、以下のようにして行った。
【００７９】
（１）皮膜外観
各サンプルについて、皮膜外観の均一性（ムラの有り無し）を目視で評価した。評価基準は以下の通りである。
○ ：ムラが全く無い均一な外観
△ ：ムラが若干目立つ外観
× ：ムラが目立つ外観
（２）耐白錆性
各サンプルについて、塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）を施し、１６８時間経過後の白錆面積率で評価した。評価基準は以下の通りである。
◎ ：白錆面積率５％未満
○ ：白錆面積率５％以上、１０％未満
○−：白錆面積率１０％以上、２５％未満
△ ：白錆面積率２５％以上、５０％未満
× ：白錆面積率５０％以上
【００８０】
（３）アルカリ脱脂後の耐白錆性
各サンプルについて、アルカリ脱脂後に塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）を施し、７２時間経過後の白錆面積率で評価した。
評価基準は以下の通りである。
◎ ：白錆面積率５％未満
○ ：白錆面積率５％以上、１０％未満
○−：白錆面積率１０％以上、２５％未満
△ ：白錆面積率２５％以上、５０％未満
× ：白錆面積率５０％以上
（４）導電性
ＪＩＳ Ｃ２５５０により層間絶縁抵抗値を測定した。評価基準は以下の通りである。
○ ：３Ω・ｃｍ^２／枚未満
△ ：３〜５Ω・ｃｍ^２／枚
× ：５Ω・ｃｍ^２／枚超え
【００８１】
（５）塗料密着性
各サンプルについて、メラミン系の焼付塗料を塗装（膜厚３０μｍ）した後、沸水中に２時間浸漬し、直ちに、碁盤目（１０×１０個，１ｍｍ間隔）のカットを入れて接着テープによる貼着・剥離を行い、塗膜の剥離面積率を測定した。評価基準は以下の通りである。
◎：剥離なし
○：剥離面積率５％未満
△：剥離面積率５％以上、２０％未満
×：剥離面積率２０％以上
【００８２】
【表１】

【００８３】
【表２】

【００８４】
【表３】

【００８５】
【表４】

【００８６】
【表５】

【００８７】
【表６】

【００８８】
【表７】

【００８９】
【表８】

【００９０】
以下の表９〜表２０中に記載の＊１〜＊９は下記の内容を指す。
＊１：表１に記載のＮｏ．(めっき鋼板)
＊２：表２に記載のＮｏ．(水性エポキシ樹脂分散液)
＊３：表３に記載のＮｏ．(ウレタン樹脂水分散体)
＊４：表４に記載のＮｏ．(シランカップリング剤)
＊５：表５に記載のＮｏ．(リン酸および／またはヘキサフルオロ金属酸)
＊６：表６に記載のＮｏ．(水溶性無機成分)
＊７：表７に記載のＮｏ．(非クロム系防錆添加剤)
＊８：表８に記載のＮｏ．(固形潤滑剤)
＊９：質量部
【００９１】
【表９】

【００９２】
【表１０】

【００９３】
【表１１】

【００９４】
【表１２】

【００９５】
【表１３】

【００９６】
【表１４】

【００９７】
【表１５】

【００９８】
【表１６】

【００９９】
【表１７】

【０１００】
【表１８】

【０１０１】
【表１９】

【０１０２】
【表２０】

【０１０３】
【発明の効果】
以上述べたように本発明の表面処理鋼板は、皮膜中にクロムを含まないにもかかわらず非常に優れた耐白錆性を有し、また皮膜外観や塗料密着性についても優れた特性を有している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-chromium type surface-treated steel sheet that exhibits excellent white rust resistance without containing hexavalent chromium in the film, and is particularly suitable for use in automobiles, home appliances, and building materials, and a method for producing the same.
[0002]
[Prior art]
Steel sheets for home appliances, steel sheets for building materials, and steel sheets for automobiles have been used for the purpose of improving corrosion resistance (white rust resistance, red rust resistance) on the surface of zinc-based plated steel sheets or aluminum-based plated steel sheets. Steel plates subjected to chromate treatment with a treatment liquid (treatment liquid containing hexavalent chromium) containing dichromic acid or a salt thereof as a main component are widely used. This chromate treatment is an economical treatment method that provides a surface-treated film with excellent corrosion resistance and can be performed relatively easily.
The chromate treatment uses hexavalent chromium, which is a pollution-controlling substance, but recently there has been a movement to restrict or prohibit the use of hexavalent chromium from the viewpoint of environmental protection. With an emphasis on the degree of contribution to the environment, efforts to reduce the use and emission of hexavalent chromium that have been used are accelerating.
[0003]
For this reason, in order to prevent the occurrence of white rust in zinc-based plated steel sheets, many chromium-free treatment techniques have been proposed in place of chromate treatment. For example, there is a method of forming a thin film by a method such as immersion, coating, or electrolytic treatment using an inorganic compound, an organic compound, an organic polymer material, or a solution combining these.
Specifically, the following methods can be mentioned.
(1) A method of forming a film by immersing or applying a treatment liquid in a treatment liquid containing an organic resin, a silane coupling agent or colloidal silica, and lithium silicate (for example, Patent Document 1, Patent Document) 2)
(2) A method of forming a film with a treatment liquid in which a polyhydric phenol carboxylic acid such as tannic acid and a silane coupling agent are blended in an organic resin (see, for example, Patent Document 3 and Patent Document 4)
(3) A method of forming a film with a treatment liquid in which an organic resin and a silane coupling agent are blended (see, for example, Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8, Patent Document 9, and Patent Document 10)
[0004]
[Patent Document 1]
JP 2000-45078 A
[Patent Document 2]
Japanese Patent Laid-Open No. 10-209971
[Patent Document 3]
JP-A-8-325760
[Patent Document 4]
Japanese Patent Laid-Open No. 10-209972
[Patent Document 5]
JP-A-11-106945
[Patent Document 6]
JP 2000-319787 A
[Patent Document 7]
JP 2000-248384 A
[Patent Document 8]
Japanese Patent Laid-Open No. 2000-177871
[Patent Document 9]
JP 2000-199076 A
[Patent Document 10]
JP 2001-11656 A
[0005]
[Problems to be solved by the invention]
As the method (1), there is a method in which a film composed of a silane coupling agent or colloidal silica (Si component), lithium silicate (Li component) and an organic resin is formed. However, corrosion resistance is not sufficient when the main component is a urethane or acrylic resin.
Further, as a method of (2) above, Patent Document 4 discloses a combination of tannic acid, a silane coupling agent, and an organic resin. However, although the protective film formed by this technique contributes to the improvement of corrosion resistance, the obtained corrosion resistance is not sufficient, and coloring derived from tannic acid also occurs.
[0006]
Among the methods (3), Patent Documents 6 and 7 disclose a film made of an organic resin and a silane coupling agent, and further a thiocarbonyl compound, a phosphoric acid compound, and a vanadium compound. The acrylic olefin resin does not have sufficient corrosion resistance. In Patent Document 9, an acid-modified epoxy resin is used. In Patent Document 8, a resin containing a hydroxyl group, carboxyl group, glycidyl group, or phosphate group-containing monomer as a copolymerization component is added to a silane coupling agent and a phosphate compound, respectively. Although a blended film is disclosed, excellent corrosion resistance cannot be obtained even if such an organic resin is used. Furthermore, Patent Document 5 discloses a film in which a polyvinylphenol derivative is mixed with an etching agent such as a silane coupling agent or phosphoric acid. However, this film also cannot provide corrosion resistance equivalent to that of chromate treatment. Moreover, when the said film | membrane is a single layer film, the corrosion resistance after alkali degreasing is especially inadequate. Further, Patent Document 10 discloses a hydrazine derivative having active hydrogen coated as an organic resin film. However, since this is a two-layer film, the production line is limited, leading to an increase in cost. There is a drawback.
[0007]
Accordingly, the object of the present invention is to provide a single-layer surface-treated steel sheet that exhibits excellent corrosion resistance comparable to that of a surface-treated steel sheet that has been chromated without chromating, and that is less susceptible to restrictions on the line and can be manufactured at low cost. Is to provide.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have conducted the following investigation on the principle of corrosion inhibition for inhibiting corrosion of the plated steel sheet.
The corrosion of the zinc-based plated steel sheet on which the surface treatment film is formed proceeds in the following process.
(1) Corrosion factors (oxygen, water, chlorine ions, etc.) permeate into the surface treatment film and diffuse to the plating film / surface treatment film interface.
(2) Zinc dissolves by the following oxidation-reduction reaction at the plating film / surface treatment film interface.
Cathode reaction: 2H₂O + O₂+ 4e⁻ → 4OH⁻
Anode reaction: 2Zn → 2Zn²⁺+ 4e⁻
[0009]
Therefore, to improve the corrosion resistance of the galvanized steel sheet, it is essential to suppress the progress of both reactions (1) and (2).
(1) Advanced barrier layer that acts as a diffusion barrier for corrosion factors (mainly acts to suppress the cathode reaction)
(2) Reaction layer with plating metal that inactivates the surface of the plating film (mainly acts to suppress the anode reaction)
It is most effective to have a film configuration that has a self-repairing action when a defect occurs in the reaction layer.
[0010]
The inventor of the present invention does not form such a film structure by a single coating, but a double-layer film formed by coating the barrier layer forming component and the reaction layer forming component separately as in the prior art. Realization in the layer coating, specifically, the barrier layer (1) above (organic rich layer) above the coating and the reaction layer (inorganic rich layer) (2) above the coating respectively. Thus, it has been found that a remarkable effect of improving corrosion resistance can be obtained. When such a single-layer coating is defined as a pseudo-two-layer coating, the barrier layer and the reaction layer constituting the pseudo-two-layer coating are between the two-layer coating formed by the conventional double coating. There is no clear interface. On the contrary, it is considered that a high degree of corrosion resistance improvement effect that cannot be obtained by the conventional single layer coating can be exhibited by making the both compositions in a gradient composition.
[0011]
As a result of intensive studies by the present inventors, the pseudo-bilayer film as described above is obtained by reacting an epoxy group-containing resin with an active hydrogen-containing compound that is partially or entirely made of a hydrazine derivative having active hydrogen. Applying a surface treatment composition containing a silane coupling agent and a specific acid component (phosphoric acid and / or hexafluorometal acid) to the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet, It was found to be obtained by drying.
[0012]
A silane coupling agent is known to have an action of improving the adhesion between an inorganic compound and an organic compound so far, and can improve the adhesion between a plating metal and an organic resin. In contrast to the known effects of the silane coupling agent, in the specific surface treatment composition described above, the acid component contained in the surface treatment composition activates the plating film surface by etching, and the silane coupling agent It is considered that extremely excellent adhesion between the plating metal and the film-forming resin can be obtained by chemically bonding with both the activated plating metal and the film-forming resin. That is, by adding a silane coupling agent and a specific acid component to the surface treatment composition, the adhesion between the plating metal and the film-forming resin is markedly greater than when the silane coupling agent is added alone. This is considered to contribute to the improvement of corrosion resistance.
[0013]
Although the mechanism by which the pseudo two-layer film having the above-described film structure is formed is not necessarily clear, the reaction between the acid component in the surface treatment composition and the surface of the plating film may be involved in the film formation. On the other hand, the following actions involving a silane coupling agent are also conceivable. That is, since the silane coupling agent hydrolyzed in an aqueous solution has a silanol group (Si—OH), the hydrogen bonding adsorption action of the silane coupling agent on the surface of the plating metal activated by the acid component is promoted. When the silane coupling agent is concentrated on the metal surface and then dried, a dehydration condensation reaction takes place and a strong chemical bond is formed, thereby forming a reaction layer at the bottom of the film and a water-dispersible resin concentrated at the top of the film. There is also a possibility that the barrier layer is formed by the mechanism. In addition, there is a possibility that the above-described action occurs in a composite manner. In addition, in the film formation process as described above, it is considered that a reaction product (compound) between a dissolved plating metal such as zinc and an acid component is deposited in the film.
[0014]
Although the anticorrosion mechanism of such a pseudo two-layer coating is not necessarily clear, each of the anticorrosion mechanisms includes a dense organic polymer by adding a hydrazine derivative to the epoxy group-containing resin as the barrier layer of the above (1). A film is formed, which suppresses the permeation of corrosion factors (oxygen, water, chlorine ions, etc.) and effectively suppresses the cathodic reaction that causes corrosion, and also coats the plated metal ions eluted by the corrosion reaction. The free hydrazine derivative traps and forms a stable insoluble chelate compound layer. Also, the reaction layer (2) inactivates the surface layer of the plating film and effectively prevents the anode reaction that causes corrosion. In addition, the deposited compounds deposited in the film dissolve in a corrosive environment and acid components (such as phosphate ions) are generated. A self-repairing action that captures metal ions such as zinc ions eluted from the plating film (bonds with metal ions to form an insoluble compound) is obtained, and the silane coupling agent is activated by the acid component. It is possible to form a dense film with high adhesion by binding firmly to the plated metal surface, suppressing dissolution of the plated metal, and bonding with the film-forming resin. Therefore, it is considered that extremely excellent corrosion resistance (white rust resistance) can be obtained.
[0015]
Based on the above findings, the present inventors have repeatedly studied the composition of the surface treatment composition in order to further improve the white rust resistance. As a result, an aqueous dispersion of a modified epoxy resin obtained by reacting a primary or secondary amine compound with an epoxy group-containing organic resin and a hydrazine derivative having active hydrogen as a water-dispersible resin is used. The present inventors have found that further excellent white rust resistance can be obtained by adding a urethane resin aqueous dispersion together with the above-described silane coupling agent and specific acid component to the aqueous epoxy resin dispersion. It has also been found that white rust resistance, particularly after alkaline degreasing, can be effectively improved by adding a water-soluble inorganic component or a non-chromium rust preventive additive to the surface treatment composition.
[0016]
  The present invention has been made based on such findings, and the features thereof are as follows.
[1] On the surface of galvanized steel plate or aluminum galvanized steel plate,
  (A) an active hydrogen-containing compound (C) comprising an epoxy group-containing resin (A), a primary amine compound and / or a secondary amine compound (B), and a hydrazine derivative partly or entirely having active hydrogen An aqueous epoxy resin dispersion in which a modified epoxy resin obtained by reacting with water is dispersed in water;
  (B) a nonionic or cationic polyurethane emulsion;
  (C) a silane coupling agent;
  (D) phosphoric acid and / or hexafluorometal acid;
ContainsIn addition, the content of the silane coupling agent (c) is 15 to 50 parts by mass with respect to 100 parts by mass of the solid content of the organic resin, and the content of the phosphoric acid and / or hexafluorometal acid (d) is the organic resin. It is 5-50 mass parts with respect to 100 mass parts of solid content, and the mixing ratio of the said aqueous epoxy resin dispersion liquid (a) and nonionic or cationic polyurethane emulsion (b) is solid content mass ratio (a). / (B) = 75 / 25-25 / 75A surface-treated steel sheet excellent in white rust resistance, characterized by having a surface-treated film having a film thickness of 0.01 to 5 µm formed by applying and drying a surface-treating composition.
[0017]
[2] In the surface-treated steel sheet according to [1], the hydrazine derivative containing active hydrogen has a 5-membered or 6-membered ring structure, and a pyrazole compound having a nitrogen atom in the ring structure and / or Surface treatment with excellent white rust resistance, characterized by being a triazole compoundsteel sheet.
[ Three ]Above [1]Or 2 ]In the surface-treated steel sheet, the surface treatment composition further contains a water-soluble inorganic component in an amount of 0.1 to 60 parts by mass with respect to 100 parts by mass of the solid content of the organic resin. Excellent surface-treated steel sheet.
[0018]
[ Four ]the above[ Three ]In the surface-treated steel sheet, the cation species of the water-soluble inorganic component is one selected from Mg, Ca, Y, Ti, Zr, Nb, Zn, Mn, Co, Ni, Zn, Al, In, Ce, and La, or A surface-treated steel sheet excellent in white rust resistance, characterized in that there are two or more types, and the anionic species is one or more types selected from nitric acid, sulfuric acid, acetic acid, carbonic acid, phosphoric acid and chloride .
[ Five ]Above [1] ~[ Four ]In any one of the surface-treated steel sheets, the surface treatment composition further contains 0.1 to 50 parts by mass of a solid content of the non-chromium-based rust preventive additive with respect to 100 parts by mass of the solid content of the organic resin. A surface-treated steel sheet with excellent white rust resistance.
[ 6 ]Above [1] ~[ Five ]In any of the surface-treated steel sheets, the surface-treated composition contains at least one silane coupling agent having an amino group as a reactive functional group, and is excellent in white rust resistance. .
[ 7 ]Above [1] ~[ 6 ]In addition to the organic resin film having a film thickness of 0.01 μm or more and less than 5 μm, on the upper layer of the surface-treated film in which the film thickness of any one of the surface-treated steel sheets is 0.01 μm or more and less than 5 μm, A surface-treated steel sheet excellent in white rust resistance, wherein the total film thickness of the surface-treated film is 5 μm or less.
[0019]
[ 8 ]On the surface of galvanized steel plate or aluminum galvanized steel plate,
  (A) an active hydrogen-containing compound (C) comprising an epoxy group-containing resin (A), a primary amine compound and / or a secondary amine compound (B), and a hydrazine derivative partly or entirely having active hydrogen An aqueous epoxy resin dispersion in which a modified epoxy resin obtained by reacting with water is dispersed in water;
  (B) a nonionic or cationic polyurethane emulsion;
  (C) a silane coupling agent;
  (D) phosphoric acid and / or hexafluorometal acid;
ContainingThe content of the silane coupling agent (c) is 15 to 50 parts by mass with respect to 100 parts by mass of the solid content of the organic resin, and the content of the phosphoric acid and / or hexafluorometal acid (d) is solid of the organic resin. The blending ratio of the aqueous epoxy resin dispersion (a) and the nonionic or cationic polyurethane emulsion (b) is (a) / (solid content mass ratio). b) = 75/25 to 25/75,A surface treatment composition having a pH of 0.5 to 6 is applied and dried by heating at an ultimate plate temperature of 50 ° C. to 300 ° C. without washing with water to form a surface treatment film with a film thickness of 0.01 to 5 μm. A method for producing a surface-treated steel sheet excellent in white rust resistance, characterized by forming.
[ 9 ]the above[ 8 ]An organic resin film having a film thickness of 0.01 μm or more and less than 5 μm is formed on the surface treatment film having a film thickness of 0.01 μm or more and less than 5 μm. A method for producing a surface-treated steel sheet having excellent white rust resistance, wherein the total film thickness is 5 μm or less.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The details of the present invention and the reasons for limitation will be described below.
Examples of the zinc-based plated steel sheet used as the base of the surface-treated steel sheet of the present invention include galvanized steel sheet, Zn-Ni alloy-plated steel sheet, Zn-Fe alloy-plated steel sheet (electroplated steel sheet and galvannealed steel sheet), Zn-Cr. Alloy-plated steel sheet, Zn-Mn alloy-plated steel sheet, Zn-Co alloy-plated steel sheet, Zn-Co-Cr alloy-plated steel sheet, Zn-Cr-Ni alloy-plated steel sheet, Zn-Cr-Fe alloy-plated steel sheet, Zn-Al alloy plating Steel plate (for example, Zn-5% Al alloy plated steel plate, Zn-55% Al alloy plated steel plate, etc.), Zn-Mg alloy plated steel plate, Zn-Al-Mg alloy plated steel plate (for example, Zn-6% Al-3%) Mg alloy-plated steel sheet, Zn-11% Al-3% Mg alloy-plated steel sheet), and metal oxides and polymers in the plated film of these plated steel sheets. Zinc-based composite-plated steel sheet containing dispersed (e.g., Zn-SiO₂(Dispersed plated steel sheet) can be used.
[0021]
Moreover, the multilayer plating steel plate which plated two or more layers of the same kind or different kind among the above plating can be used.
Moreover, as an aluminum system plated steel plate used as the base of the surface treatment steel plate of this invention, an aluminum plating steel plate, an Al-Si alloy plating steel plate, etc. can be used.
Moreover, as a plated steel plate, the steel plate surface may be plated with a thin plate such as Ni in advance, and the above-described various types of plating may be performed thereon.
As a plating method, any feasible method among an electrolytic method (electrolysis in an aqueous solution or electrolysis in a nonaqueous solvent), a melting method, and a gas phase method may be adopted.
[0022]
Further, for the purpose of preventing blackening of the plating (blackening resistance), one or more trace elements of Ni, Co, and Fe are deposited in the plating film at a concentration of about 0.1 to 2000 ppm, or The surface of the plating film may be subjected to a surface conditioning treatment with an alkaline aqueous solution or an acidic aqueous solution containing one or more of Ni, Co, and Fe to precipitate these elements. In order to achieve both excellent corrosion resistance and blackening resistance, for example, an aqueous solution of “CL-342” (trade name) manufactured by Nihon Parkerizing Co., Ltd., which mainly contains condensed phosphoric acid, is used. It is desirable that the content of at least one of Ni, Co, and Fe is 0.5 to 50 ppm, more preferably 1 to 20 ppm. In order to obtain a beautiful appearance, the concentration of the “CL-342” is preferably 5 to 50 g / l, more preferably 10 to 30 g / l.
[0023]
Next, the surface treatment film formed on the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet and the surface treatment composition for forming the film will be described.
In the surface-treated steel sheet of the present invention, the surface-treated film formed on the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet,
(A) an active hydrogen-containing compound (C) comprising an epoxy group-containing resin (A), a primary amine compound and / or a secondary amine compound (B), and a hydrazine derivative partly or entirely having active hydrogen An aqueous epoxy resin dispersion in which a modified epoxy resin obtained by reacting with water is dispersed in water;
(B) an aqueous dispersion of urethane resin;
(C) a silane coupling agent;
(D) phosphoric acid and / or hexafluorometal acid;
It is the surface treatment film | membrane formed by apply | coating the surface treatment composition containing this and drying. This surface treatment film does not contain Cr at all.
[0024]
First, the components (A) to (C), which are constituent components of the aqueous epoxy resin dispersion (a), will be described.
The epoxy group-containing resin as the component (A) is a resin containing one or more epoxy groups in the molecule. For example, an epoxy resin, a modified epoxy resin, an epoxy group-containing monomer and other monomers are copolymerized. The acrylic copolymer resin, polybutadiene resin having an epoxy group, polyurethane resin having an epoxy group, and an adduct or condensate of these resins may be used alone or in admixture of two or more. it can.
[0025]
The epoxy resin is formed by reacting a polyphenol such as bisphenol A, bisphenol F, or novolak type phenol with an epihalohydrin such as epichlorohydrin to introduce a glycidyl group, or further adding a polyphenol to the glycidyl group-introduced reaction product. An aromatic epoxy resin obtained by reacting with an aromatic epoxy resin; further, an aliphatic epoxy resin, an alicyclic epoxy resin, and the like are used, and one of these may be used alone or in combination of two or more. Can do. These epoxy resins preferably have a number average molecular weight of 1500 or more, particularly when film formation at low temperatures is required.
Examples of the modified epoxy resin include resins obtained by reacting various modifiers with epoxy groups or hydroxyl groups in the epoxy resin. For example, an epoxy ester resin reacted with a dry oil fatty acid; an epoxy acrylate resin modified with a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid; a urethane-modified epoxy resin reacted with an isocyanate compound;
[0026]
As the acrylic copolymer resin, an unsaturated monomer having an epoxy group and a polymerizable unsaturated monomer component essentially containing an acrylic ester or methacrylic ester are prepared by a solution polymerization method, an emulsion polymerization method or a suspension polymerization method. A synthesized resin can be mentioned. Examples of the polymerizable unsaturated monomer component include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-, iso- or tert-butyl (meth) acrylate, hexyl (meth) acrylate, C1-C24 alkyl ester of acrylic acid or methacrylic acid such as 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate; acrylic acid, methacrylic acid, styrene, vinyltoluene, acrylamide, acrylonitrile , N-methylol (meth) acrylamide, N-methylol (meth) acrylamide having 1 to 4 carbon ethers, N, N-diethylaminoethyl methacrylate, and the like. Moreover, as an unsaturated monomer which has an epoxy group, if it has an epoxy group and a polymerizable unsaturated group, such as glycidyl methacrylate, glycidyl acrylate, 3,4 epoxy cyclohexyl-1-methyl (meth) acrylate, etc. It is not limited.
The acrylic copolymer resin may be a resin modified with a polyester resin, an epoxy resin, a phenol resin, or the like.
[0027]
Particularly preferred as the epoxy resin is a resin represented by the following chemical structural formula, which is a reaction product of bisphenol A and epiparohydrin, and is particularly suitable because of its excellent corrosion resistance.
[Chemical 1]

In said chemical structural formula, q is an integer of 0-50, Preferably it is an integer of 1-40, Most preferably, it is an integer of 2-20.
Such a bisphenol A type epoxy resin can be obtained by a production method widely known in the art.
[0028]
The primary or secondary amine compound which is the component (B) is an essential part for exhibiting the water dispersibility of the epoxy group-containing resin.
Specific examples include monoethylamine, mono-n- or iso-propylamine, mono-n- or iso-butylamine, monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, 2-hydroxy-2 ′. Primary amine compounds such as (aminopropoxy) ethyl ether; second amines such as diethylamine, dibutylamine, methylethylamine, diethanolamine, di-n- or -ios-propanolamine, N-methylethanolamine, N-ethylethanolamine A class amine compound etc. are mentioned. These primary amine compounds and secondary amine compounds can be used singly or in combination of two or more. Of these, diethanolamine is particularly preferred from the viewpoints of easy reaction, controllability, and water dispersibility.
[0029]
The active hydrogen-containing compound comprising a hydrazine derivative partly or entirely having active hydrogen, which is the component (C), is an essential component for imparting high corrosion resistance to the surface treatment film. Specific examples of the hydrazine derivative having active hydrogen include the following.
(1) Carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, thiocarbohydrazide, 4,4'-oxybisbenzenesulfonylhydrazide, benzophenone hydrazone Hydrazide compounds such as
[0030]
(2) Pyrazole compounds such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole;
(3) 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino -3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (monohydrate), 6- Triazole compounds such as methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyridazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine;
[0031]
(4) tetrazole compounds such as 5-phenyl-1,2,3,4-tetrazole and 5-mercapto-1-phenyl-1,2,3,4-tetrazole;
(5) Thiadiazole compounds such as 5-amino-2-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole;
(6) Maleic hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, 6-methyl-4,5-dihydro-3-pyridazone, etc. Pyridazine compounds;
Of these, pyrazole compounds and triazole compounds having a 5- or 6-membered ring structure and having a nitrogen atom in the ring structure are particularly preferred from the viewpoint of corrosion resistance and the like.
The hydrazine derivatives listed above can be used alone or in combination of two or more.
[0032]
Moreover, in this invention, active hydrogen containing compounds other than a hydrazine derivative can be used as a part of active hydrogen containing compound (C).
Examples of the active hydrogen-containing compound other than the bidrazine derivative include the following.
・ Organic acids such as ammonia and carboxylic acids
・ Hydrogen halides such as hydrogen chloride
・ Alcohols and thiols
A quaternary chlorinating agent which is a mixture of a hydrazine derivative or a tertiary amine and an acid having no active hydrogen
[0033]
The quaternary chlorinating agent that can be used as a part of the active hydrogen-containing compound can react with an epoxy group because a hydrazine derivative or a tertiary amine that does not have an active hydrogen is not reactive with an epoxy group by itself. Therefore, it is a mixture with an acid. The quaternary chlorinating agent reacts with an epoxy group in the presence of water as necessary to form a quaternary salt with the epoxy group-containing resin. The acid used to obtain the quaternary chlorinating agent may be any of organic acids such as acetic acid and lactic acid, and inorganic acids such as hydrochloric acid. Examples of the hydrazine derivative having no active hydrogen used for obtaining a quaternary chlorinating agent include 3,6-dichloropyridazine, and examples of the tertiary amine include dimethylethanolamine, triethylamine, Examples include trimethylamine, triisopropylamine, and methyldiethanolamine.
[0034]
The proportion of the hydrazine derivative having active hydrogen in the active hydrogen-containing compound (C) is 10 to 100 mol%, more preferably 30 to 100 mol%, and still more preferably 40 to 100 mol%. . If the ratio of the hydrazine derivative having active hydrogen is less than 10 mol%, the surface treatment film cannot be provided with a sufficient rust prevention function, and the resulting rust prevention effect is obtained by simply mixing the film-forming organic resin and the hydrazine derivative. There is no big difference from the case.
[0035]
The modified epoxy resin of the aqueous epoxy resin dispersion (a) used in the present invention is partially or wholly composed of an epoxy group-containing resin (A), a primary amine compound and / or a secondary amine compound (B). Although obtained by reacting with an active hydrogen-containing compound (C) comprising a hydrazine derivative having active hydrogen, the reaction is usually 10 to 300 ° C., preferably 50 to 150 ° C., for about 1 to 8 hours. It is desirable to do.
[0036]
This reaction may be performed by adding an organic solvent, and the type of the organic solvent to be used is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, cyclohexanone; ethanol, butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether , Propylene glycol, propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other alcohols and ethers containing a hydroxyl group; ethyl acetate, butyl acetate, ethylene glycol monobutyl ether acetate and other esters; toluene, xylene Aromatic hydrocarbons such as It can be used one or two or more thereof. Of these, ketone-based or ether-based solvents are particularly preferable from the viewpoints of solubility with an epoxy resin, film formation, and the like.
[0037]
The mixing ratio of the epoxy group-containing resin (A) to the primary amine compound and / or the secondary amine compound (B) is such that the primary amine compound and the epoxy group in the epoxy group-containing resin (A) It is appropriate that the secondary amine compound (B) is 20 to 80 mol%, preferably 30 to 70 mol%, more preferably 40 to 60 mol%, and the amount of the secondary amine compound (B) with respect to the remaining epoxy groups after the reaction. It is advantageous in terms of corrosion resistance, water dispersibility and the like to react with a hydrazine derivative having a corresponding active hydrogen. That is, the blending amount of the hydrazine derivative having active hydrogen is 80 to 20 mol%, preferably 70 to 30 mol%, more preferably 60 to 40 mol% with respect to the epoxy group in the epoxy group-containing resin (A). Is appropriate.
[0038]
As a method for obtaining a water-based epoxy resin dispersion by dispersing the modified epoxy resin obtained by reacting the components (A) to (C) in water, a well-known method for amino groups contained in the modified epoxy resin is known. A method of neutralizing with water, such as acetic acid, formic acid, phosphoric acid, etc., and dispersing in water is effective. The neutralization equivalent is not particularly limited, but is 0.2 to 0.8 equivalent, preferably 0.3 to 0.7 equivalent, more preferably 0.4 to 0.6 equivalent, based on the amino group. Is suitable from the viewpoint of dispersion properties and water resistance.
The modified epoxy resin obtained by reacting the components (A) to (C) or the aqueous epoxy resin dispersion obtained by dispersing this in water may be a mixture of two or more.
[0039]
The aqueous epoxy resin dispersion (a) can form a film having good adhesion to the plating film even if the components (b) to (d) are added and used as it is, but forms a denser barrier film. For this purpose, it is desirable to add a curing agent to the aqueous epoxy resin dispersion and heat cure the organic film. Examples of the curing agent include polyisocyanate compounds and amino resin compounds.
The polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and includes an aliphatic isocyanate compound, an alicyclic isocyanate compound (including a heterocyclic ring), an aromatic isocyanate compound; Examples thereof include compounds partially reacted with a monohydric alcohol, and some or all of the isocyanate groups in these polyisocyanate compounds may be blocked with a blocking agent.
[0040]
Examples of the polyisocyanate compound include the following.
(1) m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, o- or p-xylylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate;
(2) The compound of (1) above or a mixture thereof and a polyhydric alcohol (dihydric alcohols such as ethylene glycol and propylene glycol; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as pentaerythritol; A reaction product with a hexahydric alcohol such as sorbitol and dipentaerythritol), in which at least two isocyanates remain in one molecule;
These polyisocyanate compounds can be used individually by 1 type or in mixture of 2 or more types.
[0041]
Examples of the blocking agent include (1) aliphatic monoalcohols such as methanol, ethanol, propanol, butanol and octyl alcohol; (2) monoethers of ethylene glycol and / or diethylene glycol such as methyl, ethyl, Monoethers such as propyl (n-, iso) and butyl (n-, iso, sec); (3) aromatic alcohols such as phenol and cresol; (4) oximes such as acetooxime and methyl ethyl ketone oxime can be used; By reacting one or more of these with the polyisocyanate compound, a polyisocyanate compound that is stably protected at least at room temperature can be obtained.
[0042]
Examples of the amino resin compound include methylolated amino resins obtained by reacting amino components such as melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, and dicyandiamide with aldehyde. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. In addition, those obtained by etherifying this methylolated amino resin with an appropriate alcohol can be used. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, and n-butyl. Alcohol, i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol, etc. are mentioned. Among amino resin compounds, a methylolated melamine resin in which at least a part of the methylol group is alkyl etherified is particularly suitable.
The blending ratio of the modified epoxy resin (D) and the curing agent (E) in the aqueous epoxy resin dispersion (a) is (D) / (E) = 95/5 to 55/45 in terms of the solid mass ratio. Preferably, (D) / (E) = 90/10 to 65/35 is appropriate from the standpoints of film adhesion, suitability for top coating, and the like.
[0043]
Furthermore, it is desirable to use a known curing accelerating catalyst in order to increase the low temperature crosslinking property. As a curing accelerating catalyst when a polyisocyanate compound is used as a curing agent, for example, N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, stannous chloride, zinc naphthenate, bismuth nitrate, and the like can be used. As the curing accelerating catalyst when an amino resin compound is used as the curing agent, for example, phosphoric acid, a sulfonic acid compound or an amine neutralized product of a sulfonic acid compound is preferably used. Representative examples of the sulfonic acid compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like. The amine in the amine neutralized product of the sulfonic acid compound may be any of primary amine, secondary amine, and tertiary amine.
[0044]
Next, an aqueous dispersion of urethane resin as the component (b) will be described.
An aqueous dispersion of a urethane resin is a urethane emulsion using a product obtained by reacting a polyisocyanate compound with a polyhydroxy compound such as polyether diol or polyester diol.
For example, this urethane emulsion converts a polyisocyanate compound and a polyhydroxy compound into a hydroxyl group of the polyhydroxy compound in the presence or absence of a hydrophilic organic solvent that does not have active hydrogen capable of reacting with an isocyanate group in the molecule. On the other hand, it can be easily obtained by reacting with an excess of isocyanate groups of the polyisocyanate compound. If necessary, this reaction product (polymer), an amine and water are mixed to carry out an amine extension reaction, It can be obtained by mixing with a nonionic or ionic emulsifier and adding water to emulsify and disperse, and if necessary, distill off the organic solvent.
[0045]
Moreover, a urethane emulsion can be obtained without using an emulsifier by using a polyhydroxy compound having a nonionic, anionic or cationic hydrophilic group in the urethane resin skeleton.
Examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate and isophorone diisocyanate; tolylene diisocyanate and 4,4′-diphenylmethane. Examples include organic diisocyanates such as aromatic diisocyanates such as diisocyanates, cyclized polymers of the above organic diisocyanates, and isocyanurates and biurets of the above organic diisocyanates. One or two of these The above can be used.
As the urethane resin aqueous dispersion (b), a nonionic or cationic polyurethane emulsion is particularly suitable from the viewpoint of mixing stability with the aqueous epoxy resin dispersion (a).
[0046]
When the surface treatment composition contains an aqueous dispersion (b) of a urethane resin, white rust resistance can be effectively enhanced. The reason for this is that by adding an appropriate amount of an aqueous dispersion of a urethane resin, the film-forming property of the surface treatment composition is improved. As a result, the effect of inhibiting the permeation of corrosion factors is increased, and the antirust component in the film This is thought to be due to the suppression of outflow.
The blending ratio of the aqueous epoxy resin dispersion (a) and the urethane resin aqueous dispersion (b) in the surface treatment composition is (a) / (b) = 95/5 to 5/95 in terms of solid content. Preferably, it is appropriate to set to 75/25 to 25/75. If the blending ratio of the urethane resin aqueous dispersion (b) to the aqueous epoxy resin dispersion (a) is below the lower limit, the film-forming property derived from the urethane resin is not sufficient, and the inhibiting action of the corrosion factor is insufficient. The white rust resistance tends to decrease. On the other hand, when the blending ratio of the urethane resin aqueous dispersion (b) to the aqueous epoxy resin dispersion (a) exceeds the upper limit, the active hydrogen-containing compound comprising the hydrazine derivative having active hydrogen in the surface treatment composition. Since the ratio decreases, the white rust resistance also tends to decrease in this case.
[0047]
Further, in the surface treatment composition, as the water-dispersible resin and / or water-soluble resin other than the specific water-dispersible resin (modified epoxy resin, urethane resin) described above, for example, acrylic resin, polyester resin, epoxy resin You may mix | blend 1 type (s) or 2 or more types of resin, ethylene-type resin, alkyd-type resin, phenol resin, and olefin resin by the ratio in the total resin solid content about 25 mass%.
[0048]
Next, the silane coupling agent which is the component (c) will be described.
Examples of the silane coupling agent include vinyl methoxy silane, vinyl ethoxy silane, vinyl trichloro silane, vinyl trimethoxy silane, vinyl triethoxy silane, β- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane, and γ-glycid. Xylpropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ -Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-me Tacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-isocyanatopropyl Triethoxysilane, γ-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- (vinylbenzylamine) -β-aminoethyl-γ-aminopropyltri Etc. can be mentioned Tokishishiran, these one may be used alone or in combination of two or more.
In order to improve the surface treatment composition by including a silane coupling agent together with a specific acid component, the reasons described above can be considered.
[0049]
Among the silane coupling agents, a silane coupling agent having an amino group as a reactive functional group is particularly preferable from the viewpoint of having a functional group highly reactive with the aqueous epoxy resin dispersion (a). . Examples of such silane coupling agents include N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ. -Aminopropyltrimexysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc., specifically, “KBM-903” and “KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd. , “KBM-603”, “KBE-602”, “KBE-603” (all are trade names), and the like.
[0050]
The compounding quantity of a silane coupling agent is 1-300 mass parts with respect to 100 mass parts of solid content of the organic resin in a surface treatment composition, Preferably it is 5-100 mass parts, More preferably, it is 15-50 mass parts. Is appropriate. If the blending amount of the silane coupling agent is less than 1 part by mass, the corrosion resistance is inferior. On the other hand, if it exceeds 300 parts by mass, a sufficient film cannot be formed, so the effect of improving the adhesion and barrier properties with the water-dispersible resin cannot be exhibited. Corrosion resistance decreases.
[0051]
Next, phosphoric acid and / or hexafluorometal acid as the component (d) has an action of activating the metal surface by acting on the surface of the inactive plating film. And as a result of the adhesiveness of the plating metal surface activated in this way and the film forming resin being remarkably improved through the silane coupling agent, the corrosion resistance is remarkably improved. The phosphoric acid and hexafluorometal acid may be used alone or in combination.
The type of hexafluorometal acid is not particularly limited, but from the viewpoint of effectively forming the reaction layer of the pseudo-bilayer film described above, in particular, fluorinated titanic acid, fluorinated zirconic acid, silicic acid, etc. Hexafluorometal acids containing one or more elements selected from Ti, Si, and Zr are preferred, and one or more of these can be used.
[0052]
The blending amount of phosphoric acid and / or hexafluorometal acid (total blending amount when used in combination) is 0.1 to 80 parts by weight with respect to 100 parts by weight of the solid content of the organic resin in the surface treatment composition. The amount is preferably 1 to 60 parts by mass, more preferably 5 to 50 parts by mass. When the blending amount of phosphoric acid and / or hexafluorometal acid is less than 0.1 parts by mass, the corrosion resistance is inferior.
[0053]
The surface treatment composition preferably further contains a water-soluble inorganic component for the purpose of improving the corrosion resistance. As this water-soluble inorganic component, one or two kinds of cationic species selected from Mg, Ca, Y, Ti, Zr, Nb, Zn, Mn, Co, Ni, Zn, Al, In, Ce, and La are used. As described above, an inorganic component in which the anionic species is one or more selected from nitric acid, sulfuric acid, acetic acid, carbonic acid, phosphoric acid, and chloride is preferable. Specific examples include Mg nitrate, Co nitrate, Ti sulfate, Ni sulfate, Zn acetate, Ce acetate, Mn carbonate, and the like, and one or more of these can be used.
[0054]
The reason why white rust resistance after alkali degreasing is improved by blending such a water-soluble inorganic component is that the denseness of the inorganic rich layer in the pseudo two-layer film is increased, and the inorganic rich layer by alkali treatment is improved. This is considered to be because destruction is suppressed.
Further, from the viewpoint of obtaining particularly excellent white rust resistance, those having Al, Mn, Zr, Co, Mg as the cationic species of the water-soluble inorganic component are particularly desirable, and one or two selected from these are selected. It is preferable to use a water-soluble inorganic component containing more than one element.
The amount of the water-soluble inorganic component is 0.1 to 60 parts by mass, preferably 0.5 to 40 parts by mass, based on 100 parts by mass of the organic resin solids in the surface treatment composition. The amount is preferably 1 to 30 parts by mass. If the blending amount of the water-soluble inorganic component is less than 0.1 parts by mass, the effect of improving the corrosion resistance is not sufficient.
[0055]
A non-chromium rust preventive additive can be blended with the surface treatment composition as needed for the purpose of improving corrosion resistance. In particular, it is preferable to use one or two or more selected from the group of the following (e1) to (e4) as the non-chromium rust preventive additive.
(E1) Silicon oxide
(E2) Calcium or / and calcium compound
(E3) Insoluble phosphate compound
(E4) An organic compound containing one or more S atoms selected from triazoles, thiols, thiadiazoles, thiazoles, and thiurams
The details and anticorrosion mechanism of these non-chromium rust preventive additives (e1) to (e4) are as follows.
[0056]
First, as the component (e1), colloidal silica or dry silica, which is fine particle silica, can be used. From the viewpoint of corrosion resistance, calcium ion-exchanged silica in which calcium is bound to the surface is used. Is preferred.
As colloidal silica, for example, Snowtex O, 20, 30, 40, C, S (all trade names) manufactured by Nissan Chemical Co., Ltd. can be used, and fumed silica is manufactured by Nippon Aerosil Co., Ltd. AEROSIL R971, R812, R811, R974, R202, R805, 130, 200, 300, 300CF (all trade names) can be used. Examples of calcium ion exchange silica include SHIELDEX C303, SHIELDEX AC3, and SHIELDEX AC5 (all are trade names) manufactured by WRGrace & Co., SHIELDEX and SHIELDEX SY710 (all are trade names) manufactured by Fuji Silysia Chemical Co., Ltd. Can do. These silicas contribute to the production of dense and stable zinc corrosion products in a corrosive environment, and the corrosion products are formed densely on the plating surface, thereby suppressing the promotion of corrosion.
[0057]
The calcium compound as the component (e2) may be any of calcium oxide, calcium hydroxide, and calcium salt, and one or more of these can be used. In addition, there are no particular restrictions on the type of calcium salt. In addition to simple salts containing only calcium as a cation such as calcium silicate, calcium carbonate, calcium phosphate, etc., other than calcium such as calcium phosphate / zinc, calcium phosphate / magnesium, etc. A double salt containing the cation may be used. This (e2) component is preferentially dissolved in base metal over zinc and aluminum, which are plating metals, in a corrosive environment, and this is generated by the cathode reaction.⁻As a dense and sparingly soluble product, it seals the defect and suppresses the corrosion reaction. Further, when blended with silica as described above, calcium ions are adsorbed on the surface, and the surface charge is electrically neutralized and aggregated. As a result, a dense and hardly soluble protective film is generated to block the corrosion starting point and suppress the corrosion reaction.
[0058]
Moreover, as a poorly soluble phosphoric acid compound which is said (e3), a hardly soluble phosphate can be used. This sparingly soluble phosphate includes all types of salts such as simple salts and double salts. Moreover, there is no limitation in the metal cation which comprises it, and any metal cation, such as poorly soluble zinc phosphate, magnesium phosphate, calcium phosphate, aluminum phosphate, may be sufficient. Further, there is no limitation on the skeleton or the degree of condensation of phosphate ions, and any of normal salt, dihydrogen salt, monohydrogen salt or phosphite may be used. In addition, orthophosphate may be polyphosphate other than orthophosphate. Includes all condensed phosphoric acids such as salts. This sparingly soluble phosphorus compound forms a dense and sparingly soluble protective film by complexing reaction with phosphate ions dissociated by hydrolysis by zinc and aluminum, which are eluted by corrosion, thereby blocking the corrosion starting point. Suppress.
[0059]
Moreover, as an organic compound which has the S atom of said (e4), the following can be mentioned, for example. That is, as triazoles, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2, 4-triazole, 1H-benzotriazole, etc., as thiols, 1,3,5-triazine-2,4,6-trithiol, 2-mercaptobenzimidazole, etc., and as thiadiazoles, 5- Amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, and the like, and as thiazoles, 2-N, N-diethylthiobenzothiazole, 2- Examples include mercaptobenzothiazoles, and examples of thiurams include tetraethylthiuram disulfide.These organic compounds exhibit self-repairing properties due to the adsorption effect. That is, zinc and aluminum eluted by corrosion are adsorbed on polar groups containing sulfur contained in these organic compounds to form an inactive film, thereby blocking the corrosion starting point and suppressing the corrosion reaction.
[0060]
The compounding amount of the non-chromium rust preventive additive is 0.1 to 50 parts by mass, preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the organic resin solids in the surface treatment composition. Part, more preferably 1 to 20 parts by weight. If the blending amount of the non-chromium rust preventive additive is less than 0.1 parts by mass, the effect of improving the corrosion resistance after alkali degreasing cannot be sufficiently obtained. In addition, the corrosion resistance is reduced, which is not preferable.
Two or more rust preventive additives (e1) to (e4) may be added in combination.
[0061]
In order to improve the workability (scratch resistance) and continuous wear of the film, a lubricant can be blended with the surface treatment composition as necessary. As this lubricant, for example, a fatty acid ester wax which is an esterified product of a polyol compound and a fatty acid, a silicone wax, a fluorine wax, a polyolefin wax such as polyethylene, a lanolin wax, a montan wax, a microcrystalline wax, a carnauba wax, etc. There is no particular limitation. These lubricants can be used alone or in combination of two or more.
[0062]
The blending amount of the lubricant is suitably 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the solid content of the organic resin in the surface treatment composition. When the blending amount of the lubricant is less than 0.1 parts by mass, the resulting coating film has low slipperiness, so that the coating film is easily damaged when subjected to severe processing, whereas it exceeds 20 parts by mass. The paintability of the resulting coating film is reduced and at the same time the flexibility is lowered, and the continuity of the coating film is impaired when severe processing is performed.
[0063]
In the surface treatment composition, other oxide fine particles (for example, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, antimony oxide, etc.), phosphomolybdate (for example, phosphomolybdic acid) are used as corrosion inhibitors. Aluminum), organic phosphoric acid and its salts (eg, phytic acid, phytate, phosphonic acid, phosphonate, and their metal salts, alkali metal salts, alkaline earth metal salts, etc.), organic inhibitors (eg, 1 type, or 2 or more types, such as a hydrazine and its derivative (s), a thiol compound, a thiocarbamate, etc. can be added.
[0064]
Further, if necessary, in the surface treatment composition, as an additive, an organic coloring pigment (for example, a condensed polycyclic organic pigment, a phthalocyanine organic pigment), a coloring dye (for example, a water-soluble azo metal dye) Inorganic pigment (for example, titanium oxide), conductive pigment (for example, metal powder such as zinc, aluminum, nickel, iron phosphide, antimony-doped tin oxide, etc.), coupling agent (for example, titanium coupling agent) 1 type, or 2 or more types, such as a melamine and cyanuric acid adduct, can be added.
[0065]
The surface treatment film formed by the surface treatment composition as described above has a dry film thickness of 0.01 to 5 μm, preferably 0.1 to 3 μm, and more preferably 0.3 to 2 μm. When the dry film thickness is less than 0.01 μm, the corrosion resistance is insufficient. On the other hand, when the dry film thickness exceeds 5 μm, the conductivity and workability deteriorate.
Moreover, an organic resin film can be formed as a second layer film on the upper layer of the surface treatment film described above. In this case, the film thickness of the organic resin film that is the second layer is 0.01 μm or more and less than 5 μm, and the film thickness of the surface treatment film that is the first layer film is 0.01 μm or more and less than 5 μm, It is preferable that the total does not exceed 5 μm.
[0066]
In order to form the above-mentioned surface treatment film on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet, a surface treatment composition (treatment liquid) having the above-described composition is applied to the plated steel sheet so that the dry film thickness is in the above range. And heat-dried without washing with water.
It is appropriate to adjust the surface treatment composition (treatment liquid) to pH 0.5-6, preferably 1-4. If the pH of the surface treatment composition is less than 0.5, the reactivity of the treatment liquid is too strong, resulting in uneven appearance. On the other hand, if the pH exceeds 6, the reactivity of the treatment liquid becomes low, and the bonding between the plating metal and the film is reduced. Becomes insufficient, and the corrosion resistance decreases.
[0067]
As a method for forming the surface treatment composition on the surface of the plated steel plate, any of a coating method, a dipping method, and a spray method may be used. As a coating treatment method, any method such as a roll coater (3-roll method, 2-roll method, etc.), a squeeze coater, or a die coater may be used. In addition, after the coating process with a squeeze coater or the like, or the dipping process and the spray process, the coating amount can be adjusted, the appearance can be made uniform, and the film thickness can be made uniform by an air knife method or a roll drawing method.
[0068]
After coating the surface treatment composition, drying is performed without washing with water. As the heating and drying means, a dryer, a hot air furnace, a high frequency induction heating furnace, an infrared furnace or the like can be used. It is appropriate to perform the heat treatment in the range of 30 ° C. to 300 ° C., preferably 40 ° C. to 250 ° C., at the ultimate plate temperature. If this heating temperature is less than 30 ° C., a large amount of moisture remains in the film, resulting in insufficient corrosion resistance. Moreover, when it exceeds 300 degreeC, it will not only be uneconomical but a defect will arise in a membrane | film | coat and corrosion resistance will fall.
Further, when an organic resin film is formed as a second layer film on the upper layer of the surface treatment film formed as described above, the treatment composition for the second layer film is formed to have the above-described film thickness. It is applied to the surface treatment film surface and dried. Application | coating and heat drying of a process composition should just be performed according to the method used for formation of the surface treatment mentioned above.
[0069]
Therefore, the production method of the present invention and preferred embodiments thereof are as follows.
[1] On the surface of zinc-plated steel sheet or aluminum-plated steel sheet,
(A) an active hydrogen-containing compound (C) comprising an epoxy group-containing resin (A), a primary amine compound and / or a secondary amine compound (B), and a hydrazine derivative partly or entirely having active hydrogen An aqueous epoxy resin dispersion in which a modified epoxy resin obtained by reacting with water is dispersed in water;
(B) an aqueous dispersion of urethane resin;
(C) a silane coupling agent;
(D) phosphoric acid and / or hexafluorometal acid;
A surface treatment composition having a pH of 0.5 to 6 is applied and dried by heating at an ultimate plate temperature of 50 ° C. to 300 ° C. without washing with water, and the film thickness is 0.01 to 5 μm. A method for producing a surface-treated steel sheet having excellent white rust resistance, wherein a surface-treated film is formed.
[0070]
[2] In the production method of [1], the hydrazine derivative containing active hydrogen has a 5-membered or 6-membered ring structure, and a pyrazole compound and / or triazole having a nitrogen atom in the ring structure A method for producing a surface-treated steel sheet having excellent white rust resistance, which is a compound.
[3] In the production method of [1] or [2] above, the surface treatment composition comprises 1 to 300 parts by mass of phosphoric acid and / or hexagonal silane coupling agent based on 100 parts by mass of organic resin solids. The manufacturing method of the surface treatment steel plate excellent in white rust resistance characterized by containing 0.1-80 mass parts of fluoro metal acids with respect to 100 mass parts of solid content of organic resin.
[0071]
[4] In the production method according to any one of [1] to [3], the surface treatment composition further contains a water-soluble inorganic component in a solid content of 0.1 to 60 parts by mass with respect to 100 parts by mass of the solid content of the organic resin. The manufacturing method of the surface treatment steel plate excellent in the white rust resistance characterized by containing a mass part.
[5] In the production method of [4], the cation species of the water-soluble inorganic component is Mg, Ca, Y, Ti, Zr, Nb, Zn, Mn, Co, Ni, Zn, Al, In, Ce, or La. 1 type or 2 types or more selected from among them, and the anionic species is 1 type or 2 types or more selected from nitric acid, sulfuric acid, acetic acid, carbonic acid, phosphoric acid and chloride A method for producing a surface-treated steel sheet having excellent properties.
[6] In the production method according to any one of [1] to [5], the surface treatment composition may further contain a non-chromium rust preventive additive in a solid content of 0.1 parts by weight with respect to 100 parts by weight of the solid content of the organic resin. The manufacturing method of the surface treatment steel plate excellent in the white rust resistance characterized by containing 1-50 mass parts.
[0072]
[7] The method according to any one of [1] to [6], wherein the surface treatment composition contains at least one silane coupling agent having an amino group as a reactive functional group. A method for producing a surface-treated steel sheet having excellent white rust resistance.
[8] The film thickness of the surface-treated steel sheet obtained by the production method according to any one of the above [1] to [7] is 0.01 μm or more on the upper layer of the surface-treated film having a film thickness of 0.01 μm or more and less than 5 μm. A method for producing a surface-treated steel sheet having excellent white rust resistance, wherein an organic resin film having a thickness of less than 5 μm is formed such that the total film thickness with the surface-treated film thickness is 5 μm or less.
[0073]
The above-mentioned surface treatment film may be formed on either one side or both sides of the plated steel sheet. Examples of combinations of film formation on the front and back surfaces of the plated steel sheet include, for example, a single layer film (surface treatment film) / no treatment, two Layer film (surface treatment film + organic resin film) / No treatment, Single layer film (surface treatment film) / Double layer film (surface treatment film + organic resin film), Double layer film (surface treatment film + organic resin film) / It can be set as arbitrary forms, such as a two-layer film (surface treatment film + organic resin film).
[0074]
【Example】
As the resin composition for the surface treatment composition, an aqueous epoxy resin dispersion shown in Table 2 was used, and an urethane resin aqueous dispersion (Table 3), a silane coupling agent (Table 4), phosphoric acid or hexafluorometal acid was used. (Table 5), water-soluble inorganic component (Table 6), non-chromium rust preventive additive (Table 7), solid lubricant (Table 8) are appropriately blended, and further, aqueous ammonia, nitric acid, acetic acid, sulfuric acid, phosphoric acid Then, after adjusting the pH to 0.5 to 6 with hexafluorometal acid or the like, the mixture was stirred for a required time using a paint disperser (sand grinder) to prepare a surface treatment composition.
[0075]
Production Examples 1 to 5 of the aqueous epoxy resin dispersion shown in Table 2 are shown below.
・ Production Example 1
To a glass four-necked flask equipped with a thermometer, a stirrer, and a condenser tube, 787.4 g of Epicoat 1007 (epoxy resin, manufactured by Shell Japan Co., Ltd., epoxy equivalent 2000) and 425 g of propylene glycol monobutyl ether were added, and 110 ° C. The mixture was stirred and mixed and cooled to 100 ° C., and 20.7 g of diethanolamine was added and reacted for 1 hour. Then, the epoxyamine value was measured to confirm that it was a theoretical value. 16.5 g of 3-amino-1,2,4-triazole (molecular weight 84) was added and reacted for 5 hours. Thereafter, 250 g of propylene glycol monobutyl ether was added to obtain a modified epoxy resin. To this modified epoxy resin, 23.3 g of phosphoric acid was added, and water was mixed and dropped to obtain an aqueous epoxy resin dispersion E1 having a solid concentration of 20%.
[0076]
・ Production example 2
Into a glass four-necked flask equipped with a thermometer, a stirrer, and a condenser tube, 546 g of Epicoat 1004 (epoxy resin, manufactured by Shell Japan Co., Ltd., epoxy equivalent 925) and 311 g of propylene glycol monobutyl ether were added and stirred at 110 ° C. Then, after becoming uniform and transparent, it was cooled to 100 ° C., 31.5 g of diethanolamine was added and reacted for 1 hour, and then the epoxyamine value was measured to confirm that it was a theoretical value. -1,2,4-Triazole (molecular weight 84) 25.2 g was added and reacted for 5 hours. Thereafter, 182.6 g of propylene glycol monobutyl ether was added to obtain a modified epoxy resin. To this modified epoxy resin, 35.3 g of phosphoric acid was added, and water was mixed and dropped to obtain an aqueous epoxy resin dispersion E2 having a solid content concentration of 20%.
・ Production Example 3
A modified epoxy resin was obtained by carrying out the reaction under the same conditions as in Production Example 1 except that the amount of diethanolamine was 12.4 g and the amount of 3-amino-1,2,4-triazole was 23.1 g. Water was mixed with this modified epoxy resin to obtain an aqueous epoxy resin dispersion E3 having a solid content concentration of 20%.
[0077]
-Production Example 4 (Comparative Example)
In a glass four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, Epicoat 1001 (epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of about 475, number average molecular weight of about 900) 186.6 g and propylene glycol monobutyl ether 115.2 g was added, the temperature was raised to 110 ° C., and the mixture was stirred and mixed. After the liquid became uniform and transparent, the solution was cooled to 100 ° C., 25.5 g of diethanolamine was added, and the temperature was maintained at 100 ° C. for 1 hour. Thereafter, 68.0 g of propylene glycol monobutyl ether was added to obtain a modified epoxy resin. To this modified epoxy resin, 23.3 g of phosphoric acid was added and mixed while dripping water to obtain an aqueous epoxy resin dispersion E4 having a solid concentration of 20%.
-Production Example 5 (Comparative Example)
The modified epoxy resin was reacted under the same conditions as in Production Example 1 except that 16.5 g of 3-amino-1,2,4-triazole used in Production Example 1 was replaced with 14.7 g of N-methyl-ethanolamine. Got. Water was mixed with this modified epoxy resin to obtain an aqueous epoxy resin dispersion E5 having a solid content concentration of 20%.
[0078]
Plated steel sheets for household appliances, building materials, and automobile parts shown in Table 1 based on cold-rolled steel sheets were used as processing original sheets. In addition, the predetermined plate thickness was employ | adopted for the plate | board thickness of the steel plate according to the objective of evaluation. After the surface of this plated steel sheet was subjected to alkaline degreasing treatment, water washing and drying, the above surface treatment composition was applied by a roll coater and heat dried at various temperatures without water washing. The film thickness of the film was adjusted by the solid content (heating residue) of the surface treatment composition or coating conditions (roll rolling force, rotational speed, etc.). Tables 9 to 20 show the results of the tests of the film composition and quality performance (film appearance, white rust resistance, white rust resistance after alkali degreasing, conductivity, paint adhesion) of the obtained surface-treated steel sheets. . The quality performance was evaluated as follows.
[0079]
(1) Appearance of film
About each sample, the uniformity (existence of unevenness) of the film | membrane external appearance was evaluated visually. The evaluation criteria are as follows.
○: Uniform appearance with no unevenness
Δ: Appearance in which unevenness is slightly noticeable
×: Appearance in which unevenness is conspicuous
(2) White rust resistance
About each sample, the salt spray test (JIS-Z-2371) was given and it evaluated by the white rust area rate after progress of 168 hours. The evaluation criteria are as follows.
: White rust area ratio less than 5%
○: White rust area ratio 5% or more, less than 10%
○-: White rust area ratio of 10% or more and less than 25%
Δ: White rust area ratio of 25% or more and less than 50%
×: White rust area ratio of 50% or more
[0080]
(3) White rust resistance after alkaline degreasing
About each sample, the salt spray test (JIS-Z-2371) was given after alkali degreasing, and the white rust area rate after 72-hour progress evaluated.
The evaluation criteria are as follows.
: White rust area ratio less than 5%
○: White rust area ratio 5% or more, less than 10%
○-: White rust area ratio of 10% or more and less than 25%
Δ: White rust area ratio of 25% or more and less than 50%
×: White rust area ratio of 50% or more
(4) Conductivity
The interlayer insulation resistance value was measured according to JIS C2550. The evaluation criteria are as follows.
○: 3Ω · cm²/ Less than
Δ: 3-5 Ω · cm²/Sheet
×: 5Ω · cm²/ More than
[0081]
(5) Paint adhesion
For each sample, melamine-based baking paint was applied (film thickness 30 μm), then immersed in boiling water for 2 hours, immediately cut into grids (10 × 10, 1 mm interval), and adhered with adhesive tape -Peeling was performed, and the peeled area ratio of the coating film was measured. The evaluation criteria are as follows.
A: No peeling
○: Peel area ratio less than 5%
Δ: peeling area ratio 5% or more, less than 20%
X: Peel area ratio 20% or more
[0082]
[Table 1]

[0083]
[Table 2]

[0084]
[Table 3]

[0085]
[Table 4]

[0086]
[Table 5]

[0087]
[Table 6]

[0088]
[Table 7]

[0089]
[Table 8]

[0090]
* 1 to * 9 described in the following Tables 9 to 20 indicate the following contents.
* 1: No. described in Table 1. (Plated steel plate)
* 2: No. in Table 2 (Water-based epoxy resin dispersion)
* 3: No. described in Table 3 (Urethane resin water dispersion)
* 4: No. in Table 4 (Silane coupling agent)
* 5: No. in Table 5 (Phosphoric acid and / or hexafluorometal acid)
* 6: No. in Table 6 (Water-soluble inorganic component)
* 7: No. in Table 7 (Non-chromium rust preventive additive)
* 8: No. in Table 8 (Solid lubricant)
* 9: Mass part
[0091]
[Table 9]

[0092]
[Table 10]

[0093]
[Table 11]

[0094]
[Table 12]

[0095]
[Table 13]

[0096]
[Table 14]

[0097]
[Table 15]

[0098]
[Table 16]

[0099]
[Table 17]

[0100]
[Table 18]

[0101]
[Table 19]

[0102]
[Table 20]

[0103]
【The invention's effect】
As described above, the surface-treated steel sheet of the present invention has excellent white rust resistance despite the fact that it does not contain chromium in the film, and also has excellent characteristics regarding the film appearance and paint adhesion. is doing.

Claims (9)

On the surface of galvanized steel plate or aluminum galvanized steel plate,
(A) an active hydrogen-containing compound (C) comprising an epoxy group-containing resin (A), a primary amine compound and / or a secondary amine compound (B), and a hydrazine derivative partly or entirely having active hydrogen An aqueous epoxy resin dispersion in which a modified epoxy resin obtained by reacting with water is dispersed in water;
(B) a nonionic or cationic polyurethane emulsion;
(C) a silane coupling agent;
(D) phosphoric acid and / or hexafluorometal acid;
The content of the silane coupling agent (c) is 15 to 50 parts by mass with respect to 100 parts by mass of the solid content of the organic resin, and the content of the phosphoric acid and / or hexafluorometal acid (d) is It is 5-50 mass parts with respect to 100 mass parts of solid content of organic resin, and the mixture ratio of the said aqueous epoxy resin dispersion liquid (a) and nonionic or cationic polyurethane emulsion (b) is solid content mass ratio ( a) / (b) = 75 / 25-25 / 75 The surface treatment composition formed by applying and drying the surface treatment composition has a surface treatment film having a thickness of 0.01 to 5 μm. Surface-treated steel sheet with excellent white rust resistance.   The hydrazine derivative containing active hydrogen is a pyrazole compound and / or triazole compound having a 5-membered or 6-membered ring structure and having a nitrogen atom in the ring structure. A surface-treated steel sheet excellent in white rust resistance as described in 1. Surface treatment composition is further characterized by containing 0.1 to 60 parts by weight on a solids soluble inorganic component with respect to 100 parts by weight of the solid content of the organic resin, resistance according to claim 1 or 2 Surface-treated steel sheet with excellent white rust. The cation species of the water-soluble inorganic component is one or more selected from Mg, Ca, Y, Ti, Zr, Nb, Zn, Mn, Co, Ni, Zn, Al, In, Ce, and La. The surface excellent in white rust resistance according to claim 3 , wherein the anionic species is one or more selected from nitric acid, sulfuric acid, acetic acid, carbonic acid, phosphoric acid, and chloride. Treated steel sheet. Surface treatment composition is further characterized by containing 0.1 to 50 parts by weight on a solids relative to 100 parts by weight of the solid content of the chromium-free rust-preventive additive organic resin of claim 1-4 A surface-treated steel sheet excellent in white rust resistance according to any one of the above. The surface treatment composition contains at least one silane coupling agent having an amino group as a reactive functional group, and has excellent white rust resistance according to any one of claims 1 to 5 . Surface treated steel sheet. The surface-treated steel sheet according to any one of claims 1 to 6 , further comprising an organic resin film having a film thickness of 0.01 µm or more and less than 5 µm on an upper layer of the surface-treated film having a film thickness of 0.01 µm or more and less than 5 µm. A surface-treated steel sheet excellent in white rust resistance, wherein the total film thickness of the organic resin film and the surface-treated film is 5 μm or less. On the surface of galvanized steel plate or aluminum galvanized steel plate,
(A) an active hydrogen-containing compound (C) comprising an epoxy group-containing resin (A), a primary amine compound and / or a secondary amine compound (B), and a hydrazine derivative partly or entirely having active hydrogen An aqueous epoxy resin dispersion in which a modified epoxy resin obtained by reacting with water is dispersed in water;
(B) a nonionic or cationic polyurethane emulsion;
(C) a silane coupling agent;
(D) phosphoric acid and / or hexafluorometal acid;
The content of the silane coupling agent (c) is 15 to 50 parts by mass with respect to 100 parts by mass of the solid content of the organic resin, and the content of the phosphoric acid and / or hexafluorometal acid (d) is It is 5-50 mass parts with respect to 100 mass parts of solid content of organic resin, and the mixture ratio of the said aqueous epoxy resin dispersion liquid (a) and nonionic or cationic polyurethane emulsion (b) is solid content mass ratio ( a) / (b) = 75 / 25-25 / 75, the surface treatment composition prepared to have a pH of 0.5-6 is applied, and the plate temperature is 50 ° C.-300 ° C. without washing with water. A method for producing a surface-treated steel sheet excellent in white rust resistance, wherein the surface-treated film having a film thickness of 0.01 to 5 μm is formed by heating and drying. An organic resin film having a film thickness of 0.01 μm or more and less than 5 μm is formed on an upper surface of the surface-treated film having a film thickness of 0.01 μm or more and less than 5 μm obtained by the manufacturing method according to claim 8 , A method for producing a surface-treated steel sheet excellent in white rust resistance, characterized in that the film is formed so that the total thickness of the surface-treated film is 5 μm or less.