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TW201119848A - Precoated steel sheet and process for producing same - Google Patents

Precoated steel sheet and process for producing same Download PDF

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Publication number
TW201119848A
TW201119848A TW099135420A TW99135420A TW201119848A TW 201119848 A TW201119848 A TW 201119848A TW 099135420 A TW099135420 A TW 099135420A TW 99135420 A TW99135420 A TW 99135420A TW 201119848 A TW201119848 A TW 201119848A
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Taiwan
Prior art keywords
layer
steel sheet
clean
film
resin
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TW099135420A
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Chinese (zh)
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TWI532591B (en
Inventor
Toshiyuki Okuma
Akihiko Furuta
Susumu Satoh
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Jfe Galvanizing & Amp Coating Co Ltd
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    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • B32B15/08—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 synthetic resin
    • 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
    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B05D2202/00—Metallic substrate
    • 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
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B05D2601/24—Titanium dioxide, e.g. rutile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

A precoated steel sheet including a photocatalyst layer (coating film) as the outermost layer is provided in which a decrease in aesthetic appearance caused by processing unevenness or interference color streaks is prevented by forming the photocatalyst layer as a discontinuous (network) layer. The precoated steel sheet has performances required of precoated steel sheets, such as appearance evenness and processability, and further has various excellent properties such as a high degree of weatherability, durability of the aesthetic appearance, and resistance to decomposition with the photocatalyst. Also provided is a process for producing the precoated steel sheet. The precoated steel sheet comprises a steel sheet base, a clear coating layer (A) formed over at least one surface of the base, the layer (A) comprising a silicon compound as a main component and containing water-repellent fine particles dispersed therein, and a clear coating layer (B) superposed on the clear coating layer (A), the layer (B) containing, as a main component, fine titanium oxide particles which show photocatalytic activity.

Description

201119848 六、發明說明： 【發明所屬之技術領域】 本發明係關於電性機器製品之外裝材和建築用内•外裝 材、道路用零件等所用的預塗鋼板。特別，關於加工性和耐 候性、美觀耐久性及環境淨化性等優異的預塗鋼板及其製造 方法。 【先前技術】 預塗鋼板由於在成形加工後不必塗佈，可省略加工製造商 的步驟和改善作業環境等，故以電性機器製品之各種零件和 建築物之屋頂和壁等之外裝材、間隔壁等之内裝材等型式使 用於廣泛領域。 此種預塗鋼板，通常，以加壓成形、輥成形或壓紋成形施 以包含90°彎曲和180°彎曲等各式各樣加工供使用，故要求 優異的加工性以及塗膜耐久性。因此，作為預塗鋼板所用之 塗膜用樹脂，可使用於200°C以上烘烤形成硬化塗膜之熱硬 化型的聚S旨系樹脂、和对候性優異的氟系樹脂等。 又，近年來，對於預塗鋼板的高性能化和高機能化的要求 增加，其中亦要求美觀耐久性。即，要求防止因長期附著菌 類、藻類及黴菌等和大氣中的浮游煤煙、各種油性煙霧、廢 氣、碳黑等燃燒產物、其他物質附著造成預塗鋼板的美觀受 損的對策。 關於個別賦予抗菌·防黴機能和耐污染機能般機能的預 099135420 3 201119848 塗鋼板，直到目前雖已開發，但關於含有其他機能之複合機 能的預塗鋼板，其實情為仍未開發。 另外，所謂賦予抗菌·防黴機能的預塗鋼板，係使塗膜中 分散含有銀和銅等之化合物者。經由該等化合物的抗菌作用 使塗膜表面的黴菌和菌類、藻類的成長受到抑制或死滅者。 另一方面，所謂賦予耐污染機能的預塗鋼板，係經由儘可能 使塗膜表面保持親水性，使得該表面附著的污染成分與雨水 共同被流洗，抑制附著物的堆積者。 特別，作為具有抗菌機能及耐污染機能的預塗鋼板，利用 經由光觸媒分解附著有機物等的方法。將具有光觸媒活性之 物質分散於鋼板表面的塗膜中，欲使經由生成活性氧而附著 的有機物被分解。但是，此利用光觸媒的技術，在其光觸媒 分解鋼板表面附著之有機物等表面附著物之同時，基質塗膜 本身亦慢慢分解，故具有發生白亞化和塗膜消耗快之問題。 作為其對策，以往，提案使用難被分解之無機質和氟樹脂 或有機-無機複合體作為光觸媒的基質塗膜（專利文獻 1〜3)。又，提案在金屬板的至少一面，形成含有介隔著無機 質塗料所形成之保護膜的光觸媒和氟樹脂蠟的光觸媒層的 方法(專利文獻4)。亦提案對基材上之二氧化矽等作為基質 的光觸媒性塗膜，形成具有潤滑效果和緩衝效果之氟樹脂分 散而成之表面層的零件（專利文獻5、6)。 一般，光觸媒皮膜層為高折射率，故易經由光觸媒活性物 099135420 4 201119848 質之附著量不均勻等而呈現干擾色。特別於處理之基底素材 表面為两光澤之情況和表面粗度愈小且平者，處理不勻愈顯 著’察見條紋狀干擾色等損害美觀的問題。 作為其對策’提案在基材上，使光觸媒膜以島狀分散且不 連續被黏，使式樣性和耐久性優異之同時，不會發生龜裂， 一直使光觸媒層於基材上安定保持的方法（專利文獻7、專 利文獻8)。 [先前技術文獻] [專利文獻] [專利文獻1] [專利文獻2] [專利文獻3] [專利文獻4] [專利文獻5 ] [專利文獻6] 曰本專利特開 曰本專利特開 曰本專利特開 曰本專利特開 曰本專利特開 WO 97/45502 2007-55207 號公報 2006-233073 號公報 2006- 192716 號公報 2007- 181951 號公報 2001-64539 號公報 [專利文獻7]曰本專利特開2000-246115號公報 [專利文獻8]日本專利特開2009-131987號公報 【發明内容】 (發明所欲解決之問題） 關於專利文獻1所揭示之技術，就具有光觸媒活性之物質 於無機貝塗膜中分散方面，雖在變極色等之耐候性優異，但 因塗膜本身缺乏柔軟性’故若將塗膜直接應用於預塗鋼板， 099135420 严 201119848 則在&仃$曲力和深拉伸加工時易發生裂痕’具有塗膜剝 離之大問題。 專^文獻2所揭示之技術，關於將具有光觸媒活性之物質 於氟树&㈣巾分散的鋼板，但若將此純使用於位於屋外 南面的外裝材，具麵微經由光觸媒使基質塗膜分解的缺 點。此缺點雖可増厚塗膜厚度而加以解決，但膜厚若變厚， 則缺乏柔軟性’產生加工性降低的新問題。 又’專利文獻3所揭示之技術，係關於具有光觸媒活性之 物質分散於有機-無機複合體而成之塗膜中所構成的表面處 理金屬，相比於專利文獻1之無機質塗膜，加工性雖為若干 優異，但在滿足預塗鋼板所必要之加工性程度上，必須薄膜 化，結果具有導致光觸媒機能降低的問題。 更且，專利文獻4所揭示之塗佈金屬板，應用於外裂材之 情況，亦具有經由光觸媒使基質塗膜分解的問題。 又’專利文獻5及6所揭示之技術，雖然在防止擦傷和抓 傷等具有效果，但在進行加壓成形等伴隨變形加工之情況， 因為光觸媒皮膜具有易被弄傷專問題點，故難應用作為予貝 '塗 鋼板。 又，專利文獻7所揭示之技術’係將光觸媒皮膜形成島狀 之方法，為複雜’且於形成安定的皮膜上，需要特別的带置 此外’專利文獻7及8所揭示之技術，在進行加壓成形和镜 成形等加工之情況’不可避免光觸媒皮膜被弄傷等之傷宝， 099135420 6 201119848 故難以應用於預塗鋼板。 以上’先前技術均難應用於預塗鋼板，或者無法滿足作為 預塗鋼板特徵所要求的加工性和耐候性、利用光觸媒機能的 美觀耐久性、以及基質塗膜對於光觸媒的耐分解性，且並非 為充分考慮處理不勻和干擾色對策。 於是，本發明之目的在於解決上述先前技術所具有的上述 問’將成為最外層的光觸媒層（皮膜)作成不連續狀態（網孔 狀），防止因處理不勻和干擾色而以條紋狀察見所造成的美 觀低之同時，除了作為預塗鋼板所必要之外觀均勻性、力17 性等性能以外’提供高度之耐候性、美觀耐久性以及對於’ 觸媒之耐分解性能等各種特性優異之預塗鋼板及其製邊方 法。 (解決問題之手段） 發明者等人，解決先前技術所具有之上述問題，作為f 上述月的之有效方法，提案下述要旨構成的新穎技術。 本發明係在鋼板基材的至少一面，具有主成分由矽牝含物 所構成，分散含有撥水性微粒子之乾淨皮膜層（A)、和衣此 乾淨皮膜層（A)上積層之含有以顯示光觸媒活性之氧彳b鉢祕 粒子作為主成分的乾淨皮膜層（B)為其特徵的預塗鋼板。 另外，於本發明之預塗鋼板中， (1)上述乾淨皮膜層（A)中之撥水性微粒子的至少〆郄々 由乾淨皮膜層（B)表面突出並以島狀分散、 099135420 201119848 (2) 上述乾淨皮膜層（B)表面與水的接觸角為22〜6〇产、 (3) 上述乾淨皮膜層（A)中之撥水性微粒子的至少一部八 具有比乾淨皮膜層（A)膜厚更大的粒徑、 刀 (4) 上述乾淨皮膜層（A)中之撥水性微粒子由氟系樹月匕养 子、氟樹脂糸共聚合體樹脂粒子、秒樹脂粒子、咬表面紅= 等樹脂塗敷而成之粒子所構成、 Λ (5 )上述乾淨皮膜層（A)中的矽化合物為丙烯酸系石夕樹月匕 面的附著量 (6)上述乾淨皮膜層（B)中的氧化鈦粒子，每— 以換具Ti〇2計為lOmg/m〗〜2000mg/m2、 (7)上述乾淨皮膜層（B)以銳鈦礦型結晶質氧化鈦微粒子和 非晶質氧化鈦的混合物作為主成分、 (8)上述鋼板基材，在鍍鋅系鋼板的至少一面，具有化成 處理皮膜和其上所形成之樹脂皮膜，上述樹脂皮膜由含有防 銹顏料之熱硬化性樹脂所構成之塗底層、和著色樹脂層所構 成、 ()上述著色树月曰層以聚偏氟乙稀與丙烯酸系樹脂之質量 15 50. 50之有機溶膠系烘烤型氟樹脂作為主成分 為更佳的解決方法。 人本土明提案於鋼板基材之至少一面，依序積層以石夕化 ^乍為主成刀之乾淨皮臈層（A)及顯示光觸媒活性之氧化 3粒子作為主成分之乾淨皮膜卵⑽叙預塗鋼板的製 、、、中使上述乾淨皮膜層（A)中分散含有撥水性微粒 099135420 201119848 子’並請縣淨皮m(m於賴水錄粒子存在部分 及其附近的被覆量，使得該撥水性微粒子的至少一部分由乾 淨皮膜層（B)之表面突出之狀態呈島狀分散為其特徵之預塗 鋼板的製造方法。 另外，於本發明之預塗鋼板之製造方法中，上述乾淨皮膜 層（A)中之撥水性微粒子的至少一部分，具有比乾淨皮膜層 (A)之膜厚更大的粒徑為更佳解決方法。 [發明效果] 若根據如上述所構成之本發明的預塗鋼板及其製造方 法’則可期待如下之效果。 (1) 於鋼板基材表面，積層作為基底層之含有撥水性粒子 的乾淨皮膜層⑷’再於其上，積層分散含有具有光觸媒活 性之氧化鈦微粒子而成的乾淨皮膜層（B)，使得成為最外層 的乾/爭皮膜層（B)，於乾淨皮膜層（A)之撥水性粒子存在部分 未=成且變成不連續（網孔狀），其結果，以預塗鋼板型式施 订”4曲加工和深拉伸加工等時，在乾淨皮膜層難發生裂 痕、 (2) 並且，可防止因乾淨皮膜層（B)之處理不勻和干擾色等 l成美Η降低。另外，於乾淨皮膜層(A)存在撥水性粒子的 ^刀，因在預塗鋼板表面露出該乾淨皮膜層（Α)，故附著至 預塗鋼板皮膜表φ的各種有機物等，㈣最外層露出之乾淨 皮膜層（Α)(撥水性粒子)部分被彈開之同時，經由乾淨皮膜 099135420 9 201119848 =⑻(光觸媒層）而被分解清淨化，可永續維持表面的美觀 ⑺如上述於預塗鋼板表面露出之乾淨歧層㈧中 水性微粒子，具有作為騎劑和緩衝_作用，故在施行管 曲加工和深拉伸加工等時，可抑制於鋼板表面發生損傷等二 (4)因為在鋼板基材表面具有之著色樹脂層、與成為最 層之乾淨皮膜卵)之間m魏合物作為主成分奸 淨皮膜層(A)，故乾淨賴層⑻可對絲猶效發揮耐分^ 性能’且抑制下層之著色樹脂層目直接接觸光觸媒而分解、 惡化’可作成具有良好之加工性、耐候性及美觀耐久性 塗鋼板。 $ 【實施方式】 本發明之預塗鋼板的基本構成，係於鋼板基材的至少一 面，依序將分散含有撥水性微粒子，且以矽化合物作為主成 分的乾淨皮膜層（A)，和在該乾淨皮膜層（A)上，將含有具光 觸媒活性之氧化鈦粒子的乾淨皮膜層積層而成者。 本發明中，特別以上述乾淨皮膜層⑷，分散含有撥水性 微粒子為其特徵，藉此，成為上層的乾淨皮膜層⑻，經由 乾淨皮膜層（A)中的撥水性微粒子彈開變成不連續狀態（網 孔狀）’撥水性微粒子的至少一部分由乾淨皮膜層⑻之表面 突出分散成島狀。其結果，以預塗鋼板型式加工時，在成為 最外層的乾淨皮膜層（B)難發生裂痕等之同時，可防止因乾 099135420 10 201119848 淨皮膜層（B)之處理不勻和干擾色等造成外觀的美觀性降 低0 並且’如上述撥水性微粒子存在之部分，乾淨皮膜層（A) 以露出鋼板表面之狀態，此撥水性微粒子擔任作為潤滑劑、 緩衝劑之作用，故以預塗鋼板型式進行彎曲加工和深拉伸加 工等時可抑制於鋼板表面發生瑕疫等。 以下’使用圖面詳細說明本發明之預塗鋼板。 本發明之預塗鋼板，如圖1示出其剖面構造之一實施形態 般’在鍍鋅系鋼板1的至少一面，依序積層化成處理皮膜2、 於其上形成之樹脂皮膜（塗底層3、著色樹脂層4)及2種乾 #皮膜層（乾淨皮膜層（A)5、乾淨皮膜層⑻6)而;^者為較佳 之實施形態。 作為本發明中適當使用之鍍鋅系鋼板1，以可成形加工 者例如電錢鋅鋼板、'熔融鍍鋅鋼板、熔融鐘鋅-5質量％鋁 合金鋼板、㈣__55 f量％|呂合金鋼板等作為對象。此 鍵敷鋼板的厚度並無特別限定，但由成形加卫方面而言，以 0.2〜1.6mn左右者為佳。 本毛月中在上述鑛鋅糸鋼板1的一面或兩面，在形成上 述塗底層3之前，首先形成化成處理皮膜2。此化成處理皮 膜係強口鍵鋅系鋼板1與塗底層3的密合性，並且賦予咐 银性而形成者。 作為本發明中適當使用之化成處理皮膜2,例如，填酸鹽 099135420 201119848 地里皮臈、路酸鹽處理皮膜、含二氧化石夕之鉻酸鹽處理皮 裳、各種金屬氧化物所構成之無鉻酸鹽系防·、有機樹脂 寺之早獨錢合物所構成，制為了提高密合性及耐純， :機树月曰與金屬氧化物、填酸系化合物及域含有絡酸之 “:斤構成為佳此時，作為有機樹脂，期望使用將水分散 树月曰例如丙烯酸系樹脂和胺基曱酸酯樹脂以乳化劑分散 者。 此種化成處理皮膜成分中，鉻酸作用為取得化成處理皮臈 與鍍鋅系層之密合性的黏合劑。另一方面，有機樹脂作用為 提高化成處理皮膜、與後述塗底層的密合。另外，化成處理 皮膜中之鉻含量’以金屬鉻換算量為20mg/m2以上為佳。 其係因鉻含量未滿2〇mg/m2之情況，無法充分取得作為預 塗鋼板的耐姓性。 又，作為化成處理皮膜成分的無鉻酸鹽系防銹劑，含有矽 酸及/或矽酸化合物、鈣或鈣化合物、锆酸及/或锆酸化合 物、釩酸及/或釩酸化合物、鉬酸化合物、磷酸及/或磷酸系 化合物中之1種以上，且含量為0.3〜3.Og/m2為佳。將此無 鉻酸鹽系防銹劑的含量定為0.3〜3.Og/m2的理由，係因未滿 〇.3g/m2,則無法取得作為預塗鋼板的耐餘性和密合性，又， 超過3.Og/m2，則導致加工性降低。又，作為黏合劑’例如 亦可使用水分散性的丙烯酸系樹脂和胺基曱酸酯樹脂。 本發明之預塗鋼板，在如上述處理之鑛鋅系鋼板1的至少 099135420 12 201119848 2表面上，首形成作為第 形成作為第1201119848 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a precoated steel sheet for use in exterior materials for electrical equipment products, interior and exterior materials for construction, road parts, and the like. In particular, the precoated steel sheet excellent in workability, weather resistance, aesthetic durability, and environmental cleanability, and a method for producing the same. [Prior Art] Since the precoated steel sheet does not need to be coated after the forming process, the steps of the processing manufacturer can be omitted and the working environment can be improved. Therefore, the various parts of the electrical machine product and the roof and walls of the building are not used. Types such as partitions and the like are used in a wide range of fields. Such a precoated steel sheet is usually subjected to various types of processing such as 90° bending and 180° bending by press molding, roll forming or embossing, and therefore requires excellent workability and coating film durability. Therefore, as the resin for coating film used for the precoated steel sheet, a thermosetting polystyrene resin which is used for baking to form a cured coating film at 200 ° C or higher, and a fluorine-based resin excellent in weather resistance can be used. Further, in recent years, there has been an increase in demand for high performance and high performance of precoated steel sheets, and aesthetic durability is also required. In other words, it is required to prevent the appearance of the precoated steel sheet from being damaged due to long-term adhesion of bacteria, algae, mold, and the like, and the combustion products such as floating soot in the atmosphere, various oily smoke, exhaust gas, carbon black, and the like. About the pre-applied anti-bacterial, anti-mold function and anti-pollution function. 099135420 3 201119848 The coated steel plate has been developed until now, but the pre-coated steel plate with other functions of composite function is still undeveloped. In addition, the precoated steel sheet to which the antibacterial and antifungal function is applied is such that a compound containing silver or copper is dispersed in the coating film. By the antibacterial action of these compounds, the growth of molds, fungi, and algae on the surface of the coating film is suppressed or killed. On the other hand, the precoated steel sheet to which the pollution resistance function is applied is such that the surface of the coating film is kept hydrophilic as much as possible, so that the contaminated component adhering to the surface is flushed together with the rainwater, and the deposit of the deposit is suppressed. In particular, as a precoated steel sheet having an antibacterial function and a stain resistance function, a method of decomposing and attaching an organic substance or the like via a photocatalyst is used. The material having photocatalytic activity is dispersed in the coating film on the surface of the steel sheet, and the organic substance adhering through the generation of active oxygen is decomposed. However, this photocatalyst technique uses a photocatalyst to decompose surface adhering substances such as organic substances adhered to the surface of the steel sheet, and the matrix coating film itself is slowly decomposed, so that it has a problem of whitening and rapid consumption of the coating film. As a countermeasure against this, it has been proposed to use a matrix coating film in which an inorganic substance which is difficult to be decomposed and a fluororesin or an organic-inorganic composite are used as a photocatalyst (Patent Documents 1 to 3). Further, a method of forming a photocatalyst layer containing a photocatalyst and a fluororesin wax interposed between a protective film formed of an inorganic coating material on at least one surface of a metal plate has been proposed (Patent Document 4). A photocatalytic coating film which is a substrate such as cerium oxide on a substrate, and a surface layer in which a fluororesin having a lubricating effect and a buffering effect is dispersed is formed (Patent Documents 5 and 6). Generally, the photocatalyst film layer has a high refractive index, so that it is easy to exhibit an interference color through the photocatalyst active material 099135420 4 201119848. Especially in the case where the surface of the substrate material to be treated is two-gloss and the surface roughness is smaller and flat, the unevenness of the treatment becomes more remarkable, and the problem of damage to the appearance such as streaky interference color is observed. As a countermeasure, it is proposed that the photocatalyst film is dispersed in an island shape and is discontinuously adhered to the substrate, so that the pattern and the durability are excellent, cracking does not occur, and the photocatalyst layer is kept stable on the substrate. Method (Patent Document 7 and Patent Document 8). [Prior Art Document] [Patent Document] [Patent Document 1] [Patent Document 2] [Patent Document 3] [Patent Document 4] [Patent Document 5] [Patent Document 6] Japanese Laid-Open Patent Publication No. WO 97/45502, No. 2007-55207, No. 2006-233073, No. 2006- 192, 716, No. JP-A-2000-246115 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2009-131987 (Draft of the Invention) (Problems to be Solved by the Invention) With regard to the technique disclosed in Patent Document 1, a substance having photocatalytic activity is In the dispersion of the inorganic shell coating film, although it is excellent in weather resistance such as extreme color, the coating film itself lacks flexibility. Therefore, if the coating film is directly applied to the precoated steel sheet, 099135420 严201119848 is in the & It is prone to cracks during force and deep drawing processing, which has a big problem of peeling off the film. The technique disclosed in the literature 2 relates to a steel sheet in which a material having photocatalytic activity is dispersed in a fluorine tree & (4) towel, but if this is purely used for an exterior material located on the south side of the house, the surface is coated with a photocatalyst. The disadvantage of membrane decomposition. Although this disadvantage can be solved by thickening the thickness of the coating film, if the film thickness is thick, the lack of flexibility is a new problem that the workability is lowered. Further, the technique disclosed in Patent Document 3 is a surface-treated metal composed of a coating film in which a photocatalyst-active substance is dispersed in an organic-inorganic composite, and is more processable than the inorganic coating film of Patent Document 1. Although it is excellent in some extent, it must be thinned to the extent necessary to satisfy the workability required for the precoated steel sheet, and as a result, there is a problem that the photocatalytic function can be lowered. Further, in the case where the coated metal sheet disclosed in Patent Document 4 is applied to an outer split material, there is also a problem that the base coating film is decomposed via a photocatalyst. Further, in the techniques disclosed in Patent Documents 5 and 6, although it is effective in preventing scratches and scratches, it is difficult to perform deformation processing such as press molding because the photocatalyst film has a problem of being easily injured. It is applied as a coated steel plate. Further, the technique disclosed in Patent Document 7 is a method of forming a photocatalytic film into an island shape, which is complicated and requires a special tape to be formed on the film which is stable, and the techniques disclosed in Patent Documents 7 and 8 are being carried out. In the case of processing such as press forming and mirror forming, it is inevitable that the photocatalyst film is injured, etc., 099135420 6 201119848, so it is difficult to apply to precoated steel sheets. The above 'previous techniques are difficult to apply to precoated steel sheets, or fail to meet the processability and weather resistance required for the characteristics of precoated steel sheets, the aesthetic durability of photocatalytic functions, and the resistance of matrix coatings to photocatalysts, and are not In order to fully consider the treatment of unevenness and interference color countermeasures. Accordingly, an object of the present invention is to solve the above-mentioned problem of the above-mentioned prior art, in which the photocatalyst layer (film) which becomes the outermost layer is made into a discontinuous state (mesh shape), and is prevented from being streaked due to unevenness in processing and interference color. In addition to the appearance of uniformity and strength, which are required for pre-coated steel sheets, it provides excellent weather resistance, aesthetic durability, and various properties such as 'catalytic resistance to decomposition. Precoated steel sheet and its method of making edges. (Means for Solving the Problems) The inventors and the like have solved the above-mentioned problems of the prior art, and propose a novel technique constituted by the following gist as an effective method of the above-mentioned month. The present invention is characterized in that at least one surface of the steel sheet substrate has a main component composed of an anthracene, and the clean coating layer (A) containing the water-repellent fine particles and the layer on the clean coating layer (A) are dispersed to be displayed. A precoated steel sheet characterized by a photocatalytic active oxo b fine particle as a main component of the clean film layer (B). Further, in the precoated steel sheet of the present invention, (1) at least the ruthenium of the water-repellent fine particles in the clean coating layer (A) protrudes from the surface of the clean coating layer (B) and is dispersed in an island shape, 099135420 201119848 (2) The surface of the clean coating layer (B) has a contact angle with water of 22 to 6 Å, and (3) at least one of the water-repellent granules in the clean coating layer (A) has a cleaner film layer (A) film. Larger particle size, knives (4) The water-repellent fine particles in the above clean film layer (A) are coated with a resin such as a fluorine tree eutropha, a fluororesin yttrium copolymer resin particle, a second resin particle, a bite surface red = (5) The ruthenium compound in the above-mentioned clean film layer (A) is an adhesion amount of the acrylic saplings (6) titanium oxide particles in the clean film layer (B), Each - in the case of Ti〇2, lOmg / m〗 〖2000mg / m2, (7) The above clean film layer (B) with a mixture of anatase-type crystalline titanium oxide particles and amorphous titanium oxide as a main component (8) The steel sheet substrate has a chemical conversion treatment on at least one side of the galvanized steel sheet a film and a resin film formed thereon, the resin film is composed of a primer layer composed of a thermosetting resin containing a rust preventive pigment, and a colored resin layer, and () the colored tree layer is made of polyvinylidene fluoride An organosol-based baking type fluororesin having a mass of 15 50.50 with an acrylic resin is a more preferable solution. The human skin is proposed to be on at least one side of the steel plate substrate, and the clean skin layer (A) with the cerium oxide as the main component and the oxidized 3 particles showing the photocatalytic activity as the main component (10) In the pre-coated steel sheet, the above-mentioned clean coating layer (A) is dispersed and contains water-repellent particles 099135420 201119848 child's and the county's net skin m (m in the Lai Shui recorded particle presence and its surrounding coverage, so that the dial A method for producing a precoated steel sheet in which at least a part of the aqueous fine particles are protruded from the surface of the clean coating layer (B) in an island shape. Further, in the method for producing a precoated steel sheet according to the present invention, the clean coating layer It is more preferable that at least a part of the water-repellent fine particles in (A) has a larger particle diameter than the film thickness of the clean coating layer (A). [Effect of the Invention] According to the precoat of the present invention constituted as described above The steel sheet and the method for producing the same can be expected as follows. (1) On the surface of the steel sheet substrate, a clean coating layer (4) containing water-repellent particles as a base layer is laminated thereon, and the layered dispersion is contained thereon. A clean film layer (B) having photocatalytic activity of titanium oxide fine particles, so that the outermost layer of the dry film layer (B), the water-repellent particles in the clean film layer (A) are partially not formed and become In the case of the continuous coating (mesh shape), it is difficult to cause cracks in the clean coating layer when the four-curve processing and deep drawing processing are applied by the pre-coated steel sheet type, and (2) and the clean coating layer (B) can be prevented. The treatment unevenness and interference color are reduced. In addition, in the clean coating layer (A), there is a water-repellent particle, and the clean coating layer is exposed on the surface of the pre-coated steel sheet. (4) The clean film layer (Α) (the water-repellent particles) partially exposed at the outermost layer is bounced off, and is decomposed and purified through a clean film 099135420 9 201119848 = (8) (photocatalyst layer). It can maintain the appearance of the surface forever (7) as described above, the water-based fine particles in the clean dispersing layer (8) exposed on the surface of the pre-coated steel sheet have the function of riding agent and buffering, so when performing pipe bending processing and deep drawing processing, etc. Suppressed steel Damage to the surface of the board, etc. (4) Because the colored resin layer on the surface of the steel sheet substrate and the clean film of the top layer are the main components of the film (A), it is clean. The layer (8) can exert a resistance to the yarn effect and suppress the lowering of the colored resin layer to directly decompose and deteriorate with the photocatalyst. The steel sheet can be formed with good workability, weather resistance and aesthetic durability. The basic structure of the precoated steel sheet of the present invention is based on at least one side of the steel sheet substrate, and the clean coating layer (A) containing the water-repellent fine particles and containing the ruthenium compound as a main component, and the clean coating layer are sequentially dispersed. In (A), a clean film layer containing photocatalyst-active titanium oxide particles is laminated. In the present invention, in particular, the clean film layer (4) is characterized in that the water-repellent fine particles are dispersed and dispersed, whereby the upper clean film layer (8) is opened and becomes discontinuous via the water-repellent particles in the clean film layer (A). (Mesh-like) At least a part of the water-repellent fine particles are protruded and dispersed into an island shape by the surface of the clean coating layer (8). As a result, when the pre-coated steel sheet type is processed, it is difficult to cause cracks or the like in the clean coating layer (B) which becomes the outermost layer, and it is possible to prevent uneven processing and interference color of the dry coating layer (B) due to dry 099135420 10 201119848. The aesthetic appearance of the appearance is lowered by 0 and 'as in the above-mentioned part where the water-repellent fine particles are present, the clean film layer (A) is exposed to the surface of the steel sheet, and the water-repellent fine particles serve as a lubricant and a buffering agent, so the pre-coated steel sheet is used. When the type is subjected to bending processing and deep drawing processing, it is possible to suppress plague on the surface of the steel sheet. The precoated steel sheet of the present invention will be described in detail below using the drawings. The precoated steel sheet according to the present invention has a resin film formed on at least one surface of the galvanized steel sheet 1 in accordance with one embodiment of the cross-sectional structure of Fig. 1, and a resin film formed thereon (coating layer 3) The colored resin layer 4) and the two types of dry film layers (clean film layer (A) 5 and clean film layer (8) 6) are preferred embodiments. The galvanized steel sheet 1 suitably used in the present invention is a moldable processor such as a bento zinc steel sheet, a 'hot-dip galvanized steel sheet, a molten clock zinc--5 mass% aluminum alloy steel sheet, (four) __55 f%%|lu alloy steel sheet, and the like. As an object. The thickness of the bonded steel sheet is not particularly limited, but it is preferably from 0.2 to 1.6 nm in terms of forming and curing. In the present month, on one or both sides of the above-mentioned mineral zinc-coated steel sheet 1, the chemical conversion treatment film 2 is first formed before the above-mentioned coating underlayer 3 is formed. This chemical conversion film is formed by adhering the strong-bond zinc-based steel sheet 1 to the undercoat layer 3 and imparting silveriness. The chemical conversion treatment film 2 which is suitably used in the present invention is, for example, a sulphate 099135420 201119848 celestial sputum, a sulphate-treated film, a chromate-treated skin with a cerium dioxide, and various metal oxides. It is composed of a non-chromate-based anti-corrosion compound and an organic resin temple. In order to improve adhesion and purity, it is made of a metal oxide, an acid-filled compound, and a domain containing a complex acid. ": The composition of the jin is preferable. In this case, as the organic resin, it is desirable to use a dispersing agent such as an acrylic resin and an amino phthalate resin as an emulsifier. In this chemical conversion treatment component, the chromic acid function is The adhesive for chemically treating the adhesion between the skin and the galvanized layer is obtained. On the other hand, the organic resin acts to improve the chemical conversion coating and the adhesion to the undercoat layer described later. The amount of metal chromium is preferably 20 mg/m2 or more. When the chromium content is less than 2 〇mg/m2, the surname of the precoated steel sheet cannot be sufficiently obtained. Further, the chromic acid which is a component of the chemical conversion treatment is not obtained. A rust inhibitor containing citric acid and/or citric acid compounds, calcium or calcium compounds, zirconic acid and/or zirconic acid compounds, vanadic acid and/or vanadic acid compounds, molybdic acid compounds, phosphoric acid and/or phosphate compounds. One or more kinds, and the content is preferably 0.3 to 3. Og/m2. The reason why the content of the chromate-free rust inhibitor is 0.3 to 3. Og/m2 is due to less than 3 g/ In m2, the durability and adhesion of the precoated steel sheet cannot be obtained, and when it exceeds 3.0 g/m2, the workability is lowered. Further, as the binder, for example, a water-dispersible acrylic resin can also be used. And an amino phthalate resin. The precoated steel sheet of the present invention is formed on the surface of at least 099135420 12 201119848 2 of the mineral zinc-based steel sheet 1 treated as described above, as the first formation as the first

及取得耐蝕性而形成之層。 σ 、 一面形成的化成處理皮膜 皮膜的塗 脂所構成 脂層4、 此塗底層3的層厚為2μιη以上、1〇师以下為佳，此層厚 未滿2阳’财法取得充分的防鎊性，另—方面，超過 之情況’導致加工性降低且為不佳。 作為塗低層3主體的熱硬化性樹脂，並無特別限定，但以 使用聚S旨系樹脂和環氧系樹脂等之1種或2種以上為佳，作 為聚酷系樹脂，可使用㈣A加成㈣樹脂等。又，作為 袁氧树知，可將一部分經胺基曱酸酯樹脂、酚樹脂、胺樹脂 等所取代者，可使用雙紛A、雙齡F、雙盼AD等之雙_、 與表氯醇或/3曱基表氣醇所構成的環氧化合物或其共聚合 體等。更且，該等環氧化合物之單羧酸或二羧酸改質物、單、 -或夕醇改質物、單或二胺改質物、單、二或多酚改質物亦 可使用作為環氧樹脂。 另外，將塗底層3的主體限定於熱硬化性樹脂的理由，係 因若使用常溫乾燥型樹脂和熱可塑性樹脂，則在其上形成上 層皮膜（著色樹脂層、乾淨皮膜層）時，因烘烤溫度伴隨軟化 而發生變形和惡化，具有無法取得與上層皮膜之強固密合性 等問題。 £ 099135420 13 201119848 作為塗低層3的硬化劑，可使用聚異氰酸酯化合物及/或 胺基樹脂。作為聚異氰酸酯化合物，可使用以一般製法所得 之1，6-己>一異鼠酸S旨（以下’ HDI)及其衍生物、曱笨二異氰 酸酯（以下’ TDI)及其衍生物、4,4’-二苯基曱烧二異氰酸酯 (以下’ MDI)及其化合物、苯二亞曱基二異氰酸酯（以下， XDI)及其衍生物、異I爾酮二異氰酸醋（以下，IpDl)及其衍 生物、三曱基己二異氰酸酯（以下，TMDI)及其衍生物、氫 化TDI及其衍生物、氫化MDI及其衍生物、氫化xm及其 衍生物等之化合物。特別，使用可作為一液型塗料之苯酚、 甲酚、芳香族二胺、三級醇、内醯胺、肟等之黏合劑所封黏 化的聚異氰酸酯化合物為佳。此封黏化聚異氰酸酯化合物可 以一液保存，且可輕易使用作為塗料。 又，作為上述硬化劑所用之胺樹脂，可為脲、苯并胍胺、 二聚氰胺等與曱酸反應所得之樹脂、及該等經曱醇、丁醇等 之醇類予以烧基⑽化者。具體而言，可列舉甲基化脈樹脂、 正丁基化苯并胍胺樹脂、曱基化三聚氰胺樹脂、正丁基化三 聚氰胺樹脂、異丁基化三聚氰胺樹脂等。 塗底層3之硬化劑的配合比，於樹脂固形份中之比例為 9〜50質買％為佳’係因未滿9質量％則塗膜硬度不夠充分， 超過50質量％則加工性不夠充分。 更且’於此塗底層3中，根據目的和用途亦可使用對_曱 苯磺酸、辛酸錫、二丁基錫二月桂酸酯等之硬化觸媒。又， 099135420 201119848 亦可添加碳酸鈣、高嶺土、黏土等之體質顏料、氧化鈦、紅 色氧化鐵、雲母、碳黑、鋁粉等之著色顏料、消泡劑和勻塗 劑等各種添加齊1卜 '、 本發明中，於塗底層3 +，在進行成形加工作為預塗鋼板 之情況、和在屋外長期使用時之防止自切斷邊緣部和塗膜瑕 疵部之塗膜膨脹和鍍敷腐蝕，含有5質量％〜5〇質量％的防 銹顏料。其係因防銹顏料之含量未滿5質量％，則無提高耐 蝕性之效果，超過5〇質量％ ,則伴隨塗膜可撓性的降低， 加工性惡化故為不佳。 作為防銹顏料，以使用鉻酸鹽、二氧化矽系顏料、亞磷酸 鹽系顏料、i弓化合物、鋁氧化物、錯酸或/及錯酸化合物、 釩酸或/及鈒酸化合物、鉬酸化合物、磷酸或/及碟酸系化合 物等中之任1種或混合2種以上者為佳，其中亦以使用鉻酸 鹽，就更加提高防銹性方面為佳。 其次，說明關於著色樹脂層4。著色樹脂層4在上述塗底 層3上形成。作為此著色樹脂層4的樹脂，以與塗底層3 的密合性優異，且在預塗鋼板製造設備中可連續塗佈之樹 脂，例如，聚酯系樹脂、氟系樹脂、丙烯酸系樹脂、胺基曱 酸酯系樹脂或將該等成分予以複合化的樹脂為有利適合。 特別，本發明中，為了提高預塗鋼板的加工性、屋外之耐 久性（耐候性），作為著色樹脂層4之主體樹脂，使用聚偏氟 乙烯與丙烯酸系樹脂，以質量比85: 15〜5〇:5〇、較佳為85 : 099135420 15 201119848 15〜75 : 25之比例配合而成的有機溶膠系烘烤型氟樹脂為 佳。其係因經由使用聚偏氟乙烯與丙烯酸系樹脂混合而成的 有機溶膠系烘烤型氟樹脂，則可抑制結晶性樹脂聚偏氟乙烯 的結晶化之同時，可提高耐久性（耐候性)和加工性，更且可 提高成為著色樹脂層4之下層的上述塗底層3、與成為上層 之乾淨皮膜層（A)5的密合性。 另外上述有機溶膠系烘烤型氟樹脂的聚偏氟乙稀若超過 85質量％，則塗佈性降低並發展聚偏氟乙烯的結晶化，加工 改降低另一方面，此量若未滿50質量％，則聚偏氟乙烯 所具有的耐久性性大幅降低，故為不佳。 作為上述有機溶㈣烘烤型氟樹脂巾所含之丙烯酸系樹 脂’可單獨或複合使用熱可塑性__樹脂及熱硬化性丙 烯酸系樹脂。作為熱可紐㈣酸讀脂。由與聚偏氣乙稀 之相溶性觀點而言，可使用(甲基)丙烯酸甲酯、(曱基)丙烯 酸乙醋、（甲基）丙稀酸丙酿、（甲基)丙烯酸丁醋、（曱基）丙 婦I戊自9之1種或2㈣上之單體聚合體、或該等單體與丙 稀W笨乙稀等之共聚合體。另—方面，作為熱硬化性丙烯 酸系樹脂’可使用由具_基、絲、環氧丙基、異氰酸醋 基專父聯性官能基的叫L脂、舰基化三聚氰胺、多 元醇、聚醯胺等之硬化劑所構成者。 另卜著色Μ月日層4為支配預塗鋼板的外觀色調者，於塗 膜中配α氧化鈦、紅色氧化鐵、雲母、碳黑、般燒石炭黑、欽 099135420 201119848 黃、黃色氧化鐵、酞菁藍、酞菁綠等各種著色顏料。此著色 顏料含有15質量％〜60質量％左右。其理由為，於此含量範 圍中了心成目彳示之隱蔽色相的安定塗膜。此外，視需要， 亦了配5合成一氧化石夕等之光澤調節劑、用以改善塗佈作業 性的消泡劑、表面調整劑、防止塗膜刮傷劑等之添加劑。 上述著色樹脂層4作成8〜25μιη之層厚為佳。此層厚未滿 8μιη，則伴隨著隱蔽性降低使色調變得不安定，無法取得充 分的耐久性、加工性及加工部耐蝕性。另一方面，此層厚超 過25Mm，則發生腋部（發泡）等，易發生皮膜缺陷，更且伴 P遺著加卫時之内部歪斜增加而發生等導致性能降低，故 為不佳。 上述著色樹脂層4可根據製造預塗鋼板之普通方法，例 如，將有機溶劑稀釋的藥液以輥塗敷器和幕塗敷器，在铲鋅 系鋼板之上述塗底層3面上塗佈，並以230〜27〇°c左右、田 度烘烤，則可連續形成。 咖 其次，說明關於乾淨皮膜層(A)5。此乾淨皮膜層(A)% 上述著色樹脂層4上形成。具有提高成為其上層之乾 層⑼6與成為下層之著色樹麟4之相互密合性的作用、 更且，此乾淨皮膜雜)5，亦具有抑制著色樹脂層4，㈣ 乾淨皮膜層⑻6中所配合之氧化鈦微粒子的光觸媒作用， 經時分解、惡化的作用。 乾淨皮膜層(A)5的主成分由石夕化合物，例如内歸酸系石夕 099135420 201119848 Γ有氧基魏及絲合物、科料㈣及其縮合 、土羥基矽烷及其縮合物、或該等組成物與二 的複合組成物所構成，特別使用丙雜彻旨為=: 此丙烯酸糸功也此 作為 、 示7树如，可使用將丙烯酸酯和矽複合化、共聚合 〆、/、他交聯劑予以交聯者、和使用含有丙烯酸酯或矽之 交聯劑予以交聯者等。 婦久氱石夕氧樹脂的丙烯酸酯成分’在提高乾淨皮膜層層 (Α)5之柔軟性之同時，具有提高與下層著色樹脂層4之密 一、史用。作為丙烯酸醋成分’可使用丙烯酸甲g旨、甲基 丙婦k甲g旨等之含有絲之丙烯酸系單體和低聚物或聚合 丙烯自文2-說乙醋等之含有經基之丙烯酸系單體、低聚 物或聚合物、兩烯酸等之乙烯性不飽和羧酸系單體、低聚物 或聚α物，以及含有醯胺基和環氧丙基之丙烯酸系單體、低 聚物或聚合物等之1種或2種以上。 另方面，丙烯酸聚矽氧樹脂之矽成分，具有強固與上層 形成之乾淨皮膜層（Β)6的密合性之同時，具有抑制乾淨皮 膜層（Β)6所含之光觸媒使乾淨皮膜層（Α)5本身分解、惡化 的作用。 作為石夕成分，例如可使用曱基三乙氧基矽烷、二甲基二乙 氧基矽烷、笨基曱基二乙氧基矽烷、γ_環氧丙氧基丙基三甲 氧基石夕烧等之烷氧基矽烷化合物和其水解物、或其縮合物之 1種或2種以上。 099135420 201119848 此乾淨皮膜層（A)5的層F % 0、m以上。另一方面 淨〇’2/lm以上為佳’更佳為 特別限定，於組成物本身缺=皮膜層（Μ的上限厚度並無 性降低，以更加薄膜為佳H軟性之情況’為了抑制加工 物之種類可取得良好的加工^別於1㈣以下，則不論組成 其次，於本發明中，石π 八私八士 4 上述’於此乾淨皮膜層（A)5中， 刀政3有撥水性微粒子7為苴 膜層⑻6,經由乾淨皮膜j、” P，4上層的乾淨皮 f分及其附近未㈣覆，故乾淨皮 胰層⑴)6未以連績薄膜狀形成。士里Λ丄 時，抑制乾淨皮膜層⑻6 & 成預塗鋼板 勻和條紋狀之干擾色等造錢觀且可防止因處理不 四發揮上述效果的撥水性微粒子7,可為聚 Η名 氣乙婦或全氟燒氧基氟樹脂等之氟系樹 曰a、四m六氟聚丙烯絲合體或· /、 共聚合體等之氟樹脂系共聚合體樹脂粒子、销脂::乙： _塗敷的粒子’特別1氟_所構成的微 子=二二例:使用聚…歸所構成之撥水性微粒 :且如圖！所不般，在乾淨皮膜層⑷5中，含有 八膜厚更大粒徑的微粒子7之情況 八有 層㈧5的表面，即， 喊教子7在乾淨皮膜 預金鋼板的表面露出，使得該微粒子7 099135420 201119848 更有效作用為彎曲加工成預塗鋼板等時之潤滑劑和缓衝 劑，且可抑制發生瑕疵等。作為此種氟系樹脂微粒子7，有 住友3M公司製之Dini〇nTF微粉末等。 另外’撥水性微粒子7的粒徑以（平均）粒徑為0.3〜10/xm 者為佳，其理由係因未滿〇.3μιη，則撥水效果降低，乾淨皮 膜層（Β)6以連續薄膜狀形成，成為外觀不勻（干擾色）的原 因’具有加工性降低等問題，另一方面，超過1〇μιη，為了 在乾淨皮膜層（Α)5中分散，必須充分加厚該乾淨皮膜層（α)5 的厚度，對費用不利之同時’乾淨皮膜層（Α)5本身難以安 定形成。 又，關於乾淨皮膜層（Α)5中之撥水性微粒子7的配合量， 以固形份比為0.5〜20質量％左右為佳，更佳為1〜1〇質量％。 配合^:未滿0.5質量％，則無法取得上述效果，若超過2〇 質量％ ’則皮膜白濁，塗佈困難故為不佳。 於此乾淨皮膜層（Α)5中，在不會改變色調的範圍中可添 加各種添加劑’例如二氧化矽微粒子、分散劑、偶合劑或紫 外線吸收劑等。作為以連續塗佈流線形成乾淨皮臈層（α)5 的方法，可將有機溶劑中稀釋的溶液以幕塗敷器、輥塗敷器 或字模塗敷器予以塗佈、烘烤的方法。另外，使用丙烯酸聚 矽氧樹脂作為乾淨皮膜層（Α)5之主成分之情況，塗佈後， 以150〜200°C左右之溫度烘烤為佳。 其次，說明關於成為本發明預塗鋼板最外層的乾淨皮膜層 099135420 20 201119848 (B)6。此乾淨皮膜層（B)6係在上述乾淨皮膜層（A)5上形成。 本發明中，因為在成為下層之乾淨皮膜層（A)5中含有撥水 性微粒子7，故若將此乾淨皮膜層（B)6以水系分散液型式， 例如以連續塗佈流線以輥塗敷法予以塗佈，則該乾淨皮膜層 (B)6未被覆撥水性微粒子7上及其附近，以不連續狀態（網 孔狀)形成。藉此，如上述加工成預塗鋼板時，在成為最外 層之乾淨皮臈層（B)6難發生裂痕等，更且，亦可抑制乾淨 皮膜層（B)6以連續薄臈狀形成時所發生的條紋狀干擾色， 可防止表面美觀降低。 另外，如上述，乾淨皮膜層（B)未被覆乾淨皮膜層（A)中所 含有分散之撥水性微粒子7的存在部分及其附近，該撥水性 微粒子在乾淨皮膜層（B)的表面露出，此乾淨皮膜層⑻表面 與水的接觸角為⑼度以下，較佳為22〜5()度。其係因水的 接觸角超過60度，則無法取得自我清潔效果(在屋外的雨條 紋狀污穢經由降雨而自我洗淨的效果），此效果特別在接觸 角為50度以下的情況明確取得。又，水的接觸角若未滿^ 度’則因乾淨皮膜層（A)巾含有分散龍水性微粒子導致效 果（作為預塗鋼板的朗力叫生、附著污染物的擦拭性）降 低，為不佳。 此乾乎皮膜層（B)6對預塗鋼板具有新機能，即，將預塗 鋼板使闕為心卜料_，將其表_著的各種有機物 等分解、清淨化，使表Φ的錢性永續維持的有效機能。此 099135420 201119848 機:能係、經由皮膜層（B)6中 鈦微粒子所發揮。所3有之具有光觸媒活性的氧化 子作為射^準搞媒科的氧化欽微粒 :氣:：晶質氧化鈦為佳。作為銳鈦鑛型結晶 ::觸=具有。〜一左右粒子直徑者， 先觸媒特財㈣最適，作為此缝鈦射 欽，可列舉例如，石原產咖製之咖、财、ST1L 等。 銳鈦礦型結晶質氧化鈦，一般，對於紫外線領域之短波長 先顯不活性，故將預塗鋼板使用作為外裝零件之情況，可經 由太陽光所含有的紫外線發揮光觸媒特性，另-方面，將預 T板使时為㈣科之情況，使料見顧答 鑛型結晶質氧化鈦為佳，作為此可見光應答型氧化欽，可使 用換混氮和硫或韻氧化鈦、缺氧型之氧化鈦、增強色素型 之乳化鈦、金屬擔持型之氧化鈦等。 、 於此乾淨皮膜層⑽+，如上述之銳欽鑛型結晶質氧化 鈦同時，亦可配合非晶皙氢各 貝氧化鈦。此日寸，銳鈦礦型結晶質氧 化鈦與非晶質氧化鈦的混合比，以f量比為m、2〇 為佳。另外，非晶質氧化鈇具有提高塗佈藥液之安定性的同 時，具有作為皮膜黏合_作用、提高作為皮膜的加工性和 耐久性的作用。 量 此乾淨皮膜層⑻6,於鍍鋅鋼板單面之氧化鈦粒子附著And a layer formed by obtaining corrosion resistance.脂 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Pound, another aspect, exceeding the situation' leads to reduced processability and is not good. The thermosetting resin which is the main body of the lower layer 3 is not particularly limited, and one or two or more kinds of the poly-S resin and the epoxy resin are preferably used. As the poly-based resin, (A) A plus can be used. Into (four) resin and so on. Further, as Yuan Oxygen, a part of the product may be replaced by an amine phthalate resin, a phenol resin, an amine resin or the like, and it is possible to use double bis, A double age F, double expectant AD, etc. An epoxy compound or a copolymer thereof composed of an alcohol or a /3 fluorenyl alcohol. Furthermore, the monocarboxylic or dicarboxylic acid modification of the epoxy compound, the mono- or --alcohol modification, the mono- or diamine modification, the mono-, di- or polyphenol modification can also be used as the epoxy resin. . In addition, the reason why the main body of the undercoat layer 3 is limited to the thermosetting resin is that when a normal temperature drying type resin and a thermoplastic resin are used, when the upper layer film (colored resin layer, clean film layer) is formed thereon, it is baked. The baking temperature is deformed and deteriorated with softening, and there is a problem that the strong adhesion to the upper film cannot be obtained. £ 099135420 13 201119848 As the hardener for coating the lower layer 3, a polyisocyanate compound and/or an amine-based resin can be used. As the polyisocyanate compound, 1,6-hex>-isoxanate S (hereinafter referred to as 'HDI) and its derivative, smectic diisocyanate (hereinafter 'TDI) and its derivatives, 4 can be used. , 4'-diphenyl sulfonium diisocyanate (hereinafter 'MDI) and its compound, benzodiamidylene diisocyanate (hereinafter, XDI) and its derivatives, iso-Ilone diisocyanate (hereinafter, IpDl And its derivatives, tridecyl hexamethylene diisocyanate (hereinafter, TMDI) and its derivatives, hydrogenated TDI and its derivatives, hydrogenated MDI and its derivatives, hydrogenated xm and its derivatives, and the like. In particular, a polyisocyanate compound which is viscous as a one-liquid type coating material such as phenol, cresol, aromatic diamine, tertiary alcohol, decylamine or hydrazine is preferably used. The blocked polyisocyanate compound can be stored in one liquid and can be easily used as a coating. Further, the amine resin used as the curing agent may be a resin obtained by reacting ruthenic acid such as urea, benzoguanamine or melamine, and an alcohol such as decyl alcohol or butanol (10). The person. Specific examples thereof include methylated pulse resin, n-butylated benzoguanamine resin, thiolated melamine resin, n-butylated melamine resin, and isobutylated melamine resin. The blending ratio of the hardener of the undercoat layer 3 is preferably from 9 to 50% by mass of the resin in the solid portion of the resin. The coating film hardness is insufficient due to less than 9% by mass, and the processability is insufficient when it exceeds 50% by mass. . Further, in the undercoat layer 3, a curing catalyst such as p-benzoic acid, tin octylate or dibutyltin dilaurate may be used depending on the purpose and use. Also, 099135420 201119848 can also add body pigments such as calcium carbonate, kaolin, clay, titanium oxide, red iron oxide, mica, carbon black, aluminum powder and other colored pigments, defoamers and leveling agents, etc. In the present invention, in the case of applying the underlayer 3 +, in the case of performing the forming process as the precoated steel sheet, and in the case of long-term use outside the house, the coating film expansion and plating corrosion from the cut edge portion and the coating film portion are prevented, It contains 5% by mass to 5% by mass of rust preventive pigment. When the content of the rust preventive pigment is less than 5% by mass, the effect of improving the corrosion resistance is not obtained. When the content is more than 5% by mass, the flexibility of the coating film is lowered, and the workability is deteriorated, which is not preferable. As the rust preventive pigment, a chromate, a cerium oxide pigment, a phosphite pigment, an i-bow compound, an aluminum oxide, a wrong acid or/and a wrong acid compound, a vanadium acid or/and a phthalic acid compound, or a molybdenum is used. Any one of the acid compound, the phosphoric acid or the acid-based compound, or a mixture of two or more of them is preferable, and in the case where chromate is used, it is preferable to further improve the rust preventive property. Next, the colored resin layer 4 will be described. The colored resin layer 4 is formed on the above-mentioned undercoat layer 3. The resin of the colored resin layer 4 is excellent in adhesion to the undercoat layer 3, and can be continuously applied to a precoated steel sheet manufacturing apparatus, for example, a polyester resin, a fluorine resin, an acrylic resin, An amino phthalate-based resin or a resin obtained by combining these components is advantageously used. In particular, in the present invention, in order to improve the workability of the precoated steel sheet and the durability (weather resistance) of the exterior, the polyvinylidene fluoride and the acrylic resin are used as the main resin of the colored resin layer 4 at a mass ratio of 85:15~ 5〇: 5〇, preferably 85: 099135420 15 201119848 15~75 : 25 ratio of the organosol baking fluororesin is preferred. By using an organosol-based baking fluororesin which is obtained by mixing polyvinylidene fluoride and an acrylic resin, it is possible to suppress the crystallization of the crystalline resin polyvinylidene fluoride and improve the durability (weather resistance). Further, the workability is improved, and the adhesion between the undercoat layer 3 which is the lower layer of the colored resin layer 4 and the clean coating layer (A) 5 which becomes the upper layer can be improved. In addition, when the polyvinylidene fluoride of the above-mentioned organosol-based baking type fluororesin exceeds 85% by mass, the coating property is lowered and the crystallization of polyvinylidene fluoride is progressed, and the processing is lowered. On the other hand, if the amount is less than 50% When the mass %, the durability of polyvinylidene fluoride is greatly lowered, which is not preferable. The acrylic resin contained in the organic solvent-containing fluororesin towel can be used alone or in combination with a thermoplastic resin and a thermosetting acrylic resin. As a heat (4) acid read grease. From the viewpoint of compatibility with polyethylene glycol, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid, and (meth)acrylic acid butyl vinegar can be used. (曱基) A copolymer of a monomer of 9 or 2 (d), or a copolymer of such a monomer with propylene, ethylene, and the like. On the other hand, as the thermosetting acrylic resin, it is possible to use a L-fat, a stellate melamine, a polyhydric alcohol, which has a functional group of a parent, a silk, a glycidyl group or an isocyanate group. It is composed of a hardener such as polyamine. In addition, the coloring layer 4 is the appearance of the pre-coated steel sheet, and is coated with α-titanium oxide, red iron oxide, mica, carbon black, burnt charcoal black, Qin 099135420 201119848 yellow, yellow iron oxide, Various coloring pigments such as phthalocyanine blue and phthalocyanine green. This colored pigment contains about 15% by mass to 60% by mass. The reason for this is that the stable coating film of the hidden hue is clearly shown in this content range. Further, if necessary, an additive such as a glossator for synthesizing nitric oxide or the like, an antifoaming agent for improving coating workability, a surface conditioner, and a coating film scratching agent may be added. The colored resin layer 4 is preferably formed to have a layer thickness of 8 to 25 μm. When the thickness of the layer is less than 8 μm, the color tone becomes unstable as the concealability is lowered, and sufficient durability, workability, and corrosion resistance of the processed portion cannot be obtained. On the other hand, when the thickness of the layer exceeds 25 Mm, the crotch portion (foaming) or the like occurs, and film defects are liable to occur, and the internal skew increases when P is left behind, and the performance is deteriorated, which is not preferable. The colored resin layer 4 may be coated on the surface of the undercoat layer 3 of the shovel zinc-based steel sheet by a common method of manufacturing a pre-coated steel sheet, for example, a chemical solution diluted with an organic solvent by a roll coater and a curtain applicator. It can be continuously formed by baking at a temperature of about 230~27〇°c. Coffee Next, explain about the clean film layer (A) 5. This clean film layer (A)% is formed on the above colored resin layer 4. It has an effect of improving the adhesion between the dry layer (9) 6 which becomes the upper layer and the colored tree lining 4 which becomes the lower layer, and further, this clean film layer 5 also has the coloring resin layer 4, and (4) the clean film layer (8) 6 The photocatalytic action of the titanium oxide fine particles to be combined with the action of decomposition and deterioration over time. The main component of the clean coating layer (A) 5 is composed of a compound of Shixia, such as an internal acid system, Shijiao 099135420 201119848, an oxime-containing ketone, a medicinal material (4), a condensation thereof, a soil hydroxy decane, and a condensate thereof, or the like. It is composed of a composite composition of two and two, and the use of propylene is specifically used as: = This acrylic acid is also used as a 7-tree, and it is possible to use acrylate and ruthenium complex, copolymerization 〆, /, he The crosslinking agent is to be cross-linked, and the crosslinking agent is used by using a crosslinking agent containing acrylate or hydrazine. The acrylate component of gynecological oxime resin has the advantage of improving the flexibility of the clean film layer 5 while improving the adhesion to the underlying colored resin layer 4. As the acrylic vinegar component, it is possible to use an acrylic acrylic monomer and an oligomer or a polymerized propylene, such as acrylic acid, methyl methacrylate, or the like. An ethylenically unsaturated carboxylic acid monomer, an oligomer or a polyalphalate which is a monomer, an oligomer or a polymer, an alkenoic acid, or the like, and an acrylic monomer containing a mercaptoamine group and a glycidyl group, One or two or more kinds of oligomers or polymers. On the other hand, the bismuth component of the acrylic polyoxyl resin has a strong adhesion to the clean film layer 6 formed by the upper layer, and has a photocatalyst which is contained in the clean film layer (6) to clean the film layer ( Α) 5 itself decomposes and deteriorates. As the shi shi component, for example, mercaptotriethoxy decane, dimethyldiethoxy decane, cumyl decyl diethoxy decane, γ-glycidoxypropyltrimethoxy sulphur, etc. can be used. One or two or more kinds of the alkoxydecane compound, the hydrolyzate thereof, or a condensate thereof. 099135420 201119848 The layer F % 0, m or more of the clean coating layer (A) 5 or more. On the other hand, the net 〇 '2 / lm or more is better' is particularly limited, and the composition itself is lacking = the film layer (the upper limit thickness of yttrium is not reduced, and the film is better than the softness of the film H) in order to suppress the processing. The type of the object can be well processed, and it is not more than 1 (four), regardless of the composition. In the present invention, the stone π 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八The microparticles 7 are the ruthenium film layer (8) 6, and are cleaned by the clean film j, "P, 4, and the clean skin of the upper layer, and the vicinity of the clean skin layer (1)) 6, so that the clean skin pancreatic layer (1)) 6 is not formed in a continuous film shape. When the clean coating layer (8) 6 & is formed into a pre-coated steel sheet and the streak-like interference color and the like, and the water-repellent fine particles 7 which can prevent the above effects from being treated, can be prevented, and the polyfluorene-known woman or the perfluorocarbon can be used. A fluororesin-based copolymer resin particle such as a fluorine-based saponin, a tetra-m-hexafluoropolypropylene, or a copolymer such as a copolymer, and a pin fat: B: _ coated particles 1 fluoro_ composed of neutrinos = 22 cases: the use of poly... In the clean film layer (4) 5, in the case of the clean film layer (4) 5, the surface of the fine particle 7 having a larger film size of eight layers has the surface of the layer (8) 5, that is, the shrine 7 is exposed on the surface of the clean film pre-gold plate. The fine particles 7 099135420 201119848 are more effectively used as a lubricant and a buffer for bending a pre-coated steel sheet, etc., and suppressing the occurrence of flaws, etc. As such a fluorine-based resin fine particle 7, there is a Dini〇nTF manufactured by Sumitomo 3M Co., Ltd. Further, the particle size of the water-repellent fine particles 7 is preferably 0.3 to 10/xm, and the reason is that the water-repellent effect is lowered due to less than 3 μm, and the clean film layer is cleaned. 6) is formed in a continuous film form, and causes unevenness in appearance (interference color), which has problems such as a decrease in workability. On the other hand, in order to disperse in a clean film layer 5, it must be sufficiently added. Thickness of the thickness of the clean film layer (α) 5 is unfavorable for the cost, and the clean film layer (Α) 5 itself is difficult to form. Further, regarding the amount of the water-repellent fine particles 7 in the clean film layer (Α) 5, Solid form The ratio is preferably from 0.5 to 20% by mass, more preferably from 1 to 1% by mass. When the ratio is less than 0.5% by mass, the above effect cannot be obtained, and if it exceeds 2% by mass, the film is cloudy and difficult to apply. Therefore, in the clean coating layer 5, various additives such as cerium oxide microparticles, a dispersing agent, a coupling agent, an ultraviolet absorber, etc. may be added in a range in which the color tone is not changed. The cloth streamline forms a method for cleaning the skin layer (α) 5, and the solution diluted in the organic solvent can be coated and baked by a curtain applicator, a roll coater or a die coater. When the acrylic polyoxyl resin is used as the main component of the clean coating layer 5, it is preferably baked at a temperature of about 150 to 200 ° C after coating. Next, a description will be given of a clean film layer which is the outermost layer of the precoated steel sheet of the present invention 099135420 20 201119848 (B) 6. This clean film layer (B) 6 is formed on the above-mentioned clean film layer (A) 5. In the present invention, since the water-repellent fine particles 7 are contained in the clean coating layer (A) 5 which becomes the lower layer, if the clean coating layer (B) 6 is in the form of an aqueous dispersion, for example, a continuous coating flow line is used for roll coating. When the coating method is applied, the clean coating layer (B) 6 is not formed on the aqueous fine particles 7 and in the vicinity thereof, and is formed in a discontinuous state (mesh shape). Therefore, when the precoated steel sheet is processed as described above, it is difficult to cause cracks or the like in the clean skin layer (B) 6 which becomes the outermost layer, and it is also possible to prevent the clean coating layer (B) 6 from being formed in a continuous thin shape. The streaky interference color that occurs can prevent the appearance of the surface from deteriorating. Further, as described above, the clean coating layer (B) is not covered by the portion of the dispersed water-repellent fine particles 7 contained in the cleaned coating layer (A) and the vicinity thereof, and the water-repellent fine particles are exposed on the surface of the cleaned coating layer (B). The contact angle of the surface of the clean coating layer (8) with water is (9) degrees or less, preferably 22 to 5 (degrees). In the case where the contact angle of the water exceeds 60 degrees, the self-cleaning effect (the effect of self-cleaning of the rain stains on the rain outside the house) is not obtained, and this effect is specifically obtained when the contact angle is 50 degrees or less. In addition, if the contact angle of the water is not full, the effect is caused by the fact that the clean film layer (A) towel contains the dispersed water-based fine particles (the squeezing of the pre-coated steel sheet and the wiping property of the attached contaminant) is not good. The dry film layer (B) 6 has a new function on the pre-coated steel sheet, that is, the pre-coated steel sheet is used as a heart material, and the various organic substances on the surface thereof are decomposed and purified, so that the money of the table Φ is forever Continued effective function of maintenance. This 099135420 201119848 machine: the energy system can be played through the titanium particles in the film layer (B)6. The oxidized oxidized particles having photocatalytic activity are preferably used as the oxidized granules of the radioactive medium: gas: crystalline titanium oxide is preferred. As anatase crystals :: touch = have. ~ One of the particle diameters is the most suitable for the first time. For example, the stone is made of coffee, money, ST1L, etc. Anatase-type crystalline titanium oxide is generally inactive for short wavelengths in the ultraviolet field. Therefore, when a precoated steel sheet is used as an exterior part, the photocatalytic characteristics can be exhibited by ultraviolet rays contained in sunlight. In the case of the pre-T plate, the time is (4), so that it is preferable to use the crystal-type titanium oxide. As the visible-light-reactive type, it is possible to use a mixed nitrogen and sulfur or rhythm titanium oxide and anoxic type. Titanium oxide, emulsified titanium which enhances pigment type, and titanium supported by metal. In this case, the clean film layer (10)+, such as the above-mentioned sharp crystal mineralized titanium oxide, may also be combined with amorphous hydrogen fluoride. In this case, the mixing ratio of the anatase type crystalline titanium oxide to the amorphous titanium oxide is preferably m or 2 Å. Further, the amorphous cerium oxide has an effect of improving the stability of the coating chemical solution, and has a function as a film adhesion-action to improve workability and durability as a film. The clean coating layer (8)6 is attached to the titanium oxide particles on one side of the galvanized steel sheet.

S 099135420 22 201119848 以Ti02換算量為l〇mg/m2〜2000mg/m2、更佳為 50mg/m2〜2000mg/m2。此附著量未滿i0nig/m2之情況，光觸 媒特性大為降低’無法形成均勻皮膜，另一方面，超過 2000mg/m2，於施行各種成形加工作成預塗鋼板時，在皮膜 發生裂痕和剝離，視情況，裂痕有傳播至下層著色樹脂層4 之虞。 於此乾淨皮膜層（B)6中，除了氧化鈦微粒子以外，亦可 含有形成皮膜用之黏合劑和作為添加劑之矽'鋁、鍅等金屬 氧化物和化合物、或碟酸化合物之！種或2種以上的 合物。 …、、匕 於此乾淨皮膜層（B)6 +，在不改變色調之範圍亦可添加 銀化合物等之抗_、活性破和彿石等之吸黏劑，且 等之添加可更加提高抗菌性等之美觀耐久性。 ^ 作為將乾淨皮膜層（Β)6,以連續塗佈流線在 =皮膜層⑷5上形成的方法，可在_系鋼板之料^ 層3形成面上，將水或有機㈣稀釋的藥 ' ::模一’並™。。左右之“烤:: 二基材“或兩面，特別設 乾粒子之 平面圖所示般’成為上層的乾淨皮膜層(•經:= 099135420 ^ 23 201119848 層（A)5中的撥水性微粒子7被彈開，無法被覆該微粒子7 的存在部分及其附近’該撥水性微粒子7由預塗鋼板(乾淨 皮膜層（B)6)的表面露出並且以橫跨乾淨皮膜層（A)5與乾淨 皮膜層（B)6兩者般存在。藉此，本發明之預塗鋼板，可取 得因光觸媒造成的美觀耐久性'對於光觸媒的耐分解性能、 及優異的外觀均勻性和加工性。 又’作為上述鋼板基材’經由介隔著化成處理皮膜2設置 上述之塗底層3和著色樹脂層4，則可經由各層的相互作用 取得作為預塗鋼板所要求的上述各種特性。 另外，上述各皮膜層係在鋼板基材的至少一面形成，但於 另一面（裏面）亦可形成同一皮膜層，又，在裏面，於化成處 理後，形成通常預塗鋼板所用之丨塗敷、丨烘烤之所謂的維 修區（service court)亦無妨。 [實施例] 根據以下之實施例說明本發明。 (本發明例1) 於此本發明例1中，作為鋼板基材，使用施行含有二氧化 矽之塗佈型鉻酸鹽處理以附著量為換算金屬鉻為40mg/m2 之厚度0.5mm的熔融55%鍍鋁-鋅合金鋼板(鍍敷附著量為 一側80g/m2)。對此熔融鍍鋅鋼板，將作為防銹顏料之含有 約20質量％鉻酸勰的三聚氰胺硬化型聚酯樹脂塗料 「Precolor Primer FX-2(BASF Coating japan(股）製）」以乾燥 099135420 24 201119848 塗膜厚為5/xm般以棒塗敷器塗佈，並以約23〇。〇烘烤6〇秒 鐘’形成塗底層（a-Ι)。 其次，於此塗底層上，將聚偏氟乙烯與丙烯酸系樹脂以質 量比80 : 20之有機溶膠系烘烤型氟樹脂rprec〇1〇r N〇 8800(BASF Coating Japan(股）製）」中混合作為著色顏料的氧 化鈦、和煅燒碳黑混合煅燒二氧化矽作為調整表面用之塗料 (b-Ι) ’以乾燥塗膜厚為22μιη般以棒塗敷器塗佈後，以約 240°C烘烤60秒鐘，形成著色樹脂層（光澤值以6〇度光澤法 為 10)。 其次，於此著色樹脂層上，將作為丙烯酸成分之丙烯酸正 丁酉曰和甲基丙烯酸曱酯、和作為石夕成分之曱基丙烯醯氧丙 基三乙氧基矽烷所構成之重量平均分子量為約2萬的丙烯 酸系石夕樹脂溶液中’配合5質量％平均粒徑》4/|m之聚四 氟乙烯微粒子（住友3M(股）公司製Dini〇n TF92〇7)的塗料 (cl)以乾燥膜厚為2μιη般以塗敷器塗佈後，以約1乾 燥30秒鐘，形成乾淨皮膜層（A)。 更且，在乾淨皮膜層（A)上，將作為銳鈦礦型氧化鈦之石 原產業（股）製ST_21以固形份比2〇 f量％般，於非晶質氧化 鈦分散液「日本Parkerizing(股）製PTI-5600」中混合的水分 散液(d-1)，以附著量換算Ti〇2為} 5 〇mg/m2般以輥塗敷器塗 佈後以約200 C乾燥20秒鐘，形成乾淨皮膜層（b)，取得 本發明之預塗鋼板(本發明例1)。 099135420 25S 099135420 22 201119848 The amount of Ti02 is l〇mg/m2 to 2000 mg/m2, more preferably 50 mg/m2 to 2000 mg/m2. When the amount of adhesion is less than i0nig/m2, the photocatalytic characteristics are greatly reduced. 'The uniform film cannot be formed. On the other hand, when it exceeds 2000 mg/m2, cracks and peeling occur in the film when various types of forming work are performed to form a precoated steel sheet. In the case, the crack propagates to the lower layer of the colored resin layer 4. In addition to the titanium oxide fine particles, the clean coating layer (B) 6 may contain a binder for forming a film and a metal oxide and a compound such as aluminum or ruthenium as an additive, or a disc acid compound! Species or more than two compounds. ..., 匕 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净 干净Aesthetic durability of sex. ^ As a method of forming a clean coating layer (Β) 6 with a continuous coating flow line on the = film layer (4) 5, water or organic (four) diluted medicine can be formed on the surface of the layer 3 of the _ series steel sheet. ::Mold one 'and TM. . Left and right "baked:: two substrates" or two sides, especially as shown in the plan view of dry particles 'become the upper layer of clean film layer (• by: = 099135420 ^ 23 201119848 layer (A) 5 in the water-repellent particles 7 Bounced, unable to cover the existing portion of the fine particles 7 and its vicinity 'The water-repellent fine particles 7 are exposed from the surface of the precoated steel sheet (clean coating layer (B) 6) and across the clean coating layer (A) 5 and the clean film The layer (B) 6 is both present. Thus, the precoated steel sheet of the present invention can attain the aesthetic durability due to the photocatalyst, the decomposition resistance to the photocatalyst, and the excellent appearance uniformity and processability. When the above-mentioned coating underlayer 3 and colored resin layer 4 are provided via the chemical conversion treatment film 2, the above-described various characteristics required for the precoated steel sheet can be obtained through the interaction of the respective layers. It is formed on at least one side of the steel sheet base material, but the same film layer can be formed on the other side (inside), and in the inside, after the chemical conversion treatment, the enamel coating and the enamel baking which are usually used for the pre-coated steel sheet are formed. The present invention is also described based on the following examples. (Example 1 of the present invention) In the first example of the present invention, as the steel sheet substrate, the use of cerium oxide is used. The coated chromate treatment was performed on a molten 55% aluminized-zinc alloy steel sheet having a thickness of 0.5 mm and a metal chromium of 40 mg/m 2 (the plating adhesion amount was 80 g/m 2 on one side). The steel sheet is a melamine-curable polyester resin coating "Precolor Primer FX-2 (manufactured by BASF Coating japan) containing about 20% by mass of strontium chromate as a rust preventive pigment to dry 099135420 24 201119848. /xm is coated with a bar coater and baked at about 23 〇. 〇 baked for 6 〇 seconds to form a primer layer (a-Ι). Next, on the primer layer, polyvinylidene fluoride and acrylic The resin is mixed with titanium oxide as a coloring pigment and calcined carbon black in a mass ratio of 80:20 in an organosol-based fluororesin rprec〇1〇r N〇8800 (manufactured by BASF Coating Japan). Cerium oxide as a coating for adjusting the surface (b-Ι) 'dry coating thickness After coating with a bar coater as 22 μm, it was baked at about 240 ° C for 60 seconds to form a colored resin layer (gloss value was 10 in a 6-degree gloss method). Next, on the colored resin layer, Acrylic ruthenium resin solution having an acrylic acid component of n-butyl acrylate and methacrylate, and a fluorenyl propylene oxypropyl triethoxy decane as a component of yoke as a weight average molecular weight of about 20,000 The coating (cl) of the polytetrafluoroethylene fine particles (Dini〇n TF92〇7 manufactured by Sumitomo 3M Co., Ltd.) of '5 mass% average particle diameter>> 4/|m is coated with a dry film thickness of 2 μm After coating, the film was dried at about 1 for 30 seconds to form a clean film layer (A). Further, in the clean coating layer (A), ST_21, which is an anatase type titanium oxide, is made into a solid titanium oxide dispersion "ST_21" in the form of a solid content of 2%, "Parkerizing" The aqueous dispersion (d-1) mixed in the PTI-5600" is dried by a roll applicator and then dried at about 200 C for 20 seconds in terms of adhesion amount of Ti〇2 to 5 〇mg/m2. The bell was formed into a clean coating layer (b), and the precoated steel sheet of the present invention (Example 1 of the present invention) was obtained. 099135420 25

S 201119848 (本發明例2〜8、比較例1〜8) 除了將本發明例1之塗底層、著色樹脂層、乾淨皮膜層 (A)、乾淨皮膜層（B)改變成表1所示之各種條件以外，同本 發明例1處理製作本發明之預塗鋼板(本發明例2〜8)及比較 例之預塗鋼板（比較例1~8)。另外，關於比較例7，於乾淨 皮膜層（A)上’將上述種類(d-Ι)的水分散液以喷霧塗佈，使 光觸媒以島狀分散般被覆。 表1中之著色樹脂層的種類(b-2)，係將作為著色顏料之氧 化欽與奴黑犯合的二^^鼠1:¾•硬化型聚|旨樹脂（「prec〇j〇r ]^〇.3800」（^3?(：〇^1^坤&11(股）製），厚度15)11111、光澤值 60。 又’乾淨皮膜層（A)之種類（c-2)，係於與種類(c_i)相同之 丙烯酸系矽樹脂溶液中，將平均粒徑8jUm之聚四氟乙烯微 粒子（住友3M公司DinionTF9205)以固形份比3質量％般配 合者’種類(c-3)係於與種類(c_i)相同之丙烯酸系矽樹脂溶液 中’未配合撥水性微粒子者’種類(c_4)係丙烯酸系樹脂系乳 液塗料’種類（c-5)係對於種類（c_3)之溶液，將種類(心1)之粉 末以固形份比30%、或撥水性微粒子（住友（3M) Dinion TF9207)以固形份比3〇/〇般配合者。 更且’乾淨皮膜層（B)之種類(d_2)，係由種類(d-Ι)中除去 銳欽礦型氧化鈦者，種類(d_3)，係於種類之水分散液 中’將撥水性微粒子(住友3M Dini〇n TF9207)以固形份比3% 099135420 26 201119848 般配合者。 將根據上述製造之全部預塗鋼板(本發明例1〜8、比較例 1〜8)，供於下述之各種試驗，其結果示於表1。 (試驗•評估方法） (1) 外觀均勻性 以目視評估所得預塗鋼板的外觀。另外，評估基準如下。 ◎:未發生干擾色，外觀良好 〇：猶微發生干擾色，但未發生不勻、變色等，外觀良好 △:若干發生不勻、變色（干擾色等） X:明顯發生不勻、變色（干擾色等） (2) 彎曲加工性 於室内（20°C)，如圖3所示般重疊相同的2枚鋼板，並將 該等鋼板的上端部以折彎成180。的預塗鋼板夾住，以目視 評估此折彎凸部（上端部）中的皮膜狀態（有無裂痕）。評估基 準如下。 未觀察到裂痕 〇： 稍微觀察到裂痕 明顯發生裂痕 X: 激烈發生裂痕 (3) 加工瑕疵性 以皮膜面為凸側般進行加壓彎曲加工，評估皮膜面的外觀 及帶瑕疵狀態。彎曲加工係以内側半徑為0.8mm之條件， 099135420 27 201119848 於20°C之室内進行。 〇：未發生瑕疵 ^在接觸加壓之金屬模具部分有《微瑕減生變色 X·塗膜顯著發生瑕疵 (4) 耐候性 評估外觀。 /下列條件實施麵小時促進耐候性試驗 評估基準如下。 ◎:幾乎未觀察到色調•光澤變化。 〇.稍微觀察到色調•光澤變化。 △:明顯觀察到色調•光澤變化。 X:顯著觀察到激烈的白亞化等色調•光澤變化 <促進耐候性試驗條件> 日照碳弧燈數 ：1燈（未使用濾光鏡）S 201119848 (Inventive Examples 2 to 8 and Comparative Examples 1 to 8) The coating base layer, the colored resin layer, the clean coating layer (A), and the clean coating layer (B) of Example 1 of the present invention were changed to those shown in Table 1. The precoated steel sheets of the present invention (Inventive Examples 2 to 8) and the precoated steel sheets of Comparative Examples (Comparative Examples 1 to 8) were produced in the same manner as in the first embodiment of the present invention except for various conditions. Further, in Comparative Example 7, the above-mentioned (d-Ι) aqueous dispersion was spray-coated on the clean coating layer (A), and the photocatalyst was coated as an island-like dispersion. The type (b-2) of the colored resin layer in Table 1 is a kind of resin that is used as a coloring pigment for oxidized chin and slave black. 1:3⁄4•hardened type poly resin ("prec〇j〇r ]^〇.3800"(^3?(:〇^1^坤&11(share) system), thickness 15) 11111, gloss value 60. Also 'clean film layer (A) type (c-2) In the acrylic enamel resin solution of the same type (c_i), the polytetrafluoroethylene fine particles (Sumitomo 3M Dinion TF9205) having an average particle diameter of 8 μm were blended in a solid content ratio of 3% by mass. In the acrylic enamel resin solution of the same type (c_i), the type (c-5) is a solution of the type (c_3). The powder of the type (heart 1) is compounded at a solid content ratio of 30% or water-repellent fine particles (Sumitomo (3M) Dinion TF9207) in a solid form ratio of 3 〇/〇. Further, 'clean coating layer (B) Type (d_2), which is a type (d-Ι) in which the sharp-mined type of titanium oxide is removed, and the type (d_3) is in the type of aqueous dispersion. 'Water-repellent fine particles (Sumitomo 3M Dini〇n TF9) 207) The same as the solid content ratio of 3% 099135420 26 201119848. All of the precoated steel sheets produced according to the above (Inventive Examples 1 to 8 and Comparative Examples 1 to 8) were subjected to the following various tests, and the results are shown. (Table 1) (Testing and evaluation methods) (1) Appearance uniformity The appearance of the precoated steel sheets obtained was visually evaluated. The evaluation criteria were as follows: ◎: No interference color occurred, and the appearance was good 〇: Judgment of interference color, but No unevenness, discoloration, etc., good appearance △: Some unevenness, discoloration (interference color, etc.) X: Significant unevenness, discoloration (interference color, etc.) (2) Bending workability indoors (20 ° C), The same two steel sheets were stacked as shown in Fig. 3, and the upper end portions of the steel sheets were sandwiched by a precoated steel sheet bent at 180 to visually evaluate the state of the film in the bent convex portion (upper end portion). (There are no cracks.) The evaluation criteria are as follows. No cracks were observed. Cracks were observed in the cracks. X: Intense cracks occurred. (3) Machining properties were measured by pressing and bending the film surface as a convex side. Appearance and ribbon The bending process is carried out under the condition of an inner radius of 0.8 mm, 099135420 27 201119848 in a room of 20 ° C. 〇: no occurrence of 瑕疵 ^ in the metal mold part of the contact pressure has "micro-reduction color change X · coating film Significant occurrence of 瑕疵(4) Appearance of weather resistance evaluation. / The following conditions were used to evaluate the weather resistance test. The evaluation criteria were as follows: ◎: No change in color tone or gloss was observed. 〇. A slight change in color tone and gloss was observed. △: A change in hue and gloss was observed. X: Significantly observed color tone and gloss change such as intense whitening <promoting weather resistance test conditions> Number of sunshine carbon arc lamps: 1 lamp (no filter used)

電源、電壓 ：單相交流180〜230V 滅燈-照射之周期：60分鐘_60分鐘 照射時的條件Power supply, voltage: Single-phase AC 180~230V Off-lighting period: 60 minutes _60 minutes Conditions at the time of irradiation

平面面板溫度計之顯示溫度 • 63±3% 相對濕度 :50±5°/〇 滅燈時的條件 空氣溫度 ：30°C 才目對濕度 :98%以上 冷却水於試驗片裏面的溫度 :約 7〇C 099135420 28 201119848 水對於試驗片表面的喷射 ：未進行 試驗片表面承受的放射照度 ：於300〜700mm為285士 50W/m2 (5)美觀耐久性 將切斷成200mmx300mm正方之本發明例及比較例的預 塗鋼板，於 (A) 鄰接道路的建物壁（地上約的高度） (B) 鄰接水稻田的小屋壁（接觸地上） ’以垂直站立狀態分別放置4個月，評估其後的外觀。評估 基準如下。 〇成乎無表面附著物，維持美觀 △ &覆蓋附著物’初期的美觀大約消失 X存在即使洗淨亦無法除去程度的激烈附著物（藻類等 生物、碳等），初如认L , 初期的吳觀消失 (6)水之接觸角 #將本發S例及比較例之預塗鋼板表面，以的黑光(東 芝 Lilac 股份亡 77有限公司製FL20S-BLB)以紫外線強度 的條件照射24小時後，在該表面滴下水，並以 自動接觸角°十（協和界面下學股份有限公司製DM-500)測定 3秒後的水接觸角。其結果示於表！。Display temperature of flat panel thermometer • 63±3% Relative humidity: 50±5°/Conditions when annihilating the lamp Air temperature: 30°C Only for the humidity: 98% or more The temperature of the cooling water inside the test piece: about 7 〇C 099135420 28 201119848 Water spray on the surface of the test piece: Irradiation of the test piece surface is not carried out: 285 ± 50 W/m2 at 300 to 700 mm (5) The aesthetic durability is cut into 200 mm x 300 mm square. The precoated steel sheet of the comparative example was placed in (A) adjacent to the construction wall of the road (about the height of the ground) (B) adjacent to the dam wall of the paddy field (contacting the ground), and placed in a vertical standing state for 4 months, and evaluated thereafter. Exterior. The evaluation criteria are as follows. 〇 无 表面 , , , , △ △ △ △ △ △ △ △ △ △ 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖 覆盖The disappearance of Wu Guan (6) The contact angle of water # The surface of the precoated steel sheet of the S example and the comparative example was irradiated with black light (FL20S-BLB manufactured by Toshiba Lilac Co., Ltd.) for 24 hours under ultraviolet light intensity conditions. After that, water was dropped on the surface, and the water contact angle after 3 seconds was measured at an automatic contact angle of 10 (DM-500, manufactured by Kyowa Interface Co., Ltd.). The results are shown in the table! .

S 099135420 29 201119848S 099135420 29 201119848

〔I^J 評估結果 水之接觸角 (度） cn οο CO Ό CS Ό fO m cn cn a\ CO v〇 00 寸 00 r—H 美觀 耐久性 〇 〇 〇 〇 〇 〇 〇 〇 X X 〇 X <1 〇 〇 <1 耐候性 ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ X 〇 〇 X 加工 瑕疵性 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 X 〇 0 X X < 彎曲 加工性 ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ 〇 〇 0 ◎ ◎ 〇 〇 < 外觀 均勻性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 乾淨皮膜層 (B) 換算Ti02 含有量 (mg/m2) 150 150 150 Ο CN 1200 100 150 800 150 1 150 150 150 150 100 1 種類 T3 T3 T3 -ύ T3 1-H 碟 T3 cs T3 cn 1 m 乾淨皮膜層 (A) 膜厚 (y m) CN 寸 CN Ο CN CS CN o 1 CM (N (N <N (N 種類 r-H 1 〇 η 1 Ο 1 Ο 1 〇 秦 o CN 1 〇 1 o 1-H 1 〇 碟 1 〇 ΓΟ 1 〇 1 〇 寸 1 〇 m 1 〇 1 〇 1 ϋ 著色樹脂層 種類 i_ 1 χ> 1 Xi 1 1 X> 1 X> b-2 b-2 (N 1 1 1 1 Xi 1 Xi 1 X) 1 塗底層 種類 T-^ 1 Λ 1 α 1 cd 1 1 cd 1 cs 1 a 1 Λ 1 a 1 1 a 1 cd 1 cd 1 rt T-H 1 d 1 cd 本發明例1 本發明例2 本發明例3 本發明例4 本發明例5 本發明例6 i |本發明例7 1 本發明例8 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 οε §s§ s 201119848 由表1之結果，本發明例1〜8 異的性能。 於全部的糾試驗中取得 優 相對地’於比較例卜因未形成乾淨皮媒層认卜故在加 工瑕疵性、耐候性及美觀耐久性全部觀察到劣化 又，於比較例2，因未形成乾淨皮膜層（^，匕故無法取得 光觸媒所造成的效果，於美觀耐久性觀察到劣化 於比較例3之預塗鋼板’如圖4(a)剖面圖对 __ 久囫4(b)平面圖 所示般，因乾淨皮膜層（Α)5中未含有撥水性微粒子，古 為其上層的乾淨皮膜層（Β)6以連續薄膜狀形成 、 生加工瑕疵。 Χ 於比較例4，因乾淨皮膜層（Β)中未含有氧化鈦，故無法 發揮光觸媒所造成的美觀对久性效果，於比較例5，因^爭 皮膜層（A)由丙烯酸系樹脂系乳液塗料所構成，未含有石夕化 合物和撥水性微粒子，故經由光觸媒使乾淨皮膜層（A)分 解、劣化’於耐候性和加工性觀察到劣化。 更且’於比較例6，因在乾淨皮膜層（B)的塗佈液中混合 撥水性微粒子’故如圖5(a)剖面圖及圖5(b)平面圖所示般， 撥水性微粒子7僅存在於乾淨皮膜層（b)6。因此，雖然經由 撥水性微粒子7使乾淨皮膜層（B)6呈現不連續狀態並且顯 不優異的外觀均勻性，但該微粒子7於乾淨皮膜層（B)6中 的保持力弱’於加工時易發生瑕疵，且其大半脫落。 於比較例7，如圖6(a)剖面圖及圖6(b)平面圖所示般，在 099135420 201119848 乾淨皮膜層(A)5的表面媒層8以島狀(*連續）分散(其 表面被覆率為90面積％)、皮臈層中不含撥水性微粒子7， 故在進行加壓成形和輥成形之情況，表面發生瑕疵。 比較例8係在乾淨皮棋層⑷中介存在撥水性微粒子和光 觸媒粒子之例’如圖7(a)剖面圖及圖7(b)平面圖所示般，撥 水性微粒子7由乾淨皮_(a)5的表面露出之狀態。此比 較例8之預塗鋼板，雖經由撥水性微粒子7的效果而顯示優 異的彎曲加工性’但光觸媒粒子8進入乾淨皮膜層(A)5的 内部，故财候性降低。 又，比較例1〜8之水接觸角均為超過22〜6〇度範固的結 果。 [產業上之可利用性] 本發明之預塗鋼板及其製造方法為加工性和耐候性、美觀 性等優異，當然適合作為電性機器製品的外裝材和建築用 内·外裝材，除此以外亦可使用於要求上述性能的用途。 【圖式簡單說明】 圖1示出本發明之預塗鋼板之一實施形態的剖面圖。 圖2(a)示出本發明之預塗鋼板之其他實施形態的剖面圖。 圖2(b)示出本發明之預塗鋼板之其他實施形態的平面圖。 圖3示出預塗鋼板之彎曲加工性之評估方法的說明圖。 圖4(a)示出實施例之比車父例3之預塗鋼板構造的面圖。 圖4(b)示出實施例之比較例3之預塗鋼板構造的平面圖。 099135420 32 201119848 圖5 (a)示出實施例之比較例6之預塗鋼板構造的剖面圖。 圖5(b)示出實施例之比較例6之預塗鋼板構造的平面圖。 圖6(a)示出實施例之比較例7之預塗鋼板構造的剖面圖。 圖6(b)示出實施例之比較例7之預塗鋼板構造的平面圖。 圖7(a)示出實施例之比較例8之預塗鋼板構造的剖面圖。 圖7(b)示出實施例之比較例8之預塗鋼板構造的平面圖。 【主要元件符號說明】 1 鍍敷鋼板 2 化成處理皮膜 3 塗底層 4 著色樹脂層 5 乾淨皮膜層（A) 6 乾淨皮膜層（B) 7 撥水性微粒子 8 光觸媒粒子、光觸媒層 099135420 33[I^J evaluation result water contact angle (degrees) cn οο CO Ό CS Ό fO m cn cn a\ CO v〇00 inch 00 r-H beautiful durability XX 〇X < 1 〇〇 <1 Weather resistance ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ X 〇〇 X Machining 〇〇〇〇〇〇〇〇 X 〇 X 〇 0 XX < Bending workability ◎ ◎ ◎ ◎ 〇◎ ◎ ◎ 〇〇0 ◎ ◎ 〇〇< Appearance uniformity 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇Clean film layer (B) Conversion Ti02 content (mg/m2) 150 150 150 Ο CN 1200 100 150 800 150 1 150 150 150 150 100 1 Type T3 T3 T3 - ύ T3 1-H Disc T3 cs T3 cn 1 m Clean film layer (A) Film thickness (ym) CN 寸CN Ο CN CS CN o 1 CM (N (N <N (N type rH 1 〇η 1 Ο 1 Ο 1 〇 Qin o CN 1 〇 1 o 1-H 1 〇碟1 〇ΓΟ 1 〇1 〇 inch 1 〇m 1 〇1 〇 1 着色 Colored resin layer type i_ 1 χ> 1 Xi 1 1 X> 1 X> b-2 b-2 (N 1 1 1 1 Xi 1 Xi 1 X) 1 Coating underlayer type T-^ 1 Λ 1 α 1 cd 1 1 cd 1 Cs 1 a 1 Λ 1 a 1 1 a 1 cd 1 cd 1 rt TH 1 d 1 cd Inventive Example 1 Inventive Example 2 Inventive Example 3 Inventive Example 4 Inventive Example 5 Inventive Example 6 i | Inventive Example 7 1 Inventive Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 οε §s§ s 201119848 From the results of Table 1, the present invention examples 1 to 8 The performance was obtained in all the correction tests. In the comparative example, since the clean skin layer was not formed, all the defects were observed in the processing properties, weather resistance and aesthetic durability. In Comparative Example 2, A clean film layer was not formed (^, so that the effect of the photocatalyst could not be obtained, and the pre-coated steel sheet of Comparative Example 3 was observed to be deteriorated in aesthetic durability as shown in Fig. 4(a). __久囫4(b As shown in the plan view, since the clean film layer (Α) 5 does not contain water-repellent fine particles, the upper clean film layer 6 is formed in a continuous film form and processed.比较 In Comparative Example 4, since the titanium oxide layer was not contained in the clean coating layer, the effect of the photocatalytic effect on the photocatalyst was not exhibited. In Comparative Example 5, the coating layer (A) was made of an acrylic resin. Since the emulsion coating material does not contain the Shiki compound and the water-repellent fine particles, the clean coating layer (A) is decomposed and deteriorated by the photocatalyst, and deterioration is observed in weather resistance and workability. Further, in Comparative Example 6, since the water-repellent fine particles were mixed in the coating liquid of the clean coating layer (B), the water-repellent fine particles 7 were as shown in the cross-sectional view of Fig. 5 (a) and the plan view of Fig. 5 (b). Only present in the clean film layer (b) 6. Therefore, although the clean coating layer (B) 6 is rendered discontinuous via the water-repellent fine particles 7, and the appearance uniformity is not excellent, the retention of the fine particles 7 in the clean coating layer (B) 6 is weak during processing. It is prone to sputum, and most of it falls off. In Comparative Example 7, as shown in the cross-sectional view of Fig. 6(a) and the plan view of Fig. 6(b), the surface dielectric layer 8 of the clean coating layer (A) 5 is dispersed in an island shape (* continuous) at 099135420 201119848 (the surface thereof) The coverage ratio was 90 area%), and the water-repellent fine particles 7 were not contained in the skin layer. Therefore, in the case of press molding and roll forming, flaws occurred on the surface. Comparative Example 8 is an example in which water-repellent fine particles and photocatalyst particles are interposed in a clean leather chess layer (4). As shown in the cross-sectional view of Fig. 7(a) and the plan view of Fig. 7(b), the water-repellent fine particles 7 are made of clean skin_a The state in which the surface of 5 is exposed. In the precoated steel sheet of Comparative Example 8, the excellent bending workability was exhibited by the effect of the water-repellent fine particles 7, but the photocatalyst particles 8 entered the inside of the clean coating layer (A) 5, so that the fiscal property was lowered. Further, the water contact angles of Comparative Examples 1 to 8 were all more than 22 to 6 范 degrees. [Industrial Applicability] The precoated steel sheet and the method for producing the same according to the present invention are excellent in workability, weather resistance, and aesthetics, and are of course suitable as exterior materials for electrical equipment products and interior and exterior materials for construction. In addition to this, it can also be used for applications requiring the above properties. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a precoated steel sheet of the present invention. Fig. 2 (a) is a cross-sectional view showing another embodiment of the precoated steel sheet of the present invention. Fig. 2 (b) is a plan view showing another embodiment of the precoated steel sheet of the present invention. Fig. 3 is an explanatory view showing a method of evaluating the bending workability of a precoated steel sheet. Fig. 4 (a) is a plan view showing the structure of the precoated steel sheet of the example of the vehicle of the parent. Fig. 4 (b) is a plan view showing the structure of a precoated steel sheet of Comparative Example 3 of the example. 099135420 32 201119848 Fig. 5 (a) is a cross-sectional view showing the structure of a precoated steel sheet of Comparative Example 6 of the example. Fig. 5 (b) is a plan view showing the structure of a precoated steel sheet of Comparative Example 6 of the example. Fig. 6 (a) is a cross-sectional view showing the structure of a precoated steel sheet of Comparative Example 7 of the example. Fig. 6 (b) is a plan view showing the structure of a precoated steel sheet of Comparative Example 7 of the example. Fig. 7 (a) is a cross-sectional view showing the structure of a precoated steel sheet of Comparative Example 8 of the example. Fig. 7 (b) is a plan view showing the structure of a precoated steel sheet of Comparative Example 8 of the example. [Description of main component symbols] 1 Plated steel plate 2 Chemical treatment film 3 Undercoat layer 4 Colored resin layer 5 Clean film layer (A) 6 Clean film layer (B) 7 Water-repellent particles 8 Photocatalyst particles, photocatalyst layer 099135420 33

Claims (1)

201119848 七、申請專利範圍： 1.一種預塗鋼板，其特徵為在鋼板基材的至少一面具有： 主成分由石夕化合物所構成，並分散含有撥水性微粒子的乾 淨皮膜層（A);和 在該乾淨皮膜層（A)上積層之含有以顯示光觸媒活性的氧 化鈦微粒子作為主成分的乾淨皮膜層⑻。 2.如申°月專利範圍第1項之預塗鋼板，其中，上述乾淨皮 膜層（A)中之撥水性微粒子的至少其—部分係由乾淨皮膜層 (B)之表面突出並且以島狀分散。 3·如申清專利範圍第1或2項之預塗鋼板，其中，上述乾 淨皮膜層（B)表面與水的接觸角 為22〜60度。 如申明專利範圍第丨至3項中任一項之預塗鋼板，其 中，上述乾淨皮膜層（A)中之撥水性微粒子的至少具一部 分’係具有Mt淨賴層⑷之鮮更大的粒徑。 5·如申#專利關第1至4項巾任-項之預塗鋼板，1 1 ^上述乾淨皮膜層⑷巾之撥水性餘子動㈣樹脂粒 …鼠樹W共聚合體樹脂粒子、㈣絲子、或表面塗敷 該等樹脂而成的粒子所構成。 ::如申請專利範圍第…項中任一項之預塗鋼板，; 上迷乾命皮膜層⑷中的石夕化合物為丙稀酸系石夕樹月旨。 中，上圍第1至6項十任-項之預塗鋼板，， 述乾淨皮膜層⑻中的氧化鈦粒子於每-面的附著. S 099135420 34 201119848 以換算 Tl〇2 計為 1〇mg/m2〜2〇〇〇mg/m2。 8·如申請專利範圍第i i 7項中任—項之預塗鋼板，其 中，上述乾淨皮膜層（B)係以銳鈦礦型結晶質氧化欽微粒子 和非晶質氧化鈦的混合物作為主成分。 9·如申請專利範圍第！至8項中任—項之預塗鋼板，其 中，上述鋼板基材係於鍍鋅系鋼板之至少一 理皮膜、與於其上形成的樹脂皮膜者， 〃有化成處 上述樹脂皮膜係由含有防銹顏料之熱硬化性樹脂所構成 的塗底層、和著色樹脂層所構成。 10. 如申請專利範圍第9項之預塗鋼板，其中，上述著色 樹脂層以聚偏氟乙烯與丙烯酸系樹脂之質量比為85: 15〜50 : 50之有機溶膠系烘烤型氟樹脂作為主成分。 11. 一種預塗鋼板之製造方法，其特徵係在鋼板基板的至 少-面’依序積層以魏合物作為主成分的乾淨皮膜層⑷ 及以顯示光觸媒活性之氧化鈦微粒子作為域分的乾淨皮 臈層（B)而成之預塗鋼板的製造方法中， 使上述乾#皮膜層⑷巾分散含有撥水性微粒子，抑制乾 淨皮膜層⑻對於該撥水性㈣子所存在之部分及其附近的 被覆量，藉此成為該撥水性微粒子的至少其—部分由乾淨皮 膜層（B)表面突出之狀態並以島狀分散。 12.如申請專利範圍第u項之預塗鋼板之製造方法，其 中，上述乾淨皮膜層（A)中之撥水性微粒子的至少其一部 分，係具有比乾淨皮膜層（A)之膜厚更大的粒徑。 S 099135420 35201119848 VII. Patent application scope: 1. A pre-coated steel sheet characterized in that at least one side of the steel sheet substrate has: a main component composed of a compound of Shixia, and a clean coating layer (A) containing water-repellent fine particles dispersed; A clean film layer (8) containing a titanium oxide fine particle exhibiting photocatalytic activity as a main component is laminated on the clean film layer (A). 2. The precoated steel sheet according to claim 1, wherein at least a portion of the water-repellent fine particles in the clean coating layer (A) protrudes from the surface of the clean coating layer (B) and is island-shaped. dispersion. 3. The precoated steel sheet according to claim 1 or 2, wherein the surface of the dry coating layer (B) has a contact angle with water of 22 to 60 degrees. The precoated steel sheet according to any one of claims 3 to 3, wherein at least a part of the water-repellent fine particles in the clean coating layer (A) has a larger grain of the Mt net layer (4). path. 5·如申#Patents for the first to fourth items of the towel--the pre-coated steel plate, 1 1 ^ the above clean film layer (4) the water-repellent remaining of the towel (four) resin particles... rat tree W copolymer resin particles, (four) silk The particles are formed by coating the particles with the surface of the resin. :: Pre-coated steel sheet according to any one of the claims of the invention, wherein the stone compound in the dry film layer (4) is an acrylic acid stone tree. In the above, the first pre-coated steel sheets of the first to the sixth items, the titanium oxide particles in the clean coating layer (8) are attached to each side. S 099135420 34 201119848 The conversion T1〇2 is 1〇mg /m2~2〇〇〇mg/m2. 8. The precoated steel sheet according to any one of the items ii 7 of the patent application, wherein the clean coating layer (B) is composed of a mixture of anatase type crystalline oxidized fine particles and amorphous titanium oxide as a main component. . 9. If you apply for a patent scope! The precoated steel sheet according to any one of the preceding claims, wherein the steel sheet substrate is at least one of a galvanized steel sheet and a resin film formed thereon, and the resin film is contained in the chemical film. A primer layer composed of a thermosetting resin of a rust preventive pigment and a colored resin layer. 10. The precoated steel sheet according to claim 9, wherein the colored resin layer is an organosol-based baking fluororesin having a mass ratio of polyvinylidene fluoride to acrylic resin of 85:15 to 50:50. main ingredient. A method for producing a precoated steel sheet, characterized in that a clean coating layer (4) containing a Wei compound as a main component and a titanium oxide microparticle exhibiting photocatalytic activity as a domain are sequentially laminated on at least a surface of the steel sheet substrate. In the method for producing a precoated steel sheet obtained by the skin layer (B), the dry film layer (4) is dispersed to contain water-repellent fine particles, and the clean film layer (8) is inhibited from being present in the portion of the water-repellent layer (4) and its vicinity. The coating amount is such that at least a part of the water-repellent fine particles protrudes from the surface of the clean coating layer (B) and is dispersed in an island shape. 12. The method of producing a precoated steel sheet according to the invention of claim 5, wherein at least a part of the water-repellent fine particles in the clean coating layer (A) has a larger film thickness than the clean coating layer (A). Particle size. S 099135420 35
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