TWI477662B - 鍍錫鋼板之製造方法及鍍錫鋼板暨化學轉化處理液 - Google Patents
鍍錫鋼板之製造方法及鍍錫鋼板暨化學轉化處理液 Download PDFInfo
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Description
本發明係關於一種用於DI罐(drawing and Ironing can)、餐盒、飲料罐等之鍍錫鋼板,特別是關於一種在表面上具有不含鉻(Cr)的化學轉化處理皮膜之鍍錫鋼板之製造方法及鍍錫鋼板暨化學轉化處理液。
作為罐用表面處理鋼板,先前以來一直廣泛使用稱為「馬口鐵皮」之鍍錫鋼板。此種鍍錫鋼板通常藉由在含有重鉻酸等6價鉻化合物之水溶液中浸漬鋼板、或者於該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。其原因在於:藉由形成鉻酸鹽皮膜,可防止因長期保管時等而易引起之鍍錫表面之氧化,從而可抑制外觀劣化(黃變),並且於塗裝使用時可防止因錫(Sn)氧化膜之成長所造成之凝聚破壞,且可確保與塗料等有機樹脂之密著性(以下簡稱為塗料密著性)。
另一方面,根據近來之環境問題,限制使用Cr之活動正於各領域內進行,而於罐用鍍錫鋼板方面亦提出了幾種代替鉻酸鹽處理之化學轉化處理技術。例如,專利文獻1中揭示有藉由在磷酸系溶液中將鍍錫鋼板作為陰極,進行直流電解而形成化學轉化處理皮膜之鍍錫鋼板之表面處理法。專利文獻2中揭示有含有磷酸離子、氯酸鹽及溴酸鹽中之一種或兩種以上,以及錫離子之pH值為3~6的化學轉化處理液。專利文獻3中揭示有以皮膜厚度為15 μg/cm2
以下之方式塗佈磷酸鈣、磷酸鎂、磷酸鋁中之一種或者兩種以上的馬口鐵皮之表面處理法。專利文獻4中揭示一種於鋼板面上依序形成鐵(Fe)-鎳(Ni)擴散層、Ni層、Ni-Sn合金層、非合金化Sn層,再設置以磷(P)換算計為1~100 mg/m2
之磷酸皮膜層的容器用表面處理鋼板。
然而,專利文獻1~4中所揭示之化學轉化處理皮膜與先前之鉻酸鹽皮膜相比,其無法抑制因鍍錫表面之氧化而引起之外觀劣化或塗料密著性降低。
相對於此,專利文獻5中揭示一種鍍錫鋼板之製造方法,其係於實施鍍錫後,浸漬於含有錫離子及磷酸離子之化學轉化處理液中,或者於化學轉化處理液中進行陰極電解,繼而加熱至60~200℃而形成化學轉化處理皮膜,藉此可抑制因鍍錫表面之氧化而引起之外觀劣化或塗料密著性降低。
專利文獻1:日本專利特公昭55-24516號公報
專利文獻2:日本專利特公昭58-41352號公報
專利文獻3:日本專利特開昭49-28539號公報
專利文獻4:日本專利特開2005-29808號公報
專利文獻5:日本專利特開2007-239091號公報
專利文獻5中所揭示之化學轉化處理皮膜具有與先前之鉻酸鹽皮膜同等以上的優異性能。然而,為了形成該化學轉化處理皮膜,需要使用高價之氯化亞錫、氯化錫、硫酸錫等作為錫離子源,進而於化學轉化處理後需要加熱設備,故而有化學轉化處理成本較高之問題。
本發明之目的在於提供一種不使用Cr而可抑制因鍍錫表面之氧化而引起之外觀劣化或塗料密著性降低,且可低價地進行化學轉化處理之鍍錫鋼板之製造方法及鍍錫鋼板,暨以此為目的之化學轉化處理液。
本發明者等對不使用Cr而可抑制因鍍錫表面之氧化所引起之外觀劣化或塗料密著性降低,且可低價地進行化學轉化處理之鍍錫鋼板進行了反覆深入研究,結果發現有效的是:以Sn之附著量為每單面0.05~20 g/m2
之方式形成含Sn之鍍敷層後,於含有超過18 g/L且200 g/L以下之磷酸二氫鋁(monobasic aluminum phosphate)、且pH值為1.5~2.4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化學轉化處理皮膜。
本發明係基於此種見解而完成者,其提供一種鍍錫鋼板之製造方法,其特徵在於:於鋼板之至少單面上以Sn之附著量為每單面0.05~20 g/m2
之方式形成含Sn之鍍敷層後,於含有超過18 g/L且200 g/L以下之磷酸二氫鋁、且pH值為1.5~2.4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以10 A/dm2
以下之電流密度實施陰極電解處理,繼而進行乾燥而形成化學轉化處理皮膜。
本發明之製造方法中,較佳的是形成包含Sn層之鍍敷層、Fe-Sn層與Sn層依序積層而成之鍍敷層中的任一種鍍敷層,以作為含Sn之鍍敷層。又,較佳的是於未滿60℃之溫度下進行乾燥。更佳的是將化學轉化處理液之溫度設定為70℃以上而實施陰極電解處理。
本發明又提供一種鍍錫鋼板,其係藉由此種鍍錫鋼板之製造方法製造而成者。
於本發明之鍍錫鋼板中,較佳的是化學轉化處理皮膜之附著量以P換算計每單面為1.5~10 mg/m2
,化學轉化處理皮膜中之Al與P之質量比(Al/P)為0.20~0.87。
本發明進而提供一種化學轉化處理液,其含有超過18 g/L且200 g/L以下之磷酸二氫鋁,且pH值為1.5~2.4。
根據本發明,可製造不使用Cr而可抑制因鍍錫表面之氧化所引起之外觀劣化或塗料密著性降低,且可低價地進行化學轉化處理之鍍錫鋼板。又,本發明之鍍錫鋼板之化學轉化處理皮膜與現狀之鉻酸鹽處理的情況相同,可以300 m/分鐘以上之高速的線速形成。
首先,於使用低碳鋼或極低碳鋼等之普通的罐用冷軋鋼板(cold-rolled steel)之至少單面上形成:包含Sn層之鍍敷層(以下記為Sn層)、於Fe-Sn層上積層Sn層之兩層構造之鍍敷層(以下記為Fe-Sn層/Sn層)、於Fe-Sn-Ni層上積層Sn層之兩層構造之鍍敷層(以下記為Fe-Sn-Ni層/Sn層)、於Fe-Ni層上依序積層Fe-Sn-Ni層與Sn層之三層構造之鍍敷層(以下記為Fe-Ni層/Fe-Sn-Ni層/Sn層)等含Sn之鍍敷層。
此時,於任一種含Sn之鍍敷層之情況下,Sn之附著量必須為每單面0.05~20 g/m2
。其原因在於:若附著量未滿0.05 g/m2
則有耐蝕性變差之傾向,若超過20 g/m2
則鍍敷層會變厚,從而導致成本變高。此處,Sn之附著量可藉由電量法或者螢光X射線進行表面分析而測定。再者,本發明中含Sn之鍍敷層可為連續之層,亦可為不連續之島狀鍍錫層。
至於上述含Sn之鍍敷層之形成,可應用眾所周知之方法。例如可藉由以下方法形成:使用通常之酚磺酸鍍錫浴、甲磺酸鍍錫浴、或者鹵素系鍍錫浴,以每單面附著量為2.8 g/m2
之方式將Sn電鍍之後,於Sn之熔點231.9℃以上之溫度下進行回流焊處理而形成Fe-Sn層/Sn層之鍍敷層,並且為了除去回流焊處理後在表面上所生成之Sn氧化膜,而於10~15 g/L之碳酸鈉水溶液中在1~3 A/dm2
之陰極電解處理後進行水洗。
再者,上述含Sn之鍍敷層中的含Ni之鍍敷層均於鍍錫前進行鍍鎳,並根據需要實施退火處理,或者於鍍錫後實施回流焊處理等而形成,因此需要鍍鎳設備,且步驟變得煩雜,與不含Ni之情況相比成本變高。因此,作為含Sn之鍍敷層,較佳的是如Sn層或Fe-Sn層/Sn層之不含Ni之鍍敷層。
繼而,於上述含Sn之鍍敷層上,於含有超過18 g/L且200 g/L以下之磷酸二氫鋁、且pH值為1.5~2.4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以10 A/dm2
以下之電流密度實施陰極電解處理,繼而進行乾燥而形成化學轉化處理皮膜。此時,可於乾燥前進行水洗。
又,使用含有超過18 g/L且200 g/L以下之磷酸二氫鋁的化學轉化處理液之原因在於:若磷酸二氫鋁為18 g/L以下,則皮膜中Al之均勻分散性會降低,局部附著量過多產生而導致塗料密著性及耐蝕性劣化;若超過200 g/L,則有損化學轉化處理液之穩定性,於處理液中形成沈澱物,並附著於鍍錫鋼板之表面,而引起外觀劣化或塗料密著性降低。又,將化學轉化處理液之pH值設定為1.5~2.4之原因在於:若pH值未滿1.5,則皮膜難以析出,即使實施極長至數10秒之處理時間亦無法達到充足之附著量;若超過2.4,則會於陰極電解處理時引發激烈之析出反應,附著量隨著電流密度之變動而發生較大變動,故而難以控制附著量。此種pH值之調整可藉由添加磷酸、硫酸或氫氧化鈉等酸或鹼來實現。再者,化學轉化處理液中亦可適當添加另外的FeCl2
、NiCl2
、FeSO4
、NiSO4
、氯酸鈉、亞硝酸鹽等促進劑,氟離子等蝕刻劑,十二烷基硫酸鈉、乙炔乙二醇等界面活性劑。
現狀之鉻酸鹽處理通常係以300 m/分鐘以上之線速來進行,考慮到生產性極高,較理想的是代替鉻酸鹽處理之新穎的化學轉化處理亦可以現狀之線速來處理。其原因在於,若處理時間變長則必須增大處理槽之尺寸,或增加槽數,從而導致設備成本或維持成本增大。為了不進行設備改造而以300 m/分鐘以上之線速進行化學轉化處理,較佳的是與現狀之鉻酸鹽處理相同,將處理時間設定為2.0秒以下。更佳的是1秒以下。因此,為了形成本發明之化學轉化處理皮膜,而必須於上述化學轉化處理液中實施浸漬處理或者陰極電解處理。又,陰極電解處理時之電流密度必須為10 A/dm2
以下,其原因在於,若超過10 A/dm2
,則隨著電流密度之變動而附著量變動幅度會變大,故而難以確保穩定之附著量。再者,為了形成化學轉化處理皮膜,除了浸漬處理或陰極電解處理之外,亦有塗佈或陽極電解處理之方法,但前者塗佈中容易產生表面之反應不勻,故而難以獲得均勻之外觀,又,後者陽極電解處理中皮膜容易析出成粉狀,故而容易產生外觀劣化或塗料密著性劣化,因此該等方法不適宜。
於浸漬處理或陰極電解處理後進行乾燥,較佳的是於未滿60℃之溫度下進行乾燥。其原因在於,在本發明之製造方法中,即使乾燥溫度未滿60℃亦可充分抑制Sn氧化膜之成長,而無需特別之加熱設備。如此即使於未滿60℃之低溫下亦可充分抑制Sn氧化膜之成長的理由未必明顯,但可認為:藉由向皮膜中導入Al成分,而形成具有更牢固之阻隔性的複合磷酸鹽皮膜。再者,本發明中將乾燥溫度設定為乾燥時之最高到達鋼板溫度。又,實施陰極電解處理之化學轉化處理液之溫度較佳的是70℃以上。其原因在於,若為70℃以上,則隨著溫度上升而附著速度增大,從而可以更高速之線速進行處理。然而,若溫度過高,則來自處理液之水分之蒸發速度會變大,處理液之組成會經時發生變動,因此處理液之溫度較佳為85℃以下。
如此而形成之化學轉化處理皮膜較佳的是,其附著量以P換算計為每單面1.5~10 mg/m2
,化學轉化處理皮膜中Al與P之質量比(Al/P)為0.20~0.87。其原因在於:若P換算之附著量未滿1.5 mg/m2
、或質量比(Al/P)未滿0.20,則抑制鍍錫表面之氧化之效果會變得不充分,且外觀劣化或塗料密著性降低,又,若P換算之附著量超過10 mg/m2
,則引起化學轉化處理皮膜自身之凝聚破壞,塗料密著性容易降低。再者,作為質量比(Al/P)之上限的0.87係於皮膜之總量為磷酸鋁之情況下根據化學反應計量得出之最大值。此處,P換算之附著量可藉由螢光X射線進行表面分析而測定,質量比(Al/P)可藉由螢光X射線進行表面分析求出P與Al之附著量而算出。
為了可在短時間內達到上述P換算之附著量1.5~10 mg/m2
,較佳的是將磷酸二氫鋁設定為60~120 g/L。又,為了以高速之線速將P換算之附著量設定為1.5~10 mg/m2
,與浸漬處理相比較佳的是陰極電解處理,更佳的是藉由陰極電解而產生氫氣,而消耗鍍錫表面與處理液之界面附近的質子,從而使pH值強制地上升。
如上所述,於本發明中,由於化學轉化處理液中未添加高價之Sn,故可提供一種可低價地進行化學轉化處理之鍍錫鋼板之製造方法。再者,雖然有於化學轉化處理皮膜中除了Al或P外不可避免地自含Sn之鍍敷層混入Sn之情況,但仍可獲得相同之效果。
作為原材料之鋼板,係使用以下鋼板,即於鋼板A:板厚0.2 mm之低碳冷軋鋼板、鋼板B:板厚0.2 mm之低碳冷軋鋼板之兩面上,使用瓦特浴而以每單面100 mg/m2
之附著量形成鍍鎳層後,於10 vol.%H2
+90 vol.%N2
之環境中以700℃進行退火而使鍍鎳擴散浸透而成者;使用市售之鍍錫浴以表2所示之每單面之Sn附著量形成Sn層後,於Sn之熔點以上實施回流焊處理,而於鋼板A上形成含有Fe-Sn層/Sn層之含Sn之鍍敷層,又,於鋼板B上形成含有Fe-Ni層/Fe-Ni-Sn層/Sn層之含Sn之鍍敷層。繼而,為了除去於回流焊處理後在表面上所生成之Sn氧化膜,而於浴溫50℃、10 g/L之碳酸鈉水溶液中實施1 A/dm2
之陰極電解處理。然後,進行水洗,使用表1所示之磷酸二氫鋁之量、pH值及溫度之化學轉化處理液,以表1所示之電流密度及電解時間實施陰極電解處理後,進行水洗並以榨水輥擠壓,使用普通之鼓風機於室溫下進行乾燥而形成化學轉化處理皮膜,從而製作鍍錫鋼板之試料No.1~25。此時,試料No.13中,係於表1所示之化學轉化處理液中實施1秒浸漬處理代替陰極電解處理來形成化學轉化處理皮膜。又,試料No.12中,係不使用鼓風機而藉由使鋼板達到70℃之熱風乾燥進行最後之乾燥。再者,表1所示之化學轉化處理液之pH值係添加正磷酸來進行調整。
並且,形成各層或皮膜之後,藉由上述方法,求出含Sn之鍍敷層之Sn附著量、化學轉化處理皮膜之P換算之附著量、Al換算之附著量、及質量比(Al/P)。又,對所製作之鍍錫鋼板,藉由以下之方法來評價剛製作後之外觀、長期保管後之Sn的氧化膜量與外觀、塗料密著性、及耐蝕性。
剛製作後之外觀:目視觀察剛製作後之鍍錫鋼板之外觀並以如下方式進行評價,若為○或者◎,則認為外觀良好。
◎:表面不存在粉狀析出物,保有金屬光澤之美麗外觀
○:表面不存在粉狀析出物,雖有少許白色但亦美麗之外觀
△:表面上局部存在粉狀析出物,稍帶白色的不均勻之外觀
×:表面上存在大量粉狀析出物,帶有白色之外觀長期保管後之Sn的氧化膜量與外觀:將鍍錫鋼板於60℃、相對濕度70%之環境下保管10日,目視觀察外觀,並且於1/1000 N之HBr溶液之電解液中以25 μA/cm2
之電流密度,對形成於表面之Sn的氧化膜量進行電解,而求出電化學還原所需要之電量並以如下方式進行評價,若為○或◎,則認為長期保管後之Sn的氧化膜量較少,且外觀亦良好。
◎:還原電量未滿2 mC/cm2
,外觀優(比鉻酸鹽處理材料好)
○:還原電量為2 mC/cm2
以上且未滿3 mC/cm2
,外觀良(與鉻酸鹽處理材料相同)
△:還原電量為3 mC/cm2
以上且未滿5 mC/cm2
,外觀稍黃
×:還原電量為5 mC/cm2
以上,外觀為明顯之黃色
塗料密著性:於剛製作後之鍍錫鋼板上,以附著量50 mg/dm2
之方式塗佈環氧酚醛系塗料後,於210℃下進行10分鐘之燒製。繼而,將經塗佈.燒製之兩片鍍錫鋼板以塗裝面夾持尼龍接著膜而對向之方式積層,於壓力2.94×105
Pa、溫度190℃、壓接時間30秒之壓接條件下貼合後,將其分割為5 mm寬度之試驗片,使用拉力測試機將該試驗片剝離,進行強度測定並以如下方式進行評價,若為○或者◎,則認為塗料密著性良好。又,將鍍錫鋼板於室溫環境下保管6個月後亦進行同樣的塗料密著性之評價。
◎:19.6 N(2 kgf)以上(與焊接罐用鉻酸鹽處理材料相同)
○:3.92 N(0.4 kgf)以上且未滿19.6 N(與鉻酸鹽處理材料相同)
△:1.96 N(0.2 kgf)以上且未滿3.92 N
×:未滿1.96 N(0.2 kgf)
耐蝕性:於鍍錫鋼板上以附著量50 mg/dm2
之方式塗佈環氧酚醛系塗料後,於210℃下進行10分鐘之燒製。繼而,於市售之番茄汁中於60℃下浸漬10日,目視評價塗膜之剝離、有無產生鏽,若為○或者◎,則認為耐蝕性良好。
◎:塗膜未剝離,未產生鏽
○:塗膜未剝離,產生可忽略之點狀鏽(與鉻酸鹽處理材料相同)
△:塗膜未剝離,產生微小之鏽
×:塗膜剝離,產生鏽
結果示於表2。可知藉由本發明之製造方法所製造之鍍錫鋼板No.1~18中,剛製造後及長期保管後之外觀均良好,長期保管後之Sn的氧化膜量亦少,且塗料密著性及耐蝕性優異。
根據本發明,可製造即使不使用環境上造成問題之Cr,亦可抑制因鍍錫表面之氧化而引起之外觀劣化或塗料密著性降低,且可低價地進行化學轉化處理之鍍錫鋼板。且,本發明之鍍錫鋼板之化學轉化處理皮膜與現狀之鉻酸鹽處理之情況相同,可以300 m/分鐘以上之高速的線速來形成,故而可對產業作出較大貢獻。
Claims (5)
- 一種鍍錫鋼板之製造方法,其特徵在於:於鋼板之至少單面上,以Sn之附著量為每單面0.05~20g/m2 之方式形成含Sn之鍍敷層後,於含有60~200g/L之磷酸二氫鋁(monobasic aluminum phosphate)、且pH值為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以10A/dm2 以下之電流密度實施陰極電解處理,繼而進行乾燥而形成化學轉化處理皮膜,在上述化學轉化處理液中施行浸漬處理或施行陰極電解處理之時間係未滿1秒。
- 如申請專利範圍第1項之鍍錫鋼板之製造方法,其中,形成包含Sn層之鍍敷層、或Fe-Sn層與Sn層依序積層而成之鍍敷層中之任一種鍍敷層,作為含Sn之鍍敷層。
- 如申請專利範圍第1項之鍍錫鋼板之製造方法,其中,於未滿60℃之溫度下進行乾燥。
- 如申請專利範圍第2項之鍍錫鋼板之製造方法,其中,於未滿60℃之溫度下進行乾燥。
- 如申請專利範圍第1至4項中任一項之鍍錫鋼板之製造方法,其中,將化學轉化處理液之溫度設定為70℃以上而實施陰極電解處理。
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KR101318545B1 (ko) | 2013-10-16 |
MX353528B (es) | 2018-01-18 |
US20110091741A1 (en) | 2011-04-21 |
US20140079886A1 (en) | 2014-03-20 |
JP5633117B2 (ja) | 2014-12-03 |
KR20100124351A (ko) | 2010-11-26 |
MX2010011889A (es) | 2011-01-25 |
JP2009299183A (ja) | 2009-12-24 |
WO2009139480A1 (ja) | 2009-11-19 |
TW201002871A (en) | 2010-01-16 |
CA2721979A1 (en) | 2009-11-19 |
MY155420A (en) | 2015-10-15 |
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