TW201700284A - 容器用鋼板及容器用鋼板之製造方法 - Google Patents

容器用鋼板及容器用鋼板之製造方法 Download PDF

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TW201700284A
TW201700284A TW105111828A TW105111828A TW201700284A TW 201700284 A TW201700284 A TW 201700284A TW 105111828 A TW105111828 A TW 105111828A TW 105111828 A TW105111828 A TW 105111828A TW 201700284 A TW201700284 A TW 201700284A
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Taiwan
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chemical conversion
steel sheet
conversion treatment
ions
layer
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TW105111828A
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TWI597159B (zh
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立木光
平野茂
谷賢明
橫矢博一
柳原偉男
河端誠
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新日鐵住金股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C—CHEMISTRY; METALLURGY
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Abstract

本發明之容器用鋼板具備：鋼板；鍍Sn層，係設作前述鋼板之上層，且含有換算成金屬Sn量計為560~5600mg/m2之Sn；及化成處理皮膜層，係設作前述鍍Sn層之上層，且含有換算成金屬Zr量為3.0~30.0mg/m2之Zr化合物及換算成金屬Mg量為0.50~5.00mg/m2之Mg化合物。

Description

容器用鋼板及容器用鋼板之製造方法 發明領域
本發明係關於容器用鋼板及容器用鋼板之製造方法。
本案係依據已於2015年4月16日於日本提申之日本特願2015-83984號主張優先權並於此引申其內容。
發明背景
飲料用或食品用容器多利用以鍍Ni鋼板、鍍Sn鋼板或Sn系合金鍍覆鋼板等鍍覆鋼板製罐而成的金屬容器。這些金屬容器的表面上有時會於製罐前或製罐後塗佈塗料或層合一薄膜。用於金屬容器之表面處理的塗料及薄膜統稱為塗佈劑。
用來作為塗佈劑之底層的鍍覆鋼板上多半會施行使用6價鉻酸鹽等的表面處理(以下稱作鉻酸鹽處理)(例如，參照下述專利文獻1)，以確保與塗佈劑的密著性及耐蝕性。此外，已施行鉻酸鹽處理的鍍覆鋼板可因應需求，在賦予耐有機溶劑性、耐指紋性、耐損傷性或潤滑性等之目的下，於以鉻酸鹽處理形成之皮膜上形成一由有機樹脂所構 成的被覆層。
然而，最近因為用來進行鉻酸鹽處理的6價鉻於環境上有害，所以有預計將鍍覆鋼板之表面處理以其它的表面處理替代鉻酸鹽處理的動向。
例如，下述專利文獻2及專利文獻3中便揭示一使用含有Zr離子及F離子之化成處理液的陰極電解處理，作為鉻酸鹽處理之替代的鍍覆鋼板之表面處理。
下述專利文獻4中係揭示一使用含有磷酸離子與Ti離子及Zr離子之至少其中一者之化成處理液的陰極電解處理。
下述專利文獻5中係揭示一使用含有Zr離子、F離子及磷酸離子之化成處理液的陰極電解處理。
下述專利文獻6中係揭示一使用含有Zr離子及有機物之化成處理液的陰極電解處理。
下述專利文獻7中係揭示一使用含有Zr離子、磷酸離子及有機物之化成處理液的陰極電解處理。
下述專利文獻8及專利文獻9中係揭示一使用含有Zr離子、磷酸離子及硝酸離子之化成處理液的陰極電解處理。尤其，在下述專利文獻9中係揭示藉由增加硝酸離子，來促進利用陰極電解處理形成之皮膜(以下稱作化成處理皮膜層)形成的方法。
先前技術文獻 專利文獻
專利文獻1：日本國特開2000-239855號公報
專利文獻2：日本國特開2005-325402號公報
專利文獻3：日本國特開2005-23422號公報
專利文獻4：日本國特開昭54-68734號公報
專利文獻5：日本國特開2006-9047號公報
專利文獻6：日本國特開2008-50641號公報
專利文獻7：日本國特開2009-1851號公報
專利文獻8：日本國特開2009-84623號公報
專利文獻9：國際公開第2011/118588號公報
發明概要
然而，上述專利文獻2~專利文獻8中所揭示之技術中，含有Zr化合物之化成處理皮膜層的形成需要相當長的時間，所以有無法獲得優良生產性的課題。要以上述專利文獻9中揭示之技術在短時間內形成化成處理皮膜層則需要高濃度的硝酸離子，於環境上不宜，亦為一課題。
此外，用作食品用容器的容器用鋼板須具有抗硫化黑變性，但在上述專利文獻2~專利文獻9中皆未揭示用以提升抗硫化黑變性的方法。
例如，將容器用鋼板作為以魚肉或豆類等高蛋白質食品為內容物之食品用容器使用時，容器內面與內容物之至少一者偶爾會因充填食品後之加熱殺菌(retort)處理(在水蒸氣存在下的高溫加熱滅菌處理)而變成黑色。此黑變現象稱為硫化黑變。
食品中所含之硫(S)會因加熱殺菌處理而熱分解，產生硫化氫(H2S)及硫醇類(HS-)等。該硫化氫及硫醇類會與容器內面的構成金屬產生反應，生成黑色的金屬硫化物，而產生此硫化黑變。
有時會因為該硫化黑變使容器外觀變不佳。此外，消費者有時會將所生成的黑色金屬硫化物誤解為容器內面之金屬腐蝕或內容物腐敗。所以，使用於食品用容器的容器用鋼板尤其需要極力避免產生硫化黑變。
本發明係有鑒於上述因素而執行，其目的在於提供一具有優異的生產性、環境性及抗硫化黑變性之容器用鋼板及容器用鋼板之製造方法。
本發明為了解決上述課題以達成該目的而採用以下手段。
(1)本發明一態樣之容器用鋼板具備：鋼板；鍍Sn層，係設作前述鋼板之上層，且含有換算成金屬Sn量計為560~5600mg/m2之Sn；及化成處理皮膜層，係設作前述鍍Sn層之上層，且含有換算成金屬Zr量計為3.0~30.0mg/m2之Zr化合物及換算成金屬Mg量計為0.50~5.00mg/m2之Mg化合物。
(2)在如上述(1)記載之容器用鋼板中，亦可採用前述鍍Sn層更含有Fe-Sn合金之構成。
(3)在如上述(1)或(2)記載之容器用鋼板中，亦可採用前述化成處理皮膜層更含有換算成P量合計為1.5~ 25.0mg/m2之磷酸及磷酸鹽中之至少一者的構成。
(4)本發明一態樣之容器用鋼板之製造方法具有：鍍覆步驟，係於鋼板上形成鍍Sn層，該鍍Sn層含有換算成金屬Sn量計為560~5600mg/m2之Sn；化成處理步驟，係於前述鍍覆步驟後使用化成處理液施行陰極電解處理，以於前述鍍Sn層上形成一化成處理皮膜層，該化成處理液含有100~3000ppm之Zr離子、120~4000ppm之F離子及50~300ppm之Mg離子；及正式洗淨步驟，係於前述化成處理步驟後使用40℃以上之水，對已形成有前述鍍Sn層及前述化成處理皮膜層之前述鋼板施行0.5秒以上之洗淨處理。
(5)在如上述(4)記載之容器用鋼板之製造方法中，亦可採用對已形成有前述鍍Sn層之前述鋼板施行熔融熔錫處理，以將前述鍍Sn層之至少一部分Sn與前述鋼板中之至少一部分Fe予以合金化的構成。
(6)在如上述(4)或(5)記載之容器用鋼板之製造方法中，亦可採用前述化成處理液更含有2000ppm以下之磷酸離子的構成。
(7)在如上述(4)~(6)中任一態樣記載之容器用鋼板之製造方法中，亦可採用前述化成處理液更含有合計為20000ppm以下之硝酸離子及銨離子的構成。
(8)在如上述(4)~(7)中任一態樣記載之容器用鋼板之製造方法中，亦可採用於前述正式洗淨步驟之前更具有一預洗淨步驟的構成，該預洗淨步驟係使用10℃以上且 低於40℃之水，對已形成有前述鍍Sn層及前述化成處理皮膜層之前述鋼板施行0.5秒以上之洗淨處理。
根據上述各態樣，可提供具有優異的生產性、環境性及抗硫化黑變性的容器用鋼板及容器用鋼板之製造方法。
10‧‧‧容器用鋼板
101‧‧‧鋼板
103‧‧‧鍍Sn層
105‧‧‧化成處理皮膜層
圖1係顯示本實施形態之容器用鋼板之構成的示意圖。
圖2係顯示本實施形態之容器用鋼板之製造方法流程的流程圖。
用以實施發明之形態
以下參照圖式說明實施形態之容器用鋼板及容器用鋼板之製造方法。
(容器用鋼板)
首先，說明容器用鋼板10。
圖1係顯示本實施形態之容器用鋼板10之構成的示意圖。如圖1所示，容器用鋼板10具備作為母材使用的鋼板(原板)101、形成於鋼板101上的鍍Sn103層及形成於鍍Sn層103上的化成處理皮膜層105。
鋼板101並無特別限定，通常可採用作為容器用鋼板使用的公知鋼板101。該等公知鋼板101之製造方法及材質等亦無特別限定。可採用從一般的鋼片製造步驟開始 經由熱軋延、酸洗、冷軋延、退火、調質軋壓等公知步驟所製造的鋼板101。
在容器用鋼板10中設有含Sn之鍍Sn層103作為鋼板101之上層。本實施形態的鍍Sn層103含有換算成金屬Sn量計，每單面560~5600mg/m2之Sn。
Sn具有優異的加工性、熔接性及耐蝕性，為了發揮該等效果，鍍Sn層103之Sn含量以換算成金屬Sn量計必須每單面為560mg/m2以上。
鍍Sn層103之Sn含量愈多愈能提升上述效果，惟Sn含量換算成金屬Sn量計每單面超過5600mg/m2時，上述效果即達飽和。因此，基於經濟觀點，將鍍Sn層103之Sn含量設定為換算成金屬Sn量計每單面5600mg/m2以下。
鍍Sn層103之Sn含量宜為換算成金屬Sn量計為每單面700~4500mg/m2，較宜為1200~4000mg/m2。
藉由於形成鍍Sn層103後施行熔融熔錫處理，鍍Sn層103的至少一部分會形成鋼板中之至少一部分Fe與Fe-Sn合金。藉此，可進一步提升耐蝕性及表面的外觀品質(鏡面完工品質等)。
鍍Sn層103可形成在鋼板101兩面，若從削減製造成本等觀點來看，亦可僅形成在鋼板101之一面。在對僅一面形成有鍍Sn層103的鋼板101進行製罐加工時，例如宜以形成有鍍Sn層103之面為容器內面的方式進行加工。
鍍Sn層103之Sn含量例如可利用螢光X射線法進行測定。此時係使用已知Sn含量的試料預先製作出關於Sn 含量的檢量線後，再利用該檢量線相對地測定出Sn含量。
鋼板101表面上僅形成有鍍Sn層103時(包含藉由在形成鍍Sn層103後施行熔融熔錫處理而於鋼板101表面上形成有合金鍍Sn層的情況)，即使以塗佈劑將鍍Sn層103予以表面處理，飲料或食品等中所含之硫有時還是會穿透塗佈劑與Sn結合而形成黑色之SnS或SnS2等。
此外，當鍍Sn層103存有由多數個微細孔所構成之鍍覆缺失部位時，硫可能與鋼板101中所含之Fe結合而形成黑色的FeS、Fe2S3或Fe2S。在本實施形態中，會形成SnS、SnS2、FeS、Fe2S3或Fe2S等黑色化合物的現象稱作硫化黑變。此外，相對於硫化黑變的耐性(特性)則稱作抗硫化黑變性。
為了提升抗硫化黑變性，容器用鋼板10具備一化成處理皮膜層105作為鍍Sn層103之上層。
化成處理皮膜層105含有換算成金屬Zr量計為3.0~30.0mg/m2之Zr化合物與換算成金屬Mg量計為0.50~5.00mg/m2之Mg化合物。
化成處理皮膜層105中所含Zr化合物具有提升抗硫化黑變性、密著性及加工性的功能。
本實施形態之Zr化合物可舉如氧化Zr、磷酸Zr、氫氧化Zr及氟化Zr等(並含該等之水合物)，且化成處理皮膜層105可含有多種的上述Zr化合物。
化成處理皮膜層105中之Zr含量若增加，可提升容器用鋼板10之抗硫化黑變性、密著性及加工性。具體 上，化成處理皮膜層105之Zr含量換算成金屬Zr量計為每單面3.0mg/m2以上時，可確保實用上適當的抗硫化黑變性。
另一方面，如果Zr含量換算成金屬Zr量計每單面超過30.0mg/m2，化成處理皮膜層105會變得太厚，而使化成處理皮膜層105本身的密著性劣化且抗硫化黑變性降低。此外，如果Zr含量換算成金屬Zr量計每單面超過30.0mg/m2，可能有化成處理皮膜層105之電阻上升、熔接性下降的情況。
因此，將化成處理皮膜層105之Zr含量設定為換算成金屬Zr量計每單面3.0~30.0mg/m2。Zr含量之下限值換算成金屬Zr量計宜為每單面5.0mg/m2以上，較宜為8.0mg/m2以上。Zr含量之上限值換算成金屬Zr量計宜為每單面20.0mg/m2以下，較宜為15.0mg/m2以下。
化成處理皮膜層105除了Zr化合物以外，還含有Mg化合物。如後述，形成化成處理皮膜層105時使用的化成處理液含有Mg離子，化成處理液中之Mg離子會以Mg化合物的態樣與Zr化合物一起被攝入化成處理皮膜層105中。化成處理皮膜層105中之Mg化合物在形成化成處理皮膜層105後施行的洗淨步驟中有部分會從化成處理皮膜層105除去，剩餘部分則殘存於化成處理皮膜層105中。
本發明人等發現，藉由化成處理皮膜層105含有Mg化合物，可提升抗硫化黑變性。
化成處理皮膜層105中所含Mg化合物之例可列 舉氧化Mg、氫氧化Mg、氟化Mg、磷酸Mg等(並含該等之水合物)，化成處理皮膜層105可含有多種的上述Mg化合物。該等Mg化合物一般為透明或帶白色。
此外，Mg離子會與為硫化黑變現象主體的硫醇離子(HS-)或硫化氫(H2S)鍵結，形成透明或白色的化合物。藉由Mg離子與硫醇離子或硫化氫鍵結，可抑制Fe或Sn與硫醇離子或硫化氫鍵結。
此外，化成處理皮膜層105中之Mg化合物可抑制硫醇離子及硫化氫穿透化成處理皮膜層105。又，藉由Mg離子與硫醇離子或硫化氫起反應所生成的化合物也可抑制硫醇離子及硫化氫穿透化成處理皮膜層105。
亦即，藉由化成處理皮膜層105含有Mg化合物，可減低Sn或Fe與硫醇離子或硫化氫發生反應的可能性，因而可抑制硫化黑變現象。
為了確保如上述的抗硫化黑變性，化成處理皮膜層105含有換算成金屬Mg量計為每單面0.50~5.00mg/m2之Mg化合物。
化成處理皮膜層105中之Mg含量換算成金屬Mg量計為每單面0.50mg/m2以上，藉此可具有實用上適當的抗硫化黑變性。
此外，化成處理皮膜層105含有換算成金屬Mg量計每單面超過5.00mg/m2之Mg化合物，所以必須於化成處理液中大量添加Mg化合物。化成處理液中若含有大量的Mg化合物，化成處理皮膜層105之形成可能無法順利進行，故 不適宜。此外，化成處理皮膜層105含有換算成金屬Mg量計每單面超過5.00mg/m2之Mg化合物，雖不會影響與塗佈劑的密著性(一次密著性)，但可能使加熱殺菌處理等在水蒸氣存在下高溫殺菌處理時的密著性(二次密著性)、耐鏽性或塗膜下腐蝕性劣化，故不適宜。再者，如果化成處理皮膜層105含有換算成金屬Mg量計每單面超過5.00mg/m2之Mg化合物，將容器用鋼板10使用為食品用容器時，可能有損內容物之味道或風味，故不適宜。
化成處理皮膜層105之Mg化合物含量的下限值換算成金屬Mg量計宜為每單面0.80mg/m2，較宜為1.00mg/m2。另一方面，化成處理皮膜層105之Mg化合物含量的上限值換算成金屬Mg量計宜為每單面4.00mg/m2，較宜為3.00mg/m2。
化成處理皮膜層105中之Zr化合物量或Mg化合物量係例如利用螢光X射線分析等定量分析法所定量出之化成處理皮膜層105中的金屬Zr或金屬Mg之總含量，表示在後述洗淨步驟後殘存於化成處理皮膜層105中的Zr化合物或Mg化合物之含量。
至於，當鍍Sn層103含有Mg時，可先測定出施行化成處理步驟前之鍍Sn層103的Mg化合物量，並測定出施行化成處理步驟後之容器用鋼板10的Mg化合物量，再從兩者之差分測出化成處理皮膜層105中之Mg化合物量。
化成處理皮膜層105除了Zr化合物及Mg化合物以外，亦可含有磷酸與磷酸鹽之至少一者。化成處理皮膜 層105中所含磷酸鹽之例可列舉磷酸Zr及磷酸Mg(並含該等之水合物)。化成處理皮膜層105可含有由磷酸與磷酸鹽構成之化合物中的多種化合物。
藉由化成處理皮膜層105含有磷酸與磷酸鹽中之至少一者，可獲得優異的抗硫化黑變性及密著性。磷酸與磷酸鹽之合計含量換算成P量計為每單面1.5mg/m2以上時，可獲得實用上適當的抗硫化黑變性及密著性。
磷酸與磷酸鹽之合計含量如果增加，抗硫化黑變性及密著性也會提升，惟如果磷酸與磷酸鹽之合計含量換算成P量計每單面超過25.0mg/m2，化成處理皮膜層105之磷酸或磷酸鹽的密著性便會劣化，造成與塗佈劑之密著性及塗膜下腐蝕性降低，故不適宜。此外，如果磷酸與磷酸鹽之合計含量換算成P量計每單面超過25.0mg/m2，電阻便會上升且熔接性劣化，故不適宜。
因此，化成處理皮膜層105以磷酸與磷酸鹽合計，換算成P量計含有每單面1.5~25.0mg/m2為宜。
磷酸與磷酸鹽之合計含量的下限值換算成P量計較宜為每單面2.5mg/m2，更宜為5.0mg/m2。
磷酸與磷酸鹽之合計含量的上限值換算成P量計較宜為每單面20.0mg/m2，更宜為12.5mg/m2。
化成處理皮膜層105所含磷酸與磷酸鹽之合計量例如可利用螢光X射線分析等定量分析法，定量出施行洗淨步驟後之化成處理皮膜層105中所含P量。
〔容器用鋼板10之製造方法〕
接下來，參照圖2說明容器用鋼板10之製造方法。
圖2係顯示本實施形態之容器用鋼板10之製造方法的流程圖。如圖2所示，容器用鋼板10之製造方法具有鍍覆步驟、化成處理步驟及洗淨步驟。
〔鍍覆步驟〕
首先，對鋼板101表面施行鍍Sn，形成鍍Sn層103(步驟S101)。鍍Sn方法並無特別限定，可使用電鍍法、真空蒸鍍法或濺鍍法等公知技術。Sn鍍浴可使用電鍍馬口鐵浴(ferrostan bath)等。
亦可如上述，於鍍覆步驟後施行熔融熔錫處理。
〔化成處理步驟〕
接下來進行化成處理步驟，於鍍Sn層103上層形成化成處理皮膜層105(步驟S103)。
在化成處理步驟中係施行使用化成處理液之陰極電解處理。
採用浸漬處理法作為化成處理皮膜層105之形成方法時會蝕刻底層，使化成處理皮膜層105附著不均及拉長化成處理步驟的時間，故於工業生產上不甚理想。
另一方面，在陰極電解處理中會因為強制的電荷移動及鋼板101與化成處理液界面上產生氫，令所形成之化成處理皮膜層105的表面被淨化，故為適宜。此外，在陰極電解處理可藉由化成處理液之pH上升來促進化成處理皮膜層105附著，故為適宜。
陰極電解處理的條件並無特別限定，例如可在 化成處理液溫度10℃~60℃、電流密度0.1~20.0A/dm2及處理時間0.01~30秒之條件下進行。
化成處理液之pH以3.0~4.5之範圍為宜，像以要調降pH時添加硝酸或氟氫酸等、要調升pH時添加銨等的方式適度調整即可。
在化成處理步驟中使用的化成處理液含有100~3000ppm之Zr離子。化成處理液中之Zr離子係以Zr化合物的態樣被攝入化成處理皮膜層105中。
化成處理液中之Zr離子下限值宜為500ppm，較宜為1000ppm。化成處理液中之Zr離子上限值宜為2500ppm，較宜為2000ppm。
化成處理液含有120~4000ppm之F離子。F離子具有與Zr離子形成錯離子而使化成處理液中之Zr離子穩定的作用。
至於，化成處理液中之F離子亦與Zr離子同樣地會被攝入化成處理皮膜層105中，不過化成處理皮膜層105中之F化合物宜盡可能利用後述之洗淨步驟予以去除。
化成處理液含有50~300ppm之Mg離子。
化成處理液含有Mg離子可使化成處理皮膜層105含有Mg化合物，提升抗硫化黑變性，故為適宜。此外，Mg離子可促使Zr離子析出。具體上，在化成處理液含有Mg離子之情況與不含Mg離子之情況下，比較利用化成處理步驟形成之化成處理皮膜層105中的Zr化合物量時發現，在含有Mg離子之情況下，化成處理皮膜層105中含有較多的 Zr化合物量。
吾等認為利用Mg離子所得的Zr析出促進效果原因如下。
在含有Zr離子及F離子之溶液中，如上述式(1)所示，Zr離子係與F離子一起以[ZrF6]2-等錯離子的狀態穩定存在。在陰極電解處理中，pH會因為強制的電荷移動及鋼板101與電解處理溶液界面上產生之氫而上升。藉由pH上升，上述錯離子會被水解而如上述式(1)所示變成Zr離子與F離子，其後便析出含Zr化合物之化成處理皮膜層105。
上述式(1)之反應為平衡(可逆)反應，會因為化成處理液中之F離子增加，使上述式(1)之右向反應(錯離子分解的反應)明顯受阻。
Mg離子可作為F離子之捕捉劑發揮功能，所以會減低利用F離子所得的上述式(1)之右向反應的阻礙效果。即，吾等認為，F離子係因為Mg離子存在，利用「柔和的離子相互作用」形成水溶性〔F-…Mg2+…F-〕，使〔F-…Mg2+…F-〕之析出部位附近的F離子濃度減低，而減低上述式(1)之右向反應的阻礙效果。另外，宜以〔F-…Mg2+…F-〕在與〔F-…Mg2+…F-〕析出部位分離之處解離成F離子及Mg離子的方式，來調整添加於化成處理液中的Mg離子濃 度。
如上述，藉由化成處理液含有Mg離子，可促使Zr析出。所以，本實施形態之容器用鋼板10的製造方法可縮短化成處理步驟的所需時間，具有優異的生產性。
添加於化成處理液中的Mg離子濃度以50~300ppm為宜。Mg離子濃度若小於50ppm，便無法充分發揮Zr之析出促進效果。另一方面，Mg離子濃度一旦超過300ppm，便容易形成難溶性的MgF2，故不適宜。
添加於化成處理液中的Mg離子濃度較宜為100~200ppm。
至於，Mg離子宜以硝酸Mg或硫酸Mg等易水溶性之鹽作添加。
化成處理液亦可含有2000ppm以下之磷酸離子。
藉由化成處理液含有磷酸離子，可使化成處理皮膜層105含有磷酸或磷酸鹽，進而提升抗硫化黑變性及密著性，故為適宜。
化成處理液可含有合計為20000ppm以下之硝酸離子及銨離子。化成處理液含有硝酸離子及銨離子可縮短化成處理步驟的所需時間，提升生產性，故為適宜。
至於，化成處理液宜含有硝酸離子與銨離子兩者，而非僅含硝酸離子與銨離子其中一者。其理由如下。
形成含Zr之化成處理皮膜層105時，首先會按下述式(2)之反應在陰極產生H2，且pH上升。
2H2O+4e-→H2↑+2OH-…(2)
伴隨上述式(2)之反應，Zr4+、PO4 3-會以ZrO2、Zr3(PO4)4等態樣析出而形成化成處理皮膜層105。在此皮膜形成反應中，若有硝酸離子存在，便可按下述式(3)及式(4)所示右向反應促進pH上升，於是可促使皮膜形成。此外，按下述式(3)及式(4)所示反應，可利用攪拌作用抑制阻礙皮膜形成的H2產生。藉此，可縮短化成處理步驟的所需時間。此外，銨離子被認為有促進藉硝酸離子所得之上述效果的作用。
此外，藉由化成處理液含有Mg離子、硝酸離子及銨離子而具有上述優異效果的觀點係由本發明首度明示發表。
為了進一步提升抗硫化黑變性等特性，例如首先可施行使用第一化成處理液的陰極電解處理，於鍍Sn層103側形成化成處理皮膜層105之第一層(未圖示)，接著施行使用第二化成處理液的陰極電解處理，於化成處理皮膜層105之第一層上方形成化成處理皮膜層105之第二層(未圖示)。
另，第一化成處理液與第二化成處理液含有相同成分，僅溫度不同。第一化成處理液之溫度例可列舉10℃以 上且低於40℃，第二化成處理液之溫度例可列舉45℃~60℃。
化成處理皮膜層105之第一層為緻密層，所以可適度確保抗硫化黑變性等特性。化成處理皮膜層105之第二層具有粗度粗糙的表面，所以可適度確保化成處理皮膜層105與塗佈劑之密著性。
〔洗淨步驟〕
F離子、硝酸離子及銨離子等水溶性離子種含在化成處理液中，所以會與Zr化合物一起被攝入化成處理皮膜層105中。化成處理皮膜層105中之上述離子種不會影響與塗佈劑的密著性(一次密著性)，但會成為二次密著性、耐鏽性或塗膜下腐蝕性劣化的原因。其原因認為是因為，化成處理皮膜層105中之上述離子種溶出至水蒸氣或腐蝕液中，使化成處理皮膜層105與塗佈劑之結合分解或腐蝕鋼板101所致。
所以，在本實施形態中會在施行化成處理步驟後，在至少40℃以上之水中施行0.5秒以上之洗淨處理(以下稱為正式洗淨步驟)(步驟S107)。至於，在正式洗淨步驟中之用水溫度的上限並無特別限定，例如為90~100℃。此外，正式洗淨步驟之洗淨時間上限亦無特別限定，例如為10秒。
為了將F離子、硝酸離子及銨離子等之水溶性離子種進一步從化成處理皮膜層105除去，宜於施行化成處理步驟後，在施行正式洗淨步驟之前以10℃以上且低於40 ℃之水進行0.5秒以上之洗淨處理(以下稱為預洗淨步驟)(步驟S105)。預洗淨步驟之洗淨時間上限無特別限定，例如為20秒。
預洗淨步驟及正式洗淨步驟之洗淨方法可列舉浸漬處理或噴淋處理。
利用預洗淨步驟除去在低溫下溶出之離子種，並利用正式洗淨步驟除去在高溫下溶出之離子種。藉由拉長預洗淨步驟及正式洗淨步驟之處理時間，可提升上述除去效果。另外，正式洗淨步驟中使用的洗淨液溫度愈高愈可提升除去效果。
各步驟的處理時間一旦低於0.5秒，便很難減少上述離子種。
F離子、硝酸離子及銨離子等宜以洗淨步驟盡可能地自化成處理皮膜層105除去，惟，無法全部除去而無法避免地殘存亦無大礙。
本實施形態之容器用鋼板的製造方法不使用高濃度的硝酸離子，故對環境友善。
[實施例1]
以下就本發明之實施例及比較例加以闡述。至於，以下所示實施例僅為本發明實施形態之容器用鋼板及容器用鋼板之製造方法一例，本發明實施形態之容器用鋼板及容器用鋼板之製造方法不受以下所示實施例限定。
為了檢測Mg離子的Zr之析出促進效果，將化成處理步驟之Mg離子濃度以外的條件設為相同條件，只改 變Mg離子濃度來檢測所形成之化成處理皮膜層的Zr化合物量。結果顯示於表1。
至於，表1之處理液1-1~3-2的溫度及pH皆相同，並在相同的電流密度及處理時間之條件下施行陰極電解處理。如表1所示，藉由添加Mg離子，所形成之化成處理皮膜層的Zr含量有所增加，顯示Mg離子具有Zr之析出促進效果。
[實施例2]
使用具有表2所示鍍Sn層及化成處理皮膜層之化成處理鋼板製作試驗材，並針對以下(A)~(H)之項目進行性能評估。評估結果顯示於表3。
(A)抗硫化黑變性
將試驗材裁切成60mm×60mmL之大小，以膠帶遮罩5mm長的端部(因剪切而露出鋼板端面的部分)後，浸漬於1質量%Na2S水溶液(以乳酸調整成pH=7)中，在125℃之溫度下施行加熱殺菌處理60分鐘，並以目測評估加熱殺菌處理後的各試驗材外觀。
具體上，結果比鉻酸鹽處理材更佳的情況評估為「極優」，結果比鉻酸鹽處理材稍佳的情況評估為「優」，出現與鉻酸鹽處理材同等程度之變色的情況評估為「普通」，變色程度比鉻酸鹽處理材稍大的情況評估為「尚可」，變色程度比鉻酸鹽處理材更大的情況評估為「劣等」。
(B)加工性
在200℃之溫度下於試驗材兩面貼附厚20μm之PET薄膜後，階段性地實施利用沖壓(drawing)加工及引縮加工(ironing)的製罐加工。觀察薄膜之瑕疵、浮起及剝離，由該等之面積率評估加工性。
具體上，全然未觀察到薄膜之瑕疵、浮起及剝離之情況評估為「極優」，薄膜之瑕疵、浮起及剝離的面積率為0%以上且0.5%以下之情況評估為「優」，薄膜之瑕疵、浮起及剝離的面積率為0.5%以上且15%以下之情況評估為「尚可」，薄膜之瑕疵、浮起及剝離的面積率超過15%或破斷無法加工之情況評估為「劣等」。
至於，面積率係由觀察到薄膜之瑕疵、浮起及剝離的部分面積除以貼附之PET薄膜的整體面積求得。
(C)熔接性
使用金屬線縫焊機，在熔接金屬線速度80m/min之條件下改變電流，熔接試驗材，並由適當電流範圍綜合性地進行判斷，以評估熔接性，該適當電流範圍係由可得充分之熔接強度的最小電流值以及散射與熔接濺鍍等熔接缺陷開始變醒目的最大電流值所構成。
具體上，二次側之適當電流範圍為1500A以上之情況評估為「極優」，二次側之電流適當電流範圍為800A以上且小於1500A之情況評估為「優」，二次側之電流適當電流範圍為100A以上且小於800A之情況評估為「尚可」，二次側之電流適當電流範圍小於100A之情況評估為「劣等」。
(D)薄膜密著性
在200℃之溫度下於試驗材兩面上燒黏厚20μm之PET薄膜，進行沖壓引縮(drawing and ironing)加工，製作罐體後，在125℃之溫度下施行加熱殺菌處理30分鐘，觀察薄膜之剝離狀況，並從剝離面積率評估薄膜密著性。
具體上，剝離面積率為0%之情況評估為「極優」，剝離面積率為0%以上且2%以下之情況評估為「優」、剝離面積率為2%以上且10%以下之情況評估為「尚可」，剝離面積率超過10%之情況評估為「劣等」。
(E)一次塗料密著性
於試驗材塗佈環氧-酚醛樹脂，在200℃之溫度下施行30分鐘的燒黏處理。以1mm間隔切出達基鐵之深度的格狀切口後，再以膠帶剝離。觀察剝離狀況，由剝離面積率評估一次塗料密著性。
具體上，剝離面積率為0%之情況評估為「極優」，剝離面積率為0%以上且5%以下之情況評估為「優」，剝離面積率為5%以上且30%以下之情況評估為「尚可」，剝離面積率超過30%之情況評估為「劣等」。
(F)二次塗料密著性
於試驗材塗佈環氧-酚醛樹脂，在200℃之溫度下施行30分鐘的燒黏處理。以1mm間隔切出達基鐵之深度的格狀切口後，在125℃之溫度下施行30分鐘的加熱殺菌處理。乾燥後，以膠帶剝離塗膜，觀察剝離狀況，並由剝離面積率評估二次塗料密著性。
具體上，剝離面積率為0%之情況評估為「極優」，剝離面積率為0%以上且5%以下之情況評估為「優」，剝離面積率為5%以上且30%以下之情況評估為「尚可」，剝離面積率超過30%之情況評估為「劣等」。
(G)塗膜下耐蝕性
於試驗材塗佈環氧-酚醛樹脂，在200℃之溫度下施行30分鐘的燒黏處理。其後，切出達基鐵之深度的格狀切口，浸漬於溫度45℃下之由1.5%檸檬酸-1.5%食鹽混合液所構成之試驗液中72小時。洗淨及乾燥後，剝離膠帶。觀察切出切口部分的塗膜下腐蝕狀況與平板部的腐蝕狀況，由塗膜下腐蝕之寬度及平板部之腐蝕面積率的評估，來評估塗膜下耐蝕性。
具體上，塗膜下腐蝕寬度小於0.2mm且平板部之腐蝕面積率為0%之情況評估為「極優」，塗膜下腐蝕寬度為0.2mm以上且小於0.3mm並且平板部之腐蝕面積率為0%以上且1%以下之情況評估為「優」，塗膜下腐蝕寬度為0.3mm以上且小於0.45mm並且平板部之腐蝕面積率為1%以上且5%以下之情況評估為「尚可」，塗膜下腐蝕寬度為0.45mm以上或平板部之腐蝕面積率超過5%之情況評估為「劣 等」。
(H)加熱殺菌耐鏽性
在125℃之溫度下將試驗材施行30分鐘的加熱殺菌處理。其後，觀察鏽的發生狀況，由生鏽面積率評估加熱殺菌耐鏽性。
具體上，生鏽面積率為0%之情況評估為「極優」，生鏽面積率為0%以上且1%以下之情況評估為「優」，生鏽面積率為1%以上且5%以下之情況評估為「尚可」，生鏽面積率超過5%之情況評估為「劣等」。
[表2]
[表3]
如表3所示，本發明例A1~A20在所有特性評估中皆獲「優」以上之評估，具有良好的特性。另一方面， 比較例a1~a6的所有特性皆被評估為「劣等」，特性比本發明例差。
[實施例3]
以下述方法製作化成處理鋼板。製造條件顯示於表4。
<鍍Sn鋼板>
使用以下(處理法1)或(處理法2)之方法，於板厚0.17~0.23mm之鋼板上形成鍍Sn層，製作鍍Sn鋼板。
(處理法1)
冷軋延後，將經退火及調壓後的鋼板予以脫脂及酸洗，其後利用電鍍馬口鐵浴於其兩面形成鍍Sn層，製作鍍Sn鋼板。
(處理法2)
冷軋延後，將經退火及調壓後的鋼板予以脫脂及酸洗，其後利用電鍍馬口鐵浴於其兩面形成鍍Sn層。然後，進行重熔流佈處理(reflow process)(熔融熔錫處理)，製作具有Sn合金層之鍍Sn鋼板。
<化成處理步驟>
針對以上述(處理法1)或(處理法2)之方法製作而成的鍍Sn鋼板，施行以下(處理法3)~(處理法7)中之任一方法，藉以於鍍Sn鋼板表面上形成含有Zr化合物及Mg化合物之化成處理皮膜層。至於，在處理法3~6中係在電流密度0.5~30.0A/dm2、陰極電解處理時間0.5~5.0秒及化成處理液溫度10~60℃之條件下施行陰極電解處理。此外，處 理法7係在溫度60℃且pH3.5之化成處理液中浸漬180秒之浸漬時間。
(處理法3)
利用使氟化Zr溶解並添加有硝酸Mg的化成處理液施行陰極電解處理而形成化成處理皮膜層。
利用使(處理法4)氟化Zr及磷酸並添加有硝酸Mg的化成處理液施行陰極電解處理而形成化成處理皮膜層。
利用使(處理法5)氟化Zr及硝酸銨溶解並添加有硝酸Mg的化成處理液施行陰極電解處理而形成化成處理皮膜層。
(處理法6)利用使氟化Zr、磷酸及硝酸銨溶解並添加有硝酸Mg的化成處理液施行陰極電解處理而形成化成處理皮膜層。
(處理法7)利用使氟化Zr溶解並添加有硝酸Mg的化成處理液施行浸漬處理而形成化成處理皮膜層。
<洗淨步驟>
利用上述處理形成化成處理皮膜層後，將鋼板浸漬於10℃以上且低於40℃之蒸餾水中0.5秒~5.0秒，進行預洗淨。
進行預洗淨後，將鋼板以表4所示時間浸漬於表4中所示溫度之蒸餾水中，進行正式洗淨。
<附著量測定>
鍍層中之金屬Sn量係利用螢光X射線法進行測定。此外，化成處理皮膜層之Zr含量、Mg含量及磷酸或磷酸鹽 之含量(換算成P量計)係利用螢光X射線分析等定量分析法測定。
測定結果顯示於表5。
<性能評估>
針對已實施上述處理之試驗材，就實施例2中所列舉之項目(A)~(H)以及以下記載之項目(I)進行性能評估。評估結果顯示於表6。
(I)添加Mg離子所得的Zr附著促進效果
使用從製作各試驗材時使用之化成處理液除去Mg離子後的化成處理液，除此以外之條件則係以與各試驗材相同的條件製作出容器用鋼板(以下稱為不含Mg容器用鋼板)。然後，測定不含Mg容器用鋼板之Zr含量。
藉由將各試驗材之Zr含量除以不含Mg容器用鋼板之Zr含量後所得的比率(以下稱為Zr附著促進率)，評估添加Mg離子所得的Zr附著促進效果。具體上，Zr附著促進率為1.3以上之情況評估為「極優」，1.3以下~1.2以上之情況評估為「優」，1.2以下~1.1以上之情況評估為「尚可」，1.1以下之情況評估為「劣等」。
[表4]
[表5]
[表6]
本發明例B1~B26皆具有添加Mg離子所得之Zr附著促進效果，並且具有優異的抗硫化黑變性、加工性、熔接性、薄膜密著性、一次塗料密著性、二次塗料密著性、塗膜下腐蝕性及耐蝕性。
此外，化成處理皮膜層以P量計含有1.5mg/m2以上之磷酸或磷酸鹽，藉此更加提升了薄膜密著性(包含加工性)及塗膜下腐蝕性。
另一方面，在比較例b1~b8中，不具有Zr附著促進效果，並且抗硫化黑變性、熔接性、加工性、熔接性、薄膜 密著性、一次塗料密著性、二次塗料密著性、塗膜下腐蝕性及耐蝕性之至少一部分的特性為劣等。
至於，在比較例b1及b4中，化成處理液中之F離子量很少，Zr4+離子無法以(ZrF6)2-等之錯離子的形態在溶解於處理液中之狀態下穩定存在，而以ZrO2等之形態作為不溶物析出於處理液中，即使含有Mg離子，化成處理皮膜層中之Zr化合物量也很少。所以，利用Mg離子所得的Zr析出促進效果不佳。
在比較例b2及b3中，因為化成處理液中之F離子量過量存在，所以Mg離子無法充分發揮作為F離子之捕捉劑的功能，利用Mg離子所得的Zr析出促進效果不佳。
在比較例b5中，化成處理液中之Mg離子量不足，因此利用Mg離子所得的Zr析出促進效果不佳。反之，當F離子很多時會因為(ZrF6)2-等錯離子過度穩定而難以形成皮膜。)
在比較例b6中，化成處理液中之Mg離子量過量，所以形成難溶性之MgF2，Mg離子無法作為捕捉劑充分發揮功能，利用Mg離子所得的Zr析出促進效果不佳。
比較例b8係利用浸漬處理而非陰極電解處理，即使化成處理液含有Mg離子，化成處理皮膜層中之Zr化合物量也很少。所以，利用Mg離子所得的Zr析出促進效果不佳。
以上係參照附屬圖式詳細說明本發明之適當實施形態，惟本發明不受該等例限定。顯而易見地，凡具有 本發明所屬技術領域之通識人士，皆可於申請專利範圍中記載之技術思想範疇內思及各種變更例或修正例，關於該等，應知亦理當歸屬本發明之技術範圍。
產業上之可利用性
根據上述一實施形態，可提供具有優異的生產性、環境性及抗硫化黑變性之容器用鋼板及容器用鋼板之製造方法。
10‧‧‧容器用鋼板
101‧‧‧鋼板
103‧‧‧鍍Sn層
105‧‧‧化成處理皮膜層

Claims (8)

  1. 一種容器用鋼板，特徵在於具備：鋼板；鍍Sn層，係設作前述鋼板之上層，且含有換算成金屬Sn量計為560~5600mg/m2之Sn；及化成處理皮膜層，係設作前述鍍Sn層之上層，且含有換算成金屬Zr量計為3.0~30.0mg/m2之Zr化合物及換算成金屬Mg量計為0.50~5.00mg/m2之Mg化合物。
  2. 如請求項1之容器用鋼板，其中前述鍍Sn層更含有Fe-Sn合金。
  3. 如請求項1或2之容器用鋼板，其中前述化成處理皮膜層更含有換算成P量合計為1.5~25.0mg/m2之磷酸及磷酸鹽中之至少一者。
  4. 一種容器用鋼板之製造方法，特徵在於具有：鍍覆步驟，係於鋼板上形成鍍Sn層，該鍍Sn層含有換算成金屬Sn量計為560~5600mg/m2之Sn；化成處理步驟，係於前述鍍覆步驟後使用化成處理液施行陰極電解處理，以於前述鍍Sn層上形成化成處理皮膜層，該化成處理液含有100~3000ppm之Zr離子、120~4000ppm之F離子及50~300ppm之Mg離子；及正式洗淨步驟，係於前述化成處理步驟後使用40℃以上之水，對已形成有前述鍍Sn層及前述化成處理皮膜層之前述鋼板施行0.5秒以上之洗淨處理。
  5. 如請求項4之容器用鋼板之製造方法，其係對已形成有前述鍍Sn層之前述鋼板施行熔融熔錫處理，以將前述鍍Sn層之至少一部分Sn與前述鋼板中之至少一部分Fe予以合金化。
  6. 如請求項4或5之容器用鋼板之製造方法，其中前述化成處理液更含有2000ppm以下之磷酸離子。
  7. 如請求項4至6中任一項之容器用鋼板之製造方法，其中前述化成處理液更含有合計為20000ppm以下之硝酸離子及銨離子。
  8. 如請求項4至7中任一項之容器用鋼板之製造方法，其於前述正式洗淨步驟之前更具有一預洗淨步驟，該預洗淨步驟係使用10℃以上且低於40℃之水，對已形成有前述鍍Sn層及前述化成處理皮膜層之前述鋼板施行0.5秒以上之洗淨處理。
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