JP5338163B2 - 錫めっき鋼板の製造方法 - Google Patents
錫めっき鋼板の製造方法 Download PDFInfo
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- JP5338163B2 JP5338163B2 JP2008179680A JP2008179680A JP5338163B2 JP 5338163 B2 JP5338163 B2 JP 5338163B2 JP 2008179680 A JP2008179680 A JP 2008179680A JP 2008179680 A JP2008179680 A JP 2008179680A JP 5338163 B2 JP5338163 B2 JP 5338163B2
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Description
まず、鋼板の少なくとも片面には、耐食性を付与するために、Snを含むめっき層を有する。このとき、Snの付着量は片面あたり0.05〜20g/m2とする必要がある。これは、Snの付着量が0.05g/m2未満だと耐食性が劣り、20g/m2を超えるとめっき層が厚くなり、コスト高を招くためである。ここで、Snの付着量は、電量法または蛍光X線により表面分析して測定することができる。
次に、上記したSnを含むめっき層の上には、PとSnを含む第1の化成処理皮膜を有する。これは、現状のクロメート処理の場合と同様に、300m/分以上の高速のライン速度で効率よく化成処理皮膜を形成するために、以下に詳述するように4価の錫イオンとりん酸イオンを含有する化成処理液を用いるためである。このとき、化成処理皮膜のPの付着量は片面当り0.3〜10mg/m2とする必要がある。これは、Pの付着量が0.3mg/m2未満だと、皮膜の被覆性が十分でなくなり、錫めっき表面の酸化を抑制する効果が不十分となり、10mg/m2を超えると、皮膜自体の凝集破壊が起きやすくなり、外観が劣化したり、塗料密着性が低下しやすくなるためである。
最後に、上記した第1の化成処理皮膜の上には、PとAlを含む第2の化成処理皮膜を有する。これは、このPとAlを含む化成処理皮膜を形成すれば、化成処理後に積極的に加熱せずに低温で乾燥させる程度でも外観の劣化や塗料密着性の低下を従来のクロメート皮膜と同等以上に抑制できるためである。この理由は必ずしも明確ではないが、化成処理皮膜中にAlが導入されたことにより、下層の錫めっき層の酸化に対してより強固なバリア性を有する緻密なりん酸塩の化成処理皮膜が形成されるためと考えられる。このとき、化成処理皮膜のPの付着量は片面当り1.2〜10mg/m2とし、Alの付着量は片面当り0.24〜8.7mg/m2とする必要がある。これは、Pの付着量が1.2mg/m2未満であったり、Alの付着量が0.24mg/m2未満であると、錫めっき表面の酸化を抑制する効果が不十分となり、外観が劣化したり、経時後の塗料密着性が低下し、Pの付着量が10mg/m2超えると、皮膜自体の凝集破壊が起き、塗料密着性が低下しやすくなるためである。なお、Alの付着量の上限である8.7mg/m2は、皮膜の全量が第3りん酸アルムニウムになった場合に化学量論的に導き出される値であり、Pの付着量が10mg/m2未満の場合は、この値を超えることはない。ここで、化成処理皮膜のPの付着量やAlの付着量は蛍光X線により表面分析して測定することができる。
鋼板A:板厚0.2mmの低炭素冷延鋼板
鋼板B:板厚0.2mmの低炭素冷延鋼板の両面に、ワット浴を用いて片面当り100mg/m2の付着量でニッケルめっき層を形成後、10vol.%H2+90%vol.%N2雰囲気中で700℃で焼鈍してニッケルめっきを拡散浸透させた鋼板
を使用し、市販の錫めっき浴を用い、表3に示す片面当りのSnの付着量でSn層を形成後、Snの融点以上でリフロー処理を施し、鋼板AにはFe-Sn層/Sn層のSnを含むめっき層を、また、鋼板BにはFe-Ni層/Fe-Ni-Sn層/Sn層のSnを含むめっき層を形成した。次に、リフロー処理後に表面に生成したSnの酸化膜を除去するため、浴温50℃、10g/Lの炭酸ナトリウム水溶液中で1A/dm2の陰極電解処理を施した。その後、水洗し、表1、2に示すオルトりん酸の量、塩化第2錫・5水和物の量および温度の化成処理液を用い、表1、2に示す時間の浸漬処理あるいは電流密度と時間の陰極電解処理を施した後、リンガーロールで絞り、水洗し、次いで、表1、2に示すオルトりん酸の量、第1りん酸アルミニウムの量、pHおよび温度の化成処理液を用い、表1、2に示す時間の浸漬処理あるいは電流密度と時間の陰極電解処理を施した後、リンガーロールで絞り、水洗した後、一般的なブロアを用いて室温で乾燥あるいは70℃の熱風乾燥を行い、第1の化成処理皮膜と第2の化成処理皮膜を有する錫めっき鋼板の試料No.1〜22を作製した。このとき、表1、2に示す化成処理液のpHは、酸またはアルカリで調整した。
作製直後の外観:作製直後の錫めっき鋼板の外観を目視観察して次のように評価し、○または◎であれば外観が良好であるとした。
◎: 表面に粉状の析出物が存在せず、金属光沢が保たれた美麗な外観
○: 表面に粉状の析出物が存在せず、若干白味がかっているものの、美麗な外観
△: 表面に局所的に粉状析出物が存在している、やや白味がかった不均一な外観
×: 表面に多量の粉状析出物が存在する、白味がかった外観
長期保管後のSnの酸化膜量と外観:錫めっき鋼板を60℃、相対湿度70%の環境下で10日間保管し、外観を目視観察するとともに、表面に形成されたSnの酸化膜量を、1/1000NのHBr溶液の電解液中で電流密度25μA/cm2で電解し、電気化学的還元に要した電気量を求めて次のように評価し、○または◎であれば長期保管後のSnの酸化膜量が少なく、外観も良好であるとした。
◎: 還元電気量2mC/cm2未満、外観優(クロメート処理材より良好)
○: 還元電気量2mC/cm2以上3mC/cm2未満、外観良(クロメート処理材同等)
△: 還元電気量3mC/cm2以上5mC/cm2未満、外観やや黄色み
×: 還元電気量5mC/cm2以上、外観はっきりとわかる黄色み
塗料密着性:作製直後の錫めっき鋼板に、付着量50mg/dm2となるようにエポキシフェノール系塗料を塗布後、210℃で10分間の焼付を行った。次いで、塗布・焼付を行った2枚の錫めっき鋼板を、塗装面がナイロン接着フィルムを挟んで向かい合わせになるように積層し、圧力2.94×105Pa、温度190℃、圧着時間30秒間の圧着条件下で貼り合わせた後、これを5mm幅の試験片に分割し、この試験片を引張試験機を用いて引き剥がし、強度測定を行って次のように評価し、○または◎であれば塗料密着性が良好であるとした。また、錫めっき鋼板を室温環境で6ヶ月間保管後にも同様の塗料密着性の評価を行った。
◎: 19.6N(2kgf)以上(溶接缶用クロメート処理材同等)
○: 3.92N(0.4kgf)以上19.6N未満(クロメート処理材同等)
△: 1.96N(0.2kgf)以上3.92N未満
×: 1.96N(0.2kgf)未満
耐食性:錫めっき鋼板に、付着量50mg/dm2となるようにエポキシフェノール系塗料を塗布した後、210℃で10分間の焼付を行った。次いで、市販のトマトジュースに60℃で10日間浸漬し、塗膜の剥離、錆の発生の有無を目視で評価し、○または◎であれば耐食性が良好であるとした。
◎: 塗膜剥離、錆の発生なし
○: 塗膜剥離なし、ごくわずか点状の錆の発生(クロメート処理材同等)
△: 塗膜剥離なし、微小な錆の発生
×: 塗膜剥離あり、錆発生あり
結果を表3に示す。本発明の錫めっき鋼板である試料No.1〜17では、いずれも製造直後および長期保管後の外観が良好であり、長期保管後のSnの酸化膜量も少なく、塗料密着性および耐食性に優れていることがわかる。
Claims (2)
- 鋼板の少なくとも片面に、Snの付着量が片面あたり0.05〜20g/m2となるようにSnを含むめっき層を形成した後、4価の錫イオンとりん酸イオンを含有する化成処理液中で浸漬処理を施し、あるいは該化成処理液中で陰極電解処理を施し、次いで、第1りん酸アルミニウム5〜200g/Lを含み、pHが1.5〜2.4である化成処理液中で浸漬処理を施し、あるいは該化成処理液中で陰極電解処理を施した後、乾燥することを特徴とする錫めっき鋼板の製造方法。
- 乾燥を60℃未満の温度で行うことを特徴とする請求項1に記載の錫めっき鋼板の製造方法。
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JP2008179680A JP5338163B2 (ja) | 2008-07-10 | 2008-07-10 | 錫めっき鋼板の製造方法 |
KR1020117000306A KR101290986B1 (ko) | 2008-07-10 | 2009-07-02 | 주석 도금 강판 및 그 제조 방법 |
PCT/JP2009/062493 WO2010005042A1 (ja) | 2008-07-10 | 2009-07-02 | 錫めっき鋼板およびその製造方法 |
ES09794486T ES2412781T3 (es) | 2008-07-10 | 2009-07-02 | Lámina de acero estañada y proceso para su producción |
MYPI20106102 MY152832A (en) | 2008-07-10 | 2009-07-02 | Tin-plated steel sheet and method for manufacturing the same |
EP09794486.2A EP2312017B1 (en) | 2008-07-10 | 2009-07-02 | Tin-plated steel plate and process for producing the tin-plated steel plate |
CN200980126866.4A CN102089462B (zh) | 2008-07-10 | 2009-07-02 | 镀锡钢板及其制造方法 |
US13/003,091 US20110168563A1 (en) | 2008-07-10 | 2009-07-02 | Tin-plated steel sheet and method for manufacturing the same |
TW098122645A TWI428476B (zh) | 2008-07-10 | 2009-07-03 | 鍍錫鋼板及其製造方法 |
US14/132,090 US9441310B2 (en) | 2008-07-10 | 2013-12-18 | Tin-plated steel sheet and method for manufacturing the same |
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US20200123661A1 (en) * | 2016-03-22 | 2020-04-23 | Nippon Steel & Sumitomo Metal Corporation | Chemical treatment steel sheet and method for manufacturing chemical treatment steel sheet |
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