TWI428476B - 鍍錫鋼板及其製造方法 - Google Patents

鍍錫鋼板及其製造方法 Download PDF

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TWI428476B
TWI428476B TW098122645A TW98122645A TWI428476B TW I428476 B TWI428476 B TW I428476B TW 098122645 A TW098122645 A TW 098122645A TW 98122645 A TW98122645 A TW 98122645A TW I428476 B TWI428476 B TW I428476B
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chemical conversion
tin
conversion treatment
steel sheet
film
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TW201016893A (en
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Takeshi Suzuki
Norihiko Nakamura
Hiroki Iwasa
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Jfe Steel Corp
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Description

鍍錫鋼板及其製造方法
本發明係關於一種可使用於DI罐、食罐、飲料罐等之鍍錫鋼板，特別是在表面上具有不含鉻(Cr)之化學轉化處理皮膜的鍍錫鋼板，以及其製造方法。
罐用表面處理鋼板方面，過去以來，係以稱為「馬口鐵(blik)」的鍍錫鋼板最廣為人所使用。如此之鍍錫鋼板，通常為藉由將鋼板浸漬於含有重鉻酸等之6價鉻化合物的水溶液中、或在此溶液中進行電解等之鉻酸鹽處理，而於鍍錫表面形成鉻酸鹽皮膜。此係藉由鉻酸鹽皮膜之形成而防止在長期保管時等容易產生的鍍錫表面之氧化，且抑制外觀劣化(黃變)，同時於進行塗裝而使用時，防止因錫(Sn)之氧化膜的成長所致之凝集破壞，以確保其與塗料等之有機樹脂的密著性(往後，單稱塗料密著性)。
此外，有鑑於古今的環境問題，規範Cr之使用的舉動係在各領域中進行著，即使在罐用鍍錫鋼板方面，亦有幾個更換為鉻酸鹽處理之化學轉化處理技術被提出。
例如，專利文獻1中，係揭示有一鍍錫鋼板的表面處理法，其係藉由在磷酸系溶液中使鍍錫鋼板作為陰極而進行直流電解以形成化學轉化處理皮膜。專利文獻2中，係揭示有一含有磷酸離子、氯酸鹽及溴酸鹽之1種或2種以上、且含有錫離子之pH3～6的化學轉化處理液。專利文獻3中，係揭示有塗佈將磷酸鈣、磷酸鎂、磷酸鋁之1種或2種以上為皮膜厚度15μg/cm2 以下之馬口鐵(blik)的表面處理法。專利文獻4中，係揭示有於鋼板面上，依次形成鐵(Fe)-鎳(Ni)擴散層、Ni層、Ni-Sn合金層、非合金化Sn層，更進一步設置了以磷(P)換算為1～100mg/m2 之磷酸皮膜層的容器用表面處理鋼板。
但，專利文獻1～4中所記載之化學轉化處理皮膜，與過去的鉻酸鹽皮膜比較下，並無法抑制因鍍錫表面的氧化所導致之外觀的劣化或塗料密著性的降低。
相對於此，專利文獻5中，係揭示一鍍錫鋼板的製造方法，其係在實施鍍錫後，浸漬於含有錫離子與磷酸離子的化學轉化處理液中，或於化學轉化處理液中施以陰極電解，接著，藉由加熱至60～200℃形成化學轉化處理皮膜，而可較過去的鉻酸鹽皮膜更具同等以上的程度來抑制因鍍錫表面的氧化所導致之外觀的劣化或塗料密著性的降低。
[先前技術文獻]
專利文獻1：特公昭55-24516號公報
專利文獻2：特公昭58-41352號公報
專利文獻3：特開昭49-28539號公報
專利文獻4：特開2005-29808號公報
專利文獻5：特開2007-239091號公報
但因專利文獻5中記載之方法，於化學轉化處理後必須有加熱設備，且有化學轉化處理成本高的問題。
本發明係以提供一種不使用Cr而可抑制因鍍錫表面的氧化所導致之外觀的劣化或塗料密著性的降低，且可低價地進行化學轉化處理之鍍錫鋼板及其製造方法為目的。
本發明者們，專致於研究有關不使用Cr，而可抑制因鍍錫表面的氧化所導致之外觀的劣化或塗料密著性的降低，且可低價地實施化學轉化處理之鍍錫鋼板的結果，發現若此鍍錫鋼板為鋼板表面上具有含Sn之鍍敷層，且於含Sn之鍍敷層上具有含P與Sn之第1化學轉化處理皮膜，並於第1化學轉化處理皮膜上具有含P與鋁(Al)之第2化學轉化處理皮膜的鍍錫鋼板，則在化學轉化處理後無須加熱，即可抑制外觀的劣化或塗料密著性的降低。
本發明係基於如此之見解而成者，即是提供一鍍錫鋼板，其特徵為於鋼板之至少單面上，具有Sn的附著量為每單面0.05～20g/m2 之含Sn的鍍敷層，於前述含Sn的鍍敷層上含有P與Sn，且具有P的附著量為每單面0.3～10mg/m2 之第1化學轉化處理皮膜，於前述第1化學轉化處理皮膜上含有P與Al，並具有P的附著量為每單面1.2～10mg/m2 、Al的附著量為每單面0.24～8.7mg/m2 之第2化學轉化處理皮膜。
本發明之鍍錫鋼板，係可藉由下述鍍錫鋼板之製造方法而製造，其特徵為於鋼板之至少單面上，使Sn的附著量為每單面0.05～20g/m2 形成含Sn鍍敷層後，於含有4價錫離子與磷酸離子之化學轉化處理液中實施浸漬處理、或者於該化學轉化處理液中實施陰極電解處理，接著，於含有磷酸二氫鋁(Al(H2 PO4 )3 )5～200g/L、pH為1.5～2.4之化學轉化處理液中實施浸漬處理、或者於該化學轉化處理液中實施陰極電解處理後，進行乾燥。
本發明之製造方法係以低於60℃之溫度進行乾燥為佳。
根據本發明，遂使不使用Cr而可抑制因鍍錫表面的氧化所導致之外觀的劣化或塗料密著性的降低，且不需要特別的加熱設備，即可製造能低價地進行化學轉化處理之鍍錫鋼板得以實現。又，本發明之鍍錫鋼板的化學轉化處理皮膜，係可與現狀的鉻酸鹽處理之情況同様地以300m/分以上高速的線速度形成。
[實施發明之形態]
本發明之鍍錫鋼板，係於使用低碳鋼或極低碳鋼等之一般的罐用冷延鋼板之至少單面上，依序具有含Sn之鍍敷層、含P與Sn之第1化學轉化處理皮膜，以及含P與Al之第2化學轉化處理皮膜的鍍錫鋼板。以下，就其詳細以說明之。
(1)含Sn之鍍敷層
首先，於鋼板的至少單面上，為了賦予耐蝕性而具有含Sn之鍍敷層。此時，Sn的附著量必須為每單面0.05～20g/m2 。此係因Sn的附著量若低於0.05g/m2 則耐蝕性差、若超過20g/m2 則鍍敷層會變厚，成本變高。在此，Sn的附著量係可藉由電量法或螢光X射線進行表面分析而測定。
含Sn之鍍敷層方面，雖無特別地限定，但以由Sn層所成之鍍敷層(以下記為Sn層)、於Fe-Sn層上層合Sn層所成2層構造之鍍敷層(以下記為Fe-Sn層/Sn層)、於Fe-Sn-Ni層上層合Sn層所成2層構造之鍍敷層(以下記為Fe-Sn-Ni層/Sn層)、於Fe-Ni層上依序層合Fe-Sn-Ni層與Sn層所成3層構造之鍍敷層(以下記為Fe-Ni層/Fe-Sn-Ni層/Sn層)等之鍍敷層為佳。
此外，本發明中之含Sn之鍍敷層亦可為連續鍍敷層，或不連續之島狀鍍敷層。
如此而成的含Sn之鍍敷層，係可以周知的方法形成。例如，可使用一般的苯酚磺酸鍍錫浴、甲烷磺酸鍍錫浴、或者鹵素系鍍錫浴，電鍍Sn為每單面附著量2.8g/m2 後，以Sn的熔點231.9℃以上的溫度進行回流處理而形成Fe-Sn層/Sn層之鍍敷層，且於回流處理後為了去除表面上生成之Sn氧化膜，在10～15g/L的碳酸鈉水溶液中1～3A/dm2 的陰極電解處理後，以水洗的方法形成。又，上述含Sn鍍敷層之中含Ni鍍敷層係於鍍錫前進行鎳鍍敷，且可視其需要而實施燒鈍處理，或者鍍錫後施以回流處理等而形成。
(2)第1化學轉化處理皮膜
接著，於上述含Sn之鍍敷層上，具有含P與Sn之第1化學轉化處理皮膜。此係為了與現狀的鉻酸鹽處理之情況同様地以300m/分以上高速的線速度效率佳地形成化學轉化處理皮膜，而如以下詳述地，使用含有4價的錫離子與磷酸離子之化學轉化處理液。此時，化學轉化處理皮膜的P之附著量必須為每單面0.3～10mg/m2 。此係P的附著量低於0.3mg/m2 時，皮膜的被覆性變得不充分，且抑制鍍錫表面的氧化效果不足，而若超過10mg/m2 ，容易產生皮膜自體的凝集破壞，且外觀劣化，塗料密著性容易降低。
如此之第1化學轉化處理皮膜係可藉由於含有4價錫離子與磷酸離子的化學轉化處理液中實施浸漬處理、或者於該化學轉化處理液中實施陰極電解處理而形成。此浸漬處理或陰極電解處理之後，亦可進行水洗。在此，使用含有4價的錫離子與磷酸離子之化學轉化處理液的目的，如上所述，係為了以300m/分以上高速之線速度形成化學轉化處理皮膜。意即，4價的錫離子溶解度高，可添加比2價的錫離子時更多的錫離子，且4價的錫離子因可藉由伴隨鍍錫表面之溶解所放出之電子而在鍍錫表面附近還原成2價的錫離子之故，於鍍錫表面近旁會有高濃度的2價錫離子生成，而促進反應。再者，實施陰極電解處理的話，因4價的錫離子向2價的錫離子還原受到促進，同時質子的還原反應亦受到促進，且鍍錫表面近旁的pH會上昇，促進不溶性磷酸氫錫(SnHPO4 )或磷酸錫(Sn3 (PO4 )2 )的沈澱析出之故，而使反應更受促進。因此，若使用含有4價的錫離子與磷酸離子之化學轉化處理液，可在短時間內效率佳地形成化學轉化處理皮膜。
含有4價的錫離子與磷酸離子之化學轉化處理液方面，係可舉出含有0.5～5g/L的四氯化錫‧五水合物與1～80g/L的正磷酸之水溶液。
(3)第2化學轉化處理皮膜
最後，於上述第1化學轉化處理皮膜上，具有含P與Al之第2化學轉化處理皮膜。此係若形成此含P與Al之化學轉化處理皮膜，即使於化學轉化處理後未積極地加熱而僅以低溫使其乾燥之程度，即可與過去的鉻酸鹽皮膜具有同等以上程度可抑制外觀的劣化或塗料密著性的降低。此理由雖未必明確，但可考量為藉由於化學轉化處理皮膜中導入Al，而能形成對下層之鍍錫層的氧化具有更強固的障壁性之緻密的磷酸鹽之化學轉化處理皮膜。此時，化學轉化處理皮膜的P之附著量必須為每單面1.2～10mg/m2 、Al的附著量必須為每單面0.24～8.7mg/m2 。此係若P的附著量低於1.2mg/m2 、Al的附著量低於0.24mg/m2 的話，抑制鍍錫表面的氧化的效果不足，且外觀會劣化、經時後的塗料密著性會降低，若P的附著量超過10mg/m2 ，則會產生皮膜自體的凝集破壞，且塗料密著性容易降低。此外，Al的附著量上限8.7mg/m2 係皮膜的全量為磷酸鋁(AlPO4 )時，以化學量子論所導出之值，而P的附著量低於10mg/m2 時，不會超過此值。在此，化學轉化處理皮膜之P的附著量或Al的附著量係可藉由螢光X射線進行表面分析而測定。
如此之第2化學轉化處理皮膜係可藉由含磷酸二氫鋁(Al(H2 PO4 )3 )5～200g/L、pH為1.5～2.4之化學轉化處理液中實施浸漬處理、或者於該化學轉化處理液中實施陰極電解處理、進而乾燥所形成。此浸漬處理或陰極電解處理之後，係可水洗，之後乾燥。此時，使用含磷酸二氫鋁(Al(H2 PO4 )3 )5～200g/L、pH為1.5～2.4之化學轉化處理液，係因後述之理由。意即，當磷酸二氫鋁(Al(H2 PO4 )3 )低於5g/L時，皮膜中之Al的附著量不足，且未能獲得對鍍錫層的氧化而言強固之障壁性，而若超過200g/L，則化學轉化處理液的安定性受損，處理液中有沈澱物形成且附著於鍍錫鋼板的表面，導致外觀的劣化或塗料密著性的降低。又，化學轉化處理液的pH若低於1.5，則皮膜析出困難，即使處理時間極端地延長實施至數10秒為止，仍無法確保足夠的附著量，而若超過2.4，則皮膜的析出激增，難以控制附著量。乾燥係以低於60℃之溫度進行為佳。此乃因藉由本發明之製造方法所形成的化學轉化處理皮膜，即使乾燥溫度低於60℃，仍可充分地抑制鍍錫層的氧化，並無須特別的加熱設備。在本發明中，乾燥溫度係為到達板溫。
此外，為了在短時間內使P的附著量到達1.2～10mg/m2 ，係以使磷酸二氫鋁(Al(H2 PO4 )3 )為60～120g/L較佳。又，為了以高速的線速度使P的附著量至1.2～10mg/m2 ，相較於浸漬處理，更以陰極電解處理者為佳，且因藉由陰極電解使氫氣產生而消費鍍錫表面與處理液之界面近旁的質子，並強制性地提升pH而更佳。再者，化學轉化處理液方面，為了後續所述之pH的調整或提升反應速度，係可使其含有正磷酸1～20g/L。
化學轉化處理液之pH的調整，係可藉由添加磷酸、硫酸或氫氧化鈉等之酸或鹼來進行。又，在此化學轉化處理液中，其他亦可適當地添加FeCl2 、NiCl2 、FeSO4 、NiSO4 、氯酸鈉、亞硝酸鹽等之促進劑、氟離子等之蝕刻劑、月桂基硫酸鈉、乙烯二醇等之界面活性劑。又，化學轉化處理液之溫度係以70℃以上為佳。此係因70℃以上，其附著速度可隨溫度的上昇而增大，可以更加高速之線速度進行處理。但若溫度過高，從處理液來的水分蒸發速度變大，處理液的組成會經時性地變動，故處理液的溫度以85℃以下為佳。
如專利文獻5所記載般，於含有錫離子與磷酸離子之化學轉化處理液中實施浸漬處理或陰極電解處理而形成單層的化學轉化處理皮膜時，化學轉化處理後必須加熱至60～200℃。但，如本發明之鍍錫鋼板的情況，若於使用含有錫離子與磷酸離子之化學轉化處理液而形成的第1化學轉化處理皮膜上，進一步在含有磷酸二氫鋁(Al(H2 PO4 )3 )之化學轉化處理液中實施浸漬處理、或者於該化學轉化處理液中實施陰極電解處理而形成第2化學轉化處理皮膜的話，在化學轉化處理後因無須積極地加熱，故不需加熱設備，而可低價地進行化學轉化處理。
如上所述，有鑑於現狀之鉻酸鹽處理，一般係以300m/分以上的線速度施行且生產性非常地高之情形，取代鉻酸鹽處理之新的化學轉化處理亦即希望至少能以現狀的線速度來進行處理。此係因處理時間若變長，則處理槽的大小必須變大、處理槽數必須增加，而導致設備成本或其維護成本大增。在不進行設備改造下，而以300m/分以上的線速度進行化學轉化處理方面，必須與現狀之鉻酸鹽處理相同，使處理時間以合計為2.0秒以下較佳，再更佳為1秒以下。若於上述本發明之化學轉化處理液中實施浸漬處理或者陰極電解處理的話，則可因應現狀之300m/分以上的線速度。又，陰極電解處理時的電流密度係以10A/dm2 以下為佳，此係因超過10A/dm2 會導致對電流密度的變動之附著量變動幅度變大之故，而難以確保安定的附著量。此外，在形成化學轉化處理皮膜方面，除了浸漬處理或陰極電解處理之外，其他雖然還有塗佈或陽極電解處理之方法，但前者因容易產生表面的反應不均，而難以得到均一的外觀，而後者則因皮膜容易析出粉狀物，容易發生外觀的劣化或塗料密著性的劣化，故此等方法皆不適合。
 [實施例]
素材之鋼板方面，係使用
鋼板A：板厚0.2mm的低碳冷延鋼板、或者鋼板B：於板厚0.2mm的低碳冷延鋼板之兩面上，使用瓦特浴(watts bath)以每單面100mg/m2 的附著量形成鎳鍍敷層後，於10vol.%H2 +90vol.%N2 氛圍中以700℃燒鈍而使鎳鍍敷擴散浸透之鋼板，用市售的鍍錫浴，以表3所示之每單面的Sn附著量形成Sn層後，於Sn的熔點以上實施回流處理，且於鋼板A上形成Fe-Sn層/Sn層之含Sn鍍敷層；又，於鋼板B上形成Fe-Ni層/Fe-Ni-Sn層/Sn層之含Sn鍍敷層。
接著，回流處理後，為了去除表面上生成之Sn的氧化膜，係於浴溫50℃、10g/L的碳酸鈉水溶液中實施1A/dm2 的陰極電解處理。之後，進行水洗，使用條件如表1及表2所示之正磷酸的量、四氯化錫‧五水合物的量及溫度的化學轉化處理液，進行條件如表1及表2所示時間的浸漬處理或者其電流密度與時間的陰極電解處理後，以絞擰輥(wringer roll)擰絞、水洗，接著，使用條件如表1及表2所示之正磷酸的量、磷酸二氫鋁(Al(H2 PO4 )3 )的量、pH及溫度的化學轉化處理液，進行條件如表1及表2所示時間的浸漬處理或者其電流密度與時間的陰極電解處理後，以絞擰輥(wringer roll)擰絞、水洗後，使用一般的吹風機於室溫下進行乾燥或者施以70℃的熱風乾燥，製作具有第1化學轉化處理皮膜與第2化學轉化處理皮膜之鍍錫鋼板的試料No.1～22。此時，表1及表2中所示之化學轉化處理液的pH，係酸或鹼進行調整。
然後，形成各層或皮膜後，以上述的方法，測定含Sn鍍敷層之Sn的附著量、第1化學轉化處理皮膜之P的附著量、第2化學轉化處理皮膜之P的附著量及Al的附著量。又，針對所製得之鍍錫鋼板，以下述之方法，評價剛完成製作後的外觀、長期保管後之Sn的氧化膜量與外觀、塗料密著性、及耐蝕性。
剛完成製作後的外觀：以目視觀察剛完成製作後的鍍錫鋼板之外觀，評價如下，若為○或◎，表示外觀良好。
◎：表示表面無粉狀析出物存在，而且保有金屬光澤之美麗的外觀
○：表示表面無粉狀析出物存在，而僅有一點點泛白之美麗的外觀
△：表示表面上局部存在有粉狀析出物，稍有泛白之不均一的外觀
×：表示表面上存在大量的粉狀析出物，而全面泛白的外觀
長期保管後之Sn的氧化膜量與外觀：將鍍錫鋼板置於60℃、相對濕度70%的環境下保管10天，目視觀察外觀，同時使表面所形成之Sn的氧化膜量，於1/1000N之HBr溶液的電解液中以電流密度25μA/cm2 進行電解，求取電化學性還原所需之電量後，評價如下，若為○或◎則表示長期保管後之Sn的氧化膜量少、外觀亦良好。
◎：表示還原電量低於2mC/cm2 、外觀優(較鉻酸鹽處理材更為良好)
○：表示還原電量為2mC/cm2 以上且低於3mC/cm2 、外觀良(與鉻酸鹽處理材同等)
△：表示還原電量為3mC/cm2 以上且低於5mC/cm2 、外觀稍呈黃色
×：表示還原電量5mC/cm2 以上、外觀明顯地為黃色
塗料密著性：在剛完成製作後的鍍錫鋼板上，塗佈環氧苯酚系塗料使附著量為50mg/dm2 後，於210℃下進行10分鐘的燒著。接著，將經塗佈‧燒著之2片鍍錫鋼板，以塗裝面挾著耐隆接著薄膜而相向之方式層合，並在壓力2.94×105 Pa、溫度190℃、壓著時間30秒鐘的壓著條件下貼合後，將此分割成5mm幅寬的試驗片，使用拉伸試驗機拉剝此試驗片，進行強度測定，且評價如下，若為○或◎，則表示塗料密著性良好。又，將鍍錫鋼板置於室溫環境下保管6個月後，亦進行同様的塗料密著性評價。
◎：19.6N(2kgf)以上(與溶接罐用鉻酸鹽處理材同等)
○：3.92N(0.4kgf)以上且低於19.6N(與鉻酸鹽處理材同等)
△：1.96N(0.2kgf)以上且低於3.92N
×：低於1.96N(0.2kgf)
耐蝕性：於鍍錫鋼板上，塗佈環氧苯酚系塗料使附著量為50mg/dm2 後，於210℃下進行10分鐘的燒著。接著，於60℃下浸漬於市售的蕃茄汁中10天，以目視來評價塗膜有無剝離、有無生鏽，若為○或◎，則表示耐蝕性良好。
◎：表示塗膜無剝離、無生鏽
○：表示塗膜無剝離，且僅有極小點狀生鏽(與鉻酸鹽處理材同等)
△：表示塗膜無剝離，但稍微生鏽
×：表示塗膜剝離，且有生鏽
結果顯示於表3。由結果得知，本發明之鍍錫鋼板試料No.1～17，任一者其剛製造完成後及長期保管後的外觀皆良好，且長期保管後之Sn的氧化膜量也少、塗料密著性及耐蝕性方面表現優異。
[產業上之可利用性]
藉由本發明，係可實現製造一種不使用Cr，而可抑制因鍍錫表面的氧化所導致之外觀的劣化或塗料密著性的降低、且無須特別的加熱設備，即可低價地進行化學轉化處理之鍍錫鋼板。又，本發明之鍍錫鋼板的化學轉化處理皮膜，係可與現狀的鉻酸鹽處理之情況同様地以300m/分以上高速的線速度形成。因此，可大幅地應用於產業上。

Claims (3)

  1. 一種鍍錫鋼板，其特徵係於鋼板之至少單面上，具有Sn的附著量為每單面0.05~20g/m2 之含Sn鍍敷層，於前述含Sn鍍敷層上，具有不含Al而含有P與Sn且P的附著量為每單面0.3~10mg/m2 之第1化學轉化處理皮膜，於前述第1化學轉化處理皮膜上，具有含有P與Al且P的附著量為每單面1.2~10mg/m2 、Al的附著量為每單面0.24~8.7mg/m2 之第2化學轉化處理皮膜。
  2. 一種鍍錫鋼板的製造方法，其特徵係於鋼板之至少單面上，使Sn的附著量為每單面0.05~20g/m2 形成含Sn鍍敷層之後，於含有4價錫離子與磷酸離子之化學轉化處理液中實施浸漬處理、或者於該化學轉化處理液中實施陰極電解處理，接著，於含有磷酸二氫鋁5~200g/L、pH為1.5~2.4之化學轉化處理液中實施浸漬處理、或者於該化學轉化處理液中實施陰極電解處理之後，進行乾燥。
  3. 如申請專利範圍第2項之鍍錫鋼板的製造方法，其係以低於60℃之溫度進行乾燥。
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