TW201111523A - Clear-coated stainless steel sheet with excellent design properties and manufacturing method thereof - Google Patents

Clear-coated stainless steel sheet with excellent design properties and manufacturing method thereof Download PDF

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TW201111523A
TW201111523A TW99137242A TW99137242A TW201111523A TW 201111523 A TW201111523 A TW 201111523A TW 99137242 A TW99137242 A TW 99137242A TW 99137242 A TW99137242 A TW 99137242A TW 201111523 A TW201111523 A TW 201111523A
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stainless steel
steel sheet
annealing
steel plate
chemical conversion
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TW99137242A
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TWI370847B (en
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Masuhiro Fukaya
Naoto Ono
Haruki Ariyoshi
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Nippon Steel & Sumikin Sst
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Abstract

A clear-coated stainless steel sheet excellent in whiteness, which is a ferritic stainless steel containing 0.2 to 0.8 mass% of Si, and characterized in that the stainless steel sheet has a surface oxide film whose atomic concentration ratio of Cr, Si, Al, and Fe ((Cr+Si+Al)/Fe) from its surface to a depth of 50 Å is 0.6 or more and a chemical conversion treating agent of a coating film is composed of either one type or two types of an aminosilane type and/or epoxysilane type agent and a deposition amount of the chemical conversion treating agent is 2 to 20 mg/m2 (an amount of SiO2 is measured by X-ray fluorescence) and a thickness of a clear coating material of the coated film is between I and 10 μ m and a manufacturing method thereof.

Description

201111523 六、發明說明： 【發明所屬之技術領域】 發明領域 本發明係關於一種不鏽鋼板所具有之金屬材料特有的 優異設計性優異，塗裝時不會被黃色著色之可應用於家 電、建材、汽車等的零件之透有塗裝不鏽鋼板。 I：先前技術;3 發明背景 本發明不鏽鋼因為具有耐蝕性、設計性，所以在家電 、廚房、汽車、建材領域中被以裸露狀態加以使用。最近 則在一方面要求有不鏽鋼板的金屬光澤等優異的設計性， 一方面又要附加耐蝕性等功能的透明塗裝不鏽鋼板之家電 領域逐漸增加應用。 這些透明塗裝不鑛鋼板因其設計性，除無色的透明塗 裝之外’也漸有採用以顏料等著色之透明塗裝和添加珍珠 調或金屬調顏料的透明塗裝鋼板。然而，添加這些顏料會 讓透明皮膜的透明感降低，使具有不鏽鋼特有的金屬光澤 的質感降低。 另一方面’在無色的透明塗裝不鏽鋼板中，因底塗處 理的鉻酸鹽處理而帶有黃色的感覺，不但會損及設計性， 同時會有因視角而看起來黑黑的問題。針對這些問題，專 利文獻1和專利文獻2中檢討了會影響到鉻酸鹽皮膜的處理 液組成和塗布量。專利文獻3中針對利用磷酸和矽化物來改 善底塗不鏽鋼板的外觀性，塗膜的耐污染性與耐烘烤性作 201111523 了檢討。 【專利文獻1】特開平5-106057號公報 【專利文獻2】特開平U_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h—254585號公報 C發明内容:J 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 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 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’在透明塗臈的燒付時’不鏽鋼板表面上會發生回火色 (tempered color)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， 並且採用耐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。 不鏽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 201111523 含有Si〇2、Al2〇3的氧化皮膜的方式加以抑制。亦即，隨著 Si或湖含量增加，會變成容易形成si、A丨濃化的氧化皮 膜’财回火色性因而提高。此類不鏽鋼已知者有高_ (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⑹系不錯鋼表 面的A1或Si控制在4.5〜6原子％的耐熱透明塗裝不鐵鋼板。 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 U〜G8%的肥粒鐵系不鑛 鋼板，且S亥鋼板具有自其表面起到人的深度中之cr、Si、 A1、Fe原子濃度比（Cr+Si+Ai)/Fe為〇 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&…量），而透明塗料厚度為} 〜ΙΟμιη的塗膜。 (2) 如（1)中s己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—步含有A1 : 〇〇〇5〜 0.15%。 (3) 如（1)中a己載之白色度優異的透明塗裝不鏽鋼板其 特徵在於前述不鏽鋼板以質量％計進一步含有Nb : 〇 ι〜 5 201111523 0.7%。 (4) -種白色度優異之透明塗裝不_板，其特徵在於 前述不鏽鋼板係以質量％計含有Si : 0 2〜〇 8%、八丨：〇⑻5 〜0.15%、Nb : 0.1〜〇.7%的肥粒鐵系不_板，且該鋼板 具有自其表面起到50入的深度中之Cr、Si、a卜&原子濃度 比（Cr+Si+Al)/Fe為0.6以上的表面氧化皮臈，並且該鋼板具 有塗膜的化成處理劑係由胺基矽烷系、環氧石夕院系之丨種或 2種所組成’且化成處理劑的附著量為2〜2〇mg/m2(用榮光 X射線測定si〇2量），而透明塗料厚度為1〜1〇μηι的塗膜。 鲁 (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(t)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。 (6) —種白色度優異的透明塗裳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 : 〇.2〜0.8%、A1 : 鲁 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5〇A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 基石夕烧系、環氧石夕烧系之1種或2種所組成，該化成處理劑 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 6 S- 201111523 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： 750^T1^5xT2+12〇〇 ……1 式 -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 : 〇 2〜〇 8%、A1 : 0.005〜0.15%、Nb: 〇.1〜〇_7%的肥粒鐵系不鏽鋼板，且該 鋼板具有自其表面起到50A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Si〇2 量）’而透明塗料厚度為丨〜川口!!!的塗膜，又，該製造方法 係對》亥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TlfC)及退火環境氣體的露sT2(t)滿足i式與 2式的條件進行退火熱處理： 750^Ti^5xT2+1200 ......1 式 —70各T2各-30 ……2式。 (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 : 〇_2〜〇8%的肥粒 鐵系不鏽鋼板，且該鋼板具有自其表面起到5〇A的深度中之 &、Si、Ai、Fe原子濃度比(Cr+Si+A1)/F^〇 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 2〇1111523 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種所组成’且該化成處理劑的附著量為2〜2〇rng/m2(用螢 光X射線測定Si〇2量）’而透明塗料厚度為1〜ιομπ!的塗 膜，又，該製造方法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TlfC)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，並將經 過冷軋的肥粒鐵系不鏽鋼板於表面研磨處理後再施以最終 光輝退火： 750^Τ1^5χΤ2+1200 ......1 式 · -70ST2S-30 ......2式。 (9) 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鐵系不鏽鋼板於表面 研磨處理後再施以最終光輝退火。 (10) 如(7)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鐵系不鐵鋼板於表面 研磨處理後再施以最終光輝退火。 圖式簡單說明 鲁 第1圖為化成處理附著量，和透明塗裝不鏽鋼板之變色 △b*的關係示意圖。 第2圖為從表面起到50入的深度中之Cr、Si、A卜Fe原 子濃度比(Cr+Si+Al)/Fe，和利用224°C燒結的透明塗裝不鏽 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 8 201111523 色Ab*的關係示意圖。 第4圖為光輝退火的退火溫度Tlfc)、露點Τ2Γ〇和， 從表面起到5〇A的深度之氧化皮膜中的Cr、沿、八卜巧原子 濃度比(Cr+Si+Al)/Fe的關係示意圖。 【實施方式3 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 基石夕貌系' 環氧化矽化成處理劑，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種所組成。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2〜20mg/m2(用螢光X射線 測定Si〇2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。 201111523 第 1 圖中，在 l〇〇°C 下使日本PARKERIZING Co.，Ltd. 之E-206(胺基矽烷系）的附著量從2mg/m2起變化到50mg/ m2為止’以滾輪塗佈2μπι的丙稀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(Ab*) 係，使化成處理劑的附著量如橫軸所示般地變化，從燒結 塗裝透明塗料時之b*(l)減去鋼板素材之b*(2)而得者。Δϊ>*= b*(l)- b*(2) 〇 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0.3 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 鏞鋼的狁著性降低。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&〇2量而加以定量。 透明塗膜的厚度在Ιμηι起到ΙΟμιη以下的範圍。這是因 為1 μπι以下難以獲得安定的色調，而以上則難於以1 次塗佈進行製造，塗膜成本也會變高之故。較佳為2μπι起 到5μιη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。 201111523 本發明中，特徵在於使用具有從表面起到5〇A的深度中 之Cr、Si、Al、Fe原子濃度比（Cr+Si+Al)/Fe(後述）為〇.6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0.2質量％以上的Si之肥粒鐵系 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鏽鋼是以質量％計含有Si : 〇.2 〜0.8%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 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-A1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。 本發明中’為了在不鏽鋼板表面形成Si濃化的表面氧 化皮膜，Si有必要含有0.2%以上，此時，別也包含鱗鋼時 使用作為脫氧元素者。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Si，就會 超過泛用的肥粒鐵系不鏽鋼’例如SUS430或添加Nb的 SUS430J1L的成分範圍。亦即’添加超過〇 8%的Si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，A1以含有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。 201111523 A1被當作脫氧元素添加了 0.005%以上。添加多量的A1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 有量可以在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0.1〜0.7%的Nb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Cr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 拋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(Cr+Si+Al)/Fe調整在0.15〜3.5範圍的材料上，使附著 量成為10mg/m2,在l〇(Tc進行燒結乾燥後，以滚輪塗布2μπι 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調整成〇.6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 201111523BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal material having a stainless steel plate which is excellent in design excellence, and can be applied to home appliances and building materials without being colored by yellow during coating. Parts such as automobiles are coated with stainless steel plates. I: Prior Art; 3 Background of the Invention Since the stainless steel of the present invention has corrosion resistance and design properties, it is used in a bare state in the fields of home appliances, kitchens, automobiles, and building materials. Recently, on the one hand, excellent design properties such as metallic luster of stainless steel sheets have been demanded, and on the other hand, the field of home appliances of transparent coated stainless steel sheets to which functions such as corrosion resistance are added has been gradually increased. These transparent coated non-mineral steel sheets are gradually designed to be transparently coated with pigments and the like, and transparently coated steel sheets with pearl or metallic pigments, in addition to colorless transparent coatings. However, the addition of these pigments lowers the transparency of the clear film and lowers the texture of the metallic luster which is characteristic of stainless steel. On the other hand, in the colorless transparent coated stainless steel sheet, the chromate treatment by the primer treatment gives a yellow feeling, which not only impairs the design property, but also has a problem of appearing black due to the viewing angle. In response to these problems, Patent Document 1 and Patent Document 2 have reviewed the composition and amount of the treatment liquid which affect the chromate film. Patent Document 3 discloses a review of the appearance of a primer-coated stainless steel sheet using phosphoric acid and a telluride, and the contamination resistance and baking resistance of the coating film are reviewed 201111523. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 6) Japanese Laid-Open Patent Publication No. H-254585. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The transparent coated stainless steel sheet having excellent whiteness and high transparency cannot be obtained only when the chromate treatment method as described above is used for improvement. . 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 review by the inventors of the present invention, it is found that the coloring (yellowing) of the yellowish color of the colorless transparent coated stainless steel sheet is not the result of the chromate treatment. When paying, the tempered color will appear on the surface of the stainless steel plate. The color of the tempered color is the cause of 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, and a stainless steel plate excellent in tempering color resistance is used as the application in the transparent coated stainless steel. The stainless steel plate of the plate can achieve the result of preventing yellowing during transparent coating. The tempering color of the stainless steel sheet is known to be suppressed by forming a 201111523 oxide film containing Si〇2 and Al2〇3 on the surface of the steel sheet by performing bright annealing on the stainless steel sheet to which Si 'A1 is added. That is, as the content of Si or lake increases, it becomes an oxide film which is easy to form a concentration of Si and A ’, and thus the flammability is improved. Such stainless steels are known to have high _ (Patent Documents 4, 5) and high A1 steel (Patent Document 5). Further, Patent Document 6 discloses a heat-resistant transparent coated non-ferrous steel sheet in which the ferrite iron (6) is a good steel surface A1 or Si is controlled at 4.5 to 6 atom%. The inventors of the present invention have carefully reviewed the means for solving the above problems. As a result, as described above, the chemical conversion treatment conditions, the characteristics of the surface of the material, and the coating conditions have been reviewed, and the transparent coating using the ferrite-grained stainless steel having excellent whiteness has been 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 U to G8% of a ferrite-grained non-mineral steel sheet in mass %, and the S-hai steel sheet has a surface from the surface thereof The surface oxide film having a concentration ratio of Cr, Si, A1, and Fe in the depth (Cr+Si+Ai)/Fe is 〇6 or more, and the chemical conversion treatment agent having the coating film is composed of an amine decane system and a ring. One or two types of oxoxane are used, and the amount of the chemical conversion agent is 2 to 20 mg/m 2 (measured by fluorescent X-rays), and the thickness of the clear coating material is ～ ΙΟ μηη. (2) A transparent coated stainless steel sheet excellent in whiteness as contained in (1) is characterized in that the stainless steel sheet contains A1: 〇〇〇5 to 0.15% in mass %. (3) A transparent coated stainless steel sheet having excellent whiteness as contained in (1) is characterized in that the stainless steel sheet further contains, by mass%, Nb: 〇 ι 〜 5 201111523 0.7%. (4) A transparent coating which is excellent in whiteness, characterized in that the stainless steel sheet contains Si in a mass%: 0 2 to 〇 8%, gossip: 〇 (8) 5 to 0.15%, Nb: 0.1~ 〇.7% of the ferrite is not a plate, and the plate has a ratio of Cr, Si, ab & atomic concentration (Cr + Si + Al) / Fe of 0.6 from the surface to 50 in depth. In the above-mentioned surface oxide scale, the chemical conversion treatment agent having the coating film is composed of an amine-based decane-based or an epoxy-based compound, or a combination of two types, and the amount of the chemical conversion agent is 2 to 2 〇mg/m2 (the amount of si〇2 is measured by glory X-ray), and the coating thickness of the transparent coating is 1 to 1 〇μηι. Lu (5)—The method for producing a transparent coated stainless steel sheet material excellent in whiteness described in (1) is characterized in that it is a temperature T1 (° C.) of the final bright annealing and a dew point T2 (t) of the annealing ambient gas. Annealed heat treatment is carried out under the conditions of Equations 1 and 2: 750ST1S5XT2+1200 ......1 Formula -70ST2S-30 ......2. (6) A method for producing a transparent coated stainless steel sheet material excellent in whiteness, and the stainless steel sheet is a ferrite-based iron system containing Si: 〇.2 to 0.8% by mass%, and A1: 5.00. a stainless steel plate having a surface oxide film having a Cr, Si, Al, and Fe atomic concentration ratio (Cr+Si+Al)/Fe of 0.6 or more in a depth of 5 〇A from the surface thereof, and the whiteness The chemical conversion processing agent which has a coating film of the excellent transparent coating stainless steel plate material consists of one type or two types of an amine stone smoldering system and an epoxy smelting system, and the amount of the chemical conversion agent is 2 to 20 mg / M2 (amount of Si〇2 by fluorescent X-ray), a coating film having a transparent coating thickness of 1 to ΙΟμπι, and the manufacturing method is a transparent transparent coated stainless steel sheet material having a whiteness of 6 S-201111523 to finally The annealing temperature Tl (°c) and the annealing environment gas dew point T2 (°c) satisfy the conditions of Equations 1 and 2 for annealing heat treatment: 750^T1^5xT2+12〇〇...1 Formula-70ST2S-30 ... ...2 type. (7) A method for producing a transparent coated stainless steel sheet material excellent in whiteness, and the stainless steel sheet contains Si in a mass%: 〇2 to 〇8%, A1: 0.005 to 0.15%, Nb: 〇.1 ~ 〇 7% of the ferrite iron-based stainless steel plate, and the steel plate has a concentration of Cr, Si, A, Fe atomic concentration (Cr + Si + Al) / Fe of 0.6 or more from the surface to a depth of 50 A The surface oxide film, and the chemical conversion treatment agent which has a coating film which is excellent in whiteness is composed of one or two kinds of an amine decane type or an epoxy decane type, and the chemical conversion agent adheres. The amount of the coating is 2 to 20 mg/m2 (the amount of Si〇2 is measured by fluorescent X-rays), and the thickness of the transparent coating is 丨~川口!!!, and the manufacturing method is a transparent coating excellent in whiteness. The stainless steel plate material is subjected to annealing heat treatment at the temperature of the final glow annealing TlfC) and the exposed environment gas sT2(t) satisfying the conditions of the formulas i and 2: 750^Ti^5xT2+1200 ......1 - 70 T2 each -30 ...... 2 formula. (8) A method for producing a transparent coated stainless steel sheet material having excellent whiteness, and the stainless steel sheet contains a ferrite-based iron-based stainless steel sheet having a mass ratio of Si: 〇 2 to 〇 8%, and the steel sheet has a surface oxide film having a concentration ratio of (C+Si+A1)/F^6 or more in a depth of 5 〇A from the surface thereof, and a transparent coating excellent in whiteness Stainless steel plate material 2〇1111523 The chemical conversion treatment agent having a coating film is composed of one or two kinds of amine decane-based or epoxy decane-based compounds, and the amount of the chemical conversion treatment agent is 2 to 2 〇rng/m 2 . a coating film having a transparent coating thickness of 1 to ιομπ! (the amount of Si〇2 is measured by fluorescent X-rays), and the manufacturing method is a brightly-coated stainless steel sheet material excellent in whiteness, and finally bright-annealed. The temperature TlfC) and the dew point T2(C) of the annealing ambient gas are subjected to annealing heat treatment under the conditions of Equations 1 and 2, and the cold-rolled ferrite-grained stainless steel sheet is subjected to surface grinding treatment and then subjected to final annealing: 750 ^Τ1^5χΤ2+1200 ......1 Formula·-70ST2S-30 ......2. (9) A method for producing a transparent coated stainless steel sheet material having excellent whiteness as described in (6), wherein the cold-rolled ferrite-grained stainless steel sheet is subjected to surface polishing treatment and then subjected to final glow annealing. (10) A method for producing a transparent coated stainless steel sheet material having excellent whiteness as described in (7), wherein the cold-rolled ferrite-based iron-free steel sheet is subjected to surface polishing treatment and then subjected to final glow annealing. Brief description of the diagram Lu Figure 1 is a schematic diagram showing the relationship between the amount of deposition and the discoloration Δb* of the transparent coated stainless steel plate. Fig. 2 is a graph showing the concentration ratio of Cr, Si, A and Fe atoms (Cr + Si + Al) / Fe in the depth from 50 to the depth of the surface, and the discoloration Ab* of the transparent coated stainless steel plate sintered at 224 ° C Schematic diagram of the relationship. Fig. 3 is a view showing the relationship between the sintering temperature of the polished and polished stainless steel sheet and the bright-annealed steel sheet to which the present invention is applied, and the change of the transparent coated stainless steel sheet. Figure 4 shows the annealing temperature Tlfc), dew point Γ〇2Γ〇, and the ratio of Cr, edge, and octagonal atomic concentration (Cr+Si+Al)/Fe in the oxide film from the surface to a depth of 5 〇A. Schematic diagram of the relationship. [Embodiment 3] The best sample for carrying out the invention The inventors 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 obtained for obtaining a transparent coated stainless steel excellent in whiteness. The board is important. First, the first treatment is that the pretreatment treatment agent does not use a chromate treatment agent, but uses an amine epoxidized epoxidation treatment agent, and the adhesion 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 if such a treating agent is used, the adhesion is good, and yellow coloring can be prevented as compared with the case of using the chromate treating agent. The adhesion amount of the chemical conversion treatment agent is treated to form a state of 2 to 20 mg/m 2 (the amount of Si 〇 2 is measured by fluorescent X-ray), and the surface temperature (MT) of the stainless steel plate material is 60 to 140 ° C. Sintering and drying. 201111523 In the first figure, the adhesion amount of E-206 (amino decane series) of Japan PARKERIZING Co., Ltd. was changed from 2 mg/m2 to 50 mg/m2 at 10 °C. A 2 μm acrylic acid urethane resin-based clear coating was examined for color change of a transparent coated stainless steel plate coated at a sintering temperature of 200 °C. 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 (Ab*) of Fig. 1, the amount of deposition of the chemical conversion agent is changed as indicated by the horizontal axis, and b*(l) of the steel material is subtracted from b*(1) when the transparent coating is applied by sintering. ) and the winner. Δϊ>*= b*(l)- b*(2) The results are as shown in Fig. 1. If the amount of the chemical conversion agent exceeds 20 mg/m2, not only the gloss of the transparent coated stainless steel will decrease, but also There are some yellow tones. When the adhesion amount is 2 〇 mg/m 2 or less, Ab* becomes 0.3 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 becomes uneven, and the adhesion between the clear coating film and the non-twisted steel is lowered. Therefore, in the present invention, the amount of the chemical conversion agent to be applied is set to 2 to 20 mg/m2. Further, the amount of deposition of the chemical conversion treatment agent can be quantified by measuring the amount of the stainless steel plate by fluorescent X-ray measurement & The thickness of the clear coating film is in the range of Ιμηι to ΙΟμηη. This is because it is difficult to obtain a stable color tone of 1 μm or less, and it is difficult to manufacture it by one application, and the cost of the coating film is also high. 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. 201111523 In the present invention, it is characterized in that surface oxidation of Cr, Si, Al, and Fe atomic concentration ratio (Cr+Si+Al)/Fe (described later) is 〇.6 or more in a depth of 5 〇A from the surface. The steel plate of the film prevents the tempering color from being colored during the coating and sintering and prevents yellowing. The use of a ferrite-based iron-based stainless steel plate containing 0.2% by mass or more of Si and photo-annealing the steel sheet at a predetermined temperature and ambient gas can cause the atomic concentration on the surface of the steel sheet to fall within the above-mentioned appropriate range. The stainless steel of the transparent coated stainless steel plate is a ferrite-grained stainless steel plate containing Si: 〇.2 to 0.8% by mass. Since the element diffusion rate in the ferrite-based stainless steel is faster than that of the Vostian iron system, it is easy to concentrate the concentration of Cr and Si into the film. Therefore, the present invention is limited to a ferrite iron-based stainless steel sheet. In particular, a special steel grade (Cr-A1 steel and Cr-Si steel) containing A1 and Si is compared with that of the patents 4 and 5 of the company. 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 employ a technique for enriching Cr, Si, and A1 in the film to be described later. In the present invention, in order to form a Si-concentrated surface oxide film on the surface of the stainless steel sheet, it is necessary to contain 0.2% or more of Si, and in this case, when it is also included in the scale steel, it is used as a deoxidizing element. The upper limit of 0.8% of Si is specifically used to indicate the granular iron-based stainless steel which is widely used in the present invention. When Si is contained in an amount of more than this amount, it exceeds the range of the composition of the widely used ferrite-based iron-based stainless steel, such as SUS430 or Nb-added SUS430J1L. In other words, when Si is added in an amount of more than 8%, the solidification hardening occurs, and the workability is deteriorated, which is not suitable for general use. In the present invention, A1 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. 201111523 A1 was added as a deoxidizing element by 0.005% or more. Adding a large amount of A1 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 its content may be in the range of 16.0 to 20.0% by mass. Further, in order to produce a transparent stainless steel sheet having an excellent 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 preferred to contain 0.1 to 0.7% of Nb. 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 Cr. 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 cold-rolling annealing of SUS430 of 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 it on a material having an atomic concentration ratio (Cr+Si+Al)/Fe adjusted in the range of 0.15 to 3.5, so that the adhesion amount becomes 10 mg/m 2 , and sintering is performed at 1 〇 (Tc is performed). After drying, a 2 μm acryl urethane resin-based clear coating was applied by a roller. Fig. 2 shows the atomic concentration ratio (Cr + Si + Al) / Fe and △ at a sintering temperature of 224 ° C after application of the clear coating. The relationship of b* is evaluated by the difference of b* between the sintered material and the reference material (transparent coated stainless steel plate material). As can be seen from Fig. 2, the atomic concentration ratio (Cr + Si + Al) / Fe is adjusted to 〇 Among the materials of .6 or more, the change in color tone due to coating and sintering is small, and Ab* is less than 1 and the discoloration is small. Next, 'Preparation of atomic concentration ratio (Cr+Si+Al)/Fe is adjusted to 0.6 or more 201111523

材料，和原子濃度比(Cr+Si+Al)/Fe調整成不滿0.6的材料， 使燒結溫度從15〇°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 調成3左右。關於φ和▲，原子濃度比(Cr+Si+A1)/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調整成〇.6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 整成原子濃度比(Cr+Si+Al)/Fe不滿0.6的材料，塗裝.燒社 時的帶黃色變色現象很大，尤其是燒結溫度2〇〇它以上的高 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s普分析法(Auger Electron Spectroscopy))進行分析 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 氧化皮膜是極為重要的。此時，Si在表面氧化皮骐的外 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 '八丨而^ θ 被氧化的條件，同時Al2〇3的解離壓比Si〇j&。另外 「，雖.缺 也考慮到(Cr+Si+Al)/Fe的適當範圍會因表面氧化皮膜的1 定方法而有所差異，但是必要的表面氧化皮膜構造則和 述所載者相同。 原子濃度 冷軋退火材、研磨拋光材的表面氧化皮膜中 13 2〇llll523 比（Cr+Si+Al)/Fe在0.2左右。因此，本發明人等乃就對不鐘 鋼鋼板施行光輝退火，以使其形成從表面起到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。 光輝退火通常是在氮和氮以H2 : N〗=(1 <〜'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Tlfc)與環境氣體露點T2( C)的組合而變化。 對經過冷軋的SUS430JIL及SUS430鋼板，施以冷乳退 鲁 火或相當於Νο·4拋光(JIS G 0203 No. 5349)的機械研磨，在 多種退火溫度T1(°C)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A的深度之(Cr+Si+Al)/Fe原子 濃度比安定下來而成為0.6以上的範圍為， 750^T1^5xT2+1200 ......1 式 - 70ST2S-30 ......2式。 在1式、2式的範圍中，因為Cr成為被還原的條件，另 鲁 一方面，Si、A1成為被氧化的條件，故可藉由使有效成分(Si 、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°C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Tlfc)超過(5xT2+1200)°C時， 因為會構成比1式的範圍更屬還原側的條件，所以以和…的 選擇氧化會受到抑制，無法形成具有足约的原子濃度比之 14 201111523 氧化皮犋。因此，光輝退火的溫度Tl(t)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8〇〇。(：以上， iOOOt以下。更佳為8〇〇°C以上，900°c以下。 光輝退火的露點T2fC)如果超過-3〇t，Fe的氧化就會 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-7〇t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。較佳為一。^以上 ’不滿-35°C。 專利文獻5所載者為，在si濃度〇3%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 色评點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 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鏽鋼板。 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，其表面皮膜中&、&、八丨的濃化非 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 15 2〇lU 1523 要原因。因此，本發明中以將冷軋後的肥粒鐵系不鏽鋼板 力0以表面研磨後再施行最終光輝退火的方式為宜。透過冷 札/表面研磨-光輝退火的製造程序，可以利用1次光輝退火 同時實把用以訂作材質的軟質化退火和使Cr、Si ' A1進到 表面皮膜中的濃化（高（Cr+Si+Al)/Fe)。特別是本發明的肥 將鐵系不鏽鋼板中，為了使軟質化溫度和使Cr、Si、A1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 控制.調整再結晶溫度。而，在奥斯田鐵系不鏽鋼板的情 衫中，因為固溶化退火通常在1000°C以上，故和使Cr、Si ，/J進到表面皮膜中濃化的溫度不會達成一致。因此，冷 乳-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。 實旅例 表1中示出本發明之實施例及比較例。將肥粒鐵系不鏽 鋼板的表面抛光分成Νο.4(細目的研磨抛光）、HL(Hairline， 毛絲面的研磨拋光)及2B(酸洗後輕輕壓延的肌理）3種類。將 這些肥粒鐵系不鏽鋼板以表1的條件施以光輝退火。再者， 相對於2B拋光的肥粒鐵系不鏽鋼板是採用冷軋後施行退火 的製造程序，其他的表面拋光材因為冷軋後並未施行退 火’所以是利用光輝退火也同時實施軟質化的鋼材。另外， 在光輝退火條件的適合條件中示以〇印者，表示條件是合 適的；示以X印者表示條件並不合適。同樣地，在白色度中 也示以〇印者，表示白色度優異；示以X印者，表示白色度 差。 16 201111523The material and the atomic concentration ratio (Cr + Si + Al) / Fe were adjusted to a material of less than 0.6, and the change in color tone was observed by changing the sintering temperature from 15 ° C 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, regarding the materials of erbium and Δ, the atomic concentration ratio (Cr + Si + A1) / Fe is adjusted to about 3. Regarding φ and ▲, the atomic concentration ratio (Cr+Si+A1)/Fe is adjusted to about 0.4 and about 〇·2, respectively. The result is shown in Fig. 3, and (Cr+Si+Al)/Fe is anneal by glow annealing. Among the materials adjusted to 〇.6 or more, the change in color tone due to coating and sintering is small. On the other hand, after polishing and polishing, the material which is not subjected to the bright annealing and the material which is adjusted to the atomic concentration ratio (Cr+Si+Al)/Fe less than 0.6 by the bright annealing condition outside the scope of the present invention are coated. The yellow discoloration phenomenon is large, especially when the sintering temperature is 2 〇〇 or higher. Further, in the present invention, the components in the surface oxide film are analyzed by AES (Auger Electron Spectroscopy), and the point at which the oxygen concentration is the highest is the atomic concentration ratio (Cr+Si+Al)/ Fe. In the present invention, it is extremely important to control (Cr + Si + Al) / Fe to 0.6 or more, and to form a surface oxide film in which Cr and Si are concentrated. At this time, Si is concentrated on the surface scale, and A1 is concentrated in the inner layer near the bulk. The reason for this is that the luminescence annealing condition is a condition for reduction of Cr, a condition for oxidation of Si 'Eight ^ and θ, and a dissociation pressure ratio of Si 〇 j & In addition, although the proper range of (Cr+Si+Al)/Fe is considered to be different depending on the method of surface oxide film, the necessary surface oxide film structure is the same as that described above. In the surface oxide film of the atomic-concentration cold-rolled annealed material and the polishing and polishing material, the ratio of 13 2 〇 ll 523 to (Cr + Si + Al) / Fe is about 0.2. Therefore, the inventors of the present invention performed the glazing annealing on the steel sheet of the non-permanent steel sheet. The gloss annealing conditions in which the Cr, Si, and A Fe atomic concentration ratio (Cr+Si+Al)/Fe becomes 0.6 or more in the depth from the surface to 5 Å are reviewed. Nitrogen and nitrogen are carried out in a reducing environment gas in a ratio of H2: N = (1 <~'9) : 1 in a range of ratios. At this time, the composition of the oxide film after annealing is due to the annealing temperature Tlfc) It changes with the combination of the ambient gas dew point T2 (C). For the cold-rolled SUS430JIL and SUS430 steel sheets, a cold emulsion or a mechanical polishing using Νο·4 polishing (JIS G 0203 No. 5349) is applied. The results of the bright annealing of various annealing temperatures T1 (°C) 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 range of the (Cr+Si+Al)/Fe atomic concentration from the surface to the depth of 5〇A is set to be 0.6 or more, and is 750. ^T1^5xT2+1200 ......1 Formula - 70ST2S-30 ......2. In the range of Equations 1 and 2, because Cr becomes the condition to be restored, another aspect, Si and A1 are oxidized, so that the concentration by the selective oxidation of the active component (Si, A1) into the film can be effectively performed. The temperature of the annealing annealing T1 (°C) is less than 750°. At C, the diffusion of the effective element (Si, A1) centered on Cr becomes slow, and an oxide film having a sufficient atomic concentration ratio cannot be formed. When the temperature Tlfc) exceeds (5xT2 + 1200) ° C, because It will constitute a condition that is more on the reducing side than the range of the formula 1. Therefore, the selective oxidation with and is not suppressed, and it is impossible to form an atomic concentration ratio of 14 201111523. The temperature of the gloss annealing Tl (t It is better to determine the range of the formula 1 according to its relationship with the dew point. It is preferably 8 〇〇. (: Above, iOOOt More preferably, it is above 8 °C and below 900 °c. If the dew point of the brilliant annealing T2fC) exceeds -3〇t, the oxidation of Fe becomes severe, and the concentration effect of the oxide film on the surface of Fe cannot be avoided. Because it will change color due to tempering color, it is not suitable as a material for transparent coated stainless steel plates. However, gas dew point of less than -7 〇t is very difficult in industry. Therefore, the dew point of the glow annealing is preferably in the range of the formula 2. It is preferably one. ^ Above ‘Unsatisfied -35°C. Patent Document 5 discloses a material having less temper coloration in a Si concentration of 3%, and an example of a Si concentration of 0.3% in the same literature is a temper coloring evaluation point 3 (yellow). Can not be used as a transparent coated stainless steel plate with excellent whiteness. In the present invention, it is stipulated that the atomic concentration ratio (Cr + Si + Al) / Fe in the oxide film is 0.6 or more. The manufacturing conditions for achieving the atomic concentration ratio can be achieved by clearly specifying the low Si concentration of the Si concentration of 0.8% or less. It can still be made into a transparent coated stainless steel plate with excellent whiteness. Grinding and polishing materials that impart a unique surface appearance to stainless steel by grinding are important materials for visually designing parts. However, because of the surface-grinding stainless steel, the concentration of &, & gossip in the surface film is very small, and it becomes yellow when it is added with a clear film. It is impossible to obtain a highly transparent design with excellent whiteness. Membrane stainless steel plate. Therefore, in order to concentrate Cr, Si, and yttrium in the surface film, it is necessary to perform a photo-annealing process. However, if the ferrite-grained stainless steel plate subjected to the usual softening annealing is subjected to surface polishing and then subjected to glow annealing, the manufacturing process will be performed. It becomes cumbersome and becomes the heavy cost of 15 2〇lU 1523. Therefore, in the present invention, it is preferred that the cold-rolled iron-based stainless steel sheet is subjected to surface polishing and then subjected to final gloss annealing. Through the cold-rolling/surface-grinding-bright annealing process, it is possible to use a single-time glow annealing to simultaneously soften the annealing of the material and to concentrate the Cr and Si 'A1 into the surface film (high (Cr) +Si+Al)/Fe). In particular, in the iron-based stainless steel sheet of the present invention, in order to achieve a softening temperature and a concentration temperature at which Cr, Si, and A1 are introduced into the surface film, it is also possible to control the recrystallization temperature by using the Nb content. . On the other hand, in the case of the Osbane iron-based stainless steel plate, since the solution annealing is usually at 1000 ° C or higher, the temperature at which Cr, Si, and /J are concentrated in the surface film does not agree. Therefore, after cold milk-grinding, it is necessary to impart a secondary annealing for the solution annealing and the photo-annealing of the oxide film. Practical Examples Table 1 shows examples and comparative examples of the present invention. The surface finish of the ferrite-grained stainless steel sheet is classified into three types: Νο.4 (fine polishing), HL (Hairline, polishing of the wool surface), and 2B (texture after light pickling). These ferrite-grained stainless steel sheets were subjected to glow annealing under the conditions shown in Table 1. In addition, the ferrite-based iron-based stainless steel plate polished with respect to 2B is a manufacturing process in which annealing is performed after cold rolling, and other surface-polishing materials are not subjected to annealing after cold rolling, so that softening is also performed by glow annealing. Steel. Further, in the suitable conditions of the gloss annealing conditions, it is indicated that the conditions are suitable; the conditions indicated by the X-printer are not suitable. Similarly, in the whiteness, it is also indicated by the stencil, indicating that the whiteness is excellent; and the X-printing is used to indicate the whiteness difference. 16 201111523

破 % 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 s ^ O) η 卜 00 !2 00 R 1 如1 郜時目 飧实$ JQ O ΦΙ ^ If CN <N Ο Ον σ\ in irv m in W"1 騷 «iej W I I 1 S ! 敏 1 1 1 I i ill 00 00 00 00 oq 00 00 oq 00 I $ t 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 SS. β ? ? V ? «s< β 賴Ρ i S § § g S S S 1 寸· ί 1 寸 1 1 1 1 ! t I s. ο δ s. ο s· o O i o i δ c> 〇\ s σ\ s § § s as 2 On 2 ON s § On S ΰ 1 ν〇 Ό VO v〇 Ό § Ό ‘1».1 鄉 | i 1 1 I 1 議 ζΛ | i 1 i | i | i I 謹 tn ί (Ν m 寸 »n V〇 卜 00 σ\ o 4 Φ驭苳 (s 17 201111523 §< 擊 % 〇 〇 〇 〇 〇 〇 〇 〇 〇 oo § 卜 Ο) w 1 >r 驭_目 _实'^ *—4 〇W ^ i! in in 00 in *T) 媒 .lwi>l i i 1 i 1 I i I g 養 1 眯 III | ^ έ § 00 00 m fN $ $ ί ^ 〇 〇 〇 〇 〇 〇 〇 〇 〇 »s. P ? tn V ^ β 賴P ? s S § i S § § § 1 1 茗 1 i i s. o o s· o s. o δ ο i ο Ο m O 的 o 名 o 荠 o 另 o 另 ο I 苓 ο ο ΰ 1 v〇 VO v〇 § 1 § ON anul w 琛 議 1 i I 1 | i 1 I 1 1 1 1 1 Z rj 2 jrj r^ oo 2 •4僉驭苳 (s破% 〇〇〇〇〇〇〇〇〇〇s ^ O) η 00 !2 00 R 1 as 1 郜 飧 $ $ JQ O ΦΙ ^ If CN <N Ο Ον σ\ in irv m in W&quot ;1 骚«iej WII 1 S ! 敏1 1 1 I i ill 00 00 00 00 oq 00 00 oq 00 I $ t 〇〇〇〇〇〇〇〇〇〇SS. β ? ? V ? «s< β 赖Ρ i S § § g SSS 1 inch · ί 1 inch 1 1 1 1 ! t I s. ο δ s. ο s· o O ioi δ c> 〇\ s σ\ s § § s as 2 On 2 ON s § On S ΰ 1 ν〇Ό VO v〇Ό § Ό '1».1 Township | i 1 1 I 1 ζΛ | i 1 i | i | i I t tn ί (Ν m inch »n V〇卜00 σ\ o 4 Φ驭苳(s 17 201111523 §< 击% 〇〇〇〇〇〇〇〇〇oo § Ο Ο) w 1 >r 驭_目_实'^ *—4 〇W ^ i! In in 00 in *T) Medium.lwi>lii 1 i 1 I i I g 1 眯III | ^ έ § 00 00 m fN $ $ ί ^ 〇〇〇〇〇〇〇〇〇»s. P ? tn V ^ β 赖 P s S § i S § § § 1 1 茗 1 ii s. oos· o s. o δ ο i ο Ο m O o o o o o o o ο I 苓ο ο ΰ 1 v〇VO v〇§ 1 § ON anul w 1 1 i I 1 | i 1 I 1 1 1 1 1 Z rj 2 jrj r^ oo 2 •4佥驭苳(s

18 20111152318 201111523

(WI啭 i m ※ i 白战 X X X X X 1 1 X X 1 1 1 1 〇) Γ〇 <Ί rn f—« 1 1 寸 (Ν σ\ <N 1 1 1 1 【匕祕理 透明塗 料厚度 (μηι) 二 1 1 <S 2 2 ΓΝ 附著量 (mg^n2) ^Ti 1 叫 JQi Ο »〇 *〇 種類 胺 j 系 i 1 rnmm 1 系 胺基妙院系 系 環Κίί» 1^ 111 1^4 ^Η s il SI §1 §1 II 2 00 ψ^"4 00 1>mm4 00 00 00 00 I 皸 餅 適合 〇 X X X X X 〇 〇 〇 〇 〇 〇 〇 露點 T2(°〇 ? 靈 I ? ? ? 1 5 溫度 Tire) 8 g| 1 li〇Qj § § O 8 8 1 § 8 i <1 No4l No.4 No.4 No.4 No.4 1 No.4 No.4 No.4 No.4 No.4| Να4| No.4 No.4| t 1 1 0.02 i 0.09 「0.09 0.09 0.09 0.09 丨0別 ! 0.09 0.09 0.09 1 § 0.09 m \m\ 059 \ 函 \m\ 059 \ L〇^?J L〇^ Μ 059 059 059 039 059 1 ΰ 19.40 I 1624 「1624 162A 1624 1624 1624 1624 1624 16*24 1624 1624 鋼種 1 SUS430 SUS430 |SUS43〇| ISUS430 SUS430 1_ SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 •»w| CN Ρί 。女囫缄忘琢畲4蛘飨长<璲_ 。鎢固划鉍长啭寸※：^ί^κ·琛9长嵴ε※：wK-趄砌银长^㈡※：*?^®^^^^!※ 19 201111523 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50λ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。 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〜 2〇mg/m2〜5〇mg/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，將丙稀酸氨酯樹脂系的透明 皮膜以220°C的燒結溫度處理成1〜ΙΟμηι。 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 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 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，所以卜在2以上，白 色度差。尤其疋比較例25 ’因為可以明顯地觀察到不鏞鋼 板素材的回火色，所以就沒有測定(Cr+Si+Al)/Fe 了。比較 20 201111523 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的化成處理劑是絡酸鹽 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30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 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 係的本發明’則可在b*(色度，黃/藍的程度，JIS Z 8729) 從0到2的範圍，製造白色度優異之透明塗裝鋼板。一般的 透明塗裝不鏽鋼板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。 【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 Ab*的關係示意圖。 第2圖為從表面起到5〇人的深度中之Cr、Si、a卜Fe原 子濃度比(Cr+Si+Al)/Fe ’和利用224。(：燒結的透明塗裝不鏽 21 201111523 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。 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5〇A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）(WI啭im ※ i 白战XXXXX 1 1 XX 1 1 1 1 〇) Γ〇<Ί rn f—« 1 1 inch (Ν σ\ <N 1 1 1 1 [匕 Secret transparent paint thickness (μηι ) 2 1 1 <S 2 2 ΓΝ adhesion amount (mg^n2) ^Ti 1 is called JQi Ο »〇*〇 kind of amine j system i 1 rnmm 1 system amine system Κ 系 system Κίί» 1^ 111 1^ 4 ^Η s il SI §1 §1 II 2 00 ψ^"4 00 1>mm4 00 00 00 00 I 皲 〇 〇 〇 〇 XXXXX 〇〇〇〇〇〇〇 Dew point T2 (°〇?灵 I ? ? 1 5 Temperature Tire) 8 g| 1 li〇Qj § § O 8 8 1 § 8 i <1 No4l No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No.4| Να4| No.4 No.4| t 1 1 0.02 i 0.09 "0.09 0.09 0.09 0.09 丨0 别! 0.09 0.09 0.09 1 § 0.09 m \m\ 059 \ 函\m\ 059 \ L〇^? JL〇^ Μ 059 059 059 039 059 1 ΰ 19.40 I 1624 "1624 162A 1624 1624 1624 1624 1624 16*24 1624 1624 Steel 1 SUS430 SUS430 | SUS43〇 | ISUS430 SUS430 1_ SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 SUS430 •»w| Ρί . Female 囫缄 forget 4琢畲Long <璲_. Tungsten solid 铋 long 啭 inch ※:^ί^κ·琛9长嵴ε※:wK-趄趄银长^(2)※:*?^®^^^^!※ 19 201111523 A variety of ferrite-based iron-based stainless steel sheets after glow annealing, using AES (Auger Electron Spectroscopy) to measure the atoms of Cr, Si, and A in the oxide film from the surface to a depth of 50λ. The concentration ratio 'determined (Cr + Si + Al) / Fe. For the various ferrite-based stainless steel sheets after the radiance annealing, the chemical conversion agent e-206 of Japan PARKERIZING Co., Ltd., which is a chemical conversion treatment agent, is treated with an amine decane-based or epoxy decane-based treatment agent. It varies in the range of 2 to 2 〇 mg/m 2 to 5 〇 mg/m 2 . Further, chromate treatment was applied as a chemical treatment agent for comparison. Thereafter, the acrylic urethane resin-based clear film was treated to a temperature of 220 ° C to a temperature of 1 to ΙΟμηι. 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 iron-based stainless steel sheet is 0.6 or more, and the amount of deposition is 2% by using an amine-based decane-based or epoxy-decane-based compound or two kinds of chemical-forming agents. The treatment of 20 mg/m2 can obtain a transparent coated steel sheet having an excellent whiteness with a b* of 2 or less, and in contrast, in a comparative example, a transparent coated steel sheet with a yellow color of b* exceeding 2 is formed, and I saw a black hue because of the angle of view. In Comparative Example 20, since the Si component of the stainless steel plate fell outside the lower limit, (Cr + Si + Al) / Fe in the oxide film fell outside the lower limit, b * was 2 or more, and the whiteness was inferior. 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, the whiteness is poor. In particular, in Comparative Example 25', since the temper color of the steel sheet material was clearly observed, (Cr + Si + Al) / Fe was not measured. Comparison 20 201111523 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 deposition amount of the chemical conversion treatment agent of Comparative Example 26 fell outside the lower limit, and the adhesion property was poor. The chemical conversion treatment agent adhesion amount of Comparative Example 27 fell outside the upper limit, and the chemical conversion treatment agent of Comparative Example 28 was a complex acid treatment agent instead of The non-chromate-based treating agent of the present invention has a b* of 2 or more and a poor whiteness. 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 30 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 According to the present invention which reviews the relationship between the design of the transparent coated stainless steel sheet and the color tone, it can be from 0 to 2 in b* (degree of chromaticity, yellow/blue, JIS Z 8729). The range is to produce a transparent coated steel sheet with excellent whiteness. The general transparent coated stainless steel plate b* is from about 4 to 6, not only yellow but also dark tones due to the angle of view. 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. [Simplified description of the drawings] Fig. 1 is a schematic diagram showing the relationship between the adhesion amount of the chemical conversion treatment and the discoloration Ab* of the transparent coated non-mineral steel sheet. Fig. 2 is a graph showing the ratio of Cr, Si, a, and Fe atom concentration (Cr + Si + Al) / Fe ' and the utilization 224 in the depth from the surface to 5 〇. (: Sintered transparent coating stainless steel 21 201111523 The relationship between the discoloration of the steel plate Ab*. Fig. 3 is the grinding and polishing of the stainless steel plate, and the sintering temperature of the bright-annealed steel plate to which the invention is applied after the grinding, and the transparent coating Schematic diagram of the relationship between the discoloration of the stainless steel plate Ab*. Fig. 4 is the annealing temperature T1 (°C) of the glow annealing, the dew point T2 (°C), and the Cr, Si in the oxide film from the surface to the depth of 5〇A. Schematic diagram of the relationship between the concentration ratio of A and Fe atoms (Cr+Si+Al)/Fe. [Description of main component symbols] (none)

a： 22a: 22

Claims (1)

201111523 七、申請專利範圍： L〜種白色度優異的透明塗裝不鏽鋼板之製造方法’其特 徵在於： 在露點T2(°C)滿足2式且以H2 : N2=l : 1〜9 : 1的比 例渑合有氫與氧的退火氣體環境中，於退火溫度T1(°C) 滿足1式之條件下，對以質量％計含有Si : 0.2〜0.8%、 Al : 0.005〜0.15%、Nb : 0.1〜0_7%的肥粒鐵系不鏽鋼 • 板素材進行最終光輝退火，而製成具有表面氧化皮膿之 鋼板素材，且該鋼板素材表面至50人的深度中之Cr、Si、 A1、Fe原子濃度比(Cr+Si+Al)/Fe為0.6以上； 並使用由胺基矽烷系及環氧矽烷系中之1種或2種 所構成的化成處理劑對該鋼板素材進行化成處理，以使 该化成處理劑的附著量成為2〜20mg/m2(用螢光X射線 測定Si02量）；以及 塗敷透明塗料來形成厚度為1〜的塗膜； Φ 750^T1^5xT2+1200 ……1 式 -70^Τ2^-30 ......2式。 2.如巾請專利範圍第丨項之自色度優異的透明塗裝不鐘鋼 板之製造錢，其係將經過冷軋的前述崎㈣不癌鋼 板素材作表面研磨處理後再施以前述最終光輝退火者。 23201111523 VII. Patent application scope: L~ Manufacturing method of transparent coated stainless steel plate with excellent whiteness' is characterized by: The dew point T2 (°C) satisfies the formula 2 and H2: N2=l: 1~9 : 1 In the case of an annealing gas atmosphere in which hydrogen and oxygen are combined, in the case where the annealing temperature T1 (° C.) satisfies the formula 1, Si is contained in mass %: 0.2 to 0.8%, Al: 0.005 to 0.15%, Nb : 0.1~0_7% of ferrite-based iron-based stainless steel • The plate material is subjected to final glow annealing to form a steel plate material with surface oxidized skin pus, and the surface of the steel plate material is in the depth of 50 people, Cr, Si, A1, Fe The atomic concentration ratio (Cr+Si+Al)/Fe is 0.6 or more; and the steel sheet material is chemically treated by using a chemical conversion treatment agent composed of one or two kinds of an amine decane system and an epoxy decane system. The amount of the chemical conversion agent to be applied is 2 to 20 mg/m 2 (the amount of SiO 2 is measured by fluorescent X-ray); and a clear coating material is applied to form a coating film having a thickness of 1 〜; Φ 750^T1^5xT2+1200 ...... 1 type -70^Τ2^-30 ......2. 2. For the towel, please refer to the patent item Scope Item for the manufacture of transparent coatings with excellent chromatographic properties, which are subject to the surface grinding treatment of the cold-rolled Saki (four) non-cancer steel plate material. Brilliant annealing. twenty three
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