TWI689633B - Sn鍍敷鋼板及Sn鍍敷鋼板的製造方法 - Google Patents

Sn鍍敷鋼板及Sn鍍敷鋼板的製造方法 Download PDF

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TWI689633B
TWI689633B TW108107060A TW108107060A TWI689633B TW I689633 B TWI689633 B TW I689633B TW 108107060 A TW108107060 A TW 108107060A TW 108107060 A TW108107060 A TW 108107060A TW I689633 B TWI689633 B TW I689633B
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steel sheet
plated steel
less
zirconium oxide
zirconium
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TW108107060A
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TW201937007A (zh
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山中晉太郎
野田正和
佐藤恭彥
仲宗根信夫
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日商日本製鐵股份有限公司
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    • 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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    • B32B15/04—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
    • B32—LAYERED PRODUCTS
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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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Abstract

該Sn鍍敷鋼板具備母材鍍敷鋼板與皮膜層，該母材鍍敷鋼板係具有鋼板及位於前述鋼板的至少單面的Sn鍍敷層，該皮膜層位於前述母材敷鍍鋼板上且含鋯氧化物與氧化錫。該Sn鍍敷鋼板之每單面之Sn附著量在0.1g/m2 以上且15g/m2 以下，前述皮膜層中之前述鋯氧化物含量以金屬Zr量計在1mg/m2 以上且30mg/m2 以下之範圍內，前述皮膜層中之前述氧化錫利用X射線光電子光譜法所得Sn3d5/2 結合能波峰位置係在從金屬Sn結合能波峰位置起算1.4eV以上且小於1.6eV之範圍內，並且還原前述氧化錫所需電量在大於5.0mC/cm2 且在20mC/cm2 以下之範圍內。

Description

Sn鍍敷鋼板及Sn鍍敷鋼板的製造方法
本發明有關一種Sn鍍敷鋼板及Sn鍍敷鋼板的製造方法。 本案係依據已於2018年3月1日於日本提申之日本特願2018-036587號主張優先權，並於此援引其內容。
發明背景 錫(Sn)鍍敷鋼板係以「馬口鐵」廣為人知，除了飲料罐及食品罐等之罐用途之外，還被廣泛使用於其他方面。這係因為Sn對人體係安全的，並且為美麗的金屬。該Sn鍍敷鋼板主要以電鍍法來製造。這係因為要將屬價格較高之金屬之Sn的使用量控制在所需之最低限度的量，係以電鍍法較熔融鍍敷法更為有利。Sn鍍敷鋼板在透過鍍敷後的加熱熔融處理被賦予美麗的金屬光澤後，大多會利用使用有6價鉻酸鹽溶液的電解處理或浸漬處理等之鉻酸鹽處理，在Sn鍍敷上施予鉻酸鹽皮膜。該鉻酸鹽皮膜的效果在於：透過抑制Sn鍍敷表面的氧化來防止外觀的黃變，或是在經塗裝而使用的情況下防止因氧化錫的內聚破壞造成塗膜密著性劣化、提升耐硫化黑變性等。
另一方面，近年來，因對環境及安全的意識高漲，不僅要求最終製品不可含6價鉻，還要求不進行鉻酸鹽處理本身。然而，不存在鉻酸鹽皮膜的Sn鍍敷鋼板正如上所述，會因氧化錫的成長導致外觀黃變、塗膜密著性下降或耐硫化黑變性下降。
因此，已提出有幾種施行過可取代鉻酸鹽皮膜之皮膜處理的Sn鍍敷鋼板。
例如，以下專利文獻1中已提出一種Sn鍍敷鋼板，係藉由使用有含磷酸離子及矽烷耦合劑之溶液的處理，來形成含P與Si之皮膜。以下專利文獻2中已提出一種Sn鍍敷鋼板，係藉由使用有含磷酸鋁之溶液的處理來形成皮膜，該皮膜含有Al及P、與Ni、Co及Cu中之至少1種、及矽烷耦合劑之反應物。另，以下專利文獻3中已提出一種不具鉻酸鹽皮膜之Sn鍍敷鋼板的製造方法，係在Sn鍍敷上進行Zn鍍敷後，施以加熱處理直到Zn單獨的鍍敷層消失。又，以下專利文獻4及專利文獻5中，已提出一種容器用鋼板，係具有含鋯、磷酸及苯酚樹脂等之化學轉化處理皮膜的容器用鋼板。
先前技術文獻 專利文獻 專利文獻1：日本特開2004-60052號公報 專利文獻2：日本特開2011-174172號公報 專利文獻3：日本特開昭63-290292號公報 專利文獻4：日本特開2007-284789號公報 專利文獻5：日本特開2010-13728號公報
非專利文獻 非專利文獻1：日本表面科學會編，「表面分析化學選書 X射線光電子光譜法」，丸善股份有限公司，P.83
發明概要 發明欲解決之課題 然而，經本發明人等研討之結果，明確指出以上述專利文獻1~專利文獻5所提出之Sn鍍敷鋼板及其製造方法，並無法充分抑制因時間經過而造成之氧化錫成長，而有耐黃變性及塗膜密著性不足的情況。
本發明係有鑑於上述問題而作成者，其目的在於提供一種Sn鍍敷鋼板並提供Sn鍍敷鋼板的製造方法，該Sn鍍敷鋼板係不進行以往之鉻酸鹽處理，而可在耐黃變性、塗膜密著性及耐硫化黑變性上更加優異。
用以解決課題之手段 為解決上述課題以達成相關目的，本發明人等進行了精闢研討。結果，發現了藉由在Sn鍍敷鋼板表面形成含鋯氧化物與氧化錫之層，便可不進行鉻酸鹽處理，而實現在耐黃變性、塗膜密著性及耐硫化黑變上更加優異之Sn鍍敷鋼板。基於上述知識見解而完成之本發明，其主旨如下。
[1]本發明一態樣之Sn鍍敷鋼板具備：母材鍍敷鋼板，係具有鋼板及位於前述鋼板的至少單面上之Sn鍍敷層；及皮膜層，位於前述母材敷鍍鋼板上且含鋯氧化物與氧化錫；前述Sn鍍敷鋼板之每單面之Sn附著量在0.1g/m2 以上且在15g/m2 以下；並且前述皮膜層中之前述鋯氧化物含量以金屬Zr量計在1mg/m2 以上且30mg/m2 以下之範圍內，前述皮膜層中之前述氧化錫利用X射線光電子光譜法所得Sn3d5/2 結合能波峰位置，係在從金屬Sn結合能波峰位置起算1.4eV以上且小於1.6eV之範圍內，且還原前述氧化錫所需電量在大於5.0mC/cm2 且在20mC/cm2 以下之範圍內。 [2]本發明一態樣之Sn鍍敷鋼板的製造方法包含以下步驟：第1步驟，係對母材鍍敷鋼板實施浸漬於含鋯離子溶液中的浸漬處理或在含鋯離子溶液中的陰極電解處理，藉此形成含鋯氧化物之鋯氧化物層，該母材鍍敷鋼板係在鋼板的至少單面形成有含0.1g/m2 以上且在15g/m2 以下的Sn之Sn鍍敷層者；及，第2步驟，係在前述第1步驟後，在含氧之氣體環境下，將形成有前述鋯氧化物層之前述母材鍍敷鋼板於同時滿足以下式1及式2之條件下進行加熱處理，該式1及式2係關於單位為K的加熱溫度T及單位為小時的加熱時間t。 0.11×exp(2400/T)＜t＜0.65×exp(2400/T)・・・(式1) 308＜T＜373 ・・・(式2) [3]在上述[2]之態樣中，前述第2步驟中之前述加熱處理亦可在含有氧且水蒸氣量在60體積%以上且90體積%以下之範圍內的氣體環境下實施。 [4]在上述[2]或[3]之態樣中，前述含鋯離子溶液的鋯離子濃度亦可在100ppm以上且在4000ppm以下，且前述含鋯離子溶液的pH值亦可在3以上且在5以下。 [5]在上述[2]~[4]中任1項之態樣中，前述第1步驟中，亦可利用陰極電解處理形成前述鋯氧化物層，且可令前述陰極電解處理中之電流密度為0.05A/dm2 以上且在50A/dm2 以下。
發明效果 如以上所說明，根據本發明之上述各態樣，可提供一種不進行以往之鉻酸鹽處理，而在耐黃變性、塗膜密著性及耐硫化黑變性上更加優異之Sn鍍敷鋼板及Sn鍍敷鋼板的製造方法。
發明實施形態 以下詳細說明本發明一實施形態。
以下說明之本實施形態係關於可廣泛運用於食品罐、飲料罐等罐用途及其他方面之Sn鍍敷鋼板、及該Sn鍍敷鋼板的製造方法。詳言之，係關於一種不進行以往之鉻酸鹽處理，而在耐黃變性、塗膜密著性及耐硫化黑變性上更加優異之Sn鍍敷鋼板、及該Sn鍍敷鋼板的製造方法。
(關於Sn鍍敷鋼板) 如圖1所示，本實施形態之Sn鍍敷鋼板10係在母材鍍敷鋼板3的表面具有皮膜層4，該母材鍍敷鋼板3係在鋼板1的至少一表面1a形成有Sn鍍敷層2者，該皮膜層4含有預定量之鋯氧化物與氧化錫。
詳言之，本實施形態之Sn鍍敷鋼板1具有母材鍍敷鋼板3和皮膜層4，該母材鍍敷鋼板3係在鋼板1的至少單面形成有Sn鍍敷層2者，該皮膜層4位於該母材鍍敷鋼板3上且含鋯氧化物與氧化錫，並且Sn鍍敷層2之每單面的Sn附著量為0.1g/m2 以上且在15g/m2 以下。 又，在圖1中，係示出僅在鋼板1的單面即表面1a依序形成有Sn鍍敷層2及皮膜層4之情況，但不僅限於該形態。亦即，除了上述構成之外，亦包含在鋼板1之背面1b依序形成Sn鍍敷層2及皮膜層4的情況。如上述於兩面形成Sn鍍敷層2的情況可為以下情形：形成於表面1a之Sn鍍敷層2的Sn附著量為0.1g/m2 以上且在15g/m2 以下，同時，形成於背面1b之Sn鍍敷層2的Sn附著量亦為0.1g/m2 以上且在15g/m2 以下。此外，亦可為以下情形：在鋼板1的兩面形成Sn鍍敷層2，而在該兩面之其中一面之Sn鍍敷層2的Sn附著量為0.1g/m2 以上且在15g/m2 以下，然而另一面之Sn鍍敷層2的Sn附著量在0.1g/m2 以上且15g/m2 以下之範圍外。
本實施形態之Sn鍍敷鋼板10中，該皮膜層4中之鋯氧化物含量以金屬Zr量計，係每單面1mg/m2 以上且在30mg/m2 以下。另外，本實施形態之Sn鍍敷鋼板10中，皮膜層4中之氧化錫利用XPS(X-ray Photoelectron Spectroscopy：X射線光電子光譜法)所得Sn3d5/2 結合能波峰位置，係在從金屬Sn結合能波峰位置起算1.4eV以上且小於1.6eV之範圍內，並且，還原氧化錫所需電量在大於5.0mC/cm2 且在20mC/cm2 以下之範圍內。 又，在測定皮膜層4中之鋯氧化物含量及利用XPS所得Sn3d5/2 結合能波峰位置時，必須排除因皮膜層4的最表層之髒污而造成對測定精度之影響。故，宜蝕刻被膜層4的最表層，並在從皮膜層4的稍微進入內部之位置(例如，較蝕刻前的表層位置深0.5nm之位置)起到5nm深之位置的範圍內進行測定。
以下，詳細說明具有上述結構之Sn鍍敷鋼板10。
＜關於鋼板1＞ 作為本實施形態之Sn鍍敷鋼板10之母材使用的鋼板1，並沒有特別規定，只要係一般容器用之Sn鍍敷鋼板所用鋼板，即可使用任意之鋼板。作為如上述之鋼板1，可例舉如低碳鋼或極低碳鋼等。另外，關於所用之鋼板1的製造方法或材質，亦無特別規定，可適當利用例如鑄造後歷經熱軋延、酸洗、冷軋延、退火及調質軋延等步驟而製出之鋼板。
＜關於Sn鍍敷層2＞ 在如上述之鋼板1的至少單面實施Sn鍍敷，形成Sn鍍敷層2。藉由該Sn鍍敷層2，可使鋼板1的塗裝後耐蝕性提升。又，在本說明書中，所謂「Sn敷鍍」並不單指金屬Sn之鍍敷，亦包含在金屬Sn中混入了不純物之鍍敷、或在金屬Sn中含有微量元素之鍍敷。
在鋼板1的表面1a實施Sn鍍敷之方法沒有特別規定，而譬如以周知之電鍍法為宜，亦可使用藉由將鋼板1浸漬於熔融之Sn中來進行鍍敷之熔融法。電鍍法可利用例如使用了周知的費洛斯坦浴、鹵素浴或鹼浴等的電解法。
又，Sn鍍敷後亦可施行加熱熔融處理，該加熱熔融處理係將經施予Sn鍍敷層2後之鋼板1加熱至Sn的熔點即231.9℃以上。藉由該加熱熔融處理，可使Sn鍍敷鋼板10的表面出現光澤，並且能在Sn鍍敷2與鋼板1之間形成Sn與Fe的合金層，使塗裝後耐蝕性更加提升。
＜關於含鋯氧化物與氧化錫之皮膜層4＞ 本實施形態之Sn鍍敷鋼板10係在具有如上述之Sn鍍敷層2之母材鍍敷鋼板3的表面，具有含鋯氧化物與氧化錫之兩者的皮膜層4。如前述，該皮膜層4中之鋯氧化物含量以金屬Zr量計，係在每單面1mg/m2 以上且30mg/m2 以下之範圍內。皮膜層4中之氧化錫，其利用XPS所得Sn3d5/2 結合能波峰位置係在從金屬Sn的結合能波峰位置起算1.4eV以上且小於1.6eV之範圍內，並且，還原氧化錫所需電量在大於5.0mC/cm2 且在20mC/cm2 以下之範圍內。
又，如上述非專利文獻1所記載，上述所謂「Sn3d5/2 」意指Sn中的電子之能階。詳言之，意指在Sn中，自旋呈平行狀態之3d電子之能階。
本實施形態之Sn鍍敷鋼板10藉由在Sn鍍敷層2的表面2a上，具有如上述之鋯氧化物與氧化錫共存之皮膜層4，可進一步提升耐黃變性、塗膜密著性及耐硫化黑變性。又，若僅有鋯氧化物或僅有氧化錫，則無法充分改善耐黃變性、塗膜密著性及耐硫化黑變性。其理由尚不明確，但藉由本發明人等詳細調查後認為如下。
氧化錫在以往一直被視為黃變的原因，但經本發明人等研討之結果，得知了若在Sn鍍敷鋼板上生成均勻且充足的量之氧化錫，則耐黃變性反而有提升之傾向。並且，也得知若在Sn鍍敷鋼板上生成均勻且充足的量之氧化錫，除了耐黃變性的提升之外，同時耐硫化黑變性也有提升的傾向。上述被認為係由於對於黃變係因Sn鍍敷鋼板上重複發生微觀之金屬錫的溶出與氧化現象而產生之情事，藉由以氧化錫被覆Sn鍍敷表面，便可抑制微觀之金屬錫的溶出之故。為了獲得該效果，須設為以下氧化錫量：還原氧化錫所需電量在大於5.0mC/cm2 且在20mC/cm2 以下之範圍內。還原氧化錫所需電量若大於20mC/cm2 ，則塗膜密著性差，故不佳。而還原氧化錫所需電量的下限值宜為7.0mC/cm2 ，更宜為8mC/cm2 。另外，還原氧化錫所需電量的上限值宜為15mC/cm2 ，更宜為12mC/cm2 。又，所謂「還原氧化錫所需電量」係表示求出用以還原去除Sn鍍敷鋼板10的皮膜層4中之氧化錫所需的時間與電流值之積以作為電量，且其實質上會係對應於皮膜層4的量(膜厚)之數值。
為了獲得氧化錫所帶來之上述效果，需有鋯氧化物共存於皮膜層4中。這係由於鋯氧化物可改善含氧化錫之皮膜的脆性，而使塗膜密著性提升之故。另外，藉由鋯氧化物本身，也有提升耐硫化黑變性的效果。為了獲得該效果，鋯氧化物含量以金屬Zr量計須設在1mg/m2 以上且30mg/m2 以下之範圍內。金屬Zr量若小於1mg/m2 ，便無法抑制含氧化錫之皮膜的脆化。另一方面，金屬Zr量若大於30mg/m2 ，則鋯氧化物含量過多，反而會使塗膜密著性降低。鋯化合物含量的下限值宜為3mg/m2 ，更宜為5mg/m2 。並且，鋯化合物含量的上限值宜為10mg/m2 ，更宜為8mg/m2 。
又，氧化錫利用XPS所得Sn3d5/2 結合能波峰位置，必須在從金屬Sn結合能波峰位置起算1.4eV以上且小於1.6eV之範圍內。氧化錫若具有上述範圍外之結合能值的話，則塗膜密著性會不穩定。
含該等鋯氧化物與氧化錫之皮膜層4，既可是兩者混合的狀態，也可是氧化物的固溶體，其存在狀態不拘。另外，即使在該等氧化物中更含有如P、Fe、Ni、Cr、Ca、Na、Mg、Al及Si等的任何元素，皆無礙。亦即，作為皮膜層4的成分，除了鋯氧化物與氧化錫之外，亦可更含有其他成分(磷化合物或氟化物等)。
此處，上述Zr附著量設為以下之值：將本實施形態之於表面形成有皮膜層4之Sn鍍敷鋼板10，浸漬於例如氟酸與硫酸等之酸性溶液中進行溶解後，利用高頻感應耦合電漿(Inductively Coupled Plasma：ICP)發光分析法等之化學分析來測定所得溶解液而得之值。或者，利用螢光X射線測定來求算上述Zr附著量也無礙。
還原氧化錫所需電量，可以如以下之方法測定。亦即，在經利用氮氣之起泡等除去溶存氧後的0.001mol/L氫溴酸水溶液中，以0.06mA/cm2 的定電流將本實施形態之Sn鍍敷鋼板10進行陰極電解。此時，可從用以還原去除氧化錫所需的時間與電流值之積，求算還原氧化錫所需的電量。
另外，利用XPS所得Sn3d5/2 結合能波峰位置，可利用周知的XPS測定裝置並根據周知方法來測定。
＜Sn鍍敷鋼板的Sn附著量＞ 在本實施形態之Sn鍍敷鋼板10中，每單面的Sn附著量以金屬Sn量而言，係設為0.1g/m2 以上且在15g/m2 以下。如以下詳述，本實施形態之Sn鍍敷鋼板10之皮膜層4係以以下方式形成：將已形成有鋯氧化物層之Sn鍍敷鋼板(胚料)在預定條件下進行加熱處理，使Sn鍍敷層2中的Sn在鋯氧化物層中擴散。因此，上述每單面的Sn附著量係本實施形態之Sn鍍敷鋼板10中存在於Sn鍍敷層2中而未擴散至皮膜層4中的Sn含量、與存在於皮膜層4中之氧化錫的金屬Sn換算量之合計值。
在本實施形態之Sn鍍敷鋼板10中，每單面的Sn附著量若小於0.1g/m2 ，則塗裝後耐蝕性差，故不佳。另外，每單面的Sn附著量若大於15g/m2 ，則Sn之提升塗裝後耐蝕性的效果已足夠，更進一步增加附著量由經濟觀點看來並不宜，而且塗膜密著性也有下降的傾向。就本實施形態之Sn鍍敷鋼板10，每單面的Sn附著量下限值宜為1.0g/m2 ，更宜為2.0g/m2 。並且，每單面的Sn附著量上限值宜為10g/m2 ，更宜為7.0g/m2 。
此處，如上述之每單面的Sn附著量，係設為利用例如JIS G 3303所記載之電解法或螢光X射線法測定而得之值。
(關於Sn鍍敷鋼板10的製造方法) 以下，針對本實施形態之Sn鍍敷鋼板的製造方法詳加說明。本實施形態之Sn鍍敷鋼板的製造方法中，係使用母材鍍敷鋼板3作為胚料，該母材鍍敷鋼板3係在鋼板1的至少單面形成Sn鍍敷層2，使每單面的Sn附著量成為0.1g/m2 以上且在15g/m2 以下。
此處，關於母材鍍敷鋼板3的製造方法並無特別限定，可藉由以下方式來製造：對具有所欲機械強度(例如拉伸強度等)的周知鋼板1，透過周知方法實施Sn鍍敷，使每單面的Sn鍍敷附著量成為0.1g/m2 以上且在15g/m2 以下。另外，也可使用事先以每單面的附著量在上述範圍內的方式施予Sn鍍敷的周知Sn鍍敷鋼板(胚料)，來作為母材鍍敷鋼板3。
接著，詳細說明含鋯氧化物及氧化錫之皮膜層4的形成方法。為了形成本實施形態之皮膜層4，首先係對成為母材鍍敷鋼板3之Sn鍍敷層2上，形成含鋯氧化物之鋯氧化物層。
含鋯氧化物之鋯氧化物層，可藉由對形成有如上述之Sn鍍敷層2之母材鍍敷鋼板3，實施浸漬於含鋯離子溶液中之浸漬處理或在含鋯離子溶液中之陰極電解處理，來形成於母材鍍敷鋼板3上。
但是，在浸漬處理中，係因屬基底之母材鍍敷鋼板3的表面被蝕刻而形成含鋯氧化物之鋯氧化物層，因此，其附著量容易變得不均勻，且處理時間也變長，而不利於工業生產。另一方面，陰極電解處理中，強制性之電荷移動及在鋼板界面產生氫所行之表面淨化、與pH值上升所致之促進附著的效果也會互相起作用，而可獲得均勻的皮膜。再者，在該陰極電解處理中，因處理液中有硝酸離子與銨離子共存，可實現數秒到數十秒左右的短時間處理，故在工業上極為有利。因此，要形成本實施形態之含鋯氧化物之鋯氧化物層，係以利用陰極電解之方法(陰極電解處理)為宜。
以下，將詳細說明進行陰極電解處理來形成鋯氧化物層的情況，而針對除了電流密度等陰極電解處理特有的條件以外的溶液相關條件，在利用浸漬處理來形成鋯氧化物層的情況下亦同樣可適用。
此處，用以實施陰極電解處理的溶液中的鋯離子濃度，只要視生產設備或生產速度(能力)來適當調整即可。溶液中的鋯離子濃度宜為例如100ppm以上且在4000ppm以下。又，含鋯離子的溶液中，即使包含氟離子、銨離子、硝酸離子及硫酸離子等其他成分亦無礙。
此處，用以進行陰極電解之溶液(陰極電解液)之液溫並無特別規定，而以設為例如10℃以上且50℃以下之範圍為宜。藉由在50℃以下進行陰極電解，可形成由非常細微的粒子所形成之細密且均勻的皮膜組織。另一方面，液溫低於10℃時，形成皮膜之效率差，而當夏天等外部氣溫高時會需要冷卻溶液，不僅不經濟，且塗裝後耐蝕性也可能會降低。又，當液溫高過50℃時，所形成之鋯氧化物皮膜組織不均勻，會產生缺陷、裂縫及微小裂痕等而難以形成細密的皮膜， 並且可能成為腐蝕等之起點，故不佳。
又，陰極電解液之pH值並無特別規定，宜為3以上且在5以下。pH値若小於3，則鋯氧化物的生成效率可能會降低，而pH值若大於5，於溶液中會產生大量沉澱，可能使連續生產性降低。
又，為了調整陰極電解液的pH值或為了使電解效率提升，也可在陰極電解液中含有譬如硝酸、氨水等。特別是，為了實現陰極電解處理的短時間化，宜使陰極電解液中含有硝酸及氨水。
另外，陰極電解處理中的電流密度，宜設為例如0.05A/dm2 以上且在50A/dm2 以下之範圍內。電流密度若小於0.05A/dm2 ，會導致鋯氧化物的形成效率降低，而變得難以穩定形成含鋯氧化物之皮膜層，不僅會使耐黃變性或耐硫化黑變性降低，也可能造成塗裝後耐蝕性降低，故不佳。另一方面，電流密度若大於50A/dm2 ，則鋯氧化物的形成效率會過大，可能形成粗大且密著性低劣的鋯氧化物，故不佳。電流密度範圍之下限值較宜為1A/dm2 ，更宜為2A/dm2 。而電流密度範圍之上限值較宜為10A/dm2 ，更宜為6A/dm2 。
此外，在形成鋯氧化物層時，陰極電解的時間不拘。對於目標的Zr附著量，只要視電流密度來適當調整陰極電解的時間即可，而例如在如上述之電流密度範圍內進行陰極電解處理時，通電時間可設為0.3~5秒左右。
另外，作為陰極電解處理所用溶液的溶劑，可使用例如蒸餾水等，但不限於蒸餾水等之水，可視要溶解的材料或形成方法等來適當選擇。
陰極電解中的鋯可使用譬如像H2 ZrF6 之類的鋯錯合物來作為鋯的供給源。如上述之鋯錯合物中的Zr會因陰極電極界面中pH值上升而成為Zr4 ＋ ，存在於陰極電解液中。如上述之鋯離子在陰極電解液中會進一步反應，而成為鋯氧化物。電解液中含磷酸的情況下，也會形成磷酸鋯。
又，陰極電解時之通電態樣，不論是連續通電或斷續通電皆無礙。
本實施形態之含鋯氧化物與氧化錫之皮膜層4，可藉由在預定條件下將母材鍍敷鋼板3進行加熱處理而獲得，且該母材鍍敷鋼板3已形成有如上述之含鋯氧化物之鋯氧化物層。具體而言，係在母材鍍敷鋼板3的Sn鍍敷層2上形成鋯氧化物層後，在含氧氣體環境下，於可同時滿足有關溫度T(單位：K)及時間t(單位：小時)之以下之式101及式102的條件下進行加熱，藉此便可獲得本實施形態之Sn鍍敷鋼板10。亦即，利用如以下詳述之加熱處理，使Sn鍍敷層2中的Sn擴散至鋯氧化物層，藉此，擴散之Sn便會氧化而變成氧化錫。透過該加熱處理，氧化錫的生成量會係對應於上述之還原所需的電量，且氧化錫利用XPS所得Sn3d5/2 結合能波峰位置會在上述範圍內。
0.11×exp(2400/T)＜t＜0.65×exp(2400/T)・・・(式101) 308＜T＜373 ・・・(式102)
上述製造方法中的加熱方法並無限定，可應用例如：大氣加熱、感應加熱或通電加熱等周知加熱方法。此處，加熱溫度如上述式102所示，須設為大於308K且小於373K(亦即，高於35℃且低於100℃)。加熱溫度若在308K以下，則氧化錫會不均勻地形成，無法提升性能。另一方面，若加熱溫度在373K以上，則氧化錫的結構會變化，導致外觀劣化，故不適宜。
此處，上述式101，係本發明人等分別改變加熱處理時的加熱溫度及加熱時間，並就所獲得之Sn鍍敷鋼板10是否在本實施形態之範圍內進行驗證，藉此以實驗方式而得。亦即，本發明人等分別改變加熱處理時的加熱溫度T(K)與加熱時間t(小時)，來製造Sn鍍敷鋼板10，並且驗證所獲得的Sn鍍敷鋼板10是否在本實施形態之範圍內。而且，對於以加熱時間t(小時)及加熱溫度T(K)劃定的座標平面，在對應於各Sn鍍敷鋼板10之加熱條件的位置將所得驗證結果標出記號。其後，為了獲得劃出本實施形態之範圍內的領域邊界之曲線，對座標平面上的記號，在以上述式102規定的加熱溫度T(K)範圍內，利用周知之數值演算應用程式套用非線性最小平方法。透過如上述之事前驗證，本發明人等獲得了以上述式101所示關係。
經本發明人等進行上述之研討，結果明確指出加熱處理步驟中的加熱溫度T[K]及加熱時間t[小時]宜滿足以下式103，更宜滿足以下式104。
0.22×exp(2400/T)＜t＜0.55×exp(2400/T)・・・(式103) 0.33×exp(2400/T)＜t＜0.44×exp(2400/T)・・・(式104)
又，關於加熱處理步驟中的升溫速度及冷卻速度，並無特別限定，只要依據周知方法適宜設定即可。另外，只要係含氧氣體環境，則加熱之氣體環境也無特別限定，而以令含氧氣體環境中的水蒸氣量在60~90體積%之範圍內為宜。吾等認為藉由在該範圍內進行加熱處理，可更加均勻生成氧化錫，而可改善性能。
實施例 接著，示出實施例，並具體說明本實施形態之Sn鍍敷鋼板10及Sn鍍敷鋼板10的製造方法。又，以下所示實施例僅為一示例，本發明之Sn鍍敷鋼板及Sn鍍敷鋼板的製造方法並不僅限定於下述示例。
(實施例1) ＜試驗材＞ 對板厚0.2mm的低碳冷軋鋼板(對應於鋼板1)，進行電解鹼脫脂、水洗、稀硫酸浸漬酸洗及水洗作為前處理之後，使用酚磺酸浴來施行Sn電鍍，之後更進行了加熱熔融處理。Sn鍍敷的附著量係以每單面約2.8g/m2 為標準，但有一部分的試驗材係藉由改變通電時間來改變Sn鍍敷的附著量。另外，也一併製作了Sn電鍍後不進行加熱熔融處理的試驗材。Sn鍍敷的附著量，可利用螢光X射線法(Rigaku公司製ZSX Primus)進行測定而特定出來。
將以上述方式製出之Sn鍍敷鋼板在含氟化鋯之水溶液中進行陰極電解，以在Sn鍍敷鋼板上形成鋯氧化物層。陰極電解液中的鋯濃度設為1400ppm。另外，陰極電解液的浴溫設為35℃，且調整成陰極電解液的pH値為3以上且在5以下，並且視目標之Zr附著量來適當調整電流密度及陰極電解時間。各試驗材之製作時的電流密度及陰極電解時間，如以下表1所示。
接著，將形成有鋯氧化物層的Sn鍍敷鋼板維持在以下表1所示的各種加熱溫度及加熱時間下，以形成含鋯氧化物與氧化錫之皮膜層。又，作為比較，也一併製作了僅形成鋯氧化物層而不實施加熱處理的試驗材(No.1B、No.3B)、及不形成鋯氧化物而僅實施加熱處理的試驗材(No.7B)。另外，一部分試驗材係在鋯氧化物形成前，在碳酸鈉水溶液中進行陽極電解處理，使氧化錫結構改變 (No.5B、No.6B)。對於以上述方式製得之Sn鍍敷鋼板，進行以下所示之各種評估。另外，一部分試驗材則藉由在含氟化鋯之水溶液中交互重覆陰極電解與陽極電解的交替電解處理，來形成鋯氧化物(No.9B)。
[Zr附著量] 各試驗材的皮膜層之每單面Zr附著量，可用Rigaku公司製的ZSX Primus，以螢光X射線法來測定。將所得Zr附著量一併示於以下表1。
[氧化錫量] 對於各試驗材，在經利用氮氣之起泡除去溶存氧後的0.001mol/L氫溴酸水溶液中，以0.06mA/cm2 的定電流進行陰極電解，根據至還原去除氧化錫為止所需的時間與電流之積，測定還原氧化錫所需電量。將所測得之電量一併示於以下表1之「氧化錫量」欄位。
[以XPS所得波峰位置] 對於各試驗材，利用XPS(ULVAC-PHI製PHI Quantera SXM)來測定Sn3d5/2 結合能波峰位置，並算出從金屬Sn結合能波峰位置起算的波峰位置偏移量。將所得偏移量一併顯示於以下表1的「Sn3d5/2 之結合能波峰位置」欄位。
[耐黃變性] 耐黃變性係以如下方式評估。 進行濕潤試驗，該試驗係將以上述方式製出之各試驗材載置於維持在40℃且相對濕度80%之恆溫恆濕槽中4週，並且求算濕潤試驗前後之色座標b* 値之變化量△b*，以進行評估。若變化量△b*在1以下則評為3分，若大於1且在2以下評為2分，若為2~3的話評為1分，大於3的話則評為0分，並且以評估在1分以上為合格。又，色座標b* 可用屬市售色差計之須賀試驗機製SC-GV5來測定，色座標b*的測定條件設為光源C、全反射及測定直徑30mm。
[耐硫化黑變性] 耐硫化黑變性係以如下方式評估。 在以上述方式製出之各試驗材的表面以乾燥質量計塗布7g/m2 之市售罐用環氧樹脂塗料後，在200℃下燒結10分鐘，並置於室溫下24小時。其後，將所得各試驗材裁切為預定尺寸，並浸漬於分別含有0.3質量%的磷酸二氫鈉、0.7質量%的磷酸氫鈉及0.6質量%的L-半胱胺酸鹽酸鹽之水溶液中，在密閉容器中進行121℃及60分鐘的甑餾(retort)處理，並根據試驗後的外觀進行評估。在試驗前後若完全確認不到外觀變化的話評為2分，若確認到僅些微黑變(若黑變的面積在10%以下)的話評為1分，而在大於試驗面的10%之區域中確認到黑變的話則評為0分，並且以評估在1分以上為合格。
[塗膜密著性] 塗膜密著性係以如下方式評估。 將以上述方式製出之各試驗材，以上述[耐黃變性]所記載之方法進行濕潤試驗後，於表面以乾燥質量計塗布7g/m2 之市售罐用環氧樹脂塗料，並在200℃下燒結10分鐘後，置於室溫下24小時。其後，對於所得各試驗材，以棋盤格狀的方式劃出到達鋼板表面之傷痕(以3mm為間隔之橫縱各7條的傷痕)，並進行該部位之膠帶剝離試驗，藉此進行評估。若膠帶黏貼部位的塗膜完全沒有剝離的話評為2分，若在棋盤格的傷痕部位周圍確認到塗膜剝離的話評為1分，而在棋盤格的格子內確認到塗膜剝離的話則評為0分，並且以評估在1分以上為合格。
[塗裝後耐蝕性] 塗裝後耐蝕性係以如下方式評估。 在經以上述[塗膜密著性]所記載之方法製出並進行濕潤試驗後之各試驗材表面，以乾燥質量計塗布7g/m2 之市售罐用環氧樹脂塗料後，在200℃下燒結10分鐘，並置於室溫下24小時。其後，將所得各試驗材裁切為40mm×40mm之尺寸，並在60℃的溫度環境下浸漬於市售蕃茄汁中7天後，以目視評估有無產生鏽。若完全沒有確認到鏽的話評為2分，若確認到僅些微的鏽(生鏽面積為5%以下的話)評為1分，而確認到大於5%的鏽的話則評為0分，並且以評估在1分以上為合格。
[綜合性能] 另外，作為綜合性能，係求算各種性能的評分之合計，並且將該合計值為8分或9分時評為「尤佳」，6分或7分時評為「佳」，4分或5分評為「尚可」，當在任何一個性能中存在0分時則合計值視為0分並評為「差」，以評分為尤佳、佳及尚可為合格。
[表1]
Figure 02_image001
由上述表1明白可知：相當於發明例的試驗材，不論哪個性能皆為良好。另一方面，亦可得知：相當於比較例的試驗材在耐黃變性、塗膜密著性、耐硫化黑變性及塗裝後耐蝕性的任一者上較為低劣。
(實施例2) 對板厚0.2mm之低碳冷軋鋼板進行電解鹼脫脂、水洗、稀硫酸浸漬酸洗及水洗作為前處理後，使用酚磺酸浴來施行Sn電鍍，之後更進行了加熱熔融處理。Sn附著量係製成為每單面2.8g/m2 。
將以上述方式製出之Sn鍍敷鋼板在含氟化鋯之水溶液中進行陰極電解，以在Sn鍍敷鋼板上形成鋯氧化物層。陰極電解液中之鋯濃度設為1400ppm。另外，陰極電解液之浴溫設為35℃，且調整成陰極電解液的pH値為3以上且在5以下，並且適當調整電流密度及陰極電解時間，使Zr附著量成為5mg/m2 。
接著，將形成有鋯氧化物層之Sn鍍敷鋼板維持在各種加熱溫度及加熱時間下，以形成含鋯氧化物與氧化錫之皮膜層後，將所得之各個Sn鍍敷鋼板當作試驗材。
對於所得各試驗材，與上述實施例1所記載之方法同樣地評估各種性能，並根據各評估項目的合計分數來進行綜合性能之評估。綜合性能之評估基準係與實施例1相同。結果彙整於以下表2。另外，在以加熱溫度T[℃]及加熱時間t[小時]所劃定之座標平面上，在各試驗材的加熱溫度及加熱時間的組合之對應位置，將所得之綜合性能評估結果標出記號。並且於圖2示出所得記號。
[表2]
Figure 02_image003
又，圖2中，一併圖示出以上述式101、式103及式104各自的最左邊及最右邊劃定之曲線。
從圖2明白可知：在本實施形態之範圍內的條件下實施加熱處理時，可獲得良好性能，而另一方面，在本實施形態之範圍外的條件下實施加熱處理時，無法獲得良好性能。
以上，已詳細說明了本發明之較佳實施形態，惟本發明不限於僅該等示例。且顯而易見地，只要係具有本發明所屬技術領域之通常知識者，皆可在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，並知悉該等亦理當歸屬本發明之技術範圍。
產業上之可利用性 如上所述，本發明之Sn鍍敷鋼板，因不需以往之鉻酸鹽處理，即具優異耐黃變性、塗膜密著性及耐硫化黑變性，而可作為友善環境之罐用材料，廣泛運用於食品罐和飲料罐等，在產業上具有極高的利用價值。
1‧‧‧鋼板 2‧‧‧Sn鍍敷層 3‧‧‧母材鍍敷鋼板 4‧‧‧皮膜層 10‧‧‧Sn鍍敷鋼板 2a‧‧‧表面(Sn鍍敷層的) 1b‧‧‧背面 (鋼板的) 1a‧‧‧表面 (鋼板的)
圖1係示出本發明一實施形態之Sn鍍敷鋼板之圖，且係沿著其板厚方向之截面圖。 圖2係示出在實施例2中改變加熱處理時的溫度與時間的情況下之結果的圖表。

Claims (6)

  1. 一種Sn鍍敷鋼板，具備：母材鍍敷鋼板，係具有鋼板及位於前述鋼板之至少單面的Sn鍍敷層；及皮膜層，位於前述母材敷鍍鋼板上且含鋯氧化物與氧化錫；前述Sn鍍敷鋼板之每單面之Sn附著量為0.1g/m2以上且在15g/m2以下；並且前述皮膜層中之前述鋯氧化物含量以金屬Zr量計在1mg/m2以上且30mg/m2以下之範圍內，前述皮膜層中之前述氧化錫利用X射線光電子光譜法所得Sn3d5/2結合能波峰位置，係在從金屬Sn結合能波峰位置起算1.4eV以上且小於1.6eV之範圍內，且還原前述氧化錫所需之電量在大於5.0mC/cm2且在20mC/cm2以下之範圍內。
  2. 一種Sn鍍敷鋼板的製造方法，包含以下步驟：第1步驟，係對母材鍍敷鋼板實施浸漬於含鋯離子溶液中的浸漬處理或在含鋯離子溶液中的陰極電解處理，藉此形成含鋯氧化物之鋯氧化物層，該母材鍍敷鋼板係在鋼板的至少單面形成有含0.1g/m2以上且在15g/m2以下的Sn之Sn鍍敷層者；及第2步驟，係在前述第1步驟後，在含氧之氣體環境下，將形成有前述鋯氧化物層之前述母材鍍敷鋼板於同時 滿足以下式1及式2之條件下進行加熱處理，該式1及式2係關於單位為K的加熱溫度T及單位為小時的加熱時間t；0.11×exp(2400/T)<t<0.65×exp(2400/T)．．．(式1) 308<T<373．．．(式2)。
  3. 如請求項2之Sn鍍敷鋼板的製造方法，其中前述第2步驟中之前述加熱處理係在含有氧且水蒸氣量在60體積%以上且90體積%以下之範圍內的氣體環境下實施。
  4. 如請求項2或3之Sn鍍敷鋼板的製造方法，其中前述含鋯離子溶液的鋯離子濃度在100ppm以上且在4000ppm以下，且前述含鋯離子溶液的pH值在3以上且在5以下。
  5. 如請求項2或3之Sn鍍敷鋼板的製造方法，其中前述第1步驟中，係利用陰極電解處理形成前述鋯氧化物層，且令前述陰極電解處理中之電流密度為0.05A/dm2以上且在50A/dm2以下。
  6. 如請求項4之Sn鍍敷鋼板的製造方法，其中前述第1步驟中，係利用陰極電解處理形成前述鋯氧化物層，且令前述陰極電解處理中之電流密度為0.05A/dm2以上且在50A/dm2以下。
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