201104016 六、發明說明： I：發明戶斤屬之技術領域3 發明領域 本發明係有關於在作為基材之具有有機樹脂被覆層的 預塗金屬板（以後，記為「基材預塗金屬板」）之表面，更具 有至少2層之顯示光觸媒活性的皮膜且耐污染性優異之預 塗金屬板、其製造方法、及可較佳地製造預塗金屬板之表 面處理液。更詳而言之，本發明係有關於預塗金屬板與其 製造方法，該預塗金屬板係藉於表面具有至少2層以上之皮 膜，經長時間可得光觸媒活性，且耐候性或皮膜密著性優 異者，前述皮膜含有具光觸媒活性之物質、因光觸媒產生 之劣化少的無機-有機複合體樹脂、及提高密著性之無機系 平板狀粒子。又，本發明係有關於用以較佳地製造該預塗 金屬板之表面處理液者。 L先前技術3 發明背景 一般而言，以提升耐久性為目的、或以得到美麗之外 觀為目的係塗裝由鐵所代表之金屬材料來使用，經塗裝之 金屬板廣泛地使用於家電、汽車、建材、屋外構造物等領 域。其中，特別是於屋外之用途方面，因暴露於風、雨、 砂塵等之下，除了耐蝕性之外亦要求耐污染性之優異。 光觸媒技術係利用具有光觸媒粒子之光觸媒活性將表 面親水化的技術、及分解、去除以有機物為中心之污染物 質的技術，係於預塗金屬板中，藉使光觸媒活性優異之粒 201104016 子在表面之皮膜中分散、含有，以期待耐污染性或自淨化 效果者。該技術中，對於表面之污染物質的分解、去除可 得優異之效果，但於使光觸媒粒子分散於有機樹脂系之塗 膜時、或於有機樹脂系之塗膜表面形成有光觸媒皮膜時， 藉由光觸媒效果有機樹脂系塗膜將逐漸分解，而進行劣 化，故經長時間使用是困難的。 其對應方法，有人提出了用以抑制塗膜之劣化的技 術。例如，專利文獻1、專利文獻2中所揭示之使用無機系 成分作為構成皮膜之樹脂的方法。又，揭示有於有機樹脂 中，因氟樹脂對光觸媒較為安定，故使用其作為皮膜成分 的方法（專利文獻3)。此外，分別於專利文獻4與專利文獻5 中揭示了特別是於預塗金屬板之用途上，要求對光觸媒之 高穩定性與加工性，但相對於該目的，而使用以二氧化矽-有機矽烷系樹脂作為皮膜成分之方法、以使用藉由丙烯酸 樹脂與有機烷氧矽烷之聚合反應所得的矽酸烷基酯作為皮 膜成分之方法。又，於專利文獻6揭示有使用偏二氟乙烯樹 脂及丙烯酸樹脂之方法。 發明人等亦提出了可高度地滿足對相對於具有機樹脂 塗膜之預塗金屬板仍可使用之光觸媒的高穩定性，即優異 之财候性與加工性的皮膜樹脂成分。（專利文獻7〜9) 又，亦正進行有藉於包含光觸媒物質之皮膜層與下層 之有機樹脂系塗膜層之間，相隔有不含光觸媒物質之保護 層，以防止有機樹脂系塗膜之劣化。 先前技術文獻 201104016 專利文獻 專利文獻1 :特開平07-113272號公報 專利文獻2 :特開平08-164334號公報 專利文獻3 :特開平07-171408號公報 專利文獻4 :特開平10-225658號公報 專利文獻5 :特開2000-317393號公報 專利文獻6 :特開2000-063733號公報 專利文獻7 :特開2006-192716號公報 專利文獻8 :特開2006-192717號公報 專利文獻9 :特開2007-268761號公報 C發明内容3 發明概要 發明欲解決之課題 依據發明人等之檢討，即使於使用前述之耐候性優異 的樹脂時，具有光觸媒活性之皮膜（以下，「光觸媒皮膜」） 將因光觸媒作用使皮膜劣化，而產生粉化(Chalking)，故會 逐漸地損耗。結果，可知於表面之光觸媒皮膜消失時，喪 失光觸媒機能，污染性、自淨化性能顯著地下降。 迄今’以後塗(post-coat)法作為光觸媒皮膜之形成方法 係為主流。因此，於將金屬材料加工成最終製品之形狀後， 或當為建材、屋外構造物時，於現場施工時形成光觸媒皮 膜的方法係為一般。該方法中，於形成最終製品之形狀後 塗裝皮膜、或將塗裝作為現場之施工項目，故不需限制構 成皮膜之樹脂或塗裝之膜厚等，可對應所需求之性能形成 201104016 皮膜。 然而，於預先塗裝後供使用者使用之狀態，即經進行 最表面之塗裝後之狀態下出貨之預塗金屬板，由加工性之 限制或成本的觀點來看，難以形成一定以上之厚度的皮 膜，且於該限制中，以可經長時間維持耐污染性、自淨化 性之預塗金屬板為佳。又，依據預塗金屬板表面之有機樹 脂被覆層（基底被覆層）的材質、具有光觸媒活性之物質的種 類或添加量，亦有光觸媒皮膜與基底被覆層之密著性不 佳，未能得到充分之自淨化性能的情形。特別是，有於彎 曲加工部之密著性不佳、經長時間未能得到充分之自淨化 性的問題。 本發明係為解決該課題而作成者，係提供一種於皮膜 厚度等限制存在之狀態下，可長時間地維持因光觸媒產生 之耐污染性、及自淨化機能的預塗金屬板者。又，目的係 提供用以較佳地製造前述預塗金屬板之方法及表面處理液。 用以欲解決課題之手段 對於前述之課題，發明人等致力地進行檢討，結果， 發現藉由將具有機樹脂被覆層之預塗金屬板作為基材，並 於該基材預塗金屬板表面具有至少2層之皮膜的預塗金屬 板，即可解決課題，而完成本發明，且前述皮膜係於無機-有機複合體樹脂中摻合具有光觸媒活性之物質及無機系平 板狀粒子者。詳而言之，本發明之預塗金屬板係為保護光 觸媒皮膜下層之有機樹脂塗膜，而於光觸媒皮膜與有機樹 脂塗膜之間所設之習知保護層中亦添加光觸媒，且，於光 201104016 觸媒皮膜中添加有無機系平板狀粒子的預塗金屬板。藉於 光觸媒皮膜與有機樹脂塗膜之間所設之習知㈣層中亦添 加光觸媒，可維持作為保護有機樹脂之保護層的機能，且 =上層之光觸媒皮膜層損耗、消失後，亦可藉由添加於保 善層之光_發揮耐污祕、自淨化機能。藉於光觸媒皮 膜中添加有無機系平板狀粒子，光觸媒皮膜層與有機樹脂 塗膜之密著性變得良好，且具有紫外線遮蔽效果之皮膜會 成於表面。具體而言，本發明之要旨係如以下所述。 ^ ()種預塗金屬板，係於基底金屬板及其表面具有機 樹月曰破覆層之基材預塗金屬板上形成至少2層之具有光觸 =活性的皮膜者，其特徵在於，該至少2層之具有光觸媒活 ，的皮膜含有無機·有機複合體樹脂、具有光觸媒活性之物 質、及無機系平板狀粒子，前述無機·有機複合體樹脂係由 下述所構成群組所選出之烷氧矽烷的縮合物所構成·具有 選自由碳數1以上12以下之烧基、芳基、減、經基、及該 等之組合所構成之群之有機基眺氧㈣、具有環氧基之 燒氧魏、具有絲之⑥氧雜、四錄㈣、及該等之 、、且δ且其所含有之具有光觸媒活性之物質的含有量係在 位於最外層之皮膜為最多，越内層側之皮膜越少。 (2) 如前述(1)之預塗金屬板，其中包含於前述無機-有機 複合體樹脂之有機基係甲基、或苯基。 (3) 如前述（1)或(2)之預塗金屬板，其中前述皮膜之各層 中的具有光觸媒活性之物質的含有量係各層之全質量的 0,1%〜50%。 201104016 (4) 如則述(1) (3)中任味之預塗金屬板，其中與有機 樹脂被覆層相接之最内層側皮膜中的光觸媒物質之含有量 係該皮膜之全質量的〇.〇5%〜25%。 (5) 如前述⑴〜(4)中任1者之預塗金屬板，其中 前述具 有光觸媒活性之物質係包含銳鈦麵鱗的氧化鈦。 ⑹如則述⑴〜（5)中任丨者之預塗金腐板，其中 前述皮 膜之各層中的無機系平板狀粒子之含有量係該皮膜之全質 量的0.05%〜30%。 (7) 如則述（1)〜（6)中任丨者之預塗金屬板，其中前述無 機系平板狀粒子係包含雲母者。 (8) 如前述（1)〜（7)中任丨者之預塗金屬板，其中前述基 底金屬板係選自於鋼板、不鏽鋼板、鈦板、鈦合金板、鋁 板、鋁合金板或於該等金屬板經電鍍處理之電鍍金屬板。 (9) 一種表面處理液，其特徵在於，含有無機-有機複合 料月曰原料、具有光觸媒活性之物質、及無機系平板狀粒子， 則述無機-有機複合樹脂原料包含有：具有由碳數1以上12 以下之燒基、芳基、羧基、羥基、及該等之組合所構成之 群中所選出之有機基的烧氧石夕烧、具有環氧基之烧氧石夕 元具有胺基之烧氧矽院、四炫氧石夕烧、及其等之組合所 構成之群中所選出之烷氧矽烷(al);該烷氧矽烷(al)之水解 物(a2)，及/或該烷氧矽烷(al)之縮合物（a3)。 (1〇)~種預塗金屬板之製造方法，其特徵在於，包含 古 · • (a)準備於金屬層、及其表面具有機樹脂被覆層之基材 預塗金屬板的步驟；（b)將作為如前述(9)之表面處理液的第 201104016 1表面處理液使用於前述基材預塗金屬板上，而形成未硬化 之第1表面被覆層的步驟；（C)藉由加熱，使前述未硬化之第 1表面被覆層硬化，而形成第1表面皮膜的步驟；（d)將作為 如前述(9)之表面處理液的第2表面處理液使用於第丨表面皮 膜上，而形成未硬化之第2表面被覆層的步驟；及(^)藉由加 熱，使前述未硬化之第2表面被覆層硬化，而於第丨表面皮 膜上形成第2表面皮膜的步驟。 (11)一種預塗金屬板之製造方法，其特徵在於，包含 有：（a)準備於金屬層、及其表面具有機樹脂被覆層之基材 預塗金屬板的步驟；（b)將作為如前述(9)之表面處理液的第 1表面處理液使用於前述基材預塗金屬板上，形成未硬化之 第1表面被覆層的步驟；（c)將作為如前述⑼之表面處理液 的第2表面處理液使用於未硬化之第〖表面被覆層上，形成 未硬化之第2表面被覆層的步驟；及⑷藉由加熱，使前述未 硬化之第！表面被覆層及前述未硬化之第2表面被覆層硬 化’形成第1表面皮膜及第2表面皮膜的步驟。 發明效果 依據本發明，可輕易地得到可長時間地維持、持續因 莊觸媒產生之耐/亏染性、及自淨化機能的預塗金屬板。又， 二吏用本I明之製造方法及表面處理液，可適當地製造 月，J述之預塗金屬板。 【實施冷式】 用以實施發明之形態 本發明之耐污染性優異的預塗金屬板係於經在金屬板 201104016 表面施行有機樹脂塗裝之一般的預塗金屬板之經塗裝表 面，設有至少2層之顯現耐污染性之加強塗裝皮膜的預塗金 屬板。加強塗裝皮膜之各層含有預定之無機-有機複合體樹 脂、具有光觸媒活性之物質、及無機系平板狀粒子。因加 強塗裝皮膜產生之耐污染性的顯現，係來自於該各層含有 對表面之污染物質的分解、去除顯示優異之效果之光觸媒 活性的物質（光觸媒物質）。加強塗裝皮膜之各層含有的無機 系平板狀粒子除了有助於對皮膜之基底有機樹脂被覆層的 密著性與預塗金屬板之耐蝕性的提升，亦有助於因紫外光 之遮蔽效果而對基底有機樹脂被覆層之保護、因皮膜本身 之光觸媒而對劣化的抑制。 針對本發明特徵之一，加強塗裝皮膜之各層含有光觸 媒物質乙事，進行說明。 目前為止已知的是，於預塗金屬板之經塗裝的表面， 設有藉包含光觸媒物質而有助於耐污染性之加強塗裝皮膜 層的層構成之預塗金屬板。此種習知之預塗金屬板中，包 含光觸媒物質之皮膜層與有機樹脂系材料且一般均形成之 基材預塗金屬板的塗膜層接觸，藉由光觸媒物質之光觸媒 效果，基底之預塗金屬板的塗膜層將逐漸分解，而進行劣 化，故經長時間使用是困難的。特別是，對於密封污染等 即使以光觸媒仍不亦分解之污染，為了發揮優異之效果而 必須添加多量之光觸媒，而有基材預塗金屬板表面之塗膜 層的劣化顯著，且光觸媒層本身之損耗亦快速的狀況。 為了避免該缺點，以往，進行了於包含光觸媒物質之 10 201104016 皮膜層與下層之有機樹脂系塗膜層之間，隔有未含光觸媒 物質的保護層。此時，光觸媒層及保護層為維持光觸媒耐 性而以無機成分為主體是為一般，但以無機成分為主體之 皮膜的加工性不佳，故形成一定以上之皮膜厚度是困難 的。因此，該方法中，必須使光觸媒層變薄至形成保護層 皮膜之厚度，而有耐污染性、自淨化性縮短之缺點。 本發明係於以避免包含光觸媒物質之皮膜層與下層之 有機樹脂系塗膜層的直接接觸為目的而使用之保護層中， 添加較其上層之光觸媒物質含有量少的光觸媒，藉此，比 較如習知技術地，（1)於有機樹脂系塗膜層上直接設有包含 光觸媒物質之層（光觸媒層）的情形、及(2)於有機樹脂系塗 膜層上依序設有未含光觸媒物質之保護層與包含光觸媒物 質之層的情形，而成功地作成可卓越地維持預塗金屬板之 而才污染性者(例如，實施例7與比較例1之耐污染性效果的持 續時間分別係約40年與約32年（參照表3之「自淨化性持續 期間」））。 如此，本發明係以避免以往之包含光觸媒物質的皮膜 層之光觸媒效果影響下層之有機樹脂系塗膜層為目的，基 於下述目前所未見之獨特知識而作成者，該獨特知識係為 避免包含光觸媒物質的皮膜層與有機樹脂系塗膜層直接接 觸，藉於未含光觸媒物質之存在於該等之間的保護層，添 加光觸媒物質，反倒可延長对污染性效果之持續時間。 於經塗裝之狀態出貨，使用者不需塗裝而成形加工之 預塗金屬板，由加工性之觀點來看，全體之塗裝膜厚受到 11 201104016 限制。依據相較於習知技術可延長耐污染性效果之持續時 間的本發明，可於如此之塗裝膜厚的限制内，提供耐污染 性效果更為優異之預塗金屬板。 依據本發明之預塗金屬板中，藉設置至少2層之含有光 觸媒物質之層以延長对污染性效果的理由，可如下述發想。 迄今，顯示因光觸媒效果產生之耐污染性機能的預塗 金屬板代表之塗膜構成，眾所周知的係如上述，（1)於基材 預塗金屬板之有機樹脂系塗膜層上直接設有光觸媒層者、 及(2)於基材預塗金屬板之有機樹脂系塗膜層與光觸媒層之 間設有未含光觸媒物質之保護層者。該等情形中，檢討光 觸媒層因本身之光觸媒作用而劣化，結果光觸媒層因損耗 至消失的期間A、及與光觸媒層相接之基材預塗金屬板的有 機樹脂塗膜之表面因光觸媒效果至劣化的期間B。（1)中因 光觸媒層直接接觸基材（此處，係指基底金屬板與形成於其 表面之有機樹脂塗膜層所構成的預塗金屬板）之有機樹脂 塗膜層，一般而言，相較於劣化之光觸媒層因損耗至消失 的期間A1，有機樹脂塗膜之表面因光觸媒效果至劣化的期 間B1較短，即呈A1>B1之關係。（2)中因有機樹脂塗膜層被 保護層保護，故有機樹脂塗膜之表面因光觸媒效果至劣化 的期間B2較劣化之光觸媒層因損耗至消失的期間A2大幅 地長，即呈A2«B2之關係。因此，因光觸媒而進行之耐污 染性、自淨化機能的持續期間於（1)的情形下受B1支配，於 (2)之情形下受A2支配。 另一方面，本發明中，因以往之保護層皮膜中亦添加 12 201104016 有光觸媒，故藉由調整光觸媒添加量或皮膜 雜一劣化之光觸媒層因損耗至消 係有機樹Μ膜之表面因光麟效果至劣化的㈣換言 之，與於有機樹脂設有同料度之㈣相較，依據 本發明’滅於前述⑴或⑺，經最長時間可持續因光觸媒 效果產生之耐污染性、自淨化效果，且於受到塗膜厚度限 制之預塗金屬板中可得到優異的效果。 此處，於前述習知（1)之情況下，藉由提高光觸媒層表 面附近之光觸媒濃度，並降低有機樹脂系塗膜層附近之光 觸媒濃度，即形成傾斜組成塗膜層，可得與上述本發明之 效果相同的效果。然而，於一層塗膜中，於厚度方向上控 制光觸媒濃度係極為困難。依據本發明之預塗金屬板中， 因可於2層以上皮膜之各層變更光觸媒添加量，故可輕易地 設定非污染、自淨化機能的持續時間。 此外’藉亦於習知保護層中添加光觸媒，亦可期待下 述效果°最上層之光觸媒層雖會因光觸媒效果而逐漸損 耗’但並不一定是均勻地損耗，於詳細觀察後，發現存在 有皮膜殘留多（皮膜損耗少）之領域與皮膜殘留少（皮膜損耗 多）之領域’ 一面於厚度方向形成凹凸一面損耗。於光觸媒 皮膜下設有保護層之習知情形中，在光觸媒皮膜損耗，與 且保護層之界面露出時，因保護層未具有自淨化效果，故 於一定比例之保護層露出時，自淨化性會顯著地下降。相 對於此’於保護層中亦添加光觸媒之本發明的情況下，因 保護層中亦可具有自淨化機能，故保護層於露出後亦可維 13 201104016 持優異之自淨化性。換士 觸媒之習知表面處理預塗金屬:二中:加光 層殘留夕灿能丁 _ 丨便於最上層之光觸媒 層殘留之狀態下’因保護層之 ψ ,Λ 出導致自淨化性下降，於 保邊層中亦添加光觸媒之本 中，於句合#+ 乃的表面處理預塗金屬板 於包3㈣層相之光觸 自淨化性。 叹联綫留時，可得充分之 丁只至金屬板 棋，沐曰金^^士入 口於保護層中亦添加光觸 媒，相較於未於保護層令添加光觸 有有機樹脂塗膜容易劣化 ' 卜，屬板， ===添加量較上層之光觸媒層少，因保護 層中之先觸媒造成有機樹脂塗膜之劣化小 護層中添加光觸媒時，劣化之光至= 冊g膜之表_光觸媒效果至劣化的期間 B=’有A2<<B2的關係，因相較於一係姆 為f時間’故依據本發明，藉於保護層中添加光觸媒而對 ^短之影響小。因此，依據本發明，可知相較藉於保護 層中添加光觸媒的缺點，藉增加自淨化機能之壽命的效果 係非常地大。 總結以上，依據本發明，亦於與有機樹脂塗膜相接之 保護層中添加光觸媒，可於形成在基㈣塗金屬板之光觸 媒皮膜存在的所有期間巾，親耐污祕、自淨化性，又， 於-定比例之倾層露出後，亦可^㈣述之效果，故可 知可卓越地延長自淨化壽命。 接著，針對本發明之另-特徵，加強塗裝皮膜（光觸媒 14 201104016 皮膜)含有無機系平板狀粒子乙事，進行i兒曰月 本發明之預塗金屬板表面的光觸:皮:含有無機系平 板狀粒子。添加該粒子之優點之一，# 係可確保優異之密著 性與财齡。添加之粒子因騎板形狀，齡皮 某 材預塗金屬板表面平行地配向，可提升 、/、土 欠升先觸媒皮膜與基材 預塗金屬板表面之有機樹脂被覆層'或構成光觸媒皮膜之 層之間的密著性。特別是，可提升預塗金屬板中最大課 之彎曲加工部的密著性。粒子於皮膜中配向之機構 縱橫比大之平板形狀’故於II如後述之浸沾塗布法、嘴 法、棒式塗布法、輥塗布法、旋轉塗布法、簾塗布法 行塗裝時，粒子將與金屬面並行地配向'積層。之後， 行乾燥、伽，形成賴’但平板狀粒子將維持顧本2 態，於最後形成皮膜後亦維持配向、積層狀態。 又’藉於皮膜中積層平板形狀之粒子，可防 子的侵人’提料絲。舉腐_子之__的水分為例進〜 說明，通常，水分係通過皮财之空隙移動，到達基= 金屬表面，但藉於皮财積層平板狀粒子，到達鋼板表面 之距離變長，結果提升耐蝕性。 此外，因光觸媒皮膜内層側之皮膜層堅固地與基材預 塗金屬板密著，於藉”曲加卫在外層側之皮膜層產生裂 縫夺亦可殘留皮膜。藉Φ存在光觸媒皮臈可顯現自淨化 機旎之本發明的預塗金屬板，即使於皮膜產生裂縫，金屬 板表面仍存在有光觸媒皮膜，故可顯現自淨化機能。 添加平板狀粒子之第2個優點，係如前述，於皮膜+， 15 201104016 因粒子與基材預塗金屬板面平行地配向，故有紫外光之遮 蔽效果。光不易到達内層側之皮膜，不僅可有效地保護美 材預塗金屬板表面之有機樹脂層，亦可提升光觸媒皮膜本 身之耐光觸媒性。於光觸媒皮膜表面，因具有預定量之光 觸媒活性的物質亦與平板狀粒子一同存在，故並不會特別 才貝害到表面之自淨化機能。又，因平板狀粒子係無機系粒 子，故不會因光觸媒而劣化。換言之，藉於光觸媒皮膜中 添加無機系之平板狀粒子，不會降低自淨化性能，亦可長 奇命化。 另外，另一個重要的優點，係可有效地抑制於乾燥、 加熱固化光觸媒皮犋時的裂縫。一般而言，光觸媒皮膜之 使用較多係使用無機系樹脂，但當無機系樹脂丨次之塗布量 過多時會有容易產生裂縫的缺點。因此’通常為避免過度 地塗布，進行了藉由數次之塗布以確保預定之膜厚等方 法。本發明係有關於預塗金屬板者，故無皮膜塗成顯著之 厚度的樣態，而有可以1次之塗布步驟，不會產生裂縫地形 成所期厚度之皮膜的優點。 總結以上’藉添加無機系之平板狀粒子，可提升光觸 媒皮膜與基材預塗金屬板、及構成光觸媒皮膜之層之間的 密著性’特別是可顯著地提升彎曲加工部的密著性。又， 可期待藉由平板狀之具特徵的形狀所產生之遮蔽紫外光的 效果’且亦可一併有效地防止於形成皮膜時產生之裂縫。 藉由該等效果，可長時間地維持起因於具有光觸媒活性之 物質的自淨化效果。 201104016 結果，例如，可知相對於比較例1所示之自淨化性持續 時間約32年，實施例7中達成了約40年之卓越的長壽命化。 本發明之預塗金屬板表面的皮膜具有於含有具光觸媒 活性之物質（以下，稱「光觸媒」）時，亦不易產生裂化的成 分、構造。具體而言，表面之皮膜，光觸媒之含有量於最 外層皮膜中是最多，具有於越内層皮膜越少的多層構造， 且包含無機-有機複合體樹脂，該無機-有機複合體樹脂係由 下述所構成：具有碳數1以上12以下之烷基、芳基、羧基、 羥基、及選自於由該等之組合所構成之群之有機基的烷氧 矽烷、具有環氧基之烷氧矽烷、具有胺基之烷氧矽烷、四 烷氧矽烷、及選自於由該等之組合所構成之群之烷氧矽烷 的縮合物。此處，烷氧矽烷的縮合物係指將作為原料使用 之烧氧碎烧水解，於生成水解物後，以形成皮膜時之乾燥 燒附（熱處理）步驟縮合而生成者。如此，構成表面皮膜之基 質的材料係於以矽作為主成分之無機系樹脂中摻合有機 物，故表面之皮膜係除了對光觸媒之優異的穩定性、耐候 性，亦為加工性優異之皮膜。 此處，碳數1以上12以下之烷基，可舉例如：甲基、乙 基、丙基、丁基、己基、2-乙基己基、十二基等，芳基可 舉例如：苯基、甲苯基、二曱苯基、萘基等。又，羧基係 指-COOH、胺基係指-NH2、羥基係指-OH。其中，特別適 合作為本發明之有機基使用的是，曱基、或苯基。又，本 發明中使用之有機成分亦可同時使用2種以上者。 本發明之表面處理預塗金屬板係於其表面具有至少2 17 201104016 層之包含光觸媒的皮膜（此處，稱作「光觸媒皮膜」）。這是 為了長時間維持因光觸媒產生之耐污染性、或自淨化效 果。習知光觸媒皮膜，於因光觸媒皮膜之劣化、或粉化使 基材之未具有光觸媒機能的有機樹脂被覆層露出的階段 中，自淨化性會顯著地急速下降。相對於此，本發明之預 塗金屬板中因形成至少2層之光觸媒皮膜，且該兩者中含有 光觸媒，故可長期地持續因光觸媒產生之自淨化性。 又，藉使至少2層之光觸媒皮膜越靠近基材預塗金屬板 之内層側的皮膜之光觸媒含有量越少，即使失去光觸媒含 有量多之外側的光觸媒皮膜，雖無法持續如初期狀態般之 顯著效果，但經長時間仍可得必要充分之自淨化性。如此， 本發明之多層構造的光觸媒皮膜亦可抑制光觸媒皮膜層本 體之劣化，故可得經長時間仍未受污染的預塗金屬板。 本發明中使用之具有光觸媒活性的物質之代表例係光 觸媒粒子，但於本發明之預塗金屬板中，不僅是粒子，亦 可包含使用將無法稱作粒子之溶膠狀物質、金屬錯合物加 熱後生成之物質。 2層以上之皮膜中所包含之光觸媒含有量於最外層皮 膜為最多，越接近内層皮膜越少。這是為了藉由取得光觸 媒效果之維持與皮膜之損耗的均衡，而使其長期地顯現耐 污染性、自淨化性。 光觸媒以包含銳鈦礦型構造之氧化鈦為有名，亦為最 適合作為本發明之光觸媒使用者。然而，本發明之光觸媒 並未限定為銳鈦礦型之氧化鈦，亦可適當地使用其他光觸 18 201104016 媒’例如：Ti〇3、SrTi03、FeTi03、W03、Sn02、Bi2〇3、 ln203、ZnO、Fe2〇3、ru〇2、Cd〇、CdFe〇3、LaRh〇3、她2〇5 Zr〇2、Ta2〇5等’可依據所需之性能等適當地選擇。 又，大部分的情況下，以使用光觸媒粒子作為光觸媒 係為一般’但本發明中使用之光觸媒粒子的性狀並未特別 受到限定。然而’為得到高觸媒活性，以盡量使用細的粒 子為佳。光觸媒粒子大小以初級粒子直徑為0.5μιη以下為 佳，較佳者是0·1帅以下，更佳者為0·05μπι以下。粒子尺寸 之下限並未特別受到限定，但因過細將不易處理，故通常 以使用初級粒子直徑為5nm以上者為佳。 田使用粒子徑細且活性高之粒子作為觸媒時，可得優 異之觸媒效果’即污染物質之去除效果，但通常因同時保 持光觸媒之皮膜基質部劣化，故經長時間將無法顯現耐污 木I·生自淨化性°本發明中使用之皮膜基質部因大幅地抑 因光觸媒粒子產生之劣化故可特別無障礙地使用粒子 ‘細且活性冋之光觸媒粒子。又’於使用微細之光觸媒粒 子時ϋ散困難’可知皮膜中有形成凝集體之可能性。 然而’通常’該等凝集體之間隙中，不存在構成皮膜之樹 脂成分的情形多’故亦可知有污染物質容易到達觸媒表面 的優點。 皮膜中之光觸媒物質以均一地分散為佳，但旅不一定 需要追求完全之均1、均質性。例如，如上所述，可舉 例如’形成有凝集體的情形、粒子之含有度於最表面部與 内部相異的情形、 或於含有濃度中具傾斜的情形等，該等 201104016 狀態下亦可適當地使用。 皮膜中含有之光觸媒的量，並未特別受到限定而可於 可得所期之效果的範圍内適當地決定。此時，為不損及皮 膜之均一性、平滑性等，通常，係相對於皮膜全體之質量 比例為50%以下，以40%以下為佳，較佳者是30%以下。添 加量之下限並未特別受到限定，通常係相對於皮膜全體之 質量比例為0.1%以上，以0.5%以上為佳。當添加量超過前 述範圍過多時，如上述，不僅不易成為均一且平滑之皮膜， 亦不符合經濟。又，當添加量較前述範圍過少時，未能得 到所期之效果的情形較多。 本發明中使用之至少2層的光觸媒皮膜中所含之光觸 媒量，於最表層皮膜為最多，越靠近内層皮膜越少。結果， 於最表層皮膜劣化、產生粉化後消失，第2層之皮膜露出 時，雖然較依之前的最表層所得之自淨化性略不佳，但可 期待持續之耐污染效果，至基材之預塗金屬板表面露出的 長時間中，可得到優異之耐污染性、自淨化效果。又，因 可階段性地減少光觸媒含有量，故可抑制越内層側之皮膜 皮膜的劣化，可顯著地長時間維持優異之自淨化性。 使光觸媒之含有量變化的皮膜中光觸媒之量並未特別 受到限定，可適當地於前述之光觸媒量的範圍内決定。例 如，於形成2層皮膜時，表層皮膜與内層皮膜之光觸媒量的 組合，可設定為相對於各皮膜全體之質量比例為 50%/20%、35%/10%或20%/5%等。又，於3層皮膜時，表層 皮膜與中間皮膜與最内層皮膜之光觸媒料的組合，可設定 20 201104016 為相對於各皮膜全體之質量比例為50%/30%/io%、 3 5 %/20%/1 〇% 或 20%/15 %/1 % 等。 以將最内層側皮膜中之光觸媒的含有量設為相對於最 内層側皮膜全體之質量比例為〇 〇5%〜3〇%為佳。最内層皮 膜因與以形成於基材預塗金屬板表面之聚酯、胺曱酸乙 =、丙烯酸、環氧等有機樹脂為主成分的皮膜相接，故以 3有所的以上之光觸媒為佳。最内層側皮膜中之光觸媒量 以相對於最内層側皮膜全體之質量比例為0.05%〜25。/。為 佳，較佳者是0_05%〜2〇%，更佳者為〇 ι% 〜15%。 二有光觸媒活性之物，貞„其原本之㈣存在於皮膜 中’亦可使用’㈣可於承載於紐表面之狀態下使用。 藉使用載體’可減少光觸媒與構成皮膜之基質的直接接觸 舍，、可抑制因光觸媒所造成之皮膜的損耗、劣化。又， ^ :政困難之塗料(樹脂)與光觸媒粒子的組合時，藉由選 皮：：：材質作為載體，更可得光觸媒之分散狀態優異的 特別以*體巾係使用對光觸媒穩定之無機系的氧化物， 氧化料騎。减f鎮、氧化錯、氧化鐵、 声以上:Γ使用之光觸媒皮膜的厚度，可分別獨立地於2 如每^ 定。依_需之魏或用料有不同， 為佳，較佳者是 之膜厚時下。此外，於嚴格限制製品預塗金屬板 過該等範圍而為薄時U 為佳°當皮膜厚度超 ’' :形成均一之皮膜後顯現預定之特 21 201104016 性是困難的’另—方面’當皮膜超過前述範圍而過厚時， 無法付到作為預塗金屬板所需之成形加工性 、或有成形加 工時之皮膜密著性不充分的可能性。 本發明之預塗金屬板表面的光觸媒皮膜具有含有無機 系之平板狀粒子的特徵。添加該物f之效果與優祕如前述。 平板狀粒子之形態以平面方向之平均粒子徑除以厚度 之平均值所得的值為5以上為佳’較佳者是30以上，更佳者 為60以上。又，含有粒子之大小只要不過大的話係可使用， 考量到光觸媒皮膜之厚纟，平Φ方向之粒子徑 以120μπι以 下為佳，較佳者是60^m以下，更佳者為30μηι以下。藉將前 述之平板狀粒子層狀地制於歧巾，可麵密著性，產 生紫外光遮蔽效果，並抑制誠時等產生之錢，或藉由 防止水之渗透而確保财姓性。 〜处厂/丨伯 丁田乃问之干岣粒子徑」，係由平板面之 ，積（係指粒子之投影面積為最大時該投影面上的面積)換 算成圓等效直徑之值的平均值，可藉“電子鏡觀察 平薄板形狀之粒子而求得。另—方面’「厚度之平均值」係 指平板狀粒子之厚度（與粒子之投影面積為最大時之投影 面垂直方向上的最大粒子尺寸)的平均值，同樣地可藉由以 電子顯微鏡觀察而求得。於追求「平㈣向之平均粒子户」 與「厚度的平均值」時，以盡量觀察多數粒子為佳，但依 據發明人4之檢討，可知觀察職左以 f察多錄子之結果大軸同。換言之，财法中^ 察5〇個粒子之結果，可代表「平面方向之平均粒子徑」與 22 201104016 「厚度的平均值」。 前述之平板狀粒子以相對於皮膜之質量比例來看，以 含有0.05〜30%之範圍為佳，較佳者是0.05〜25%之範圍， 更佳者為0.1〜20%之範圍。當含有量超過前述範圍為少 時，無法確保充分之密著性，又，無法抑制皮膜形成時之 劣縫，有無法得到充分之耐蝕性的效果。相反地，當超過 前述範圍過多時，因皮膜中之添加物粒子過多，故無法得 到良好外觀之皮膜，或者密著性或硬度、強度等皮膜特性 亦不充分。 添加之平板狀粒子以選自於黏土礦物、石墨及石墨化 碳黑中之任一者為佳，特別以選自於黏土礦物來使用為 佳。添加之粒子可為一種，亦可組合添加二種以上之粒子。 此處，黏土礦物係指層狀矽酸鹽礦物全體，眾所周知的有： 高嶺土、雲母、葉蠟石、綠土、蛭石、水滑石類等。其中， 本發明之平板狀粒子特別以使用雲母為佳。雲母係具有 XYn(Si,Al)4O10(OH，F)2(式中之X=K、Ca、Na 等，Y=Mg、 A卜Li、Fe、Μη、Ti等，n=2〜3)之化學組成的層狀鋁矽酸 鹽，眾所周知的有：白雲母、黑雲母、金雲母等。 本發明之皮膜中作為無機-有機複合體樹脂之金屬成 分係包含有Si，但仍可添加選自於B、Al、Ge、Ti、Y、Zr、 Nb、Ta等一種以上之金屬元素作為其以外之元素。其中， Al、Ti、Nb、Ta係顯示於添力口完作為觸媒之酸後，用以使 皮膜之固化於低溫或短時間内完成之觸媒性作用者。將酸 作為觸媒添加至該等金屬烷氧化物後，環氧之開環速度變 23 201104016 快，而可以低溫短時間進行皮膜硬化。特別經常使用的是 Ti，Ti-乙氧化物' Ti_異丙氧化物等Ti之烷氧化物則作為原 料使用。又，添力〇有Zr之系中，為顯著地改善皮膜之而驗 性，故特別地以用於需耐鹼性方面為佳。 成為本發明之預塗金屬板之基材的預塗金屬板，可不 分材質使用任何適合者。可使用例如：鋼材、不錄鋼、鈦、 鋁、鋁合金 '或使用於該等進行電鍍處理再進行有機樹脂 被覆者。其中特佳之預塗金屬板，可舉例如：不鏽鋼板、 欽板、绍板、紐合金板、或於該等經進行電鍵處理之電鍛 金屬板表面形成有有機塗膜者。電鍍鋼板’可舉例如：鋅 電鍵鋼板、鋅-鋏合金電鍵鋼板、鋅-鎮合金電鍍鋼板、鋅_ 鉻合金電鍍鋼板、鋅-鋁合金電鍍鋼板、鋁電鍍鋼板、鋅-雀呂-鎮合金電鑛鋼板、辞銘_鎮夕合金電鑛鋼板、紹-碎合金 電鍍鋼板、鋅電鍍不鏽鋼板、鋁電鍍不鏽鋼板等。不鏽鋼 板，可舉例如：肥粒鐵系不鏽鋼板、麻田散鐵系不鏽鋼板、 沃斯田鐵系不鏽鋼板等。不鑛鋼板之厚度’可舉例如：由 厚如l〇mm左右者至藉壓延變薄至左右之不鏽鋼箔。 不鏽鋼板及不鏽鋼箔之表面亦可施行輝面退火、擦光等表 面處理。鋁合金板，可舉例如：JIS1000號系（純A1系）、 JIS2000號系（Al-Cu 系）、JIS3000號系（Al-Mn 系）、JIS4000號 系（Al-Si系）、JIS5000號系（Al-Mg系）、JIS6000號系（Al-Mg-Si 系）、JIS7000號系（Al-Zn系）等。 適合用以製造本發明之預塗金屬板的處理液係含有無 機-有機複合樹脂原料、具有光觸媒活性之物質、及無機系 24 201104016 平板狀粒子所構成之液，前述無機-有機複合樹脂原料包含 有：具有碳數1以上12以下之烷基、芳基、羧基、羥基、及 選自於由該等之組合所構成之群之有機基的烷氧矽烷、具 有環氧基之烷氧矽烷、具有胺基之烷氧矽烷、四烷氧矽烷、 及選自於由該等之組合所構成之群之烷氧矽烷(al);該烷 氧矽烷（al)之水解物（a2);及/或該烷氧矽烷(al)之縮合物 (a3)。 具有碳數1〜12之烷基的烷氧矽烷，可舉例如：甲基三 曱氧基矽烷、二曱基二曱氧基矽烷、甲基三乙氧基矽烷、 二甲基二乙氧基矽烷、己基三甲氧基矽烷、己基三乙氧基 矽烷、癸基三甲氧基矽烷、癸基三乙氧基矽烷等。具有芳 基之烷氧矽烷，可舉例如：苯基三甲氧基矽碎、二苯基二 甲氧基矽烷、苯基三乙氧基矽烷、二苯基二乙氧基矽烷等。 具有環氧基之烷氧矽烷，可較佳地使用：γ-環氧丙氧 基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基三丙氧基矽烷、γ-環氧丙氧基丙基三丁氧 基矽烷、3,4-環氧環己基曱基三曱氧基矽烷、3,4-環氧環己 基曱基三乙氧基矽烷、β-(3,4-環氧環己基）乙基三曱氧基矽 烷、β-(3,4-環氧環己基）乙基三乙氧基矽烷等，由處理容易、 反應性等方面來看，特別以使用γ-環氧丙氧基丙基三乙氧 基矽烷為佳。 具有胺基之烧氧石夕院，可較佳地使用：胺基丙基三曱 氧基石夕炫>、胺基丙基三乙氧基石夕烧、（β-胺基乙基)-β-胺基 丙基三曱氧基矽烷、（β-胺基乙基)-β-胺基丙基甲基二甲氧 25 201104016 基石夕烧、（β-胺基乙基)个胺基^三甲氧基 由處理容易等方面來看，特別以使用胺基内基其中， 院為佳。又，四燒氧石夕烷，可舉例如：四甲^乙氧基石夕 乙氧基石夕烧、四丙氧基錢、四丁氧基石夕境^基砂燒 '四 摻合具有環氧基之炫氧外'具有胺基以 優點，係可㈣光觸媒相與作為基材之⑼^砂烧的 著性、及對光卿皮獻_制就性板的密 詳細說明，但推測储由添加環氧基或胺基，=由雖無法 膜與基材健金屬板表面之有機職層之卩切，觸媒皮 合，而提升密著性，結果，不易產生皮膜之=堅固地結 而提升皮膜之穩定性。 々或制離’ 本發明處理液中含有具有光觸媒活性之物 前述重複’但本發”姻之具有光職^ > °雖又與 受到限定，亦可包含使用始至前述光__=未特別 粒子的溶膠狀物質、如金屬錯合物之物質。* =無法稱作 物質係指於處理液巾藉由金狀氧化物之^洛膠狀 出物、或經分散、穩定化於水或有機溶劑中 成的析 之極細微的膠 體。其中，本發明之光觸媒特別以使用銳鈦礦型之氧化鈦 粒子為佳。光觸媒粒子之性狀亦非特別受到限定者，但為 得高觸媒活性以盡量使用粒徑小的粒子為佳。光觸媒粒子 之大小以0·5μηι以下，較佳者是〇.igm以下，更佳者為 〇.〇5μΐπ以下。粒子尺寸的下限並未特別受到限定，但因過 細將不易處理，故通常係使用初級粒子直徑為5nm以上者。 處理液中所含之光觸媒物質的量並未特別受到限定， 26 201104016 可適當地於形成皮膜後可得所期之效果的範圍内決定 時，為了不損及形成皮膜後之均一性、平滑性等，、欠。此 除了用以形成最内層側之皮膜的處理液以外，私* 液中之不揮發分全體之質量比例，光觸媒物I理 以下，以慨以下為佳，更佳者是遍以下。添力^係50% 並未特別$5，丨限定，通常相對包含於處理液之㈣八下限 量比例’光觸媒物質的量係0·5%以上，以1Q%二的質 光觸媒物質之量，於用以形成最内層側之皮膜的佳。 液時’相對於處理液巾之不揮發分全制質f比例t處理 以下，以聰以下為佳，更佳者㈣以下。添加量f5% 並未特別受到限定，通常相對包含於處理液之固^下限 量比例係0.05%以上。 /刀的質 2加量超過前述範圍過多時，雖於處理液 異吊的情況，但不僅不总 會有 需要量以上之觸媒，故亦不符合《。又，當添加 述範圍過少時，未能得到所期之效果的情形較多車父則 粒子目之^理液中含有無機系之平板狀粒子。平板狀 中選擇料心， 由黏土礦物、石墨及石墨化碳黑 為特仙選自於黏土礦物來使用為佳。添加之 粒子可為—種，亦可組合添加二種以上之粒子。此處，黏 土礦物係指’層狀錢鹽礦物全體，輯周知的有：高旗 土、雲母、葉織石、綠土、虫至石、水滑石類等。其中，本 發明之平板狀粒子特別以使用雲母為佳。、 乂平板狀粒子以相對於處理液中之不揮發分全體的質 27 201104016 量比例於0.05〜30%之範圍内含有為佳，較佳者是〇〇5〜 ，更佳者為(^〜汕％之範圍。當含有量超過前述範圍 為少時，無法確保作為本發明之預塗金屬板表面之皮膜充 分的密著性，x，產生未能得到充分之耐純效果、無法 抑制皮膜形成時之裂縫等不良情形。相反地，當超過前述 軏圍過多時，因皮膜中之平板狀粒子過多，故無法得到良 子卜觀之皮膜，或者社、著性或硬度、強度等皮膜特性亦不 充分。 本發明之處理液中，亦可視需要，將烷氧矽烷以外之 金屬成分的烷氧化物作為添加物使用。特別是，添加選自 於Τι A卜Ta、Nb之至少1種以上的金屬之烷氧化物，並使 用乙酸作為酸觸媒時’環氧基之開環速度變快，而特別增 大低溫短時間硬化之效果。烧氧魏以外之金狀氧化物 中亦可水解所有之烷氧基、或一部分。 本發明之處理液中，可視需要，含有锆之化合物，例 如.錐烷氧化物、其水解物、或氧化鍅(二氧化鍅)溶膠之至 夕1種。该成分係改善本發明之處理液的耐鹼化學腐蝕性之 成分。藉由添加本成分，雖未必清楚係以哪個機構改善耐 鹼性，但Zr取代構成矽氧烷鍵之Si的位置，且形成以二氧 化砂與錯作為h之·結構，可知雌具有安定化。又， 現需要，可添加除了氧化錯溶膠以外之無機粒子。 本發明之處理液中，以提升塗膜之設計性、耐蝕性、 耐摩耗性、觸媒機能等為目的，亦可添加著色顏料、體質 顏料、觸媒、防鏽顏料、金屬粉末、高頻損耗劑、骨材等。 28 201104016 著色顏料，可舉例如：Ti、Al等氧化物或複合氧化物、 A末Alh末等金屬粉末等。防鑛顏料，以使用使於不 a % i兄污染物質之銦酉㈣、伽酸辦、翻酸紹的鱗酸鹽、 辦孤ig鹽等非鉻酸顏料為佳。又，高頻損耗劑可舉2打韻 肥粒鐵為例，骨材可舉欽酸鉀纖㈣為例。 又本發明之處理液中，可視需要添加酸觸媒。酸觸 媒可舉例如·甲酸、順丁稀二酸、苯甲酸等有機酸、鹽 -文肖m機酸’但特別以乙酸為佳。藉使用酸作為觸 某矛、了作為原料使用之院氧石夕院呈適合製膜之聚合狀態 乂外於使用乙酸作為觸媒時，將促進環氧基之開環，增 大低溫短時間硬化之效果。 又，本發明之處理液中，可混合使用作為添加劑之均 染效果劑、抗氧化劑、紫外線吸收劑、穩㈣、可塑劑、 躐、添加型紫外線穩定料。又，可㈣要，亦可於不損 及皮膜之_性#_ '或不產生光觸媒所造成之劣化的 !:包含氧樹脂、聚醋樹脂、胺甲酸㈣脂軸 該4添加劑可僅使用1種，亦可適當地混合2種以上使用。 本發明之處理液係藉於可使對象物質適當地分散一 解的有機溶射，添加具有碳數⑴上^以下之院義2 基、幾基、經基、及選自於由該 凡土、方 機基㈣氧傾、具有《叙妓群之有201104016 VI. Description of the invention: I: Technical field of the invention of the invention 3 Field of the invention The present invention relates to a precoated metal sheet having an organic resin coating layer as a substrate (hereinafter, referred to as "substrate precoated metal sheet" The surface of the film) has at least two layers of a precoated metal sheet which exhibits photocatalytic activity and is excellent in stain resistance, a method for producing the same, and a surface treatment liquid which can preferably produce a precoated metal sheet. More specifically, the present invention relates to a precoated metal sheet which has at least two or more layers of a film on its surface, which is photocatalyticly active over a long period of time, and which is weather resistant or densely coated. When the film is excellent, the film contains a photocatalytic activity, an inorganic-organic composite resin which is less deteriorated by a photocatalyst, and an inorganic plate-like particle which improves adhesion. Further, the present invention relates to a surface treatment liquid for preferably producing the precoated metal sheet. L. Prior Art 3 In general, a metal material represented by iron is used for the purpose of improving durability or for obtaining a beautiful appearance, and the coated metal plate is widely used in home appliances, Automobiles, building materials, and structures outside the house. Among them, especially in the use outside the house, due to exposure to wind, rain, sand, etc., in addition to corrosion resistance, it is also required to be excellent in pollution resistance. Photocatalyst technology is a technique for hydrophilizing a surface by photocatalytic activity of photocatalyst particles, and a technique for decomposing and removing organic matter-centered contaminants, which is applied to a precoated metal sheet, and the photocatalyst is excellent in activity. The film is dispersed and contained in order to expect contamination resistance or self-cleaning effect. In this technique, an excellent effect can be obtained by decomposing and removing a contaminant on the surface. However, when the photocatalyst particles are dispersed in an organic resin-based coating film or a photocatalyst film is formed on the surface of the organic resin-based coating film, The photocatalytic effect organic resin coating film is gradually decomposed and deteriorated, so it is difficult to use it for a long period of time. As a corresponding method, a technique for suppressing deterioration of a coating film has been proposed. For example, Patent Document 1 and Patent Document 2 disclose a method of using an inorganic component as a resin constituting a film. Further, in the organic resin, since the fluororesin is relatively stable to the photocatalyst, it is used as a film component (Patent Document 3). Further, Patent Document 4 and Patent Document 5 disclose that, in particular, for the use of a precoated metal sheet, high stability and workability to a photocatalyst are required, but for this purpose, cerium oxide-organic is used. A method of using a decane-based resin as a film component, and a method of using a alkyl phthalate obtained by polymerization of an acrylic resin and an organic alkoxysilane as a film component. Further, Patent Document 6 discloses a method of using a vinylidene fluoride resin and an acrylic resin. The inventors have also proposed a film resin component which can highly satisfy the high stability of a photocatalyst which can be used with respect to a precoated metal sheet having an organic resin coating film, that is, excellent economical properties and workability. (Patent Documents 7 to 9) Further, a protective layer containing no photocatalyst substance is interposed between the coating layer containing the photocatalyst substance and the organic resin coating layer layer of the lower layer to prevent the organic resin coating film Deterioration. CITATION LIST Patent Literature Patent Literature No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 5: JP-A-2000-317393, JP-A-2006-192733, JP-A-2006-192716, JP-A-2006-192716 In the review of the inventors, the film having photocatalytic activity (hereinafter, "photocatalyst film") will be caused by the inventors' review. The photocatalytic action degrades the film and causes chalking, so it is gradually lost. As a result, it was found that when the photocatalyst film on the surface disappeared, the photocatalytic function was lost, and the pollution and self-purification performance were remarkably lowered. The "post-coat" method as a method of forming a photocatalyst film has hitherto been the mainstream. Therefore, in the case of processing a metal material into the shape of a final product, or as a building material or an exterior structure, a method of forming a photocatalyst film during on-site construction is generally employed. In this method, after the shape of the final product is formed, the film is applied, or the coating is applied as a construction item on site, so that it is not necessary to limit the thickness of the resin constituting the film or the coating, and the film can be formed in accordance with the required properties. . However, it is difficult to form a pre-coated metal sheet which is shipped to the user after pre-coating, that is, after the surface coating is carried out, from the viewpoint of workability limitation or cost. The film of the thickness is preferably a precoated metal sheet which can maintain the stain resistance and self-cleaning property over a long period of time. Further, depending on the material of the organic resin coating layer (base coating layer) on the surface of the precoated metal sheet, the type or amount of the material having photocatalytic activity, the adhesion between the photocatalytic film and the underlying coating layer is not good, and the adhesiveness is not obtained. Fully self-cleaning performance. In particular, there is a problem that the adhesion in the bent portion is poor and the self-cleaning property is not sufficiently obtained over a long period of time. In order to solve this problem, the present invention provides a precoated metal sheet which can maintain the stain resistance due to the photocatalyst and the self-cleaning function for a long period of time in a state where the thickness of the film or the like is limited. Further, it is an object of the invention to provide a method and a surface treatment liquid for preferably producing the aforementioned precoated metal sheet. In order to solve the problem, the inventors have made a review of the above-mentioned problems, and as a result, it has been found that a precoated metal plate having a resin coating layer is used as a substrate, and the surface of the metal plate is precoated on the substrate. The pre-coated metal sheet having at least two layers of a film can solve the problem, and the present invention is completed, and the film is made of an inorganic-organic composite resin in which a photocatalytic activity substance and an inorganic plate-like particle are blended. In detail, the precoated metal sheet of the present invention is an organic resin coating film for protecting the lower layer of the photocatalyst film, and a photocatalyst is also added to the conventional protective layer provided between the photocatalyst film and the organic resin coating film, and Light 201104016 Precoated metal plate with inorganic flat particles added to the catalyst film. By adding a photocatalyst to the conventional (four) layer provided between the photocatalyst film and the organic resin coating film, the function as a protective layer for protecting the organic resin can be maintained, and the photocatalyst film layer of the upper layer can be lost or disappeared. It is added to the light of the shinning layer _ to play a stain-resistant, self-cleaning function. By adding inorganic plate-like particles to the photocatalyst film, the adhesion between the photocatalytic film layer and the organic resin coating film is good, and the film having an ultraviolet shielding effect is formed on the surface. Specifically, the gist of the present invention is as follows. ^ () a pre-coated metal sheet, which is formed on a base metal sheet and a substrate precoated metal sheet having a machine layer of a sapphire layer on the surface thereof to form at least two layers of photocatalyst-active film, characterized in that The film having at least two layers of photocatalytic activity contains an inorganic/organic composite resin, a photocatalytic activity, and inorganic plate-like particles, and the inorganic/organic composite resin is selected from the group consisting of The condensate of the alkoxy oxane has an organic ruthenium (IV) having a group selected from the group consisting of an alkyl group having 1 to 12 or less carbon atoms, an aryl group, a minus group, a trans group, and the like, and having an epoxy group. The content of the material of the calcined oxygen, the silky 6 oxa, the four recorded (four), and the δ and the photocatalytic activity thereof is the most in the outermost layer, the inner layer The less the side of the film. (2) The precoated metal sheet according to the above (1), which comprises an organic group-based methyl group or a phenyl group of the inorganic-organic composite resin. (3) The precoated metal sheet according to (1) or (2) above, wherein the content of the photocatalytic activity in each layer of the film is from 0,1% to 50% of the total mass of each layer. 201104016 (4) The pre-coated metal sheet of any of the above-mentioned (1) (3), wherein the content of the photocatalyst substance in the innermost side film which is in contact with the organic resin coating layer is the total mass of the film. .〇5%~25%. (5) The precoated metal sheet according to any one of (1) to (4) above, wherein the material having photocatalytic activity is titanium oxide containing anatase scale. (6) A precoated gold-plated plate according to any one of (1) to (5), wherein the content of the inorganic tabular particles in each layer of the film is 0.05% to 30% of the total mass of the film. (7) A precoated metal sheet according to any one of (1) to (6), wherein the inorganic plate-like particles comprise mica. (8) The precoated metal sheet according to any one of (1) to (7) above, wherein the base metal sheet is selected from the group consisting of a steel sheet, a stainless steel sheet, a titanium plate, a titanium alloy plate, an aluminum plate, an aluminum alloy plate, or The metal plates are plated and plated with metal plates. (9) A surface treatment liquid comprising an inorganic-organic composite material, a material having photocatalytic activity, and inorganic plate-like particles, wherein the inorganic-organic composite resin material comprises: having a carbon number An alkoxylated group having an organic group selected from the group consisting of a group of 12 or more and 12 or less, an aryl group, a carboxyl group, a hydroxyl group, and a combination thereof, and an alkoxy group having an epoxy group An alkoxy decane (al) selected from the group consisting of a combination of a oxy-brom, a sulphur, and the like; a hydrolyzate (a2) of the alkoxy oxane (al), and/or a condensate of the alkoxydecane (al) (a3). (1) a method for producing a precoated metal sheet, comprising: (a) a step of preparing a metal layer on a metal layer and a substrate having a resin coating layer on the surface thereof; (b) a step 201104016 1 surface treatment liquid as the surface treatment liquid of the above (9) is applied to the substrate precoated metal sheet to form an unhardened first surface coating layer; (C) by heating, a step of forming the first surface coating layer by curing the first hardened first surface coating layer; (d) applying a second surface treatment liquid as the surface treatment liquid of the above (9) to the second surface treatment film, and a step of forming an uncured second surface coating layer; and (2) a step of curing the uncured second surface coating layer by heating to form a second surface coating film on the second surface coating film. (11) A method of producing a precoated metal sheet, comprising: (a) a step of preparing a metal layer and a substrate precoated with a metal resin layer on the surface thereof; (b) The first surface treatment liquid of the surface treatment liquid according to the above (9) is used for the substrate precoated metal sheet to form an uncured first surface coating layer; (c) the surface treatment liquid as the above (9) The second surface treatment liquid is used on the uncured surface coating layer to form an uncured second surface coating layer; and (4) the first unhardened portion is heated by heating! The surface coating layer and the uncured second surface coating layer are hardened to form a first surface film and a second surface film. EFFECTS OF THE INVENTION According to the present invention, it is possible to easily obtain a precoated metal sheet which can maintain and sustain the resistance/defective property due to the catalyst and self-cleaning function for a long period of time. Further, the pre-coated metal sheet described in the above paragraph can be suitably produced by using the production method and the surface treatment liquid of the present invention. [Embodiment of the invention] The precoated metal sheet excellent in the stain resistance of the present invention is applied to the coated surface of a precoated metal sheet which is applied to the surface of the metal sheet 201104016 by an organic resin coating. There are at least 2 layers of precoated metal sheets that enhance the coating resistance of the coating film. Each layer of the reinforced coating film contains a predetermined inorganic-organic composite resin, a material having photocatalytic activity, and inorganic plate-like particles. The appearance of the stain resistance by the application of the coating film is a substance (photocatalyst substance) derived from the photocatalytic activity which decomposes the surface pollutants and removes the excellent effect of the coating. The inorganic flat plate particles contained in each layer of the reinforced coating film contribute to the adhesion of the base organic resin coating layer to the film and the corrosion resistance of the precoated metal sheet, and also contribute to the shielding effect by ultraviolet light. The protection of the base organic resin coating layer and the deterioration of the film due to the photocatalyst of the film itself. One of the features of the present invention will be described in which each layer of the coating film is reinforced with a photocatalytic substance. It has heretofore been known that a precoated metal sheet having a layer structure of a coating film layer which is resistant to contamination by a photocatalyst substance is provided on the surface to be coated of the precoated metal sheet. In the conventional precoated metal sheet, the film layer containing the photocatalyst material is in contact with the organic resin material and the coating layer of the substrate precoated metal sheet which is generally formed, and the precoating of the substrate is performed by the photocatalytic effect of the photocatalyst material. The coating layer of the metal plate is gradually decomposed and deteriorated, so it is difficult to use it for a long period of time. In particular, in the case of contamination such as sealing contamination, which is not decomposed by the photocatalyst, it is necessary to add a large amount of photocatalyst in order to exhibit an excellent effect, and the coating layer on the surface of the substrate precoated metal sheet is deteriorated remarkably, and the photocatalyst layer itself is remarkable. The loss is also a fast condition. In order to avoid this disadvantage, conventionally, a protective layer containing no photocatalyst substance was interposed between the coating layer 1010404016 containing the photocatalyst substance and the organic resin coating layer layer of the lower layer. In this case, it is common for the photocatalyst layer and the protective layer to maintain the photocatalyst resistance, and the inorganic component is mainly used. However, the film having the inorganic component as the main component is inferior in workability, so that it is difficult to form a certain thickness or more. Therefore, in this method, it is necessary to thin the photocatalyst layer to the thickness of the protective layer film, and it is disadvantageous in that the stain resistance and the self-cleaning property are shortened. In the protective layer used for the purpose of avoiding direct contact between the film layer containing the photocatalyst substance and the lower organic resin coating layer, a photocatalyst having a smaller photocatalytic substance content than the upper layer is added, thereby comparing (1) In the case where the layer containing the photocatalyst substance (photocatalyst layer) is directly provided on the organic resin coating layer, and (2) the organic resin coating layer is sequentially provided not included. The protective layer of the photocatalyst substance and the layer containing the photocatalyst substance are successfully formed to be excellent in maintaining the pre-coated metal sheet and being polluting (for example, the duration of the contamination resistance effect of Example 7 and Comparative Example 1) They are about 40 years and about 32 years respectively (refer to "Self-purification duration" in Table 3). Thus, the present invention is aimed at avoiding the effect of the photocatalytic effect of the conventional film layer containing the photocatalyst substance on the underlying organic resin-based coating layer, and is based on the following unique knowledge that has not been seen so far. The film layer containing the photocatalyst substance is in direct contact with the organic resin coating layer, and the photocatalyst substance is added by the protective layer which does not contain the photocatalyst substance, and the duration of the pollution effect can be extended. The pre-coated metal sheet which is shipped in the state of being coated and which is formed by the user without painting is limited by the processing point of view, and the coating film thickness of the whole is limited by 11 201104016. According to the present invention, which can extend the duration of the antifouling effect as compared with the prior art, it is possible to provide a precoated metal sheet which is more excellent in the stain resistance effect within the limitation of such a coating film thickness. In the precoated metal sheet according to the present invention, the reason for providing a photocatalytic substance-containing layer of at least two layers to prolong the effect of contamination can be as follows. Heretofore, a coating film structure represented by a precoated metal sheet which exhibits a stain resistance function due to a photocatalytic effect is known, and as described above, (1) directly provided on an organic resin coating layer of a substrate precoated metal sheet The photocatalyst layer is provided, and (2) a protective layer containing no photocatalyst substance is provided between the organic resin coating layer of the substrate precoated metal sheet and the photocatalyst layer. In these cases, the photocatalyst layer is degraded by the photocatalytic action of the photocatalyst layer, and the photocatalyst layer is depleted to the disappearance period A, and the surface of the organic resin coating film of the substrate precoated with the photocatalyst layer is photocatalyzed by the photocatalyst effect. To the period B of deterioration. (1) an organic resin coating layer in which a photocatalyst layer directly contacts a substrate (here, a precoated metal plate composed of a base metal plate and an organic resin coating layer formed on the surface thereof), generally, The period B1 in which the surface of the organic resin coating film is deteriorated by the photocatalytic effect is shorter than the period A1 in which the deteriorated photocatalyst layer is lost to disappear, that is, in the relationship of A1 > B1. (2) Since the organic resin coating layer is protected by the protective layer, the surface of the organic resin coating film is greatly elongated due to the period from the photocatalytic effect to the deterioration of the photocatalyst layer which is deteriorated to the disappearance period A2, that is, A2« The relationship between B2. Therefore, the staining resistance by the photocatalyst and the duration of the self-purification function are governed by B1 in the case of (1) and by A2 in the case of (2). On the other hand, in the present invention, since the photocatalyst is added to the conventional protective layer film, the photocatalyst layer which is degraded by the amount of photocatalyst or the deterioration of the film is depleted to the surface of the organic tree film due to loss. (4) In other words, compared with (4) which is provided with the same degree of organic resin, according to the invention, the above-mentioned (1) or (7) can be used for the longest time to achieve the pollution resistance and self-purification effect due to the photocatalytic effect. Excellent results can be obtained in precoated metal sheets which are limited by the thickness of the coating film. Here, in the case of the above-mentioned conventional (1), by increasing the concentration of the photocatalyst in the vicinity of the surface of the photocatalyst layer and lowering the concentration of the photocatalyst in the vicinity of the organic resin-based coating layer, that is, forming the inclined composition coating layer, The effects of the present invention are the same. However, in a coating film, it is extremely difficult to control the concentration of the photocatalyst in the thickness direction. According to the precoated metal sheet of the present invention, since the amount of photocatalyst added can be changed in each of the two or more layers, the duration of non-contamination and self-cleaning functions can be easily set. In addition, by adding a photocatalyst to the conventional protective layer, the following effects can also be expected. The photocatalyst layer of the uppermost layer is gradually lost due to the photocatalytic effect, but it is not necessarily uniformly lost. After detailed observation, it is found that There are many areas where the film remains (less film loss) and the area where the film remains less (the film loss is large), and the surface is uneven in the thickness direction. In the conventional case where a protective layer is provided under the photocatalyst film, when the photocatalyst film is lost and the interface of the protective layer is exposed, since the protective layer does not have a self-cleaning effect, when a certain proportion of the protective layer is exposed, self-cleaning property Will drop significantly. In contrast to the present invention in which a photocatalyst is also added to the protective layer, since the protective layer can also have a self-cleaning function, the protective layer can also exhibit excellent self-cleaning properties after being exposed. Conventional surface treatment of the exchange of catalysts: pre-coated metal: two: the addition of light layer 夕 灿 能 _ 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨In the photo-catalyst, the photo-catalyst is added to the surface layer of Yuzhanhe, and the surface-treated pre-coated metal plate of Yuzhehe is applied to the light of the layer 3 (four) layer. When the sigh link is left, it is enough to get the metal board chess. The 曰 曰 gold ^^ 士 inlet also adds photocatalyst to the protective layer. Compared with the protective layer, the organic resin coating film is easily deteriorated. ' Bu, belongs to the board, === less added than the upper photocatalyst layer, due to the deterioration of the organic resin coating film caused by the first catalyst in the protective layer, when the photocatalyst is added to the small protective layer, the degraded light to the = g film Table _ Photocatalyst effect to the period of deterioration B = 'With A2 < The relationship of <B2 is based on the present invention, because the photocatalyst is added to the protective layer, and the influence on the short is small. Therefore, according to the present invention, it is understood that the effect of increasing the life of the self-purifying function is extremely large compared to the disadvantage of adding a photocatalyst to the protective layer. To summarize the above, according to the present invention, a photocatalyst is also added to the protective layer which is in contact with the organic resin coating film, and can be formed in all the period of the photocatalyst film formed on the base (four) coated metal plate, and is resistant to dirt and self-cleaning. Moreover, the effect described in (4) can be obtained after the tilting of the scale is revealed, so that it is known that the self-cleaning life can be prolonged. Next, in another feature of the present invention, the reinforced coating film (photocatalyst 14 201104016 film) contains an inorganic flat particle, and the light touches on the surface of the precoated metal plate of the present invention: skin: inorganic It is a tabular particle. One of the advantages of adding this particle is that it ensures excellent adhesion and financial age. The added particles are aligned in the shape of the board, and the surface of the pre-coated metal sheet of the aged skin can be aligned in parallel, and the organic resin coating layer on the surface of the pre-coated metal sheet of the substrate and the substrate can be lifted, or the photocatalyst is formed. The adhesion between the layers of the film. In particular, the adhesion of the bent portion of the largest course in the precoated metal sheet can be improved. When the particle is aligned in the film, the aspect ratio of the mechanism is large. Therefore, when the coating is applied by the dip coating method, the nozzle method, the bar coating method, the roll coating method, the spin coating method, or the curtain coating method described later, the particles are coated. It will be aligned with the metal surface in the 'layer. Thereafter, the film is dried and galvanized to form a ray, but the plate-like particles are maintained in a state of 2, and the alignment and the layered state are maintained after the film is finally formed. In addition, by using the particles in the shape of a flat plate in the film, it is possible to prevent the invading of the person's wire. For example, in general, the water system moves through the gap of the skin, and reaches the base = the metal surface, but the distance from the surface of the steel sheet to the surface of the steel sheet becomes longer by the surface of the sheet. The result is improved corrosion resistance. In addition, since the film layer on the inner layer side of the photocatalyst film is firmly adhered to the pre-coated metal plate of the substrate, the film may be left by the crack on the outer layer side of the film, and the film may be left by the photocatalyst skin. Since the precoated metal sheet of the present invention has a photocatalytic film on the surface of the metal sheet, the self-cleaning function can be exhibited on the surface of the metal sheet. The second advantage of adding the tabular particles is as described above. Film+, 15 201104016 Because the particles are aligned with the pre-coated metal plate surface of the substrate, there is a shielding effect of ultraviolet light. The light does not easily reach the film on the inner layer side, which not only effectively protects the organic resin on the surface of the precoated metal plate of the US material. The layer can also enhance the photocatalytic resistance of the photocatalyst film itself. On the surface of the photocatalyst film, a substance having a predetermined amount of photocatalytic activity is also present together with the plate-like particles, so that the self-purification function of the surface is not particularly affected. Further, since the tabular particles are inorganic particles, they are not deteriorated by the photocatalyst. In other words, the inorganic layer is added to the photocatalyst film. The particles do not reduce the self-purification performance, and can also be long-lived. In addition, another important advantage is that it can effectively inhibit cracks when drying and heating the photocatalyst skin. Generally, the use of photocatalyst film Although an inorganic resin is used in many cases, when the coating amount of the inorganic resin is too large, cracks are likely to occur. Therefore, 'in general, to avoid excessive coating, coating is performed several times to ensure a predetermined film. Thickness, etc. The present invention relates to a pre-coated metal sheet, so that no film is applied to a significant thickness, and there is an advantage that the coating step can be applied once without causing cracks to form a film of a desired thickness. Summarizing the above, by adding inorganic-type flat-shaped particles, the adhesion between the photocatalyst film and the pre-coated metal plate of the substrate and the layer constituting the photocatalyst film can be improved, in particular, the adhesion of the bent portion can be remarkably improved. Moreover, it is expected that the effect of shielding ultraviolet light by the characteristic shape of the flat plate can be expected to effectively prevent the crack generated when the film is formed. By these effects, the self-purifying effect due to the photocatalytic activity can be maintained for a long period of time. 201104016 As a result, for example, it can be seen that the self-cleaning duration shown in Comparative Example 1 is about 32 years, and Example 7 In the surface of the precoated metal sheet of the present invention, the film having a photocatalytic activity (hereinafter referred to as "photocatalyst") is less likely to cause cracking. Specifically, the surface film and the photocatalyst are most contained in the outermost film, and have a multilayer structure in which the outer layer film is less, and an inorganic-organic composite resin is contained, and the inorganic-organic composite resin is The alkylene group, the aryl group, the carboxyl group, the hydroxyl group having an alkyl group, an aryl group, a carboxyl group, a hydroxyl group, and an alkyl group selected from the group consisting of these combinations, and an alkoxy group having an epoxy group. A condensate of a decane, an alkoxy oxane having an amine group, a tetraalkoxy decane, and an alkoxy decane selected from the group consisting of the combinations. Here, the alkoxysilane condensate is produced by hydrolyzing the calcined oxygen used as a raw material, and is formed by condensation in a drying and baking (heat treatment) step after forming a hydrolyzate. In this way, since the material constituting the surface film is made of an inorganic resin containing ruthenium as a main component, the film on the surface is excellent in workability and excellent in stability and weather resistance to the photocatalyst. Here, the alkyl group having 1 or more and 12 or less carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a 2-ethylhexyl group or a dodecyl group, and the aryl group may, for example, be a phenyl group. , tolyl, diphenyl, naphthyl and the like. Further, the carboxyl group means -COOH, the amine group means -NH2, and the hydroxyl group means -OH. Among them, those which are particularly suitable for use in the organic group of the present invention are a mercapto group or a phenyl group. Further, the organic component used in the present invention may be used in combination of two or more kinds. The surface-treated precoated metal sheet of the present invention is a film containing a photocatalyst (herein referred to as "photocatalyst film") having at least 2 17 201104016 layers on its surface. This is to maintain the pollution resistance or self-cleaning effect caused by the photocatalyst for a long time. In the conventional photocatalytic film, the self-cleaning property is remarkably lowered in a stage where the photocatalytic film is deteriorated or pulverized to expose the organic resin coating layer having no photocatalytic function of the substrate. On the other hand, in the precoated metal sheet of the present invention, at least two layers of the photocatalyst film are formed, and both of them contain a photocatalyst, so that the self-cleaning property by the photocatalyst can be continued for a long period of time. In addition, the photocatalyst film having a photocatalyst film of at least two layers closer to the inner layer side of the substrate precoated metal plate has a smaller amount, and the photocatalyst film on the outer side of the photocatalyst is not able to continue as in the initial state. Significant effect, but sufficient self-purification can be obtained over a long period of time. Thus, the photocatalyst film of the multilayer structure of the present invention can also suppress the deterioration of the photocatalyst film layer body, so that a precoated metal plate which has not been contaminated for a long period of time can be obtained. Representative examples of the photocatalytic activity used in the present invention are photocatalyst particles, but in the precoated metal sheet of the present invention, not only particles but also sol-like substances and metal complexes which cannot be called particles are used. The substance formed after heating. The photocatalyst contained in the film of two or more layers is the most abundant in the outermost film, and the closer to the inner layer film, the less. This is to achieve a long-term resistance to contamination and self-cleaning by achieving a balance between the maintenance of the photocatalytic effect and the loss of the film. The photocatalyst is known as titanium oxide containing an anatase structure and is also most suitable as a photocatalyst user of the present invention. However, the photocatalyst of the present invention is not limited to anatase type titanium oxide, and other light contacts 18 201104016 medium can be suitably used, for example: Ti〇3, SrTi03, FeTi03, W03, Sn02, Bi2〇3, ln203, ZnO, Fe2〇3, ru〇2, Cd〇, CdFe〇3, LaRh〇3, her 2〇5 Zr〇2, Ta2〇5, etc. can be appropriately selected depending on the desired properties and the like. Further, in most cases, the photocatalyst particles are generally used as a photocatalyst. However, the properties of the photocatalyst particles used in the present invention are not particularly limited. However, in order to obtain high catalytic activity, it is preferred to use fine particles as much as possible. The size of the photocatalyst particles is preferably 0.5 μm or less in the primary particle diameter, preferably 0·1 or less, and more preferably 0·05 μm or less. The lower limit of the particle size is not particularly limited, but it is difficult to handle because it is too fine. Therefore, it is usually preferred to use a primary particle diameter of 5 nm or more. When a particle having a fine particle diameter and high activity is used as a catalyst, an excellent catalyst effect, that is, a removal effect of a contaminant, can be obtained. However, since the film matrix portion of the photocatalyst is simultaneously deteriorated, the resistance cannot be exhibited for a long period of time. Stained wood I. Self-cleaning property The film matrix portion used in the present invention can be used particularly in an unobstructed manner because of the deterioration of the photocatalytic particles, which makes it possible to use the fine and active photocatalyst particles. Further, it is difficult to form agglomerates in the film when the fine photocatalyst particles are used. However, in the gaps of the aggregates, there are many cases in which the resin component constituting the film is not present. Therefore, it is also known that there is an advantage that the contaminant easily reaches the surface of the catalyst. It is better to uniformly disperse the photocatalyst in the film, but the brigade does not necessarily need to pursue completeness and homogeneity. For example, as described above, for example, when agglomerates are formed, the degree of inclusion of particles is different from the inside of the outermost surface portion, or the case where the concentration is inclined, the 201104016 state may be used. Use as appropriate. The amount of the photocatalyst contained in the film is not particularly limited and can be appropriately determined within the range in which the desired effect can be obtained. In this case, the mass ratio of the film to the entire film is 50% or less, preferably 40% or less, and preferably 30% or less, in order not to impair the uniformity and smoothness of the film. The lower limit of the amount of addition is not particularly limited, and is usually 0.1% or more with respect to the mass ratio of the entire film, and preferably 0.5% or more. When the amount added exceeds the above range, as described above, it is not easy to be a uniform and smooth film, and it is not economical. Further, when the amount of addition is too small as compared with the above range, the effect of the desired period is often not obtained. The amount of photocatalyst contained in at least two layers of the photocatalyst film used in the present invention is the most in the outermost layer film, and the closer to the inner layer film. As a result, the outermost layer of the film deteriorates and disappears after pulverization, and when the film of the second layer is exposed, although the self-cleaning property obtained from the outermost layer is slightly lower, the continuous contamination resistance effect can be expected to the substrate. The long-term exposure of the surface of the precoated metal sheet provides excellent stain resistance and self-cleaning effect. Further, since the photocatalyst content can be reduced stepwise, deterioration of the coating film on the inner layer side can be suppressed, and excellent self-cleaning property can be remarkably maintained for a long period of time. The amount of the photocatalyst in the film which changes the content of the photocatalyst is not particularly limited, and can be appropriately determined within the range of the amount of the photocatalyst described above. For example, when a two-layer film is formed, the combination of the photocatalytic amount of the surface film and the inner film can be set to 50%/20%, 35%/10% or 20%/5%, etc., based on the mass ratio of each film. . Further, in the case of the three-layer film, the combination of the surface film and the photocatalyst of the inner film and the innermost film can be set to 20 201104016 as a mass ratio of 50%/30%/io% to the entire film, and 35 %/ 20%/1 〇% or 20%/15%/1%, etc. The content of the photocatalyst in the innermost layer side film is preferably 5% to 3% by mass based on the mass ratio of the entire innermost layer side film. The innermost film is in contact with a film mainly composed of a polyester, an amine bismuth acid, an acrylic acid, an epoxy or the like which is formed on the surface of the substrate precoated metal plate, so that the photocatalyst of 3 or more is used. good. The amount of photocatalyst in the innermost side film is 0.05% to 25 by mass with respect to the entire innermost side film. /. Preferably, it is 0_05%~2〇%, and the better is ι%%~15%. 2. The photocatalyst active substance, 其 „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ „ It can suppress the loss and deterioration of the film caused by the photocatalyst. Moreover, when the combination of the paint (resin) and the photocatalyst particles of the political difficulty is used, the dispersion of the photocatalyst can be obtained by selecting the skin::: material as the carrier. In particular, the body towel is made of an inorganic oxide which is stable to the photocatalyst, and is oxidized. It is less than f town, oxidized, iron oxide, and sound: the thickness of the photocatalyst film used can be independently 2 If each is determined, it is better to use the Wei or the material to be used, preferably the film thickness is now. In addition, when the pre-coated metal sheet of the product is strictly limited, the thickness is U.佳° When the film thickness exceeds '': a uniform film is formed after the film is formed. 21 201104016 Sex is difficult 'other side' When the film is too thick beyond the above range, it cannot be obtained as a pre-coated metal plate. The moldability and the film adhesion at the time of the forming process may be insufficient. The photocatalyst film on the surface of the precoated metal sheet of the present invention has the characteristics of containing inorganic plate-like particles. The effect of adding the substance f is excellent. The shape of the tabular particles is preferably 5 or more, and the value obtained by dividing the average particle diameter in the planar direction by the average value of the thickness is preferably 30 or more, more preferably 60 or more. If the size is not too large, it can be used. Considering the thickness of the photocatalyst film, the particle diameter in the flat Φ direction is preferably 120 μm or less, preferably 60 μm or less, and more preferably 30 μηι or less. The granules are layered on the shawl, which can be surface-adhesive, produce an ultraviolet light shielding effect, and suppress the money generated by Cheng Shi, etc., or ensure the possession of the property by preventing the penetration of water. "Ding Tian is asked about the particle diameter of the dry", which is the average value of the equivalent diameter of the circle by the flat surface, which is the area of the projection surface where the projected area of the particle is the largest. Mirror observation The average value of the thickness of the flat particle is the average value of the thickness of the flat particle (the largest particle size in the direction perpendicular to the projection surface when the projected area of the particle is maximum). The same can be obtained by observation with an electron microscope. In the pursuit of "average particle size" and "average thickness", it is better to observe the majority of particles as much as possible. However, according to the review of the inventor 4, it can be seen that the observation of the left is to see the result of the multi-record. with. In other words, the result of examining 5 particles in the financial method can represent the "average particle diameter in the plane direction" and 22 201104016 "the average value of the thickness". The above-mentioned tabular particles are preferably contained in a range of 0.05 to 30%, preferably 0.05 to 25%, more preferably 0.1 to 20%, in terms of mass ratio with respect to the film. When the content is less than the above range, sufficient adhesion cannot be ensured, and the inferior seam at the time of formation of the film cannot be suppressed, and the effect of sufficient corrosion resistance cannot be obtained. On the other hand, when it exceeds the above range, since the amount of the additive particles in the film is too large, a film having a good appearance cannot be obtained, or the film properties such as adhesion, hardness, and strength are also insufficient. The plate-like particles to be added are preferably selected from the group consisting of clay minerals, graphite, and graphitized carbon black, and are preferably selected from clay minerals. The particles to be added may be one type, and two or more types of particles may be added in combination. Here, the clay mineral refers to the entire layered citrate mineral, and is well known as kaolin, mica, pyrophyllite, smectite, vermiculite, hydrotalcite, and the like. Among them, the tabular particles of the present invention are particularly preferably mica. Mica has XYn(Si,Al)4O10(OH,F)2 (where X=K, Ca, Na, etc., Y=Mg, Ab Li, Fe, Μη, Ti, etc., n=2~3) The layered aluminosilicates of the chemical composition are well known as muscovite, biotite, and phlogopite. In the film of the present invention, as the metal component of the inorganic-organic composite resin, Si is contained, but one or more metal elements selected from the group consisting of B, Al, Ge, Ti, Y, Zr, Nb, and Ta may be added as the metal element thereof. Other than the elements. Among them, Al, Ti, Nb, and Ta are those which are used to cure the film at a low temperature or in a short period of time after the acid is used as a catalyst. When an acid is added as a catalyst to the metal alkoxide, the ring opening speed of the epoxy is changed to 23 201104016, and the film hardening can be performed at a low temperature for a short period of time. It is particularly frequently used as a raw material of Ti, such as Ti, Ti-ethoxy oxide 'Ti_isopropoxide or the like. Further, in the system of Zr, it is preferable to use it in order to remarkably improve the film. The precoated metal sheet which becomes the substrate of the precoated metal sheet of the present invention can be used without any material. For example, steel, non-recorded steel, titanium, aluminum, or aluminum alloy can be used or the organic resin coating can be carried out by plating treatment. Among them, a pre-coated metal plate may be, for example, a stainless steel plate, a Qin plate, a plate, a new alloy plate, or an organic coating film formed on the surface of the electric forged metal plate subjected to the electric key treatment. The plated steel sheet may be, for example, a zinc electric key steel plate, a zinc-bismuth alloy electric key steel plate, a zinc-town alloy plated steel plate, a zinc-chromium alloy plated steel plate, a zinc-aluminum alloy plated steel plate, an aluminum plated steel plate, a zinc-queen-alloy alloy. Electro-mineral steel plate, Ciming _ Zhenxi alloy electric ore plate, Shao-shred alloy plated steel plate, zinc plated stainless steel plate, aluminum plated stainless steel plate, etc. Examples of the stainless steel plate include a ferrite-based iron-based stainless steel plate, a Matian-dispersed iron-based stainless steel plate, and a Worthfield iron-based stainless steel plate. The thickness of the non-mineral steel sheet may be, for example, a stainless steel foil having a thickness of about 10 mm or so as to be thinned to the left and right by rolling. The surface of the stainless steel plate and the stainless steel foil can also be subjected to surface treatment such as glow annealing and polishing. The aluminum alloy plate may, for example, be JIS No. 1000 (pure A1), JIS 2000 (Al-Cu), JIS 3000 (Al-Mn), JIS 4000 (Al-Si), JIS 5000 (Al-Mg system), JIS 6000 system (Al-Mg-Si system), JIS 7000 system (Al-Zn system), and the like. The treatment liquid suitable for producing the precoated metal sheet of the present invention contains an inorganic-organic composite resin material, a photocatalyst-active material, and a liquid composed of inorganic-based 24 201104016 tabular particles, and the inorganic-organic composite resin material contains And an alkoxysilane having an alkyl group, an aryl group, a carboxyl group, a hydroxyl group having a carbon number of 1 or more and 12 or less, and an organic group selected from the group consisting of the combinations, an alkoxysilane having an epoxy group, An alkoxy oxane having an amine group, a tetraalkoxy decane, and an alkoxy decane (al) selected from the group consisting of the combinations; a hydrolyzate (a2) of the alkoxy decane (al); Or the condensate (a3) of the alkoxydecane (al). The alkoxydecane having an alkyl group having 1 to 12 carbon atoms may, for example, be methyltrimethoxy decane, dimethyl decyloxy decane, methyltriethoxy decane or dimethyldiethoxy group. Decane, hexyltrimethoxydecane, hexyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, and the like. The alkoxysilane having an aryl group may, for example, be phenyltrimethoxy mash, diphenyldimethoxydecane, phenyltriethoxydecane or diphenyldiethoxydecane. The alkoxy decane having an epoxy group can be preferably used: γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-glycidoxypropane Propyl tripropoxydecane, γ-glycidoxypropyl tributoxydecane, 3,4-epoxycyclohexyldecyltrimethoxy decane, 3,4-epoxycyclohexyl fluorenyl Triethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltriethoxy decane, etc. In terms of reactivity, etc., it is particularly preferable to use γ-glycidoxypropyltriethoxydecane. An alkoxylated stone having an amine group can be preferably used: aminopropyltrimethoxyxanthene>, aminopropyltriethoxylate, (β-aminoethyl)-β -Aminopropyltrimethoxy decane, (β-aminoethyl)-β-aminopropylmethyldimethoxy 25 201104016 基石, (β-Aminoethyl) amide The oxy group is particularly easy to handle, and the like, in particular, an amine-based internal group is preferred. Further, the four alkoxyline may be, for example, tetramethyl ethoxy ethoxy ethoxylate, tetrapropoxy valence, tetrabutoxy sulphate, sulphate, and the like. In addition to the advantages of the amine group, it is possible to use (4) the photocatalyst phase and the (9)^ as the substrate, and the detailed description of the plate, but the storage is added. Epoxy or amine group, = can not be caused by the film and the organic layer on the surface of the substrate, and the catalyst is bonded to improve the adhesion. As a result, the film is not easily formed. The stability of the film. 々 制 制 制 制 制 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本a sol-like substance of a particular particle, such as a substance of a metal complex. * = cannot be referred to as a substance, which means that the treatment liquid towel is dispersed or stabilized in water by a gold oxide-like substance or A fine colloid which is precipitated in an organic solvent. Among them, the photocatalyst of the present invention is particularly preferably an anatase-type titanium oxide particle. The properties of the photocatalyst particle are not particularly limited, but are highly catalytically active. It is preferable to use particles having a small particle size as much as possible. The size of the photocatalyst particles is not more than 0.5 μm, preferably 〇.igm or less, more preferably 〇.5 μΐπ or less. The lower limit of the particle size is not particularly limited. However, since it is too fine to be easily handled, the primary particle diameter is usually 5 nm or more. The amount of the photocatalyst contained in the treatment liquid is not particularly limited, and 26 201104016 can be suitably obtained after the formation of the film. When it is determined within the range of the effect, the non-volatile matter in the private liquid is not included in order to not impair the uniformity and smoothness after the formation of the film, except for the treatment liquid for forming the film on the innermost layer side. The mass ratio, photocatalyst I, below, is better than the following, and the better is the following. Adding force is 50%, not special $5, 丨 limited, usually relative to the ratio of (four) eight lower limit of the treatment liquid The amount of the photocatalyst substance is 0.5% or more, and the amount of the photocatalyst substance of 1Q% is preferably used to form the film on the innermost layer side. When the liquid is liquid, it is a non-volatile total of the processing liquid towel. The ratio t is the following, and the following is better, and the better is (4) or less. The addition amount f5% is not particularly limited, and is usually 0.05% or more relative to the ratio of the solid solution to the treatment liquid. When the amount exceeds the above range, the treatment liquid may be differently suspended. However, not only does the catalyst need to be more than necessary, so it does not conform to ". Moreover, when the addition range is too small, the desired period is not obtained. The effect of the situation is more than the father of the particle The liquid contains inorganic plate-like particles. The core is selected from the flat shape, and the clay mineral, graphite, and graphitized carbon black are preferably selected from clay minerals. The added particles may be Two or more kinds of particles are added in combination. Here, the clay mineral refers to the whole of the layered money salt minerals, and the well-known ones include: high flag soil, mica, leaf peony, smectite, insect to stone, hydrotalcite, and the like. In particular, the tabular particles of the present invention are preferably made of mica, and the tabular particles are preferably contained in a ratio of 0.05 to 30% relative to the mass of the non-volatile portion of the treatment liquid in the range of 0.05 to 30%. The preferred one is 〇〇5~, and the more preferable one is (^~汕%). When the content is less than the above range, the film which is the surface of the precoated metal sheet of the present invention cannot be sufficiently adhered, x There is a problem that a sufficient effect of preventing the pureness is not obtained, and cracks in the formation of the film cannot be suppressed. On the other hand, when the amount exceeds the above-mentioned enthalpy, the film-like particles in the film are too large, so that the film of the sage is not obtained, or the film properties such as social properties, hardness, and strength are insufficient. In the treatment liquid of the present invention, an alkoxide of a metal component other than alkoxysilane may be used as an additive as needed. In particular, when an alkoxide of at least one metal selected from the group consisting of Τι A, Ta, and Nb is added, and when acetic acid is used as the acid catalyst, the ring opening speed of the epoxy group is increased, and the low temperature is particularly short. The effect of time hardening. All of the alkoxy groups, or a portion thereof, may be hydrolyzed in the gold oxide other than the oxygenated Wei. In the treatment liquid of the present invention, a compound containing zirconium, for example, a conical oxide, a hydrolyzate or a cerium oxide (cerium oxide) sol may be used as it is. This component is a component which improves the alkali chemical resistance of the treatment liquid of the present invention. By adding this component, it is not necessarily clear which mechanism is used to improve alkali resistance, but Zr replaces the position of Si which constitutes a siloxane bond, and forms a structure in which sulphur dioxide and smear are h, and it is known that the female has stability. . Further, it is now required to add inorganic particles other than the oxidized sol. In the treatment liquid of the present invention, coloring pigment, body pigment, catalyst, rust preventive pigment, metal powder, and high frequency may be added for the purpose of improving the design property, corrosion resistance, abrasion resistance, and catalytic function of the coating film. Loss agents, aggregates, etc. 28 201104016 The coloring pigment may, for example, be an oxide such as Ti or Al, a composite oxide, or a metal powder such as A-end Alh. For the anti-mineral pigments, it is preferred to use non-chromic acid pigments such as indium bismuth (tetra), gamma acid, sulphate, and so-called ig salt which are not contaminated by the brothers. In addition, the high-frequency loss agent can be exemplified by two rhyme, ferrite iron, and the bone material can be exemplified by potassium silicate (four). Further, in the treatment liquid of the present invention, an acid catalyst may be added as needed. The acid catalyst may, for example, be an organic acid such as formic acid, cis-butyl diacid or benzoic acid or a salt-messional acid, but particularly preferably acetic acid. By using acid as a spear, the oxygen stone court used as a raw material is in a polymerization state suitable for film formation. When acetic acid is used as a catalyst, it will promote the opening of the epoxy group and increase the low temperature and short-time hardening. The effect. Further, in the treatment liquid of the present invention, a leveling effect agent, an antioxidant, an ultraviolet absorber, a stable (four), a plasticizer, a hydrazine, and an additive type ultraviolet stabilizer which are additives can be used in combination. In addition, (4) can also be used without damaging the film's _ sex #_ ' or without the photocatalyst caused by deterioration!: Containing oxygen resin, polyester resin, urethane (4) grease shaft, the 4 additives can be used only 1 The mixture may be used in combination of two or more kinds as appropriate. The treatment liquid of the present invention is obtained by adding an organic solvent which can appropriately disperse a target substance, and adding a group having a carbon number of (1) or less, a group, a base group, and a selected from the earth, Square machine base (4) Oxygen dumping, with "Sui Qun group
::…選自_等之組合所構C 之炫乳魏㈣，並視需要地水解、縮聚合而_。有機: 29 201104016 劑，以 各種醇類、用例如：甲醇、乙醇、丙醇、丁醇等 叶碉、丙酮、苯、甲 機溶劑等為佳。 —曱本、乙苯等芳香族系有 於該有機溶劑溶液中 機系平板狀粒子，_/、力匕、有光觸媒活性之物質與無 农邗表面處理液。 表作之表面處理液 厚來使用。—俨而一 有機溶劑或水稀釋成需要之膜 0.2〜5_r )，進行稀釋使1:1 欠之塗布所得的膜厚於 圍。然而， 板狀叛子n ,、本發明之處理液中含有無機系平 ^ ^形成較厚之皮膜。又，亦可藉由多 裝形成其以上之厚产。丨 』糾厂人之塗 水解生成之醇㈣彳面’亦可將作為溶劑使用或 '的一。卩分於常壓或減壓下蒸餾後塗布。 矣而卢發月之預塗金屬板表面的光觸媒皮膜可藉由將前述 处理液塗布於作為基材之預塗金屬板表面後，乾燥、 ^化㈣成°塗布可藉由’浸沾塗布法、噴塗法、棒式塗 法*親塗布法 '旋轉塗布法等進行。 藉本發明之處理液而形成之塗膜的硬化，通常係藉由 加熱進行。標準之加熱條件，以於15G°C以上4GG°C左右之 '皿度範圍内’進行1小時至數秒左右之熱處理為佳。-般而 5，§熱處理溫度高時，可以短之熱處理時間進行皮膜之 硬化，當熱處理溫度低時，則需長時間的處理。又，當於 乾燥或熱處理中未賦與充分之溫度、時間時，於進行乾燥、 燒附硬化後’可視需要於室溫下放置1〜5日放置。經過該 步驟’可期待從形成塗膜後塗膜之硬度變高的效果。又， 藉於塗布處理液後放置於室溫下，亦可得硬化後之皮膜。 30 201104016 然而，此時’至成為實用上所需之硬度需花長時間的情況 較多。 依據本發明之光觸媒量相異的2層以上皮膜，可藉由將 本發明之光觸媒含有量相異的2種以上表面處理液依序塗 布於基材預塗金屬板上並使其硬化而得。另一方面，於將 光觸媒含有量相異的2種以上表面處理液同時塗布於基材 預塗金屬板表面後，同時乾燥燒附，可形成於預塗金屬板 表面積層有具光觸媒活性之粒子的含有量相異的2層以上 皮膜之多層皮膜。又’於形成包含有機樹脂層為3層以上之 皮膜時，例如，於形成1層有機樹脂層與2層光觸媒皮膜時， 藉同時塗布、燒附包含有機系樹脂之塗料(χ )、及光觸媒含 有量相異的2種表面處理液(Α)、（Β)，可形成3層以上之皮 膜。於同時塗布、乾燥燒附依據本發明之表面處理液(或有 機系樹脂層用之塗料與表面處理液）時，以使用多層簾幕式 塗布器等的方法為佳。 實施例 藉由以下之實施例具體地說明本發明。 (實施例1〜10、比較例1、2) 充分地攪拌以如表1所示之比例摻合的γ環氧丙氧基 丙基三乙氧基石規(GPTES)、苯基三乙氧基石作(phTES): 四乙氧基㈣(TEOS)、四乙氧化鈦(TE)後，使用經乙醇稀 釋之蒸财，於乙酸紐Tit行切。此處，添加胺基丙 基二乙氧基矽烷(APTES)，並使用蒸餾水/乙醇混合溶液進 仃水解，調製以無機-有機複合樹脂作為主成分之塗布液。 31 201104016::... selected from the combination of _ and the like, the condensed milk Wei (4), and if necessary, hydrolyzed, condensed and polymerized. Organic: 29 201104016 Agent, various alcohols, such as: methanol, ethanol, propanol, butanol, etc., leafhopper, acetone, benzene, machine solvent, etc. are preferred. - An aromatic such as sputum or ethylbenzene is used in the organic solvent solution. The plate-like particles, _/, 匕, photocatalyst-active substance and non-farm surface treatment liquid. The surface treatment liquid used for the surface is thick. - The organic solvent or water is diluted into the desired film 0.2~5_r), and the film thickness obtained by the coating of 1:1 is diluted. However, the plate-like renegade n, the treatment liquid of the present invention contains an inorganic system to form a thick film. Further, it is also possible to form a thick product of the above by multi-packing.丨 』 纠 人 人 人 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解The mash is applied after distillation under normal pressure or reduced pressure. The photocatalyst film on the surface of the precoated metal sheet of Lufayue can be dried by coating the surface of the precoated metal sheet as a substrate, and then drying and chemically coating the coating layer by dipping coating method. , spraying method, bar coating method * pro-coating method 'spin coating method, etc. The hardening of the coating film formed by the treatment liquid of the present invention is usually carried out by heating. The standard heating conditions are preferably carried out at a temperature of from 15 G ° C to about 4 GG ° C for a period of from 1 hour to several seconds. - Generally, when the heat treatment temperature is high, the film can be hardened by a short heat treatment time. When the heat treatment temperature is low, it takes a long time to process. Further, when sufficient temperature and time are not imparted in the drying or heat treatment, it may be left to stand at room temperature for 1 to 5 days after drying and sintering hardening. Through this step, the effect of increasing the hardness of the coating film after the formation of the coating film can be expected. Further, by coating the treatment liquid and then standing at room temperature, a cured film can be obtained. 30 201104016 However, at this time, it takes a long time to become a practically required hardness. According to the two or more layers of the photocatalyst having different amounts of photocatalyst according to the present invention, two or more kinds of surface treatment liquids having different photocatalyst contents of the present invention can be sequentially applied to a substrate precoated metal sheet and cured. . On the other hand, two or more types of surface treatment liquids having different photocatalyst contents are simultaneously applied to the surface of the precoated metal sheet of the substrate, and then dried and baked to form a photocatalytic active particle on the surface layer of the precoated metal sheet. A multilayer film of two or more layers having different contents. In the case of forming a film containing three or more layers of the organic resin layer, for example, when one layer of the organic resin layer and the two layers of the photocatalyst film are formed, the coating containing the organic resin and the photocatalyst are simultaneously applied and baked. Two kinds of surface treatment liquids (Α) and (Β) having different contents can form three or more layers of the film. When the surface treatment liquid (or the coating material for the organic resin layer and the surface treatment liquid) according to the present invention is simultaneously coated and dried, it is preferred to use a method such as a multi-layer curtain coater. EXAMPLES The present invention will be specifically described by way of the following examples. (Examples 1 to 10, Comparative Examples 1, 2) γ-glycidoxypropyltriethoxy stone gauge (GPTES) and phenyltriethoxysilane blended in a ratio as shown in Table 1 were sufficiently stirred. (phTES): Tetraethoxy (tetra) (TEOS), tetra-titanium oxide (TE), and then distilled in ethanol and digested with acetic acid. Here, aminopropyl propyl diethoxy decane (APTES) was added and hydrolyzed using a distilled water/ethanol mixed solution to prepare a coating liquid containing an inorganic-organic composite resin as a main component. 31 201104016
水解係添加充足分I 分濃度為20質量。/ 使塗布液於15〇t乾燥時的固形 粒子與作為該塗布液中，添加表1所示之光觸媒 處理液。光觸媒< 板狀粒子的雲母，製作塗布用之表面 外層側皮膜之㈣承加量係使内層側皮膜之光觸媒量成為 的添加量係相對於=量的I表1中之光觸媒粒子與雲母 例。使用之光 面處理液所含之固形分全體的質量比 10nm。雲母之平均：子的粒子徑’ Zn〇約6〇_、邮約 子徑/厚度平均值，、厚度約㈣㈣平均粒 於辞=11施例1〜)10之光觸媒皮膜的預塗金屬板係將 於辞電鍍鋼板表面 聚酷皮膜的o.6mm厚 度約15吨之三聚氰胺交聯之 之趣…“之預塗鋼板作為基材而製作。2層構造 板=Γ的第1層(内層側)之皮膜係於基材預塗金屬 板以棒式塗布器塗希 39 ^,ni>l 内層側皮膜用之表面處理液’並使用 =Γ!成為25°。。的升溫條件，以最高溫度_ 仃” & j而形成。形成之皮膜的厚度 側)之皮膜係於形成有第】層之皮膜的表面以棒式塗布(= 1外層側皮膜用之表面處理液，並使用使5G秒後之板溫成 為肌的升溫條件，以最高溫度靴進行熱處理^ 成形成之皮膜的厚度約3_。比較材則準備了與實施例7 相同之樹脂組成、光觸媒添加量中未摻合平板狀粒子之光 觸媒皮膜的預塗金屬板(比較例】)、及與實施例_同之樹 腊組成、光觸媒添加量尹未摻合平板狀粒子之光觸媒皮膜 的預塗金屬板(比較例2)。 、 32 201104016 形成有光觸媒皮膜之 下方法進行。 預塗金屬板的評價試驗係 藉由以 ()進仃於料之暴路試驗，評價mu 係設置成將職有光觸媒㈣之面㈣南側，且相對於地 面垂直。 (2) 塗膜(基材預塗金屬板之有機樹脂皮膜)之劣化(損 傷）狀況係藉由大致隔-個月測定暴露試驗片表面之顏色 與光澤來調查。光觸皮膜因偏白呈透明，故顏色 '光澤 之測定結果可大致反映出下層㈣皮膜的狀態。 (3) fe輕地以手指搓前述暴露試驗片表面，判斷粉化的 狀況。 (4)每經過6個月，觀察皮膜截面，測定皮膜厚度之減 少’藉此推定自淨化機能大約的持續期間。 試驗結果之評價除了皮膜厚度之減少及自淨化機能的 持續期間以外’由高至低的順序分成@、〇、△、χ4個階 段。於表2顯示個別之評價基準。 於表3顯示結果。實施例之預塗金屬板均具有優異之耐 雨滴污染性。實施例中，皮膜之劣化少，且粉化性較為良 好。皮膜厚度係適度地減少，但因為2層皮膜，故自淨化性 的持續期間較通常之光觸媒皮膜可長時間地維持。 雖於表中未記載，但於進行〇Τ、1Τ、2Τ彎曲加工試驗 時，實施例之預塗金屬板中，於〇Τ、1Τ、2Τ彎試驗中幾均 未發現皮膜之破裂、剝離’顯示良好之彎曲加工性’但實 施例3之預塗金屬板的〇τ彎曲試驗中，發現了皮膜之破裂與 33 201104016 些微之剝離（實施例3之總合評價的〇係反映了此情形）。 另一方面，未添加平板狀粒子之比較例1中，自淨化（耐 雨滴污染）性、皮膜之劣化、及粉化性等外觀變化係與實施 例7同等，但皮膜厚度之減少較實施例大，結果，自淨化性 持續期間較實施例7短。並且，於進行〇Τ、IT、2T彎曲加 工試驗時，於2T彎曲中發現皮膜之破裂與剝離，可知彎曲 加工性較實施例7不佳。 比較例2亦與比較例1相同，自淨化性持續期間較實施 例10短。又，於彎曲加工試驗中，比較例2之預塗金屬板亦 於2T彎曲中發現皮膜之破裂與剝離，可知彎曲加工性較實 施例10不佳。 總結以上’由實施例7與比較例1、實施例1〇與比較例2 的比較，可知藉由添加無機系平板狀粒子，因皮膜產生之 紫外光遮蔽效果變大，且可增長自淨化性持續時間，又， 特別地可提高彎曲加工部中之皮膜密著性。該效果係無論 光觸媒含有量之多少、平板狀粒子添加量之多少而可得 到，當比較實施例3與實施例4時，因實施例3之密著性略不 佳，故可推測於平板狀粒子之添加量少時，有前述自淨化 性之長壽命化、密著性提升效果變小的可能性。 (實施例11〜18、比較例3〜1 〇) 充分地攪拌以如表4所示之比例掺合的γ_環氧丙氧基 丙基三乙氧基矽院(GPTES)、苯基三乙氧基矽烷(PhTES)、 曱基三乙氧基矽烷(MTES)、四乙氧基矽烷(TEOS)、四乙氧 化鈦(TE)後，使用經乙醇稀釋之蒸餾水，於乙酸酸性下進 34 201104016 行水解。此處，添加胺基科三乙氧基魏(ApTES)，並使 «铜水/乙料合溶液騎切，婦以無备錢複合樹 脂作為主成分之塗布液。水解係添加紋分量，使塗布液 於⑼。形分濃度為15„%。於該塗布液中， 添加表5所示之量的溶膠狀態之光觸媒與無⑽平板狀粒 子’製作塗布用之表面處理液A〜D。光觸媒之添加量係以 作為溶膠中所含之光觸媒的固形分換算者，作為相對於塗 布液所含之固形分全體的質量_。使狀光觸媒粒子的 拉子植’ Zn_Gnm、Ti0烟⑽、雲母之平均粒子徑係 Wm、厚度係〇_〇5_(平均粒子徑/厚度平均值=叫水滑 徑係4>、厚度飢W厚度 日組成、及光觸媒之種 類與量係分別與實施例u〜18相同，製 狀粒子之處魏(參絲6)。 ”，、《千板 實施例之基材《金屬板健厚妓5_之不 彻)=基材域，並於其表㈣切㈣酸皮膜而 依據處理液進行之塗裝，料，於基材預塗金屬板 表面使麟式塗布H塗布表面處理仙後，加熱至2听， 形成第4層蝴最__。接著，於該表面藉與表面處 液D相同之方法’依序塗布表面處理液c、表面處理液B， :成第三層、第二層皮膜。此外’於該表面以棒式塗布琴 :布表面處理液A後，加熱至赋，形成第i層皮膜(最外 皮膜）。結果’得到於基材預塗金屬板表面形成有光觸媒 35 201104016 含有量相異之4層（實施例11〜14係3層）之光觸媒皮膜的預 塗金屬板。皮膜之厚度於任一實施例之各層皮膜均為 4μιη。比較例3〜10亦藉由與實施例11〜18相同之順序，製 作形成有光觸媒皮膜的預塗金屬板。 形成有光觸媒皮膜之預塗金屬板的性能評價試驗，係 藉由與實施例1相同之方法進行耐雨滴污染性、皮膜之劣化 及1Τ彎曲密著性。結果，與實施例1同樣地以◎、〇、△、 x4的階段評價。個別之評價基準係如表2所示。 於表7顯示結果。由表7之結果，可知實施例11〜18之 表面處理預塗金屬板從最外層皮膜至最内層皮膜的耐雨滴 污染性均優異，並且因為3層或4層構造，故可長時間地維 持良好之耐污染性，又，因光觸媒效果產生之塗膜（基材預 塗金屬板之有機樹脂皮膜）的劣化少，具有耐光觸媒性，故 可長時間地維持皮膜劣化少之優異的财污染性。又，於進 行1Τ彎曲試驗以試驗彎曲加工性（皮膜密著性）日夺，均未發 現皮膜之破裂、剝離，具有優異之彎曲加工性。 另一方面，比較例3〜10之預塗金屬板之耐雨滴污染 性、皮膜之劣化雖與實施例相同為良好之結果，但密著性 不佳，且1Τ彎曲試驗中評價之密著性均為△〜X。 如以上，可於具有矽丙烯酸皮膜之預塗不鏽鋼板表面 形成多數層含有預定添加量之光觸媒粒子、無機系平板狀 粒子的皮膜。由個別皮膜之耐污染性、塗膜(基材預塗金屬 板之有機樹脂皮膜）之劣化狀況的評價結果，可知所得之表 面處理預塗不鏽鋼板經長時間可得優異之埘污染性、自淨 36 201104016 化性’且皮膜之劣化少，係皮膜之密著性優異的預塗不鐘 鋼板。 (實施例19、20) 藉由下述方法將表1中之實施例i記載的推合比例之表 面處理液塗裝於以厚度0.6mm之鋅電鍍鋼板作為基材，並 於其最表面塗裝有厚度約15,之三聚氰胺交聯之聚自旨皮 膜預塗鋼板表面，形成由2層所構成之光觸媒皮膜(實施例 ⑼。又’藉由下述方法將表以實施例9記載的摻合比例之 表面處理液與前述相同地塗裝於預塗鋼板表面，形成2層之 光觸媒皮膜（實施例20)。 光觸媒皮膜係於藉由狹縫簾幕式塗布器同時塗布2層 皮膜用之處理液後，接著以25()t加熱、硬化而形成。製二 之表面處理預塗金屬板的外觀係完全無問題，且良好。形 成之皮膜厚度，任一者之内層皮膜均約3μηι，外層皮膜約 4μηι。 相對於已作製之表面處理預塗金屬板，與實施例i同樣 地，評價依據屋外暴露試驗之雨滴污染性、皮膜之劣化(損 傷）狀況、粉化之狀況。又，推測自淨化機能大約之持續期間。 結果，關於雨滴污染性、皮膜之劣化狀況、粉化之狀 況，可得實施例19與表2所示之實施例丨、及實施例2〇與表2 所示之實施例9完全相同的試驗結果。另，自淨化機能之推 測持續期間，於實施例19之表面處理鋼板約35年，於實施 例28之表面處理鋼板約18年。 由實施例19、20 ’可知即使使用多層同時塗布法亦 37 201104016 可沒問題地製造本發明之預塗金屬板。又，可知其性能與 獨立形成各層之皮膜的情形均無差異。換言之，可知於以 實施例19、20記載之方法製造的表面處理預塗金屬板中， 亦可得良好之而^污染性、可長時間地持續自淨化性，且因 光觸媒產生之皮膜劣化少的表面處理預塗金屬板。 表1The hydrolysis system was added with a sufficient concentration of 20 parts by mass. / The solid particles when the coating liquid was dried at 15 Torr, and the photocatalyst treatment liquid shown in Table 1 were added as the coating liquid. Photocatalyst < Mica of plate-like particles; (4) The amount of the photocatalyst of the inner side film is the amount of addition of the photocatalyst to the amount of photocatalyst particles and mica in Table 1 . The mass ratio of the solid content contained in the smoothing treatment liquid used was 10 nm. The average of mica: the particle diameter of the sub- Zn 〇 about 6 〇 _, the average value of the sub-division diameter / thickness, the thickness of about (four) (four) the average particle in the word = 11 Example 1 ~) 10 photocatalyst film pre-coated metal plate system It is said that the o.6mm thickness of the plated steel plate is about 15 tons of melamine cross-linking. "The pre-coated steel sheet is produced as a substrate. The two-layer structural board = the first layer of the crucible (the inner layer side) The film is applied to the substrate pre-coated metal plate by a bar coater, and the surface treatment liquid for the inner side film of the inner layer is used, and the temperature is raised to 25°.仃" & j formed. The film on the thickness side of the formed film is applied to the surface of the film on which the layer is formed by bar coating (= 1 surface treatment liquid for the outer layer side film, and the plate temperature after 5 G seconds is used as the temperature rising condition of the muscle. The thickness of the film formed by heat treatment with the highest temperature shoe is about 3 mm. The comparative material is prepared by the same resin composition as in Example 7, and the pre-coated metal plate of the photocatalyst film in which the photocatalyst is not blended with the photocatalyst film ( Comparative Example]), and the pre-coated metal plate of the photocatalyst film of the plate-like particle mixed with the amount of the photocatalyst added in the same manner as in Example _ (Comparative Example 2), 32 201104016 The method of forming a photocatalytic film under the film The evaluation test of the precoated metal sheet was carried out by the turbulence test of () into the material, and the mu system was set to be placed on the south side of the surface (4) of the photocatalyst (4) and perpendicular to the ground. (2) Coating film The deterioration (damage) condition of the (organic resin film of the substrate precoated metal sheet) was investigated by measuring the color and gloss of the surface of the exposed test piece approximately every month. The phototact film was transparent due to white color, so the color ' Light The measurement results can roughly reflect the state of the lower layer (four) film. (3) fe lightly rubs the surface of the test piece with the finger to judge the state of the powder. (4) Each 6 months, the film section is observed, and the film thickness is measured. The reduction is based on the estimated duration of the self-purification function. The evaluation of the test results is divided into four stages of @, 〇, △, χ from the highest to the lowest in addition to the reduction of the film thickness and the duration of the self-purification function. Table 2 shows the individual evaluation criteria. The results are shown in Table 3. The precoated metal sheets of the examples all have excellent raindrop resistance. In the examples, the deterioration of the film is small, and the powdering property is good. The film thickness is moderate. Although the amount of the film is reduced, since the two-layer film is used, the photocatalytic film can be maintained for a long period of time compared with the conventional photocatalytic film. Although not shown in the table, in the case of performing the 〇Τ, 1Τ, 2Τ bending process test, the examples In the pre-coated metal sheet, no cracking or peeling of the film was observed in the 〇Τ, 1Τ, 2Τ bending test, but the pre-coated metal sheet of Example 3 was not found. In the 〇τ bending test, it was found that the rupture of the film and the slight peeling of 33 201104016 (the lanthanide of the total evaluation of Example 3 reflects this case). On the other hand, in Comparative Example 1 in which no tabular particles were added, The appearance change such as purification (falling rain pollution), deterioration of the film, and powdering property was the same as that of Example 7, but the reduction in film thickness was larger than that of the Example, and as a result, the self-cleaning duration was shorter than that of Example 7. When the enthalpy, IT, and 2T bending test were performed, cracking and peeling of the film were observed in 2T bending, and it was found that the bending workability was inferior to that of Example 7. In Comparative Example 2, the self-cleaning property was continued as in Comparative Example 1. The period was shorter than that of Example 10. Further, in the bending test, the precoated metal sheet of Comparative Example 2 was found to have cracked and peeled off the film in 2T bending, and it was found that the bending workability was inferior to that of Example 10. In summary, the comparison between Example 7 and Comparative Example 1, Example 1 and Comparative Example 2 shows that the ultraviolet light shielding effect by the film is increased by adding inorganic plate-like particles, and the self-cleaning property can be increased. In addition, in particular, the film adhesion in the bent portion can be improved. This effect is obtained regardless of the amount of the photocatalyst and the amount of the tabular particles. When Comparative Example 3 and Example 4 are compared, the adhesion in Example 3 is slightly inferior, so that it is presumed to be flat. When the amount of addition of the particles is small, there is a possibility that the self-cleaning property is prolonged and the adhesion improving effect is small. (Examples 11 to 18, Comparative Example 3 to 1 〇) γ-glycidoxypropyltriethoxy oxime (GPTES), phenyl triacetate blended in a ratio as shown in Table 4 was sufficiently stirred. After ethoxy decane (PhTES), decyltriethoxy decane (MTES), tetraethoxy decane (TEOS), and tetra-titanium oxide (TE), distilled water diluted with ethanol is used to acidify acetic acid. 201104016 Row hydrolysis. Here, an amine-based triethoxy Wei (ApTES) is added, and the «copper water/ethyl acetate solution is cut and cut, and the coating liquid containing the unprepared compound resin as a main component is used. The hydrolysis is added to the grain component to make the coating liquid (9). The coating concentration was 15%. In the coating liquid, the photocatalyst in the sol state and the (10) tabular particles in the amount shown in Table 5 were added to prepare surface treatment liquids A to D for coating. The amount of photocatalyst added was The solid content of the photocatalyst contained in the sol is the mass of the solid content contained in the coating liquid. The photocatalyst particles of the photocatalyst particles are Zn_Gnm, Ti0 smoke (10), and the average particle diameter of the mica Wm. The thickness system 〇_〇5_ (average particle diameter/thickness average = water slide diameter system 4), thickness hunger W thickness day composition, and photocatalyst type and amount are the same as those of Examples u to 18, respectively. Where Wei (Shensi 6).", "The substrate of the Thousand Plates" "metal plate thick thick 妓 5_ is not complete" = the substrate field, and in the table (four) cut (four) acid film according to the treatment liquid The coating is carried out, and the surface of the substrate is pre-coated with the surface of the metal plate so that the coating is applied to the coating surface of the coating layer, and then heated to 2 to form the fourth layer of the butterfly. Then, the surface treatment liquid c and the surface treatment liquid B are sequentially applied to the surface by the same method as the surface treatment liquid D to form a third layer and a second layer film. Further, the surface of the piano was coated with a bar: the surface treatment liquid A was heated to a weight to form an i-th layer film (outer film). As a result, a precoated metal sheet of a photocatalyst film having four layers (Examples 11 to 14 and three layers) having different amounts of photocatalyst 35 201104016 was formed on the surface of the substrate precoated metal sheet. The thickness of the film was 4 μm in each of the layers of any of the examples. In Comparative Examples 3 to 10, a precoated metal sheet on which a photocatalyst film was formed was also produced in the same manner as in Examples 11 to 18. The performance evaluation test of the precoated metal sheet on which the photocatalyst film was formed was carried out in the same manner as in Example 1 to prevent raindrop contamination, deterioration of the film, and 1Τ bending adhesion. As a result, in the same manner as in Example 1, the evaluation was carried out in the stages of ◎, 〇, Δ, and x4. The individual evaluation criteria are shown in Table 2. The results are shown in Table 7. From the results of Table 7, it is understood that the surface-treated precoated metal sheets of Examples 11 to 18 are excellent in raindrop resistance from the outermost layer film to the innermost layer film, and can be maintained for a long time because of the three-layer or four-layer structure. In addition, since the coating film (the organic resin film of the substrate precoated metal sheet) which is produced by the photocatalytic effect is less deteriorated and has photocatalytic resistance, it is possible to maintain excellent contamination of the film with little deterioration for a long period of time. Sex. Further, the bending test was performed to test the bending workability (film adhesion), and no crack or peeling of the film was observed, and the bending workability was excellent. On the other hand, the rain-resistant contamination of the precoated metal sheets of Comparative Examples 3 to 10 and the deterioration of the film were good as in the examples, but the adhesion was poor, and the adhesion evaluated in the 1 Τ bending test was evaluated. Both are △~X. As described above, a film in which a plurality of layers contain a predetermined amount of photocatalyst particles or inorganic plate-like particles can be formed on the surface of a precoated stainless steel plate having a ruthenium acrylic film. From the evaluation results of the stain resistance of the individual coatings and the deterioration of the coating film (the organic resin film of the substrate precoated metal sheet), it was found that the obtained surface-treated precoated stainless steel sheet was excellent in contamination and self-cleaning over a long period of time. 36 201104016 Chemical properties and the deterioration of the film is small, and the pre-coated steel plate is excellent in adhesion of the film. (Examples 19 and 20) The surface treatment liquid of the ratio of the ratios described in Example 1 in Table 1 was applied to a zinc-plated steel sheet having a thickness of 0.6 mm as a substrate, and coated on the outermost surface thereof. The surface of the steel sheet pre-coated with the melamine cross-linked with a thickness of about 15 is formed to form a photocatalytic film composed of two layers (Example (9). Further, the blend described in Example 9 is described by the following method. The proportioned surface treatment liquid was applied to the surface of the precoated steel sheet in the same manner as described above to form a two-layer photocatalyst film (Example 20). The photocatalyst film was coated with a two-layer film simultaneously by a slit curtain coater. After the treatment liquid, it is then heated and hardened by 25 () t. The appearance of the surface-treated precoated metal sheet of the second method is completely problem-free and good. The thickness of the formed film is about 3 μm, and the inner layer film of either one is about 3 μm. The outer layer film was about 4 μm. The surface-treated precoated metal sheet was evaluated for raindrop contamination, film deterioration (damage), and chalking in the same manner as in the example i. Self-cleaning The performance is approximately continuous. As a result, regarding the raindrop contamination, the deterioration of the film, and the state of chalking, the examples shown in Examples 19 and 2 can be obtained, and the implementations shown in Examples 2 and 2 can be obtained. The results of the test were the same in Example 9. In addition, the surface treated steel sheet of Example 19 was about 35 years from the presumption of the purifying function, and the surface treated steel sheet of Example 28 was about 18 years. It is known from Examples 19 and 20'. Even if a multi-layer simultaneous coating method is used, the precoated metal sheet of the present invention can be produced without problems. Moreover, it is understood that the performance is not different from the case where the film of each layer is formed independently. In other words, it is known that the examples 19 and 20 are described. In the surface-treated precoated metal sheet produced by the method, it is possible to obtain a surface-treated precoated metal sheet which is excellent in contamination, can be self-cleaning for a long period of time, and has less deterioration of the film due to photocatalyst.
No. GPTES (質量份) PhTES (質量份) TEOS (質量份) TE (質量份) APTES (質量份) 光觸媒 粒子 光觸媒粒子 之添加量 (質量％) 無機平板狀 粒子 (質量％) 實施例1 0 144.0 87.0 0 0 ΖηΟ 10.0(外） 5.0(内） 雲母 10_0(外） 5.0(内） 實施例2 // // 〃 〃 // 銳姑破 型 Ti〇2 10.0(外） 5.0(内） // 5.〇(外） 2.5(内） 實施例3 100 144.0 87.0 8.2 39.7 ΖηΟ 10.0(外） 5.0(内） 〃 0.0丨(外） 0.01(内） 贲施例4 〃 // // // 〃 // 10.0(外） 5.0(内） 〃 0.1(外） 〇.1(内） 實施例5 // // 〃 〃 〃 // 20.0(外） 10.0(内） // 5.0(外） 〇.5(内） 實施例6 〃 // 〃 〃 〃 〃 40.0(外） 20.0(内） // 5.0(外） 1.0(内） 實施例7 // // 〃 〃 // 銳欽礦 型 Ti02 1_〇(外） 〇_5(内） 〃 30.0(外） 10.0(内） 實施例8 〃 〃 // 〃 // 〃 5_〇(外） 2.5(内） 〃 20.0(外） 5.0(内） 實施例9 〃 〃 〃 // // // 25.0(外） 12.5(内） 〃 10_0(外） 1.0(内） 實施例10 〃 〃 〃 η 〃 〃 50.0(外） 25Ό(内） // 5.0(外） 〇.1(内） 比較例1 100 144.0 87.0 8.2 39.7 銳1大鑛 型 Ti02 1.〇(外） 〇_5(内） 無 比較例2 // 〃 // 〃 // // 50.0(外） 25.0(内） 〃 38 201104016 表2 基 準 雨滴污染 塗膜之劣化 粉化性 T彎曲密著性 (0T 〜2T# 曲） ◎ 於暴露6個月後， 無顯著之汙染 於暴露6個月後，無劣化 (光澤保持率90%以上） 以手指搓亦 完全無附著 無剝離 〇 於暴露6個月後， 附著些微污染 於暴露6個月後，有少許劣化 (光澤保持率於60〜90%) 以手指搓時 有些微附著 有些微剝離 Δ 暴露6個月後， 附著有污染 於暴露6個月後，發現劣化 (光澤保持率小於60%) 以手指搓時 有明顯附著 面積比例小於 50%之剝離 X 於暴露3個月時， 明顯地附著有污染 於暴露3個月時，發現劣化 (光澤保持率小於50%) 以手指搓時 有顯著附著 面積比例為50% 以上之剝離 表3No. GPTES (parts by mass) PhTES (parts by mass) TEOS (parts by mass) TE (parts by mass) APTES (parts by mass) Photocatalyst particles Photocatalyst particles added (% by mass) Inorganic flat particles (% by mass) Example 1 0 144.0 87.0 0 0 ΖηΟ 10.0 (outside) 5.0 (inside) Mica 10_0 (outside) 5.0 (inside) Example 2 // // 〃 〃 // Rui Gu broken type Ti〇2 10.0 (outside) 5.0 (inside) // 5. 〇 (outer) 2.5 (inside) Example 3 100 144.0 87.0 8.2 39.7 ΖηΟ 10.0 (outer) 5.0 (inside) 〃 0.0丨 (outer) 0.01 (inside) Example 4 〃 // // // 〃 / / 10.0 (outside) 5.0 (inside) 〃 0.1 (outside) 〇.1 (inside) Example 5 // // 〃 〃 〃 // 20.0 (outside) 10.0 (inside) // 5.0 (outside) 〇.5( Example 6 〃 // 〃 〃 〃 〃 40.0 (outer) 20.0 (inside) // 5.0 (outside) 1.0 (inside) Example 7 // // 〃 〃 // Ruiqin mine type Ti02 1_〇 ( Outside) 〇_5 (inside) 〃 30.0 (outer) 10.0 (inside) Example 8 〃 〃 // 〃 // 〃 5_〇 (outside) 2.5 (inside) 〃 20.0 (outer) 5.0 (inside) Example 9 〃 〃 〃 // // // 25.0 (outside) 12.5 (inside) 〃 10_0 (outside) 1.0 (inside) Example 10 〃 〃 〃 η 〃 〃 50.0 (outer) 25 Ό (inside) // 5.0 (outside) 〇.1 (inside) Comparative Example 1 100 144.0 87.0 8.2 39.7 Sharp 1 large mining type Ti02 1. 〇 (outside) 〇 _5 (内) No comparison example 2 // 〃 // 〃 // // 50.0 (outer) 25.0 (inside) 〃 38 201104016 Table 2 Deterioration of the reference raindrop contamination coating powder T-bend adhesion (0T ~ 2T#曲) ◎ After 6 months of exposure, no significant pollution after 6 months of exposure, no deterioration (gloss retention rate of more than 90%), no finger adhesion, no peeling, no adhesion after exposure for 6 months, slightly attached After 6 months of exposure, there was a slight deterioration (gloss retention rate of 60~90%). Some micro-adhesion was slightly attached to the finger. Some exposure was slightly Δ. After exposure for 6 months, the adhesion was observed after exposure for 6 months. (Gloss retention rate is less than 60%) When the finger licks, there is a significant adhesion area ratio of less than 50% of the peeling X. When exposed for 3 months, the adhesion is obviously attached to the exposed skin for 3 months, and the deterioration is found (the gloss retention rate is less than 50). %) When the finger is rubbed, there is a significant adhesion area ratio of 50% or more of the peeling table 3
No. 耐雨滴 污染 皮膜之 劣化 粉化性 皮膜厚度之減少(μηι) 自淨化性 持續期間 總合評價 6個月後 1年後 實施例1 〇 ◎ ◎ 0.2 0.4 約28年 〇 實施例2 ◎ ◎ ◎ 0.3 0.6 約20年 ◎ 實施例3 ◎ ◎ ◎ 0.2 0.4 L約25年 〇 實施例4 ◎ ◎ ◎ 0.2 0.4 約26年 〇 實施例'5 ◎ ◎ ◎ 0.3 0.6 約20年 ◎ 實施例6 ◎ 〇 〇 0.5 1.0 約12年 〇 實施例7 ◎ ◎ ◎ 0.1 0.3 約40年 ◎ 實施例8 ◎ ◎ ◎ 0.1 0.3 約36年 ◎ 實施例9 ◎ ◎ 〇 0.4 0.9 約12年 ◎ 實施例10 ◎ 〇 〇 0.6 1.3 約10年 〇 比較例] ◎ ◎ ◎ 0.2 0.3 約32年 X 比較例2 ◎ Δ △ 0.7 1.5 約7年 X 表4No. Deterioration of rain-resistant pollution film thickness Reduction of powdery film thickness (μηι) Self-purification duration total evaluation 6 months later 1 year later Example 1 〇 ◎ ◎ 0.2 0.4 About 28 years 〇 Example 2 ◎ ◎ ◎ 0.3 0.6 about 20 years ◎ Example 3 ◎ ◎ ◎ 0.2 0.4 L for about 25 years 〇 Example 4 ◎ ◎ ◎ 0.2 0.4 About 26 years 〇 Example '5 ◎ ◎ ◎ 0.3 0.6 About 20 years ◎ Example 6 ◎ 〇 〇0.5 1.0 About 12 years 〇Example 7 ◎ ◎ ◎ 0.1 0.3 About 40 years ◎ Example 8 ◎ ◎ ◎ 0.1 0.3 About 36 years ◎ Example 9 ◎ ◎ 〇 0.4 0.9 About 12 years ◎ Example 10 ◎ 〇〇 0.6 1.3 About 10 years 〇Comparative example] ◎ ◎ ◎ 0.2 0.3 About 32 years X Comparative Example 2 ◎ Δ △ 0.7 1.5 About 7 years X Table 4
No. GPTES 卜（質量份） PhTES (質量份） MTES (質量份） TEOS (質量份） Γ ΤΕ (質詈你Λ APTES f哲备公、 實施例11 100 0 106.8 87.0 8.2 1負里仍J 39.7 實施例]2 〃 // // // 〃 〃 實施例13 〃 η 〃 〃 〃 η 實施例14 〃 " // 〃 〃 〃 實施例15 100 72.0 53.4 87.0 8.2 " 39.7 // 實施例161 〃 ,, 〃 // 實施例17 // 〃 〃 〃 " 〃 實施例18 // 〃 // η // 39 201104016 表5No. GPTES Bu (mass) PhTES (mass) MTES (mass) TEOS (mass) Γ ΤΕ (Quality 詈 Λ APTES f 哲公, Example 11 100 0 106.8 87.0 8.2 1 negative still J 39.7 Embodiments] 2 〃 // // // 〃 实施 Example 13 η η 〃 〃 η 实施 Example 14 〃 " // 〃 〃 实施 Example 15 100 72.0 53.4 87.0 8.2 " 39.7 // Example 161 〃 ,, 〃 // Example 17 // 〃 〃 〃 " 实施 Example 18 // 〃 // η // 39 201104016 Table 5
表6Table 6
40 201104016 表740 201104016 Table 7
No 第1層 (最外層皮膜） 第: (第2肩 2層 皮膜） 鹄3厗 (第3層i膜） 第4層 (最内層皮膜） 皮膜密著性 (1T彎曲） 總合 評價 而十雨滴 污染 皮膜之 劣化 而ί雨滴 污染 皮膜之 劣化 耐雨滴 污染 皮膜之 劣化 而ί"雨滴 污染 皮膜之 劣化 實施例11 ◎ ◎ ◎ ◎ 無 ◎ ◎ ◎ ◎ 實施例12 ◎ ◎ ◎ ◎ 無 ◎ ◎ ◎ ◎ 實施例13 ◎ ◎ ◎ ◎ 無 〇 ◎ ◎ ◎ 實施例14 ◎ ◎ ◎ ◎ 無 ◎ ◎ ◎ ◎ 實施例15 ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ 實施例16 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 實施例17 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ 實施例18 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 比較例3 ◎ ◎ ◎ ◎ 無 ◎ ◎ Δ Δ 比較例4 ◎ ◎ ◎ ◎ 無 ◎ ◎ Δ Δ 比較例5 ◎ ◎ ◎ ◎ 無 〇 ◎ Δ Δ 比較例6 ◎ ◎ ◎ ◎ 無 ◎ ◎ X X 比較例7 ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ Δ Δ 比較例8 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ 比較例9 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ 比較例10 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ ί：圖式簡單說明3 (無） 【主要元件符號說明】 (無） 41No 1st layer (outermost layer film) No.: (2nd shoulder 2 layer film) 鹄3厗 (3rd layer i film) 4th layer (most inner layer film) Film adhesion (1T bending) Total evaluation and ten Deterioration of the raindrop-contaminated film, deterioration of the rain-fouling film, deterioration of the rain-fouling film, and deterioration of the rain-fouling film. Example 11 ◎ ◎ ◎ ◎ No ◎ ◎ ◎ ◎ Example 12 ◎ ◎ ◎ ◎ No ◎ ◎ ◎ ◎ Example 13 ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 17 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ Comparative Example 4 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ Comparative Example 5 ◎ ◎ ◎ ◎ 〇 〇 Δ Δ Comparative Example 6 ◎ ◎ ◎ ◎ No ◎ ◎ XX Comparative Example 7 ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ Δ Comparative Example 8 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ ratio Example 9 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ Example 10 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Comparative Δ Δ ί: 3 Brief Description of the drawings (no) [REFERENCE NUMERALS main components (none) 41