[0022] 如專利文獻1及專利文獻2所記載般，將Ni、Co、及In等元素添加於鋅鍍覆層之鉻酸鹽處理鋅電鍍鋼板，必須考量與鋅鍍覆層中作為雜質所存在之Pb、Cu、Ag等之使耐蝕性劣化之元素的均衡。此外，此鉻酸鹽處理鋅電鍍鋼板，即使調整該均衡，亦會因腐蝕環境下之金屬元素的價數變化及金屬的溶出等，而產生變色不均或白色度的降低等，有時會產生外觀不良。此外，鉻酸鹽處理鋅電鍍鋼板，當將Ni、Co、及In等元素添加於鋅鍍覆層而過度促進氧化反應時，有時使耐蝕性顯著降低而產生白鏽，或是變得容易產生滲透狀（黑褐色或灰褐色）的不均（以下稱為滲污）。 [0023] 如專利文獻3及專利文獻4所記載之鋅鍍覆鋼板，與專利文獻1及專利文獻2所記載之鉻酸鹽處理鋅電鍍鋼板相同，亦會因腐蝕環境下之金屬元素的價數變化及金屬的溶出等，而產生變色不均或產生白色度的降低等，有時會產生外觀不良。 [0024] 此外，考量耐蝕性、耐黑變性、與鋅鍍覆表面之密著性，以及鋼板的導電性等之均衡，亦可考量於鋅系鍍覆鋼板，例如於專利文獻1~4所記載之鋅系鍍覆鋼板上，進一步以約0.5~1μm的薄膜來形成富含無機物的皮膜或富含有機物的皮膜，作為表面處理皮膜。具體而言，可考量設置專利文獻5及專利文獻6所記載之皮膜，作為表面處理皮膜。 [0025] 然而，僅僅設置此表面處理皮膜，有時無法充分地抑制黑變現象，此外，不僅無法充分地抑制黑變現象，有時亦容易產生滲污。 [0026] 此外，尤其在高溫多濕的環境下所容易產生之滲污，會顯著地損及製品的外觀，使製品的價值降低。因此，不僅黑變現象，亦進一步要求抑制滲污的產生。 [0027] 根據本發明者們的探討，即使於鋅系鍍覆鋼板上形成表面處理皮膜，有時亦無法充分地抑制黑變現象之理由，可推測為下述理由。 [0028] 首先，如第1圖A所示，即使將表面處理皮膜11設置在鋅系鍍覆鋼板12，氧穿透性或水穿透性等之阻障性，有時會不徹底地提升。此時，如第1圖B所示，在往鋅系鍍覆鋼板12的表面之氧的供給為不足之狀態下引起氧化反應，而如上述般，於鋅系鍍覆鋼板12上生成不定形氧化物13。亦即，將表面處理皮膜11設置在鋅系鍍覆鋼板12之表面處理金屬板10，係產生黑變現象。第1圖A為顯示於鋅系鍍覆鋼板12上設置有表面處理皮膜11之表面處理金屬板10之概略圖。此外，第1圖B為顯示於第1圖A所示之表面處理金屬板10上生成有不定形氧化物13之狀態之概略圖。 [0029] 此外，於鋅系鍍覆鋼板上設置有表面處理皮膜之表面處理金屬板，不僅黑變現象，有時亦無法充分地抑制滲污的產生。滲污，可考量由於在高溫多濕環境下表面處理皮膜的阻障性降低，使成為黑變現象的原因之腐蝕反應加速進行，並由此腐蝕反應的加速進行所產生者。至本發明之探討中，係發現到滲污的產生並不限於此情形，亦可能以不同機制來產生。具體如以下內容。 [0030] 首先，當表面處理皮膜含有膠體二氧化矽時，乃著眼於無法充分地抑制滲污的產生者。將具備此表面處理皮膜之表面處理金屬板，例如放置在設定於溫度65℃、濕度95%的環境之恆溫恆濕試驗機內168小時，使其產生滲污。於產生滲污之表面處理金屬板之滲污產生部分的表面處理皮膜上劃線，使用電子束微分析儀（EPMA、日本電子股份有限公司製的JXA-8100）來實施面分析（映照/視野8×8mm）。經此分析之結果，可得知於產生滲污之部分上，Na元素濃化。從該結果中，本發明者推測滲污的原因在於Na元素的存在者。對於此Na元素濃化之原因進一步探討，本發明者係著眼於表面處理皮膜所含有之膠體二氧化矽，並推測以下內容作為產生滲污之機制。 [0031] 首先，在高溫多濕的環境下等，由於在設置有表面處理皮膜之鋅鍍覆層的表面上之極初期的腐蝕，而形成局部電池。表面處理皮膜所含有之膠體二氧化矽，一般而言，如第2圖所示，較多是含有鈉作為分散劑者，亦即為藉由Na離子達到穩定化之膠體二氧化矽。此係由於膠體二氧化矽一般是以矽酸鈉為原料所製造，並藉由陽離子交換來去除大部分的鈉，但鈉是用以形成SiO2
的穩定溶膠所使用，所以難以完全去除之故。第2圖為顯示膠體二氧化矽的狀態之概略圖。當表面處理皮膜含有此膠體二氧化矽時，於表面處理皮膜中含有來自膠體二氧化矽之Na元素。然後，此表面處理皮膜所含有之來自膠體二氧化矽之Na元素，於電池的陰極部濃化，緩慢地促進初期的腐蝕，而在鋅鍍覆層上生成不定形氧化物（不定形氧化鋅）。亦即，如第3圖A所示，將含有膠體二氧化矽14之表面處理皮膜11設置在鋅系鍍覆鋼板12上之表面處理金屬板10中，膠體二氧化矽14所含有之Na離子，往鋅系鍍覆鋼板12的鋅鍍覆層表面移動，且部分地形成不定形氧化物13。然後，當以此不定形氧化物13為起點使腐蝕進行時，如第3圖B所示，不定形氧化物13於鋅系鍍覆鋼板12與表面處理皮膜11之界面上以不均勻狀來擴散。此擴散為不均勻狀之不定形氧化物13，被觀看為滲污狀。根據此機制，可推測為於上述具備含有膠體二氧化矽之表面處理皮膜之表面處理金屬板中產生滲污。第3圖A為顯示於鋅系鍍覆鋼板12上設置有表面處理皮膜11之表面處理金屬板10上，開始產生滲污之狀態之概略圖。此外，第3圖B為顯示於鋅系鍍覆鋼板12上設置有表面處理皮膜11之表面處理金屬板10上，滲污擴散之狀態之概略圖。 [0032] 因此，本發明者係考量到當減少表面處理皮膜中所含有之Na元素的量時，如第4圖所示，可減少部分地形成之不定形氧化物13，其結果可有效地抑制滲污。第4圖為顯示於鋅系鍍覆鋼板12上設置有表面處理皮膜11之表面處理金屬板10上，抑制滲污的產生後之狀態之概略圖。 [0033] 此外，前述表面處理組成物中作為基質所含有之水系乳化液，於乳化液生成時使用氨作為中和劑時，於表面處理組成物中含有氨。並發現到此氨與鋅鍍覆層反應而部分地生成氧化鋅（ZnO）或氫氧化鋅（Zn(OH)2
）等，而進一步促進耐蝕性的劣化、黑變、及滲污的產生。 [0034] 因此，本發明者係考量到當使用不含氨者，作為形成表面處理皮膜時所使用之表面處理組成物所含有之樹脂時，表面處理組成物所含有之氨的量少，可提高耐蝕性、耐黑變性、及耐滲污性。 [0035] 本發明者根據上述探討內容，完成以下所述之本發明。本發明者進行各種探討，結果發現到提供一種耐黑變性優異，且可充分地抑制滲污的產生之表面處理金屬板之上述目的，可藉由以下本發明來達成。 [0036] 本發明的一實施形態之表面處理金屬板，如第1圖A及第3圖A等所示，具備：鋅系鍍覆鋼板12，以及層合於前述鋅系鍍覆鋼板12之至少一者的表面上之表面處理皮膜11。此表面處理皮膜11是由：含有不含氨的聚烯烴系樹脂與平均粒徑為4~6nm的膠體二氧化矽之表面處理組成物所構成。前述膠體二氧化矽的含量，相對於前述表面處理組成物100質量份為10質量份以上且未達30質量份。此外，前述表面處理皮膜的附著量為0.4~1.2 g/m2
。此外，浸漬在70~80℃的脫離子水10分鐘時之從前述表面處理皮膜所溶出之鈉離子的量為4 mg/m2
以下。 [0037] 此表面處理金屬板，其耐黑變性優異，且可充分地抑制滲污的產生。此外，與鋅鍍覆層之密著性亦優異。此可考量依據以下內容者。 [0038] 首先，此表面處理皮膜11，由於含有不含氨的聚烯烴系樹脂，所以前述表面處理組成物所含有之氨的量少。因此，可考量能夠抑制由氨與鋅鍍覆層反應所造成之耐蝕性的降低、黑變及滲污的產生。再者，由於所含有之膠體二氧化矽的平均粒徑為較小的4~6nm，所以膠體二氧化矽的分散性及活性度高，表面處理皮膜的阻障性高，可提高耐蝕性，並且亦可提高與鋅鍍覆層之密著性。以相對於前述表面處理組成物100質量份成為10質量份以上且未達30質量份之方式含有此膠體二氧化矽，並且以附著量成為0.4~1.2 g/m2
之方式形成表面處理皮膜，如此可較佳地發揮提高耐蝕性或與鋅鍍覆層之密著性等之含有膠體二氧化矽之效果。再者，此表面處理皮膜，浸漬在70~80℃的脫離子水10分鐘時之從前述表面處理皮膜所溶出之鈉離子的量為4 mg/m2
以下。如此，從表面處理皮膜所溶出之鈉離子的量少時，如上述般，可抑制滲污的產生。從此等內容來看，本實施形態之表面處理金屬板，其耐黑變性優異，且可充分地抑制滲污的產生。此外，與鋅鍍覆層之密著性（耐膠帶剝離性）亦優異。 [0039] 前述鋅系鍍覆鋼板，並無特別限定，可為鋅單獨鍍覆鋼板，或是鋅-Ni、鋅-Fe、及鋅-Al等之鋅系合金鍍覆鋼板。鍍覆法亦無特別限定，可為熔融鍍覆法、電解鍍覆法、及蒸鍍鍍覆法等之任一種所得到之鋅鍍覆鋼板。前述鋅系鍍覆鋼板，具體可列舉出熔融鋅鍍覆鋼板（GI）、合金化熔融Zn-Fe鍍覆鋼板（GA）、合金化熔融Zn-5%Al鍍覆鋼板（GF）、鋅電鍍鋼板（EG）、Zn-Ni合金電鍍鋼板等。此等當中，較佳為鋅電鍍鋼板（EG）。 [0040] 前述表面處理皮膜，如上述般是由：含有不含氨的聚烯烴系樹脂與平均粒徑為4~6nm的膠體二氧化矽之表面處理組成物所構成。 [0041] 前述聚烯烴系樹脂，只要是不含氨的聚烯烴系樹脂即可，並無特別限定。前述聚烯烴系樹脂，具體可列舉出不含氨且經乳化之聚烯烴系樹脂，亦即於乳化製造時不使用氨作為中和劑之經乳化之聚烯烴系樹脂等。此外，此聚烯烴系樹脂，例如可列舉出含有有機鹼性胺及金屬離子的至少一者且經乳化之聚烯烴系樹脂。亦即，前述聚烯烴系樹脂，可列舉出於乳化製造時使用有機鹼性胺及金屬離子的至少一者作為中和劑且經乳化之聚烯烴系樹脂等。如此，若為如此之不含氨且經乳化之聚烯烴系樹脂等之不含氨的聚烯烴系樹脂，則可抑制使用含氨且經乳化之聚烯烴系樹脂時所生成之氧化鋅（ZnO）或氫氧化鋅（Zn(OH)2
）等的產生。因此可促進耐蝕性的劣化、黑變、及滲污的產生。 [0042] 此外，前述聚烯烴系樹脂，只要是不含氨的聚烯烴系樹脂即可，並無特別限定，形成為薄膜狀時之水蒸氣穿透度，較佳為100 g/m2
/日以下，更佳為50 g/m2
/日以下。前述水蒸氣穿透度，例如為以JIS K 7129所定義之水蒸氣穿透度。該測定方法，例如可列舉出：製作約18μm的薄膜，並藉由依據JIS Z 0208之杯測法來測定該薄膜的水蒸氣穿透度之方法等。若是前述水蒸氣穿透度過大之樹脂，當欲添加前述膠體二氧化矽來提高耐蝕性等時，所得到之表面處理皮膜的水蒸氣穿透度過高，有時無法得到耐蝕性提升的效果。 [0043] 此外，前述聚烯烴系樹脂，只要是不含氨的聚烯烴系樹脂即可，並無特別限定，較佳為含有α,β-不飽和羧酸與烯烴之共聚物（烯烴-α,β-不飽和羧酸共聚物）。此外，前述烯烴-α,β-不飽和羧酸共聚物，可考量其來自α,β-不飽和羧酸的構成單位發揮提升鋅鍍覆與表面處理皮膜之密著性之作用。因此，藉由含有前述烯烴-α,β-不飽和羧酸共聚物，可在不損及前述表面處理組成物中之前述膠體二氧化矽的分散穩定性下，提升前述表面處理皮膜的阻障性。因此，可降低前述表面處理皮膜之水及氧的滲透，而更進一步提升耐蝕性及耐黑變性。 [0044] 前述烯烴-α,β-不飽和羧酸共聚物（以下亦僅稱為「烯烴-酸共聚物」）為α,β-不飽和羧酸與烯烴之共聚物。此外，在此之烯烴-酸共聚物，其來自烯烴的構成單位，於前述烯烴-酸共聚物中，較佳為50質量%以上。亦即，前述烯烴-酸共聚物，其來自α,β-不飽和羧酸的構成單位，於前述烯烴-酸共聚物中，較佳為50質量%以下。 [0045] 前述烯烴-酸共聚物，只要使烯烴與α,β-不飽和羧酸共聚合即可，可藉由已知的方法使烯烴與α,β-不飽和羧酸共聚合而製造。此外，前述烯烴-酸共聚物，於市面上亦有販售。 [0046] 可使用在前述烯烴-酸共聚物的製造之烯烴，並無特別限定，較佳為乙烯及丙烯等，尤佳為乙烯。前述烯烴-酸共聚物，其來自前述烯烴的構成單位，可僅來自1種烯烴，或是來自2種以上的烯烴。 [0047] 可使用在前述烯烴-酸共聚物的製造之α,β-不飽和羧酸，並無特別限定，可列舉出乙烯性α,β-不飽和羧酸等。此α,β-不飽和羧酸，具體可列舉出丙烯酸、甲基丙烯酸、巴豆酸、及異巴豆酸等之單羧酸，順丁烯二酸、反丁烯二酸、及伊康酸等之二羧酸等。前述α,β-不飽和羧酸，可單獨使用1種或組合2種以上而使用。前述α,β-不飽和羧酸，於上述例示的化合物中，較佳為丙烯酸、甲基丙烯酸，尤佳為丙烯酸。前述烯烴-酸共聚物，其來自前述α,β-不飽和羧酸的構成單位，可僅來自1種α,β-不飽和羧酸，或是來自2種以上的α,β-不飽和羧酸。 [0048] 前述烯烴-酸共聚物中之來自前述α,β-不飽和羧酸的構成單位，如上述般，可考量其發揮提升鋅鍍覆與表面處理皮膜之密著性之作用。為了有效地發揮此作用，前述烯烴-酸共聚物，來自前述α,β-不飽和羧酸的構成單位，於前述烯烴-酸共聚物中，較佳為5質量%以上，尤佳為10質量%以上。此外，來自前述α,β-不飽和羧酸的構成單位之含量的上限，如上述般，較佳為50質量%以下，從耐蝕性之觀點來看，尤佳為30質量%以下，更佳為25質量%以下。 [0049] 前述烯烴-酸共聚物，在可達到本發明的效果之範圍內，具體而言，在不會過度降低耐蝕性及耐黑變性等且不會未充分達到本發明的效果之範圍內，可含有來自前述烯烴及前述α,β-不飽和羧酸以外之單體（其他單體）的構成單位。來自其他單體的構成單位，於前述烯烴-酸共聚物中，較佳為10質量%以下，尤佳為5質量%以下，最佳為0質量%。亦即，最佳者為僅由來自前述烯烴的構成單位與來自前述α,β-不飽和羧酸的構成單位所構成之共聚物。此外，前述烯烴-酸共聚物，具體而言，較佳為乙烯-丙烯酸共聚物。 [0050] 此外，前述烯烴-酸共聚物，可單獨使用上述烯烴-酸共聚物中的1種或組合2種以上而使用。 [0051] 前述烯烴-酸共聚物，由於在分子內具有羧基，故藉由前述有機鹼性胺或金屬離子來中和，可將前述聚烯烴系樹脂乳化（水分散體化）。 [0052] 於乳化製造時用作為中和劑之有機鹼性胺，並無特別限定，沸點較佳為100℃以下，尤佳為90℃以下。若沸點位於上述範圍內，則在形成表面處理皮膜時之乾燥中，會揮發而不易殘存於所形成之表面處理皮膜，所以前述有機鹼性胺不易成為耐蝕性及耐黑色性的降低或滲污的產生之原因。因此可得到耐蝕性、耐黑色性及耐滲污性更優異之表面處理金屬板。此外，前述有機鹼性胺的沸點，從作業性之觀點來看，較佳為70℃以上，尤佳為80℃以上。 [0053] 前述有機鹼性胺，具體可列舉出三乙胺、N,N-二甲基丁胺、N,N-二甲基烯丙胺、N-甲基吡咯啶、四甲基二胺基甲烷、及三甲胺等之三級胺；N-甲基乙胺、二異丙胺、及二乙胺等之二級胺；丙胺、三級丁胺、二級丁胺、異丁胺、1,2-二丁基丙胺、及3-戊胺等之一級胺等。前述有機鹼性胺，於上述所例示之胺中，較佳為三級胺，尤佳為三乙胺。此外，前述有機鹼性胺，可單獨使用1種或組合2種以上而使用。 [0054] 前述有機鹼性胺的用量，只要使前述聚烯烴系樹脂較佳地乳化者即可，並無特別限定。前述有機鹼性胺的用量，例如相對於前述烯烴-酸共聚物中的羧基1莫耳，較佳為0.2~0.8莫耳（相對於前述羧基為20~80莫耳%）。此外，前述有機鹼性胺之用量的下限，相對於前述羧基1莫耳，較佳為0.2莫耳以上，尤佳為0.3莫耳以上。此外，前述有機鹼性胺之用量的上限，相對於前述羧基1莫耳，較佳為0.8莫耳以下，尤佳為0.6莫耳以下，更佳為0.5莫耳以下。若前述有機鹼性胺的用量為上述範圍內，則可達到表面處理鋼板的耐蝕性、耐黑變性、及與鋅鍍覆層之密著性（耐膠帶剝離性）優異之效果。此外，當前述有機鹼性胺的用量過少時，乳化中之聚烯烴系樹脂的粒子變大，而有難以達到該效果之傾向。此外，當前述有機鹼性胺的用量過多時，乳化液變黏，而有凝膠化之疑慮。 [0055] 此外，於前述乳化製造時用作為中和劑之金屬離子，並無特別限定，從表面處理皮膜的硬度提升之觀點來看，較佳為1價的金屬離子。前述金屬離子，具體而言，較佳為含有鈉離子、鉀離子、及鋰離子之至少1種。於前述表面處理組成物中生成此金屬離子之化合物，可列舉出包含此等金屬離子之氫氧化物、碳酸化物、及氧化物等。此化合物，具體可列舉出氫氧化鈉離、氫氧化鉀、及氫氧化鋰等，當中較佳為氫氧化鈉。 [0056] 於前述表面處理組成物中生成前述金屬離子之化合物的用量，只要使前述聚烯烴系樹脂較佳地乳化者即可，並無特別限定。前述化合物的用量，例如相對於前述烯烴-酸共聚物中的羧基1莫耳，較佳為0.02~0.4莫耳（相對於前述羧基為2~40莫耳%）。此外，前述化合物之用量的下限，相對於前述羧基1莫耳，較佳為0.02莫耳以上，尤佳為0.03莫耳以上，更佳為0.1莫耳以上。此外，前述化合物之用量的上限，相對於前述羧基1莫耳，較佳為0.4莫耳以下，尤佳為0.2莫耳以下。當前述化合物的用量過少時，會有乳化穩定性不足之傾向。此外，當前述化合物的用量過多時，耐蝕性有降低之傾向。 [0057] 於前述表面處理組成物中生成前述有機鹼性胺與前述金屬離子之化合物之各用量的較佳範圍如上所述，但此等皆用以中和前述烯烴-酸共聚物中的羧基以使聚烯烴系樹脂乳化而使用。因此，當此等的合計量（中和量）過多時，有時乳化液的黏度急遽上升而固化。再者，過剩的鹼份，由於成為耐蝕性或耐黑變性劣化的原因，所以使該鹼份揮發需耗費較多能量，故不佳。另一方面，當此等的合計量（中和量）過少時，乳化性會有不足之疑慮。從此等內容來看，於前述表面處理組成物中生成前述有機鹼性胺與前述金屬離子之化合物的合計量，相對於前述烯烴-酸共聚物中的羧基1莫耳，較佳0.3~1.0莫耳（相對於前述羧基為30~100莫耳%）。 [0058] 含有有機鹼性胺及金屬離子的至少一者且經乳化之聚烯烴系樹脂，藉由離子團簇來形成分子間聚集，而形成耐蝕性、耐黑變性、及與鋅鍍覆層之密著性（耐膠帶剝離性）等優異之表面處理皮膜。前述表面處理組成物中，為了形成更強韌的表面處理皮膜，可含有：藉由利用了官能基間反應之化學鍵，使聚烯烴系樹脂彼此交聯之交聯劑。此交聯劑為用以使聚烯烴系樹脂交聯之交聯劑，亦即，內部交聯劑為於乳化製作時使構成乳化之樹脂交聯之交聯劑，在此亦稱為內部交聯劑。 [0059] 前述內部交聯劑，只要可使聚烯烴系樹脂彼此交聯者即可，並無特別限定，例如可列舉出於分子內具有2個以上之可與羧基反應的官能基之交聯劑等。前述內部交聯劑，具體可列舉出於分子內具有2個以上的縮水甘油基之含縮水甘油基交聯劑，以及於分子內具有2個以上的氮丙啶基之含氮丙啶基交聯劑等。前述含縮水甘油基交聯劑，例如可列舉出山梨醇聚縮水甘油醚、（聚）甘油聚縮水甘油醚、新戊四醇聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、新戊二醇二縮水甘油醚、（聚）乙二醇二縮水甘油醚等之聚縮水甘油醚類；聚縮水甘油醚胺類等。此外，含氮丙啶基交聯劑，例如可列舉出4,4’-雙（乙烯亞胺基羰基胺基）二苯基甲烷、N,N’-六亞甲基-1,6-雙（1-氮丙啶羧基醯胺）、N,N’-二苯基甲烷-4,4’-雙（1-氮丙啶羧基醯胺）、及甲苯雙氮丙啶羧基醯胺等之2官能的氮丙啶化合物；三-1-氮丙啶基膦氧化物、三[1-（2-甲基）氮丙啶基]膦氧化物、三羥甲基丙烷三（β-氮丙啶基丙酸酯）、三-2,4,6-（1-氮丙啶基）-1,3,5-三嗪、及四甲基丙烷四氮丙啶基丙酸酯等之3官能以上的氮丙啶化合物；以及前述氮丙啶化合物的衍生物等。前述內部交聯劑，於例示的交聯劑中，較佳為2官能以上的氮丙啶化合物，尤佳為2官能的氮丙啶化合物，更佳為4,4’-雙（乙烯亞胺基羰基胺基）二苯基甲烷。此外，前述內部交聯劑，可單獨使用1種或組合2種以上而使用。 [0060] 前述內部交聯劑的用量，相對於前述聚烯烴系樹脂，較佳為1~20質量%，尤佳為5~10質量%。在此之用量為相對於前述聚烯烴系樹脂的固體成分100質量%之比率。當前述內部交聯劑過少時，會有無法充分地發揮添加前述內部交聯劑之效果之傾向。亦即，由化學鍵所帶來之交聯的效果不足，而有難以發揮耐蝕性或耐膠帶剝離性的提升效果之傾向。另一方面，當前述內部交聯劑過多時，表面處理皮膜的交聯密度過高，硬度上升，變得無法跟隨表面處理金屬板之模壓加工時的變形，因而產生龜裂，其結果有導致耐蝕性的降低之疑慮。 [0061] 前述烯烴系樹脂的添加量，於前述表面處理組成物中，較佳為前述烯烴系樹脂構成後述膠體二氧化矽、使表面處理皮膜交聯之交聯劑、以及潤滑劑等之以外的剩餘部分者，只要是該添加量即可，並無特別限定。前述烯烴系樹脂的添加量，例如相對於前述表面處理組成物100質量份較佳為56.5~90質量份。在此之添加量為固體成分比。 [0062] 前述膠體二氧化矽，首先，該平均粒徑為4~6nm。此外，前述膠體二氧化矽，根據上述考察，係要求從前述表面處理皮膜所溶出之鈉離子的量少。前述膠體二氧化矽，具體而言，係浸漬在70~80℃的脫離子水10分鐘時之從前述表面處理皮膜所溶出之鈉離子的量（溶出量）為4 mg/m2
以下之膠體二氧化矽。前述膠體二氧化矽，只要是此膠體二氧化矽即可，並無特別限定。 [0063] 作為前述膠體二氧化矽，具體而言，較佳為包含含有氨作為分散劑之膠體二氧化矽。此含有氨作為分散劑之膠體二氧化矽，亦即，以NH4 +
離子達到穩定化之膠體二氧化矽（氨穩定化型式），市面上有所販售。藉由使用此含有氨作為分散劑之膠體二氧化矽，與上述般僅使用一般膠體二氧化矽之含有鈉作為分散劑之膠體二氧化矽（鈉穩定化型式）時相比，可減少前述表面處理皮膜中之鈉的量。因此，可得到減少前述溶出量之表面處理皮膜。 [0064] 前述膠體二氧化矽，首先如上述般，該平均粒徑為4~6nm。當膠體二氧化矽過大時，耐蝕性或耐剝離性等降低，此外，與塗裝於表面處理金屬板上之塗膜之密著性（塗裝性）亦有降低之傾向。此可考量由於表面處理皮膜中之膠體二氧化矽的分散性及活性度降低，所以表面處理皮膜的阻障性降低，於腐蝕環境下之膠體二氧化矽的溶出量降低之故。因此，藉由使用上述粒徑的膠體二氧化矽，可得到表面處理皮膜的耐蝕性、塗裝性、耐膠帶剝離性、皮膜硬度、及加工性優異之表面處理金屬板。平均粒徑為4~6nm之膠體二氧化矽，具體可列舉出日產化學工業股份有限公司製的Snowtex NXS（ST-NXS、氨穩定化型式）、及Snowtex XS（ST-XS、鈉穩定化型式）等。使用鈉穩定化型式的ST-XS時，較佳與氨穩定化型式的ST-NXS併用。在此之膠體二氧化矽的平均粒徑，例如可列舉出當平均粒徑為1~10nm左右時，藉由Sears滴定法，平均粒徑為10~100nm左右時，藉由BET法所測定之值等。此外，於製造者的手冊中記載有公證值時，可將此公證值用作為在此之膠體二氧化矽的平均粒徑。 [0065] 此外，浸漬在70~80℃的脫離子水10分鐘時之從前述表面處理皮膜所溶出之鈉離子的量（溶出量），如上述般較少者為佳，藉由本發明者的探討，可得知若為4 mg/m2
以下，則可較佳地抑制滲污。此溶出量尤佳為3.8 mg/m2
以下，更佳為3.5 mg/m2
以下。若為此範圍內，則不僅可較佳地抑制滲污，並且亦可提升耐蝕性、耐黑變性、及耐膠帶剝離性等。此外，前述溶出量愈少愈佳，但在膠體二氧化矽的特質上，1 mg/m2
左右為臨限，前述溶出量的下限值較佳為1 mg/m2
以上。在此之溶出量，例如可列舉出以下述方式所測定之值等。將表面處理金屬板浸漬在70~80℃的脫離子水10分鐘。使用離子層析儀來測定浸漬有此表面處理金屬板之液體所含有之鈉離子的量。從所測定之鈉離子的量與表面處理金屬板的面積來算出溶出量。離子層析儀，例如可使用Thermo Fisher Scientific股份有限公司製的ICS-5000+等。 [0066] 此外，前述膠體二氧化矽之添加量的下限，相對於前述表面處理組成物100質量份為10質量份以上，較佳為15質量份以上，尤佳為20質量份以上。此外，前述膠體二氧化矽之添加量的上限，相對於前述表面處理組成物100質量份為未達30質量份較佳為28質量份以下。在此之添加量為固體成分比。藉由將膠體二氧化矽添加於表面處理皮膜以提升耐蝕性或耐黑變性之理由，可推測為起因於膠體二氧化矽在腐蝕環境下溶解並溶出，而產生pH的緩衝作用或惰態皮膜形成作用者。因此，當膠體二氧化矽的添加量過少時，無法充分發揮該作用，使耐蝕性降低，與鋅鍍覆表面之密著性亦有降低之傾向。此外，當膠體二氧化矽的添加量過多時，由於樹脂的添加量變少，表面處理皮膜變脆，而有容易產生龜裂之傾向。因此，耐黑變性降低，與鋅鍍覆表面之密著性亦降低，並且塗裝性亦可能降低。因此，當前述膠體二氧化矽的添加量位於上述範圍內時，可得到耐蝕性以及與鋅鍍覆表面之密著性等為優異之表面處理金屬板。 [0067] 此外，於前述表面處理皮膜中，除了前述樹脂及前述膠體二氧化矽之外，較佳為含有使表面處理皮膜交聯之交聯劑、以及潤滑劑。 [0068] 前述交聯劑，藉由含有其，可提高表面處理皮膜的耐蝕性、耐膠帶剝離性、及潤滑性。此交聯劑為使表面處理皮膜交聯之交聯劑，亦即於形成表面處理皮膜時，使構成表面處理皮膜之樹脂交聯之交聯劑，在此亦稱為外部交聯劑。 [0069] 前述外部交聯劑，只要可使表面處理皮膜交聯者即可，並無特別限定，從反應性之觀點來看，可較佳地使用環氧系交聯劑。前述環氧系交聯劑，例如可列舉出山梨醇聚縮水甘油醚、（聚）甘油聚縮水甘油醚、新戊四醇聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、新戊二醇二縮水甘油醚、及（聚）乙二醇二縮水甘油醚等之聚縮水甘油醚類；聚縮水甘油醚胺類等。此環氧系交聯劑，例如可取得DIC股份有限公司製的Epiclon CR5L、及Epiclon CR75等。此外，前述外部交聯劑，可單獨使用1種或組合2種以上而使用。 [0070] 此外，前述外部交聯劑的添加量並無特別限定，該下限，例如相對於前述表面處理組成物100質量份較佳為5質量份以上，尤佳為6.5質量份以上。此外，前述外部交聯劑之添加量的上限，相對於前述表面處理組成物100質量份較佳為8.5質量份以下。在此之添加量為固體成分比。當前述外部交聯劑的添加量過少時，耐蝕性、耐黑變性、耐膠帶剝離性、及潤滑性有降低之傾向。此外，當前述外部交聯劑的添加量過多時，塗裝性有降低之傾向。此外，當過度添加前述外部交聯劑時，可考量到外部交聯劑產生自我交聯，但當前述外部交聯劑的添加量為上述範圍內時，亦可抑制此情形而較佳地進行交聯反應。亦即，當前述外部交聯劑的添加量為上述範圍內時，交聯反應充分地進行，可提升表面處理皮膜的耐蝕性及耐黑變性。再者，表面處理皮膜的硬度亦提高，所以亦提升潤滑性或加工性。 [0071] 前述潤滑劑，藉由含有其，可降低表面處理皮膜的動摩擦係數，提升加工性，且亦不易形成損傷。 [0072] 前述潤滑劑並無特別限定，例如可列舉出聚乙烯、氧化聚乙烯、及聚丙烯等之聚烯烴系蠟；聚四氟乙烯、聚氟乙烯、聚偏二氟乙烯、及四氟乙烯等之氟樹脂；有機改質聚矽氧烷；石蠟等。前述潤滑劑，於上述例示中，較佳為聚烯烴系蠟，尤佳為聚乙烯蠟。此外，前述潤滑劑，可單獨使用1種或組合2種以上而使用。 [0073] 此外，聚乙烯蠟較佳為粒子狀者，例如為球形，且該平均粒徑較佳為0.1~3μm，尤佳為0.3~1μm。當此聚乙烯蠟粒子（球形聚乙烯蠟）過大時，於表面處理組成物中難以均一地分散，阻礙造膜性，而有耐蝕性降低之傾向。另一方面，當前述聚乙烯蠟粒子過小時，會有無法充分地提高潤滑性之傾向。聚乙烯蠟粒子的平均粒徑，可藉由柯特粒子計數器法來測定。藉由使用上述粒徑的聚乙烯蠟粒子，於表面處理皮膜上以球狀所存在，可有效地降低表面處理皮膜表面上的摩擦，對於抑制損傷的產生等為有效。此聚乙烯蠟粒子，例如可列舉出三井化學股份有限公司製的Chemipearl W640、Chemipearl W700、Chemipearl W950、及Chemipearl W900等。 [0074] 此外，前述潤滑劑的添加量並無特別限定，該下限，例如相對於前述表面處理組成物100質量份較佳為2質量份以上，尤佳為2.5質量份以上。此外，前述潤滑劑之添加量的上限，相對於前述表面處理組成物100質量份較佳為5質量份以下，尤佳為4質量份以下。在此之添加量為固體成分比。當前述潤滑劑的添加量過少時，潤滑性不足，表面處理金屬板的彎曲加工性等有降低之傾向。此外，當前述潤滑劑的添加量過多時，於腐蝕環境下會引起潤滑劑的水解等，耐蝕性、耐黑變性、耐滲污性、耐膠帶剝離性、及塗裝性等有降低之傾向。因此，當前述潤滑劑的添加量為上述範圍內時，可得到耐蝕性、耐黑變性、及耐滲污性等為優異之表面處理金屬板。 [0075] 前述表面處理皮膜之附著量的下限為0.4 g/m2
以上，較佳為0.45 g/m2
以上，尤佳為0.5 g/m2
以上。此外，前述表面處理皮膜之附著量的上限為1.2 g/m2
以下，較佳為0.8 g/m2
以下，尤佳為0.7 g/m2
以下。當前述表面處理皮膜的附著量過少時，阻障性劣化而促進滲透的擴散，耐滲污性有劣化之傾向。此外，當前述表面處理皮膜的附著量過少時，會有無法充分地提升表面處理金屬板的耐蝕性、耐黑變性、及耐膠帶剝離性等之傾向。此外，當前述表面處理皮膜的附著量過多時，耐膠帶剝離性降低，例如在對表面處理金屬板進行彎曲加工或模壓加工等時，表面處理皮膜有容易剝離之傾向。此外，塗裝性或導電性亦有降低之傾向，故不佳。因此，當前述表面處理皮膜的附著量位於上述範圍內時，可得到耐蝕性及耐黑變性等為優異之表面處理金屬板。表面處理皮膜的附著量，例如可藉由以下方式來測定。可藉由螢光X射線分析裝置來定量測定表面處理皮膜中之膠體二氧化矽（SiO2
）的Si元素，並從所測定之Si元素的量來算出。此時之SiO2
的比重設為2.2，樹脂的比重設為1.0來計算。 [0076] 前述表面處理金屬板，只要具備有前述鋅系鍍覆鋼板與前述表面處理皮膜即可，亦可具備其他層。例如，可在前述鋅系鍍覆鋼板與前述表面處理皮膜之間具備底層處理層。具體而言，為了提升鋅系鍍覆鋼板的表面與前述表面處理皮膜之界面密著性，可設置：藉由實施以磷酸二氫鋁、酸性膠體二氧化矽、及聚丙烯酸之組成物所構成之反應型的底層處理而得到之底層處理層。惟未反應的磷酸等，由於會使耐黑變性或耐蝕性劣化而促進滲污的產生，故較佳為水洗去除。形成前述底層處理層時所使用之組成物，例如磷酸二氫鋁與酸性膠體二氧化矽之含有比，以質量比（磷酸二氫鋁：膠體二氧化矽）計較佳為5：95~35：65。此外，聚丙烯酸，相對於磷酸二氫鋁與酸性膠體二氧化矽的合計100質量份較佳為含有1~10質量份。 [0077] 前述表面處理金屬板之製造方法，只要是可製造本實施形態之表面處理金屬板者即可，並無特別限定。前述表面處理金屬板之製造方法，具體可列舉出以下製造方法等，其係具備：調製前述表面處理組成物之步驟（調製步驟），及將前述表面處理組成物塗佈於前述鋅系鍍覆鋼板之至少一者的表面上之步驟（塗佈步驟），以及藉由使前述表面處理組成物乾燥，將前述表面處理皮膜形成於前述鋅系鍍覆鋼板之至少一者的表面上之步驟（乾燥步驟）。 [0078] 前述調製步驟，只要是可調製前述表面處理組成物者即可，並無特別限定，例如可列舉出：調製出含有不含氨且經乳化之聚烯烴系樹脂與平均粒徑為4~6nm的膠體二氧化矽之表面處理組成物之步驟等。此調製步驟，可列舉出：以使前述膠體二氧化矽的含量相對於前述表面處理組成物100質量份為10質量份以上且未達30質量份之方式，混合前述聚烯烴系樹脂與前述膠體二氧化矽之步驟等。此外，此調製步驟為調製出：浸漬在70~80℃的脫離子水10分鐘時之從前述表面處理皮膜所溶出之鈉離子的量為4 mg/m2
以下之表面處理組成物之步驟。具體而言，可列舉出使用上述含有氨作為分散劑之膠體二氧化矽，來作為前述膠體二氧化矽之方法等。 [0079] 前述塗佈步驟，只要是可將前述表面處理組成物塗佈於前述鋅系鍍覆鋼板之至少一者的表面上者即可，並無特別限定，例如可列舉出使用棒塗佈機之塗佈等。此外，前述塗佈步驟為以前述表面處理皮膜的附著量為0.4~1.2 g/m2
之方式，塗佈前述表面處理組成物之步驟。 [0080] 前述乾燥步驟，只要是藉由使前述表面處理組成物乾燥，將前述表面處理皮膜形成於前述鋅系鍍覆鋼板之至少一者的表面上者即可，並無特別限定。前述乾燥步驟，例如可列舉出90~130℃中的乾燥等。 [0081] 根據此製造方法，可較佳地製造本實施形態之表面處理金屬板。 [0082] 本說明書，如上所述，係已揭示各種樣態之技術，當中的主要技術係整理如下。 [0083] 本發明之一面向為一種表面處理金屬板，其係具備：鋅系鍍覆鋼板，以及層合於前述鋅系鍍覆鋼板之至少一者的表面上之表面處理皮膜；前述表面處理皮膜是由：含有不含氨的聚烯烴系樹脂與平均粒徑為4~6nm的膠體二氧化矽之表面處理組成物所構成；前述膠體二氧化矽的含量，相對於前述表面處理組成物100質量份為10質量份以上且未達30質量份；前述表面處理皮膜的附著量為0.4~1.2 g/m2
；浸漬在70~80℃的脫離子水10分鐘時之從前述表面處理皮膜所溶出之鈉離子的量為4 mg/m2
以下。 [0084] 根據此構成，可提供一種耐黑變性優異，且可充分地抑制滲污的產生之表面處理金屬板，亦即可提供一種耐黑變性及耐滲污性優異之表面處理金屬板。 [0085] 此外，於前述表面處理金屬板中，前述表面處理組成物較佳為進一步含有交聯劑及潤滑劑。 [0086] 根據此構成，可得到耐黑變性及耐滲污性更優異之表面處理金屬板。 [0087] 此外，於前述表面處理金屬板中，前述交聯劑的含量，相對於前述表面處理組成物100質量份較佳為5~8.5質量份。 [0088] 根據此構成，可得到耐黑變性及耐滲污性更優異之表面處理金屬板。 [0089] 此外，於前述表面處理金屬板中，前述潤滑劑的含量，相對於前述表面處理組成物100質量份較佳為2~5質量份。 [0090] 根據此構成，可得到耐黑變性及耐滲污性更優異之表面處理金屬板。 [0091] 此外，於前述表面處理金屬板中，前述膠體二氧化矽，較佳為含有氨作為分散劑之膠體二氧化矽。 [0092] 根據此構成，可得到耐黑變性及耐滲污性更優異之表面處理金屬板。 [0093] 此外，於前述表面處理金屬板中，前述聚烯烴系樹脂，較佳為含有α,β-不飽和羧酸與烯烴之共聚物。 [0094] 根據此構成，可得到耐黑變性及耐滲污性更優異之表面處理金屬板。 [0095] 本發明之另一面向為一種表面處理金屬板之製造方法，其係製造前述表面處理金屬板之表面處理金屬板之製造方法，其係具備：調製前述表面處理組成物之步驟，及將前述表面處理組成物塗佈於前述鋅系鍍覆鋼板之至少一者的表面上之步驟，以及藉由使前述表面處理組成物乾燥，將前述表面處理皮膜形成於前述鋅系鍍覆鋼板之至少一者的表面上之步驟。 [0096] 根據此構成，可製造一種耐黑變性優異，且可充分地抑制滲污的產生之表面處理金屬板，亦即可製造一種耐黑變性及耐滲污性優異之表面處理金屬板。 [0097] 根據本發明，可提供一種耐黑變性優異，且可充分地抑制滲污的產生之表面處理金屬板、及表面處理金屬板之製造方法。 [0098] 以下係列舉實施例來具體說明本發明，但本發明並不限定於此等。 [實施例] [0099] 首先說明以下實施例所使用之各評估方法。 [0100] [耐蝕性] 1. 鹽水噴霧試驗（SST平板、SST橫切） 對於與內面施以邊緣密封之試驗材料，製作出維持平板者，以及以切割刀形成橫切者。對於各試驗材料，依據JIS Z 2371，於35℃的環境下將鹽水（5%NaCl水溶液）噴霧以實施鹽水噴霧試驗。測定白鏽相對於試驗材料之產生率到達5面積%為止的時間。 [0101] （SST平板） 作為SST平板的評估基準，若白鏽相對於維持平板者之產生率到達5面積%為止的時間為240小時以上，則評估為「◎」，168小時以上且未達240小時，評估為「○」，120小時以上且未達168小時，評估為「△」，未達120小時，評估為「×」。 [0102] （SST橫切） 作為SST橫切的評估基準，若白鏽相對於形成橫切者之產生率到達5面積%為止的時間為120小時以上，則評估為「◎」，96小時以上且未達120小時者，評估為「○」，72小時以上且未達96小時者，評估為「△」，未達96小時者，評估為「×」。 [0103] 2. 鹽水噴霧循環試驗（SST循環） 對於施以邊緣密封之試驗材料（平板），依據JIS Z 2371，於35℃的環境下將鹽水（5%NaCl水溶液）噴霧以實施鹽水噴霧循環試驗。1循環為進行鹽水噴霧8小時，然後停止16小時者。測定白鏽相對於試驗材料之產生率到達5面積%為止的循環數。作為SST循環的評估基準，若此循環數為10循環以上，則評估為「◎」，7循環以上且未達10循環者，評估為「○」，5循環以上且未達7循環者，評估為「△」，未達5循環者，評估為「×」。 [0104] 3. 中性鹽水噴霧循環試驗（JASO） 對於施以邊緣密封之試驗材料（平板），依據JIS H 8502，實施中性鹽水噴霧循環試驗。1循環為進行鹽水噴霧2小時，然後進行4小時的乾燥（溫度60℃、濕度30%以上），並進行2小時的濕潤（溫度50℃、濕度95%以上）者。測定白鏽相對於試驗材料之產生率到達5面積%為止的循環數。作為JASO的評估基準，若此循環數為21循環以上，則評估為「◎」，15循環以上且未達21循環者，評估為「○」，9循環以上且未達15循環者，評估為「△」，未達9循環者，評估為「×」。 [0105] [耐黑變性] 將試驗材料保存在溫度50℃、濕度98%以上之恆溫恆濕試驗機168小時後，使用色差計來測定試驗前後的色差（ΔL）。作為耐黑變性的評估基準，若ΔL未達1，則評估為「◎」，ΔL為1以上且未達2者，評估為「○」，ΔL為2以上且未達3者，評估為「△」，ΔL為3以上者，評估為「×」。 [0106] [耐滲污性] 將試驗材料保存在溫度65℃、濕度95%以上之恆溫恆濕試驗機168小時後，以目視來觀察試驗前後的外觀變化。作為耐滲污性的評估基準，若無法確認到滲污的產生，則評估為「◎」，僅確認到極些微滲污的產生者，評估為「○」，確認到些微滲污的產生者，評估為「△」，確認到全面性滲污的產生者，評估為「×」，確認到全面性顯著地產生滲污者，評估為「××」。 [0107] [耐膠帶剝離性] 係評估高溫多濕條件下之鋅系鍍覆鋼板的鍍覆表面與表面處理皮膜之密著性。亦即，將黏著膠帶（Sliontec公司製的纖維絲膠帶No.9510：橡膠黏著劑）貼附於試驗材料，於恆溫恆濕試驗裝置中，在溫度40℃、濕度98%的環境下保存120小時後，依據JIS K 5400實施膠帶剝離試驗。然後測定實施膠帶剝離試驗後之表面處理皮膜的殘存率。最為耐膠帶剝離性的評估基準，若前述殘存率為95面積%以上，則評估為「◎」，90面積%以上且未達95面積%者，評估為「○」，80面積%以上且未達90面積%者，評估為「△」，未達80面積%者，評估為「×」。 [0108] [塗裝性（塗膜二次密著性）] 將丙烯酸系塗料（Kansai Paint股份有限公司製的Magicron #1000），以塗膜厚度成為20μm之方式對試驗材料施以棒塗佈塗裝，於溫度160℃下燒成20分鐘，以進行後塗裝。接著將進行了後塗裝之試驗材料浸漬在沸騰水1小時後，取出並放置1小時後，以切割刀刻出100個1mm方格的棋盤目，並對此進行與上述耐膠帶剝離性相同之膠帶剝離試驗。量測出未剝離而殘存之塗膜的方格數。作為塗裝性（塗膜二次密著性）的評估基準，若殘存的方格數為100個，則評估為「◎」，90個以上99個以下者，評估為「○」，80個以上89個以下者，評估為「△」，79個以下者，評估為「×」。 [0109] [潤滑性（動摩擦係數）] 使用如第5圖所示之摩擦係數測定裝置，測定試驗材料的動摩擦係數。具體而言，如第5圖所示，以壓模平板52、53夾入試驗材料51，並以加壓力P將壓模平板53朝向試驗材料51加壓。於此狀態下，將試驗材料51從壓模平板52與壓模平板53之間拉出。測定此時的拉出荷重F，從所測定之F中，算出各試驗材料的動摩擦係數μ（=F/2P）。測定條件如下所述。第5圖為顯示用以評估潤滑性之摩擦係數測定裝置之概略圖。 [0110] 樣本大小：40×300mm 加壓力P：5.4MPa 拉出速度：300mm/分 壓模平板材質：SKD11 無塗油 [0111] 作為潤滑性的評估基準，若動摩擦係數μ未達0.09，則評估為「◎」，0.09以上且未達0.15者，評估為「○」，0.15以上且未達0.2者，評估為「△」，0.2以上者，評估為「×」。 [0112] [試驗例1（樹脂）] 構成表面處理皮膜之樹脂，使用以下樹脂。 [0113] （樹脂A：不含氨且經乳化之聚烯烴系樹脂） 將水626質量份、乙烯-丙烯酸共聚物（丙烯酸單元：20質量%、熔解指數MI：300）160質量份，加入於具有具備攪拌機、溫度計、及溫度控制器之乳化設備之高壓釜，接著添加相對於乙烯-丙烯酸共聚物的羧基1莫耳為40莫耳%的三乙胺、以及15莫耳%的氫氧化鈉。然後於150℃、5Pa下進行高速攪拌後，冷卻至40℃。相對於乙烯-丙烯酸共聚物的固體成分100質量份，將5質量份之作為交聯劑的4,4’-雙（乙烯亞胺基羰基胺基）二苯基甲烷（日本觸媒股份有限公司製的Chemitite DZ-22E）添加於此。藉此可得到經乳化之乙烯-丙烯酸共聚物（乙烯-不飽和羧酸共聚物水分散液）。將此設為樹脂A。此樹脂A，平均分子量為60000，平均粒徑為55nm。此外，使用此樹脂A，藉由上述方法來測定水蒸氣穿透度為50 g/m2
/日。 [0114] （樹脂B：含有氨且經乳化之聚烯烴系樹脂） 將使用氨且經乳化之乙烯-丙烯酸共聚物（乙烯-不飽和羧酸共聚物水分散液）（東邦化學工業股份有限公司製的Hitec S-7024），用作為樹脂B。此樹脂B，於乳化時，與樹脂A時不同，係使用乳化用氨水來製造。此樹脂B，平均分子量為30000，平均粒徑為40nm。此外，使用此樹脂B，藉由上述方法來測定水蒸氣穿透度為115 g/m2
/日。 [0115] （樹脂C：含羧基聚胺甲酸酯樹脂水分散液） 將60質量份之作為多元醇成分的聚四亞甲基醚二醇（平均分子量：1000、保土谷化學工業股份有限公司製）、14質量份之1,4-環己烷二甲醇、20質量份之二羥甲基丙酸，裝入於具備攪拌機、溫度計、及溫度控制器之合成裝置，然後加入30質量份之作為反應溶劑的N-甲基吡咯啶酮。裝入104質量份之作為異氰酸酯成分的甲苯二異氰酸酯（TDI），升溫至80℃~85℃並反應5小時。所得到之預聚物的NCO含量為8.9質量%。然後加入三乙胺16質量份以進行中和，加入乙二胺16質量份與水480質量份之混合水溶液，於50℃進行4小時的乳化，同時進行鏈延長反應。藉此得到含羧基聚胺甲酸酯樹脂水分散液（聚胺甲酸酯樹脂水分散液）（非揮發性樹脂成分：29.1質量%、酸值：41.4）。將此設為樹脂C。使用此樹脂C，藉由上述方法來測定水蒸氣穿透度為1500 g/m2
/日。 [0116] （樹脂D：改質環氧樹脂水分散液） 使用改質環氧樹脂水分散液（荒川化學工業股份有限公司製的Modepics 302）作為樹脂D。 [0117] （樹脂E：聚酯樹脂水分散液） 使用聚酯樹脂水分散液（東洋紡股份有限公司製的Bionarl MD1200）作為樹脂E。 [0118] （表面處理金屬板No.1） 以固體成分比計，添加72質量份之樹脂A與28質量份之平均粒徑4~6nm的膠體二氧化矽（日產化學工業股份有限公司製的ST-NXS；氨穩定化型式），調製出表面處理組成物。 [0119] 使用鋅電鍍鋼板（鋅附著量20 g/m2
、板厚0.8mm）作為金屬板。然後對此金屬板施以下述底層處理。底層處理，首先將50質量%的磷酸二氫鋁水溶液（日本工業股份有限公司製）與酸性膠體二氧化矽（日產化學工業股份有限公司製的Snowtex O），以使該固體成分比以質量比（磷酸二氫鋁：膠體二氧化矽）計成為12：88，且此等的濃度成為1.5質量%之方式混合，並以成為0.1g/L之方式，將聚丙烯酸粉末（東亞合成股份有限公司製的AC-10LP）添加於該混合液，調製出底層處理液。使用噴霧器裝置，將此底層處理液噴霧在金屬板之鋅電鍍鋼板的表面，然後進行水洗及乾燥。藉此對金屬板施以底層處理，而在金屬板上形成底層處理層。 [0120] 於形成有底層處理層之金屬板的單面上，藉由棒塗佈機塗佈前述表面處理組成物，以板溫100℃進行乾燥，而得到形成有皮膜附著量0.7 g/m2
的表面處理皮膜之表面處理鋼板。皮膜附著量，如上述般，可藉由螢光X射線分析裝置來定量測定皮膜中之膠體二氧化矽（SiO2
）的Si元素並算出。此外，將此表面處理鋼板浸漬在70~80℃的脫離子水10分鐘，並藉由離子層析儀（Thermo Fisher Scientific股份有限公司製的ICS-5000+）來測定所溶出之鈉（Na+
）的量，其結果為，Na+
溶出量為2.0 mg/m2
。 [0121] （表面處理金屬板No.2~5） 表面處理金屬板No.2~5，除了分別使用樹脂B~E來取代樹脂A之外，其他與表面處理金屬板No.1相同而製造。皮膜附著量，亦與表面處理金屬板No.1相同為0.7 g/m2
，Na+
溶出量亦分別為2.0 mg/m2
。 [0122] 對此等表面處理金屬板No.1~5進行上述評估，該結果如下述第1表所示。 [0123][0124] 此外，第6圖及第7圖分別顯示SST平板與SST循環的評估中之白鏽產生率的變遷。第6圖為顯示SST平板的評估中之白鏽產生率隨時間經過的變化之圖表。此外，第6圖中，線61~65分別顯示表面處理金屬板No.1~5之結果。第7圖為顯示SST循環的評估中之白鏽產生率相對於循環數之變遷之圖表。此外，第7圖中，線71~75分別顯示表面處理金屬板No.1~5之結果。 [0125] 從此等結果中，可得知併用了不含氨且經乳化之聚烯烴系樹脂與平均粒徑為4~6nm的膠體二氧化矽時（表面處理金屬板No.1），與使用即使是聚烯烴系樹脂，亦含有氨且經乳化之樹脂時（表面處理金屬板No.2），或是使用其他樹脂時（表面處理金屬板No.3~5）相比，耐蝕性、耐黑變性、耐滲污性、及耐膠帶剝離性優異。 [0126] [試驗例2（膠體二氧化矽）] 構成表面處理皮膜之膠體二氧化矽，使用日產化學工業股份有限公司製的以下所示者。 [0127] ST-NXS、ST-NS、ST-N、及ST-N40為氨穩定化型式，各平均粒徑如第2表所示。ST-NXS、ST-NS、ST-N、及ST-N40所含有之Na2
O的量，分別為300ppm以下、400 ppm以下、400 ppm以下、2000 ppm以下。 [0128] 此外，ST-XS、ST-S、ST-30、及ST-50為鈉穩定化型式，各平均粒徑如第2表所示。ST-XS、ST-S、ST-30、及ST-50所含有之Na2
O的量，分別為3000~6000ppm、6000 ppm以下、6000 ppm以下、6000 ppm以下。 [0129] （表面處理金屬板No.6~13） 以固體成分比計，添加61質量份之樹脂A、28質量份之第2表所示之膠體二氧化矽、7.5質量份之作為交聯劑的含縮水甘油基交聯劑（DIC股份有限公司製的Epiclon CR5L）、及3.5質量份之作為潤滑劑的球形聚乙烯蠟（三井化學股份有限公司製的Chemipearl W700），而調製出表面處理組成物。 [0130] 表面處理金屬板No.6~13，除了使用上述表面處理組成物之外，其他與表面處理金屬板No.1相同而製造。皮膜附著量，亦與表面處理金屬板No.1相同為0.7 g/m2
，Na+
溶出量分別為第2表所示之值。 [0131] 對此等表面處理金屬板No.6~13進行上述評估，該結果如下述第2表所示。 [0132][0133] 從第2表中，可得知平均粒徑為4~6nm，且浸漬在70~80℃的脫離子水10分鐘時之從表面處理皮膜所溶出之鈉離子的量（Na+
溶出量）為4 mg/m2
以下之膠體二氧化矽，於上述膠體二氧化矽中，僅有ST-NXS。 [0134] 此外，使用ST-NXS時（表面處理金屬板No.6），與使用平均粒徑為8nm以上者時（表面處理金屬板No.8~13）相比，可得知耐蝕性、耐黑變性、耐膠帶剝離性、潤滑性、及塗裝性優異。此可考量當膠體二氧化矽增大時，表面處理皮膜中之膠體二氧化矽的分散性及活性度降低，使表面處理皮膜的阻障性降低，腐蝕環境下之膠體二氧化矽的溶出量降低之故。 [0135] 此外，使用ST-NXS時（表面處理金屬板No.6），與使用Na+
溶出量超過4 mg/m2
之膠體二氧化矽者時（表面處理金屬板No.7、9、11、13）相比，可得知耐黑變性及耐滲污性優異。例如，表面處理金屬板No.7，使用平均粒徑與表面處理金屬板No.6為同等程度之膠體二氧化矽，但當Na+
溶出量超過4 mg/m2
時，可得知耐黑變性、耐滲污性、耐膠帶剝離性、及塗裝性劣化。 [0136] 接著如以下所示般，混合2種膠體二氧化矽以調整來自表面處理皮膜的Na+
溶出量。 [0137] （表面處理金屬板No.14~18） 表面處理金屬板No.14~18，除了使用以成為第3表所示的混合比率之方式所混合之膠體二氧化矽物之外，其他與表面處理金屬板No.6相同而製造。皮膜附著量，亦與表面處理金屬板No.6相同為0.7 g/m2
，Na+
溶出量分別為第3表所示之值。 [0138][0139] 第3表為混合ST-NXS與ST-XS以調整來自表面處理皮膜的Na+
溶出量之結果。單獨使用ST-NXS時（表面處理金屬板No.14），Na+
溶出量為2.0 g/m2
，可發揮良好的耐滲污性。即使提高ST-XS的混合比率，使Na+
溶出量成為3.9 g/m2
時（表面處理金屬板No.17），與表面處理金屬板No.14~16相同，亦可發揮良好的耐滲污性。當此單獨使用ST-XS時（表面處理金屬板No.18），Na+
溶出量成為5.0 g/m2
，產生滲污而使耐滲污性降低。 [0140] 此外，第8圖為顯示來自表面處理皮膜的Na+
溶出量與滲污之關係之圖表。第8圖中之滲污的排序，「5」相當於上述耐滲污性的評估基準中之「◎」，「4」~「1」分別相當於「○」「△」「×」「××」。從此第8圖中，亦可得知若Na+
溶出量為4.0 mg/m2
以下，則可抑制滲污的產生，當Na+
溶出量超過4.0 mg/m2
時，無法抑制滲污的產生。 [0141] 再者，關於表面處理金屬板No.18中的耐膠帶剝離性及塗裝性，與其他情形相比為較差之結果。此可考量在高溫多濕的環境下或沸騰水浸漬等的條件下，表面處理皮膜中的Na+
溶出而促進性能劣化者。 [0142] 此外，從第3表中，可得知Na+
溶出量為4.0 mg/m2
以下時（表面處理金屬板No.14~17），與表面處理金屬板No.18相比，如上述般，不僅耐滲污性優異，耐黑變性、耐膠帶剝離性、及塗裝性亦優異。 [0143] 再者，從第3表中，可得知Na+
溶出量為3.7 mg/m2
以下時（表面處理金屬板No.14~16），即使與表面處理金屬板No.17相比，耐黑變性及塗裝性亦更優異。此外，從第3表中，可得知Na+
溶出量為3.2 mg/m2
以下時（表面處理金屬板No.14、15），即使與表面處理金屬板No.16相比，耐膠帶剝離性亦更優異。 [0144] [試驗例3（各添加量）] （表面處理金屬板No.19~25） 以第4表所示之組成，添加樹脂A、平均粒徑為4~6nm的膠體二氧化矽（日產化學工業股份有限公司製的ST-NXS；氨穩定化型式）、作為交聯劑的含縮水甘油基交聯劑（DIC股份有限公司製的Epiclon CR5L）、及作為潤滑劑的球形聚乙烯蠟（三井化學股份有限公司製的Chemipearl W700），而調製出表面處理組成物。 [0145] 表面處理金屬板No.19~25，除了使用上述表面處理組成物之外，其他與表面處理金屬板No.1相同而製造。皮膜附著量，亦與表面處理金屬板No.1相同為0.7 g/m2
，Na+
溶出量分別為第4表所示之值。 [0146] 對此等表面處理金屬板No.19~25進行上述評估，該結果如下述第4表所示。 [0147][0148] 從第4表中，可得知前述膠體二氧化矽的含量相對於前述表面處理組成物100質量份為10質量份以上且未達30質量份時（表面處理金屬板No.19~23），與該含量未達10質量份時（表面處理金屬板No.24）相比，耐蝕性、耐黑變性、及耐膠帶剝離性優異。此外，表面處理金屬板No.19~23，與30質量份以上時（表面處理金屬板No.25）相比，耐黑變性、耐膠帶剝離性、及塗裝性優異。此等結果，可考量當前述膠體二氧化矽的含量為10質量份以上且未達30質量份時，由於膠體二氧化矽在腐蝕環境下溶解並溶出，故能夠較佳地形成可充分發揮產生pH的緩衝作用或惰態皮膜形成作用之作用之表面處理皮膜之故。 [0149] 再者，從第4表中，可得知前述膠體二氧化矽的含量相對於前述表面處理組成物100質量份為15質量份以上28質量份以下時（表面處理金屬板No.20~23），不僅耐黑變性及耐滲污性等為優異，與表面處理金屬板No.19相比，耐膠帶剝離性及潤滑性亦優異。 [0150] 此外，從第4表中，可得知前述膠體二氧化矽的含量相對於前述表面處理組成物100質量份為20質量份以上28質量份以下時（表面處理金屬板No.21~23），不僅耐黑變性及耐滲污性等為優異，與表面處理金屬板No.19或20相比，耐蝕性亦優異。 [0151] （表面處理金屬板No.26~31） 以第5表所示之組成，添加樹脂A、平均粒徑為4~6nm的膠體二氧化矽（日產化學工業股份有限公司製的ST-NXS；氨穩定化型式）、作為交聯劑的含縮水甘油基交聯劑（DIC股份有限公司製的Epiclon CR5L）、及作為潤滑劑的球形聚乙烯蠟（三井化學股份有限公司製的Chemipearl W700），而調製出表面處理組成物。 [0152] 表面處理金屬板No.26~31，除了使用上述表面處理組成物之外，其他與表面處理金屬板No.1相同而製造。皮膜附著量，亦與表面處理金屬板No.1相同為0.7 g/m2
，Na+
溶出量分別為第5表所示之值。 [0153] 對此等表面處理金屬板No.26~31進行上述評估，該結果如下述第5表所示。 [0154][0155] 從第5表中，可得知前述交聯劑的含量相對於前述表面處理組成物100質量份為5~8.5質量份時（表面處理金屬板No.26~29），與該含量未達5質量份時（表面處理金屬板No.30）相比，耐蝕性及耐黑變性優異。此外，表面處理金屬板No.26~29，耐黑變性及耐滲污性優異，再者，與超過8.5質量份時（表面處理金屬板No.31）相比，可得知塗裝性優異。此等結果，可考量當前述交聯劑的含量為5~8.5質量份時，可抑制外部交聯劑產生自我交聯，而能夠較佳地進行交聯反應之故。 [0156] 再者，前述交聯劑的含量相對於前述表面處理組成物100質量份為6.5~8.5質量份時（表面處理金屬板No.27~29），不僅耐黑變性及耐滲污性優異，與表面處理金屬板No.26相比，耐蝕性、耐膠帶剝離性及潤滑性亦優異。此可考量由於交聯反應的進行，使表面處理皮膜的硬度亦提高之故。 [0157] （表面處理金屬板No.32~38） 以第6表所示之組成，添加樹脂A、平均粒徑為4~6nm的膠體二氧化矽（日產化學工業股份有限公司製的ST-NXS；氨穩定化型式）、作為交聯劑的含縮水甘油基交聯劑（DIC股份有限公司製的Epiclon CR5L）、及作為潤滑劑的球形聚乙烯蠟（三井化學股份有限公司製的Chemipearl W700），而調製出表面處理組成物。 [0158] 表面處理金屬板No.32~38，除了使用上述表面處理組成物之外，其他與表面處理金屬板No.1相同而製造。皮膜附著量，亦與表面處理金屬板No.1相同為0.7 g/m2
，Na+
溶出量分別為第6表所示之值。 [0159] 對此等表面處理金屬板No.32~38進行上述評估，該結果如下述第6表所示。 [0160][0161] 從第6表中，可得知前述潤滑劑的含量相對於前述表面處理組成物100質量份為2~5質量份時（表面處理金屬板No.32~36），與該含量未達2質量份時（表面處理金屬板No.37）相比，潤滑性優異。此外，表面處理金屬板No.32~36，與超過5質量份時（表面處理金屬板No.38）相比，可得知耐蝕性、耐黑變性、及耐滲污性優異。此可考量為可抑制腐蝕環境下之潤滑劑的水解等所造成之耐蝕性及耐黑變性等的降低，同時提高潤滑劑所帶來之潤滑性者。 [0162] 再者，從第6表可得知，前述潤滑劑的含量相對於前述表面處理組成物100質量份為2.5~5質量份時（表面處理金屬板No.33~36），不僅耐黑變性及耐滲污性等為優異，與表面處理金屬板No.32相比，潤滑性亦優異。從該結果中，可得知前述潤滑劑的含量相對於前述表面處理組成物100質量份尤佳為2.5質量份以上。 [0163] 此外，從第6表可得知，前述潤滑劑的含量相對於前述表面處理組成物100質量份為2~4質量份時（表面處理金屬板No.32~35），不僅耐黑變性及耐滲污性等為優異，與表面處理金屬板No.36相比，耐蝕性、耐膠帶剝離性、及塗裝性亦優異。從該結果中，可得知前述潤滑劑的含量相對於前述表面處理組成物100質量份尤佳為4質量份以下。 [0164] [試驗例4（皮膜附著量）] （表面處理金屬板No.39~46、50、及51） 以固體成分比計，添加61質量份之樹脂A、28質量份之平均粒徑為4~6nm的膠體二氧化矽（日產化學工業股份有限公司製的ST-NXS；氨穩定化型式）、7.5質量份之作為交聯劑的含縮水甘油基交聯劑（DIC股份有限公司製的Epiclon CR5L）、及3.5質量份之作為潤滑劑的球形聚乙烯蠟（三井化學股份有限公司製的Chemipearl W700），而調製出表面處理組成物。 [0165] 表面處理金屬板No.39~46、50、及51，除了使用上述表面處理組成物，並將皮膜附著量調整為第7表所示之值之外，其他與表面處理金屬板No.1相同而製造。Na+
溶出量分別為第7表所示之值。 [0166] （表面處理金屬板No.47~49） 表面處理金屬板No.47~49，係使用：採用此ST-NXS與日產化學工業股份有限公司製的ST-XS之混合物來取代日產化學工業股份有限公司製的ST-NXS以作為平均粒徑為4~6nm的膠體二氧化矽之表面處理組成物，並將皮膜附著量調整為第7表所示之值，除此之外，其他與表面處理金屬板No.1相同而製造。Na+
溶出量分別為第7表所示之值。此外，表面處理金屬板No.47，ST-NXS與ST-XS之混合比（ST-NXS：ST-XS），以質量比計為2：1。此外，表面處理金屬板No.48，ST-NXS與ST-XS之混合比（ST-NXS：ST-XS），以質量比計為1：1。此外，表面處理金屬板No.49，ST-NXS與ST-XS之混合比（ST-NXS：ST-XS），以質量比計為1：2。 [0167] 對此等表面處理金屬板No.39~51進行上述評估，該結果如下述第7表所示。 [0168][0169] 從第7表中，可得知前述表面處理皮膜的附著量為0.4~1.2 g/m2
時（表面處理金屬板No.39~49），與該附著量未達0.4 g/m2
時（表面處理金屬板No.50）相比，耐蝕性、耐黑變性、耐膠帶剝離性、及潤滑性優異。此外，表面處理金屬板No.39~49，與超過1.2 g/m2
時（表面處理金屬板No.51）相比，可得知塗裝性優異。 [0170] 再者，從第7表中，可得知前述表面處理皮膜的附著量為0.45 g/m2
時（表面處理金屬板No.40），與前述表面處理皮膜的附著量為0.4 g/m2
之表面處理金屬板No.39相比，耐黑變性、耐滲污性、耐膠帶剝離性、及潤滑性優異。 [0171] 此外，前述表面處理皮膜的附著量為0.5 g/m2
時（表面處理金屬板No.41），與前述表面處理皮膜的附著量為0.4 g/m2
之表面處理金屬板No.40相比，耐蝕性優異。 [0172] 從以上結果中，可得知前述表面處理皮膜的附著量較佳為0.45 g/m2
以上，尤佳為0.5 g/m2
以上。 [0173] 此外，從第7表中，可得知前述表面處理皮膜的附著量為0.8 g/m2
時（表面處理金屬板No.44），與前述表面處理皮膜的附著量為1 g/m2
之表面處理金屬板No.45相比，耐黑變性優異。 [0174] 此外，從第7表中，可得知前述表面處理皮膜的附著量為0.7 g/m2
時（表面處理金屬板No.43），與前述表面處理皮膜的附著量為0.8 g/m2
之表面處理金屬板No.44相比，塗裝性優異。 [0175] 從以上結果中，可得知前述表面處理皮膜的附著量較佳為0.8 g/m2
以下，尤佳為0.7 g/m2
以下。 [0176] 本申請案係以於2016年8月5日提出申請之日本國特許出願特願2016-154609以及於2017年6月1日提出申請之日本國特許出願特願2017-108966為基礎，該內容包含於本申請案。 [0177] 為了表現本發明，於上述中係一面參考圖面一面透過實施形態來適切且充分地說明本發明，對該業者而言，應明瞭的是能夠容易地對上述實施形態進行變更及/或改良。因此，該業者所實施之變更形態或改良形態，只要是不脫離申請專利範圍所記載之請求項的權利範圍之等級者，該變更形態或該改良形態皆應解釋為涵蓋於該請求項的權利範圍。 [產業上之可應用性] [0178] 根據本發明，可提供一種耐黑變性優異，且可充分地抑制滲污的產生之表面處理金屬板、及表面處理金屬板之製造方法。[0022] As described in Patent Literature 1 and Patent Literature 2, chromate-treated zinc electroplated steel plates in which elements such as Ni, Co, and In are added to a zinc plating layer must be considered as impurities in the zinc plating layer. Equilibrium of elements such as Pb, Cu, and Ag that deteriorates corrosion resistance. In addition, even if the chromate-treated zinc-plated steel sheet is adjusted for the equilibrium, the color change unevenness and the decrease of whiteness may occur due to the change in the valence of metal elements and the dissolution of metals in a corrosive environment. Defective appearance. In addition, when zinc-plated steel sheet treated with chromate is added with elements such as Ni, Co, and In to the zinc plating layer and the oxidation reaction is excessively promoted, the corrosion resistance may be significantly reduced, white rust may be generated, or it may become easy. Penetration (black-brown or gray-brown) unevenness (hereinafter referred to as "bleeding") occurs. [0023] The zinc-plated steel sheets described in Patent Documents 3 and 4 are the same as the chromate-treated zinc-plated steel sheets described in Patent Documents 1 and 2, and they are also affected by the value of metal elements in a corrosive environment. In some cases, color change, metal dissolution, etc. may cause discoloration unevenness or decrease in whiteness, which may cause appearance defects. [0024] In addition, the balance of corrosion resistance, black resistance, adhesion to the zinc-plated surface, and the electrical conductivity of the steel sheet can also be considered. For example, zinc-plated steel sheets can be considered, for example, in Patent Documents 1 to 4. On the zinc-based plated steel sheet described, a thin film of about 0.5 to 1 μm is further used to form an inorganic-rich film or an organic-rich film as a surface treatment film. Specifically, the film described in Patent Document 5 and Patent Document 6 can be considered as a surface-treated film. [0025] However, merely by providing the surface treatment film, the blackening phenomenon may not be sufficiently suppressed, and not only the blackening phenomenon may not be sufficiently suppressed, but also bleeding may occur easily. [0026] In addition, the bleed easily generated especially in a high temperature and humid environment will significantly damage the appearance of the product and reduce the value of the product. Therefore, not only the blackening phenomenon, but also the need to suppress the occurrence of bleeding. [0027] According to the investigations made by the present inventors, even if a surface treatment film is formed on a zinc-based plated steel sheet, the reason why the blackening phenomenon may not be sufficiently suppressed may be presumed as follows. [0028] First, as shown in FIG. 1A, even if the surface-treated film 11 is provided on the zinc-based plated steel sheet 12, barrier properties such as oxygen permeability and water permeability may not be completely improved. . At this time, as shown in FIG. 1B, an oxidation reaction is caused when the supply of oxygen to the surface of the zinc-based plated steel sheet 12 is insufficient, and as described above, an irregular shape is generated on the zinc-based plated steel sheet 12 Oxide 13. That is, when the surface-treated film 11 is provided on the surface-treated metal plate 10 of the zinc-based plated steel sheet 12, a blackening phenomenon occurs. FIG. 1A is a schematic view showing a surface-treated metal plate 10 provided with a surface-treated film 11 on a zinc-based plated steel sheet 12. In addition, FIG. 1B is a schematic view showing a state where the amorphous oxide 13 is formed on the surface-treated metal plate 10 shown in FIG. 1A. [0029] In addition, in a surface-treated metal plate provided with a surface-treated film on a zinc-based plated steel sheet, not only the phenomenon of blackening, but also the occurrence of staining cannot be sufficiently suppressed. Staining can be considered due to the reduction of the barrier properties of the surface treatment film in a high-temperature and humid environment, which accelerates the corrosion reaction, which is the cause of the blackening phenomenon, and accelerates the corrosion reaction. In the discussion of the present invention, it has been found that the occurrence of seepage is not limited to this case, and may occur through different mechanisms. The details are as follows. [0030] First, when the surface treatment film contains colloidal silicon dioxide, the focus is on those who cannot sufficiently suppress the generation of stains. The surface-treated metal plate provided with the surface-treated film is, for example, placed in a constant temperature and humidity test machine set at an environment of a temperature of 65 ° C. and a humidity of 95% for 168 hours to cause staining. Scoring was performed on the surface-treated film of the stain-producing part of the surface-treated metal plate where the stain occurred, and surface analysis was performed using an electron beam microanalyzer (EPMA, JXA-8100 manufactured by Japan Electronics Co., Ltd.) 8 × 8mm). As a result of this analysis, it can be seen that the Na element is concentrated on the part where the bleeding occurs. From this result, the present inventors speculate that the cause of the bleed is the existence of the Na element. To further explore the cause of the concentration of Na element, the inventors focused on the colloidal silicon dioxide contained in the surface-treated film, and speculated that the following was taken as a mechanism for the generation of stains. [0031] First, in a high-temperature and humid environment, etc., a local battery is formed due to extremely early corrosion on the surface of the zinc plating layer provided with a surface treatment film. In general, the colloidal silicon dioxide contained in the surface treatment film is, as shown in FIG. 2, mostly those containing sodium as a dispersant, that is, colloidal silicon dioxide stabilized by Na ions. This is because colloidal silicon dioxide is generally manufactured using sodium silicate as the raw material, and most of the sodium is removed by cation exchange, but sodium is used to form SiO2
The stable sol is used, so it is difficult to completely remove it. Fig. 2 is a schematic view showing a state of colloidal silicon dioxide. When the surface treatment film contains the colloidal silica, the surface treatment film contains Na element derived from the colloidal silica. Then, the Na element derived from colloidal silicon dioxide contained in this surface treatment film is concentrated at the cathode portion of the battery, and the initial corrosion is slowly promoted to form an amorphous oxide (unshaped zinc oxide) on the zinc plating layer. ). That is, as shown in FIG. 3A, the surface-treated film 11 containing colloidal silicon dioxide 14 is provided on a surface-treated metal plate 10 on a zinc-based plated steel sheet 12, and Na ions contained in the colloidal silicon dioxide 14 It moves toward the surface of the zinc plating layer of the zinc-based plated steel sheet 12, and an amorphous oxide 13 is partially formed. Then, when the corrosion proceeds from the amorphous oxide 13 as a starting point, as shown in FIG. 3B, the amorphous oxide 13 is unevenly formed on the interface between the zinc-based plated steel sheet 12 and the surface treatment film 11. diffusion. This diffused irregular oxide 13 is viewed as bleed. Based on this mechanism, it can be presumed that the above-mentioned surface-treated metal plate provided with the surface-treated film containing colloidal silicon dioxide has caused staining. FIG. 3A is a schematic diagram showing a state where staining is started on the surface-treated metal plate 10 provided with the surface-treated film 11 on the zinc-based plated steel sheet 12. In addition, FIG. 3B is a schematic view showing a state where the stain is diffused on the surface-treated metal plate 10 provided with the surface-treated film 11 on the zinc-based plated steel sheet 12. [0032] Therefore, the inventors have considered that when the amount of Na element contained in the surface treatment film is reduced, as shown in FIG. 4, the amorphous oxide 13 that is partially formed can be reduced, and the result can be effectively Suppresses soiling. FIG. 4 is a schematic view showing a state after the generation of the stain is suppressed on the surface-treated metal plate 10 provided with the surface-treated film 11 on the zinc-based plated steel sheet 12. [0033] In addition, when the aqueous emulsion contained in the surface treatment composition as a matrix is used when ammonia is used as a neutralizing agent when the emulsion is generated, ammonia is included in the surface treatment composition. And it was found that the ammonia reacted with the zinc coating to partially generate zinc oxide (ZnO) or zinc hydroxide (Zn (OH)2
), Etc., to further promote the deterioration of corrosion resistance, blackening, and generation of bleed. [0034] Therefore, the inventors have considered that when a resin containing no ammonia is used as the resin contained in the surface treatment composition used in forming the surface treatment film, the amount of ammonia contained in the surface treatment composition may be small, and Improve corrosion resistance, blackening resistance, and stain resistance. [0035] Based on the above discussion, the present inventors have completed the present invention described below. The present inventors conducted various investigations, and as a result, found that the above-mentioned object of providing a surface-treated metal plate which is excellent in blackening resistance and sufficiently suppresses the generation of stains can be achieved by the following invention. [0036] As shown in FIGS. 1A and 3A, a surface-treated metal sheet according to an embodiment of the present invention includes a zinc-based plated steel sheet 12 and a layer laminated on the zinc-based plated steel sheet 12. The surface treatment film 11 is on the surface of at least one of them. The surface treatment film 11 is composed of a surface treatment composition containing a polyolefin-based resin not containing ammonia and colloidal silica having an average particle diameter of 4 to 6 nm. The content of the colloidal silica is 10 parts by mass or more and less than 30 parts by mass based on 100 parts by mass of the surface treatment composition. In addition, the adhesion amount of the aforementioned surface treatment film is 0.4 to 1.2 g / m2
. In addition, the amount of sodium ions dissolved from the surface-treated film when immersed in deionized water at 70 to 80 ° C for 10 minutes was 4 mg / m2
the following. [0037] This surface-treated metal plate is excellent in blackening resistance and can sufficiently suppress the occurrence of staining. In addition, it has excellent adhesion to the zinc plating layer. This can be considered based on the following. [0038] First, the surface treatment film 11 contains a polyolefin-based resin that does not contain ammonia, so that the amount of ammonia contained in the surface treatment composition is small. Therefore, it can be considered that it is possible to suppress the decrease in corrosion resistance, the blackening, and the occurrence of staining caused by the reaction between ammonia and zinc plating. In addition, since the average particle size of the colloidal silica contained is 4 to 6 nm, the dispersibility and activity of the colloidal silica are high, the barrier properties of the surface treatment film are high, and the corrosion resistance can be improved. It can also improve the adhesion to the zinc plating layer. The colloidal silica is contained so that it is 10 parts by mass or more and less than 30 parts by mass based on 100 parts by mass of the surface treatment composition, and the adhesion amount is 0.4 to 1.2 g / m.2
In this way, a surface treatment film is formed, so that the effect of colloidal silica containing colloidal silica, such as improving the corrosion resistance or the adhesion with the zinc plating layer, can be better exerted. In addition, the amount of sodium ions dissolved from the surface-treated film when the surface-treated film was immersed in deionized water at 70 to 80 ° C for 10 minutes was 4 mg / m.2
the following. As described above, when the amount of sodium ions eluted from the surface-treated film is small, as described above, the occurrence of bleeding can be suppressed. From these points of view, the surface-treated metal plate of this embodiment is excellent in blackening resistance and can sufficiently suppress the occurrence of staining. In addition, it has excellent adhesion to the zinc plating layer (resistance to tape peeling). [0039] The zinc-based plated steel sheet is not particularly limited, and may be a zinc-plated steel sheet alone, or a zinc-based alloy plated steel sheet such as zinc-Ni, zinc-Fe, and zinc-Al. The plating method is also not particularly limited, and may be a zinc-plated steel sheet obtained by any one of a melt plating method, an electrolytic plating method, and an evaporation plating method. Specific examples of the zinc-based plated steel sheet include a molten zinc plated steel sheet (GI), an alloyed molten Zn-Fe plated steel sheet (GA), an alloyed molten Zn-5% Al plated steel sheet (GF), and zinc plating. Steel plate (EG), Zn-Ni alloy plated steel plate, etc. Among these, zinc plated steel sheet (EG) is preferred. [0040] As described above, the surface treatment film is composed of a surface treatment composition containing a polyolefin resin that does not contain ammonia and colloidal silica having an average particle diameter of 4 to 6 nm. [0041] The polyolefin-based resin is not particularly limited as long as it is a polyolefin-based resin that does not contain ammonia. Specific examples of the polyolefin-based resin include an emulsified polyolefin-based resin that does not contain ammonia, that is, an emulsified polyolefin-based resin that does not use ammonia as a neutralizing agent during emulsification production. Examples of the polyolefin-based resin include an emulsified polyolefin-based resin containing at least one of an organic basic amine and a metal ion. That is, the polyolefin-based resin includes emulsified polyolefin-based resins that use at least one of an organic basic amine and a metal ion as a neutralizing agent during emulsification production. In this way, if it is such an ammonia-free and emulsified polyolefin-based resin, such as a polyolefin-free resin that does not contain ammonia, zinc oxide (ZnO) generated when using an ammonia-containing and emulsified polyolefin-based resin can be suppressed. ) Or zinc hydroxide (Zn (OH)2
) And so on. Therefore, deterioration of corrosion resistance, blackening, and generation of bleed can be promoted. [0042] In addition, the polyolefin resin is not particularly limited as long as it is a polyolefin resin that does not contain ammonia, and the water vapor transmission rate when formed into a film is preferably 100 g / m2
/ Day or less, preferably 50 g / m2
/ Day or less. The water vapor transmission rate is, for example, a water vapor transmission rate defined by JIS K 7129. Examples of the measurement method include a method of making a thin film of about 18 μm, and measuring the water vapor transmission rate of the thin film by a cup measurement method in accordance with JIS Z 0208. In the case of the resin having excessive water vapor permeability, when the colloidal silica is added to improve the corrosion resistance, etc., the water vapor permeability of the obtained surface-treated film is too high, and the effect of improving the corrosion resistance may not be obtained in some cases. . [0043] The polyolefin-based resin is not particularly limited as long as it is a polyolefin-based resin that does not contain ammonia, and is preferably a copolymer containing an α, β-unsaturated carboxylic acid and an olefin (olefin-α , β-unsaturated carboxylic acid copolymer). In addition, in the aforementioned olefin-α, β-unsaturated carboxylic acid copolymer, the constituent units derived from the α, β-unsaturated carboxylic acid may be considered to play a role in improving the adhesion of zinc plating and surface treatment film. Therefore, by containing the olefin-α, β-unsaturated carboxylic acid copolymer, the barrier properties of the surface-treated film can be improved without impairing the dispersion stability of the colloidal silica in the surface-treatment composition. Sex. Therefore, the penetration of water and oxygen of the surface treatment film can be reduced, and the corrosion resistance and blackening resistance can be further improved. [0044] The aforementioned olefin-α, β-unsaturated carboxylic acid copolymer (hereinafter also referred to simply as "olefin-acid copolymer") is a copolymer of α, β-unsaturated carboxylic acid and olefin. The olefin-acid copolymer herein has a constituent unit derived from an olefin, and is preferably 50% by mass or more in the olefin-acid copolymer. That is, the olefin-acid copolymer has a constituent unit derived from an α, β-unsaturated carboxylic acid, and is preferably 50% by mass or less in the olefin-acid copolymer. [0045] The olefin-acid copolymer may be prepared by copolymerizing an olefin with an α, β-unsaturated carboxylic acid, and can be produced by copolymerizing an olefin with an α, β-unsaturated carboxylic acid by a known method. In addition, the aforementioned olefin-acid copolymers are also commercially available. [0046] The olefin that can be used in the production of the olefin-acid copolymer is not particularly limited, and ethylene and propylene are preferred, and ethylene is particularly preferred. The olefin-acid copolymer may be derived from a constituent unit of the olefin, may be derived from only one olefin, or may be derived from two or more olefins. [0047] The α, β-unsaturated carboxylic acid used in the production of the olefin-acid copolymer is not particularly limited, and examples thereof include ethylenic α, β-unsaturated carboxylic acid. Examples of the α, β-unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid, maleic acid, fumaric acid, and itaconic acid. Dicarboxylic acids and the like. The α, β-unsaturated carboxylic acid may be used alone or in combination of two or more. Among the compounds exemplified above, the α, β-unsaturated carboxylic acid is preferably acrylic acid or methacrylic acid, and particularly preferably acrylic acid. The olefin-acid copolymer may be derived from the constituent units of the α, β-unsaturated carboxylic acid, may be derived from only one type of α, β-unsaturated carboxylic acid, or may be derived from two or more types of α, β-unsaturated carboxylic acid. acid. [0048] As mentioned above, the constituent units derived from the aforementioned α, β-unsaturated carboxylic acid in the olefin-acid copolymer can be considered to play a role in improving the adhesion of zinc plating and surface treatment film. In order to effectively exert this effect, the aforementioned olefin-acid copolymer is derived from the constituent units of the aforementioned α, β-unsaturated carboxylic acid. In the aforementioned olefin-acid copolymer, it is preferably 5 mass% or more, and particularly preferably 10 mass. %the above. The upper limit of the content of the constituent units derived from the α, β-unsaturated carboxylic acid is preferably 50% by mass or less as described above, and from the viewpoint of corrosion resistance, it is particularly preferably 30% by mass or less, and more preferably It is 25% by mass or less. [0049] The aforementioned olefin-acid copolymer is within a range where the effects of the present invention can be achieved, specifically, within a range where the corrosion resistance and blackening resistance are not excessively reduced and the effects of the present invention are not sufficiently achieved. It may contain a constituent unit derived from a monomer (other monomer) other than the olefin and the α, β-unsaturated carboxylic acid. The constituent unit derived from other monomers is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 0% by mass in the olefin-acid copolymer. That is, the most preferable one is a copolymer composed of the structural unit derived from the aforementioned olefin and the structural unit derived from the aforementioned α, β-unsaturated carboxylic acid. The olefin-acid copolymer is specifically preferably an ethylene-acrylic acid copolymer. [0050] The olefin-acid copolymer may be used alone or in combination of two or more kinds. [0051] Since the olefin-acid copolymer has a carboxyl group in the molecule, the polyolefin-based resin can be emulsified (water-dispersed) by neutralizing the organic basic amine or metal ion. [0052] The organic basic amine used as a neutralizing agent in emulsification production is not particularly limited, and the boiling point is preferably 100 ° C or lower, and particularly preferably 90 ° C or lower. If the boiling point is within the above range, it will be volatilized during drying when the surface-treated film is formed and will not easily remain in the formed surface-treated film. Therefore, the organic alkaline amine is unlikely to reduce the corrosion resistance and the black resistance or bleed. The reason for it. Therefore, a surface-treated metal plate having more excellent corrosion resistance, black resistance, and stain resistance can be obtained. The boiling point of the organic basic amine is preferably 70 ° C or higher, and more preferably 80 ° C or higher, from the viewpoint of workability. [0053] Specific examples of the organic basic amine include triethylamine, N, N-dimethylbutylamine, N, N-dimethylallylamine, N-methylpyrrolidine, and tetramethyldiamine group. Tertiary amines such as methane and trimethylamine; secondary amines such as N-methylethylamine, diisopropylamine, and diethylamine; propylamine, tertiary butylamine, secondary butylamine, isobutylamine, 1, Primary amines such as 2-dibutylpropylamine and 3-pentylamine. Among the amines exemplified above, the organic basic amine is preferably a tertiary amine, and particularly preferably triethylamine. Moreover, the said organic basic amine can be used individually by 1 type or in combination of 2 or more types. [0054] The amount of the organic basic amine used is not particularly limited as long as the polyolefin-based resin is preferably emulsified. The use amount of the organic basic amine is, for example, preferably 0.2 to 0.8 mol relative to 1 mol of the carboxyl group in the olefin-acid copolymer (20 to 80 mol% relative to the carboxyl group). In addition, the lower limit of the amount of the organic basic amine used is preferably 0.2 mol or more, and more preferably 0.3 mol or more, relative to 1 mol of the carboxyl group. In addition, the upper limit of the amount of the organic basic amine used is preferably 0.8 mol or less, more preferably 0.6 mol or less, and more preferably 0.5 mol or less relative to the 1 mol of the carboxyl group. When the amount of the organic basic amine is within the above range, it is possible to achieve the effects of excellent corrosion resistance, blackening resistance, and adhesion to the zinc plating layer (resistance to tape peeling) of the surface-treated steel sheet. In addition, when the amount of the organic basic amine used is too small, the particles of the polyolefin-based resin during emulsification become large, and this effect tends to be difficult to achieve. In addition, when the amount of the aforementioned organic basic amine is too large, the emulsion becomes sticky and there is a possibility of gelation. [0055] In addition, the metal ion used as a neutralizing agent in the aforementioned emulsion production is not particularly limited, and from the viewpoint of improving the hardness of the surface-treated film, a monovalent metal ion is preferred. The metal ion is preferably at least one of sodium ion, potassium ion, and lithium ion. Examples of the compound that generates the metal ion in the surface treatment composition include hydroxides, carbonates, and oxides containing the metal ions. Specific examples of this compound include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Among them, sodium hydroxide is preferred. [0056] The amount of the compound that generates the metal ion in the surface treatment composition is not particularly limited as long as the polyolefin resin is preferably emulsified. The amount of the compound to be used is, for example, preferably from 0.02 to 0.4 mol (2 to 40 mol% relative to the carboxyl group) relative to 1 mol of the carboxyl group in the olefin-acid copolymer. In addition, the lower limit of the amount of the compound is preferably 0.02 mol or more, particularly preferably 0.03 mol or more, and more preferably 0.1 mol or more relative to the 1 mol of the carboxyl group. In addition, the upper limit of the amount of the compound used is preferably 0.4 mol or less, and more preferably 0.2 mol or less, relative to 1 mol of the carboxyl group. When the amount of the aforementioned compound is too small, the emulsification stability tends to be insufficient. In addition, when the amount of the aforementioned compound is too large, the corrosion resistance tends to decrease. [0057] The preferred ranges of the respective amounts of the compounds for generating the aforementioned organic basic amine and the aforementioned metal ion in the aforementioned surface treatment composition are as described above, but these are all used to neutralize the carboxyl group in the aforementioned olefin-acid copolymer It is used for emulsifying polyolefin resin. Therefore, when such a total amount (neutralization amount) is too large, the viscosity of the emulsion may rapidly increase and solidify. Furthermore, the excessive alkali content is not good because it causes corrosion resistance or blackening resistance to deteriorate, so it takes a lot of energy to volatilize the alkali content. On the other hand, when the total amount (neutralization amount) is too small, there is a concern that the emulsification property is insufficient. From these points of view, the total amount of the compound that generates the organic basic amine and the metal ion in the surface treatment composition is preferably 0.3 to 1.0 moles relative to 1 mole of the carboxyl group in the olefin-acid copolymer. Ear (30 to 100 mole% relative to the aforementioned carboxyl group). [0058] The emulsified polyolefin-based resin containing at least one of an organic basic amine and a metal ion forms an intermolecular aggregation by an ion cluster to form corrosion resistance, black resistance, and a zinc plating layer. Excellent surface treatment film such as adhesiveness (resistance to tape peeling). The surface treatment composition may contain a cross-linking agent that cross-links polyolefin resins by using a chemical bond using a reaction between functional groups in order to form a stronger surface treatment film. This cross-linking agent is a cross-linking agent used to cross-link a polyolefin-based resin, that is, an internal cross-linking agent is a cross-linking agent that cross-links a resin constituting an emulsion during emulsification, and is also referred to herein as an internal cross-linking agent.联 剂。 Union agent. [0059] The internal cross-linking agent is not particularly limited as long as the polyolefin-based resin can be cross-linked to each other, and examples thereof include cross-linking of two or more functional groups capable of reacting with a carboxyl group in a molecule. Agent. Specific examples of the internal cross-linking agent include glycidyl-containing cross-linking agents having two or more glycidyl groups in the molecule, and nitrogen-containing propidyl cross-linking having two or more aziridinyl groups in the molecule.联 剂 Such as. Examples of the glycidyl-containing cross-linking agent include sorbitol polyglycidyl ether, (poly) glycerol polyglycidyl ether, neopentyltetraol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and neopentyl. Polyglycidyl ethers such as glycol diglycidyl ether, (poly) ethylene glycol diglycidyl ether; polyglycidyl ether amines, etc. Examples of the nitrogen-containing propidyl group cross-linking agent include 4,4'-bis (ethyleneiminocarbonylamino) diphenylmethane and N, N'-hexamethylene-1,6-bis (1-aziridinecarboxamidine), N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamidine), and toluene diaziridinecarboxamide, etc. 2 Functional aziridine compounds; tri-1-aziridinylphosphine oxide, tri [1- (2-methyl) aziridinyl] phosphine oxide, trimethylolpropane tri (β-aziridine) Tripropionate), tri-2,4,6- (1-aziridinyl) -1,3,5-triazine, and tetramethylpropane tetraaziridinylpropionate, etc. Aziridine compounds; and derivatives of the aforementioned aziridine compounds. The aforementioned internal cross-linking agent is, among the exemplified cross-linking agents, preferably a bifunctional or more aziridine compound, more preferably a bifunctional aziridine compound, and more preferably 4,4'-bis (ethyleneimine). Carbonylamino) diphenylmethane. Moreover, the said internal crosslinking agent can be used individually by 1 type or in combination of 2 or more types. [0060] The amount of the internal cross-linking agent is preferably 1 to 20% by mass, and more preferably 5 to 10% by mass relative to the polyolefin-based resin. The amount used here is a ratio of 100% by mass to the solid content of the polyolefin resin. When the internal crosslinking agent is too small, the effect of adding the internal crosslinking agent tends to be insufficient. That is, the effect of cross-linking by chemical bonds is insufficient, and it is difficult to exhibit the effect of improving the corrosion resistance or the resistance to peeling of the tape. On the other hand, when the internal crosslinking agent is too much, the cross-linking density of the surface-treated film is too high, the hardness increases, and it becomes impossible to follow the deformation during the molding process of the surface-treated metal plate, which causes cracking, which results in Concerns about reduced corrosion resistance. [0061] The added amount of the olefin-based resin in the surface treatment composition is preferably other than the olefin-based resin constituting colloidal silica described later, a cross-linking agent that cross-links the surface-treated film, and a lubricant. The remaining amount is not particularly limited as long as it is the added amount. The added amount of the olefin-based resin is, for example, preferably 56.5 to 90 parts by mass based on 100 parts by mass of the surface treatment composition. The amount added here is the solid content ratio. [0062] In the aforementioned colloidal silicon dioxide, first, the average particle diameter is 4 to 6 nm. In addition, the colloidal silicon dioxide is required to have a small amount of sodium ions eluted from the surface-treated film based on the above observation. Specifically, the colloidal silica is the amount of sodium ions (dissolution amount) dissolved from the surface treatment film when immersed in deionized water at 70 to 80 ° C for 10 minutes (dissolution amount) is 4 mg / m2
The following colloidal silica. The colloidal silica is not particularly limited as long as it is the colloidal silica. [0063] As the colloidal silica, specifically, colloidal silica containing ammonia as a dispersant is preferably contained. This colloidal silica containing ammonia as a dispersant, that is, NH4 +
Colloidal silica (ammonia-stabilized version) whose ions have been stabilized is commercially available. By using this colloidal silica containing ammonia as a dispersant, the aforementioned surface can be reduced compared with the case where colloidal silica containing sodium as a dispersant (sodium-stabilized type) is used only as a general colloidal silica. Treat the amount of sodium in the membrane. Therefore, a surface-treated film having a reduced amount of the aforementioned elution can be obtained. [0064] The aforementioned colloidal silicon dioxide first has an average particle diameter of 4 to 6 nm as described above. When the colloidal silicon dioxide is too large, the corrosion resistance or peel resistance is reduced, and in addition, the adhesiveness (paintability) with the coating film coated on the surface-treated metal plate also tends to decrease. This can be considered because the dispersibility and activity of the colloidal silica in the surface treatment film are reduced, so the barrier property of the surface treatment film is reduced, and the amount of dissolution of colloidal silica in a corrosive environment is reduced. Therefore, by using the colloidal silica having the above-mentioned particle diameter, a surface-treated metal plate having excellent corrosion resistance, coating property, resistance to peeling off of tape, film hardness, and processability can be obtained. Colloidal silicon dioxide with an average particle diameter of 4 to 6 nm. Specific examples include Snowtex NXS (ST-NXS, ammonia stabilized type) and Snowtex XS (ST-XS, sodium stabilized type) manufactured by Nissan Chemical Industry Co., Ltd. )Wait. When a sodium-stabilized type ST-XS is used, it is preferably used in combination with an ammonia-stabilized type ST-NXS. The average particle diameter of the colloidal silica here includes, for example, when the average particle diameter is about 1 to 10 nm, the average particle diameter is about 10 to 100 nm, and the average particle diameter is measured by the BET method. Value, etc. In addition, when a notarized value is described in the manufacturer's manual, this notarized value can be used as the average particle diameter of the colloidal silica here. [0065] In addition, the amount of sodium ions (dissolution amount) eluted from the surface treatment film when immersed in deionized water at 70 to 80 ° C. for 10 minutes is preferably as small as described above. Discussion, we can know that if it is 4 mg / m2
In the following, staining can be suppressed better. This dissolution is particularly good at 3.8 mg / m2
Below, more preferably 3.5 mg / m2
the following. Within this range, not only can staining be suppressed, but also corrosion resistance, blackening resistance, and tape peeling resistance can be improved. In addition, the smaller the amount of dissolution mentioned above, the better, but in the properties of colloidal silica, 1 mg / m2
The left and right are the thresholds, and the lower limit of the dissolution amount is preferably 1 mg / m2
the above. Examples of the amount of dissolution herein include values measured in the following manner. The surface-treated metal plate was immersed in deionized water at 70 to 80 ° C for 10 minutes. The amount of sodium ions contained in the liquid impregnated with the surface-treated metal plate was measured using an ion chromatograph. The eluted amount was calculated from the measured amount of sodium ions and the area of the surface-treated metal plate. As the ion chromatograph, for example, ICS-5000 + manufactured by Thermo Fisher Scientific Co., Ltd. can be used. [0066] In addition, the lower limit of the amount of the colloidal silica added is 10 parts by mass or more, preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more with respect to 100 parts by mass of the surface treatment composition. The upper limit of the amount of the colloidal silica added is less than 30 parts by mass and preferably 28 parts by mass or less with respect to 100 parts by mass of the surface treatment composition. The amount added here is the solid content ratio. The reason that colloidal silicon dioxide is added to the surface treatment film to improve corrosion resistance or blackening resistance can be presumed to be caused by the buffering effect of pH or inert film due to the dissolution and dissolution of colloidal silicon dioxide in a corrosive environment. Formation of actors. Therefore, when the amount of colloidal silica added is too small, this effect cannot be fully exerted, the corrosion resistance is reduced, and the adhesion with the zinc-plated surface tends to decrease. In addition, when the amount of colloidal silica added is excessive, the amount of resin added is reduced, the surface-treated film becomes brittle, and cracking tends to occur. As a result, the blackening resistance is reduced, the adhesion to the zinc-plated surface is also reduced, and the paintability may be reduced. Therefore, when the amount of the colloidal silica added is within the above range, a surface-treated metal plate having excellent corrosion resistance and adhesion to a zinc-plated surface can be obtained. [0067] Further, in the surface-treated film, in addition to the resin and the colloidal silica, it is preferable to contain a cross-linking agent for crosslinking the surface-treated film and a lubricant. [0068] By including the cross-linking agent, the surface treatment film can be improved in corrosion resistance, resistance to tape peeling, and lubricity. This cross-linking agent is a cross-linking agent that cross-links the surface-treated film, that is, a cross-linking agent that cross-links the resin constituting the surface-treated film when forming the surface-treated film, and is also referred to herein as an external cross-linking agent. [0069] The external crosslinking agent is not particularly limited as long as it can crosslink the surface-treated film, and from the viewpoint of reactivity, an epoxy-based crosslinking agent can be preferably used. Examples of the epoxy-based crosslinking agent include sorbitol polyglycidyl ether, (poly) glycerol polyglycidyl ether, neopentyltetraol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and neopentyl Polyglycidyl ethers such as glycol diglycidyl ether and (poly) ethylene glycol diglycidyl ether; polyglycidyl ether amines and the like. This epoxy-based crosslinking agent can be obtained, for example, Epiclon CR5L and Epiclon CR75 manufactured by DIC Corporation. Moreover, the said external crosslinking agent can be used individually by 1 type or in combination of 2 or more types. [0070] The amount of the external crosslinking agent added is not particularly limited, and the lower limit is, for example, preferably 5 parts by mass or more, and particularly preferably 6.5 parts by mass or more, based on 100 parts by mass of the surface treatment composition. The upper limit of the amount of the external crosslinking agent added is preferably 8.5 parts by mass or less with respect to 100 parts by mass of the surface treatment composition. The amount added here is the solid content ratio. When the amount of the external crosslinking agent added is too small, corrosion resistance, black resistance, tape peel resistance, and lubricity tend to decrease. Moreover, when the addition amount of the said external crosslinking agent is too much, there exists a tendency for paintability to fall. In addition, when the external cross-linking agent is excessively added, self-crosslinking by the external cross-linking agent may be considered, but when the amount of the external cross-linking agent is within the above-mentioned range, this situation may be suppressed and performed better. Cross-linking reaction. That is, when the addition amount of the external crosslinking agent is within the above range, the crosslinking reaction proceeds sufficiently, and the corrosion resistance and blackening resistance of the surface-treated film can be improved. Furthermore, since the hardness of the surface-treated film is also increased, the lubricity or processability is also improved. [0071] The lubricant described above, by containing it, can reduce the coefficient of dynamic friction of the surface-treated film, improve workability, and is less prone to damage. [0072] The lubricant is not particularly limited, and examples thereof include polyolefin waxes such as polyethylene, oxidized polyethylene, and polypropylene; polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, and tetrafluoro Fluorine resins such as ethylene; organically modified polysiloxanes; paraffin. In the above examples, the lubricant is preferably a polyolefin-based wax, and particularly preferably a polyethylene wax. Moreover, the said lubricant can be used individually by 1 type or in combination of 2 or more types. [0073] In addition, the polyethylene wax is preferably particulate, for example, spherical, and the average particle diameter is preferably 0.1 to 3 μm, and more preferably 0.3 to 1 μm. When the polyethylene wax particles (spherical polyethylene wax) are too large, it is difficult to uniformly disperse them in the surface treatment composition, hindering film formation, and tending to reduce corrosion resistance. On the other hand, when the polyethylene wax particles are too small, there is a tendency that the lubricity cannot be sufficiently improved. The average particle diameter of the polyethylene wax particles can be measured by a Cote particle counter method. By using the polyethylene wax particles having the above-mentioned particle size to exist in a spherical shape on the surface-treated film, the friction on the surface of the surface-treated film can be effectively reduced, and it is effective to suppress the occurrence of damage and the like. Examples of the polyethylene wax particles include Chemipearl W640, Chemipearl W700, Chemipearl W950, and Chemipearl W900 manufactured by Mitsui Chemicals Corporation. [0074] The amount of the lubricant added is not particularly limited, and the lower limit is, for example, preferably 2 parts by mass or more, and particularly preferably 2.5 parts by mass or more, based on 100 parts by mass of the surface treatment composition. The upper limit of the amount of the lubricant added is preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less, based on 100 parts by mass of the surface treatment composition. The amount added here is the solid content ratio. When the amount of the lubricant is too small, the lubricity is insufficient, and the bending workability of the surface-treated metal plate tends to decrease. In addition, when the amount of the lubricant is too large, the lubricant may be hydrolyzed in a corrosive environment, and the corrosion resistance, black resistance, stain resistance, tape peeling resistance, and paintability tend to decrease. . Therefore, when the amount of the lubricant is within the above range, a surface-treated metal plate having excellent corrosion resistance, blackening resistance, and stain resistance can be obtained. [0075] The lower limit of the adhesion amount of the surface treatment film is 0.4 g / m2
Above, preferably 0.45 g / m2
Above, especially 0.5 g / m2
the above. In addition, the upper limit of the adhesion amount of the surface-treated film is 1.2 g / m2
Below, preferably 0.8 g / m2
Below, particularly preferably 0.7 g / m2
the following. When the amount of adhesion of the surface treatment film is too small, the barrier properties are deteriorated to promote the diffusion of permeation, and the stain resistance tends to be deteriorated. In addition, when the amount of adhesion of the surface-treated film is too small, there is a tendency that the corrosion resistance, blackening resistance, and peeling resistance of the surface-treated metal plate cannot be sufficiently improved. In addition, when the adhesion amount of the surface-treated film is too large, the resistance to peeling of the tape is reduced. For example, when the surface-treated metal plate is subjected to a bending process or a stamping process, the surface-treated film tends to be easily peeled. In addition, paintability and electrical conductivity tend to decrease, which is not good. Therefore, when the adhesion amount of the surface-treated film is within the above range, a surface-treated metal plate having excellent corrosion resistance, blackening resistance, and the like can be obtained. The adhesion amount of the surface-treated film can be measured, for example, in the following manner. Quantitative determination of colloidal silicon dioxide (SiO2
), And calculated from the measured amount of Si element. SiO at this time2
The specific gravity was calculated to be 2.2, and the specific gravity of the resin was calculated to be 1.0. [0076] The surface-treated metal sheet may be provided with the zinc-based plated steel sheet and the surface-treated film, and may be provided with other layers. For example, a primer layer may be provided between the zinc-based plated steel sheet and the surface-treated film. Specifically, in order to improve the adhesion between the surface of the zinc-based plated steel sheet and the surface treatment film, it may be provided by implementing a composition composed of aluminum dihydrogen phosphate, acid colloidal silicon dioxide, and polyacrylic acid. The underlying processing layer obtained by the reactive underlying processing. However, unreacted phosphoric acid or the like is preferred to remove it by washing with water because it may cause blackening resistance or corrosion resistance and promote the generation of stains. The composition used when forming the aforementioned underlayer treatment layer, for example, the content ratio of aluminum dihydrogen phosphate to acidic colloidal silicon dioxide is preferably 5:95 to 35 in terms of mass ratio (aluminum dihydrogen phosphate: colloidal silicon dioxide): 65. The polyacrylic acid preferably contains 1 to 10 parts by mass based on 100 parts by mass of the total of aluminum dihydrogen phosphate and acidic colloidal silicon dioxide. [0077] The method for producing the surface-treated metal plate is not particularly limited as long as it can produce the surface-treated metal plate of this embodiment. The method for manufacturing the surface-treated metal plate specifically includes the following manufacturing methods, which include a step of preparing the surface-treated composition (preparation step), and applying the surface-treated composition to the zinc-based plating A step (coating step) on the surface of at least one of the steel plates, and a step of forming the surface treatment film on the surface of at least one of the zinc-based plated steel plates by drying the surface treatment composition ( Drying step). [0078] The preparation step is not particularly limited as long as it can prepare the surface treatment composition, and examples thereof include preparing a polyolefin resin containing ammonia and emulsified and having an average particle diameter of 4 ~ 6nm steps of colloidal silica surface treatment composition. This preparation step may include mixing the polyolefin resin and the colloid so that the content of the colloidal silicon dioxide is 10 parts by mass or more and less than 30 parts by mass with respect to 100 parts by mass of the surface treatment composition. Steps for silicon dioxide, etc. In addition, the preparation step is to prepare: the amount of sodium ions dissolved from the aforementioned surface treatment film when immersed in deionized water at 70 to 80 ° C for 10 minutes is 4 mg / m2
The following steps of the surface treatment composition. Specifically, a method of using the above colloidal silica containing ammonia as a dispersant as the colloidal silica is mentioned. [0079] The coating step is not particularly limited as long as the surface treatment composition can be coated on the surface of at least one of the zinc-based plated steel sheets, and for example, rod coating is used. Machine coating. In addition, in the aforementioned coating step, the adhesion amount of the surface-treated film is 0.4 to 1.2 g / m.2
In this way, the step of applying the aforementioned surface treatment composition. [0080] The drying step is not particularly limited as long as the surface treatment composition is formed on the surface of at least one of the zinc-based plated steel plates by drying the surface treatment composition. Examples of the drying step include drying at 90 to 130 ° C. [0081] According to this manufacturing method, the surface-treated metal plate of this embodiment can be manufactured preferably. [0082] As described above, this specification has disclosed various aspects of technology, and the main technologies among them are as follows. One aspect of the present invention is a surface-treated metal plate comprising: a zinc-based plated steel sheet, and a surface-treated film laminated on a surface of at least one of the zinc-based plated steel sheets; The film is composed of: a surface treatment composition containing a polyolefin resin that does not contain ammonia and a colloidal silica having an average particle diameter of 4 to 6 nm; the content of the colloidal silica is 100% of that of the surface treatment composition The mass part is 10 parts by mass or more and less than 30 parts by mass; the adhesion amount of the aforementioned surface treatment film is 0.4 to 1.2 g / m2
; The amount of sodium ions dissolved from the aforementioned surface treatment film when immersed in deionized water at 70 ~ 80 ° C for 10 minutes was 4 mg / m2
the following. [0084] According to this configuration, it is possible to provide a surface-treated metal plate that is excellent in blackening resistance and can sufficiently suppress the occurrence of staining, and can also provide a surface-treated metal plate that is excellent in blackening resistance and staining resistance. [0085] In the surface-treated metal plate, the surface-treated composition preferably further contains a crosslinking agent and a lubricant. [0086] According to this configuration, a surface-treated metal plate having more excellent blackening resistance and stain resistance can be obtained. [0087] In the surface-treated metal plate, the content of the cross-linking agent is preferably 5 to 8.5 parts by mass relative to 100 parts by mass of the surface-treated composition. [0088] According to this configuration, a surface-treated metal plate having more excellent blackening resistance and stain resistance can be obtained. [0089] In the surface-treated metal plate, the content of the lubricant is preferably 2 to 5 parts by mass based on 100 parts by mass of the surface-treated composition. [0090] According to this configuration, a surface-treated metal plate having more excellent blackening resistance and stain resistance can be obtained. [0091] In the surface-treated metal plate, the colloidal silicon dioxide is preferably colloidal silicon dioxide containing ammonia as a dispersant. [0092] According to this configuration, a surface-treated metal plate having more excellent blackening resistance and stain resistance can be obtained. [0093] In the surface-treated metal plate, the polyolefin-based resin is preferably a copolymer containing an α, β-unsaturated carboxylic acid and an olefin. [0094] According to this configuration, a surface-treated metal plate having more excellent blackening resistance and stain resistance can be obtained. [0095] Another aspect of the present invention is a method of manufacturing a surface-treated metal plate, which is a method of manufacturing a surface-treated metal plate of the aforementioned surface-treated metal plate, which includes: a step of preparing the aforementioned surface-treated composition, and A step of applying the surface treatment composition to at least one of the surfaces of the zinc-based plated steel sheet, and drying the surface treatment composition to form the surface-treated film on the zinc-based plated steel sheet At least one step on the surface. [0096] According to this configuration, a surface-treated metal plate having excellent blackening resistance and sufficiently suppressing the generation of stains can be produced, and a surface-treated metal plate having excellent blackness and stain resistance can also be produced. [0097] According to the present invention, it is possible to provide a surface-treated metal plate which is excellent in blackening resistance and can sufficiently suppress the occurrence of staining, and a method for manufacturing the surface-treated metal plate. [0098] The following series of examples illustrate the present invention in detail, but the present invention is not limited to these. [Examples] [0099] First, each evaluation method used in the following examples will be described. [0100] [Corrosion resistance] 1. Salt water spray test (SST flat plate, SST cross-cutting) For the test material that is edge-sealed to the inner surface, a person who maintains the flat plate and a cross-cutting person with a cutting blade are produced. For each test material, according to JIS Z 2371, brine (5% NaCl aqueous solution) was sprayed under an environment of 35 ° C to perform a brine spray test. The time until the generation rate of white rust with respect to the test material reached 5 area% was measured. [0101] (SST flat plate) (1) As an evaluation standard of the SST flat plate, if the time until the generation rate of white rust with respect to the flat plate holder reaches 5 area% is 240 hours or more, the evaluation is "◎", and 168 hours or more and less than 240 hours, evaluated as "○", 120 hours or more and less than 168 hours, evaluated as "△", and less than 120 hours, evaluated as "x". [0102] (SST cross-cutting) As an evaluation criterion of SST cross-cutting, if the time until the generation rate of white rust with respect to the cross-cutting person reaches 5 area% is 120 hours or more, the evaluation is "◎" and 96 hours or more Those who did not reach 120 hours were evaluated as "○", those who were 72 hours or longer and less than 96 hours were evaluated as "△", and those who were less than 96 hours were evaluated as "x". [0103] 2. Brine spray cycle test (SST cycle) For a test material (flat plate) with edge seal, according to JIS Z 2371, brine (5% NaCl aqueous solution) was sprayed at 35 ° C to perform a brine spray cycle. test. One cycle is one in which saline spray is performed for 8 hours and then stopped for 16 hours. The number of cycles until the generation rate of white rust with respect to the test material reached 5 area% was measured. As the evaluation standard of the SST cycle, if the number of cycles is more than 10 cycles, the evaluation is "◎", if the number of cycles is 7 or more and less than 10 cycles, the evaluation is "○", and if it is 5 or more and less than 7 cycles, the evaluation It was evaluated as "△" if it had not reached 5 cycles. 0 [0104] 3. Neutral saline spray cycle test (JASO) For a test material (flat plate) with an edge seal, a neutral saline spray cycle test was performed in accordance with JIS H 8502. The 1 cycle is one in which salt water spray is performed for 2 hours, followed by 4 hours of drying (temperature 60 ° C, humidity 30% or more), and 2 hours of humidity (temperature 50 ° C, humidity 95% or more). The number of cycles until the generation rate of white rust with respect to the test material reached 5 area% was measured. As the evaluation standard of JASO, if the number of cycles is 21 or more, it will be evaluated as "◎", if the number of cycles is 15 or more and less than 21 cycles, it will be evaluated as "○", and if it is 9 or more and less than 15 cycles, it will be evaluated as "△" means that those who have not reached 9 cycles are evaluated as "×". [0105] [Black discoloration resistance] After the test material was stored in a constant temperature and humidity tester at a temperature of 50 ° C and a humidity of 98% or more for 168 hours, the color difference (ΔL) before and after the test was measured using a color difference meter. As a criterion for evaluating the resistance to blackening, if ΔL is less than 1, the evaluation is "◎", ΔL is 1 or more and less than 2 and the evaluation is "○", and ΔL is 2 or more and less than 3, the evaluation is " Δ ”and ΔL were 3 or more, and evaluated as“ × ”. [0106] [Stain resistance] 保存 After the test material was stored in a constant temperature and humidity tester at a temperature of 65 ° C and a humidity of 95% or more for 168 hours, the appearance change before and after the test was visually observed. As a criterion for evaluating the resistance to staining, if the occurrence of staining cannot be confirmed, it is evaluated as "◎", only the producer of extremely slight staining is confirmed, and the evaluation is "○", and the creator of slight staining is confirmed , The evaluation is "△", the producer of comprehensive infiltration is confirmed, and the evaluation is "×", and the person who has produced significant infiltration in overall, is evaluated as "×". [0107] [Resistance to Tape Peeling Resistance] The system evaluates the adhesion between the plating surface and the surface treatment film of a zinc-based plated steel sheet under high temperature and humidity conditions. That is, an adhesive tape (fiber silk tape No. 9510 manufactured by Sliontec Co., Ltd.) was attached to the test material, and stored in a constant temperature and humidity test device for 120 hours under a temperature of 40 ° C and a humidity of 98%. Thereafter, a tape peeling test was performed in accordance with JIS K 5400. Then, the residual ratio of the surface-treated film after the tape peeling test was performed was measured. The evaluation criterion for the resistance to peeling of the tape is “◎” if the residual ratio is 95 area% or more, and “○” if it is 90 area% or more and less than 95 area%. Those who reached 90% by area were evaluated as "△", those who did not reach 80% by area were evaluated as "×". [Paintability (Secondary Adhesion of Coating Film)] 丙烯酸 Acryl-based paint (Magicron # 1000 manufactured by Kansai Paint Co., Ltd.) was applied to the test material so that the thickness of the coating film became 20 μm. After coating, firing was performed at a temperature of 160 ° C for 20 minutes for post-coating. Next, the post-coating test material was immersed in boiling water for 1 hour, then taken out and left for 1 hour, and then 100 tessellated 1 mm squares were engraved with a cutting knife, and this was performed in the same manner as the above-mentioned tape peel resistance Tape peel test. The number of squares of the coating film remaining without peeling was measured. As a criterion for evaluating the paintability (secondary adhesion of the coating film), if the number of remaining cells is 100, the evaluation is "◎", and those with 90 or more and 99 or less are evaluated as "○" and 80 Those above 89 or below were evaluated as "△", and those below 79 were evaluated as "×". [0109] [Lubricity (Coefficient of Dynamic Friction)] The coefficient of dynamic friction of the test material is measured using a friction coefficient measuring device as shown in FIG. 5. Specifically, as shown in FIG. 5, the test material 51 is sandwiched between the stamper plates 52 and 53, and the stamper plate 53 is pressed toward the test material 51 by a pressing force P. In this state, the test material 51 is pulled out between the stamper plate 52 and the stamper plate 53. The pull-out load F at this time was measured, and from the measured F, the dynamic friction coefficient μ (= F / 2P) of each test material was calculated. The measurement conditions are as follows. Fig. 5 is a schematic diagram showing a friction coefficient measuring device for evaluating lubricity. [0110] Sample size: 40 × 300mm Pressing force P: 5.4MPa Pull-out speed: 300mm / min. Die plate material: SKD11 No oiling [0111] As a criterion for evaluating lubricity, if the dynamic friction coefficient μ does not reach 0.09, then The evaluation was "◎", those who were 0.09 or more and less than 0.15 were evaluated as "○", those who were 0.15 or more and less than 0.2 were evaluated as "△", and those who were 0.2 or more were evaluated as "x". [0112] [Test Example 1 (Resin)] 之 As a resin constituting a surface-treated film, the following resins were used. [Resin A: Ammonia-free and emulsified polyolefin-based resin] (1) Add 626 parts by mass of water and 160 parts by mass of ethylene-acrylic acid copolymer (acrylic unit: 20% by mass, melting index MI: 300) to An autoclave having an emulsifying device equipped with a stirrer, a thermometer, and a temperature controller, followed by adding 40 mol% triethylamine and 15 mol% sodium hydroxide to 1 mol of the carboxyl group of the ethylene-acrylic acid copolymer . After stirring at 150 ° C and 5Pa at high speed, it was cooled to 40 ° C. 5 parts by mass of 4,4'-bis (ethyleneiminocarbonylamino) diphenylmethane as a crosslinking agent with respect to 100 parts by mass of the solid content of the ethylene-acrylic acid copolymer (Nippon Catalysts Co., Ltd. Chemitite DZ-22E) was added here. Thereby, an emulsified ethylene-acrylic acid copolymer (ethylene-unsaturated carboxylic acid copolymer aqueous dispersion) can be obtained. Let this be resin A. This resin A had an average molecular weight of 60,000 and an average particle diameter of 55 nm. In addition, using this resin A, the water vapor transmission rate measured by the above method was 50 g / m2
/day. [Resin B: Emulsified polyolefin resin containing ammonia] 乳化 Ammonia-emulsified ethylene-acrylic copolymer (ethylene-unsaturated carboxylic acid copolymer aqueous dispersion) will be used (Dongbang Chemical Industry Co., Ltd.) Hitec S-7024), which was used as resin B. This resin B is produced using ammonia water for emulsification, unlike the resin A at the time of emulsification. This resin B had an average molecular weight of 30,000 and an average particle diameter of 40 nm. In addition, using this resin B, the water vapor transmission rate measured by the above method was 115 g / m2
/day. (Resin C: Carboxyl-containing Polyurethane Resin Aqueous Dispersion) 60 parts by mass of polytetramethylene ether glycol (average molecular weight: 1000, Hodogaya Chemical Industry Co., Ltd.) as a polyol component (Manufactured), 14 parts by mass of 1,4-cyclohexanedimethanol, and 20 parts by mass of dimethylolpropionic acid, put in a synthesis device equipped with a stirrer, a thermometer, and a temperature controller, and then added 30 parts by mass of N-methylpyrrolidone as a reaction solvent. 104 parts by mass of toluene diisocyanate (TDI) as an isocyanate component was charged, the temperature was raised to 80 ° C to 85 ° C, and the reaction was carried out for 5 hours. The NCO content of the obtained prepolymer was 8.9% by mass. Then, 16 parts by mass of triethylamine was added for neutralization, a mixed aqueous solution of 16 parts by mass of ethylenediamine and 480 parts by mass of water was added, and emulsification was performed at 50 ° C. for 4 hours while a chain extension reaction was performed. Thus, a carboxyl group-containing polyurethane resin aqueous dispersion (polyurethane resin aqueous dispersion) (non-volatile resin component: 29.1% by mass, acid value: 41.4) was obtained. Let this be resin C. Using this resin C, the water vapor permeability was measured by the above method to be 1500 g / m2
/day. [0116] (Resin D: Modified epoxy resin aqueous dispersion) A modified epoxy resin aqueous dispersion (Modepics 302 manufactured by Arakawa Chemical Industries, Ltd.) was used as the resin D. [0117] (Resin E: Polyester resin aqueous dispersion) 液 A polyester resin aqueous dispersion (Bionarl MD1200 manufactured by Toyobo Co., Ltd.) was used as the resin E. [0118] (Surface-treated metal plate No. 1) 72In terms of solid content ratio, 72 parts by mass of resin A and 28 parts by mass of colloidal silicon dioxide (manufactured by Nissan Chemical Industry Co., Ltd.) having an average particle diameter of 4 to 6 nm are added. ST-NXS (ammonia-stabilized type) to prepare a surface treatment composition. 01 [0119] Using zinc electroplated steel sheet (zinc adhesion 20 g / m2
, Plate thickness 0.8mm) as a metal plate. This metal plate was then subjected to the underlying treatment described below. In the bottom treatment, first, a 50% by mass aqueous solution of aluminum dihydrogen phosphate (manufactured by Japan Industrial Co., Ltd.) and acid colloidal silicon dioxide (Snowtex O manufactured by Nissan Chemical Industry Co., Ltd.) are used so that the solid content ratio becomes (Aluminum dihydrogen phosphate: colloidal silicon dioxide) was 12:88, and these concentrations were mixed so that they became 1.5% by mass, and polyacrylic acid powder (East Asia Synthetic Co., Ltd.) was used so as to become 0.1 g / L. AC-10LP) was added to the mixed solution to prepare a bottom treatment solution. Using a sprayer device, this base treatment liquid is sprayed on the surface of the zinc-plated steel plate of the metal plate, and then washed and dried. In this way, a base layer is applied to the metal plate, and a base layer is formed on the metal plate. [0120] On one side of the metal plate on which the underlying treatment layer was formed, the surface treatment composition was coated by a bar coater, and dried at a plate temperature of 100 ° C. to obtain a film adhesion amount of 0.7 g / m.2
Surface-treated steel sheet. The film adhesion amount, as described above, can be quantitatively measured by colloidal silicon dioxide (SiO2
) And calculate the Si element. In addition, this surface-treated steel sheet was immersed in deionized water at 70 to 80 ° C for 10 minutes, and the dissolved sodium (Na) was measured by an ion chromatograph (ICS-5000 + manufactured by Thermo Fisher Scientific Co., Ltd.).+
), The result is, Na+
Dissolution rate is 2.0 mg / m2
. [0121] (Surface-treated metal plates No. 2 to 5) Surface-treated metal plates No. 2 to 5 are manufactured in the same manner as Surface-treated metal plate No. 1 except that resins B to E are used instead of resin A, respectively. . The film adhesion amount is the same as that of the surface-treated metal plate No. 1. 0.7 g / m2
, Na+
Dissolution is also 2.0 mg / m2
. [0122] These surface-treated metal plates Nos. 1 to 5 were evaluated as described above, and the results are shown in Table 1 below. [0123][0124] In addition, FIGS. 6 and 7 show changes in the white rust generation rate in the evaluation of the SST plate and the SST cycle, respectively. Fig. 6 is a graph showing the change of the white rust generation rate over time in the evaluation of the SST plate. In Fig. 6, the lines 61 to 65 show the results of the surface-treated metal plates Nos. 1 to 5, respectively. Fig. 7 is a graph showing the change of the white rust generation rate with respect to the number of cycles in the evaluation of the SST cycle. In addition, in Fig. 7, lines 71 to 75 show the results of the surface-treated metal plates Nos. 1 to 5, respectively. [0125] From these results, it can be seen that when an emulsified polyolefin-based resin containing no ammonia and colloidal silica having an average particle diameter of 4 to 6 nm (surface-treated metal plate No. 1) are used in combination, Corrosion resistance and resistance when compared to polyolefin resins containing ammonia and emulsified resin (surface-treated metal plate No. 2) or when other resins are used (surface-treated metal plate No. 3 to 5) Excellent black discoloration, stain resistance, and tape peel resistance. [0126] [Test Example 2 (colloidal silica)] 之 As the colloidal silica constituting the surface-treated film, the followings manufactured by Nissan Chemical Industry Co., Ltd. were used. [0127] ST-NXS, ST-NS, ST-N, and ST-N40 are ammonia-stabilized types, and each average particle size is shown in Table 2. Na in ST-NXS, ST-NS, ST-N, and ST-N402
The amount of O is 300 ppm or less, 400 ppm or less, 400 ppm or less, and 2000 ppm or less, respectively. [0128] In addition, ST-XS, ST-S, ST-30, and ST-50 are sodium-stabilized types, and each average particle size is shown in Table 2. Na contained in ST-XS, ST-S, ST-30, and ST-502
The amount of O is 3000 to 6000 ppm, 6000 ppm or less, 6000 ppm or less, and 6000 ppm or less, respectively. [0129] (Surface-treated metal plate No. 6 to 13) As a solid content ratio, 61 parts by mass of resin A, 28 parts by mass of colloidal silicon dioxide shown in Table 2 and 7.5 parts by mass were added as crosslinks. Glycidyl-containing crosslinking agent (Epiclon CR5L manufactured by DIC Corporation) and 3.5 parts by mass of a spherical polyethylene wax (Chemipearl W700 manufactured by Mitsui Chemicals Co., Ltd.) as a lubricant, to prepare a surface treatment组合 物。 Composition. [0130] The surface-treated metal plates No. 6 to 13 are manufactured in the same manner as the surface-treated metal plate No. 1 except that the above-mentioned surface-treated composition is used. The film adhesion amount is the same as that of the surface-treated metal plate No. 1. 0.7 g / m2
, Na+
The amounts of dissolution are the values shown in Table 2. [0131] These surface-treated metal plates No. 6 to 13 were evaluated as described above, and the results are shown in Table 2 below. [0132][0133] From Table 2, the amount of sodium ions (Na) dissolved from the surface-treated film when the average particle diameter was 4 to 6 nm and immersed in deionized water at 70 to 80 ° C. for 10 minutes (Na+
Dissolution) is 4 mg / m2
The following colloidal silicas are ST-NXS. [0134] In addition, when using ST-NXS (Surface-treated metal plate No. 6), compared with the case where the average particle diameter is 8 nm or more (Surface-treated metal plate No. 8 to 13), the corrosion resistance, Excellent black discoloration resistance, tape peel resistance, lubricity, and paintability. This can be considered when the colloidal silica is increased, the dispersibility and activity of the colloidal silica in the surface treatment film is reduced, the barrier property of the surface treatment film is reduced, and the dissolution amount of the colloidal silica in a corrosive environment is reduced. The reason for lowering. [0135] In addition, when using ST-NXS (surface-treated metal plate No. 6),+
Dissolution rate exceeds 4 mg / m2
In the case of colloidal silicon dioxide (surface-treated metal plates Nos. 7, 9, 11, and 13), it can be seen that the resistance to blackening and staining is excellent. For example, for the surface-treated metal plate No. 7, a colloidal silica having an average particle diameter equivalent to that of the surface-treated metal plate No. 6 is used, but when+
Dissolution rate exceeds 4 mg / m2
At this time, it was found that the resistance to black discoloration, stain resistance, tape peeling resistance, and paintability were deteriorated. [0136] Next, as shown below, two kinds of colloidal silica were mixed to adjust the Na from the surface treatment film.+
Dissolution amount. [0137] (Surface-treated metal plates No. 14 to 18) Surface-treated metal plates No. 14 to 18, except for using colloidal silicon dioxide mixed in a manner such that the mixing ratio shown in Table 3 is used. It was manufactured in the same manner as the surface-treated metal plate No. 6. The film adhesion amount is the same as that of the surface-treated metal plate No.6, which is 0.7 g / m.2
, Na+
The amounts of dissolution are the values shown in Table 3. [0138][0139] The third table is a mixture of ST-NXS and ST-XS to adjust Na from the surface treatment film.+
Dissolution results. When using ST-NXS alone (surface-treated metal plate No. 14), Na+
Dissolution rate is 2.0 g / m2
, Can show good stain resistance. Even increasing the mixing ratio of ST-XS to make Na+
Dissolution rate becomes 3.9 g / m2
(Surface-treated metal plate No. 17) is the same as surface-treated metal plate Nos. 14 to 16, and it also exhibits good stain resistance. When using ST-XS alone (surface-treated metal plate No. 18), Na+
Dissolution rate becomes 5.0 g / m2
, Pollution occurs and the stain resistance is reduced. [0140] FIG. 8 shows Na from the surface-treated film.+
A graph of the relationship between dissolution and fouling. In the ranking of stains in Figure 8, "5" corresponds to "◎" in the above evaluation criteria for stain resistance, and "4" to "1" correspond to "○" "△" "×" "× × ". From this figure 8, we can also know that if Na+
Dissolution rate is 4.0 mg / m2
The following can suppress the generation of bleed, when Na+
Dissolution rate exceeds 4.0 mg / m2
In this case, the occurrence of staining cannot be suppressed. [0141] In addition, the tape peeling resistance and paintability in the surface-treated metal plate No. 18 were inferior to those in other cases. This can consider the Na in the surface treatment film under the conditions of high temperature and humidity and immersion in boiling water.+
Dissolved to promote performance degradation. [0142] In addition, from Table 3, it can be found that Na+
Dissolution rate is 4.0 mg / m2
In the following cases (surface-treated metal plates No. 14 to 17), compared with surface-treated metal plate No. 18, as described above, not only is it excellent in stain resistance, but also black resistance, tape peeling resistance, and paintability. Excellent. [0143] Furthermore, from Table 3, it can be found that Na+
Dissolution rate is 3.7 mg / m2
In the following cases (Surface-treated metal plate No. 14 to 16), the blackening resistance and paintability are more excellent than those of the surface-treated metal plate No. 17. In addition, Table 3 shows that Na+
Dissolution rate is 3.2 mg / m2
In the following cases (surface-treated metal plates Nos. 14 and 15), even when compared to surface-treated metal plates No. 16, the tape peeling resistance is more excellent. [Experimental Example 3 (Each Additive Amount)] (Surface-treated Metal Plate Nos. 19 to 25) (1) Colloidal silica (with a composition shown in Table 4 and an average particle diameter of 4 to 6 nm was added ( ST-NXS manufactured by Nissan Chemical Industry Co., Ltd .; ammonia-stabilized version), glycidyl-containing crosslinking agent (Epiclon CR5L manufactured by DIC Corporation) as a crosslinking agent, and spherical polyethylene wax as a lubricant (Chemipearl W700 manufactured by Mitsui Chemicals Co., Ltd.), and a surface treatment composition was prepared. [0145] The surface-treated metal plates No. 19 to 25 were manufactured in the same manner as the surface-treated metal plate No. 1 except that the above-mentioned surface-treated composition was used. The film adhesion amount is the same as that of the surface-treated metal plate No. 1. 0.7 g / m2
, Na+
The amounts of dissolution were the values shown in Table 4. [0146] These surface-treated metal plates Nos. 19 to 25 were evaluated as described above, and the results are shown in Table 4 below. [0147][0148] As can be seen from Table 4, when the content of the colloidal silica is 10 parts by mass or more and less than 30 parts by mass based on 100 parts by mass of the surface treatment composition (Surface-treated metal plate No. 19 ~ 23) Compared with when the content is less than 10 parts by mass (surface-treated metal plate No. 24), it has excellent corrosion resistance, blackening resistance, and resistance to tape peeling. In addition, the surface-treated metal plates Nos. 19 to 23 are superior in blackening resistance, tape peeling resistance, and paintability as compared with the case of 30 parts by mass or more (surface-treated metal plate No. 25). These results can be considered when the content of the colloidal silica is 10 parts by mass or more and less than 30 parts by mass, since the colloidal silica is dissolved and eluted in a corrosive environment, it can be formed better and can be fully exerted. The surface treatment of the film due to the buffering effect of pH or the effect of inert film formation. [0149] Furthermore, it can be seen from Table 4 that when the content of the colloidal silica is 15 parts by mass or more and 28 parts by mass or less with respect to 100 parts by mass of the surface treatment composition (Surface-treated metal plate No. 20) ~ 23). Not only is it excellent in blackening resistance and stain resistance, but it is also superior in peeling resistance and lubricity compared to surface-treated metal plate No.19. [0150] In addition, it can be seen from Table 4 that when the content of the colloidal silica is 100 parts by mass or more and 28 parts by mass or less with respect to 100 parts by mass of the surface treatment composition (surface treatment metal plate No. 21 to 21) 23). Not only is it excellent in resistance to blackening and staining, but it is also superior in corrosion resistance compared to surface-treated metal plates No. 19 or 20. [0151] (Surface-treated metal plate Nos. 26 to 31) (1) Colloidal silicon dioxide (ST-manufactured by Nissan Chemical Industry Co., Ltd.) was added with resin A and an average particle diameter of 4 to 6 nm in the composition shown in Table 5. NXS; ammonia-stabilized type), glycidyl-containing crosslinking agent (Epiclon CR5L, manufactured by DIC Corporation), and spherical polyethylene wax (Chemipearl W700, manufactured by Mitsui Chemicals Co., Ltd.) as a crosslinking agent ), And the surface treatment composition is prepared. [0152] The surface-treated metal plates No. 26 to 31 are manufactured in the same manner as the surface-treated metal plate No. 1 except that the above-mentioned surface-treated composition is used. The film adhesion amount is the same as that of the surface-treated metal plate No. 1. 0.7 g / m2
, Na+
The amounts of dissolution were the values shown in Table 5. [0153] These surface-treated metal plates No. 26 to 31 were evaluated as described above, and the results are shown in Table 5 below. [0154][0155] From Table 5, it can be seen that when the content of the cross-linking agent is 5 to 8.5 parts by mass relative to 100 parts by mass of the surface treatment composition (surface-treated metal plate Nos. 26 to 29), When it is less than 5 parts by mass (surface-treated metal plate No. 30), it has excellent corrosion resistance and blackening resistance. In addition, the surface-treated metal plates Nos. 26 to 29 are excellent in blackening resistance and stain resistance, and it is found that the coating properties are superior to those when the surface-treated metal plates exceed 8.5 parts by mass (surface-treated metal plate No. 31). . As a result of these results, when the content of the cross-linking agent is 5 to 8.5 parts by mass, the external cross-linking agent can be inhibited from self-crosslinking, and the cross-linking reaction can be performed better. [0156] In addition, when the content of the cross-linking agent is 6.5 to 8.5 parts by mass relative to 100 parts by mass of the surface-treated composition (surface-treated metal plate Nos. 27 to 29), not only resistance to blackening and stain resistance Excellent, compared with surface-treated metal plate No. 26, it is also excellent in corrosion resistance, tape peel resistance, and lubricity. This can be considered because the hardness of the surface-treated film is also increased due to the progress of the crosslinking reaction. [0157] (Surface-treated metal plate Nos. 32 to 38) (1) Colloidal silicon dioxide (ST-manufactured by Nissan Chemical Industry Co., Ltd.) with resin A and an average particle diameter of 4 to 6 nm was added in the composition shown in Table 6. NXS; ammonia-stabilized type), glycidyl-containing crosslinking agent (Epiclon CR5L, manufactured by DIC Corporation), and spherical polyethylene wax (Chemipearl W700, manufactured by Mitsui Chemicals Co., Ltd.) as a crosslinking agent ), And the surface treatment composition is prepared. [0158] The surface-treated metal plates No. 32 to 38 are manufactured in the same manner as the surface-treated metal plate No. 1 except that the above-mentioned surface-treated composition is used. The film adhesion amount is the same as that of the surface-treated metal plate No. 1. 0.7 g / m2
, Na+
The amounts of dissolution were the values shown in Table 6. [0159] These surface-treated metal plates No. 32 to 38 were evaluated as described above, and the results are shown in Table 6 below. [0160][0161] From Table 6, it can be seen that when the content of the lubricant is 2 to 5 parts by mass relative to 100 parts by mass of the surface treatment composition (surface treatment metal plate Nos. 32 to 36), When it reaches 2 parts by mass (surface-treated metal plate No. 37), it has excellent lubricity. In addition, compared with the case where the surface-treated metal plate Nos. 32 to 36 were more than 5 parts by mass (surface-treated metal plate No. 38), it was found that the corrosion resistance, the blackening resistance, and the stain resistance were excellent. This can be considered to reduce the corrosion resistance and blackening resistance caused by the hydrolysis of the lubricant in a corrosive environment, and improve the lubricity brought by the lubricant. [0162] Furthermore, it can be seen from Table 6 that when the content of the lubricant is 2.5 to 5 parts by mass relative to 100 parts by mass of the surface treatment composition (surface treatment metal plate Nos. 33 to 36), it is not only resistant to It is excellent in blackening and staining resistance, and has superior lubricity compared to surface-treated metal plate No.32. From this result, it can be understood that the content of the lubricant is more preferably 2.5 parts by mass or more with respect to 100 parts by mass of the surface treatment composition. [0163] In addition, it can be seen from Table 6 that when the content of the lubricant is 2 to 4 parts by mass based on 100 parts by mass of the surface treatment composition (surface treatment metal plate No. 32 to 35), it is not only resistant to black It has excellent denaturation, stain resistance, etc., and is also superior to surface-treated metal plate No. 36 in corrosion resistance, tape peel resistance, and paintability. From this result, it can be understood that the content of the lubricant is particularly preferably 4 parts by mass or less with respect to 100 parts by mass of the surface treatment composition. [Test Example 4 (Film Adhesion)] (Surface-treated Metal Plate Nos. 39 to 46, 50, and 51) In terms of solid content ratio, 61 parts by mass of Resin A and 28 parts by mass of the average particle diameter were added. 4 to 6 nm of colloidal silicon dioxide (ST-NXS manufactured by Nissan Chemical Industry Co., Ltd .; ammonia-stabilized type) and 7.5 parts by mass of a glycidyl-containing cross-linking agent (manufactured by DIC Corporation) Epiclon CR5L) and 3.5 parts by mass of a spherical polyethylene wax (Chemipearl W700 manufactured by Mitsui Chemicals Co., Ltd.) as a lubricant to prepare a surface treatment composition. [0165] The surface-treated metal plates Nos. 39 to 46, 50, and 51 are the same as those of the surface-treated metal plate except that the above-mentioned surface-treated composition is used and the film adhesion amount is adjusted to the values shown in Table 7. .1 are manufactured identically. Na+
The amounts of dissolution were the values shown in Table 7. [0166] (Surface-treated metal plate Nos. 47 to 49) Surface-treated metal plate Nos. 47 to 49 are used: This mixture of ST-NXS and ST-XS manufactured by Nissan Chemical Industry Co., Ltd. is used instead of Nissan Chemical ST-NXS manufactured by Industrial Co., Ltd. is a surface treatment composition of colloidal silicon dioxide having an average particle diameter of 4 to 6 nm, and the film adhesion amount is adjusted to the values shown in Table 7. It was manufactured in the same manner as the surface-treated metal plate No. 1. Na+
The amounts of dissolution were the values shown in Table 7. In addition, the surface-treated metal plate No. 47, the mixing ratio of ST-NXS and ST-XS (ST-NXS: ST-XS), is 1: 1 by mass ratio. In addition, the surface treatment metal plate No. 48, the mixing ratio of ST-NXS and ST-XS (ST-NXS: ST-XS), is 1: 1 by mass ratio. In addition, the mixing ratio of surface-treated metal plate No. 49, ST-NXS and ST-XS (ST-NXS: ST-XS) is 1: 2 in terms of mass ratio. [0167] These surface-treated metal plates No. 39 to 51 were evaluated as described above, and the results are shown in Table 7 below. [0168][0169] From Table 7, it can be seen that the adhesion amount of the surface-treated film is 0.4 to 1.2 g / m.2
(Surface-treated metal plate No. 39 ~ 49), and the adhesion amount does not reach 0.4 g / m2
(Surface-treated metal plate No. 50) is superior in corrosion resistance, blackening resistance, tape peel resistance, and lubricity. In addition, surface-treated metal plates No. 39 to 49, and more than 1.2 g / m2
(Surface-treated metal plate No. 51), it was found that the paintability was excellent. [0170] Furthermore, from Table 7, it can be seen that the adhesion amount of the surface-treated film is 0.45 g / m2
(Surface-treated metal plate No.40), the adhesion amount to the aforementioned surface-treated film is 0.4 g / m2
Compared with the surface-treated metal plate No. 39, it has excellent blackening resistance, stain resistance, tape peel resistance, and lubricity. [0171] In addition, the adhesion amount of the surface treatment film was 0.5 g / m.2
(Surface-treated metal plate No. 41), the adhesion amount to the aforementioned surface-treated film was 0.4 g / m2
Compared with the surface-treated metal plate No. 40, it has excellent corrosion resistance. [0172] From the above results, it can be seen that the adhesion amount of the aforementioned surface treatment film is preferably 0.45 g / m2
Above, especially 0.5 g / m2
the above. [0173] In addition, from Table 7, it can be seen that the adhesion amount of the surface-treated film is 0.8 g / m.2
(Surface-treated metal plate No.44), the adhesion amount to the aforementioned surface-treated film is 1 g / m2
Compared with the surface-treated metal plate No. 45, it has excellent blackening resistance. [0174] In addition, from Table 7, it can be seen that the adhesion amount of the surface-treated film is 0.7 g / m.2
(Surface-treated metal plate No. 43), the adhesion amount to the aforementioned surface-treated film was 0.8 g / m2
Compared with the surface-treated metal plate No.44, it has excellent paintability. [0175] From the above results, it can be seen that the adhesion amount of the aforementioned surface treatment film is preferably 0.8 g / m2
Below, particularly preferably 0.7 g / m2
the following. [0176] The present application is based on the Japan Patent Application Request 2016-154609, filed on August 5, 2016, and the Japan Patent Application Request, 2017-108966, filed on June 1, 2017, This content is included in this application. [0177] In order to express the present invention, the present invention is appropriately and fully explained through the embodiments while referring to the drawings, and it should be clear to the practitioner that the above embodiments can be easily changed and / Or improvement. Therefore, as long as the change form or improvement form implemented by the industry is a level that does not depart from the scope of the right of the claim described in the scope of the patent application, the change form or improvement form should be interpreted as covering the right of the claim range. [Industrial Applicability] [0178] According to the present invention, it is possible to provide a surface-treated metal plate which is excellent in blackening resistance and can sufficiently suppress the occurrence of staining, and a method for producing a surface-treated metal plate.