JP2004176113A - Rust-preventive steel sheet for high corrosion resistant fuel tank - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rust-prevenetive steel sheet which has excellent corrosion resistance as the stock for an automobile fuel tank, and also combines satisfactory resistance weldability and press formability. <P>SOLUTION: The rust-preventive steel sheet for a fuel tank is obtained by applying an organic film with a film thickness of 5 to 30 μm comprising (A) a resin having an urethane bond and (B) an electroconductive pigment to at least one side of a surface treated steel sheet. The resin having an urethane bond is an organic resin obtained from a film formable resin raw material comprising polyester polyol in which the number of functional groups is at least 3, and a blocked substance of organic poloyisocyanate or a blocked substance of a prepolymer with an NCO group at a terminal obtained by the reaction between organic polyisocyanate and an active hydrogen compound. Also, the surface roughness of the organic film is 0.3 to 2.5 μm by the center line average roughness Ra. <P>COPYRIGHT: (C)2004,JPO

Description

【００４０】
（式中、Ｘはハロゲンで置換されていてもよいフェニレン基又はシクロヘキシレン基をあらわし、ｎは０．５〜１２である）
ラクトン化合物又はアルキレンオキサイドの付加量は、該エポキシ樹脂約９５〜６０質量部に対して、約５〜４０質量部程度である。特に、該エポキシ樹脂約９０〜７０質量部に対して、ラクトン化合物又はアルキレンオキサイドは約１０〜３０質量部が好ましい。
【００４１】
上記一般式（１）で表されるエポキシ樹脂の中で、Ｘがｐ−フェニレン基のもので、ｎは２〜９のものが好ましい。ハロゲンとしては、例えば、臭素、塩素等が挙げられる。この置換基の数は通常、１〜３程度で、その位置はフェニレン基もしくはシクロヘキシレン基のいずれの位置でもよい。
【００４２】
ラクトン化合物としては、例えば、β−プロピオンラクトン、ブチロラクトン、γ−バレロラクトン、γ−カプロラクトン、δ−バレロラクトン、δ−カプロラクトン、ε−カプロラクトン等が挙げられるが、これらのなかで、特にε−カプロラクトンが好ましい。アルキレンオキサイドとしては、例えば、エチレンオキサイド、プロピレンオキサイド、スチレンオキサイド、グリシジルメタクリレート、エピクロルヒドリン等が挙げられるが、特にエチレンオキサイドが好ましい。
【００４３】
２級の水酸基を少なくとも１個有するエポキシ樹脂もしくはエポキシ樹脂にラクトン化合物又はアルキレンオキサイドを付加させた物の配合割合は、ポリオール成分中、約１０〜７０質量％の割合であるが、特に約１０〜６０質量％の範囲で用いるのが好ましい。配合割合が１０質量％未満では耐薬品性が悪くなることがある。また、７０質量％を超えると硬度が非常に低下し、プレス成型時に傷つきやすくなることがある。
【００４４】
本発明に用いられる成膜性樹脂原料は、前述のポリオール（イ）、（ハ）とブロック化物（ロ）であり、ポリオールとブロック化物の配合割合はＯＨ基／再生ＮＣＯ基の当量比が約１／２〜２／１、特に１／１．２〜１／０．８が好ましい。
【００４５】
次に、導電性顔料について述べる。
【００４６】
有機皮膜中に、金属、金属元素の合金又は金属元素の導電性化合物の導電性顔料を添加することで、有機皮膜被覆鋼板に電気抵抗溶接性や耐食性の向上等の機能を付与することができる。含有量としては、固形分換算で有機皮膜層全体の５〜５０容量％、好ましくは２０〜４０容量％である。５容量％未満では十分な溶接性が得られず、５０容量％超では加工時における皮膜の追従性が低下する恐れがある。
【００４７】
導電性顔料を構成する金属、金属元素の合金又は金属元素の導電性化合物の粒子は、例えば、固体の粉砕や、溶融物を気相や水相に噴出する等の公知の方法で粒子化したものを用いて良い。粒子は、例えば、Ｍｇ、Ａｌ、Ｓｉ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｓｒ、Ｉｒ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｉｎ、Ｓｎ等の金属や、Ｍｇ、Ａｌ、Ｓｉ、Ｐ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｓ、Ｓｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｔｅ等の合金又は導電性化合物を用いることができる。
【００４８】
前述の金属、金属元素の合金又は化合物の粒子のうち、工業的に比較的安価かつ安定的に入手できるものとして、Ｍｇ、Ａｌ、Ｓｉ、Ｃｒ、Ｆｅ、Ｎｉ、Ｚｎ、Ｓｎ、Ｚｎ−Ａｌ合金、Ｚｎ−Ａｌ−Ｍｇ合金、Ｚｎ−Ａｌ−Ｍｇ−Ｓｉ合金、Ｚｎ−Ｆｅ合金、Ｚｎ−Ｃｒ合金、Ｚｎ−Ｎｉ合金、Ｆｅ−Ｎｉ合金、Ｆｅ−Ｃｒ合金、ステンレス鋼、フェロシリコン、リン化鉄等が挙げられる。特に、ステンレス鋼、Ｚｎ、Ａｌ、Ｎｉ、フェロシリコン、リン化鉄の１種以上を用いることが性能と工業性のバランスの面から好ましい。
【００４９】
前述の粒子には、その粒径が有機皮膜の平均膜厚に対して５倍以下のもの含まれることが好ましい。さらに好ましくは、粒径が有機皮膜の平均膜厚に対して２倍以下のものが良い。塗工時に、有機皮膜に粒子を有効に転写するため、及び、有機皮膜の原料塗料中における粒子の沈降・分離を防止するためである。
【００５０】
塗装鋼板のさらなる高耐食性を実現するには、前述の粒子において、フェロシリコンを必須成分とするのが望ましい。その効果は、腐食環境においてＳｉを含有する保護皮膜が形成される為と考えられる。本発明においては、特にＳｉ４０質量％以上のフェロシリコンを用いることが好ましい。具体的には、Ｓｉ７５〜８０質量％のＪＩＳ２号フェロシリコン、Ｓｉ４５〜５０質量％のＪＩＳ３号フェロシリコン等を導電性粒子として用いることで導電性を確保できると同時に、飛躍的に耐食性が向上する。
【００５１】
有機皮膜中に防錆顔料を添加することで、さらに耐食性を向上させることができる。添加量としては、固形分換算で有機皮膜層全体に対し、１〜４０容量％、好ましくは３〜３０容量％である。１容量％では十分な防錆効果が得られず、４０容量％超では、皮膜形成有機樹脂の比率が下がり、皮膜の凝集力が低下する恐れがある。
【００５２】
防錆顔料は、例えば、ストロンチウムクロメート、カルシウムクロメートのような６価Ｃｒ酸塩等の公知の防錆顔料を用いることができる。防錆顔料として、６価Ｃｒ化合物の使用を回避したい場合は、ケイ酸イオン、リン酸イオン、バナジン酸イオンの内、一種類以上を放出するもの等を用いることができる。有機皮膜の防錆力を発揮させるためには、有機皮膜層中にリン酸イオンとバナジン酸イオンが共存することが好ましく、リン酸イオン及びバナジン酸イオンがそのまま存在しても、水及び酸素の存在する環境下でリン酸イオンとバナジン酸イオンを放出する物質を含んでもよい。
【００５３】
リン酸イオンは、水溶液中において単独で存在することが少なく、種々の形態、例えば、縮合体として存在する。防錆顔料に用いられるリン化物は、オルトリン酸、縮合リン酸、種々の金属のオルトリン酸塩又は縮合リン酸塩、五酸化リン、リン酸塩鉱物、市販の複合リン酸塩顔料、又はこれらの混合物が挙げられる。ここで言うオルトリン酸塩の中には、その一水素塩（ＨＰＯ_４ ^２−）の塩、二水素塩（Ｈ_２ＰＯ_４ ⁻）も含むものとする。また、縮合リン酸塩の中にも水素塩を含むものとする。さらに、縮合リン酸塩にはメタリン酸塩も含み、通常のポリリン酸塩、ポリメタリン酸塩も含むものとする。リン化合物の具体例としては、モネタイト、トルフィル石、ウィトロック石、ゼノタイム、スターコライト、ストルーブ石、ラン鉄鉱石等のリン酸塩鉱物や、ポリリン酸シリカ等の市販の複合リン酸塩顔料や、ピロリン酸、メタリン酸等の複合リン酸や、メタリン酸塩、テトラメタリン酸塩、ヘキサメタリン酸塩、ピロリン酸塩、酸性ピロリン酸塩、トリポリリン酸塩等の複合リン酸塩、あるいは、これらの混合物が挙げられる。
【００５４】
リン酸塩を形成する金属種は、特に限定するものでなく、アルカリ金属、アルカリ土類金属、その他の典型元素の金属種及び遷移金属が挙げられる。好ましい金属種の例としては、Ｍｇ、Ｃａ、Ｓｒ、Ｖ、Ｔｉ、Ｚｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ａｌ、Ｐｂ、Ｓｎ等が挙げられる。この他にバナジル、チタニル、ジルコニル等、オキソカチオンも含まれる。これらの中で、特に好ましいのは、Ｃａ、Ｍｇである。アルカリ金属の多量の使用は好ましくない。アルカリ金属のリン酸塩を用いた場合、焼成生成物が水に溶解しすぎる傾向にある。しかしながら、アルカリ金属のリン酸塩を用いた場合において、水への溶解性の制御を防錆剤製造時あるいはその他の時点で実施できれば使用しても良い。そのような制御は、例えば、水への溶解性の防止のためのマトリクス材（特に、ガラス状物質）の使用、あるいはコーティング等、種々の態様が挙げられる。
【００５５】
防錆顔料に用いるバナジウム化合物は、バナジウムの原子価が０、２、３、４又は５のいずれか、又はこれらの２種以上の原子価を有する化合物であり、これらの酸化物、水酸化物、種々の金属の酸素酸塩、バナジル化合物、ハロゲン化物、硫酸塩、金属粉等が挙げられる。これらは、加熱時又は水の存在下で分解して、酸素と反応し高級化する。例えば、バナジウムの金属粉又は２価の化合物は、最終的に３、４、５価のいずれかの化合物に変化する。５価のバナジウム化合物を１つの成分として含むものが好ましい。０価バナジウム金属粉は、上記の理由で使用可能であるが、酸化反応が不十分等の問題があるので実用上好ましくない。５価のバナジウム化合物はバナジン酸イオンを有し、リン酸イオンと加熱反応し、ヘテロポリマーを作りやすい。バナジウム化合物の具体例としては、酸化バナジウム（ＩＩ）、水酸化バナジウム（ＩＩ） 等のバナジウム（ＩＩ）化合物、酸化バナジウム等のバナジウム（ＩＩＩ）化合物、酸化バナジウム（ＩＶ）、ハロゲン化バナジル等のバナジウム（ＩＶ）化合物、酸化バナジウム（Ｖ）等のバナジウム（Ｖ）化合物、種々の金属のオルトバナジン酸塩、メタバナジン酸塩又はピロバナジン酸塩、ハロゲン化バナジル等のバナジン酸塩、又はこれらの混合物が挙げられる。バナジン酸塩の金属種はリン酸塩で示したものと同じ物が挙げられる。これはバナジウムの酸化物と種々の金属の酸化物、水酸化物、炭酸塩等とを６００℃以上に焼成して作っても良い。この場合もアルカリ金属は溶解性の故にあまり好ましくないが、リン酸塩において説明した適当な処理をして溶解性を制御すれば、これらの使用も差し支えない。また、ハロゲン化物、硫酸塩も同様である。配合するリン酸イオン源とバナジン酸イオン源との比は、Ｐ_２Ｏ_５とＶ_２Ｏ_５のモル比に換算して１：３〜１００：１とするのが好ましい。
【００５６】
また、有機皮膜層における導電性顔料及び／又は防錆顔料の配合量は、固形分換算で併せて有機皮膜層全体の５〜７０容量％、好ましくは２０〜６０容量％である。５容量％未満だと、先に述べた添加効果が十分発現されず、７０容量％を超えると、硬化後の皮膜の凝集力が低下し、十分な皮膜強度が得られない。
【００５７】
塗装下地鋼板としては、各種表面処理鋼板が使用できるが、中でも耐食性、溶接性、加工性のバランスからＺｎ系めっき鋼板、Ａｌ系めっき鋼板、Ｓｎ系めっき鋼板が好ましい。Ｚｎ系とは、ＺｎもしくはＺｎが５０％以上含有される合金系を示す。例えば、Ｚｎ、Ｚｎ−Ｎｉ合金、Ｚｎ−Ｆｅ合金、Ｚｎ−Ａｌ合金、Ｚｎ−Ｃｏ合金、Ｚｎ−Ｍｇ合金、Ｚｎ−Ｍｇ−Ａｌ合金等が挙げられる。Ａｌ系めっき、Ｓｎ系めっきも同様に、ＡｌもしくはＡｌが５０％以上含有される合金系、ＳｎもしくはＳｎが５０％以上含有される合金系であり、例えば、Ａｌ、Ａｌ−Ｓｉ合金、Ａｌ−Ｆｅ合金、Ａｌ−Ｚｎ合金、Ａｌ−Ｍｇ合金、Ａｌ−Ｍｇ−Ｓｉ−Ｚｎ合金等、例えば、Ｓｎ、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｍｇ合金等が挙げられる。タンク材用途に使用する際に高度な抵抗溶接性（スポット溶接，シーム溶接等）が要求され、そのとき電極のＣｕとめっき金属とは化合物を形成しやすいために，めっきの付着量が溶接性へ大きく影響する。また、めっき付着量は当然耐食性への影響も大きい。めっき付着量が大きいほど耐食性という点では有利に，また、溶接性という点では不利に働くため、付着量として、片面当たり２０〜６０ｇ／ｍ^２が好ましい。
【００５８】
また、燃料タンクは高度な加工性を要求されるため、加工性に優れたＩＦ鋼（Ｉｎｔｅｒｓｔｉｔｉａｌ Ｆｒｅｅ鋼）の適用が望ましく、さらには溶接後の溶接気密性、二次加工性等を確保するためにＢを０．０００２質量％以上０．００３質量％以下添加した鋼板が望ましい。
【００５９】
めっき方法については、電気めっき、溶融めっき、気相めっき等、従来の製造方法で製造可能である。鋼板に直接めっきすることも当然可能であるし、また、めっき前にプレめっき処理を施すことも可能である。プレめっきは、溶融めっきにおいてめっき性を向上させるために施すもので，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｓｎ，Ｚｎ，Ｃｕの単独めっき、あるいはこれらを含有する合金めっきが有り得る。厚みは通常０．１μｍ程度であるが、特に限定するものではない。
【００６０】
本発明では、表面処理鋼板と導電性顔料を含有する有機皮膜の間に、さらに下地処理皮膜を施しても良い。これにより、良好な密着性を得ると共に、さらに良好な耐食性を得ることができる。下地処理皮膜としては、例えば、クロメート皮膜等があり、耐食性、溶接性、塗装後耐食性等の特性に影響する。クロメート皮膜は、耐食性と塗装性に優れたものでこれまで多用されてきたが、６価Ｃｒは環境への負荷が大きいため、近年はこれを代替する後処理皮膜も多く提案されている。本発明においては、これらの後処理皮膜を下地処理皮膜として適用することも可能である。後処理皮膜としては、３価Ｃｒ皮膜やノンクロメート皮膜が好ましく、例えば、電解により形成する方法、反応を利用して形成する方法、塗布により形成する方法等がある。
【００６１】
下地処理層としては、公知の６価クロム酸を主成分とし、微粒シリカやシランカップリング剤等を必要に応じて添加した水溶液の塗布・乾燥で得られる皮膜、６価クロム酸を主成分とし、微粒シリカやシランカップリング剤等を必要に応じて添加した水溶液とめっき表面とを接触して下地処理層を成膜した上で洗浄・乾燥して得られる皮膜、３価クロム酸を主成分として６価クロム酸を含有しない水溶液に、必要に応じて微粒シリカやシランカップリング剤等を添加した水溶液の塗布・乾燥で得られる皮膜、クロム酸水溶液中での電解によりめっき表面に３価クロムを主成分とする皮膜を析出後に洗浄・乾燥して得られる皮膜、Ｚｎ、Ｎｉ、Ｆｅ等のリン酸塩をめっき面に析出して得られる皮膜、等のうちいずれか一つ又は複数の方法の組合せにて形成する皮膜を用いて良い。さらに、水性樹脂を主成分とし、微粒シリカ、シランカップリング剤、リン酸、タンニン、タンニン酸の内、少なくとも１種類を含有する水溶液をめっき表面に塗布・乾燥して形成する皮膜を用いても良い。６価Ｃｒの使用を回避したい場合には、３価Ｃｒ、各種金属のリン酸塩、又は水性樹脂により形成される皮膜を下地処理層として用いればよい。
【００６２】
下地処理層の水性樹脂としては、水溶性樹脂のほか、本来水不溶性でありながらエマルジョンやサスペンジョンのように水中に微分散された状態になりうる樹脂を含めて言う。このような水性樹脂として使用できるものは、例えば、ポリオレフィン系樹脂、アクリルオレフィン系樹脂、ポリウレタン系樹脂、ポリカーボネート系樹脂、エポキシ系樹脂、ポリエステル系樹脂、アルキド系樹脂、フェノール系樹脂、その他の熱硬化型樹脂が挙げられ、架橋可能な樹脂が望ましい。特に好ましい樹脂は、アクリルオレフィン系樹脂、ポリウレタン系樹脂、フェノール樹脂、及びそれらの混合樹脂である。これらの水性樹脂の２種類以上を混合あるいは重合して使用しても良い。
【００６３】
シランカップリング剤は、有機樹脂の存在下で、めっきと皮膜の両者と強固に結合し、皮膜の密着性を飛躍的に向上させ、ひいては耐食性を向上させる。シランカップリング剤としては、例えば、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、アミノシラン、γ−メタクリロキシプロピルトリメトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピ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−メルカプトプロピルトリメトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、オクタデシルジメチル［３−（トリメトキシシリル）プロピル］アンモニウムクロライド、γ−クロロ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メチルジメトキシシラン、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン等を挙げることができる。
【００６４】
シランカップリング剤を水性樹脂による下地処理層に用いる際の含有量は、固形分換算で、水性樹脂１００質量部に対して、０．１〜３０００質量部であることが望ましい。０．１質量部未満では、シランカップリング剤の量が不十分であるため、加工時に十分な密着性が得られず耐食性が劣る。３０００質量部を越えると、密着性向上効果が飽和するため不経済である。
【００６５】
また、表面をエッチングして密着性をさらに良好化するため、及びシランカップリング剤の安定化のために、リン酸を適量添加するのが好ましい。添加量は、固形分換算で、水性樹脂１００質量部に対して、０．１〜３０００質量部であることが望ましい。０．１質量部未満では、リン酸の量が不十分であるため、加工時に十分な密着性が得られず耐食性が劣る。３０００質量部を越えると、密着性向上効果が飽和するため不経済である。
【００６６】
水性樹脂による下地処理層のタンニン又はタンニン酸の役割は、めっき層と強固に反応して密着することと、一方で水性樹脂とも密着することにある。タンニン又はタンニン酸と密着した水性樹脂は、その上に塗装される樹脂と強固に密着し、その結果としてめっき層と皮膜が従来から使用されてきたクロメート処理を使用せずとも、強固に密着するようになるものと考えられる。また、タンニンやタンニン酸そのものが、水性樹脂を仲立ちとせずに、めっき鋼板と皮膜の結合に関与している部分も存在するものと考えられる。
【００６７】
タンニンやタンニン酸は、水性樹脂の存在下で、めっき層と皮膜の両者と強固に結合し、皮膜の密着性を飛躍的に向上させ、ひいては耐食性を向上させる。タンニン又はタンニン酸としては、加水分解できるタンニンでも縮合タンニンでもよく、これらの一部が分解されたものでも良い。タンニンやタンニン酸としては、ハマメタタンニン、五倍子タンニン、没食子タンニン、ミロバロンのタンニン、ジビジビのタンニン、アルガロビラのタンニン、バロニアのタンニン、カテキン等が挙げられるが、特に限定するものではなく、市販のもの、例えば「タンニン酸：ＡＬ」（富士化学工業製）等を使用することができる。
【００６８】
タンニンやタンニン酸の含有量は樹脂１００質量部に対して、０．２〜５０質量部がよい。タンニンやタンニン酸の含有量が、０．２質量部未満では、これらを添加した効果が見られず、皮膜密着性や加工部の耐食性が不十分である。一方、５０質量部を越えると、逆に耐食性が低下したり、処理液を長期間貯蔵しておくとゲル化したりして、問題がある。
【００６９】
さらに、微粒シリカを添加すると耐擦り傷性、皮膜密着性、耐食性が向上する。本発明において、微粒シリカとは、微細な粒径をもつために水中に分散させた場合に安定に水分散状態を維持でき、半永久的に沈降が認められないような特色を有するシリカを総称していうものである。このような微粒シリカとしては、ナトリウム等の不純物が少なく、弱アルカリ系のものであれば、特に限定されない。例えば、「スノーテックスＮ」（日産化学工業社製）、「アデライトＡＴ−２０Ｎ」（旭電化工業社製）等の市販のシリカ等を用いることができる。
【００７０】
微粒シリカの含有量は固形分換算で、水性樹脂１００質量部に対して１〜２０００質量部、さらに好ましくは１０〜４００質量部である。１質量部未満では添加した効果が少なく、２０００質量部を越えると耐食性向上の効果が飽和して不経済である。
【００７１】
また、エッチング性フッ化物を添加すると皮膜密着性が向上される。ここで、エッチング性フッ化物としては、フッ化亜鉛四水和物、ヘキサフルオロケイ酸亜鉛六水和物等を使用することができる。エッチング性フッ化物の含有量は固形分換算で、水性樹脂１００質量部に対して１〜１０００質量部であることが好ましい。１質量部未満では添加の効果が少なく、１０００質量部を越えるとエッチングの効果が飽和して皮膜密着性が改善されないので不経済である。
【００７２】
また、必要に応じて界面活性剤、防錆抑制剤、発泡剤等を添加しても良い。
【００７３】
下地処理層の乾燥後の付着量は、１０〜１０００ｍｇ／ｍ^２が好適である。１０ｍｇ／ｍ^２未満では密着性が劣り加工部の耐食性が不十分となる恐れがある。一方、１０００ｍｇ／ｍ^２を越えると不経済であるばかりか溶接性の低下が生じる恐れがある。
【００７４】
下地処理皮膜や導電性顔料を含有する有機皮膜の塗布方法は、特別限定するものではなく、一般に公知の塗装方法、例えば、ロールコート、カーテンフローコート、エアースプレー塗装、エアーレススプレー塗装、静電塗装、浸漬、はけ塗り等が適用できる。塗料の形態も紛体、固体、溶剤系、水系等、特に限定するものではない。塗布後の乾燥・焼き付けは、熱風炉、誘導加熱炉、近赤外線炉、等公知の方法あるいはこれらを組み合わせた方法で行えばよい。また、使用する水性樹脂の種類によっては、紫外線や電子線等によって硬化させることもできる。あるいは強制乾燥を用いずに自然乾燥してもよいし、めっき鋼板を予め加熱しておいて、その上に塗布して自然乾燥してもよい。本発明では、それらの乾燥・硬化中もしくは硬化後にショットブラスト、スキンパス圧延等の表面粗度及びテクスチャ制御プロセスを入れることが有り得る。
【００７５】
さらに、本発明の鋼板を実際に使用する際、通常の製造プロセスにおいては、成形後、シーム、スポット等の抵抗溶接を行った後、使用されるため、溶接後補修塗装を施すことにより、高い信頼性を得ることができる。使用する補修塗料は市販のもので良く、有機皮膜との密着性が良く、水分等の腐食因子の浸透を抑制できるものであれば良い。本発明の防錆鋼板は、このような補修塗装を行っても、従来技術に後塗装を施した場合に比べ、十分に低いコストで製造することが可能である。
【００７６】
【実施例】
以下に、実施例によって本発明を更に詳細に説明する。ただし、本発明はこれらの実施例に限定されるものではない。
【００７７】
表１に示す成分の鋼を通常の転炉−真空脱ガス処理により溶製し、鋼片とした後、通常の条件で熱間圧延、冷延を行い、冷延鋼板（板厚０．８ｍｍ）を得た。これを材料として、各種表面処理鋼板を製造した。溶融めっきは、ゼンジマー方式又はフラックス方式のラインを使用して実施した。ゼンジマー方式の場合、焼鈍はライン内で行った。焼鈍温度は８００〜８５０℃とした。めっき後、ガスワイピング法で、めっき付着量を調節した。この際のめっき温度は、めっき組成によって異なり、めっき組成の融点＋４０℃とした。電気めっきは、冷延鋼板を焼鈍した後、電気めっきラインにて行った。
【００７８】
【表１】

【００７９】
こうして製造した表面処理鋼板に、表８に示す組成の下地処理皮膜をロールコーターにより両面に所定の付着量塗布し、２００℃の温風にて焼付乾燥を行った。そして、更に表２〜７に示す組成の導電性顔料を含有する有機皮膜をロールコーターにより両面もしくは片面（外面側）に所定の付着量塗布し、２５０℃の温風にて焼き付け乾燥を行った。一部水準には、表面処理鋼板及び有機皮膜塗装後にスキンパス圧延を加え、表面の粗度及びテクスチャを調整した。このようにして得た防錆鋼板の仕様を表９〜１２に示す。
【００８０】
【表２】

【００８１】
【表３】

【００８２】
【表４】

【００８３】
【表５】

【００８４】
【表６】

【００８５】
【表７】

【００８６】
【表８】

【００８７】
こうして製造した鋼板の燃料タンクとしての適性を、下記に示す方法により評価した。
【００８８】
（１） 耐食性評価
（ａ） 外面耐食性
塗装後の鋼板を塗装面が外側になるように円筒カップ絞り成形した後にサイクル腐食試験を行った。円筒カップ絞りは、ポンチ径５０ｍｍ、しわ抑え圧９．８ｋＮで、防錆油を塗布後１時間〜１時間３０分間立てかけて静置した後、絞り比２．０で絞り成型した。
【００８９】
サイクル腐食試験は、塩水噴霧２時間、乾燥４時間、湿潤２時間の合計８時間を１サイクルとして実施した。塩水噴霧の条件は、ＪＩＳ−Ｋ５４００に準拠した。乾燥条件は、温度５０℃、湿度３０％ＲＨ以下、湿潤条件は、温度３５℃、湿度９５％ＲＨ以上である。
【００９０】
耐食性の評価は以下である。
【００９１】
評点４＋：３００サイクル後も、鋼板の板厚減少を示す赤錆が発生せず、めっき層の腐食を示す白錆がサンプルを覆う面積率が全体の５％未満の場合
評点４：３００サイクル後も、鋼板の板厚減少を示す赤錆が発生せず、めっき層の腐食を示す白錆がサンプルを覆う面積率が全体の５％以上５０％未満の場合
評点３：３００サイクル後も鋼板の板厚減少を示す赤錆が発生しない場合
評点２：１００サイクル後には赤錆が見られず３００サイクルで赤錆が見られる場合
評点１：１００サイクルで赤錆が見られる場合
（ｂ） 内面耐食性
ガソリンに対する耐食性を評価した。方法は、油圧成型試験機によりフランジ幅２０ｍｍ、直径５０ｍｍ、深さ２５ｍｍの平底円筒深絞りした試料に、試験液を入れて、シリコンゴム製リングを介してガラスで蓋をした。この試験後の腐食状況を目視観察した。
【００９２】
（試験条件）
試験液：ガソリン＋蒸留水１０％＋ギ酸２００ｐｐｍ
試験期間：４０℃で３ヶ月放置
（評価基準）
評点４：変化無し
評点３：白錆発生１％以下
評点２：赤錆発生５％以下，又は白錆発生１％〜５０％
評点１：赤錆発生５％超又は白錆顕著
（２） プレス加工性評価
油圧成型試験機により、直径５０ｍｍの円筒ポンチを用いて、絞り比２．３で成形試験を行った。このときのしわ抑え圧４．９ｋＮで行い、成形性の評価は次の指標によった。
【００９３】
評点４：成形可能で、めっき層の欠陥なし。皮膜状態は加工部にツヤひけ等みられず全く正常。
【００９４】
評点３：成形可能で、めっき層にわずかに疵発生。皮膜加工部に色調変化見られるものの亀裂や剥離は見られない。
【００９５】
評点２：成形可能で、めっき層に大きな疵発生、皮膜に割れが認められるもの。
【００９６】
評点１：成形不可。
（３） 溶接性評価
溶接性はスポット溶接連続打点性、シーム溶接性により評価した。
【００９７】
（ａ） スポット溶接
先端径６ｍｍ−Ｒ４０のＣｒ−Ｃｕ電極を用い、溶接電流１０ｋＡ、加圧力１．９６ｋＮ、溶接時間１２サイクルでスポット溶接を行い、ナゲット径が４√ｔを切った時点までの連続打点数を評価した。
【００９８】
評点４：連続打点５００点超
評点３：連続打点３００〜５００点未満
評点２：連続打点１００〜３００点未満
評点１：連続打点１００点未満
（ｂ） シーム溶接
先端Ｒ６ｍｍ−φ２５０ｍｍの電極輪を用い、溶接電流１１ｋＡ、加圧力４．９ｋＮ、通電２ｏｎ−１ｏｆｆで１０ｍのシーム溶接を行った後、ＪＩＳ−Ｚ−３１４１に示される試験片を作製し、漏れ試験を実施した。
【００９９】
評点４：漏れ無し
評点３：漏れ無いが、溶接部表面がやや荒れているもの
評点２：漏れ無いが、溶接部表面に割れ等の欠陥が発生しているもの
評点１：漏れ発生
【０１００】
【表９】

【０１０１】
【表１０】

【０１０２】
【表１１】

【０１０３】
【表１２】

【０１０４】
【表１３】

【０１０５】
【表１４】

【０１０６】
評価結果は、表１３、１４に示すとおりで、本発明の実施例は、耐食性試験、加工性試験、溶接性試験のいずれにおいても評点３以上を示した。また、実施例の構成によっては、評点４とより良好な性能を示している。特に、有機樹脂皮膜の表面粗度をＲａで０．３μｍ以上２．５μｍ以下、Ｒｍａｘで２０μｍ以下、表面テクスチャのＰｃをカウントレベル０．３μｍで１０ｍｍ長さ当たり１０以上２００以下に制御したものは、安定した溶接作業性と耐食性を示した。また、有機皮膜として（イ）官能基数が少なくとも３のポリエステルポリオール、（ロ）有機ポリイソシアネートのブロック化物又は有機ポリイソシアネートと活性水素化合物との反応により得られる末端にＮＣＯ基を有するプレポリマーのブロック化物に、さらに（ハ）２級の水酸基を少なくとも１個有するエポキシ樹脂又はその付加物を加えた成膜性樹脂原料を用いた系、および導電性顔料としてフェロシリコンを用いた系では良好な外面耐食性を示した。
【０１０７】
表１４の比較例１〜１２は、本発明の範囲を外れた塗装鋼板の例を記した。比較例１は、有機皮膜の膜厚が薄く、耐食性、加工性が不足している。また、Ｐｃが高いためシーム溶接性がやや悪い。比較例２は、Ｒａ値が高いためスポット溶接性が悪く、シーム溶接において不具合が発生した。比較例３は、皮膜厚みが厚すぎるため溶接性が悪い。比較例４、５、６は、表面粗度Ｒａが高く、Ｒｍａｘ及び／又は表面テクスチャＰｃが高く、スポット溶接性、シーム溶接性が悪い。比較例７は、皮膜中に導電性顔料が無いため溶接性が悪い。比較例８、９、１０、１１、１２は、本発明を外れる樹脂皮膜であり、加工後耐食性に劣る。導電性顔料の含まれていない比較例８、９は溶接性も悪い。比較例１２は下地処理皮膜が無く、加工性が悪く、それに伴って耐食性も低下している。
【０１０８】
【発明の効果】
以上の説明から明らかなように、本発明の構成によって、自動車の燃料タンク用素材として優れた耐食性を有し、かつ安定した抵抗溶接性とプレス成形性を兼備する防錆鋼板を提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a rustproof steel sheet having excellent corrosion resistance as a material for a fuel tank of an automobile, and having both good resistance weldability and press formability.
[0002]
[Prior art]
Since an automobile fuel tank often has a complicated shape, excellent workability (deep drawing property) is required. In addition, since it is an important safety component for automobiles, the material used is a material that does not have corrosion products that may lead to filter clogging, has no concern about perforated corrosion, and can be easily and stably welded. It is important that there is.
[0003]
As a material having these various properties, a Pb-Sn-based alloy-plated steel sheet (Japanese Patent Publication No. 57-61833) has been widely used as a material for an automobile fuel tank. This material has stable chemical properties to gasoline, and is excellent in press formability due to excellent plating lubricity, and also excellent in resistance weldability such as spot welding and seam welding. However, in recent years, materials that do not use Pb have been demanded from the viewpoint of load on the environment, and Sn-based alloy-plated steel sheets (for example, JP-A-8-269733), Al-based alloy-plated steel sheets (for example, JP-A-9-15627), Techniques such as a Zn-based alloy plated steel sheet coated with a metal or organic film (for example, JP-A-8-296834) are disclosed.
[0004]
However, in recent years, in North America, there has been a demand for further strengthening of rust prevention specifications such that there is no perforation for 15 years, and with this, there has been a problem that the corrosion resistance of these conventional technologies is insufficient. On the other hand, long-term rust prevention can be achieved by applying a number of coatings after manufacturing the tank through molding and welding, but in this case, there has been a problem that the cost is greatly increased. Further, for example, Japanese Patent Application Laid-Open No. 6-306637 discloses a technique in which an organic film containing a metal powder is applied to an Al-based alloy-plated steel sheet. When receiving and molded, there is a concern that the coating cannot follow the deformation of the steel sheet, causing cracking or peeling of the plating layer or the coating, which lowers the corrosion resistance of the processed part, and to ensure sufficient corrosion resistance If the film is made thicker, there is a problem that welding becomes more difficult and stable production becomes more difficult, and there is a concern that cost may be disadvantageous. Japanese Patent Publication No. 3-25349 discloses a technique in which an organic coating containing various metal powders is applied to a Zn-based plated steel sheet. However, there is a concern that filter clogging may occur due to the generation of corrosion products due to organic acids and condensed water generated when gasoline deteriorates, and high external corrosion resistance is required.Thus, thicker organic coatings are required on both the inner and outer surfaces. In addition, there has been a problem that the difficulty in welding increases and stable production becomes difficult, and there is a concern that the cost is disadvantageous.
[0005]
[Patent Document 1]
JP-B-57-61833
[Patent Document 2]
JP-A-8-269733
[Patent Document 3]
JP-A-9-156027
[Patent Document 4]
JP-A-8-296834
[Patent Document 5]
JP-A-6-306637
[Patent Document 6]
Japanese Patent Publication No. 3-25349
[0006]
[Problems to be solved by the invention]
The present invention overcomes the above-mentioned performance and manufacturing problems, realizes high corrosion resistance on the inner and outer surfaces, and provides a rust-preventive steel sheet that enables good formability and stable welding. Aim.
[0007]
[Means for Solving the Problems]
The present inventors have conducted various studies on rust-preventive steel sheets for tanks having excellent corrosion resistance, and excellent weldability and formability.As a result, a resin having a urethane bond containing a conductive pigment on at least one surface of a surface-treated steel sheet is mainly used. The thickness of the film is 5 μm or more and 30 μm or less, and the surface roughness of the film is 0.3 μm or more and 2.5 μm or less in Ra, or 20 μm or less in Rmax and / or Pc of the surface texture. By controlling the count level to 10 or more and 200 or less per 10 mm length at a count level of 0.3 μm, it was found that good press formability and stable continuous weldability were obtained, and that corrosion resistance was also satisfied. The resin having a urethane bond includes (a) a polyester polyol having at least 3 functional groups, (b) a blocked product of an organic polyisocyanate, or a prepolymer having a terminal NCO group obtained by reacting an organic polyisocyanate with an active hydrogen compound. An organic resin obtained from a film-forming resin raw material containing a blocked polymer. These are, at the same time, (a) good moldability and corrosion resistance obtained based on the embodiment of the organic resin, and (b) good weldability and corrosion resistance obtained based on the embodiment of the conductive pigment. The present invention has found the conditions of the surface roughness and the surface texture and the method of producing the same so as to effectively express them. Further, when the resin having a urethane bond further contains (c) an epoxy resin having at least one secondary hydroxyl group or an adduct thereof as a resin component, it undergoes large deformation due to processing under severe conditions. In addition, sufficient corrosion resistance can be ensured in the processed part, and even better properties can be obtained with a coating composed of an organic coating, a conductive pigment, and a rust-preventive pigment in an appropriate mixing ratio. Using at least one metal powder consisting of steel, Zn, Al, Ni, ferrosilicon, iron phosphide; an alloy or a compound containing a conductive pigment in a certain content or more; the organic film and the surface; It has been found that a further improvement in corrosion resistance can be obtained by applying an undercoating film to the treated steel sheet.
[0008]
In particular,
(1) A rust-preventive steel sheet having, on at least one surface of a surface-treated steel sheet, an organic film containing (A) a resin having a urethane bond and (B) a conductive pigment in a film thickness of 5 μm or more and 30 μm or less, The resin (A) having a urethane bond is (A) a polyester polyol having at least 3 functional groups, (B) a blocked product of an organic polyisocyanate or an NCO group at a terminal obtained by the reaction of an organic polyisocyanate with an active hydrogen compound. A blocked prepolymer having, a film-forming resin material containing the organic resin, and the surface roughness of the organic film is not less than 0.3 μm and not more than 2.5 μm in center line average roughness Ra. Rust-proof steel plate for highly corrosion-resistant fuel tanks,
(2) The corrosion-resistant steel sheet for a fuel tank according to (1), wherein the content of the conductive pigment (B) in the organic film is 5 to 50% by volume in terms of solid content.
(3) The high corrosion resistance and high corrosion resistance according to (1) or (2), wherein the conductive pigment is made of at least one of stainless steel, Zn, Al, Ni, ferrosilicon, and iron phosphide. Rust-proof steel plate for fuel tanks,
(4) The high corrosion resistance according to any one of (1) to (3), wherein the conductive pigment is an alloy or a compound containing 40% by mass or more of Si, or a composite thereof. Corrosion-resistant steel plates for fuel tanks,
(5) The organic film further contains 1 to 40% by volume of a rust preventive pigment in terms of solid content, and the sum of the conductive pigment and the rust preventive pigment is 5 to 70% by volume in terms of solid content. The corrosion-resistant steel sheet for a fuel tank having high corrosion resistance and high corrosion resistance according to any one of (1) to (4),
(6) The rust-preventive steel sheet for a highly corrosion-resistant fuel tank according to (1), wherein (A) the resin having a urethane bond further comprises (c) an epoxy resin having at least one secondary hydroxyl group or an adduct thereof.
(7) The rust-preventive steel plate for a highly corrosion-resistant fuel tank according to (1), wherein the surface roughness of the organic film is 20 μm or less at a maximum height Rmax.
(8) The surface roughness of the organic film is 10 to 200 per 10 mm in length when the count level is 0.3 μm in the peak count Pc of the surface texture, according to (1) or (7). Anti-corrosion steel plate for high corrosion resistant fuel tanks as described,
(9) The rust-preventive steel sheet for a highly corrosion-resistant fuel tank according to any one of claims 1 to 8, further comprising an undercoating film between the organic film and the surface-treated steel sheet.
(10) The adhesion amount of the undercoating film is 10 to 1000 mg / m.²(9) The corrosion-resistant steel plate for a highly corrosion-resistant fuel tank according to (9),
It is.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0010]
The rust-proof steel sheet of the present invention has (A) a resin having a urethane bond and (B) an organic film containing a conductive pigment on at least one surface of the surface-treated steel sheet, and has an organic film thickness of 5 μm or more and 30 μm or less. The surface roughness of the organic resin film is 0.3 μm or more and 2.5 μm or less in Ra, more preferably 20 μm or less in Rmax, and Pc of the surface texture is 10 or more and 200 or less per 10 mm length at a count level of 0.3 μm. Is controlled.
[0011]
The thickness of the organic coating layer of the present invention is 5 μm or more and 30 μm or less. If it is less than 5 μm, depending on the combination with the surface-treated steel sheet or the undercoat film, the contribution to the rust prevention effect is not sufficient, and if it is more than 30 μm, the effect is saturated and uneconomical, and the weldability starts to be adversely affected. In order to obtain stable corrosion resistance, workability, and weldability, the thickness is more preferably 8 μm or more and 20 μm or less.
[0012]
The surface roughness and texture can be controlled by adjusting the paint, such as adjusting the paint viscosity, adding a leveling agent, adding a surfactant, adding a solvent having a different specific gravity, and adding a filler having a controlled particle size. . Further, the surface can be adjusted by a mechanical method such as temper rolling by a skin pass roll after application and surface control by shot blast. If the center line average roughness Ra is less than 0.3 μm, the contact area with the mold increases during processing, causing an increase in the coefficient of friction and a reduction in workability. Continuous workability at the time decreases. Therefore, Ra is set to 0.3 μm or more and 2.5 μm or less. More preferably, it is 0.6 μm to 1.5 μm. When the maximum height Rmax is more than 20 μm, irregularities locally occur in the regular roughness of the surface defined by Ra, and uneven energization such as local energization easily occurs at this location. As a result, there is a high possibility that continuous workability during welding is reduced. Therefore, Rmax is preferably 20 μm or less. Further, the peak count Pc is preferably 10 or more and 200 or less per 10 mm length at a count level of 0.3 μm. If the number of Pc is less than 10, the contact area with the mold increases during processing, thereby increasing the coefficient of friction and reducing the workability. If the number of Pc is more than 200, the variation in texture from place to place increases. Therefore, there is a high possibility that continuous workability during welding is reduced. In particular, when these three parameters are satisfied at the same time, better weldability, workability, and corrosion resistance are exhibited. These surface roughness and texture can be measured using a normal roughness meter. The roughness per 10 mm of the length of an arbitrary portion is measured in the L direction and the C direction of the steel sheet, and the suitability is determined based on whether each value falls within the range of the present invention. Alternatively, the surface roughness and texture may be measured with a three-dimensional roughness meter, and converted into two dimensions for determination.
[0013]
Next, an organic film containing a conductive pigment will be described.
[0014]
The organic film is a resin having a urethane bond, (a) a polyester polyol having at least 3 functional groups, (b) a blocked product of an organic polyisocyanate, or a terminal obtained by a reaction between an organic polyisocyanate and an active hydrogen compound. By using an organic resin obtained from a film-forming resin material containing a blocked prepolymer having an NCO group, it has good followability to bending deformation and drawing deformation caused by press working, and has high hardness and gasoline resistance. An excellent film having high property can be obtained. Further, when the organic resin is combined with (c) an epoxy resin having at least one secondary hydroxyl group or a resin obtained by adding a lactone compound or an alkylene oxide to an epoxy resin, further excellent characteristics can be obtained.
[0015]
The polyester polyol (a) having at least 3 functional groups used in the resin used in the present invention can be obtained by esterifying a dicarboxylic acid, a glycol and a polyol having at least three OH groups.
[0016]
Examples of the dicarboxylic acid used in the production of the polyester polyol include, for example, succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecane diacid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, dimer acid, Aliphatic systems, for example, phthalic acid, phthalic anhydride, isophthalic acid, dimethyl isophthalate, terephthalic acid, dimethyl terephthalate, 2,6-naphthalenedicarboxylic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexane Examples thereof include aromatic or alicyclic compounds such as dicarboxylic acid, cyclohexanedicarboxylic acid dimethyl ester, methylhexahydrophthalic anhydride, hymic anhydride, and methylhymic anhydride.
[0017]
Examples of the glycol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Neopentyl glycol ester of hydroxydivalic acid, triethylene glycol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl -1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, polycaprolactone diol, polypropylene glycol, polytetramethylene ether glycol, polycarbonate diol, 2-n-butyl-2-ethyl- Aliphatic compounds such as 2,3-propanediol and 2,2-diethyl-1,3-propanediol, for example, cyclohexanedimethanol, cyclohexanediol, 2-methyl-1,1-cyclohexanedimethanol, xylylene glycol Aliphatic or aromatic ones, such as bishydroxyethyl terephthalate, 1,4-bis (2-hydroxyethoxy) benzene, hydrogenated bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A Is mentioned.
[0018]
Examples of the polyol having at least three OH groups include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, diglycerin, or ethylene oxide using these polyols as an initiator. An adduct, a propion oxide adduct or an ε-caprolactan adduct may be used.
[0019]
Examples of the blocked product of (b) used in the resin used in the present invention include compounds having at least two NCO groups, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- Propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 2,6-diisocyanate methyl caproate And aliphatic diisocyanates such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanatomethyl. 3,5,5-trimethylhexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane Cycloalkylene diisocyanates such as 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane and trans-cyclohexane-1,4-diisocyanate; -Phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate Aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, and, for example, ω, ω′-diisocyanate-1, 3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, α, α, α ′, α′-tetramethylmetaxylylene diisocyanate Araliphatic diisocyanates and, for example, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, ω-isocyanateethyl-2, Triiso such as 6-diisocyanato caproate Anate, for example, a blocked product of tetraisocyanate such as 4,4'-diphenylmethylmethane-2,2 ', 5,5'-tetraisocyanate, dimer, trimer, buret, allophanate, carbodiimide, polymethylene polyphenylpoly Blocked derivatives of isocyanate compounds such as isocyanates (crude MDI, c-MDI, polymeric MDI) and crude TDI, or prepolymer blocks having NCO groups at the terminals obtained by reacting them with active hydrogen compounds Compounds.
[0020]
When weather resistance is required for the organic film, hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,4-bis (isocyanatomethyl) may be used among the compounds having an NCO group. ) Use of isocyanate compounds such as cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′-methylenebis (cyclohexyl isocyanate), α, α, α ′, α′-tetramethylmetaxylylene diisocyanate. preferable.
[0021]
These prepolymers having an NCO group at the terminal obtained by the reaction of an isocyanate compound and an active hydrogen compound are obtained by reacting the isocyanate monomer with an active hydrogen compound in an excess of isocyanate groups. Examples of the active hydrogen compound used for producing the prepolymer include ethylene glycol, propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol. , Neopentyl glycol, neopentyl glycol hydroxydivalate, triethylene glycol, hydrogenated bisphenol A, xylylene glycol, dihydric alcohols such as 1,4-butylene glycol, for example, glycerin, trimethylolethane, and trimethylolpropane And low molecular weight polyols such as trihydric alcohols such as 1,2,6-hexanetriol, for example, tetrahydric alcohols such as pentaerythritol, and propylene oxide or ethylene of the above polyols. And polyether polyol oxide adducts, include high molecular weight polyols such as those obtained by aliphatic denatured in making the polyester polyols or polyester polyols obtained by reacting a low molecular weight polyol and a dicarboxylic acid described above. These polyols may be used alone or as a mixture.
[0022]
The prepolymer generally reacts at an equivalent ratio of NCO groups / OH groups of about 2.0 to 15, preferably about 4.0 to 8.0, usually at 40 to 140 ° C, preferably 70 to 100 ° C. After that, if necessary, it can be obtained by removing unreacted isocyanate monomer by a thin film distillation method or an extraction method which is usually performed. For this reaction, an organometallic catalyst such as a Sn-based, Pb-based, Zn-based, or Fe-based catalyst may be used.
[0023]
The above-mentioned blocked isocyanate monomer or prepolymer thereof can be obtained by reacting the isocyanate monomer or prepolymer thereof with a blocking agent by a known method. Examples of the blocking agent used in this reaction include phenol, lactam, active methylene, active methylene, alcohol, mercaptan, acid amide, imide, amine, imidazole, urea, and carbamic acids. Any of a salt-based, imine-based, oxime-based, or sulfite-based blocking agent may be used, and particularly, a phenol-based, oxime-based, lactam-based, imine-based blocking agent and the like are advantageously used. The following are specific examples of the blocking agent.
[0024]
Phenolic blocking agents: phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, p-hydroxydiphenyl, t-butyl ether, o-isopropylphenol, o-sec-butylphenol, p-nonylphenol, pt-octylphenol, Hydroxybenzoic acid, hydroxybenzoic acid ester and the like.
[0025]
Lactam blocking agents: ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-prosolactam and the like.
[0026]
Active methylene blocking agents: diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone and the like.
[0027]
Alcohol blocking agents: methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol Glycolic acid esters such as monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, distyrene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methoxymethanol, glycolic acid, methyl glycolate, ethyl glycolate, ethyl glycolate and butyl glycolate Lactic acid esters such as lactic acid, methyl lactate, ethyl lactate, butyl lactate, and methylol Element, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene epibromohydrin, 1,3-dichloro-2-propanol, .omega. hydroperoxide fluoroalcohol, aceto cyanohydrin like.
[0028]
Mercaptan-based blocking agents: butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, ethylthiophenol and the like.
[0029]
Acid amide blocking agents: acetanilide, acetoanisidide, acetoloid, acrylamide, methacrylamide, acetate amide, stearamide, benzamide and the like.
[0030]
Imide-based blocking agents: succinimide, phthalimide, maleic imide and the like.
[0031]
Amine-based blocking agents: diphenylamine, phenylnaphthylamine, xylidine, n-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, butylphenylamine and the like.
[0032]
Imidazole blocking agents: imidazole, 2-imidazole and the like.
[0033]
Urea-based blocking agents: urea, thiourea, ethylene urea, ethylene thiourea, 1,3-diphenyl urea and the like.
[0034]
Carbamate-based blocking agents: phenyl n-phenylcarbamate, 2-oxazolidone and the like.
[0035]
Imine-based blocking agents: ethyleneimine, propyleneimine and the like.
[0036]
Oxime blocking agents: formamidoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexane oxime and the like.
[0037]
Sulfite blocking agents: sodium bisulfite, potassium bisulfite, etc.
[0038]
In the present invention, better properties can be obtained by further adding (c) an epoxy resin having at least one secondary hydroxyl group or an adduct thereof to the polyol component. As a resin obtained by adding a lactone compound or an alkylene oxide to an epoxy resin having at least one secondary hydroxyl group, a lactone compound or an alkylene oxide is added to an epoxy resin represented by the following general formula (1) by a known means. One.
[0039]
Embedded image

[0040]
(In the formula, X represents a phenylene group or a cyclohexylene group which may be substituted with halogen, and n is 0.5 to 12.)
The addition amount of the lactone compound or alkylene oxide is about 5 to 40 parts by mass based on about 95 to 60 parts by mass of the epoxy resin. In particular, the lactone compound or alkylene oxide is preferably used in an amount of about 10 to 30 parts by mass with respect to about 90 to 70 parts by mass of the epoxy resin.
[0041]
In the epoxy resin represented by the general formula (1), X is preferably a p-phenylene group, and n is preferably 2 to 9. Examples of the halogen include bromine and chlorine. The number of the substituents is usually about 1 to 3, and the position may be any position of a phenylene group or a cyclohexylene group.
[0042]
Examples of the lactone compounds include, for example, β-propionlactone, butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and among them, particularly ε-caprolactone. Is preferred. Examples of the alkylene oxide include ethylene oxide, propylene oxide, styrene oxide, glycidyl methacrylate, epichlorohydrin and the like, with ethylene oxide being particularly preferred.
[0043]
The compounding ratio of the epoxy resin having at least one secondary hydroxyl group or a product obtained by adding a lactone compound or an alkylene oxide to the epoxy resin is about 10 to 70% by mass in the polyol component, and particularly about 10 to 70% by mass. It is preferable to use it in the range of 60% by mass. If the compounding ratio is less than 10% by mass, the chemical resistance may deteriorate. On the other hand, if it exceeds 70% by mass, the hardness is extremely reduced, and it may be easily damaged during press molding.
[0044]
The film-forming resin raw materials used in the present invention are the above-mentioned polyols (a) and (c) and the blocked product (b), and the mixing ratio of the polyol and the blocked product is such that the equivalent ratio of OH group / regenerated NCO group is about 1/2 to 2/1, particularly preferably 1 / 1.2 to 1 / 0.8.
[0045]
Next, the conductive pigment will be described.
[0046]
By adding a conductive pigment of a metal, an alloy of a metal element or a conductive compound of a metal element to an organic coating, it is possible to impart functions such as improvement of electric resistance weldability and corrosion resistance to the organic coating coated steel sheet. . The content is 5 to 50% by volume, preferably 20 to 40% by volume of the entire organic coating layer in terms of solid content. If it is less than 5% by volume, sufficient weldability cannot be obtained, and if it exceeds 50% by volume, there is a possibility that the followability of the coating during processing may be reduced.
[0047]
The metal constituting the conductive pigment, the alloy of the metal element or the particles of the conductive compound of the metal element are, for example, pulverized solid, or granulated by a known method such as jetting a melt into a gas phase or an aqueous phase. Anything can be used. The particles are, for example, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Ir, Zr, Nb, Mo, Tc, Ru. , Rh, Pd, Ag, Cd, In, Sn, and other metals, Mg, Al, Si, P, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge , As, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, and other alloys or conductive compounds can be used.
[0048]
Among the above-mentioned metal, metal element alloy or compound particles, those which can be obtained industrially at relatively low cost and stably include Mg, Al, Si, Cr, Fe, Ni, Zn, Sn and Zn-Al alloys. , Zn-Al-Mg alloy, Zn-Al-Mg-Si alloy, Zn-Fe alloy, Zn-Cr alloy, Zn-Ni alloy, Fe-Ni alloy, Fe-Cr alloy, stainless steel, ferrosilicon, phosphide Iron and the like. In particular, it is preferable to use one or more of stainless steel, Zn, Al, Ni, ferrosilicon, and iron phosphide from the viewpoint of a balance between performance and industrial properties.
[0049]
It is preferable that the above-mentioned particles include those having a particle size of 5 times or less the average film thickness of the organic film. More preferably, the particle size is twice or less the average film thickness of the organic film. This is because the particles are effectively transferred to the organic film at the time of coating, and the particles are prevented from settling and separating in the raw material paint of the organic film.
[0050]
In order to realize further high corrosion resistance of the coated steel sheet, it is desirable to use ferrosilicon as an essential component in the aforementioned particles. This effect is considered to be due to the formation of a protective film containing Si in a corrosive environment. In the present invention, it is particularly preferable to use ferrosilicon of 40% by mass or more of Si. Specifically, by using 75 to 80% by mass of JIS No. 2 ferrosilicon, 45 to 50% by mass of JIS No. 3 ferrosilicon, etc. as the conductive particles, the conductivity can be ensured and the corrosion resistance is dramatically improved. .
[0051]
Corrosion resistance can be further improved by adding a rust preventive pigment to the organic film. The amount of addition is 1 to 40% by volume, preferably 3 to 30% by volume, based on the total amount of the organic coating layer in terms of solid content. At 1% by volume, a sufficient rust-preventing effect cannot be obtained, and at more than 40% by volume, the ratio of the film-forming organic resin decreases, and the cohesive force of the film may decrease.
[0052]
As the rust preventive pigment, a known rust preventive pigment such as hexavalent Cr salt such as strontium chromate and calcium chromate can be used. When it is desired to avoid using a hexavalent Cr compound as a rust preventive pigment, a pigment that releases one or more of silicate ions, phosphate ions, and vanadate ions can be used. In order to exhibit the rust-preventive effect of the organic film, it is preferable that phosphate ions and vanadate ions coexist in the organic film layer. It may contain a substance that releases phosphate ions and vanadate ions in an existing environment.
[0053]
Phosphate ions rarely exist alone in an aqueous solution, and exist in various forms, for example, as a condensate. Phosphides used for rust preventive pigments are orthophosphoric acid, condensed phosphoric acid, orthophosphate or condensed phosphate of various metals, phosphorus pentoxide, phosphate minerals, commercially available composite phosphate pigments, or these. Mixtures are mentioned. Some of the orthophosphates mentioned here include their monohydrogen salts (HPO₄ ^2-), Dihydrogen salts (H₂PO₄ ⁻). In addition, a hydrogen salt is included in the condensed phosphate. Further, the condensed phosphates include metaphosphates, and include ordinary polyphosphates and polymetaphosphates. Specific examples of the phosphorus compound include monetite, tolfillite, witlockite, xenotime, starcolite, struvite, ore iron ore, and commercially available complex phosphate pigments such as polyphosphate silica. Phosphoric acid, complex phosphoric acid such as metaphosphoric acid, or complex phosphate such as metaphosphate, tetrametaphosphate, hexametaphosphate, pyrophosphate, acid pyrophosphate, tripolyphosphate, or a mixture thereof Is mentioned.
[0054]
The metal species forming the phosphate is not particularly limited, and examples thereof include alkali metals, alkaline earth metals, metal species of other typical elements, and transition metals. Examples of preferred metal species include Mg, Ca, Sr, V, Ti, Zr, Mn, Fe, Co, Ni, Zn, Al, Pb, Sn and the like. In addition, oxo cations such as vanadyl, titanyl, and zirconyl are also included. Of these, Ca and Mg are particularly preferred. The use of large amounts of alkali metals is not preferred. When an alkali metal phosphate is used, the calcined product tends to be too soluble in water. However, when an alkali metal phosphate is used, it may be used if the solubility in water can be controlled during the production of the rust preventive or at another time. Such control includes various modes such as, for example, use of a matrix material (particularly, a glassy substance) for prevention of solubility in water, and coating.
[0055]
The vanadium compound used for the rust preventive pigment is a compound having a valence of vanadium of 0, 2, 3, 4, or 5, or a compound having two or more of these valences. And oxyacid salts of various metals, vanadyl compounds, halides, sulfates, metal powders and the like. These decompose during heating or in the presence of water, react with oxygen, and are upgraded. For example, vanadium metal powder or a divalent compound is ultimately changed to a trivalent, tetravalent, or pentavalent compound. Those containing a pentavalent vanadium compound as one component are preferred. Zero-valent vanadium metal powder can be used for the above-mentioned reason, but is not practically preferable because it has a problem such as insufficient oxidation reaction. The pentavalent vanadium compound has a vanadate ion, reacts with a phosphate ion by heating, and easily forms a heteropolymer. Specific examples of the vanadium compound include vanadium (II) compounds such as vanadium (II) oxide and vanadium (II) hydroxide, vanadium (III) compounds such as vanadium oxide and the like, vanadium (IV) oxide and vanadium such as vanadyl halide and the like. (IV) compounds, vanadium (V) compounds such as vanadium (V) oxide, orthovanadate, metavanadate or pyrovanadate of various metals, vanadates such as vanadyl halide, and mixtures thereof. Can be Examples of the metal species of vanadate include the same as those described for phosphate. This may be produced by firing a vanadium oxide and various metal oxides, hydroxides, carbonates and the like to 600 ° C. or more. Also in this case, alkali metals are not preferred because of their solubility. However, if the solubility is controlled by an appropriate treatment described for the phosphate, the use of these metals can be used. The same applies to halides and sulfates. The ratio of the phosphate ion source and the vanadate ion source to be blended is P₂O₅And V₂O₅Is preferably from 1: 3 to 100: 1 in terms of the molar ratio.
[0056]
The amount of the conductive pigment and / or rust-preventive pigment in the organic coating layer is 5 to 70% by volume, preferably 20 to 60% by volume of the entire organic coating layer in terms of solid content. If it is less than 5% by volume, the above-mentioned effect of addition cannot be sufficiently exhibited, and if it exceeds 70% by volume, the cohesive strength of the cured film is reduced, and sufficient film strength cannot be obtained.
[0057]
Various types of surface-treated steel sheets can be used as the base steel sheet for painting, but among them, Zn-based plated steel sheets, Al-based plated steel sheets, and Sn-based plated steel sheets are preferable in view of the balance between corrosion resistance, weldability, and workability. The Zn system refers to Zn or an alloy system containing 50% or more of Zn. For example, Zn, Zn-Ni alloy, Zn-Fe alloy, Zn-Al alloy, Zn-Co alloy, Zn-Mg alloy, Zn-Mg-Al alloy and the like can be mentioned. Similarly, Al-based plating and Sn-based plating are also Al or an alloy system containing 50% or more of Al, or Sn or an alloy system containing 50% or more of Sn. For example, Al, Al-Si alloy, Al- Fe alloy, Al-Zn alloy, Al-Mg alloy, Al-Mg-Si-Zn alloy and the like, for example, Sn, Sn-Zn alloy, Sn-Ag alloy, Sn-Mg alloy and the like can be mentioned. When used for tank materials, high resistance weldability (spot welding, seam welding, etc.) is required. At this time, since the electrode Cu and the plated metal are apt to form a compound, the amount of plating adherence is limited. Greatly affect In addition, the amount of plating has a large effect on corrosion resistance. The larger the coating weight, the more advantageous in terms of corrosion resistance and the more disadvantageous in terms of weldability, so that the coating weight is 20 to 60 g / m per side.²Is preferred.
[0058]
In addition, since the fuel tank is required to have high workability, it is desirable to use IF steel (Interstitial Free steel) having excellent workability. Further, in order to ensure welding airtightness after welding, secondary workability, and the like. It is desirable to use a steel sheet in which B is added in an amount of 0.0002 to 0.003% by mass.
[0059]
Regarding the plating method, it can be manufactured by a conventional manufacturing method such as electroplating, hot-dip plating, and vapor phase plating. It is naturally possible to plate directly on the steel sheet, and it is also possible to apply a pre-plating treatment before plating. The pre-plating is performed in order to improve the plating property in the hot-dip plating, and may be a single plating of Ni, Co, Fe, Cr, Sn, Zn, or Cu, or an alloy plating containing these. The thickness is usually about 0.1 μm, but is not particularly limited.
[0060]
In the present invention, an undercoating film may be further provided between the surface-treated steel sheet and the organic film containing the conductive pigment. Thereby, good adhesion can be obtained, and further good corrosion resistance can be obtained. The undercoating film includes, for example, a chromate film, which affects properties such as corrosion resistance, weldability, and corrosion resistance after painting. Chromate coatings have been used frequently because they have excellent corrosion resistance and paintability. However, hexavalent Cr has a large burden on the environment, and in recent years, many post-treatment coatings have been proposed to replace it. In the present invention, it is also possible to apply these post-treatment films as a base treatment film. As the post-treatment film, a trivalent Cr film or a non-chromate film is preferable, and examples thereof include a method of forming by electrolysis, a method of forming by utilizing a reaction, and a method of forming by coating.
[0061]
As the base treatment layer, a film obtained by applying and drying an aqueous solution containing a known silica (chromic acid) as a main component, fine silica or a silane coupling agent as needed, and a hexavalent chromic acid as a main component A coating obtained by contacting the plating surface with an aqueous solution to which fine silica or a silane coupling agent has been added as required, forming a base treatment layer, and then washing and drying the film. A film obtained by applying and drying an aqueous solution containing fine silica or a silane coupling agent as needed to an aqueous solution not containing hexavalent chromic acid, and trivalent chromium on the plating surface by electrolysis in a chromic acid aqueous solution Any one or a plurality of methods, such as a film obtained by washing and drying after depositing a film containing as a main component, a film obtained by depositing a phosphate such as Zn, Ni, and Fe on a plating surface. Union It may be used a film to be formed in. Furthermore, a film formed by applying and drying an aqueous solution containing at least one of fine-particle silica, a silane coupling agent, phosphoric acid, tannin, and tannic acid on a plating surface, which is mainly composed of an aqueous resin, may be used. good. When it is desired to avoid the use of hexavalent Cr, a film formed of trivalent Cr, phosphates of various metals, or an aqueous resin may be used as the base treatment layer.
[0062]
The term “aqueous resin” used in the undercoating layer includes, in addition to a water-soluble resin, a resin that is inherently insoluble in water but can be finely dispersed in water, such as an emulsion or a suspension. Those usable as such aqueous resins include, for example, polyolefin resins, acrylic olefin resins, polyurethane resins, polycarbonate resins, epoxy resins, polyester resins, alkyd resins, phenol resins, and other thermosetting resins. And a crosslinkable resin. Particularly preferred resins are acrylic olefin resins, polyurethane resins, phenol resins, and mixed resins thereof. Two or more of these aqueous resins may be mixed or polymerized for use.
[0063]
The silane coupling agent, in the presence of the organic resin, firmly bonds to both the plating and the film, dramatically improving the adhesion of the film, and thus improving the corrosion resistance. Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, aminosilane, γ-methacryloxypropyltrimethoxysilane, N- β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [ 3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchloro Mention may be made of the run, and the like.
[0064]
The content of the silane coupling agent when used in the base treatment layer with the aqueous resin is desirably 0.1 to 3000 parts by mass based on 100 parts by mass of the aqueous resin in terms of solid content. If the amount is less than 0.1 part by mass, the amount of the silane coupling agent is insufficient, so that sufficient adhesiveness cannot be obtained during processing and the corrosion resistance is poor. If it exceeds 3,000 parts by mass, the effect of improving the adhesion is saturated, which is uneconomical.
[0065]
Further, it is preferable to add an appropriate amount of phosphoric acid for further improving the adhesion by etching the surface and for stabilizing the silane coupling agent. The addition amount is desirably 0.1 to 3000 parts by mass based on 100 parts by mass of the aqueous resin in terms of solid content. If the amount is less than 0.1 part by mass, the amount of phosphoric acid is insufficient, so that sufficient adhesion cannot be obtained during processing, and the corrosion resistance is poor. If it exceeds 3,000 parts by mass, the effect of improving the adhesion is saturated, which is uneconomical.
[0066]
The role of the tannin or tannic acid in the base treatment layer by the aqueous resin is to strongly react and adhere to the plating layer and to adhere to the aqueous resin. The aqueous resin adhered to tannin or tannic acid adheres firmly to the resin coated thereon, and as a result, the plating layer and the film adhere firmly without using the conventionally used chromate treatment. It is thought that it becomes. In addition, it is considered that there is a portion where tannin or tannic acid itself participates in bonding between the plated steel sheet and the film without mediating the aqueous resin.
[0067]
Tannin and tannic acid are firmly bonded to both the plating layer and the film in the presence of the aqueous resin, thereby dramatically improving the adhesion of the film and, consequently, the corrosion resistance. The tannin or tannic acid may be a hydrolyzable tannin or a condensed tannin, or a partially decomposed tannin. Examples of the tannins and tannic acids include hamametanetan, quintuple tannin, gallic tannin, milobarone tannin, dividibine tannin, argarovira tannin, baronia tannin, catechin, and the like. For example, "tannic acid: AL" (manufactured by Fuji Chemical Industry) or the like can be used.
[0068]
The content of tannin or tannic acid is preferably 0.2 to 50 parts by mass with respect to 100 parts by mass of the resin. If the content of tannin or tannic acid is less than 0.2 parts by mass, the effect of adding them is not seen, and the film adhesion and the corrosion resistance of the processed portion are insufficient. On the other hand, if it exceeds 50 parts by mass, there is a problem that on the contrary, the corrosion resistance is lowered, or the processing solution is gelled when stored for a long time.
[0069]
Further, the addition of fine silica improves scratch resistance, film adhesion, and corrosion resistance. In the present invention, fine-particle silica is a generic term for silica having a characteristic that can stably maintain a water-dispersed state when dispersed in water because of having a fine particle size and in which semi-permanent sedimentation is not recognized. It is something. Such fine-grained silica is not particularly limited as long as it has a small amount of impurities such as sodium and is weakly alkaline. For example, commercially available silica such as "Snowtex N" (manufactured by Nissan Chemical Industries, Ltd.) and "Adelite AT-20N" (manufactured by Asahi Denka Kogyo KK) can be used.
[0070]
The content of the fine silica is 1 to 2,000 parts by mass, more preferably 10 to 400 parts by mass, based on 100 parts by mass of the aqueous resin in terms of solid content. If the amount is less than 1 part by mass, the effect of addition is small, and if it exceeds 2,000 parts by mass, the effect of improving corrosion resistance is saturated and uneconomical.
[0071]
Further, the addition of an etching fluoride improves the film adhesion. Here, as the etching fluoride, zinc fluoride tetrahydrate, zinc hexafluorosilicate hexahydrate, or the like can be used. The content of the etching fluoride is preferably 1 to 1000 parts by mass in terms of solid content based on 100 parts by mass of the aqueous resin. If the amount is less than 1 part by mass, the effect of addition is small, and if it exceeds 1000 parts by mass, the effect of etching is saturated and the film adhesion is not improved, so that it is uneconomical.
[0072]
Further, a surfactant, a rust inhibitor, a foaming agent and the like may be added as necessary.
[0073]
The adhesion amount of the undercoat layer after drying is 10 to 1000 mg / m²Is preferred. 10mg / m²If it is less than the above, the adhesion may be poor and the corrosion resistance of the processed portion may be insufficient. On the other hand, 1000 mg / m²If it exceeds, it is not only uneconomical, but also there is a possibility that the weldability may be reduced.
[0074]
The method of applying the undercoating film or the organic film containing a conductive pigment is not particularly limited, and generally known coating methods, for example, roll coating, curtain flow coating, air spray coating, airless spray coating, and electrostatic coating. Painting, dipping, brushing and the like can be applied. The form of the paint is not particularly limited, such as powder, solid, solvent-based, and water-based. Drying and baking after the application may be performed by a known method such as a hot air oven, an induction heating oven, a near infrared oven, or a combination thereof. In addition, depending on the type of the aqueous resin used, the resin can be cured by ultraviolet rays, electron beams, or the like. Alternatively, natural drying may be performed without using forced drying, or a plated steel sheet may be heated in advance, applied thereon, and naturally dried. In the present invention, a process for controlling surface roughness and texture such as shot blasting and skin pass rolling may be included during or after the drying / curing.
[0075]
Furthermore, when the steel sheet of the present invention is actually used, in a normal manufacturing process, after forming, after performing resistance welding such as seam, spot, etc., it is used. Reliability can be obtained. Commercially available repair paints may be used as long as they have good adhesion to the organic film and can suppress penetration of corrosion factors such as moisture. Even if such repair coating is performed, the rust-proof steel sheet of the present invention can be manufactured at a sufficiently low cost as compared with the case where post-coating is performed on the conventional technology.
[0076]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples.
[0077]
A steel having the components shown in Table 1 was melted by a normal converter-vacuum degassing process to obtain a billet, which was then hot-rolled and cold-rolled under normal conditions to obtain a cold-rolled steel sheet (sheet thickness 0.8 mm). ) Got. Using this as a material, various surface-treated steel sheets were manufactured. The hot-dip plating was performed using a line of a Zenzimer system or a flux system. In the case of the Sendzimer method, annealing was performed in-line. The annealing temperature was 800 to 850 ° C. After plating, the amount of plating was adjusted by a gas wiping method. The plating temperature at this time depends on the plating composition, and was set to the melting point of the plating composition + 40 ° C. The electroplating was performed in an electroplating line after annealing the cold-rolled steel sheet.
[0078]
[Table 1]

[0079]
A base coat having the composition shown in Table 8 was applied to both sides of the surface-treated steel sheet manufactured in this manner by a roll coater in a predetermined amount, and baked and dried with hot air at 200 ° C. Further, an organic film containing a conductive pigment having a composition shown in Tables 2 to 7 was further applied to both surfaces or one surface (outer surface side) with a predetermined amount by a roll coater, and baked and dried with hot air at 250 ° C. . To some level, the surface roughness and texture were adjusted by applying skin pass rolling after coating the surface-treated steel sheet and the organic film. Tables 9 to 12 show the specifications of the rustproof steel sheet obtained in this manner.
[0080]
[Table 2]

[0081]
[Table 3]

[0082]
[Table 4]

[0083]
[Table 5]

[0084]
[Table 6]

[0085]
[Table 7]

[0086]
[Table 8]

[0087]
The suitability of the steel sheet thus manufactured as a fuel tank was evaluated by the following method.
[0088]
(1) Evaluation of corrosion resistance
(A) External corrosion resistance
After the painted steel plate was drawn into a cylindrical cup so that the painted surface was on the outside, a cyclic corrosion test was performed. The cylindrical cup squeezer was punched at a squeezing ratio of 2.0 after standing with a punch diameter of 50 mm and a wrinkle suppressing pressure of 9.8 kN for 1 hour to 1 hour and 30 minutes after applying the rust preventive oil.
[0089]
The cycle corrosion test was performed with a total of 8 hours of salt spray 2 hours, dry 4 hours, and wet 2 hours as one cycle. The conditions of salt spray were based on JIS-K5400. The drying condition is a temperature of 50 ° C. and a humidity of 30% RH or less, and the wet condition is a temperature of 35 ° C. and a humidity of 95% RH or more.
[0090]
The evaluation of corrosion resistance is as follows.
[0091]
Rating 4+: Red rust indicating a decrease in the thickness of the steel sheet was not generated even after 300 cycles, and the area ratio of white rust indicating corrosion of the plating layer covering the sample was less than 5% of the whole.
Score 4: Red rust indicating a decrease in the thickness of the steel sheet was not generated even after 300 cycles, and the area ratio of white rust indicating the corrosion of the plating layer covering the sample was 5% or more and less than 50% of the whole.
Score 3: When red rust indicating a decrease in the thickness of the steel sheet does not occur even after 300 cycles.
Score 2: When red rust is not seen after 100 cycles and red rust is seen after 300 cycles
Rating 1: When red rust is seen in 100 cycles
(B) Inner corrosion resistance
The corrosion resistance to gasoline was evaluated. The method was as follows. A test solution was poured into a flat-bottomed cylindrical sample having a flange width of 20 mm, a diameter of 50 mm, and a depth of 25 mm drawn by a hydraulic molding tester, and was covered with glass via a silicon rubber ring. The state of corrosion after this test was visually observed.
[0092]
(Test condition)
Test liquid: gasoline + distilled water 10% + formic acid 200ppm
Test period: Leave at 40 ° C for 3 months
(Evaluation criteria)
Rating 4: No change
Rating 3: White rust generation 1% or less
Rating 2: Red rust generation 5% or less, or white rust generation 1% to 50%
Score 1: Red rust generation is more than 5% or white rust is remarkable
(2) Press workability evaluation
Using a hydraulic molding tester, a molding test was performed with a drawing ratio of 2.3 using a cylindrical punch having a diameter of 50 mm. The wrinkle suppressing pressure at this time was 4.9 kN, and the evaluation of formability was based on the following index.
[0093]
Rating 4: Formable, no defect in plating layer. The film condition is completely normal with no shiny marks seen in the processed part.
[0094]
Rating 3: Formable and slightly flawed in plating layer. Although a change in color tone is observed in the film-processed portion, no crack or peeling is observed.
[0095]
Rating 2: Formable, with large flaws in the plating layer and cracks in the film.
[0096]
Rating 1: No molding possible.
(3) Weldability evaluation
Weldability was evaluated by continuous spot welding and seam weldability.
[0097]
(A) Spot welding
Using a Cr-Cu electrode with a tip diameter of 6 mm-R40, spot welding was performed at a welding current of 10 kA, a pressing force of 1.96 kN, and a welding time of 12 cycles, and the number of continuous hitting points until the nugget diameter fell below 4 t was evaluated. did.
[0098]
Score 4: More than 500 consecutive hit points
Rating 3: Continuous RBI 300 to less than 500
Rating 2: Continuous RBI 100 to less than 300
Rating 1: Continuous RBI less than 100 points
(B) Seam welding
After performing 10 m seam welding with a welding current of 11 kA, a pressing force of 4.9 kN, and a current of 2 on-1off using an electrode wheel having a tip R of 6 mm-φ250 mm, a test piece shown in JIS-Z-3141 was prepared, and a leak test was performed. Was carried out.
[0099]
Score 4: No leakage
Rating 3: No leakage, but the surface of the weld is slightly rough
Rating 2: No leakage, but defects such as cracks occurred on the welded surface
Score 1: Leakage occurred
[0100]
[Table 9]

[0101]
[Table 10]

[0102]
[Table 11]

[0103]
[Table 12]

[0104]
[Table 13]

[0105]
[Table 14]

[0106]
The evaluation results are as shown in Tables 13 and 14, and the examples of the present invention showed a score of 3 or more in any of the corrosion resistance test, the workability test, and the weldability test. In addition, depending on the configuration of the example, a rating of 4 and better performance are shown. In particular, those in which the surface roughness of the organic resin film is controlled to 0.3 μm or more and 2.5 μm or less in Ra, 20 μm or less in Rmax, and Pc of the surface texture controlled to 10 or more and 200 or less per 10 mm length at a count level of 0.3 μm , Stable welding workability and corrosion resistance. In addition, (a) a polyester polyol having at least 3 functional groups, (b) a blocked product of an organic polyisocyanate, or a block of a prepolymer having an NCO group at an end obtained by reacting an organic polyisocyanate with an active hydrogen compound as an organic film. Good external surface in a system using a film-forming resin material obtained by adding an epoxy resin having at least one secondary hydroxyl group or an adduct thereof to a compound, and a system using ferrosilicon as a conductive pigment. It showed corrosion resistance.
[0107]
Comparative Examples 1 to 12 in Table 14 describe examples of the coated steel sheet outside the scope of the present invention. In Comparative Example 1, the thickness of the organic film was thin, and the corrosion resistance and workability were insufficient. In addition, seam weldability is somewhat poor due to high Pc. In Comparative Example 2, spot weldability was poor due to a high Ra value, and a defect occurred in seam welding. Comparative Example 3 is poor in weldability because the film thickness is too thick. Comparative Examples 4, 5, and 6 have high surface roughness Ra, high Rmax and / or surface texture Pc, and have poor spot weldability and seam weldability. Comparative Example 7 has poor weldability because there is no conductive pigment in the film. Comparative Examples 8, 9, 10, 11, and 12 are resin films that deviate from the present invention, and are inferior in corrosion resistance after processing. Comparative Examples 8 and 9 containing no conductive pigment also have poor weldability. In Comparative Example 12, there was no undercoating film, the workability was poor, and the corrosion resistance was also reduced.
[0108]
【The invention's effect】
As is clear from the above description, according to the configuration of the present invention, it is possible to provide a rust-preventive steel plate having excellent corrosion resistance as a material for a fuel tank of an automobile and having both stable resistance weldability and press formability.

Claims (10)

A rustproof steel sheet having an organic film containing (A) a resin having a urethane bond and (B) a conductive pigment on at least one surface of a surface-treated steel sheet with a coating thickness of 5 μm or more and 30 μm or less. A) a resin having a urethane bond, (a) a polyester polyol having at least 3 functional groups, (b) a blocked product of an organic polyisocyanate, or a prepolymer having a terminal NCO group obtained by reacting an organic polyisocyanate with an active hydrogen compound. A blocked product of a polymer, an organic resin obtained from a film-forming resin raw material containing, and the surface roughness of the organic film is not less than 0.3 μm and not more than 2.5 μm in center line average roughness Ra. Rustproof steel plate for high corrosion resistant fuel tanks. The rustproof steel sheet for a fuel tank having high corrosion resistance and high corrosion resistance according to claim 1, wherein the content of the conductive pigment (B) in the organic film is 5 to 50% by volume in terms of solid content. The rust prevention for a high corrosion resistant and high corrosion resistant fuel tank according to claim 1 or 2, wherein the conductive pigment is made of at least one of stainless steel, Zn, Al, Ni, ferrosilicon, and iron phosphide. steel sheet. The high corrosion resistance and high corrosion resistance fuel tank according to any one of claims 1 to 3, wherein the conductive pigment is an alloy or a compound containing 40% by mass or more of Si, or a composite thereof. Rust steel plate. The organic coating further contains 1 to 40% by volume of a rust preventive pigment in terms of solid content, and the sum of the conductive pigment and the rust preventive pigment is 5 to 70% by volume in terms of solid content. The rust-preventive steel sheet for a fuel tank having high corrosion resistance and high corrosion resistance according to claim 1. The rust-preventive steel plate for a highly corrosion-resistant fuel tank according to claim 1, wherein the resin (A) having a urethane bond further comprises (c) an epoxy resin having at least one secondary hydroxyl group or an adduct thereof. The rust-preventive steel plate for a highly corrosion-resistant fuel tank according to claim 1, wherein the surface roughness of the organic film is 20 µm or less at a maximum height Rmax. The rust prevention for a highly corrosion resistant fuel tank according to claim 1 or 7, wherein the surface texture of the organic coating is 10 to 200 per 10 mm in length when the count level is 0.3 μm in peak count Pc. steel sheet. The rust-preventive steel sheet for a highly corrosion-resistant fuel tank according to any one of claims 1 to 8, further comprising an undercoat film between the organic film and the surface-treated steel sheet. High corrosion resistant fuel tank for anticorrosive steel sheet according to claim 9, wherein the amount of deposition is 10 to 1000 mg / ^{m 2} of the surface treatment coating.