丄乃4029 了檢討。 【專利文獻1】特開平5-106057號公報 【專利文獻2】特開平11-269660號公報 【專利文獻3】特開平8-281864號公報 【專利文獻4】特開昭62-156253號公報 【專利文獻6】特開平11-254585號公報 C 明内】 【發明欲解決之課題】 僅以如上所述之鉻酸鹽處理方法來進行改善時並無法 1〇獲得白色度優異，而且透明度高的透明塗裝不鏽鋼板。本發 明檢討化成處理條件、素材表面的特性及塗裝條件，而以提 供白色度優異之透明塗裝不鏽鋼板及其製造方法為課題。 【用以解決課題的手段】 本發明人等檢討的結果得知，關於無色的透明塗裝不 15鏽鋼板之帶黃色調的著色（黃變）除了是起因於鉻酸鹽處理 外’在透明塗膜的燒付時，不鏽鋼板表面上會發生回火色 (tempered col0r)的著色，這種回火色的著色情形色是造成 黃變的原因。同時得知，藉由使化成處理從鉻酸鹽處理變 更成無鉻酸鹽處理，同時使化成處理皮膜的厚度最適化， 20並且採用财回火色性優異的不鏽鋼板作為應用在透明塗裝 不鏽鋼板的不鏽鋼板的作法，就可以在透明塗裝時實現防 止黃變的結果。 不鑛鋼板的回火色已知可以藉由對增加了 Si、A1的不 鏽鋼板進行光輝退火(bright annealing)而在鋼板表面形成 6 含有Si〇2、Α】2〇3的氧化皮膜的方式加以抑制。亦即，隨著 Si或Α1的含量增加，會變成容易形成&、八丨濃化的氧化皮 膜，耐回火色性因而提高。此類不鏽鋼已知者有高&鋼（專 利文獻4、5)及高A1鋼（專利文獻5)等。 另外’專利文獻6中已揭示將肥粒鐵(ferrite)系不鏽鋼表 面的A1或Si控制在4.5〜6原子％的耐熱透明塗裝不鏽鋼板。 本發明人等銳意地檢討解決前述課題的手段，結果如 上所述地檢討了化成處理條件、素材表面的特性及塗裝條 件，確立了白色度優異之使用了肥粒鐵系不鏽鋼的透明塗 裝不鏽鋼板及其製造方法。 本發明之主要内容如下所述。 (1) 一種白色度優異的透明塗裝不鏽鋼板，特徵在於該 不鏽鋼板係以質量％計含有Si : 0.2〜0.8%的肥粒鐵系不鑛 鋼板’且該鋼板具有自其表面起到5〇人的深度中之cr、si、 A卜Fe原子濃度比（Cr+Si+Al)/Fe為0.6以上的表面氧化皮 膜，並且該鋼板具有塗膜的化成處理劑係由胺基石夕院系、 環氧矽烧系之1種或2種所組成，且化成處理劑的附著量為2 〜20mg/m2(用螢光X射線測定Si〇2量），而透明塗料厚度為i 〜ΙΟμηι的塗膜。 (2) 如（1)中記載之白色度優異的透明塗裝不鏽鋼板，特 徵在於前述不鏽鋼板以質量％計進一步含有Α1: 0.005〜 0.15%。 (3) 如（1)中記載之白色度優異的透明塗裝不鏽鋼板，其 特徵在於前述不鐘鋼板以質量％計進一步含有Nb : 〇. 1〜 1354029 0.7%。 (4)一種白色度優異之透明塗裝不鑛鋼板，其特徵在於 前述不鏽鋼板係以質量％計含有Si : 〇.2〜0.8%、Al : 〇.〇〇5 〜0.15%、Nb : 0.1〜0.7%的肥粒鐵系不鏽鋼板，該鋼板 5具有自其表面起到50A的深度中之Cr、Si、Al、Fe原子濃度 比（Cr+Si+Al)/Fe為0.6以上的表面氧化皮膜，並且該鋼板具 有塗膜的化成處理劑係由胺基矽烷系、環氧矽烷系之1種或 2種所組成，且化成處理劑的附著量為2〜20mg/m2(用螢光 X射線測定Si02量），而透明塗料厚度為1〜ΙΟμπχ的塗膜。 10 (5)—種（1)中記載之白色度優異的透明塗裝不鏽鋼板 素材的製造方法，特徵在於其係以最終光輝退火的溫度 T1(°C)及退火環境氣體的露點T2(°C)滿足1式與2式的條件 進行退火熱處理： 750^T1^5xT2+1200 ......1 式 15 -70ST2S-30 ......2式。 (6)—種白色度優異的透明塗裝不鏽鋼板素材之製造方 法，而該不鏽鋼板是以質量％計含有si : 〇.2〜〇·8%、A1 : 0.005〜0.15%的肥粒鐵系不鏽鋼板’且該鋼板具有自其表 面起到50人的深度中之Cr、Si、Al、Fe原子濃度比 20 (Cr+Si+Al)/Fe為0.6以上的表面氧化皮膜’並且該白色度優 異的透明塗裝不鏽鋼板素材具有塗膜的化成處理劑係由胺 基矽烷系、環氧矽烷系之1種或2種所組成’ s亥化成處理劑 的附著量為2〜20mg/m2(用螢光X射線測定Si〇2量）’透明塗 料厚度為1〜ΙΟμπι的塗膜，又，該製造方法係對該白色度 8 1354029 優異的透明塗裝不鏽鋼板素材，以最終光輝退火的溫度 Tl(°c)及退火環境氣體的露點T2(°c)滿足1式與2式的條件 進行退火熱處理： 750ST1S5XT2+1200 ……1 式 5 -70ST2S-30 ……2式。 (7) —種白色度優異的透明塗裝不鏽鋼板素材之製造方 法，而該不鏽鋼板係以質量％計含有Si : 0.2〜0.8%、A1 : 0.005〜0.15%、Nb : 0.1〜0.7%的肥粒鐵系不鏽鋼板，且該 鋼板具有自其表面起到5〇A的深度辛之Cr、Si、A卜Fe原子 10 濃度比（Cr+Si+Al)/Fe為0.6以上的表面氧化皮膜，並且該白 色度優異的透明塗裝不鏽鋼板素材具有塗膜的化成處理劑 係由胺基矽烷系、環氧矽烷系之1種或2種所組成，且該化 成處理劑的附著量為2〜20mg/m2(用螢光X射線測定Si02 量），而透明塗料厚度為1〜ΙΟμπι的塗膜，又，該製造方法 15 係對該白色度優異的透明塗裝不鏽鋼板素材，以最終光輝 退火的溫度T1(°C)及退火環境氣體的露點T2(°C)滿足1式與 2式的條件進行退火熱處理： 750ST1S5XT2+1200 ……1 式 -70ST2S-30 ......2式。 20 (8)—種白色度優異的透明塗裝不鏽鋼板素材之製造方 法，而該不鏽鋼板係以質量％計含有Si : 0.2〜0.8%的肥粒 鐵系不鏽鋼板，且該鋼板具有自其表面起到50人的深度中之 Cr、Si、A卜Fe原子濃度比(Cr+Si+Al)/Fe為0.6以上的表面 氧化皮膜，並且該白色度優異的透明塗裝不鏽鋼板素材具 9 有塗膜的减處理_由絲魏系、環氧錢系之i種或 2種所組成，且該化成處理劑的附著量為2〜2〇mg/m2(用螢 光X射線測定Si〇2量）’而透明塗料厚度為丨〜川叫^的塗 媒’又’該製造方法係對該白色度優異的透明塗裝不鑛鋼 板素材，以最终光輝退火的溫度丁1(。〇及$火環境氣體的 露點丁2(。〇滿足1式與2式的條件進行退火熱處理，並將經 過冷軋的練齡不鏽鋼板於表面研磨處理後再施以最終 光輝退火： 750^T1^5xT2+12〇〇 ......丄式 -70^12^-30 ...…2式。 ⑼如(6)中記載之白色度優異的透明塗裝不鏽鋼板素 材之製造方法，係將經過冷軋的肥粒㈣不鏽鋼板於表面 研磨處理後再施以最終光輝退火。 (10)如⑺中記載之白色度優異的透明塗裝不鏽鋼板素 材之製造方法，係將，料冷㈣肥域纟不_板於表面 研磨處理後再施以最終光輝退火。 圖式簡單說明 第1圖為化成處理附著量，和透明塗裝不鐵鋼板之變色 △b*的關係示意圖。 第2圖為從表面起到50人的深度中之Cr、Si、八卜以原 子濃度比(Cr+Si+Al)/Fe ’和利用224〇C燒結的透明塗裝不鏽 鋼板之變色的關係示意圖。 第3圖為研磨拋光不鏽鋼板，和研磨後施以本發明範圍 的光輝退火之鋼板的燒結溫度，和透明塗裝残鋼板之變 色Ab*的關係示意圖。 第4圖為光輝退火的退火溫度T1fc)、露點T2fC)和， 從表面起到50A的深度之氧化皮膜中的Cr、Si、A卜Fe原子 濃度比(Cr+Si+Al)/Fe的關係示意圖。 【實施方式】 【實施發明之最佳態樣】 本發明人等對透明塗裝不鏽鋼板的設計性中有關前處 理和素材表面特性加以研的結果發現，以下2點對於獲得白 色度優異的透明塗裝不鏽鋼板而言是重要的。首先，第1點 是前處理的化成處理劑中不用鉻酸鹽處理劑，而是使用胺 基矽烷系、環氡化矽化成處理劑，同時使該化成處理劑的 附著量落在最適範圍。第2是使不鏽鋼板素材在表面部分富 含Cr、Si、A1的成分，以防止塗裝燒結時因回火色著色作 用所造成之素材的變色。再者’關於無色的透明塗料，可 以使用聚酯樹脂系、丙烯酸樹脂系、丙烯酸氨酯樹脂（acrylic urethane resin)系、環氧變性聚酯樹脂系等之任一者。 以下將就本發明之透明化成處理作說明。 本發明之透明化成處理劑係由胺基矽烷系、環氧矽烷 系之1種或2種所组成。選擇胺基矽烷系和環氧矽烷系的理 由是因為，如果使用這類處理劑’則附著性良好，而且和 使用鉻酸鹽處理劑的情形相比，可以防止黃色著色。將化 成處理劑的附著量處理成形成2〜2〇mg/m2(用螢光X射線 測定Si02量）的狀態，再以不鏽鋼板素材的表面溫度(MT)為 60〜140°C的條件加以燒結乾燥。 1354029 第1圖中，在100°C下使日本PARKERIZING Co.，Ltd.之 E-206(胺基石夕炫系）的附著量從2mg/m2起變化到50mg/ m2 為止，以滾輪塗佈2μπι的丙烯酸氨酯樹脂系透明塗料，調 查以200°C的燒結溫度進行塗裝之透明塗裝不鏽鋼板的色 5 調變化。由於透明塗裝中所採用的不鏽鋼板素材係使用從 表面起到5〇A的深度中之Cr、Si、Al、Fe原子濃度比 (Cr+Si+Al)/Fe(後述）為0.6以上之SUS430/光輝退火材，使 得起因於回火色著色的黃變極度地減少。第1圖的縱軸(ΔΙ)*) 係’使化成處理劑的附著量如橫轴所示般地變化，從燒結 10 塗裝透明塗料時之b*⑴減去鋼板素材之b*(2)而得者。△“= b*(l)- b*(2)。 其結果如第1圖所示，化成處理劑的附著量如果超過 20mg/m2 ’不但透明塗裝不鏽鋼的光澤會降低，同時會帶 有些許的黃色調。附著量在2〇mg/m2以下時，Ab*變成〇.3 15 以下，因化成處理所造成之色調變化少。另一方面，當化 成處理未達2mg/m2時，皮膜會變得不均勻，透明塗膜與不 鑛鋼的密著性降低。因此，本發明中將化成處理劑的附著 量定為2〜20mg/m2。再者，關於化成處理劑的附著量可以 藉由對不鏽鋼板表面用螢光X射線測定Si02i而加以定量。 20 透明塗膜的厚度在Ιμιη起到ΙΟμηι以下的範圍。這是因 為1以下難以獲得安定的色調，而ΙΟμπι以上則難於以1 次塗佈進行製造，塗膜成本也會變高之故。較佳為2μπι起 到5μηι的範圍。 接著將就本發明透明塗裝不鏽鋼板的素材加以敘述。 12 1354029 本發明中，特徵在於使用具有從表面起到50A的深度中 之Cr、Si、Al、Fe原子濃度比(Cr+Si+Al)/Fe(後述）為0.6以 - 上之表面氧化皮膜的鋼板，藉而防止塗裝燒結時之回火色 - 著色並防止黃變。使用含有〇.2質量％以上的Si之肥粒鐵系 5 不鏽鋼板，並在預定的溫度和環境氣體下對該鋼板進行光輝 退火，可以使鋼板表面的原子濃度落在上述合適的範圍中。 透明塗裝不鏽鋼板的不鑛鋼是以質量％計含有Si : 〇.2 φ 〜〇·8%的肥粒鐵系不鏽鋼板。因為肥粒鐵系不鏽鋼中的元 素擴散速度比沃斯田鐵系快，所以易於使Cr和Si進入皮膜 10中的濃度濃化。因此，本發明限定於肥粒鐵系不鏽鋼板》 尤其是用含有A1和Si的特殊鋼種（cr-Al鋼和Cr-Si鋼）比較 谷易，專利文獻4及5中已有記載。然而，本發明之肥粒鐵 系不鏽鋼板，亦即含有Si : 0.2〜0.8%的鋼中，必須採用後 述之用於使皮膜中的Cr、Si、A1濃化的技術。 15 I發明中，為了在不鏽鋼板表面形成Si濃化的表面氧 φ 化皮膜’ Sl有必要含有〇·2%以上，此時，Si也包含鑄鋼時 使用作為脫氧兀素者。Si的上限0.8%是特別用來表示本發 明所泛用的粒鐵系不鏽鋼。如果含有該量以上的&，就會 超過泛用的肥粒鐵系不鏽鋼’例如SUS43〇或添加Nb的 20 SUS430J1L的成分範圍。亦即，添加超過08%的&會發生固 熔硬化作用，使加工性劣化，並不適合泛用的用途。 本發明中，椒含有0.005%以上、〇 15%以下的微量為 宜。這是因為A1和Si同樣地，如以下所述，會在光輝退火 皮膜中濃化，故有抑制透明塗膜燒結時之b*增加的效果。 13 1被g作脫氧元素添加了 0.005%以上。添加多量的Ai會使 加工性劣化。因此，A1以0.005〜0.15%為佳。 本發明中’ Cr是肥粒鐵系不鏽鋼板的基板成分，其含 有置可以在16.0〜20.0質量％的範圍。此外，為了製作白色 度優異的透明不鏽鋼板，Cr含有量以儘可能多者為佳。這 是因為光輝退火時有促進Cr在皮膜中的濃化之作用。此外 ’本發明中以含有〇.1〜〇.7%的灿為宜。這是因為考慮到Nb 的氧化物比Cr氧化物在熱力學上更為安定，又具有和&同 樣的作用之故。 接著將就用於在含有Si : 0.2〜0.8%的肥粒鐵系不鏽鋼 中使表面氧化皮膜中的Cr、Si、A1濃化的技術作說明。 肥粒鐵系不鏽鋼之SUS430的冷軋退火後，將No.4研磨 抛光的材料施以光輝退火’利用使光輝退火的溫度和環境 氣體變化之作法，使氧化皮膜中的Cr、Si、A卜Fe之比例 改變。化成處理是將胺基矽烷系化成處理劑塗布在原子濃 度比(〇+5丨+八1)/卩6調整在0.15〜3.5範圍的材料上，使附著 量成為10mg/m2’在l〇〇°c進行燒結乾燥後，以滾輪塗布2μιη 的丙烯酸氨酯樹脂系透明塗料。第2圖中所示為，透明塗料 塗布後的燒結溫度224°C時’原子濃度比(Cr+Si+Al)/Fe和 △b*的關係。以燒結後和基準材(透明塗裝不鏽鋼板素材）的 b*之差來進行評估。從第2圖可知，在原子濃度比 (Cr+Si+Al)/Fe調整成0.6以上的材料中，因塗裝.燒結所造 成的色調變化少，Ab*未滿1且變色少。 接著，準備原子濃度比(Cr+Si+Al)/Fe調整成0.6以上的 1354029 材料，和原子濃度比(Cr+Si+Al)/Fe調整成不滿〇·6的材料， 使燒結温度從150°C變化到250°C為止，觀察色調的變化。 除了溫度的差異及品種的差異以外，和上述第2圖的情形相 同。第3圖中’關於〇和△的材料，原子濃度比(Cr+Si+A1)/Fe 5調成3左右。關於參和▲’原子濃度比(Cr+Si+Al)/Fe分別調 成0.4左右、〇·2左右。其結果如第3圖所示，藉光輝退火將 (Cr+Si+Al)/Fe調整成0.6以上的材料中，因塗裝.燒結所導 致之色調變化少。另一方面，研磨加工拋光後，未進行光 輝退火的材料和以本發明範圍外的光輝退火條件處理，調 10 王成原子ί辰度比(Cr+Si+Al)/Fe不滿0.6的材料，塗裝.燒結 時的帶黃色變色現象很大，尤其是燒結溫度20(rc以上的高 溫時特別顯著。 再者’本發明中，表面氧化皮膜中的成分以AES(奥傑 電子光έ普分析法(AUger Electron Spectroscopy))進行分析， 15以氧濃度最高的點為原子濃度比(Cr+Si+Al)/Fe。本發明中 ’將(Cr+Si+Al)/Fe控制在0.6以上，形成Cr和Si濃化的表面 氧化皮膜是極為重要的。此時，Si在表面氧化皮膜的外層 濃化’ A1在表體(bulk)附近的内層濃化。其理由係因，光輝 退火條件是，對Cr而言是被還原的條件，對Si、A1而言是 20 被氧化的條件，同時Al2〇3的解離壓比Si〇2低。另外，雖然 也考慮到(Cr+Si+Al)/Fe的適當範圍會因表面氧化皮膜的測 定方法而有所差異，但是必要的表面氧化皮膜構造則和上 述所載者相同。 冷軋退火材、研磨拋光材的表面氧化皮膜中原子濃度 15 比(Cr+Si+Al)/Fe在〇·2左右。因此，本發明人等乃就對不鏽 鋼鋼板施行光輝退火，以使其形成從表面起到50Α的深度中 之Cr、Si ' Fe原子濃度比(Cr+Si+Al)/Fe變成0.6以上之 光輝退火條件進行檢討。 光輝退火通常是在氫和氮以氏：N2=(l〜9) : 1範圍的 比例混合而成之還原性環境氣體中進行，此時，退火後之 氧化皮膜中的成分會因退火溫度丁1(。〇與環境氣體露點丁2( C)的組合而變化。 對經過冷軋的SUS430JIL及SUS430鋼板，施以冷軋退 火或相當於No.4拋光(Jis G 0203 No. 5349)的機械研磨，在 多種退火溫度TlfC )與環境氣體露點T2fC)進行光輝退火 的結果示於表4。以退火溫度T1為橫軸，環境氣體露點丁2 為縱軸，各個從表面起到5〇人的深度之(Cr+Si+A1)/Fe原子 濃度比安定下來而成為〇.6以上的範圍為， 750ST1S5XT2+1200 ……is 2式 -70^T2^-30 在1式、2式的範圍中，因為Cr成為被還原的條件，另 -方面’ Si、A1成為被氧化的條件，故可藉由使有效成分⑸ 、A1)進入皮膜中之選擇性氧化所造成的濃化有效地進行。 光輝退火的溫度T1(°C)未滿750。(：時，以Cr為中心之有效元 素(Si、A1)的擴散移動會變慢，無法形成具有足夠的原子濃 度比之氧化皮膜。而當溫度丁〗(。〇超過(5xT2+12〇〇)〇c時， 因為會構成比1式的範圍更屬還原側的條件，所以幻和…的 選擇氧化會受_制，無法形成具有足_原子漢度比之 1354029 氧化皮膜。因此，光輝退火的溫度Tifc)以在根據其與露 點的關係來決定之1式的範圍者為佳。較佳為以上， 1000°C以下。更佳為80(TC以上，90(TC以下。 光輝退火的露點T2(t)如果超過-3〇t，Fe的氧化就會 5變劇烈，Fe進入表面的氧化皮膜的濃化效應就無法避免， 由於會因回火色而變色，故不適於作為透明塗裝不鏽鋼板 的素材。而，未達-70°C的氣體露點在業上是很困難的。因 此，光輝退火的露點以2式的範圍為宜。較佳為_6(rc以上 ，不滿-35°C。 10 專利文獻5所載者為，在Si濃度0.3%中，回火色著色少 的材料，相同文獻中之Si濃度0.3%的實施例則是回火色著 色評點3(黃色），這並無法作為白色度優異的透明塗裝不鏽 鋼板。本發明中’明確規定氧化皮膜中的原子濃度比 (Cr+Si+Al)/Fe為0.6以上’透過明確訂定可以實現該原子濃 15度比的製造條件，即使Si濃度0.8%以下的低Si濃度，依然 可以作成白色度優異的透明塗裝不鑪鋼板。 利用研磨目來賦予不鏽鋼獨特的表面模樣之研磨拋光 材在作為視視設計性的零件上是重要資材。然而，因為施 過表面研磨的不鏽鋼’其表面皮膜$Cr、Si'八丨的濃化非 20常少，加上透明塗膜時會變黃，無法獲得白色度優異之高 設計性的透明塗膜不鏽鋼板。因此，為了使Cr、Si、乂在 表面皮膜中濃化’必須施行光輝退火，但是如果將施行過 通常的軟化退火之肥粒鐵系不鏽鋼板加以表面研磨後再施 行光輝退火時’製造程序會變得煩雜，成為成本上昇的重 17 j354〇29 要廣因。因此’本發明中以將冷軋後的肥粒鐵系不鏽鋼板 妒以表面研磨後再施行最終光輝退火的方式為宜。透過冷 軋一表面研磨-光輝退火的製造程序，可以利用1次光輝退火 - 同時實施用以訂作材質的軟質化退火和使Cr、Si、A1進到 - 5表面皮膜中的濃化（高（Cr+Si+Al)/Fe)。特別是本發明的肥 雜鐵系不鏽鋼板中，為了使軟質化溫度和使Cr、Si、…進 到表面皮膜中的濃化溫度達成一致，亦可利用Nb的含量來 控剎.調整再結晶溫度。而，在奥斯田鐵系不鏽鋼板的情 φ 衫中’因為固溶化退火通常在1〇〇〇。(：以上，故和使Cr、Si 1〇 ，Al進到表面皮膜中濃化的溫度不會達成一致。因此，冷 軋-研磨後，必須賦予用於固溶化退火和形成氧化皮膜的光 輝退火之2次退火。 【實施例】 表1中示出本發明之實施例及比較例。將肥粒鐵系不鏽 15鋼板的表面抛光分成No 4(細目的研磨抛光）、叫H献ne， φ 毛糸面的研磨拋光)及2B(酸洗後輕輕壓延的肌理)3種類。將 % 4鐵系不鏽鋼板以表1的條件施以光輝退火。再者， ,;抛光的肥粒鐵系不鏽鋼板是採用冷軋後施行退火 火 私序，其他的表面拋光材因為冷軋後並未施行退 x是利用光輝退火也同時實施軟質化的鋼材。另外， 適=輝I火條件的適合條件中示以〇印者，表示條件是合 也厂/不Μχ印者表示條件並不合適。同樣地，在白色度中 : ^者，表示白色度優異；示以X印者，表示白色度 18 1354029Yan Nai 4029 had a review. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 6] Japanese Laid-Open Patent Publication No. Hei 11-254585 (C) The problem to be solved by the invention is that it is not possible to obtain an excellent whiteness and a high transparency when the chromate treatment method is improved as described above. Transparent coated stainless steel plate. The present invention reviews the processing conditions, the characteristics of the surface of the material, and the coating conditions, and provides a transparent coated stainless steel sheet excellent in whiteness and a method for producing the same. [Means for Solving the Problem] As a result of the review by the inventors, it was found that the coloring (yellowing) with a yellow tint of the colorless transparent coating is not caused by the chromate treatment. When the coating film is burned, the color of the tempered col0r is generated on the surface of the stainless steel plate, and the color of the tempered color is the cause of the yellowing. At the same time, it is known that the chemical conversion treatment is changed from the chromate treatment to the chromate-free treatment, and the thickness of the chemical conversion treatment film is optimized, 20 and a stainless steel plate excellent in fiscal color is used as the application in the transparent coating. The stainless steel plate of the stainless steel plate can achieve the result of preventing yellowing during transparent coating. The tempering color of the non-mineral steel sheet is known to be formed by forming an oxide film containing Si〇2, Α2〇3 on the surface of the steel sheet by bright annealing of a stainless steel plate having Si and A1 added thereto. inhibition. In other words, as the content of Si or lanthanum 1 increases, it becomes easy to form an oxide film which is concentrated and concentrated, and the temper resistance is improved. Such stainless steels are known as high & steel (patent literature 4, 5) and high A1 steel (patent document 5). Further, Patent Document 6 discloses a heat-resistant transparent coated stainless steel sheet in which A1 or Si of a ferrite-based stainless steel surface is controlled to 4.5 to 6 at%. The present inventors have intensively reviewed the means for solving the above problems, and as a result, the chemical conversion processing conditions, the characteristics of the surface of the material, and the coating conditions were examined as described above, and the transparent coating using the ferrite-grained stainless steel having excellent whiteness was established. Stainless steel plate and its manufacturing method. The main contents of the present invention are as follows. (1) A transparent coated stainless steel sheet excellent in whiteness, characterized in that the stainless steel sheet contains Si: 0.2 to 0.8% of a ferrite-grained non-mineral steel sheet by mass% and the steel sheet has a surface from the surface thereof a surface oxide film having a ratio of Cr, Si, A, Fe atomic concentration (Cr+Si+Al)/Fe of 0.6 or more in the depth of the deaf person, and the chemical conversion treatment agent having the coating film of the steel plate is composed of an amine-based stone system And one or two kinds of epoxy-based smoldering systems, and the amount of the chemical conversion agent is 2 to 20 mg/m 2 (the amount of Si 〇 2 is measured by fluorescent X-ray), and the thickness of the transparent coating is i ΙΟ ΙΟ μηι Coating film. (2) The transparent coated stainless steel sheet having excellent whiteness as described in (1) is characterized in that the stainless steel sheet further contains Α1: 0.005 to 0.15% by mass%. (3) The transparent coated stainless steel sheet having excellent whiteness as described in (1), wherein the non-clockwise steel sheet further contains Nb: 〇. 1 to 1354029 0.7% by mass%. (4) A transparent coated non-mineral steel sheet excellent in whiteness, characterized in that the stainless steel sheet contains Si in a mass%: 〜.2 to 0.8%, Al: 〇.〇〇5 to 0.15%, Nb: 0.1 ~0.7% of ferrite-based iron-based stainless steel sheet having surface oxidation of Cr, Si, Al, Fe atomic concentration ratio (Cr+Si+Al)/Fe of 0.6 or more from the surface to a depth of 50A The chemical conversion treatment agent having a coating film is composed of one or two kinds of an amine-based decane-based or an epoxy-decane-based compound, and the amount of the chemical conversion treatment agent is 2 to 20 mg/m 2 (using a fluorescent X) The SiO 2 amount was measured by ray, and the transparent coating was a coating film having a thickness of 1 to ΙΟμπχ. (5) A method for producing a transparent coated stainless steel sheet material excellent in whiteness as described in (1), characterized in that the temperature T1 (° C.) of the final bright annealing and the dew point T2 (° of the annealing ambient gas) are used. C) Annealing heat treatment is carried out under the conditions of Equations 1 and 2: 750^T1^5xT2+1200 ......1 Equation 15 -70ST2S-30 ......2. (6) A method for producing a transparent coated stainless steel sheet material excellent in whiteness, and the stainless steel sheet contains, by mass%, a ferrite iron containing si: 〇.2~〇·8%, A1: 0.005~0.15% a stainless steel plate' having a surface oxide film having a Cr, Si, Al, Fe atomic concentration ratio of 20 (Cr+Si+Al)/Fe of 0.6 or more from a surface thereof to a depth of 50 Å and the white The chemical conversion treatment agent having a coating film having excellent coating properties is composed of one or two kinds of amine decane-based or epoxy decane-based compounds. The adhesion amount of the s-hai chemical treatment agent is 2 to 20 mg/m 2 . (Measurement of the amount of Si〇2 by fluorescent X-rays) 'The coating film having a transparent coating thickness of 1 to ΙΟμπι, and the manufacturing method is a transparent transparent coated stainless steel plate material having a whiteness of 8 1354029, which is finally bright-annealed. The temperature Tl (°c) and the dew point T2 (°c) of the annealing ambient gas satisfy the conditions of Equations 1 and 2 for annealing heat treatment: 750ST1S5XT2+1200 ......1 Equation 5 -70ST2S-30 ......2. (7) A method for producing a transparent coated stainless steel sheet material having excellent whiteness, and the stainless steel sheet contains Si: 0.2 to 0.8% by mass%, A1: 0.005 to 0.15%, and Nb: 0.1 to 0.7%. A ferrite-rich iron-based stainless steel plate having a surface oxide film having a concentration ratio of Cr, Si, and A Fe atoms of 10 Å to a thickness of (Cr+Si+Al)/Fe of 0.6 Å from the surface thereof In addition, the chemical conversion treatment agent having a coating film which is excellent in whiteness is composed of one or two kinds of an amine-based decane-based or an epoxy-nonane-based material, and the amount of the chemical conversion treatment agent is 2 ~20mg/m2 (the amount of SiO2 is measured by fluorescent X-ray), and the transparent coating has a thickness of 1~ΙΟμπι, and the manufacturing method 15 is a transparent coating of stainless steel material with excellent whiteness. Annealing temperature T1 (°C) and annealing environment gas dew point T2 (°C) satisfy the conditions of Equation 1 and Type 2 for annealing heat treatment: 750ST1S5XT2+1200 ......1 Formula-70ST2S-30 ......2 . 20 (8) - a method for producing a transparent coated stainless steel sheet material excellent in whiteness, and the stainless steel sheet contains Si: 0.2 to 0.8% of a ferrite-grained stainless steel sheet in mass%, and the steel sheet has The surface has an oxide film having a Cr, Si, and A atom concentration ratio of (Cr+Si+Al)/Fe of 0.6 or more in a depth of 50, and the transparent coated stainless steel sheet material having excellent whiteness is 9 There is a reduction treatment of the coating film _ consisting of the silk or the epoxy type, or the amount of the chemical treatment agent is 2 to 2 〇mg/m 2 (the measurement of Si 用 by fluorescent X-ray) 2)) and the thickness of the transparent coating is 涂~chuan called ^'s coating medium' and the manufacturing method is the transparent coating of the non-mineral steel plate material with excellent whiteness, and the temperature of the final brilliant annealing is 1 (. $ Dew point of fire environment gas ( 2 (. 〇 meets the conditions of type 1 and type 2 for annealing heat treatment, and the cold-rolled stainless steel sheet is surface-polished and then subjected to final glow annealing: 750^T1^5xT2 +12〇〇...丄式-70^12^-30 ......2. (9) Transparent coating excellent in whiteness as described in (6) The method for producing the stainless steel sheet material is to subject the cold-rolled fertilizer (four) stainless steel sheet to a surface polishing treatment and then to perform final bright annealing. (10) Manufacture of transparent coated stainless steel sheet material having excellent whiteness as described in (7) The method is that the material is cooled (four), and the surface of the ferrite is not subjected to surface polishing treatment, and then the final bright annealing is applied. The simple description of the drawing is shown in Fig. 1 for the amount of deposition of the chemical treatment, and the discoloration of the transparent coated non-ferrous steel plate △b Schematic diagram of the relationship between * and Fig. 2 is a transparent coated stainless steel sintered at a concentration of (Cr+Si+Al)/Fe' from the surface to a depth of 50 people and atomic concentration ratio (Cr+Si+Al)/Fe' Schematic diagram of the relationship between the discoloration of the plate. Fig. 3 is a schematic view showing the relationship between the sintering temperature of the polished and polished stainless steel plate and the gloss annealing of the steel plate of the present invention after polishing, and the discoloration Ab* of the transparent coated residual steel plate. The relationship between the annealing temperature T1fc), the dew point T2fC), and the concentration ratio of Cr, Si, and A in the oxide film having a depth of 50 A from the surface (Cr+Si+Al)/Fe. [Embodiment] The inventors of the present invention have studied the pretreatment and the surface characteristics of the material in the design of the transparent coated stainless steel sheet, and found that the following two points are excellent in obtaining whiteness. It is important to coat stainless steel plates. First, in the first-stage chemical conversion treatment agent, the chromate treatment agent is not used, and an amine decane-based or cyclization-forming treatment agent is used, and the amount of the chemical conversion treatment agent falls within an optimum range. The second is to make the stainless steel sheet material rich in components of Cr, Si, and A1 on the surface portion to prevent discoloration of the material due to temper coloring during coating sintering. Further, as the colorless clear coating material, any of a polyester resin type, an acrylic resin type, an acrylic urethane resin type, and an epoxy modified polyester resin type can be used. The transparent formation process of the present invention will be described below. The clearing treatment agent of the present invention is composed of one or two kinds of an amine decane type or an epoxy decane type. The reason for selecting the amine decane type and the epoxy decane type is because the adhesion is good if such a treating agent is used, and yellow coloring can be prevented as compared with the case of using the chromate treating agent. The amount of deposition of the chemical conversion treatment agent is treated to form a state of 2 to 2 〇mg/m 2 (the amount of SiO 2 is measured by fluorescent X-ray), and then the surface temperature (MT) of the stainless steel plate material is 60 to 140 ° C. Sintering and drying. 1354029 In Fig. 1, the adhesion amount of E-206 (Amine Shih Hyun) of Japan PARKERIZING Co., Ltd. was changed from 2 mg/m2 to 50 mg/m2 at 100 ° C, and 2 μm was coated with a roller. The urethane acrylate resin was a clear coating, and the color change of the transparent coated stainless steel plate coated at a sintering temperature of 200 ° C was investigated. The stainless steel plate material used in the transparent coating uses a Cr, Si, Al, and Fe atomic concentration ratio (Cr+Si+Al)/Fe (described later) of 0.6 or more in a depth of 5 〇A from the surface. The SUS430/glow-annealed material greatly reduces the yellowing caused by the temper color. In the vertical axis (ΔΙ)*) of Fig. 1, the amount of deposition of the chemical conversion treatment agent is changed as shown on the horizontal axis, and b*(1) when the transparent paint is applied by sintering 10 is subtracted from b* (2) of the steel material. ) and the winner. △ "= b*(l)-b*(2). As shown in Fig. 1, if the amount of the chemical conversion agent exceeds 20 mg/m2, the gloss of the transparent coated stainless steel will decrease, and some will be somewhat When the adhesion amount is 2 〇mg/m2 or less, Ab* becomes 〇.3 15 or less, and the change in color tone due to the chemical conversion treatment is small. On the other hand, when the chemical conversion treatment is less than 2 mg/m2, the film is formed. In the present invention, the adhesion amount of the chemical conversion treatment agent is set to 2 to 20 mg/m 2 , and the amount of the chemical conversion treatment agent can be adjusted. The surface of the stainless steel plate is quantified by measuring the SiO 2 by fluorescent X-rays. 20 The thickness of the transparent coating film is in the range of ΙΟμηη or less. This is because it is difficult to obtain a stable color tone of 1 or less, and it is difficult to obtain a stable color tone of 1 or less. The coating is applied and the cost of the coating film is also increased. It is preferably in the range of 2 μm to 5 μm. Next, the material of the transparent coated stainless steel sheet of the present invention will be described. 12 1354029 In the present invention, it is characterized in that it is used. Has a surface from 50A A steel sheet having a surface oxide film having a concentration ratio of Cr, Si, Al, and Fe in a depth of (Cr + Si + Al) / Fe (described later) is 0.6 to prevent tempering color during coating sintering - coloring And preventing yellowing. Using a ferrite-based iron-based 5 stainless steel plate containing more than 2% by mass of Si, and subjecting the steel sheet to a bright annealing at a predetermined temperature and ambient gas, the atomic concentration on the surface of the steel sheet may fall above In the appropriate range, the non-mineral steel of the transparent coated stainless steel plate is a ferrite-based iron-based stainless steel plate containing Si: 〇.2 φ 〇 8% 8% by mass%. The Beverly field iron system is fast, so it is easy to concentrate the concentration of Cr and Si into the film 10. Therefore, the present invention is limited to the ferrite iron-based stainless steel plate, especially the special steel type (Cr-Al) containing A1 and Si. Steel and Cr-Si steel are compared with those of the patent documents 4 and 5. However, in the ferrite-based stainless steel sheet of the present invention, that is, steel containing Si: 0.2 to 0.8%, it is necessary to adopt the following. A technique for concentrating Cr, Si, and A1 in a film. The surface oxygen oxidized film of the Si-concentrated surface of the stainless steel plate is required to contain 〇·2% or more. In this case, Si is also used as a deoxidizing element when the steel is cast. The upper limit of Si is 0.8%. The granulated iron-based stainless steel which is widely used in the present invention, when it contains more than this amount, exceeds the range of the granules of the granules of the granules of the granules of the granules of the granules, such as SUS 43 〇 or Nb. More than 08% of & will have a solid solution hardening effect, which deteriorates workability and is not suitable for general use. In the present invention, the pepper is preferably contained in an amount of 0.005% or more and 〇 15% or less. This is because A1 and Si are concentrated in the bright annealing film as described below, so that the effect of suppressing the increase in b* when the transparent coating film is sintered is suppressed. 13 1 was added as a deoxidizing element by more than 0.005%. Adding a large amount of Ai deteriorates workability. Therefore, A1 is preferably 0.005 to 0.15%. In the present invention, 'Cr is a substrate component of a ferrite-based iron-based stainless steel sheet, and the content thereof may be in the range of 16.0 to 20.0% by mass. Further, in order to produce a transparent stainless steel sheet excellent in whiteness, the Cr content is preferably as much as possible. This is because the glow annealing promotes the concentration of Cr in the film. Further, in the present invention, it is preferable to contain 〇.1 to 〇.7%. This is because it is considered that the oxide of Nb is thermodynamically more stable than the Cr oxide, and has the same effect as & Next, a technique for concentrating Cr, Si, and A1 in the surface oxide film in a ferrite-based iron-based stainless steel containing Si: 0.2 to 0.8% will be described. After the cold-rolling annealing of the SUS430 of the ferrite-grained stainless steel, the material polished and polished by No. 4 is subjected to a bright annealing, and the temperature of the bright annealing and the change of the ambient gas are used to make Cr, Si, and A in the oxide film. The proportion of Fe changes. The chemical conversion treatment is carried out by applying an amine decane to a treatment agent and coating the material at a ratio of atomic concentration (〇+5丨+八1)/卩6 to a range of 0.15 to 3.5, so that the adhesion amount becomes 10 mg/m2'. After sintering and drying at °c, a 2 μm acrylamide resin-based clear coating was applied by a roller. Fig. 2 is a graph showing the relationship between the atomic concentration ratio (Cr + Si + Al) / Fe and Δb * at a sintering temperature of 224 ° C after the application of the clear paint. The evaluation was performed after the difference between b* of the sintered material and the reference material (transparent coated stainless steel plate material). As is apparent from Fig. 2, in the material in which the atomic concentration ratio (Cr + Si + Al) / Fe is adjusted to 0.6 or more, the change in color tone due to coating and sintering is small, and Ab* is less than 1 and discoloration is small. Next, prepare a 1354029 material whose atomic concentration ratio (Cr+Si+Al)/Fe is adjusted to 0.6 or more, and a material whose atomic concentration ratio (Cr+Si+Al)/Fe is adjusted to be less than 〇6, so that the sintering temperature is 150. The change in hue was observed until °C was changed to 250 °C. Except for the difference in temperature and the difference in variety, the same as in the case of Fig. 2 above. In Fig. 3, the material concentration ratio (Cr + Si + A1) / Fe 5 is about 3 in terms of 〇 and Δ. About the ▲' atomic concentration ratio (Cr+Si+Al)/Fe is adjusted to about 0.4 and about 〇·2, respectively. As a result, as shown in Fig. 3, in the material in which (Cr + Si + Al) / Fe was adjusted to 0.6 or more by the glow annealing, the change in color tone caused by the coating and sintering was small. On the other hand, after polishing and polishing, the material which is not subjected to the bright annealing and the condition which is subjected to the bright annealing condition outside the scope of the present invention, the material of which is less than 0.6 (Cr+Si+Al)/Fe is less than 0.6. Coating. The phenomenon of yellow discoloration during sintering is very large, especially when the sintering temperature is 20 (high temperature above rc is particularly remarkable. In addition, in the present invention, the composition in the surface oxide film is AES (Aojie electronic optical analysis) The method is analyzed by AUGER Electron Spectroscopy, and the point with the highest oxygen concentration is the atomic concentration ratio (Cr+Si+Al)/Fe. In the present invention, '(Cr+Si+Al)/Fe is controlled to 0.6 or more, It is extremely important to form a surface oxide film concentrated with Cr and Si. At this time, Si is concentrated in the outer layer of the surface oxide film 'A1' in the inner layer near the bulk. The reason is that the gloss annealing condition is For Cr, it is a condition to be reduced. For Si and A1, 20 is oxidized, and the dissociation pressure of Al2〇3 is lower than that of Si〇2. In addition, (Cr+Si+Al) is also considered. The appropriate range of /Fe will vary depending on the method of measuring the surface oxide film, but the necessary table The oxide film structure is the same as that described above. The atomic concentration of the surface oxide film of the cold-rolled annealed material and the polishing material is 15 (Cr+Si+Al)/Fe is about 〇·2. Therefore, the inventors of the present invention The stainless steel sheet was subjected to a light annealing treatment to form a glow annealing condition in which the Cr, Si 'Fe atom concentration ratio (Cr + Si + Al) / Fe became 0.6 or more from the surface to a depth of 50 Å. Usually, it is carried out in a reducing environment gas in which hydrogen and nitrogen are mixed in a ratio of N2=(l~9):1. At this time, the composition in the oxide film after annealing is due to the annealing temperature of 1 ( 〇 changes with the combination of ambient gas dew point 2 (C). Cold-rolled SUS430JIL and SUS430 steel sheets are subjected to cold rolling annealing or mechanical polishing equivalent to No. 4 polishing (Jis G 0203 No. 5349). The results of the bright annealing at various annealing temperatures TlfC) and ambient gas dew point T2fC) are shown in Table 4. The annealing temperature T1 is the horizontal axis, and the ambient gas dew point 2 is the vertical axis. The concentration of (Cr+Si+A1)/Fe atomic concentration from the surface to 5 〇 is stabilized and becomes 〇.6 or more. 750ST1S5XT2+1200 ......is 2 type-70^T2^-30 In the range of the formulas 1 and 2, since Cr is a condition to be reduced, the other side 'Si and A1 are oxidized conditions, so The concentration by the selective oxidation of the active ingredients (5) and A1) into the film is effectively carried out. The temperature of the brilliant annealing T1 (°C) is less than 750. (: When the effective element (Si, A1) centered on Cr is slowed down, it is impossible to form an oxide film with a sufficient atomic concentration ratio. When the temperature is 丁 (. 〇 exceeds (5xT2+12〇〇) When 〇c, since it will constitute a condition that is more on the reducing side than the range of the formula 1, the selective oxidation of the illusion and ... will be affected by the formation, and the oxide film having the ratio of the atomic ratio of the atomic ratio of 1354029 cannot be formed. Therefore, the annealing is performed. The temperature Tifc) is preferably in the range of the formula 1 determined according to the relationship with the dew point. It is preferably at least 1000 ° C. More preferably 80 (TC or more, 90 (TC or less.) Dew point of the glow annealing If T2(t) exceeds -3〇t, the oxidation of Fe becomes severe, and the concentration effect of the oxide film on the surface of Fe is unavoidable. Since it is discolored due to temper color, it is not suitable for transparent coating. The material of the stainless steel plate. However, the gas dew point of less than -70 ° C is very difficult in industry. Therefore, the dew point of the glow annealing is preferably in the range of 2, preferably _6 (rc or more, less than -35) °C. 10 Patent Document 5 discloses that the temper color is less colored in the Si concentration of 0.3%. The example in which the Si concentration of 0.3% in the same literature is tempered coloring evaluation point 3 (yellow) is not a transparent coated stainless steel sheet excellent in whiteness. In the present invention, the atom in the oxide film is clearly defined. The concentration ratio (Cr+Si+Al)/Fe is 0.6 or more. The production condition of the atomic concentration of 15 degrees can be achieved by clear definition. Even if the Si concentration is 0.8% or less, the whiteness can be made transparent. Painting of non-furnace steel sheets. Grinding and polishing materials that impart a unique surface appearance to stainless steel by grinding are important materials for visually-designed parts. However, because of the surface-grinding stainless steel's surface film $Cr, Si 'The concentration of gossip is not often 20, and it will turn yellow when it is coated with a clear film. It is impossible to obtain a high-profile transparent coated stainless steel plate with excellent whiteness. Therefore, in order to make Cr, Si, and yttrium in the surface film "Enrichment" must be performed by a glow annealing. However, if the normal soft-annealed ferrite-grained stainless steel sheet is subjected to surface polishing and then subjected to glow annealing, the manufacturing process becomes complicated. The weight of the rise is 17 j 354 〇 29. Therefore, in the present invention, it is preferable to subject the cold-rolled ferrite-grained stainless steel sheet to surface polishing and then to perform final glazing annealing. - The manufacturing process of the glow annealing can be performed by one-time glow annealing - simultaneous softening annealing for custom-made materials and concentration of Cr, Si, and A1 into the -5 surface film (high (Cr+Si+Al) In particular, in the ferro-based iron-based stainless steel sheet of the present invention, in order to agree on the softening temperature and the concentration temperature for introducing Cr, Si, ... into the surface film, it is also possible to control the content of Nb. Brake. Adjust the recrystallization temperature. However, in the case of the Osbane iron-based stainless steel plate, the solid solution annealing is usually 1 〇〇〇. (: Above, the temperature at which Cr, Si 1 , and Al are concentrated into the surface film does not agree. Therefore, after cold rolling-polishing, it is necessary to impart a bright annealing for solution annealing and formation of an oxide film. [Examples] The examples and comparative examples of the present invention are shown in Table 1. The surface polishing of the ferrite-based iron-based stainless steel 15 was divided into No 4 (fine polishing), called H. 3 kinds of grinding and polishing of φ 糸 糸 face and 2B (texture of light rolling after pickling). The % 4 iron-based stainless steel plate was subjected to a bright annealing under the conditions of Table 1. Furthermore, the polished ferrite-based iron-based stainless steel plate is subjected to an annealing furnace after cold rolling, and the other surface-polishing materials are not subjected to retreat after cold rolling. In addition, the suitable conditions for the suitability of the fire conditions are shown in the printout, indicating that the condition is that the factory is not suitable for the manufacturer. Similarly, in the whiteness: ^, indicating excellent whiteness; showing X-printed, indicating whiteness 18 1354029
ϊ 白级 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ΕΓ On ΓΟ 卜 OO > * oo i »n Η m <N in <N o <N m <N fb^a 附著量 (mg/m2) (N <N o ON in in in 璨 g 喊 1 來 成 jAj w % 绪 i s 甾 i 绪 I 蛑 I 淫 s 绪 i s rO % II 00 oo oo oo 00 00 oo 00 00 «-Μ V0 s $ $ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 >.lM ST 露點 T2(°C) | ? 5 溫度 T1CC) oo 00 s § 00 00 oo oo 表面, 抛光 _ί No.4 No.4 No.4 No.4 No.4 No.4 1_ No.4 No.4 No.4 No.4 δ o o δ o s o s c> δ ο s c> o δ o Ο ! X s ON in ON o c> Os o 〇\ o 〇\ 2 ΰ 1624 1624 1624 1624 1 1 1624 1624 1_ '1624 1624 1624 1624 鋼種 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 A <N ΓΟ 寸 卜 OO C\ Ο •4舍浮荽 /—N 赞 19 1354029ϊ white level 〇〇〇〇〇〇〇〇〇〇ΕΓ On ΓΟ 卜 > * oo i »n Η m <N in <N o <N m <N fb^a adhesion amount (mg/ M2) (N <N o ON in in in 璨g shouting 1 to jAj w % 绪 is 甾i 绪 I 蛑I 淫 s thread is rO % II 00 oo oo oo 00 00 oo 00 00 «-Μ V0 s $ $ 〇〇〇〇〇〇〇〇〇〇>.lM ST Dew point T2(°C) | ? 5 Temperature T1CC) oo 00 s § 00 00 oo oo Surface, Polished_ί No.4 No.4 No. 4 No.4 No.4 No.4 1_ No.4 No.4 No.4 No.4 δ oo δ osos c> δ ο s c> o δ o Ο ! X s ON in ON o c> Os o 〇 \ 〇 2 2 2 24 24 24 24 24 24 24 24 24 24 24 24 Like 19 1354029
(SI<(SI<
1 白色度 ί_ 〇 〇 〇 〇 〇 〇 〇 〇 〇 S ^ 12 oq σ\ 卜 卜 O) 化祕理 浮 BJ： | _实'^ Ό <Ν Ό <Ν <N <Ν oi ^Ti H in <n 附著量 (mg^n2) in tr) *〇 tn oo «Λ 種類 胺私规系 1_ 胺&系 1 i胺基明^系 胺叙媒系 胺基妙烧系 胺基明完系 胺基明完系 胺基明^系 環系 I ^ 1 m | ^ £ 寸· Os οο 2 oo m cs 辦退火麟 〇 〇 〇 〇 〇 〇 〇 〇 〇 露點 T2(°〇 卜 $ 溫度 Tire) S 00 1050 § § § § 表面 抛光 No.4 No.4 No.4 No.4 No.4 No.4 No.4 成 ^(mass%) 8 c5 〇 Ο S c> o o o ο Ο 〇\ 2 On *〇 Ο α\ tn c> a\ 2 o C\ ^T) c5 o 苓 ο 芩 Ο ό 1624 1624 1624 1624 1624 1624 1922 1922 1922 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 1 1 1 in oo ON (赞) 20 1354029 對光輝退火後的各種肥粒鐵系不鏽鋼板，以AES(奥傑電子 光譜分析法（Auger Electron Spectroscopy))測定從表面起到 5〇A的深度中之氧化皮膜中的Cr、Si、A卜Fe之原子濃度比， 求出（Cr+Si+Al)/Fe。 5 對光輝退火後的各種肥粒鐵系不鏽鋼板’就作為化成 處理劑之日本PARKERIZING Co·，Ltd.的化成處理劑E-206 採用胺基矽烷系和環氧矽烷系處理劑，使其附著量在2〜 20mg/m2〜50mg/m2的範圍變化。另外施以鉻酸鹽處理作為 化成處理劑以為比較。之後，將丙烯酸氨酯樹脂系的透明 1〇 皮膜以220°C的燒結溫度處理成1〜ΙΟμπι。 透明塗裝後的色調以b*(JIS Ζ8729)測定，評估變色的 程度。 在本發明例中’肥粒鐵系不鏽鋼板表面的氧化皮膜中 之原子濃度比在0.6以上’以胺基矽烷系、環氧矽烷系 15 種或2種所組成的化成處劑進行附著量2〜20mg/m2的處 理，可以獲得b*在2以下之白色度優異的透明塗裝鋼板，相 對地，在比較例中則是形成b*超過2之帶著黃色調的透明塗 裝鋼板，而且會因為看的角度而看到帶黑的色調。 在比較例20中’因為不鏽鋼板的Si成分落在下限以 20 外，所以氧化皮膜中的（Cr+Si+Al)/Fe落在下限之外，b*在2 以上’白色度差。比較例21〜25因為光輝退火條件的溫度 T1及露點T2中有一個落在上下限之外，所以b*在2以上，白 色度差。尤其是比較例25，因為可以明顯地觀察到不鑛鋼 板素材的回火色，所以就沒有測定（Cr+Si+Al)/Fe了。比較 22 1354029 例26〜32雖然素材的（Cr+Si+Al)/Fe在0.6以上，但是化成處 理劑的條件落在本發明範圍之外。比較例26的化成處理劑 附著量落在下限之外，密著性不良。比較例27的化成處理 劑附著量落在上限之外，比較例28的化成處理劑是鉻酸鹽 5 處理劑而非本發明之非鉻酸鹽系處理劑，因此b*在2以上， 白色度差。比較例29及31的透明塗料厚度落在下限之外， 色調不安定。比較例3〇及32的透明塗料厚度落在上限之 外，製造困難。 以上雖就本發明之較佳實施例作了說明，惟本發明並 10不限於這些實施例。在不脫離本發明目的的範圍内，可以 作各種構成的附加、省略、置換及其他變更。本發明並非 以前述說明作限定’而是以所附申請專利範圍來作限定。 【產業上的利用可能性】 若依據檢討了透明塗裝不鏽鋼板的設計性與色調之關 15係的本發明，則可在b*(色度，黃/藍的程度’ Jis Z 8729) 從〇到2的範圍’製造白色度優異之透明塗裝鋼板。一般的 透明塗裝不鑛鋼板b*是從4到6左右，不但黃黃的，而且會 因看的角度而看到暗色調。而本發明之透明塗裝鋼板則是 白白的’而且不會因為看的方向而看到暗色調。 2〇 【圖式簡單說明】 第1圖為化成處理附著量，和透明塗裝不鑛鋼板之變色 △b*的關係示意圖。 第2圖為從表面起到5〇A的深度中之Cr、Si、Al、Fe原 子濃度比(Cr+Si+Al)/Fe ’和利用224°C燒結的透明塗裝不鏽 23 1354029 鋼板之變色Ab*的關係示意圖。 第3圖為研磨拋光不鏽鋼板，和研磨後施以本發明範圍 的光輝退火之鋼板的燒結溫度，和透明塗裝不鏽鋼板之變 色Ab*的關係示意圖。 5 第4圖為光輝退火的退火溫度T1(°C)、露點T2(°C)和， 從表面起到50A的深度之氧化皮膜中的Cr、Si、A卜Fe原子 濃度比(Cr+Si+Al)/Fe的關係示意圖。 【主要元件符號說明】 (無）1 white degree ί_ 〇〇〇〇〇〇〇〇〇S ^ 12 oq σ\ 卜卜 O) 秘理理浮BJ: | _实'^ Ό <Ν Ό <Ν <N <Ν oi ^ Ti H in <n adhesion amount (mg^n2) in tr) *〇tn oo «Λ Amine steroids 1_amine & 1 1 amine-amine amide amine-based amine-based amine-based amine group The end of the amine-based amide-based amine-based ring system I ^ 1 m | ^ £ inch · Os οο 2 oo m cs Office annealing Linyi dew point T2 (° 〇 $ $ temperature Tire) S 00 1050 § § § § Surface Polishing No.4 No.4 No.4 No.4 No.4 No.4 No.4 成^(mass%) 8 c5 〇Ο S c> ooo ο Ο 〇\ 2 On *〇Ο α\ tn c> a\ 2 o C\ ^T) c5 o 苓ο 芩Ο ό 1624 1624 1624 1624 1624 1624 1922 1922 1922 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 1 1 1 in oo ON (Like) 20 1354029 For various ferrite-based stainless steel sheets after glow annealing, AES (Auger Electron Spectroscopy) is used to measure Cr and S in the oxide film from the surface to a depth of 5 〇A. The atomic concentration ratio of i and A is determined by (Cr + Si + Al) / Fe. (5) The chemical conversion agent E-206 of Japan's PARKERIZING Co., Ltd., which is used as a chemical conversion agent, is an amine decane-based and epoxy decane-based treatment agent. The amount varies in the range of 2 to 20 mg/m2 to 50 mg/m2. Further, chromate treatment was applied as a chemical treatment agent for comparison. Thereafter, the urethane acrylate resin-based transparent film was treated at a sintering temperature of 220 ° C to 1 to ΙΟμπι. The color tone after the clear coating was measured by b* (JIS Ζ 8729) to evaluate the degree of discoloration. In the example of the present invention, the atomic concentration ratio in the oxide film on the surface of the ferrite-based stainless steel sheet is 0.6 or more, and the amount of deposition is 2 by an amine-based decane-based or epoxy-decane-based composition. ～20mg/m2 treatment, a transparent coated steel sheet having an excellent whiteness with b* of 2 or less can be obtained, and in the comparative example, a transparent coated steel sheet with a yellow color of b* exceeding 2 is formed, and I will see black tones because of the angle of view. In Comparative Example 20, since the Si component of the stainless steel plate fell below the lower limit of 20, (Cr + Si + Al) / Fe in the oxide film fell outside the lower limit, and b * was 2 or more white difference. In Comparative Examples 21 to 25, since one of the temperature T1 and the dew point T2 of the bright annealing condition falls outside the upper and lower limits, b* is 2 or more, and the whiteness is poor. In particular, in Comparative Example 25, since the temper color of the non-mineral steel sheet material was clearly observed, (Cr + Si + Al) / Fe was not measured. Comparison 22 1354029 Examples 26 to 32 Although the material (Cr + Si + Al) / Fe is 0.6 or more, the conditions for the formation of the treatment agent fall outside the scope of the present invention. The amount of deposition of the chemical conversion treatment agent of Comparative Example 26 fell outside the lower limit, and the adhesion was poor. The chemical conversion treatment agent of Comparative Example 27 fell outside the upper limit, and the chemical conversion treatment agent of Comparative Example 28 was a chromate 5 treatment agent instead of the non-chromate treatment agent of the present invention, so b* was 2 or more, white. Degree difference. The transparent paint thicknesses of Comparative Examples 29 and 31 fell outside the lower limit, and the color tone was unstable. The thickness of the clear coating of Comparative Examples 3 and 32 fell outside the upper limit and was difficult to manufacture. Although the preferred embodiments of the invention have been described above, the invention is not limited to the embodiments. Additions, omissions, substitutions, and other modifications can be made in various embodiments without departing from the scope of the invention. The present invention is not limited by the foregoing description, but is defined by the scope of the appended claims. [Industrial Applicability] If the invention of the 15 series of the design and the color tone of the transparent coated stainless steel sheet is reviewed, it can be obtained from b* (chromaticity, yellow/blue degree 'Jis Z 8729) from In the range of 2 to 2, a transparent coated steel sheet excellent in whiteness is produced. The general transparent coated non-mineral steel plate b* is from about 4 to 6, not only yellow and yellow, but also sees dark tones due to the angle of view. On the other hand, the transparent coated steel sheet of the present invention is white and does not see dark shades due to the direction in which it is viewed. 2〇 [Simple description of the drawing] Fig. 1 is a schematic diagram showing the relationship between the amount of chemical treatment and the discoloration Δb* of the transparent coated non-mineral steel sheet. Figure 2 shows the Cr, Si, Al, Fe atomic concentration ratio (Cr + Si + Al) / Fe ' from the surface to the depth of 5 〇 A and the transparent coated stainless 23 1354029 steel plate sintered at 224 ° C Schematic diagram of the relationship of discoloration Ab*. Fig. 3 is a view showing the relationship between the sintering temperature of the polished and polished stainless steel sheet and the gloss-annealed steel sheet to which the present invention is applied after polishing, and the color change Ab* of the transparent coated stainless steel sheet. 5 Figure 4 shows the annealing temperature T1 (°C), dew point T2 (°C), and the ratio of Cr, Si, and A Fe atoms in the oxide film from the surface to a depth of 50 A (Cr+Si). Schematic diagram of the relationship of +Al)/Fe. [Main component symbol description] (none)
24twenty four