TW201700788A - 熔融鋅系鍍敷鋼板 - Google Patents

熔融鋅系鍍敷鋼板 Download PDF

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Publication number
TW201700788A
TW201700788A TW105110516A TW105110516A TW201700788A TW 201700788 A TW201700788 A TW 201700788A TW 105110516 A TW105110516 A TW 105110516A TW 105110516 A TW105110516 A TW 105110516A TW 201700788 A TW201700788 A TW 201700788A
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Taiwan
Prior art keywords
oxide
steel sheet
less
plated steel
molten
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TW105110516A
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English (en)
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TWI655320B (zh
Inventor
Yasuaki Kawamura
Koji Akioka
Akihiro Sengoku
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Nippon Steel & Sumitomo Metal Corp
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Publication of TWI655320B publication Critical patent/TWI655320B/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0272—After-treatment with ovens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
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    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C22C—ALLOYS
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C2/12—Aluminium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
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    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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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
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C23C22/06—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 acidic solutions with pH less than 6
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C23C22/40—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 acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
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Abstract

更簡便地提供一種熱壓後之塗膜密著性優異的熔融鋅系鍍敷鋼板。 本發明之熔融鋅系鍍敷鋼板具備：作為基材之熔融鋅系鍍敷鋼板；及表面處理層，係形成在前述熔融鋅系鍍敷鋼板之至少單面；前述表面處理層在0.2g/m2以上且2g/m2以下範圍內含有粒徑為5nm以上且500nm以下之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物。

Description

熔融鋅系鍍敷鋼板 發明領域
本發明係關於熔融鋅系鍍敷鋼板。
發明背景
近年，為了保護環境及防止地球暖化，抑制消耗化石燃料的訴求不斷攀高，且此訴求已對各種製造業造成影響。例如，作為移動手段於日常生活及活動上不可欠缺的汽車也無例外地尋求利用車體之輕量化等來提升燃耗等。然而，就汽車而言，單僅實現車體的輕量化無法滿足於製品機能，還必須確保適當的安全性。
有許多汽車構造係藉由鐵系材料尤其是鋼板形成，減低這些鋼板重量對車體輕量化而言相當重要。然而，如上述不能單僅減輕鋼板的重量，還同時尋求確保鋼板之機械強度。此種鋼板的訴求不僅是汽車製造業，許多製造業也面臨相同情況。因此，現行係藉由提高鋼板之機械強度，針對比以往使用之鋼板更薄但又可維持或提升機械強度的鋼板進行研究開發。
一般而言，具有高機械強度的材料在彎曲加工等成形加工中有形狀凍結性降低的傾向，很難成形加工成複 雜的形狀。關於這種成形性問題的解決手段之一可列舉所謂的「熱壓法(亦稱熱印模法、熱壓製法或模具淬火法)」。熱壓方法係先將成形對象之材料加熱至高溫，並對經由加熱而軟化的鋼板施行加壓加工予以成形後再行冷卻。藉由此熱壓方法，係先將材料加熱至高溫使其軟化，因此可輕易地將對象之材料加壓加工。此外，藉由成形後的冷卻之淬火效果，可提高材料的機械強度。因此，利用熱壓方法可獲得兼具良好的形狀凍結性及高度機械強度的成形品。
然而，若對鋼板適用此種熱壓方法，鋼板在加熱至800℃以上之高溫時，鋼板表面會氧化而生成鏽皮(化合物)。因此，進行熱壓加工後需要除去該鏽皮的步驟(所謂的去鏽步驟)，會降低生產性。此外，講求耐蝕性的構件等又必須於加工後對構件表面施行防鏽處理或金屬被覆，便需要表面清潔步驟及表面處理步驟，更會降低生產性。
抑制這種生產性降低的方法可舉如事先對將進行熱壓之鋼板施行被覆的方法。鋼板上之被覆一般係使用有機系材料或無機系材料等各種材料。其中，基於其本身的防蝕性能及鋼板生產技術的觀點，在汽車鋼板等多廣泛採用對鋼板具有犧牲性防蝕作用的鋅(Zn)系鍍敷鋼板。
藉由施行Zn系金屬被覆，可防止鋼板表面上生成鏽皮，便無需去鏽等步驟，所以可提升成形品之生產性。此外，Zn系金屬被覆也有防鏽效果，所以也會提升耐蝕性。下述專利文獻1~專利文獻4中即揭示了一種將鍍敷鋼板熱壓之方法且該鍍敷鋼板係已對具有既定成分組成之鋼板施 行Zn系金屬被覆者。
下述專利文獻1~專利文獻3中，熱壓用鋼板係利用熔融鍍Zn鋼板或合金化熔融鍍Zn鋼板。於熱壓利用熔融鍍Zn鋼板或合金化熔融鍍Zn鋼板，既不會於表面形成鐵氧化物(即，鏽皮)，也可成形構造構件。此外，下述專利文獻4中揭示了一項發明，其指出若在已將Zn系鍍敷鋼板予以熱壓之熱處理鋼材表面上形成一厚厚的氧化Zn層，會對熱處理鋼材之塗膜密著性或塗裝後耐蝕性造成不良影響，因此其係對熱處理鋼材施行珠粒噴擊(shot blast)以除去氧化Zn層，或是減低氧化Zn層之厚度後再進行塗裝。
另外，下述專利文獻5及專利文獻6中揭示了一項用以改善Zn系鍍敷鋼板經過熱壓之熱處理鋼材的塗膜密著性或塗裝後耐蝕性的發明。下述專利文獻5係揭示使用表面被聚矽氧樹脂皮膜被覆之熔融鍍Zn鋼板作為熱壓用鋼板的發明，而下述專利文獻6係揭示使用經由含有磷(P)及矽(Si)之障壁層(就P係舉例磷酸鹽，就Si係舉例膠質氧化矽)被覆之熔融鍍Zn鋼板作為熱壓用鋼板的發明。
又，下述專利文獻7揭示了一技術，其係於鍍Zn層中添加比Zn更容易氧化之元素(易氧化性元素)，於熱壓時在升溫期間於鍍Zn層表層形成一該等易氧化性元素之氧化物層以防止鋅揮發。
根據下述專利文獻5~專利文獻7中揭示之發明，藉由鍍Zn層被前述障壁層被覆可抑制Zn蒸發，藉此，中間塗膜或表塗塗膜可具有良好的密著性或塗裝後耐蝕性。
先前技術文獻 專利文獻
專利文獻1：日本特開2003-73774號公報
專利文獻2：日本特開2003-129209號公報
專利文獻3：日本特開2003-126921號公報
專利文獻4：日本特開2004-323897號公報
專利文獻5：日本特開2007-63578號公報
專利文獻6：日本特開2007-291508號公報
專利文獻7：日本特開2004-270029號公報
發明概要
然而，在Zn系鍍敷鋼板尤其是已將熔融鍍Zn鋼板或合金化熔融鍍Zn鋼板熱壓時，經過磷酸鹽處理而形成的磷酸鹽皮膜有時很難附著(亦即磷酸鹽處理性很低)。關於本發明視為對象之熔融Zn系鍍層，就算是不屬於以鋁(Al)為主要成分之Zn-Al系合金鍍層，也會在鍍浴及鍍敷層中含有Al。其理由如下。即，鍍浴之溫度為440~480℃左右，且在該溫度區下Zn與Fe一旦接觸，Fe與Zn便會相繼合金化而產生浮渣。藉由使鍍浴含有Al，可在Fe與Zn產生反應前先引發Fe與Al反應，結果便可抑制浮渣產生。基於該理由，通常熔融Zn鍍浴中會含有Al。
一般而言，關於熔融鍍Zn係在鍍浴中含有0.2~0.3%之Al，且在鍍敷層中含有0.2~1.0質量%之Al；在合金 化熔融鍍Zn則係在鍍浴中含有0.1~0.2%之Al，且在鍍敷層中含有0.1~0.5質量%之Al。
該鍍敷層中之Al會在形成鍍敷皮膜期間及熱壓之加熱期間擴散移動至鍍敷層之表層，形成氧化Al膜。氧化Al膜不會溶解於磷酸，因此可阻礙Zn與磷酸鹽(磷酸鋅等)之反應，而在形成有氧化Al膜之區域中就不容易形成磷酸鹽皮膜。結果，在形成有氧化Al膜之區域中磷酸鹽處理性就很低。尤其，在熱壓步驟中，藉由通電加熱或感應加熱使鋼板急速地加熱至Ac3點以上之後便迅速進行加壓成形時，磷酸鹽處理性會顯著降低。此時，塗裝密著性也會降低。
另外，本發明人等在對上述專利文獻5所揭示之使用表面被聚矽氧樹脂皮膜被覆之熔融鍍Zn鋼板作為熱壓用鋼板而獲得的熱處理鋼材進行複試時得知，如後述在重複乾濕環境之循環性腐蝕試驗中，塗裝後耐蝕性雖然良好，但塗裝密著性未必優異。因此，藉由上述專利文獻5揭示之發明製得的熱處理鋼材就不適合直接用在例如構造上容易積水的部位或構件(例如，車門下方的袋狀構造部位或引擎室內的封閉截面構件等)上。
另一方面，如上述專利文獻7所揭示，於鍍鋅層中添加易氧化性元素需要在像鍍浴溫度管理或浮渣對策等操作上另下一番工夫。
爰此，本發明係有鑑於上述問題所進行者，本發明目的在於更簡便地提供一種熱壓後之塗膜密著性優異的 熔融鋅系鍍敷鋼板。
本發明人等針對上述目的之熱壓用鍍敷鋼板進行精關研討並根據由該結果推衍的見解聯想到下述熔融鋅系鍍敷鋼板。
本發明主旨如下。
(1)一種熔融鋅系鍍敷鋼板，具備：作為基材之熔融鋅系鍍敷鋼板；及表面處理層，係形成在前述熔融鋅系鍍敷鋼板之至少單面；前述表面處理層在每單面0.2g/m2以上且2g/m2以下範圍內含有粒徑為5nm以上且500nm以下之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物。
(2)如(1)記載之熔融鋅系鍍敷鋼板，其中前述表面處理層以每單面含量計，在以下所示範圍內更含有含磷化合物、含釩化合物、含銅化合物、含鋁化合物、含矽化合物或含鉻化合物之至少任一者。
含磷化合物：以P換算計為0.0g/m2以上且0.01g/m2以下
含釩化合物：以V換算計為0.0g/m2以上且0.01g/m2以下
含銅化合物：以Cu換算計為0.0g/m2以上且0.02g/m2以下
含鋁化合物：以Al換算計為0.0g/m2以上且0.005g/m2以下
含矽化合物：以Si換算計為0.0g/m2以上且0.005g/m2以下
含鉻化合物：以Cr換算計為0.0g/m2以上且0.01g/m2以下
(3)如(1)或(2)記載之熔融鋅系鍍敷鋼板，其中前述選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物的粒徑為10nm以上且200nm以下。
(4)如(1)~(3)中任一項記載之熔融鋅系鍍敷鋼板，其中前述選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物的含量為每單面0.4g/m2以上且1.5g/m2以下。
(5)如(1)~(4)中任一項記載之熔融鋅系鍍敷鋼板，其中前述氧化物為氧化鋯或氧化鑭。
(6)如(1)~(5)中任一項記載之熔融鋅系鍍敷鋼板，其中前述表面處理層在每單面0.2g/m2以上且2g/m2以下範圍內更含有粒徑2mm以上且100nm以下之選自氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上氧化物。
(7)如(6)記載之熔融鋅系鍍敷鋼板，其中前述選自氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上氧化物的粒徑為5nm以上且50nm以下。
(8)如(6)或(7)記載之熔融鋅系鍍敷鋼板，其中前述選自氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上氧化物的含量為每單面0.4g/m2以上且1.5g/m2以下。
(9)如(6)~(8)中任一項記載之熔融鋅系鍍敷鋼板，其中前述氧化物為氧化鈦。
(10)如(1)~(9)中任一項記載之熔融鋅系鍍敷鋼板，其中前述表面處理層在每單面0.2g/m2以上且5.0g/m2以下範圍內更含有氧化鎂、氧化鈣或氧化鋅。
(11)如(10)記載之熔融鋅系鍍敷鋼板，其中前述氧化鎂、氧化鈣或氧化鋅之粒徑為5nm以上且100nm以下。
(12)如(10)或(11)記載之熔融鋅系鍍敷鋼板，其中前述氧化鎂、氧化鈣或氧化鋅之含量為每單面0.4g/m2以上且2.5g/m2以下。
(13)如(1)~(12)中任一項記載之熔融鋅系鍍敷鋼板，其為熱壓用熔融鋅系鍍敷鋼板。
如以上說明，根據本發明可以提升與熱壓後施行之塗膜的塗裝密著性。
用以實施發明之形態
以下詳細說明本發明的適當實施形態。
<1.熔融鋅系鍍敷鋼板>
本發明實施形態的熔融Zn系鍍敷鋼板於基底鋼板上具備熔融Zn系鍍敷層，並且更在該熔融Zn系鍍敷層上之至少單面具備以下詳述之表面處理層。該表面處理層係在0.2g/m2以上且2g/m2以下範圍內含有粒徑為5nm以上且500nm以下之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中的1種或2種以上氧化物。具有該構成的熔融Zn系鍍敷鋼板可適當使用於先前說明之熱壓法。以下針對該熔融Zn系鍍敷鋼板之構成詳細說明。
(1)基底鋼板
本實施形態之熔融Zn系鍍敷鋼板所使用的基底鋼板並無特別限定，可使用具有公知特性及化學組成的各種鋼板。鋼板之化學組成亦無特別限定，以可藉由淬火獲得高強度的化學組成為佳。例如，欲獲得拉伸強度達980MPa以上之熱處理鋼材時，可列舉基底鋼板係由具有下述化學組成之淬火用鋼所構成者：以質量%計含有C：0.05~0.4%、Si：0.5%以下、Mn：0.5~2.5%、P：0.03%以下、S：0.01%以下、sol.Al：0.1%以下、N：0.01%以下、B：0~0.005%、Ti：0~0.1%、Cr：0~0.5%、Nb：0~0.1%、Ni：0~1.0%及Mo：0~0.5%且剩餘部分由Fe及雜質所構成。
如欲獲得淬火時強度小於980MPa之較低強度的熱處理鋼材，基底鋼板之化學組成可不在上述範圍內。
從上述淬火時的淬火性觀點以及形成加熱後含在氧化鋅層中之Mn氧化物及Cr氧化物的觀點來看，Mn含量及Cr含量以Mn+Cr：0.5~3.0%為佳。此外，以Mn含量及Cr含量為Mn+Cr：0.7~2.5%較佳。
鋼板之化學組成中若含有Mn及Cr，熱壓後形成於表層上的氧化鋅層有一部分會成為含有Mn及Cr之複合氧化物。藉由形成該等含有Mn及Cr之複合氧化物，可進一步提升磷酸鹽系於化成處理後的塗裝密著性。詳細情況不明，吾等認為，與氧化鋅相較下，藉由形成該等複合氧化物，所形成之磷酸鹽系化成處理皮膜的耐鹼性有所提升，所以可顯現良好的塗裝密著性。
鋼板之化學組成中含有Mn及Cr時，其含量如前述以Mn+Cr計含有質量%計0.5%以上且3.0%以下之範圍為佳，較理想係質量%計0.7%以上且2.5%以下之範圍。Mn+Cr之含量低於0.5%時，熱壓後形成於表層上的氧化鋅與含有Mn及Cr之複合氧化物會不夠充分，而可能變得難以顯現較良好的塗裝密著性。另一方面，Mn+Cr之含量超過3.0%時，在塗裝密著性方面雖然不會有問題，但有成本升高、以及點熔接部之韌性明顯降低或鍍敷濕潤性顯著劣化的情況。
(2)熔融Zn系鍍敷層
本實施形態之熔融Zn系鍍敷層並無特別限定，可使用一般周知的熔融Zn系鍍層。具體上，本實施形態之熔融Zn系鍍敷層可列舉熔融Zn鍍層、合金化熔融Zn鍍層、Zn-55%Al鍍層、Zn-11%Al鍍層、Zn-11%Al-3%Mg鍍層、Zn-7%Al-3%Mg鍍層、Zn-11%Al-3%Mg-0.2%Si鍍層等。此外如先前說明，須注意即使為熔融鍍Zn及合金化熔融鍍Zn依舊含有Al。
本實施形態之具體的鍍敷操作係實施下述操作：將鋼板浸漬於保持有處於熔融狀態之Zn或Zn合金的鍍浴中並從該鍍浴取出鋼板。對於鋼板之鍍敷附著量的控制係藉由鋼板之取出速度或拭焊氣體(wiping gas)之流量及流速調整等進行，該拭焊氣體係由設置在鍍浴上方的拭焊噴嘴(wiping nozzle)噴出。此外，合金化處理係於上述鍍敷處理後，以燃氣爐、感應加熱爐或將該等併用之加熱爐等額外 將鍍敷後之鋼板加熱而進行。關於該鍍敷操作可利用卷料的連續鍍敷法或是裁切板單體的鍍敷法之任一項來進行鍍敷。
該熔融Zn系鍍敷層之厚度(即，熔融Zn系鍍敷層之附著量)以每單面20g/m2~100g/m2之範圍為佳。熔融Zn系鍍敷層之厚度若每單面小於20g/m2，將無法確保熱壓後之有效Zn量，讓耐蝕性變不夠充分，故不適宜。此外，熔融Zn系鍍敷層之厚度若每單面超過100g/m2，則熔融Zn系鍍敷層之加工性及密著性會降低，故不適宜。較適度的熔融Zn系鍍敷層厚度係每單面30g/m2~90g/m2之範圍。
(3)表面處理層
在如上述之熔融Zn系鍍敷層上更形成有一表面處理層，該表面處理層含有選自氧化鋯(ZrO2)、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物。
在此，「氧化鋯」並非意指像碳酸鋯、硝酸鋯、硫酸鋯之銨鹽、鉀鹽、鈉鹽等等以溶解於處理液中之狀態存在，而是以一次粒徑達數nm以上之固體分散於處理液中之狀態存在之以鋯(Zr)氧化物為主體的物質。藉由使用這種以固體狀態分散於處理液中之氧化鋯，可提供一在浸漬於鹽水環境下之耐久性優異的熱處理鋼材。
至於，該等選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物在表面處理層中係以粒子狀態存在。
具體上，如上述之粒狀的氧化鋯、氧化鑭、氧化 鈰及氧化釹之粒徑(一次粒徑)為5nm以上且500nm以下。從塗裝後耐蝕性的面向來看，氧化鋯、氧化鑭、氧化鈰及氧化釹之粒徑愈小愈有利，不過粒徑小於5nm者不易取得，就成本面不利。此外，氧化鋯、氧化鑭、氧化鈰及氧化釹之粒徑超過500nm時，氧化鋯、氧化鑭、氧化鈰、氧化釹與鍍敷鋼板之接觸面積會變小，在熱壓的加熱期間氧化鋯粒子及於鋼板的影響就會變小，故不適宜。氧化鋯、氧化鑭、氧化鈰及氧化釹之粒徑理想為10nm以上且200nm以下。
至於，如上述之氧化鋯、氧化鑭、氧化鈰及氧化釹的粒徑(一次粒徑)可藉由公知方法測定，例如可以下述方法進行測定：製作塗裝後截面嵌入式的試樣，在多數點測得皮膜中之氧化鋯、氧化鑭、氧化鈰及氧化釹之粒徑並將所得測定結果予以平均之值視作粒徑。
本實施形態之熔融Zn系鍍敷鋼板所具備的表面處理層係在每單面0.2g/m2以上且2g/m2以下範圍內含有如上述之具有一次粒徑之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中的1種或2種以上。該表面處理層中之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上的含量每單面為0.2g/m2以上且2g/m2以下之範圍時，加熱時表面處理層中之氧化鋯、氧化鑭、氧化鈰、氧化釹可以讓熱壓前即存在且熱壓時還會形成的Al氧化物變得無害。藉此，可促進熱壓時氧化鋅之形成，提高熱壓後的磷酸鹽處理性，進而提升塗膜密著性。關於氧化鋯、氧化鑭、氧化鈰、氧化釹可讓加熱時之Al氧化物變得無害一點詳細尚且不明，吾等認 為係因為氧化鋯、氧化鑭、氧化鈰、氧化釹使形成在鋼板表面上的Al氧化物溶解，讓緊追在Al之後容易被氧化的Zn於熱壓時得以被氧化，於是便可促進化成性優異的氧化鋅(ZnO)生成。
表面處理層之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上的含量每單面低於0.2g/m2時，熱壓後沒有充分的氧化鋯、氧化鑭、氧化鈰、氧化釹存在，鍍敷表面的Al氧化物之無害化效果會變小而無法充分確保熱壓後之塗裝密著性。另一方面，表面處理層之氧化鋯含量每單面超過2g/m2時，本實施形態之熔融Zn系鍍敷鋼板的成本不僅會上升，表面處理層之凝聚力還會減弱，熱壓後形成於表面處理層上之塗膜就容易剝離。
該表面處理層之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上的含量理想為每單面0.4g/m2以上且1.5g/m2以下。
含有氧化鋯、氧化鑭、氧化鈰及氧化釹之處理液代表性可列舉氧化鋯溶膠、氧化鑭溶膠、氧化鈰溶膠、氧化釹溶膠，具體的市售產品則可列舉日產化學(股)製NanoUse(註冊商標)系列及多木化學(股)製Ceramace系列。
於表面處理層之形成，可將如上述之氧化鋯溶膠、氧化鑭溶膠、氧化鈰溶膠、氧化釹溶膠直接塗佈於熔融Zn系鍍敷鋼板上，而為了改善處理液之穩定性及表面處理層之密著性，宜作成混合有樹脂或交聯劑之處理液後再塗佈於熔融Zn系鍍敷鋼板上。
該樹脂在使用氧化鋯溶膠、氧化鑭溶膠、氧化鈰溶膠、氧化釹溶膠時，宜採用水溶性或水分散性樹脂，就樹脂的種類而言可列舉聚胺甲酸乙酯樹脂、聚酯樹脂、環氧樹脂、(甲基)丙烯酸樹脂、聚烯烴樹脂、酚樹脂或該等樹脂之改質體等。使用氧化鋯粉末時，除了上述水系樹脂以外，亦可使用以各種溶劑作為溶媒之溶劑系樹脂。
該交聯劑可列舉碳酸鋯化合物、有機鈦化合物、唑啉聚合物、水溶性環氧化合物、水溶性三聚氰胺樹脂、水分散封端異氰酸酯、水系氮化合物等。
此外，本實施形態之表面處理層中更宜含有之其它成分可列舉選自氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上。
表面處理層中若含有選自上述氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上，即使是熱壓後因為該等氧化物存在於鋼板表面上而對電鍍時之電鍍膜凝聚析出造成某種影響，讓氧化物與電鍍膜強固密著而造成化成處理(磷酸鹽處理或FF化成處理)不夠充分，也得以顯現強固的密著性。為了更有效地獲得該效果，上述氧化物之粒徑以2nm以上且100nm以下為佳。
再加上，該等氧化物中，關於氧化鈦除了有上述特徵以外，熱壓時還可抑制過度的Zn氧化或蒸發，進而可提高熱壓後之塗膜密著性以及熱壓後之耐蝕性。吾等推測係因為氧化鈦通常係以金屬氧化物之狀態穩定存在，在熱壓之加熱時則會與所形成之氧化鋅反應而形成與氧化鋅之 複合氧化物，所以可抑制過度的Zn氧化或蒸發。為了更有效地獲得該效果，上述氧化鈦之粒徑以2nm以上且100nm以下為佳。
至於，選自上述氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上的粒徑較理想係5nm以上且50nm以下。
表面處理層含有氧化鈦、氧化鎳及氧化錫(IV)時，其含量宜在每單面0.2g/m2以上且2g/m2以下範圍內含有，較理想係每單面0.4g/m2以上且1.5g/m2以下之範圍。氧化鈦、氧化鎳及氧化錫(IV)之含量每單面低於0.2g/m2時，熱壓後該等氧化物將無法充分存在，所以可能很難顯現與電鍍膜更良好的密著性。
另一方面，當氧化鈦、氧化鎳及氧化錫(IV)之含量每單面超過2g/m2時，本實施形態之Zn系鍍敷鋼板的成本不僅會上升，表面處理層之凝聚力還會減弱，熱壓後形成於表面處理層上的塗膜便容易剝離。
此外，關於氧化鈦含量每單面低於0.2g/m2時，除了上述以外，還無法形成充分的與氧化鋅之複合氧化物，進而難以有效率地抑制Zn之氧化或蒸發。
又，本實施形態之表面處理層中更宜含有的其它成分可列舉氧化鎂、氧化鈣或氧化鋅。
表面處理層中若含有上述氧化鎂、氧化鈣或氧化鋅，熱壓後因為該等氧化物存在於表面處理層之表層上，而得以提升磷酸鹽處理性。針對磷酸鹽處理性提升之理由，吾等以為係因為氧化鎂等溶解在磷酸鹽處理液中而促進與 磷酸鹽之化成反應所致。為了更有效率地獲得該效果，上述氧化鎂、氧化鈣或氧化鋅之粒徑以5nm以上且100nm以下為佳，10nm以上且50nm以下更佳。
表面處理層含有氧化鎂、氧化鈣或氧化鋅時，其含量宜在每單面0.2g/m2以上且5g/m2以下範圍內含有，較理想係每單面0.4g/m2以上且2.5g/m2以下之範圍。氧化鎂、氧化鈣及氧化鋅之含量每單面低於0.2g/m2時，熱壓後該等氧化物將無法充分存在，因此可能難以顯現良好的磷酸鹽處理性。另一方面，氧化鎂、氧化鈣及氧化鋅之含量每單面超過2g/m2時，本實施形態之Zn系鍍敷鋼板的成本不僅會上升，表面處理層的凝聚力還會減弱，熱壓後形成於表面處理層上的塗膜便容易剝離。
本實施形態之表面處理層除了上述氧化物以外，亦可在既定含量之範圍內含有以下詳述之含P化合物、含V化合物、含Cu化合物、含Al化合物、含Si化合物或含Cr化合物之至少任一者。
含P化合物係含有磷作為構成元素的化合物。此種含P化合物可舉如磷酸、亞磷酸、膦酸、亞膦酸(phosphonous acid)、亞膦酸(phosphinic acid)、次膦酸(phosphinous acid)、膦氧化物、膦等化合物或是以該等化合物作為陰離子之離子化合物等。該等含P化合物皆已作為試藥或製品販售流通，可輕易取得。該等含P化合物係以溶解於處理液中之狀態或以粉末分散於處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
含V化合物係含有釩作為構成元素的化合物。此種含V化合物可舉如含五氧化釩之釩氧化物、含偏釩酸銨之偏釩酸系化合物、含釩酸鈉之釩化合物及其它含有V之化合物等。該等含V化合物皆已作為試藥或製品販售流通，可輕易取得。該等含V化合物係以溶解於處理液中之狀態或以粉末分散於處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
本實施形態之表面處理層以P及V換算計，在每單面0.0g/m2以上且0.01g/m2以下範圍內各含有選自上述含P化合物及含V化合物中之1種或2種以上化合物為佳。
選自上述含P化合物及含V化合物中之1種或2種以上化合物在熱壓時會被氧化而成為氧化物，偏佈在熔融Zn系鍍敷層與表面處理層之界面，形成含有P或V之至少任一者之凝聚力薄弱的氧化物層。選自含P化合物及含V化合物中之1種或2種以上化合物的含量以P及V換算計分別為每單面0.0g/m2以上且0.01g/m2以下之範圍，藉此，在熱壓時所形成之上述凝聚力薄弱的氧化物層厚度會變薄，而進一步提升熱壓後之熔融Zn系鍍敷層與表面處理層的密著性。
表面處理層中選自含P化合物及含V化合物中之1種或2種以上的含量在每單面超過0.01g/m2時，熱壓時所形成之凝聚力薄弱的氧化物層厚度會變厚，令熔融Zn系鍍敷層與表面處理層之密著性降低，於是電鍍後的密著性也跟著降低。從熱壓後之熔融Zn系鍍敷層與表面處理層之密著性的觀點來看，表面處理層中選自含P化合物及含V化合物 中之1種或2種以上化合物的含量以P及V換算計分別為每單面0.0g/m2以上且0.003g/m2以下較佳。
含Cu化合物係含有銅作為構成元素的化合物。此種含Cu化合物可舉如金屬Cu、氧化銅、各種有機銅化合物、各種無機銅化合物及各種銅錯合物等。該等含Cu化合物皆已作為試藥或製品販售流通，可輕易取得。該等含Cu化合物係以溶解於處理液中之狀態或以粉末分散於處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
本實施形態之表面處理層以Cu換算計在每單面0.0g/m2以上且0.02g/m2以下範圍內含有選自上述含Cu化合物中之1種或2種以上化合物為佳。
選自上述含Cu化合物中之1種或2種以上化合物在熱壓時會被氧化而成為氧化物，偏佈在熔融Zn系鍍敷層與表面處理層之界面，形成含有Cu之凝聚力薄弱的氧化物層。選自含Cu化合物中之1種或2種以上化合物的含量以Cu換算計每單面為0.0g/m2以上且0.02g/m2以下之範圍，藉此，熱壓時所形成之上述凝聚力薄弱的氧化物層之厚度會變薄，而進一步提升熱壓後之熔融Zn系鍍敷層與表面處理層的密著性。
表面處理層中選自含Cu化合物中之1種或2種以上的含量每單面超過0.02g/m2時，熱壓時所形成之凝聚力薄弱的氧化物層厚度會變厚，令熔融Zn系鍍敷層與表面處理層之界面密著性降低，於是電鍍後之密著性也跟著降低。 再加上，Cu係比基底鋼板主成分之Fe更貴的元素，所以耐蝕性也有降低之傾向。若從熱壓後之熔融Zn系鍍敷層與表面處理層之密著性觀點來看，表面處理層中選自含Cu化合物中之1種或2種以上化合物的含量以Cu換算計為每單面0.0g/m2以上且0.005g/m2以下較佳。
含Al化合物係含有鋁作為構成元素的化合物。此種含Al化合物可舉如金屬Al、氧化鋁、氫氧化鋁、以鋁離子作為陽離子的離子化合物等。該等含Al化合物皆已作為試藥或製品販售流通，可輕易取得。該等含Al化合物係以溶解於處理液中之狀態或以粉末分散於處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
含Si化合物係含有矽作為構成元素的化合物。此種含Si化合物可舉如Si單體、氧化矽(silica)、有機矽烷、亦可作為黏結劑樹脂使用之聚矽氧樹脂及其它含Si之化合物。該等含Si化合物皆已作為試藥或製品販售流通，可輕易取得。該等含Si化合物係以溶解於處理液中之狀態或以粉末分散於處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
本實施形態之表面處理層以Al及Si換算計在每單面0.0g/m2以上且0.005g/m2以下之範圍內各含有選自上述含Al化合物及含Si化合物中之1種或2種以上化合物為佳。
選自上述含Al化合物及含Si化合物中之1種或2種以上化合物在熱壓時會被氧化而成為氧化物，並濃化於 表面處理層表面。選自含Al化合物及含Si化合物中之1種或2種以上化合物的含量以Al及Si換算計分別為每單面0.0g/m2以上且0.005g/m2以下之範圍，藉此，熱壓時形成在表面處理層表面上之含有Al或Si之氧化物的存在比率會變小，熱壓後表面處理層與電鍍膜之密著性便會更加提升。
表面處理層中選自含Al化合物及含Si化合物中之1種或2種以上的含量每單面超過0.005g/m2時，熱壓時所形成之含有Al或Si之氧化物的存在比率會變大。該等含有Al或Si之氧化物不僅會阻礙化成處理皮膜形成，也會使熱壓後之表面處理層與電鍍膜之密著性降低，所以，熱壓時所形成之含有Al或Si之氧化物的存在比率變大會造成表面處理層與電鍍膜之密著性降低。若從熱壓後之表面處理層與電鍍膜之密著性(即，塗裝後密著性)觀點來看，表面處理層中選自含Al化合物及含Si化合物中之1種或2種以上化合物的含量以Al及Si換算計分別為每單面0.0g/m2以上且0.002g/m2以下較佳。
含Cr化合物係含有鉻作為構成元素的化合物。此種含Cr化合物可舉如金屬Cr、具有各種價數之鉻化合物及以具有各種價數之鉻離子作為陽離子的離子化合物等。該等含Cr化合物係以溶解於處理液中之狀態或以粉末分散於處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
含Cr化合物因價數不同而有不同的性能及性質，6價鉻化合物中存有多種有害的化合物。有鑑於近期力求環 境保護思慮的傾向，本實施形態之表面處理層以極力不含上述之含Cr化合物為佳，且以無鉻較佳。
基於上述觀點，本實施形態之表面處理層以Cr換算計在每單面0.0g/m2以上且0.01g/m2以下範圍內含有選自上述含Cr化合物中之1種或2種以上化合物為佳，且以不含含Cr化合物較佳。
此外，在不阻礙以含有選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上為主軸之本發明效果的前提下，表面處理層可含有碳黑、氧化鈦等顏料或已在塗裝鋼板作使用之各種防鏽顏料等。此時，表面處理層亦在每單面0.2g/m2以上且2g/m2以下範圍內含有粒狀的氧化鋯等。
藉由添加該等顏料，雖然不會直接改善熱壓後之塗膜密著性、耐蝕性，但碳黑、氧化鈦等顏料可藉由在爐上的熱壓加熱時提升鋼板表面之放射率而或可縮短加熱時間。防鏽顏料則可抑制熱壓加熱前鋼板之腐蝕。
至於，該表面處理層之形成方法將處理液塗佈於鍍鋅鋼板表面上並予以乾燥及燒附即可，該處理液含有選自粒狀之氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上。
塗佈方法並無限定特定方法，舉例有：將基底鋼板浸漬於處理液或對基底鋼板表面噴佈處理液後，以成為既定附著量的方式藉由輥件或氣體噴附控制附著量之方法、或是以輥塗器或棒塗器進行塗佈之方法。
此外，乾燥、燒附方法也只要是可使分散媒(主要為水)揮發的方法即可，不限於特定方法。在此，若過度以高溫加熱，有表面處理層之均一性降低的疑慮；反之，若過度以低溫加熱，則有生產性降低的疑慮。因此，為了穩定且有效率地製造具有優異特性的表面處理層，宜在80℃~150℃左右的溫度下將塗佈後之表面處理層加熱5秒~20秒左右。
又，表面處理層之形成在鍍敷鋼板製造線上以線內進行既經濟又實惠，不過亦可以在其它的生產線形成，或是可實施用來進行成形的沖裁(blanking)後再予以形成。
在此，表面處理層之氧化鋯、氧化鑭、氧化鈰、氧化釹或氧化鈦、氧化鎳、氧化錫(IV)又或氧化鎂、氧化鈣、氧化鋅的含量可由公知方法測得，例如事先以截面能量色散型X射線(Energy Dispersive X-ray：EDX)分析等確認各種化合物係屬氧化鋯或鹼土類金屬之氧化物後，再將皮膜溶解並使用ICP(Inductively Coupled Plasma、感應耦合電漿)發光分光分析法等進行測定。此外，關於表面處理層中之上述含P化合物、含V化合物、含Cu化合物、含Al化合物、含Si化合物及含Cr化合物的含量亦可藉由相同方法測得。
<2.關於熱壓步驟>
對先前說明之熔融Zn系鍍敷鋼板適用熱壓法時，係將熔融Zn系鍍敷鋼板加熱至既定溫度後再行加壓成形。本實施形態之熔融Zn系鍍敷鋼板在施行熱壓成形後，通常會加熱至700~1000℃，若欲在急速冷卻後形成麻田散鐵單相或 使麻田散鐵以體積率計達90%以上，令加熱溫度之下限溫度為Ac3點以上即為重要。在本發明，急速冷卻後也包含麻田散鐵/肥粒鐵之2相域的情況，因此加熱溫度以如上述定為700~1000℃為佳。
在熱壓法中有緩加熱之熱壓及急速加熱之熱壓2種方法。採用的加熱方法可列舉電爐、燃氣爐或火焰加熱、通電加熱、高頻加熱、感應加熱等，加熱時的氣體環境也無特別限制，不過就可明顯獲得本發明效果的加熱方法來說，宜採用急速加熱之通電加熱、感應加熱等。
在緩加熱之熱壓法係利用加熱爐之輻射加熱。首先，使用本實施形態之熔融Zn系鍍敷鋼板作為熱壓用鋼板並將之裝入加熱爐(燃氣爐、電爐等)。在加熱爐內將熱壓用鋼板加熱至700~1000℃，並按條件保持在該加熱溫度下(均熱)。藉此，使熔融Zn系鍍敷層中之熔融Zn與Fe結合而成為固相(Fe-Zn固溶體相)。使熔融Zn系鍍敷層中之熔融Zn與Fe結合並固相化後，再從加熱爐抽出鋼板。另外，亦可藉由均熱使熔融Zn系鍍敷層中之熔融Zn與Fe結合並以Fe-Zn固溶體相及ZnFe合金相固相化後，再從加熱爐抽出鋼板。
相對地，亦可將熔融Zn系鍍敷鋼板加熱至700~1000℃，在無保持時間或令保持時間為很短時間的情況下從加熱爐抽出鋼板。在此情況下，係在鋼板加熱至700~1000℃後，以未利用加壓成形等對鋼板賦予應力的方式冷卻至熔融Zn系鍍敷層中之熔融Zn與Fe結合而成為固相 (Fe-Zn固溶體相或ZnFe合金相)為止。具體上，係至少冷卻至鋼板溫度成為782℃以下為止。冷卻後，如以下說明使用模具加壓鋼板並同時進行冷卻。
在急速加熱之熱壓也同樣地係使用本實施形態之熔融Zn系鍍敷鋼板作為熱壓用鋼板，急速加熱至700~1000℃。急速加熱例如可藉由通電加熱或感應加熱實施。此時的平均加熱速度在20℃/秒以上。在急速加熱的情況下，係在熔融Zn系鍍敷鋼板加熱至700~1000℃後，以未利用加壓成形等對鋼板賦予應力的方式冷卻至熔融Zn系鍍敷層中之熔融Zn與Fe結合而成為固相(Fe-Zn固溶體相或ZnFe合金相)為止。具體上，係至少冷卻至鋼板溫度成為782℃以下。冷卻後，如以下說明使用模具加壓鋼板並同時進行冷卻。
已抽出之鋼板係利用模具加壓。加壓鋼板時，鋼板會被模具冷卻。模具內有冷卻介質(例如水等)循環，所以模具可將鋼板除熱並冷卻。藉由以上步驟，即可利用一般的加熱來製造熱壓鋼材。
使用具有本實施形態之表面處理層的熔融Zn系鍍敷鋼板所製出的熱壓鋼材具有優異的磷酸鹽處理性及塗裝密著性。尤其，本實施形態之熔融Zn系鍍敷鋼板在以急速加熱之熱壓或緩加熱之熱壓加熱至700~1000℃且無保持時間或令保持時間為很短時間時，可顯著發揮效果。
使用昔知之鍍敷鋼板來實施一般加熱之熱壓時，鋼板會在加熱爐內均勻受熱。此時會於熱壓用鋼板之鍍敷層表層形成一氧化Al膜，不過經由長時間的均熱，氧化Al 膜會有某程度的破裂而分斷，所以對化成處理性的不良影響很小。另一方面，實施急速加熱之熱壓時，均熱時間非常短。所以，形成於最表面的氧化Al膜很難被破壞。因此，使用昔知之鍍敷鋼板時，比起利用一般加熱的熱壓，利用急速加熱之熱壓時的熱壓鋼材之磷酸鹽處理性及塗裝密著性較低。
另外，本實施形態之熱壓用熔融Zn系鍍敷鋼板在表面處理層中含有選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上，藉此在熱壓時可使Al氧化變得無害，促進氧化鋅生成，因此可發揮良好的磷酸鹽處理性及塗裝密著性。
實施例
以下顯示實施例以進一步具體說明本發明實施形態之熔融Zn系鍍敷鋼板的作用效果。至於，以下所示實施例不過為本發明之熔融Zn系鍍敷鋼板的其中一例，本發明之熔融Zn系鍍敷鋼板不受下述實施例限定。
<基底鋼板>
以下，首先製造具有以下表1所示化學組成之熔鋼。然後使用所製造之各熔鋼以連續鑄造法製造鋼胚。將製得之鋼胚予以熱軋延，製造出熱軋鋼板。接著將熱軋鋼板酸洗後，實施冷軋延，製造冷軋鋼板，藉以製作具有表1記載之化學組成的鋼#1~#8之鋼板。如表1所示，各鋼種之鋼板板厚均為1.6mm。
<熔融Zn系鍍敷層>
對鋼#1~#8之鋼板進行熔融鍍Zn處理，然後實施合金化處理。合金化處理中之最高溫度均為530℃，加熱約30秒後冷卻至室溫而製造出合金化熔融鍍Zn鋼板(GA)。又，使用鋼#1進行熔融鍍Zn處理且未施行合金化處理而製造出熔融鍍Zn鋼板(GI)。
再來，使用熔融Zn-55%Al、熔融Zn-6%Al-3%Mg、熔融Zn-11%Al-3%Mg-0.2%Si之3種鍍浴，對鋼#1進行各種熔融鍍Zn而製造出熔融Zn系鍍敷鋼板A1~A3。
A1：熔融Zn-55%Al
A2：熔融Zn-6%Al-3%Mg
A3：熔融Zn-11%Al-3%Mg-0.2%Si
至於，關於上述熔融Zn系鍍敷鋼板之鍍敷皮膜中的Al濃度係以下述方法求得。即，從各熔融Zn系鍍敷鋼板採取試樣。將所取得之試樣的熔融Zn系鍍敷層以10%HCl水溶液溶解後，利用ICP發光分光分析法分析熔融Zn系鍍敷層之組成。根據所得分析結果求出每單面之Al濃度(質量%)。所得結果係整合顯示於以下表3。
<表面處理層>
接著，用水將下述化合物及藥劑混合，以作出以固體成分比率計為表2之組成的藥液。以棒塗器塗佈所得處理液，並在最高到達溫度100℃下保持8秒鐘之條件下使用烘箱進行乾燥，藉以製造出熱壓用鍍敷鋼板。處理液之附著量係以處理液中之不揮發成分的總附著量成為表3所示數值的 方式，藉由液體稀釋及棒塗器支數來調整。以下表2中，各成分之固體成分濃度係以屬「氧化物A」之各成分的不揮發成分相對於處理液整體之不揮發成分的比率(單位：質量%)記載。
表2中之各成分(記號)如下。
此外，如後述，亦有探討含有氧化鋁(溶膠)作為氧化鋯、氧化鑭、氧化鈰及氧化釹以外之粒狀物質的處理液，此時，氧化鋁係視為「氧化物A」。同樣地，氧化鈦、氧化鎳及氧化錫(IV)係視為「氧化物B」，氧化鎂、氧化鈣及氧化鋅為「氧化物C」。
(氧化物A)氧化鋯、氧化鑭、氧化鈰、氧化釹、氧化鋁
ZB：氧化鋯溶膠(日產化學工業(股)NanoUse(註冊商標)ZR-40BL)、粒徑70~110nm(型錄值)
ZA：氧化鋯溶膠(日產化學工業(股)NanoUse(註冊商標)ZR-30AL)、粒徑70~110nm(型錄值)
ZP：氧化鋯粉末(高純度化學研究所製氧化鋯、粒徑約1μm
La：氧化鑭溶膠(多木化學(股)BIRAL La-C10)、粒徑40nm(型錄值)
Ce：氧化鈰溶膠(多木化學(股)Needral P-10)、粒徑20nm(型錄值)
Nd：氧化釹溶膠(多木化學(股)BIRAL Nd-C10)、粒徑40nm(型錄值)
AZ：氧化鋁溶膠(日產化學工業(股)氧化鋁溶膠200)、粒徑約10nm
(氧化物B)氧化鈦、氧化鎳、氧化錫(IV)
Ti：氧化鈦溶膠(TAYCA(股)TKS-203)、粒徑約6nm
Ni：氧化鎳(Ionic Liquids Technologies(股)氧化鎳)、粒徑20nm
Sn：氧化錫(IV)溶膠(多木化學(股)Ceramace C-10)、粒徑10nm
(氧化物C)氧化鎂、氧化鈣、氧化鋅
Mg：氧化鎂(Ionic Liquids Technologies社製)、粒徑35nm(型錄值)
Ca：氧化鈣(關東化學社製)
※係使其分散於添加有樹脂之水中並以球磨機將顏料粉碎後使用。
Zn：氧化鋅(Ionic Liquids Technologies社製)、粒徑20nm(型錄值)
(iii)樹脂
A：胺甲酸乙酯系樹脂乳液(第一工業製藥(股)SUPERFLEX(註冊商標)150)
B：胺甲酸乙酯系樹脂乳液(第一工業製藥(股)SUPERFLEX(註冊商標)E-2000)
C：聚酯樹脂乳液(東洋紡(股)Vylonal(註冊商標)MD1480)
(iv)交聯劑
M：三聚氰胺樹脂(Mitsui Cytec(股)Cymel(註冊商標)325)
Z：碳酸鋯銨(Kishida Chemical(股)碳酸鋯銨溶液)
S：矽烷耦合劑(日美商事(股)sila-ace S510)(含Si化合物)
(v)顏料
CB：碳黑(三菱化學(股)三菱(註冊商標)碳黑#1000)
T：氧化鈦(石原產業(股)氧化鈦R-930)、粒徑250nm(型錄值)
至於，關於此處記載之「T」氧化鈦係主要使用於塗料中之白色顏料等且粒徑為200~400nm的顏料，比起(氧化物B)粒徑較大，因此無法滿足氧化物B可達成的性能。
PA：縮合磷酸Al(TAYCA(股)縮合磷酸鋁K-WHITE ZF150W)(含P、Al化合物)
PZ：亞磷酸鋅(東邦顏料(股)NP-530)(含P化合物)
Sil：氧化矽粒子(Fuji Silysia Chemical(股)Sylomask 02)(含Si化合物)
Si2：膠質氧化矽(日產化學(股)SNOWTEX O)(含Si化合物)
Al：氧化鋁溶膠(日產化學(股)AS-200)(含Al化合物)
V：釩酸鉀(一般試藥)(含V化合物)
Cr：氧化Cr(VI)(一般試藥)(含Cr化合物)
Cu：氧化銅(II)(一般試藥)(含Cu化合物)
<熱壓步驟>
表面處理層之形成步驟後對各試驗編號的鋼板以爐加熱及通電加熱之2種加熱方式進行熱壓加熱，實施熱壓。在爐加熱係將爐內氣體環境定為910℃且空燃比定為1.1，並在鋼板溫度到達900℃後快速地從爐內取出。在通電加熱係令加熱速度為85℃/秒及42.5℃/秒並加熱至870℃。至於，以下於表3顯示加熱時間比爐加熱更短的通電加熱結果，爐加熱之結果則顯示於表4。
熱壓加熱後進行冷卻直到鋼板溫度成為650℃。冷卻後，利用具備水冷套之平板模具夾取鋼板而製造出熱壓鋼材(鋼板)。在熱壓時冷卻速度較慢的部分也是以50℃/秒以上之冷卻速度的方式冷卻至麻田散鐵變態開始點之360℃左右，予以淬火。
<評估方法>
〔磷酸鹽處理性評估試驗〕
對以下表3~表4中記載之各試驗編號的板狀熱壓鋼材，使用Nihon Parkerizing Co.,Ltd.製表面調整處理劑PREPAREN X(商品名)在室溫下實施20秒的表面調整。再使用Nihon Parkerizing Co.,Ltd.製磷酸鋅處理液Palbond 3020(商品名)實施磷酸鹽處理。處理液之溫度係定為43℃，將板狀熱壓鋼材浸漬於處理液120秒鐘後進行水洗‧乾燥。
以1000倍之掃描型電子顯微鏡(SEM)觀察磷酸鹽處理後之熱壓鋼材表面上任意5個視野(125μm×90μm) 並獲取反射電子像(BSE像)。在反射電子像係以灰階來影像顯示出觀察區。在反射電子像內，形成有屬化成皮膜之磷酸鹽皮膜的部分與未形成磷酸鹽皮膜的部分於對比上不同。爰此，事先以SEM及EDS(能量散布型X射線分光器)決定未形成磷酸鹽皮膜之部分的明度(複數階度)之數值範圍X1。
在各視野之反射電子像中，利用影像處理求出顯示數值範圍X1內之對比區域的面積A1。接著，按以下式(1)求出各視野之透明面積率TR(%)。
TR=(A1/A0)×100…(1)
在此，上述式(1)中A0為視野之總面積(11250μm2)。而5視野之透明面積率TR(%)的平均則定義為其試驗編號之熱壓鋼材的透明面積率(%)。
表3~表4中之「磷酸鹽處理性」欄的「M」表示透明面積率為30%以上。「L」表示透明面積率為25%以上且小於30%。「K」表示透明面積率為20%以上且小於25%。「J」表示透明面積率為15%以上且小於20%。「I」表示透明面積率為13%以上且小於15%。「H」表示透明面積率為11%以上且小於13%。「G」表示透明面積率為10%以上且小於11%。「F」表示透明面積率為18%以上且小於10%。「E」表示透明面積率為6%以上且小於8%。「D」表示透明面積率為5%以上且小於6%。「C」表示透明面積率為2.5%以上且小於5%。「B」表示透明面積率為1%以上且小於2.5%。「A」表示透明面積率小於1%。在透明評估中，屬「I」、「H」、「G」、「F」、「E」、「D」、「C」、「B」或「A」之情況係判斷為磷酸鹽處 理性優異。
〔塗裝密著性評估試驗〕
實施上述磷酸鹽處理後，對各試驗編號之板狀熱壓鋼材以電壓160V之斜率(slope)通電電鍍上NIPPONPAINT Co.,Ltd.製陽離子型電鍍料，並進一步在燒附溫度170℃下燒附塗裝20分鐘。電鍍後之塗料的平均膜厚在所有的試驗編號皆為10μm。
電鍍後，將熱壓鋼材浸漬於溫度有50℃的5%NaCl水溶液中500小時。浸漬後，於試驗面60mm×120mm區塊(面積A10=60mm×120mm=7200mm2)整面黏貼聚酯製膠帶。其後再把膠帶剝去。求出因剝去膠帶而剝離的塗膜面積A2(mm2)並按式(2)求出塗膜剝離率(%)。
塗膜剝離率=(A2/A10)×100…(2)
表3~表4中之「塗裝密著性」欄的「M」表示塗膜剝離率為50.0%以上。「L」表示塗膜剝離率為35%以上且小於50%。「K」表示塗膜剝離率為20%以上且小於35%。「J」表示塗膜剝離率為10%以上且小於20%。「I」表示塗膜剝離率為8%以上且小於10%。「H」表示塗膜剝離率為6%以上且小於8%。「G」表示塗膜剝離率為5%以上且小於6%。「F」表示塗膜剝離率為4%以上且小於5%。「E」表示塗膜剝離率為3%以上且小於4%。「D」表示塗膜剝離率為2.5%以上且小於3%。「C」表示塗膜剝離率為1.3%以上且小於2.5%。「B」表示塗膜剝離率為0.5%以上且小於1.3%。「A」表示塗膜剝離率小於0.5%。在塗裝密著性評估中，屬「I」、「H」、「G」、 「F」、「E」、「D」、「C」、「B」或「A」之情況係判斷為塗裝密著性優異。
〔循環性腐蝕試驗〕
於評估面之塗裝以截切刀(荷重500gf，1gf約9.8×10-3N)切入一割痕後，將下述循環條件之循環性腐蝕試驗實施180循環。
○循環條件
以鹽水噴霧(SST、5%NaCl、35℃氣體環境)2hr→乾燥(60℃)2hr→濕潤(50℃、98%RH)4hr為1循環予以實施。
其後，在切割部1cm寬左右之區域觀察有無從中產生塗膜膨脹。
表3~表4中之「耐蝕性」欄的「E」表示有產生3.0mm以上的塗膜膨脹。「D」表示有產生2.0mm以上且小於3.0mm的塗膜膨脹。「C」表示有產生1.0mm以上且小於2.0mm的塗膜膨脹。「B」表示有產生0.5mm以上且小於1mm的微小的塗膜膨脹。「A」表示小產生小於0.5mm的極微小的塗膜膨脹。在該循環性腐蝕試驗中，屬「C」、「B」或「A」之情況係判斷為耐蝕性優異。
又，對以下表5中記載之各試驗編號的板狀熱壓鋼材實施使用水溶液之處理來替代上述磷酸鋅處理，以查驗所得試驗片之塗裝密著性及耐蝕性，該水溶液含有Zr離子及/或Ti離子與氟且含有100~1000ppm之遊離氟離子(以下稱作FF化成處理液)。
上述FF化成處理液可溶解遊離氟(以下簡稱為FF)、氧化Al皮膜及氧化Zn皮膜。所以，FF可溶解氧化Al皮膜及氧化Zn皮膜的一部分或全部，並同時將熱壓印步驟中所形成之含Zn層予以蝕刻。結果，便可形成由Zr及/或Ti之氧化物或Zr及/或Ti之氧化物與氟化物之混合物所構成的化成處理層(以下稱作特定化成處理層)。若藉由控制FF濃度以蝕刻氧化Al皮膜及氧化Zn皮膜，便可蝕刻氧化Al皮膜及氧化Zn皮膜，形成特定化成處理層。
為了獲得該FF化成處理液，將H2ZrF6(六氟鋯酸)、H2TiF6(六氟鈦酸)以既定金屬濃度放入容器內並以離子交換水稀釋。其後，於容器內放入氫氟酸及氫氧化鈉水溶液，以將溶液中之氟濃度及遊離氟濃度調整成既定值。遊離氟濃度之測定係使用市售的濃度測定器進行。調整後，以離子交換水將容器予以定容而製成FF化成處理液。
FF化成處理係以下述方式實施。首先，作為前置處理使用鹼脫脂劑(NIPPONPAINT Co.,Ltd.製EC90)在45℃下實施2分鐘的浸漬脫脂。其後在40℃下浸漬於以下表6中所示FF化成處理液中120秒，實施化成處理。化成處理後將試驗片1予以水洗乾燥。
針對所得試驗材，特定化成處理層之化成處理性係以螢光X射線分析測定Zr或Ti之附著量，並令附著量之測定值為10~100mg/m2者為「A」，附著量之測定值小於10mg/m2或超過100mg/m2者為「B」，將所得結果整合顯示於表5。至於，關於含有氧化鋯之系統係以螢光X射線分析預先測定實施Zr系FF處理前之附著量，並以化成處理後之Zr附著量減去處理前之Zr附著量的結果當作Zr系FF化成處理之附著量。此外，關於針對所得試驗材之塗裝密著性評估試驗及循環性腐蝕試驗的方法及評估基準，與針對上述形成有磷酸鹽皮膜之試驗材所實施的塗裝密著性評估試驗及循環性腐蝕試驗相同。
又，為了查驗存在於表面處理層中之含P化合物、含V化合物、含Cu化合物、含Al化合物、含Si化合物、含 Cr化合物所造成的影響，利用表2之No.97~No.164所示處理液製造出熱壓用鍍敷鋼板。此時，係以棒塗器塗佈表2之No.97~No.164所示處理液並在最高到達溫度100℃下保持8秒鐘之條件下，使用烘箱進行乾燥。處理液之附著量係以處理液中之不揮發成分的總附著量成為表7所示數值的方式，藉由液體稀釋及棒塗器支數來調整。
在表面處理層之形成步驟後，對各試驗編號的鋼板以通電加熱方式進行熱壓加熱，實施熱壓。此時，加熱速度係定為85℃/秒及42.5℃/秒而加熱至870℃。
熱壓加熱後進行冷卻直到鋼板溫度成為650℃。冷卻後，利用具備水冷套之平板模具夾取鋼板而製造出熱壓鋼材(鋼板)。在熱壓時冷卻速度較慢的部分也是以50℃/秒以上之冷卻速度的方式冷卻至麻田散鐵變態開始點之360℃左右，予以淬火。
對以下表7中記載之各試驗編號的板狀熱壓鋼材，使用Nihon Parkerizing Co.,Ltd.製表面調整處理劑PREPAREN X(商品名)在室溫下實施20秒的表面調整。再使用Nihon Parkerizing Co.,Ltd.製磷酸鋅處理液Palbond 3020(商品名)實施磷酸鹽處理。處理液之溫度係定為43℃，將板狀熱壓鋼材浸漬於處理液30秒鐘後進行水洗．乾燥。其後以與表3所示情況同樣的方式實施磷酸鹽處理性評估試驗。
又，對以下表7中記載之各試驗編號的板狀熱壓鋼材，以與表3所示情況同樣的方式個別實施塗裝密著性評 估試驗及循環性腐蝕試驗。各試驗之試驗方法及評估基準與表3所示情況相同。
由上述表3、表4、表5及表7明示可知，本發明之熔融鋅系鍍敷鋼板熱壓後不僅具有優異的塗膜密著性，亦 具有優異的化成處理性及耐蝕性。
以上係就本發明的適當實施形態詳細說明，惟本發明不受該等示例限定。顯而易見地，只要係具有本發明所屬技術領域之通識人士，皆可在申請專利範圍中所記載之技術思想範疇內思及各種變更例或修正例並知悉該等亦理當歸屬本發明之技術範圍。

Claims (13)

  1. 一種熔融鋅系鍍敷鋼板，具備：作為基材之熔融鋅系鍍敷鋼板；及表面處理層，係形成在前述熔融鋅系鍍敷鋼板之至少單面；前述表面處理層在每單面0.2g/m2以上且2g/m2以下之範圍內含有粒徑為5nm以上且500nm以下之選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物。
  2. 如請求項1之熔融鋅系鍍敷鋼板，其中前述表面處理層以每單面含量計，在以下所示範圍內更含有含磷化合物、含釩化合物、含銅化合物、含鋁化合物、含矽化合物或含鉻化合物之至少任一者；含磷化合物：以P換算計為0.0g/m2以上且0.01g/m2以下；含釩化合物：以V換算計為0.0g/m2以上且0.01g/m2以下；含銅化合物：以Cu換算計為0.0g/m2以上且0.02g/m2以下；含鋁化合物：以Al換算計為0.0g/m2以上且0.005g/m2以下；含矽化合物：以Si換算計為0.0g/m2以上且0.005g/m2以下； 含鉻化合物：以Cr換算計為0.0g/m2以上且0.01g/m2以下。
  3. 如請求項1或2之熔融鋅系鍍敷鋼板，其中前述選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物之粒徑為10nm以上且200nm以下。
  4. 如請求項1至3中任一項之熔融鋅系鍍敷鋼板，其中前述選自氧化鋯、氧化鑭、氧化鈰及氧化釹中之1種或2種以上氧化物之含量為每單面0.4g/m2以上且1.5g/m2以下。
  5. 如請求項1至4中任一項之熔融鋅系鍍敷鋼板，其中前述氧化物為氧化鋯或氧化鑭。
  6. 如請求項1至5中任一項之熔融鋅系鍍敷鋼板，其中前述表面處理層在每單面0.2g/m2以上且2g/m2以下範圍內更含有粒徑2nm以上且100nm以下之選自氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上氧化物。
  7. 如請求項6之熔融鋅系鍍敷鋼板，其中前述選自氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上氧化物之粒徑為5nm以上且50nm以下。
  8. 如請求項6或7之熔融鋅系鍍敷鋼板，其中前述選自氧化鈦、氧化鎳及氧化錫(IV)中之1種或2種以上氧化物之含量為每單面0.4g/m2以上且1.5g/m2以下。
  9. 如請求項6至8中任一項之熔融鋅系鍍敷鋼板，其中前述氧化物為氧化鈦。
  10. 如請求項1至9中任一項之熔融鋅系鍍敷鋼板，其中前述表面處理層在每單面0.2g/m2以上且5.0g/m2以下範圍內 更含有氧化鎂、氧化鈣或氧化鋅。
  11. 如請求項10之熔融鋅系鍍敷鋼板，其中前述氧化鎂、氧化鈣或氧化鋅之粒徑為5nm以上且100nm以下。
  12. 如請求項10或11之熔融鋅系鍍敷鋼板，其中前述氧化鎂、氧化鈣或氧化鋅之含量為每單面0.4g/m2以上且2.5g/m2以下。
  13. 如請求項1至12中任一項之熔融鋅系鍍敷鋼板，其為熱壓用熔融鋅系鍍敷鋼板。
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EP3272906A1 (en) 2018-01-24
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TW201842228A (zh) 2018-12-01
US10549506B2 (en) 2020-02-04
KR20170118860A (ko) 2017-10-25
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TWI655320B (zh) 2019-04-01
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