TW201119847A

TW201119847A - Coated metallic material and manufacturing method for same

Info

Publication number: TW201119847A
Application number: TW099131427A
Authority: TW
Inventors: Tomoaki Hosokawa; Kohei Ueda; Ikuya Inoue; Yuki Obara
Original assignee: Nippon Steel Corp
Priority date: 2009-09-17
Filing date: 2010-09-16
Publication date: 2011-06-16
Also published as: JP4897109B2; KR20120058547A; IN2012DN02298A; WO2011034216A1; TWI428237B; MY161009A; JPWO2011034216A1; CN102497982A; CN102497982B; KR101365279B1

Abstract

Disclosed is a coated metallic material having a coating layer comprising at least two layers: a first coating film layer which is located on part or all of the surface of a metallic material and which contains rutile titanium oxide at a solid volume concentration of 35-70%; and a second coating film layer which is laminated onto the surface side of the first coating film layer. The centre line average roughness (Ra) of the boundary surface between the first coating film layer and the second coating film layer is not less than 0.8 μ m. The disclosed coated metallic material has a higher total light reflectance than has previously been achieved and has excellent moldability. Also disclosed is a method for manufacturing the coated metallic material.

Description

201119847 - 六、發明說明：【發明戶斤屬之技術領碱3 技術領域本發明係有關於具有高反射率之塗裝金屬材及其製造方法。【先前名好；j 背景技術利用可見光線之各種裝置（例如：照明器具、AV機器、電子機器、移動式機器、液晶電視、電漿顯示器等），係藉由發射可見光線’而具有照免周圍、傳送光訊號、或映照出光影像等機能。該等機器中，亦有藉於光源周圍或背後設置反射板’使光於該反射板反射，以進行光亮度之提升、或光方向之改變等者。此時，為避免於光反射至反射板時光量降低，而於反射板表面要求高之可見光線反射率。因此’迄今’用以提高反射板表面之反射率的方法’使用有研磨金屬後作為鏡面、或塗裝反射率高之白色系塗料等。此種提咼反射率之方法’例如，專利文獻1中揭示了一種光反射薄膜技術，係於基材薄膜之單表面依序積層金屬薄膜層、含有無機微粒子之樹脂層’且該金屬薄皮膜層係由鋁所構成’使構成含有無機微粒子之樹脂層的無機微粒子之折射率nf與構成同層的樹脂之折射率nb為nf_nb 4。又，例如，專利文獻2中揭示了—種作為用於液晶顯示器之後面板的液晶顯示器之後面板用高擴散反射塗裝金屬板的技術，係於鋁板上，形成有相對於樹脂1〇〇質量份，含 201119847 有氧化鈦顏料150〜300質量份之膜厚5〇〜1〇〇μιη的下塗層與於該下塗層上，形成有相對於樹脂1〇〇質量份，含有氧化鈦顏料100〜250質量份，光澤為15以下，且膜厚1〇~3〇μιη的上塗層。又，例如，專利文獻3中揭示了一種具有高擴散反射率之被覆材料的技術，係具有至少一層相對於黏合劑100體積份，含有150體積份以上、小於15〇〇體積份之白色顏料的高濃度顏料層、或包含黏合劑與白色顏料，且其被覆層之空隙率為5體積％以上、小於35體積％的低密度層。此外，例如’專利文獻4中亦揭示了一種具有高擴散反射率之被覆材料的技術，係具有由黏合劑、金紅石型氧化鈦、及折射率較金紅石型氧化鈦低之粒子所構成，且金紅石型氧化鈦之濃度為35體積％以上、70體積％以下的可見光反射層。先前技術文獻專利文獻專利文獻1:曰本專利特開平10-730號公報專利文獻2 :曰本專利特開2002-172735號公報專利文獻3 :日本專利特開2006-192660號公報專利文獻4 :日本專利特開2008-145942號公報【發明内容】發明概要發明欲解決之課題然而，關於用於照明器具或液晶顯示器等電氣製品之 201119847 - 反射板，近年來，隨著電氣製品之構造或設計的複雜化等，對將反射板成形加工成各種形狀後使用的需求日益提升。甚之，亦趨向有要求更高度且均一地反射光之反射板的傾向。於此種現狀下，於如前述專利文獻丨所記載之技術，使用薄膜作為基材時，將積層金屬薄皮膜層或含有無機微粒子之樹脂層後的薄膜成形為目的形狀，是困難的，且於預先將4膜成形為目的形狀後，需積層金屬薄皮膜層或含有無機微粒子之樹脂層。此時，於反射板之成形形狀複雜時，有不易於加工部分使皮膜積層為均一之膜厚的不良情形。又則述專利文獻2所記載之技術中，雖可於鋁板上預先塗布下塗層與上塗層後再進行成形加工，但於以一般之 - 預塗覆塗裝生產線(Precoat COating line)進行的塗裝中，以丄 . 二欠塗裝該膜厚之下塗層（5〇〜ΙΟΟμηι)是非常困難的，且因需要重疊塗布2次以上，故有生產性低等缺點。料，於前述專利讀3及4所記載之技射，即使被覆層薄亦可得到高擴散反射率，且以一般之預塗覆塗裝生產線進行之1次塗裝仍可製作具有高擴散反射率之預塗覆、-屬板因被覆層中之黏合劑過少，故有加工性及密著性差的缺點。相對於此種情況，正在檢討藉於前述高濃度顏料層、㈣度層、可見光反射層之上下層形成低顏料濃度層，以曰、丨生及⑥、著性的技術。又，黏合劑樹脂方面，亦正藉使用分子S大之聚S旨樹脂’以提升加X性及密著 201119847 性的技術。然而，即使藉由上述任一技術，對應於對隨著電氣製品之構造或設計的複雜化之各種形狀的成形加工，，力口工性或密著性仍不充分。又，藉該等技術所製作之塗裝金屬材的全光線反射率，相對於電氣製品之反射板所要求者亦為稱不上充分的狀況。如上述，因電氣製品之構造上或設計上的理由，有需將反射板複雜地成形加工後使用的情況。此時，對塗带金屬材要求高成形性、全光線反射率、生產性等，但於前述專利文獻1〜4等所記載之塗裝金屬材中，無可滿足成形性 (加工性或密著性）或全光線反射率等性能者。本發明係有鑑於前述現狀而作成者，目的在於提供具有較以往更高之全光線反射率’且成形性優異之塗裝金屬材及其製造方法。用以欲解決課題之手段本發明人等為解決前述課題致力反覆進行研究，結果’發現藉於金屬材表面之一部分或全部被覆2層以上之被覆層’且該等被覆層包含，以高濃度含有金紅石型氧化鈦之第1塗膜層’與其上層之第2塗膜層，並增大第1塗膜層與第2塗膜層之邊界面的粗糙度，可兼具高之全光線反射率與優異之成形性，基於此種知識而完成本發明。換言之，依據本發明，可提供一種塗裝金屬材，係於金屬材表面之一部分或全部具有至少2層的被覆層，且該等被覆層包含，以固形物體積濃度計含有金紅石型氧化鈦 201119847 . 35%〜70%之第1塗膜層，與積層於前述第1塗膜層之表層側的第2塗膜層，且前述第1塗膜層與前述第2塗膜層之邊界面的中心線平均粗糙度Ra係〇.8μηι以上。此處，於前述第1塗膜層與前述第2塗膜層之邊界部分，存在混合有前述第ί塗膜層中之成分與前述第2塗膜層中之成分的混合層，且前述混合層以具有3μη1〜12μηι之厚度為佳。洳述被覆層最表面之/慮波中心線波紋（filtered center linewaviness)WCA以2μιτι以下為佳。前述被覆層中最表層之塗膜層亦可含有石夕氧樹脂或氣樹脂。前述被覆層中最表層之塗膜層亦可於形成塗膜之樹脂 - 骨架中具有-Si-0-Si-鍵結。 • 又，前述金紅石型氧化鈦之平均粒徑以20〇nm以上、 400nm以下為佳。前述第1塗膜層亦可更含有粒徑較前述金紅石型氧化鈦大，且具有較前述金紅石型氧化鈦低之折射率的粒子。以於前述第1塗膜層中存在空隙，且前述空隙之含有率為前述第1塗膜層中之固形物體積量的0_05倍以上、〇 9产以下為佳。前述第1塗膜層之膜厚以ΙΟμηι以上、80μηι以下為佳。前述第2塗膜層之膜厚以5μιη以上、30μηι以下為佳。前述被複層亦可更包含積層於前述金屬材與前述第^ 塗膜層之間的第3塗膜層。 7 201119847 刚述第3塗膜層之膜厚以5μηι以上、3〇μίη以下為佳。又’依據本發明，係提供—種製造上述塗裝金屬材之方法，該塗裝金屬材之製造方法係藉由多層同時塗布或濕疊濕方式將前述第1塗膜層之形成用塗料，與前述第2塗膜層之形成用塗料塗布於金屬材表面之—部分或全部。依據本發明’更提供-種於照明反射板使用有上述塗裝金屬材之照明器具。依據本發明，更提供-種於發光零件之反射板、或影像顯示部之反射板使用有上述塗裝金屬材的電子機器。發明效果依據本發明，可提供具有較以往更高之全錄反射率，且成形性優異之塗裝金屬材及其製造方法。圖式簡單說明第1圖係顯示本實施例中使用之亮度測定裝置之-例的截面模式圖。第2圖係由上部所見之第1圖之亮度測定裝置的模式凸狀態之一例的圖第3圖係顯示塗膜邊界面之凹【實施方式】用以實施發明之形態叫砰細地說明本發明之鲂佳實施形態。另，於本說明蚩芬節 ^ 於本說月書及_式中，實質上具有相同機月構成之構成要素係藉由明。猎由附加相同符號以省略重複說 201119847 . <塗裝金屬材之構成> 首先，說明本發明之一實施形態的塗裝金屬材之構成。本實施形態之塗裝金屬材，於作為基材之金屬材表面的一部分或全部具有至少2層之被覆層。具體而言，該被覆層具有至少包含以高濃度含有金紅石型氧化鈦之第1塗膜層（以下，稱為「高濃度顏料層」。），與積層於第1塗膜層之表層側的第2塗膜層（以下，稱為「上塗層」。）的積層構造。又，本實施形態之塗裝金屬材，亦可更於高濃度顏料層之内層側，即金屬材與高濃度顏料層之間，具有第3塗膜層（以下，稱為「下塗層」。）作為被覆層，亦可更具有其他塗膜層（例如，積層於上塗層之更表層側的塗膜層）。以下，依高濃度顏料層、上塗層、下塗層之順序，詳細地說明各塗膜 - 層之構成。 . [高濃度顏料層](概要）本實施形態之高濃度顏料層係以固形物體積濃度計含有金紅石型氧化鈦35%以上、70%以下，作為白色顏料之層，且較上塗層位於内層側，即靠作為基材之金屬材近之側。然而，於被覆層係由下塗層、高濃度顏料層及上塗層所構成之3層構造時，高濃度顏料層係位於下塗層與上塗層相接後所挾持之部分的層。又，於被覆層具有除了下塗層、高濃度顏料層及上塗層3層以外，包含其他1層以上之層之4 層以上的複層構造時，以位於上塗層與下塗層之間，且以固形物體積濃度計含有金紅石型氧化鈦3 5 %以上、7 0 %以下之所有層作為高濃度顏料層。並且，於被覆層中，於金紅 201119847 .,_匕鈦之/辰度連續地變化，各層之邊界不明確時，以滿足金紅石型氧化鈦之固形物體積濃度為35%以上、7〇%以下之條件的範圍的全部者作為高濃度顏料層。另夕匕卜’此處所稱之「金紅石型氧化鈦之固形物體積濃 ^係^，㈣於包含高濃度顏料層巾之塗膜中之樹脂⑽ 合劑)成分與顏料成分的固形物全體所占之體積，金紅石型氧化鈦所占之體積的比例，即除以塗膜中之空隙所占之於積者（5亥「金紅石型氧化鈦之固形物體積濃度」的測定方法係稍待後述）。本實施形態之高濃度顏料層中，藉以高濃度含有金紅石型氧化鈦，使乾燥、硬化後之塗膜中，金紅石型氧化鈦之粒子為最密填充以上地存在，則金紅石型氧化鈦粒子間所形成之空隙的體積將較黏合劑樹脂的體積大。因此，本貫妃形態之高濃度顏料層中，與以小於最密填充之濃度含有顏料的塗膜相異，可使未存在黏合劑樹脂之部分作為空隙存在於塗膜中。此處，一般而言，因空氣之折射率較與黏合劑一起使用之樹脂的折射率低，故金紅石型氧化鈦與空隙之折射率差較金紅石型鈦與樹脂之折射率差大。又，本貫細形態之高濃度顏料層中，於黏合劑樹脂與空隙之界面亦可反射高濃度顏料層所受的光。如此，於本實施形態之尚濃度顏料層中，因反射光之界面中的折射率差較以小於最密填充之濃度所含有之顏料的塗膜大，且可使光反射之界面的面積變大，故可得高之全光線反射率。以下，詳細地說明高濃度顏料層所含有之各成分。 10 201119847 - (金紅石型氧化鈦）本實施形態中，高濃度顏料層所含有之顏料係使用金紅石型氧化鈦。這是因為，金紅石型氧化鈦之折射率較一般所使用之其他白色顏料高，可增大與存在於作為黏合劑使用之樹脂或塗膜中之空隙的空氣之折射率差，故可更加提高顏料與樹脂之界面、及、顏料與空氣之界面中的全光線反射率。另外，銳鈦礦型氧化鈦雖亦具有較高之折射率，但因光觸媒性高’於接受螢光燈等光時，有黏合劑樹脂分解的可能性而不佳。本實施形態之塗裝金屬材因著眼於反射可見光，故人眼感度尚之波長域的全光線反射率高係為重要。人眼雖有個人差異，但可感受380nm〜780nm之波長的光，該感度之峰值係於555nm附近。因此，因本實施形態之塗裝金屬材亦 ' 以尚度反射以5 5 5 n m為中心之波長的光為佳，故高濃度顏料層使用之顏料（金紅石型氧化鈦）的粒徑亦以考量該點後選定為佳。作為顏料使用之金紅石型氧化鈦的平均粒#，當為小的話每單位體積之表面積會變大，作為光反射面之樹脂或空隙與顏料的界面之面積變大，故全光線反射率亦變高，但當顏料之平均粒徑過小的話，因長波長之光透射，全光線反射率曰下降此處，—般而言，於與波長相同能階之粒徑範圍中’有光散射大之所謂他散射領域，且粒徑為波長之1/2前後時光散射為最高是眾所周知的。由此可知，本實祕心中以將作為顏料使用之金紅石型氧化鈦的平 11 201119847 均粒徑設為可見光波長之約一半的200nm以上、4〇〇nm以下為佳，以250nm以上、350nm以下更佳。另外’本⑽形態中之金紅;δ型氧化鈦的平巧粒徑，係藉由電子顯微鏡(SEM)以1〇,〇0〇之倍率觀察塗膜欲確認之部分，映照於視野中之金紅石型氧化鈦粒子中，以數量來看去除20%之粒徑小者與5%之粒徑大的粒子後所剩之金紅石型氧化鈦粒子的粒徑之相加平均值。 <測定條件> 觀察用試料之製作方法：藉將試料填入樹脂，並研磨試料之垂直截面，以製作試料。觀察之視野：事前以500倍〜1000倍左右之光學顯微鏡或電子顯微鏡(SEM)觀察，選擇相當於高濃度顏料層之任意處。求得相加平均值之金紅石型氧化鈦粒子的選擇方法：拍攝使用電子顯微鏡(SEM)以loooo倍之倍率觀察所選之視野的影像。對映照於經拍攝之影像的金紅石型氧化鈦全粒子，測定粒徑® 各個金紅石型氧化鈦粒子之粒徑的測定方法：於金紅石型氧化鈦粒之粒徑測定中，測定各粒之最長徑與最短徑’且設成1粒之金紅石型氧化鈦粒徑=(最長徑+最短徑)/2。相加平均值之平均(?）：任意地選擇3處前述「觀察之視野」’並將該等視野各別所得之「相加平均值」進行算術平均。本實施形態中使用之金紅石型氧化鈦粒子只要為滿足 12 201119847 前述條件者的話，並無特別限制而可使用。又，本實施形態中使用之金紅石型氧化鈦粒子可為金紅石型氧化鈦之粒子單體，或者，亦可為於金紅石型氧化鈦施行有塗布二氧化石夕、氧化纟S、氧化錯、氧化辞、氧化録、各種有機物等者。使用於金紅石型氧化鈦之塗布的有機物係並非特別限定者’但可舉例如：新戊四醇、三經甲基丙燒等多元醇系化合物；三羥乙基胺、三羥曱基胺(trimethyk)lamine)之有機酸鹽等烷醇胺系化合物；矽氧樹脂、烷氣矽烷等矽系化合物等。 σ 本實施形態中，金紅石型氧化鈦亦可使用市售者，可使用例如：石原產業杜製「TIPAQUE(登錄商標）」系列、 FujiTitanhmi社製「TA」系列、TAYCA杜製「ΉΤΑΝΙχ(登錄商標）」系列等。又’如上述之金紅石型氧化鈦於高濃度顏料層中之固形物體積濃度係35%以上。當金紅石型氧化鈦之固形物體積濃度為35°/〇以上時，如上述，因於乾燥、硬化後之塗膜中’金紅石型氧化鈦之粒子係呈最密填充以上地存在，故可於塗膜中存在未存在有黏合劑樹脂之空隙。藉此，可提向南濃度顏料層之全光線反射率。於對塗裝金屬材尋求更向之反射性能時，係將上述具有200nm〜400nm之平均粒徑的金紅石型氧化鈦設為以固形物體積濃度計為5 0 %以上。此時’塗膜中之金紅石型氧化鈦與空隙的界面、金紅石型氧化欽與樹脂的界面、及樹脂與空隙的界面將有效率地有助於全光線反射率，可得高之全反射率，故為佳。 13 201119847 另一方面，當向濃度顏料層中之金紅石型氧化鈦的固形物體積濃度大於7G%時，塗膜中之金紅石型氧化欽與空隙所占之tt例過多’故鄕合劑樹脂確保塗膜之連續性(保持膜之狀態）變得1S難，高濃度顏料層本身將變得脆弱。因此，將高濃度顏料層中之金紅石型氧化鈦的固形物體積濃度設為7G%以下。由確保穩定之塗膜強度的觀點來看金紅石型氧化鈦的固形物體積濃度之較佳範圍係6 5 %以下。此處，說明本實施形態中之被覆層中的固形物體積濃度之測定方法。以被覆層係由上塗層、高濃度顏料層、下塗層所構成之3層構造時的金紅石型氧化鈦的固形物體積濃度之測定方法為例，進行說明。 (金紅石型氧化鈦的固形物體積濃度之測定方法）首先，由試料將作為測定對象之被覆層切削成各層以成為上塗層、尚濃度顏料層、下塗層，並測定削取後之塗膜面積A1及質量Ml。接著，使用坩堝將削取下之塗膜以5〇〇 °C加熱1小時，使樹脂成分分解。因可將未分解而殘留下之部分視為金紅石型氧化鈦，故測定該殘留部分之質量M2。因一般之金紅石型氧化鈦顏料的密度係 3800〜4200kg.m·3左右’故假設金紅石型氧化鈦顏料之密度為4000kg.nT3，又，因一般之聚酯樹脂的密度係 1150〜1250kg.m·3左右，故假設聚酯樹脂之密度為 1200kg.m·3，以Vl=(Ml-M2)/1200kg.m_3，求得聚酯樹脂之體積VI，以V2=M2/4000kg.m_3，求得金紅石型敦化鈦之體積V2。 14 201119847 由如此所求得之聚S旨樹脂之體積V1、金紅石型氧化錄^ 之體積V2,可以〇¥2/(¥1+¥2)><100(體積％)求得金紅石型氧化鈦之體積濃度C1。對1個測定對象(例如，高濃度顏料層）進行3次前述C1 之測定，求得其算術平均。 (其他粒子之添加）於本實施形態之高濃度顏料層中，因將上述粒徑較金紅石蜇氧化鈦大，且具有低折射率之粒子（以下，有稱為「低折射率粒子」之情形。）與金紅石塑氧化鈦併用時，可較有效率地提高全光線反射率，故為佳。藉更將粒徑較金紅石型氧化鈦大之粒子添加於高濃度顏料層，可增大高濃度顏料層中粒子間之空隙，並可含有較多之空隙，藉此，可提升全光線反射率。並且，因與金紅石型氧化鈦併用之粒徑大的粒子係低折射率之粒子，故於該低折射率粒子與金红石型氧化鈦粒子接觸之部位的接觸界面，亦可藉金紅石型氧化欽粒子與低折射率粒子之折射率差反射光，可有助於提升全光線反射率。於前述低折射率粒子之粒徑相對於金紅石型氧化鈦之粒徑過大時，將難以發揮有效率地於高濃度顏料層中含有空隙，且有效率地於低折射率粒子與氧化鈦之接觸界面得到光反射的效果。由此種觀點來看，低折射率粒子之平均粒徑，以Ιμηι以上、ΙΟμπι以下為佳，以3μηι以上' 8_較佳。該低折射率粒子與金紅石型氧化鈦之相加平均粒捏之 15 201119847 比即¥(低折射率粒子之相加平均粒徑)/(金紅石型氧化鈦之相加平均粒徑），以1/4()以上為佳，更以·〜議(特別是3/40〜10/40)為佳。另外’本實施形巾之低折射率粒子之平均粒徑係指，與金紅石型氧化鈦同樣地，藉由電子顯微鏡以10，麵，倍率觀察塗膜欲確狀部分，_、於視野巾之低折射率 2中1數量來看去除20%之粒徑小者與5%之粒徑大的之低折射率粒子的_之相加平均值(即，低折斜之粒㈣相加平均值1可與上述「金紅石型氧化欽」之情形同樣地測定）。前述⑽射率粒子似較金紅^魏化鈦低二’並非❹m定者，但^金紅石魏化鈦之折射 .’、、1以上者為佳’甚之，以訝可見光領域之光的吸收力折:且於粉末狀態下呈白色者為佳。具體而言，前述低斤射率粒子可使用例如：二氧化#@ 化矽、碳酸鈣、硫酸鋇、氧 ^無機粒子。X’除狀外，亦可使賴脂粉末等作折射率粒h «粉末<種類亦無特別限定，但吏2例如:丙烯基樹脂粉末，樹脂粉末、PTFE(聚四机&烯)粉末等作為樹脂粉末。 2述低折射率粒子之個，係如前述，可有效率地使接觸2顏料層中含有空隙，且於低折射率顏料與氧化鈦之反射光’㈣高化率。因此，即使低折射折射/⑽量為少量’仍可發_含有之量的效果，故低斤射率粒子之下限濃度並無特別限定之需要，但於(低折射 201119847 率粒子之體積/金紅石型氧化鈦之體積）小於0.05時，添加低折射率粒子之全光線反射率的提升效果減少。因此，低折射率粒子之下限濃度以（低折射率顏料之體積/金紅石型氧化鈦之體積）為0.05以上的濃度為佳。另一方面，低折射率粒子之上限濃度，於（低折射率顏料之體積/金紅石型氧化鈦之體積）為0.2以下之範圍時，隨著低折射率粒子之添加量的上升，光之反射率上升，可發現低折射率粒子之添加效果，但當超過該值而添加時，發現有光之反射率以外的性能（加工性、耐蝕性等）下降之傾向。因此，低折射率粒子之上限濃度以（低折射率顏料之體積/金紅石型氧化鈦之體積）為0.2以下的濃度為佳。又，前述低折射粒子除了提升全光線反射率之作用以外，亦具有控制高濃度顏料層與上塗層之邊界面的粗糙度之作用，詳細内容則待後述。 (塗膜中之空隙）高濃度顏料層中之空隙的含有率以固形物體積量之 0.05倍以上、0.9倍以下為佳。這是因為，當空隙之含有率小於固形物體積量之0.05倍時，藉由含有空隙所得之全光線反射率的提升效果減少，而當空隙之含有率大於固形物體積量之0.9倍時，高濃度顏料層變脆弱（機械性強度下降），有加工性及密著性不佳的可能性。該「空隙之含有率」可以後述之方法進行測定。高濃度顏料層中空隙之含有率的控制係如上述，可藉由金紅石型氧化鈦或低折射粒子等之顏料含有濃度來控 17 201119847 制，但除此之外"亦可藉由例如：調整用以形成高濃度顏料層之塗料的分散狀態來控制。換言之，因塗料中顏料之分散狀態越良好(越均-）’黏合劑樹㉝吸著於蘭而有效率地填入顏料粒子間之空隙，故空隙之含有率變少。因此，為得較高之全光線反射率，以塗布性或塗料之穩定性無問題的範圍内維持最低限度的分散狀態（塗布性或塗料之穩定性無問題之範圍下，盡可能地不為均―）為佳。另外，塗料中顏料之分散狀態可藉由調整分散機之種類、分散時間、分散劑之種類、添加量等來控制。高濃度顏料層中空隙之尺寸並未特別限定，但當為極端大之尺寸者時，有造成塗膜缺陷，使加工性或耐蝕性等塗膜性能下降的疑慮故不佳，又，因空隙之每單位體積的表面積變小，由全光線反射率之提升效果的觀點來看亦不佳。另一方面，當空隙之尺寸小時，空隙之每單位體積的表面積變大，光之反射界面的面積變大，故全光線反射率亦邊尚，但當空隙之尺寸極端地過小時，因長波長之光透射’而有全光線反射率下降之疑慮。因此，高濃度顏料層中空隙之尺寸，由光之反射率提升的觀點來看，以可見光波長之約一半200〇111〜40011111為佳，以250nm〜350nm更佳。但，因空隙尺寸之控制，特別是統一塗膜中空隙之尺寸.是困難的，故若無如上述之塗膜缺陷等問題或極端之對反射率的影響的話，空隙之尺寸係無特別問題。另，本實施形態中，空隙之尺寸係使用具有與空隙相同體積之球的直徑之等效體積直徑（equivalent 18 201119847 volume diameter)。實際上，使用掃描型電子顯微鏡(SEM) 以10000倍之倍率拍攝高濃度顏料層中垂直截面之任意處，並選擇該拍攝影像所觀察之任意空隙，再將具有與該面積相同面性之圓的直徑’定義成與具有與空隙相同之體積的球之直徑相同後可求得。電子顯微鏡拍攝影像所觀疼之空隙内’算出任意10個空隙之直徑，且可將該算術平均作為空隙之直徑。此處，說明本實施形態中之被覆層中空隙之體積％、則定方法。相對於之面切面、或首先，由試料削取作為測定對象之被覆層後，被覆面（於金屬材表面平行之面）將該被覆層於垂直下，並以* *光學顯微鏡、電子顯微鏡等觀察該截使用電磁膜厚計氺*，求得被覆層之膜厚T1。又，與金紅石型氧化鈦之體積濃度時同樣地，求出削取後之塗膜面積A1、黏合劑樹脂（例如，聚酯樹脂）之體積Vl、及顏料(例如，金紅石型氧化鈦）之體積V2。由求出之A1、\^1及乂2 , 以T2=(V1+V2)/A1求得無空隙時被覆層之膜厚T2。田如此所求出之VI、V2、Τ1及Τ2，可藉由V3=(V1+V2) χ (Τ1-Τ2)/(Τ1+Τ2)之式求得空隙之體積V3。由測定精度方面來看，前述膜厚T1之測定方法以使用光學顯微鏡或電子顯微鏡(SEM)之方法為佳。又，前述&隙體積係對同一試料（即’被覆層）測定5次，求得其算術平均 (黏合劑樹脂）本實施形態之高濃度顏料層中使用的黏合劑樹脂，並 19 201119847 未特別限定，可使用一般所使用之黏合劑樹脂，例如：聚酯樹脂、胺曱酸乙酯樹脂、環氧樹脂、丙烯酸樹脂、矽氧樹脂、氟樹脂等。但，於本實施形態之高濃度顏料層中，由因添加最密填充以上之量的金紅石型氧化鈦粒子，故塗膜容易變得脆弱之點來看，高濃度顏料層中使用之黏合劑樹脂，以使用加工性或密著性優異之樹脂為佳。具體而言，黏合劑樹脂以使用，例如，數平均分子量為19000以上、 28000以下之聚酯樹脂A為佳。這是因以下理由之故。於本實施形態之塗裝金屬材中，因以得到高之全光線反射率為目的，故需將添加於高濃度顏料層中作為白色顏料之金紅石型氧化鈦粒子設為以固形物體積濃度計係 35%〜70%的高濃度。因此，依據塗料中使用之黏合劑樹脂的種類，有接著顏料粒子間之黏合劑能力不足的情形，故有塗裝金屬材之加工性下降的問題。於是，本發明人等致力於檢討以少量之黏合劑樹脂用以確保加工性之被覆層的構成，結果，發現與顏料粒子及作為基材之金屬材之密著性優異的聚酯樹脂係最適合者，又，藉將聚酯樹脂的數平均分子量定為19000以上、28000以下，可顯現延性與強度之均衡優異的性能，故藉由使用數平均分子量為19000以上、28000以下之聚酯樹脂A，可得良好之加工性。聚酯樹脂之數平均分子量可藉由「GPC」測定。於使用市售之樹脂時，可使用製造廠商所揭示之數平均分子量的值。此處，一般而言，使用分子量為19000以上之高分子量聚酯樹脂作為黏合劑的塗料因黏度容易過高，故為確保適 20 201119847 合塗裝之黏度，有降低塗料中之固形物濃度的必要。因此，於如本發明之主要使用於厚膜塗裝的用途上，容易產生稱為發泡之塗裝缺陷’而被認為難以使用高分子量聚酯樹脂。然而’本實施形態中，因多量地添加作為白色顏料之金紅石型氧化欽，黏合劑樹脂之濃度相對地降低，即使不易降低塗料中之固形物濃度，仍可確保適合塗裝之黏度。因此’即使使用高分子量之聚酯樹脂A作為本實施形態之高礙度顏料層的黏合劑’仍可不產生起泡地進行厚膜之塗裝’可兼具塗裝性與加工性。又’當聚酯樹脂A之數平均分子量小於19〇〇〇時’因不易確保成形性，故合併上述理由，將作為本實施形態之高濃度顏料層中使用之黏合劑樹脂使用的聚酯樹脂A之數平均分子量的較佳範圍設為19000以上。另一方面，當聚酯樹脂A之數平均分子量大於28〇〇〇時’塗膜表面會過度柔軟，而有耐瑕祕不佳的疑慮，故將作為本實;^態之高濃度顏料層中使用之黏合劑使用的聚1曰Μ月日A之數平均分子量的較佳範圍設為咖以下。如上述之聚賴脂A的添加量，只要相對於黏合劑樹脂全體之聚S旨樹脂a的濃度為2()質量％以上的話，即可不產生發泡地進行相之塗裝，可兼具塗裝性與加工性，故以將相對於黏&劑祕月曰全體之聚酯樹脂A的濃度設為Μ質量％以上為佳。又，本發明人等發現，高濃度顏料層中之黏合劑樹脂除了前述聚S旨樹脂纽外，更含有數平均分子量為2000以 21 201119847 上、6000以下，且羥基價為20以上之聚酯樹脂b，並且聚面旨樹脂A與聚酯樹脂B以質量比計為0.25 $ (聚酯樹脂b)/(聚酿樹脂Α)$4，藉此，可得更優異之成形性。如上述，數平均分子量為19000以上、28000以下之高分子量的聚酯樹脂A之加工性優異，但本實施形態之高濃度顏料層因以高濃度地含有金紅石型氧化鈦等顏料，而被視為具有顏料間分散有黏合劑樹脂的構造。於此種構造中，即使為含有高分子量聚酯樹脂A之被覆層，相較於顏料濃度低之被覆層，其加工性有變低之傾向，而追求更加提升之加工性。於是，本發明人等為更加提升加工性而致力地進行檢討，結果，發現藉由組合高分子量之聚酯樹脂A與低分子量之聚酯樹脂B使用，可得較單獨使用高分子量之聚酯樹脂A 時更優異的加工性能。換s之，高分子量聚g旨樹脂A單獨以高濃度地存在於顏料之間隙時，無法充分地進入樹脂，使作為黏合劑之機能變得不充分，而有加工性些微下降之可能性。相對於此，藉由組合高分子量之聚酯樹脂A與低分子量之聚酯樹脂B使用，低分子量之聚酯樹脂8可進入高分子量之聚酯樹脂A無法進入之顏料與顏料之間，而作為顏料與顏料、或顏料與高分子量之聚酯樹脂A的黏合劑產生機能，因可&升被覆層全體之強度及密著性，故被視為可得優異之加工性。又，低分子量之聚酯樹脂B的羥基價越高，將具有更多之父聯點’可得更高之皮膜密著性。由以上觀點來看，低分子量之聚酯樹脂B係以數平均分 22 201119847 - +里為2_以上、6GGG以下，JMi基價為2G以上為佳。當聚輯脂B之數平均分子量小於2_時，皮膜強度不充分而有力1±下降之疑慮’當數平均分子量大於_叫，因聚 S曰秘月曰B不易進人_與簡之間，而有密著性之提升效果下降的疑慮。又’當聚酿樹脂B之經基價小於2〇時，顏料與顏料之交聯點變少，有密著性之提升效果下降的疑慮。此外’由皮膜性能之觀點來看，無需特別設定聚酉I樹脂B之經基價的上限值’但由樹脂之容易取得性、塗料之穩定性的觀點來看’聚酿樹脂B之經基價以2〇〇以下為佳。又，聚酉1樹脂A與聚酿樹脂B之混合比例以質量比計為 0.25$(聚醋樹脂B)/(聚酿樹脂Α)^4時，可得優異之密著性及加工性。當（聚醋樹脂別/(聚酯樹脂Α)之質量比小於〇_25 時，聚_齡之機能顯現變得不充分，故有密著性下降之 ' 疑慮，當（聚醋樹脂抑(聚酉旨樹脂Α)大於4時，聚醋樹脂Α之機能顯現變得不充分，故有加工性下降之疑慮。 (膜厚）本實施形態之高濃度顏料層之膜厚，為得高之全光線反射率以ΙΟμηι以上為佳，於追求較高之全光線反射率時’以40μπι以上更佳。另一方面，當高浪度顏料層之膜厚大於80μιη日f g]有塗膜之加卫性下降的疑慮，故高漠度顏料層之膜厚以ΙΟΟμη!以下為佳，於追求較高之加工性時，以15μη\以下更佳。此處’可如以下地測定本實施形態之高濃度顏料層的膜厚。換言之，藉相對於各塗膜層之被覆面於垂直之面切下’並以光學顯微鏡、電子顯微鏡觀察該截 23 201119847 面，可得塗膜層之膜厚。該「膜厚」測定中，係將任意5處所測定之（算術）平均作為膜厚。另外，後述之上塗層及下塗層之膜厚，亦可與高濃度顏料層之膜厚同樣地測定。又，於各塗膜層之邊界部形成有混合層的情形，係梢待後述。 [上塗層] 以上，詳細地說明了本實施形態之高濃度顏料層，緊接著，說明本實施形態之上塗層。 (概要）本實施形態之上塗層係於上述高濃度顏料層之表層側，即離作為基材之金屬材較遠之側所積層的被覆層。此處，於被覆層係由高濃度顏料層及上塗層所構成之2層構造時、除此之外更包含下塗層之3層構造時、以及複數層地存在高濃度顏料層之4層以上的構造時，上塗層係位於最表層。然而，上塗層只要係直接積層於高濃度顏料層之表層側的話，並非需要位於最表層，亦可於上塗層之更表層側積層其他被覆層。 (黏合劑）作為上塗層之黏合劑使用之樹脂，雖並非特別限定者，但由與高濃度顏料層之密著性、或後述之混合層的形成、塗料原料的共通化等觀點來看，以使用含有與高濃度顏料層相同之樹脂為佳。因此，高濃度顏料層之黏合劑，以使用數平均分子量為19000以上、28000以下之聚酯樹脂A 為佳，故上塗層中，亦以使用聚酯樹脂A作為黏合劑為佳。 24 201119847 當作為上塗層之黏合劑使用之聚酯樹脂的數平均分子量小於19000時，有加工性及密著性下降的疑慮，當數平均分子量大於28000時，塗膜表面變得過軟，有耐瑕疵性及防沾黏性劣化的疑慮。另外對上塗層之醋樹脂A的添加量，只要相對於黏合劑樹脂全體之聚醋樹脂八的濃度為8〇質量％以上的話，即可發揮加工性或密著性之提升效果故以將相對於黏合劑樹脂全體之《樹脂A的濃度設為啊量％以上為佳。 (顏料）上塗層係與高濃度顏料層相異，並不一定需要添加顏料’可視用途調整顏料添加之有無、添加顏料之種類顏料之濃度等’以賦^所需之反射雜或其他特性。首先敘述於上塗層，例如添加金紅石型氧化欽作為顏料的m藉於上塗層添加金紅石型氧化鈦可提升 :光線反射率，且金紅石贼化鈦濃度高的話，對反射性月匕有力，然而’上塗層之主要作用係保護被覆層全體，故 k 之塗_、不佳。因此’由確保塗膜之柔軟性的觀上塗層中金紅石型氧化鈦之濃度，以固形物體積 /辰度计為35%以下為彳去 ’’’、。另—方面，並不需要特別限定上 έ ，.工石型魏欽濃度之下限，亦包含完全未含有金氣，欽的情形。換言之，本實施形態之上塗層中的、氧化欽'農度’以固形物體積濃度計為0 %以上、3 5 % 二Iί °此外，於追求較高之全光線反射率化時，藉將 d之金紅石型氧化鈦濃度設為以固形物體積濃度計 25 201119847 為20%〜3 0%，可高次元地兼具藉上塗層所得到之被覆層全體的保護機能與高反射性能。另外，此處所稱之「金紅石型氧化鈦之固形物體積濃度」係，相對於包含上塗層中之塗膜中之樹脂(黏合劑)成分與顏料成分的固形物全體所占之體積，金紅石型氧化鈦所占之體積的比例。使用金紅石型氧化欽作為顏料時’該金紅石型氧化欽之平均粒徑，因較小的話每單位體積之表面積變大，且作為光反射面之樹脂或空隙與顏料之界面的面積變大，故全光線反射率亦變高，但當顏料之平均粒徑過小時，因長波長之光透射，故全光線反射率下降。因此，與高濃度顏料層的情形同樣地，以將作為上塗層中之顏料使用的金紅石型氧化鈦之平均粒徑設為2〇〇nm以上、400nm以下為佳，以設為250nm以上、350nm以下更佳。 (顏料以外之添加成分）於上塗層中，除了金紅石型氧化鈦以外，亦可添加例如’無光劑。藉於上塗層以固形物體積濃度計為3%以上、 15%以下地添加無光劑，可於與未使用無光劑時相同程度之全光線反射率下’得到幾無正反射成分的反射特性。於將具有此種反射特性之塗裝金屬材作為照明器具之反射板使用時，因無關與光源之距離、角度，可得到—定之反射光，故即使於光源數量少、或光源間之間隔大時，亦可得均一之反射光。然而，藉由添加無光劑，上塗層之表面將形成細微之凹凸，因汙染物質容易堆積於該微細之凹凸， 26 201119847 - 且以擦栻亦不易去除該汙染物質，故有耐汙染性下降之疑慮。因此，無光劑之添加量，考量到對反射光之均一性與耐汙染性下降的影響，以決定適當的量為佳。又，本貫施形態中使用之無光劑，並非特別限定者，但以例如’粒徑為3μηι〜9μηι之二氧化石夕為佳。 (膜厚）於上塗層添加金紅石型氧化鈦時，上塗層之膜厚越厚，可得到越高之加工性、密著性及全光線反射率。然而，當上塗層之膜厚大於30μιπ時，因塗裝時容易產生發泡故塗裝性劣化，又，由塗料成本之觀點來看亦不佳。另一方面，當上塗層之膜厚小於5μπι時，因依據上塗層之加工性、後著性及王光線反射率的提升效果變小，故以將上塗層之 . 膜厚設為以上、30μπι以下為佳。由確保穩定之加工性、 . 密著性、全光線反射率及塗裝性的觀點來看，較佳之上塗層的膜厚係10μηι以上、25 μιη以下。於上塗層以固形物體積濃度計添加無光劑3%以上、 15%以下時，上塗層之膜厚的範圍係與於上塗層添加有金紅石型氧化鈇時相同，以5μπι以上、3〇μηι以下為佳。當上塗層之膜厚大於3〇μηι時，因塗裝時容易產生發泡，故塗裂性劣化，又，由塗料成本之觀點來看亦不佳。另一方面，當上塗層之膜厚小於5卜1^時，有幾乎未能得到依據上塗層之加工性、密著性的提升效果、或幾無正反射成分之反射特性的疑慮。由確保穩定之加工性、密著性、反射特性及塗表丨生的觀點來看，添加有無光劑之上塗層的較佳膜厚係 27 201119847 ΙΟμπι以上、25μιη以下。 [關於高濃度顏料層與上塗層之界面的粗糙度] 本實施形態之塗裝金屬材中，上述高濃度顏料層與上塗層之邊界面的中心線平均粗糙度Ra需為〇.8μηι以上。如此，藉增大高濃度顏料層與上塗層之邊界面的Ra，高濃度顏料層與上塗層之邊界面將變粗，故可提高擴散反射率。當南濃度顏料層與上塗層之邊界面的Ra小於〇 8μιη時，未能充分地得到前述密著性之提升效果或提高反射率之效果。當為〇·9μιη以上時’因反射率較高’而較佳。當為2 〇μπ1以上時則更佳。中塗層與上塗層之邊界面的Ra係藉由將各實施例之塗膜切斷，填入樹脂後研磨，將垂直於塗膜表面的截面變得平滑，再以掃描型顯微鏡（倍率1 〇〇〇倍）拍攝的照片進行評價。由照片上方覆蓋OHP所使用之透明片，精密地描繪邊界面之凹凸後，如第3圖所示，於邊界面曲線之平均線的方向上僅取出1基準長度，並將該取出部分之平均線的方向作為X轴、縱倍率方向作為,，且於以y=f(x)表示界面曲線時，將藉由數1所求得之值作為邊界面之Ra。另夕卜，本申請案毛明中’塗膜中之任意裁面的$處，係將以前述方法測定之Ra加以平均。 |dx (邊界面之Ra的控制方法） :濃度顏料層與上塗層之邊界面的Ra可藉由下述控制·问濃度顏料層及上塗層之塗布方法、高濃度顏料層中 28 201119847 之顏料（金紅石型氧化鈦）的濃度、高濃度顏料層之顏料種類 (金紅石型氧化鈦、二氧化矽等低折射率粒子等）、高濃度顏料層及上塗層形成用塗料之低剪力下的黏度或表面張力等。另外，本開發中高濃度顏料層與上塗層的邊界面係指，以光學顯微鏡或電子顯微鏡拍攝塗膜之截面時視覺上所見之邊界面（邊界線）。具體而言，用以將高濃度顏料層與上塗層之邊界面的 Ra增大的方法有下述該等方法： (1) 將高濃度顏料層形成用塗料與上塗層形成用塗料於未乾燥之狀態下積層，即使用所謂之濕疊濕法或多層同時塗布法； (2) 將高濃度顏料層中之顏料（金紅石型氧化鈦等）提高 - 至較上塗層中之顏料濃度高； . (3)於高濃度顏料層中添加粒徑大之粒子（二氧化矽等）； (4) 降低低剪力下之高濃度顏料層形成用塗料的黏度；及 (5) 縮小高濃度顏料層形成用塗料與上塗層形成用塗料之表面張力差。首先，關於前述方法（1)，藉將高濃度顏料層形成用塗料與上塗層形成用塗料於未乾燥之狀態下積層，金紅石型氧化鈦粒子從高濃度顏料層朝上塗層擴散之力於邊界面作用，塗膜層之邊界面的Ra變大。此時，如方法(2)般地，將高濃度顏料層中之金紅石型氧化鈦的濃度提升至高濃度， 29 201119847 特別是’設成最密填充以上之濃度，藉此，與上層塗膜之漠度差變大，且金紅石型氧化鈦朝上塗層擴散之力強勁地作用’故邊界面之Ra變得更大。又’關於方法(3) ’於高濃度顏料層中添加粒徑大之粒子，並使該大粒徑之粒子存在於高濃度顏料層與上塗層之邊界面附近，藉此，因於邊界面有大粒徑之粒子所形成的凹凸’故邊界面之Ra變大。此時，如方法⑴般地，藉將高濃度顏料層形成用塗料與上塗層形成用塗料於未乾燥之狀態下積層，因大粒徑之粒子由高濃度顏料層擴散至上塗層，故大粒徑之粒子變得容易存在於高濃度顏料層與上塗層的邊界面附近。、νανπ 稭由降低低到刀F之咼濃度顏米 =成用塗料的黏度’因高濃度顏料層中之金紅石型氧七 #易住上塗層擴散’故邊界面之Ra變大。換言之，依相 ^人等之知識’以於乾燥、硬化後為最密填充以上3 度添加有微粒子（此時為金紅石型氧化鈦）的塗料會成》般所稱之濃高分m料的非牛頓流體，成為以旋轉! 黏度時’具有於低旋轉下黏度高，且於高旋轉 =低’即剪切稀化特性的塗料。濃厚分散系塗料中，^ 2中顏料粒子間之距離短，故於粒子間產生分子間力此旦於低旋轉下施加於塗料之剪力變小，故於該分子R 剪〜：下黏度變高。另一方面，於高旋轉下施加於塗* 蚀隻大’當該剪力大於分子間力時，黏度變低。於料塗裝於基材時之塗裝作業性，除了大幅地受高名 30 201119847 下之黏度影響以外，於塗裝後之乾燥、燒附硬化步驟中塗料之膜内流動方面亦大幅地受低旋轉下之黏度影響。因此，關於控制高濃度顏料層與上塗層之邊界面的Ra，調整低剪力下之塗料黏度係重要的。於此，關於低旋轉下之塗料黏度，可藉由變更塗料中之溶劑量及塗料之保管條件（保管溫度及保管期間）來調整。塗料之保管條件，係保管溫度越高、或保管期間越長，因觸變性變低，故低剪力下之塗料黏度提升。這是因為，當保管期間變長時，顏料表面與塗料之濕潤性高，較多之樹脂吸附於顏料表面，故顏料間之分子間力減弱，觸變性變低。此外，藉將分散劑等添加劑添加於塗料中，亦可調整低剪力下之塗料黏度。 - 又，關於方法(5)，當縮小高濃度顏料層形成用塗料與 - 上塗層形成用塗料的表面張力差，且，將該等塗料於未乾燥狀態下積層，同時使其乾燥及燒附硬化時，邊界面之Ra 變大。然而，高濃度顏料層形成用塗料與上塗層形成用塗料的表面張力差，因各層之樹脂種類或溶劑種類等的差異，適當之值互異，故無法一概地規定，需事前調查各塗料以取決最適值。此處，塗料之表面張力可藉由使用均染劑或消泡劑等一般稱為界面活性劑之添加劑來調整，但亦可藉由改變溶劑之種類來調整。此外，本實施形態之塗裝金屬材中，需將高濃度顏料層與上塗層之邊界面的中心線平均粗縫度Ra設為0.8μηι以上，為此較有效之方法，可舉例如：於高濃度顏料層中添 31 201119847 加粒徑200nm〜4〇〇nm之金紅石型氧化鈦，使成為相對於乾燥後塗膜之體積為最密填充以上，並將該高濃度顏料層形成用塗料與上塗層形成用塗料於未乾燥之狀態下積層，於積層後之狀態下同時使其乾燥、硬化的方法。藉於高濃度顏料層中添加最密填充以上之金紅石型氧化鈦，並於未乾燥狀態下與上塗層積層，將於各塗膜層間產生金紅石型氧化鈦粒子之濃度梯度，並產生使南濃度顏料層中之金紅石型氧化鈦粒子往上塗層側擴散的效用，此外，因於乾燥、硬化步驟施加熱，故該熱將成為驅動力使金紅石型氧化鈦擴散的效用更為顯著。另一方面，因於乾燥、硬化步驟施加熱時’形成塗膜之樹脂產生交聯反應，故產生抑制金紅石型氧化鈦粒子之層間擴散動作的效用。因此，高濃度顏料層與上塗層之邊界面成為粗糙狀態，Ra變大。又，藉由設置本實施形態之高濃度顏料層作為上塗層之下層塗膜層，可使高濃度顏料層與上塗層之邊界面的Ra 成為0·8μιη以上，但如前述(4)，低剪力下之塗料黏度大幅地影響對高濃度顏料層與上蜜層之邊界面的尺3之控制，藉由降低低剪力下之塗料黏度，可更增大高濃度顏料層與上塗層之邊界面的Ra。 [混合層] 本實施形態之塗裝金屬材中，藉由濕疊濕法或多層同時塗布法塗裝高濃度顏料層形成用塗料與上塗層形成用塗料，因咼濃度顏料層形成用塗料中之金紅石型氧化鈦會超出各層之界面而朝上塗層形成用塗料擴散，故可於高濃度 32 201119847 顏料層與上塗層之界面附近形成金紅石型氧化鈦之濃度梯度層。本發明中將本氧化鈦之濃度梯度層稱為混合層。此時，藉存在於高濃度顏料層與上塗層之邊界部分的混合層，可提升高濃度顏料層與上塗層間之密著性。又，當為預塗覆金屬材時，雖有因塗裝後之加工造成塗裝金屬材之全光線反射率下降的情形，但因存在有混合層，密著性提升，故亦可抑制加工後之全光線反射率下降。 (混合層之定義）此處，本實施形態中之「混合層」係指，因高濃度顏料層之金紅石型氧化鈦朝上塗塗膜層擴散，而形成之金紅石型氧化鈦之濃度為傾斜構造的層。更具體而言，本實施形態中，當著眼於金紅石型氧化鈦時，將高顏料濃度層之 Ti量設為X、上塗層之Ti量設為y時，令[χ+0·05 X (x-y)]〜[y-0.05x(x-y)]之部分作為混合層。各Ti量可以後述之分析方法求得，亦可將以各分析器測定Ti時之測定強度作為量進行計算。另外，亦有於後述下塗層與高濃度顏料層之間形成混合層的情形，於該情形下，混合層之定義或邊界面之定義亦與高濃度顏料層與上塗層間之混合層相同。當於高濃度顏料層包含低折射率粒子時，低折射率粒子相對於金紅石型氧化鈦之體積比，只要低折射率粒子為例如，無機顏料的話，即可藉由與求得金紅石型氧化鈦之體積濃度相同之操作求得。與金紅石型氧化鈦之區別係，例如，於加熱殘留部分中使用不會使金紅石型氧化鈦溶 33 201119847 解’僅溶解低折射率粒子之酸等化學藥品，僅溶解低折射率粒子，即可由溶解殘留部分與加熱殘留部分之質量差求得低折射率粒子的質量，且由該質量與低折射率粒子之密度，可求得低折射率粒子之體積。另一方面，當低折射率粒子如樹脂顆粒般，電子線之透射性與金紅石型氧化鈦完全相異時，有以掃描型電子顯微鏡觀察塗膜層之截面、或以切片機等薄薄地切取塗膜層，再以透射型電子顯微鏡(倍率10000倍左右）觀察其之方法等。具體而言，可藉由算出視野内所見之金紅石型氧化鈦與低折射率粒子的數量求得。然而，當數量少時，★吳差會變大，故以至少於金紅石型氧化鈦存在1〇〇個以上之範圍内計算粒子的數量為佳。又，於低折射率粒子之電子線透射性與金紅石型氧化鈦幾無差異，以掃描型電子顯微鏡或透射型電子顯微鏡難以辨別低折射率粒子與金紅石型氧化鈦的差異時，確認塗膜層截面中之元素組成，由確認後之組成可求得金紅石型氧化鈦與其他低折射率粒子之比率。元素組成可使用 ΕΡΜΑ(電子探針微分析器）、GDS(輝光放電發光分光分析裝置）等確認。 (混合層之厚度）本實施形態中，當存在上述混合層時，該混合層以具有3μΠ1以上、12^爪以下之厚度為佳。當混合層之厚度小於 3 μηι時有無法穩定地獲得混合層所產生之高濃度顏料層與上塗層間的密著性提升效果的疑慮。另一方面，當混合 34 201119847 層之厚度大於12μηι時，充分地確保分擔有必要機能之高濃度顏料層及上塗層的塗膜厚度是困難的。因此，於上塗層為最表層時，容易產生因最表層之厚度不足所造成的外觀不良等，高濃度顏料層及上塗層本身之性能維持變得困難，實質上因與藉由混合有高濃度顏料層形成用塗料與上塗層形成用塗料的塗料所形成之塗膜層為相同性能，故無法得到必要之原本高濃度顏料層及上塗層的性能。另外，將混合層之厚度控制成大於12μηι之厚度實質上是困難的。 (混合層厚度之測定方法）混合層之膜厚可藉由分析僅含有高濃度顏料層或上塗層之任一者的成分之膜厚方向的分布狀態求得。分析方法可使用眾所周知的分析方法，例如：利用* *Χ射線探針微量分析器、電子探針微分析器（ΕΡΜΑ)、X射線光電子光譜法（XPS)、奥杰電子能譜分析（AES)、輝光放電發光分析 (GDS)* *等，分析塗膜深度方向的元素濃度，或者，藉由塗膜截面中之成分分析，可由作為對象之成分的濃度分布求得混合層之膜厚。適用之成分分析的種類或方法只要對應膜厚、成分量等適當地選擇進行即可。除了 ΕΡΜΑ、XPS、 AES、GDS以外，只要是可進行深度方向之成分分析的方法，亦可適當地選擇。另外，可使用於混合層之分析的成分亦可為Ti以外者。該分析方法中，因GDS係一面由塗膜之表面朝深度方向減:鑛惰性之氬離子一面進行分析，可較準確地比較測定元素之深度方向的濃度，故為佳。本申請案發明中混合層之膜厚係測定任意5處之平均膜厚。 35 201119847 (混合層之厚度的測定方法）此a層之厚度，主要可藉由塗布方法、燒附時間來控制。塗布方法係藉由採用濕疊濕法或多層同時塗布法，而谷易形成混合層。又，藉由延長燒附時間，可充分地延長用以形成混合層之時間，故可增厚混合層之厚度，具體而言’藉將燒附時間訂為60秒〜180秒左右，可將混合層之厚度做成3μπι以上、以下。又，為形成穩定之混合層，將形成混合層之高濃度顏料層形成用塗料的表面張力（σΐ )’與形成混合層之上塗層形成用塗料的表面張力（σ2)之差（Δσ=σ2σ1)控制成 0.5 8mN/m，並且，以將形成混合層之高濃度顏料層形成用塗料的黏度⑷），與形成混合層之上塗層形成用塗料的黏度（Φ 2)之差（△必” 2- φ 1)控制為-100〜4000mPa.s為佳。如此’配合塗料種類或塗裝條件，藉由適當地將形成混合層之高濃錢㈣及上塗層職料之表面張力與黏度的關係調述條件内之適當的值，亦可控制穩定之混合層的生成與膜厚，更可控制最表面的形狀。換言之’藉由&為8福/〇1以下、或△必為4_悉8以下’可形成具充分厚度之混層，故更加提升層間密著性。另一方面’藉由Δσ為〇.5mN/m以上、或Λφ為. 上，高濃度_層及上㈣1厚可為充分者，又，最表面之形狀亦適切，可較穩定地確保性能。另外，本實施形態中’塗料之表面張力可藉由聊中之白金環拉升法測定 ⑽於此種表面張力測定之㈣，可依據獻皿⑷厂輪 36 201119847 環法」進行。）。又’塗料黏度可使用B型黏度計，以20°C、 * *6mpm* *測定。（關於此種黏度測定之細節，可依據 JIS.Z.8803.8「以單一圓筒型旋轉黏度計進行之黏度測定方法」進行）。另外，塗料之表面張力的調整，以利用界面活性劑（亦包含消泡劑或均染劑）為佳。界面活性劑可使用眾所周知者，市售者已知有，BYK社之BYK-333、BYK-307或花王社之EMULGEN等，其他亦有許多種，可對應塗料成分適當地添加。又，亦可以稀釋或混合其他溶劑等界面活性劑以外的方法進行塗料表面張力之調整。另外，當表面張力過大時’因有塗裝性惡化之可能性，故以將高濃度顏料層用塗料、上塗層用塗料之表面張力均設為40mN/m以下為佳。又’塗料黏度之調整以利用增黏劑（包含流變控制劑、黏度調整劑）為佳。增黏劑係使用眾所周知者，市售者已知有’ BYK社之BYK-411、BYK-425等’其他亦有許多種，可對應塗料成分適當地添加。又，亦可以稀釋、混合其他溶劑、或使用使固形成分之比例增加等增黏劑以外的方法，進行塗料黏度之調整。又’混合層之厚度亦可藉由調整高濃度顏料層用塗料中之顏料濃度與上塗層用塗料中之顏料濃度的差來控制。換言之，當顏料濃度之差變大的話，因由高濃度顏料層朝上塗層之顏料的擴散速度變快，故於高濃度顏料層用塗料與上塗層用塗料乾燥、硬化前可形成具充分厚度之混合層。 [關於最表面之起伏j 37 2〇1119847 本實施形態之塗裝金屬材中，以被覆層最表面之濾波中心線波紋WcA為以下為佳。如此，藉縮小被覆層最表面之WCA ’可使塗裝金屬材之清晰度提升，且可得無微小四凸之光滑表面，故汙染物質不易堆積於塗裝金屬材表面，玎使对汙染性提升。當被覆層最表面之WCA大於2μιη 時，有清晰度及耐汙染性下降的疑慮。另一方面，被覆層最表面之WCA的較佳下限值不需特別規定，但對被覆層最表面之WCA小於0·2μηι者，實質上進行控制是困難的，故由此種觀點來看’以被覆層最表面之WCA為〇.2μιη以下為佳。另外，本申請案發明之WCA係測定任意5處後再平均。另外，此處所稱之「被覆層之最表面」係指，被覆層中最表層之塗膜層的表面之意。「最表層之塗膜層」係指，如上述般地，於本實施形態之上塗層、或上塗層之表層側更積層有塗膜層時該塗膜層之意。 (最表面之WCA的控制方法）被覆層最表面之WCA係受高濃度顏料層與上塗層之邊界面的Ra影響而變化。因此，被覆層最表面之WcA主要可藉由塗布方法、低剪力下之塗料黏度來控制。具體而言，藉由以濕疊濕法或多層同時塗布法作為塗布方法，因金紅石塑氧化鈦由高濃度顏料層朝上塗層擴散，故高濃度顏料層與上塗層之邊界面的Ra變大，被覆層最表面之Wca亦變大。又，藉由降低低剪力下之高濃度顏料層形成用塗料黏度，高濃度顏料層中之金紅石型氧化鈦變得容易朝上塗層擴散，故邊界面之Ra變大，被覆層最表面之Wca亦變大。 38 201119847 如上述，因以增大高濃度顏料層與上塗層之邊界面的 Ra為佳，以縮小被覆層最表面之WCA為佳，故考量兩者之平衡，以決定低剪力下之高濃度顏料層形成用塗料之黏度的適當值為佳。 [對最表層塗膜之撥水性、撥油性的賦予] 又，本實施形態之塗裝金屬材中，金屬材上所形成之被覆層中最表層之塗膜層亦可含有矽氧樹脂或氟樹脂。此處所稱之「最表層之塗膜層」，於上述上塗層形成於最表層時，係指該上塗層，於上塗層之表層側更積層有塗膜層時，係指該塗膜層。將本實施形態之塗裝金屬材使用於預塗覆金屬板中時，被視為有因加工時之汙染物附著等造成全光線反射率下降之可能性。相對於此，本實施形態之塗裝金屬材之最表層的塗膜層之黏合劑的一部分或全部係使用矽氧樹脂或氟樹脂，故可賦予塗膜表面撥油性及撥水性。如此，藉由賦予最表層之塗膜層的表面撥油性及撥水性，汙染物將不易附著於塗膜表面，並抑制全光線反射率之下降而為佳。使前述最表層之塗膜層含有矽氧樹脂或氟樹脂的方法有：於最表層之塗膜層添加矽氧樹脂或氟樹脂的方法、或使用含有矽氧樹脂或氟樹脂者作為主樹脂的方法。添加於最表層之塗膜層的矽氧樹脂，已市售者已知有例如：BYK社製之「BYK(登錄商標）-306」、「BYK(登錄商標)-378」等，添加於最表層之塗膜層的氟樹脂，已市售者已知有例如：BYK社製之「BYK(登錄商標)-340」等，其他 39 201119847 亦有許多種，可對應塗料成分適當地添加。又，含有矽氧樹脂或氟樹脂之主樹脂，可使用：市隹之矽氧·丙烯酸共聚合樹脂（例如，東亞合成社製「SYMAC(登錄商標）」系列或「RESEDA(登錄商標）」系列、 TOKUSHIKI社製「SQ(登錄商標）100」等）、或市售之石夕氧氟共聚合樹脂(例如，富士化成工業社製「zx-ooi」等又，前述矽氧·丙烯酸共聚合樹脂或矽氧.氟共聚合樹脂亦可視需要使用一般眾所周知的交聯劑，例如，以異氣酉& 酯或三聚氰胺樹脂交聯。此時，異氰酸酯係使用一般市售者，可使用例如：住化Bayer社製「Sumidur(登錄商標）」系列、「Desmodur(登錄商標）」系列 '三井武田Chemica丨社製「TAKEN ATE(登錄商標）」系列等。三聚氰胺樹脂係使用一般市售者，可使用例如：三井Cytec社製「Cymel(登錄商標）」系列、「Mycoat(登錄商標）」系列、大日本油墨化學工業社製「BECKAMINE(登錄商標）」系列、「supER beckamine (登錄商標）」系列等。如以上’於最表層之塗膜層含有石夕氧樹脂或氣樹脂的塗裝金屬材除了照明器具之反射板的用途以外，亦適用於至内中之天化板或壁材等用途。並且，將於最表層之塗膜層含有♦氧樹脂或氟樹脂的塗裝金屬材使用於室内中之天花板或壁材等用途時，室内巾之天花板或壁材本身亦具有反射板的作用’故可以較少之光量使室内變得明亮。 [對最表層塗膜之親水性的賦予] 又，本實施形態之塗裝金屬材中，金屬材上所形成之 40 201119847 - 被覆層中最表層之塗膜層，亦可於形成塗膜之樹脂骨架中具有-Si-0-Si-鍵結。此處所稱之「最表層之塗膜層」，於上述上塗層形成於最表層時，係指該上塗層，於上塗層之表層側更積層有塗膜層時，係指該塗膜層。又，-Si-0-Si-鍵結中之Si係來自於烷氧矽烷或烷氧矽烷之水解縮合物者。將本實施形態之塗裝金屬材使用於預塗覆金屬板中時，被視為有因加工時之汙染物附著等造成全光線反射率下降之可能性。相對於此，於本實施形態之塗裝金屬材之最表層的塗膜中形成-Si-O-Si-，換言之，藉由含有來自烷氧矽烷或烷氧矽烷之水解縮合物的Si，不需損害表面光澤或加工性，即可賦予塗膜表面親水性。如此，藉將最表層之塗膜層表面作成親水性，可以水擦拭等輕易地拭除附著 - 於塗膜表面的附著物，並抑制全光線反射率下降，故為佳。 - 為於形成塗膜之樹脂骨架中形成- Si-0-Si-鍵結’只要於該最表層之塗膜形成用的塗料中添加烷氧矽烷或烷氧矽烷之水解縮合物即可。此時使用之烷氧矽烷係一般眾所周知者，可舉例如：四曱氧矽烷、四乙氧矽烷、四丙氧矽烷、四丁氧矽烷、曱基三曱氧矽烷、曱基三乙氧矽烷、乙基三甲氧矽烷、乙基三乙氧矽烷、二甲氧二乙氧矽烷、二曱氧二丙氧石夕烧等。又，烧氧石夕烧之水解縮合物可舉，上面例示之烧氧石夕烧之水解縮合物為例。如以上，於最表層之塗膜中形成有-Si-0-Si-的塗裝金屬材除了照明器具之反射板的用途以外，亦適用於室内中之天花板或壁材等用途。並且，將於最表層之塗膜中形成 41 201119847 有-Si-0-Si-的塗裝金屬材使用於室内中之天花板或壁材等用途時，室内中之天花板或壁材本身亦具有反射板的作用，故可以較少之光量使室内變得明亮。 [最表層之塗膜層的膜厚] 另外，當本實施形態之塗裝金屬材於上塗層之表層側更具有最表層之塗膜層（例如，含有上述矽氧樹脂或氟樹脂之塗膜層、或於形成塗膜之樹脂骨架中具有-Si-O-Si-鍵結的塗膜層）時，該最表層之塗膜層的膜厚只要為可得到上述撥水性、撥油性、親水性等特性左右的話，並未特別限定，較佳者係最表層之塗膜層的膜厚為Ιμηι以上、25μηι以下。當前述最表層之塗膜層的膜厚小於Ιμιη時，有撥水性、撥油性、親水性不足之可能性，當大於25μιη時，有加工性不佳的可能性，又由成本方面來看，亦不佳。 [下塗層](概要）具有本實施形態之塗裝金屬材的被覆層，除了以上說明之高濃度顏料層及上塗層以外，亦可含有下塗層。該下塗層係形成於金屬材與高濃度顏料層之間的塗膜層，當被覆層係由上塗層、高濃度顏料層及下塗層之3層所構成時，係離作為基材之金屬材最近之側的塗膜層。然而，此時，即使為離金屬材最近之側的層，以金屬材與塗膜之密著性提升或耐蝕性提升為目的而設之膜厚小於Ιμηι的被覆層，並非本實施形態之下塗層，而係以較膜厚小於Ιμιη之被覆層位於表層側的被覆層作為下塗層。 (黏合劑） 42 201119847 作為下塗層之黏合劑使用的樹脂並未特別限定，但由與高濃度顏料層之密著性、或塗料原料之共通化等觀點來看’以含有與高濃度顏料層相同的樹脂來使用為佳。因此，南濃度顏料層之黏合劑以使用數平均分子量為19000以上、28000以下的聚酯樹脂a為佳。於下塗層中亦以使用聚酉旨樹脂A作為黏合劑為佳。當作為下塗層之黏合劑使用的聚酿樹脂之數平均分子量小於19〇〇〇時，有加工性及密著性下降的疑慮。當數平均分子量大於28〇〇〇時，塗膜表面變得過軟，而有耐瑕疵性及防沾黏性劣化的疑慮。另外’對下塗層之聚酯樹脂A的添加量，只要相對於黏合劑樹脂全體之聚酯樹脂A的濃度為80質量％以上的話，因可發揮加工性或密著性提升之效果，故以將相對於黏合劑樹脂全體之聚酯樹脂A的濃度設為80質量％以上為佳。 (顏料）下塗層中，以固形物體積濃度計添加作為顏料之金紅石型氧化欽20%以上、35%以下時，4更提升反射率而為佳。以金紅石型氧化鈦作為添加至下塗層之顏料為佳的理由係’與高濃度顏料層的情形同樣地，金紅石型氧化鈦之折射率較其他一般所使用的顏料高，且可增大與作為黏合劑使用之樹脂及顏料粒子間存在的空隙部分之空氣的折射率差，藉此，可提高顏料與樹脂之界面、顏料與空氣之界面中的光反射率。使用金紅石型氧化鈦作為顏料時該金紅石型氧化鈦之平均板徑，當為小的話每單位體積之表面積會變大，作為 43 201119847 光反射面之樹脂或空隙與顏料的界面之面積變大，故全光線反射率亦變高，但當顏料之平均粒徑過小時，因長波長之光透射，全光線反射率將下降。因&，與高濃度顏料層的情形同樣地，用以作為下塗層中之顏料的金紅石型氧化鈦之平均粒徑’以20〇nm以上、4〇〇nnm下為佳，以25〇麵以上、350nm以下更佳。 (膜厚）關於下塗層之膜厚，膜厚越厚，可得越高之加工性或密著性，又，於添加有金紅石型氧化鈦作為顏料時，亦以厚膜對於反射性能越有利，故由該等之性能方面來看，不需要設定下塗層膜厚之上限值❶但是，當下塗層之膜厚大於30μηι時，因與高濃度顏料層相異，塗料中之顏料濃度低，故塗裝時容易產生起泡、塗裝性劣化，又，由塗料成本之觀點來看亦不佳。因此，下塗層之膜厚以3〇|Lim以下為佳。另一方面，當下塗層之膜厚小於5μΓΠ時，下塗層之加工性、後、著性及反射性能的提升效果變小，故下塗層之膜厚以5 μπι以下為佳。由確保穩定之加工性、密著性、反射性能及塗裝性的觀點來看，較佳之下塗層的膜厚係1〇μιηα 上、25μηι以下。 [基材(金屬材)] 本實施形態之塗裝金屬材的基材中使用之金屬材可使用一般眾所周知的金屬材料或合金材料。具體而士，金屬材可舉例如：鋼板、不銹鋼板、鋁板、鋁合金板、欽板、銅板等。亦可於該等金屬材料或合金材料之表面施行電 44 201119847 鍍。電鍍之種類可舉例如：鋅電鍍、鋁電鍍、銅電鍍、鎳電鍍等。亦可為該等之合金電鍍。當使用鋼板作為金屬材時，可使用：溶融鑛鋅鋼板、電鍵鋅鋼板、鋅-鎳合金電鑛鋼板、溶融合金化鑛鋅鋼板、銘電鑛鋼板、铭-辞合金化電鍍鋼板等，一般眾所周知的鋼板及電鍍鋼板。當於本實施形態中使用之金屬材的表面施行化學轉化處理時，因金屬材與塗膜層之密著性或耐蝕性等提升，故較佳。此種化學轉化處理可使用一般所施加者，具體而言，可舉例如：磷酸鋅系化學轉化處理、非鉻酸系化學轉化處理、塗布型鉻酸處理、電解鉻酸處理、反應鉻酸處理等。其中，塗布型鉻酸處理、電解鉻酸處理、反應鉻酸處理因包含環境負荷物質6價鉻，故不佳。又’磷酸鋅系化學轉化處理相較於其他處理，有加工密著性不佳的疑慮。因此，於本實施形態之金屬材施行之化學轉化處理以非鉻酸系處理為佳。非鉻酸系化學轉化處理有使用無機系化學轉化處理劑者、及使用有機系之化學轉化處理劑者，使用任一者均可。具體而言，非鉻酸系化學轉化處理已知的是經使用包含：石夕烧偶合劑、錄化合物、鈦化合物、丹寧或丹寧酸、樹脂、二氧化矽等之水溶液等的處理，亦可使用日本專利特開昭 53-9238號公報、曰本專利特開平9-241576號公報、曰本專利特開2001 -89868號公報、日本專利特開2001 -316845號公報、日本專利特開2002_6〇959號公報、曰本專利特開 2002-38280號公報、日本專利特開2002-266081號公報、曰 45 201119847 本專利特開2003-253464號公報等所記載之眾所周知的技術。又，為了該等化學轉化處理，可使用市售之化學轉化處理劑，例如：日本PARKERIZING社製之鉻酸處理劑「ZM-1300AN」、日本PARKERIZING社製之非鉻酸化學轉化處理劑「CT-E：300N」、日本PAINT社製之3價鉻系化學轉化處理劑「Surfcoat(登錄商標）NRC1000」等。 [關於後塗覆(post coat)金屬材] 以上之說明中，係依據主要將本發明使用於預塗覆金屬材之例來說明，但本發明並未受限於預塗覆金屬材，亦可使用於後塗覆金屬材。於後塗覆金屬材時，與預塗覆金屬材相異，未必需要求加工性、密著性等，但於作為反射板使用時，需具有高之全光線反射率。於後塗覆金屬材時’藉於高濃度顏料層中添加具有較金紅石型氧化鈦大之粒徑的低折射率粒子，若該低折射率粒子之固形物濃度高’即可將高濃度顏料層與上塗層之邊界面的Ra作為〇.8μηι以上。又，於加工後之金屬材形成有高 m度顏料後’於所形成之高濃度顏料層表面加上物理上之瑕疵等，使表面之Ra變粗為〇以上，之後，即使塗布上塗層用塗料’亦可將高濃度顏料層與上塗層之邊界面的Ra 設為0·8μπι以上。〈關於塗裝金屬材之製造方法〉以上’詳細地說明本實施形態之塗裝金屬材的構成。緊接著’ ^細地說明具有如上述構成之塗裝金屬材的製造方法。 46 201119847 本實施形態之塗裝金屬材的製造方法係，形成包含至少2層以固形物體積濃度計含有金紅石型氧化鈦35%以上 70%以下之高顏料濃度層，與積層於高濃度顏料層之表層側的上塗層之被覆層，使高濃度顏料層與上塗層之邊界面的中心線平均粗糙度Ra為0·8μιη以上的方法。以下，將塗裝金屬材分成預塗覆金屬材的情形與後塗覆金屬材的情形，詳細說明本實施形態之塗裝金屬材的製造方法。 [預塗覆金屬材的情形] 首先，說明當塗裝金屬材為預塗覆金屬材的情形中本實施形態之塗裝金屬材的製造方法。本實施形態之塗裝金屬材藉由一般之連續式塗裝生產線（continuous coating line，稱為「CCL」。）或切板用之塗裝生產線，可選擇適當必要之處理，並實施所選擇之處理來製造。塗裝生產線之代表性的製造步驟係「洗淨」—「乾燥」4「化學轉化處理」->「乾燥」4「塗裝」4「乾燥、燒附」〇「冷卻」-> 「乾燥」，但本實施形態中之塗裝金屬材的製造步驟並未限定於此。又，本實施形態之塗裝金屬材亦可如通常進行地於各被覆層重複施行塗裝與乾燥、燒附而製造，但藉由使用多層同時塗布或濕疊濕方式將高濃度顏料層形成用塗料，與上塗層形成用塗料塗布於金屬材表面之一部分或全部而製造，由各層之性能面及生產性之面來看為佳。同樣地，於本實施形態之塗裝金屬材於上塗層之表層側更具有最表層之塗膜層（例如，含有上述矽氧樹脂或氟樹脂之塗膜層）時， 47 201119847 以使用多層同時塗布或濕疊濕方式將高濃度顏料層形成用塗料、上塗層形成用塗料、及最表層之塗膜層形成用塗料塗布於金屬材表面為佳。另外，於本實施形態之金屬材為辞系電鍍鋼板時，於連續電氣電鍍鋼板設備、或連續熔融鋅電鍍鋼板設備中，藉於電鍍步驟後，以具有濕疊濕塗裝設備或同時多層塗布設備之生產線製造，可於形成電鍍金屬表面之氧化皮膜前塗布可防止因氧化皮膜造成之缺陷外觀不良。此處，多層同時塗布係指，藉由狹縫模具式塗布器或滑動漏斗(slide hopper)式之簾幕式塗布器等可由平行之2個以上的狹縫等將相異之塗料吐出而積層的裝置，於同時積層有複數之塗液的狀態下塗布於基材，使該積層後之塗液同時地乾燥燒附的方法。又，濕疊濕塗裝係指，經於基材上塗裝塗液後，於該塗液乾燥狀顧狀許，於其±更塗布其他魏，使積層之多層塗㈣時地乾燥燒_方法。具體而言，濕疊濕塗裝之方法，可舉例如：以輥塗布器、浸塗式、簾幕式流動塗布器（Curtain flow coater)、輥簾幕式塗布器等塗裝方法塗裝有1層塗膜層後，再於乾燥燒附該塗膜層前，更於其上 =簾幕式流動塗布器(Cunain ^ e_r)、輥簾幕式塗布器、滑動漏斗式簾幕式塗布器、狹賴具式塗布器等可不與基材接觸地钱的方法，施行第2層之餘後，同時乾燥燒附所積層之潮濕狀態的複層塗膜之方法等。於本實施形態中’多層同時塗布，或者，同時燒附經 48 201119847 濕疊濕塗裝之塗膜的方法係使用一般眾所周知的塗料用燒附爐，可使用例如，熱風乾燥爐、直下型加熱爐、感應加熱爐、紅外線加熱爐、或併用該等之爐等。如此，藉積層未乾燥狀態之塗液後同時塗布，各層之塗液於塗液之邊界部少量地混合，可形成混合有各層成分之混合層，藉此，可提升層間密著性。又，因以往於各層都要進行之乾燥步驟係變成一起進行，故由生產性或製造成本之觀點來說亦有利，又，亦有乾燥設備少即可完成之優點。 [後塗覆金屬材的情形] 接著，說明塗裝金屬材為後塗覆金屬材時，本實施形態之塗裝金屬材的製造方法。 - 本實施形態之藉由後塗覆所形成之塗裝金屬材，係於 . 將如上述之金屬材施行化學轉化處理等後，成形成使用本實施形態之塗裝金屬材的照明反射板、發光零件之反射板、或影像顯示部之反射板等的形狀後，再藉由後塗覆塗裝而製造。金屬材之成形方法可使用眾所周知的方法。又，後塗覆之方法，可使用眾所周知的喷霧塗裝、浸潰塗裝、藉由簾幕式流動塗布器所進行之塗裝、刷毛塗布塗裝、靜電塗裝等方法。又，於後塗覆金屬材時，亦可藉由喷霧塗裝等進行濕疊濕塗裝。 (總結） ‘ 於使用有如以上說明之本實施形態之塗裝金屬材的電子機器中，因該塗裝金屬材以高次元地兼具高之全光線反 49 201119847 射率與成形性 ’故為同一光源時可較目前為止的情形亮，又 ’即使將光源數量減至較目前為止少、或減少投入電力，仍可確保與目μ為止相同之亮度。此外，本實施形態之塗裝金屬材具有W編彡成各種形狀、或可成形成更複雜之形狀的特n &亦可期待可適用之電子機器對象的擴大、或適用之零件料紐提升之效果。可用此種特性之電子機器並未特別限定，可使用於例如.照明反射板、發光零件之反射板、或影像顯示部之反射板等°④等之較具體之例，可舉例如：照明器具、電飾从機益'移動機器、各種顯示器等，但以使用於：照月反射板内飾看板内之反射板、液晶顯示器之背光源反射板等為佳。 [實施例]201119847 - VI. DESCRIPTION OF THE INVENTION: [Technical Field] The present invention relates to a coated metal material having high reflectance and a method of manufacturing the same. [Previous name is good; j Background Art Various devices using visible light (for example, lighting fixtures, AV equipment, electronic equipment, mobile equipment, liquid crystal televisions, plasma displays, etc.) are illuminated by emitting visible light rays' Functions around, transmitting optical signals, or reflecting light images. In these machines, there is also a reflection plate disposed around or behind the light source to reflect light on the reflector for enhancing the brightness of the light or changing the direction of the light. At this time, in order to avoid a decrease in the amount of light when the light is reflected to the reflecting plate, a high visible light reflectance is required on the surface of the reflecting plate. Therefore, the method of "recently increasing the reflectance of the surface of the reflecting plate" is to use a polished metal as a mirror surface or a white paint having a high reflectance. Such a method of improving the reflectance, for example, Patent Document 1 discloses a light-reflecting film technique in which a metal thin film layer, a resin layer containing inorganic fine particles, and a thin metal film are sequentially laminated on a single surface of a base film. The layer is composed of aluminum. The refractive index nf of the inorganic fine particles constituting the resin layer containing the inorganic fine particles and the refractive index nb of the resin constituting the same layer are nf_nb 4 . Further, for example, Patent Document 2 discloses a technique for coating a metal plate with a high-diffusion reflection for a rear panel of a liquid crystal display for a liquid crystal display, which is formed on an aluminum plate and formed with 1 part by mass relative to the resin. Including 201119847, a titanium oxide pigment having a film thickness of from 150 to 300 parts by mass of a film thickness of 5 〇 to 1 〇〇 μηη is formed on the undercoat layer to form a titanium oxide pigment 100 with respect to 1 part by mass of the resin. ~250 parts by mass, an upper coat having a gloss of 15 or less and a film thickness of 1 〇 to 3 〇 μηη. Further, for example, Patent Document 3 discloses a technique of a coating material having a high diffuse reflectance, which has at least one layer of white pigment containing 150 parts by volume or more and less than 15 parts by volume relative to 100 parts by volume of the binder. A high-concentration pigment layer or a low-density layer containing a binder and a white pigment and having a void ratio of the coating layer of 5% by volume or more and less than 35% by volume. Further, for example, Patent Document 4 discloses a technique of a coating material having a high diffuse reflectance, which is composed of a binder, a rutile-type titanium oxide, and particles having a lower refractive index than rutile-type titanium oxide. Further, the concentration of the rutile-type titanium oxide is 35% by volume or more and 70% by volume or less of the visible light reflecting layer. CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, regarding the 201119847-reflector for electrical products such as lighting fixtures or liquid crystal displays, in recent years, with the construction or design of electrical products The complication and the like are increasing in the demand for forming a reflector into various shapes. Moreover, there is also a tendency to have a tilt of a reflector that requires a higher degree of light and uniform reflection. In such a state, when a film is used as a substrate in the technique described in the above-mentioned Patent Document, it is difficult to form a film having a laminated metal thin film layer or a resin layer containing inorganic fine particles into a desired shape. After the film is formed into a desired shape in advance, it is necessary to laminate a thin metal film layer or a resin layer containing inorganic fine particles. At this time, when the shape of the reflecting plate is complicated, there is a problem that the film portion is not easily processed to have a uniform film thickness. Further, in the technique described in Patent Document 2, the undercoat layer and the overcoat layer may be applied to an aluminum plate in advance, and then subjected to a forming process, but in a general-precoat COating line. In the coating, it is very difficult to apply the coating under the film thickness (5〇~ΙΟΟμηι), and it is required to be overcoated twice or more, so that there is a disadvantage of low productivity. In the above-mentioned patent readings 3 and 4, even if the coating layer is thin, a high diffusion reflectance can be obtained, and the coating can be made with a high diffusion reflection by one coating by a general precoating coating line. Since the precoating of the rate is too small because the binder in the coating layer is too small, there is a disadvantage that the workability and the adhesion are poor. With respect to such a situation, a technique of forming a low pigment concentration layer by the above-mentioned high-concentration pigment layer, (four)-degree layer, and upper layer of the visible light-reflecting layer, and the like, is being reviewed, and the technique is employed. Further, in the case of the binder resin, the technique of using the molecular S to form a resin to enhance the X-energy and the adhesion of the 201119847 is also being used. However, even with any of the above techniques, the workability or the adhesion is insufficient in accordance with the forming process for various shapes which are complicated by the structure or design of the electric product. Moreover, the total light reflectance of the coated metal material produced by these techniques is not sufficient for the reflector of the electrical product. As described above, there are cases where the reflector is required to be complicatedly formed and used for the structural or design reasons of the electrical product. In this case, the coated metal material is required to have high moldability, total light reflectance, productivity, and the like, but the coated metal materials described in Patent Documents 1 to 4 and the like do not satisfy the formability (processability or density). Performance) or full light reflectivity and other performance. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a coated metal material having a higher total light reflectance than that of the prior art and having excellent moldability and a method for producing the same. In order to solve the above-mentioned problems, the present inventors have made efforts to study the above problems. As a result, it has been found that "a coating layer of two or more layers is covered by one or all of the surface of the metal material, and the coating layer is contained at a high concentration." The first coating layer rutile containing rutile-type titanium oxide and the second coating layer on the upper layer thereof, and increasing the roughness of the boundary surface between the first coating layer and the second coating layer, and having a high total light The present invention has been completed based on such knowledge with reflectance and excellent formability. In other words, according to the present invention, it is possible to provide a coated metal material having a coating layer having at least two layers in part or all of the surface of the metal material, and the coating layers comprising rutile-type titanium oxide in a solid volume concentration. 201119847. 35% to 70% of the first coating layer, and a second coating layer laminated on the surface layer side of the first coating layer, and a boundary surface between the first coating layer and the second coating layer The center line average roughness Ra is 〇.8μηι or more. Here, at a boundary portion between the first coating layer and the second coating layer, a mixed layer in which a component of the second coating layer and a component of the second coating layer are mixed is present, and the mixing is performed. The layer preferably has a thickness of 3 μη 1 to 12 μηι. It is preferable that the filtered center line waviness WCA is 2 μm τι or less on the outermost surface of the coating layer. The coating layer of the outermost layer of the coating layer may also contain a stone oxide resin or a gas resin. The coating layer of the outermost layer of the coating layer may also have a -Si-0-Si-bond in the resin-skeleton forming the coating film. Further, the average particle diameter of the rutile-type titanium oxide is preferably 20 nm or more and 400 nm or less. The first coating layer may further contain particles having a larger particle diameter than the rutile-type titanium oxide and having a lower refractive index than the rutile-type titanium oxide. The voids are present in the first coating layer, and the content of the voids is preferably 0_05 times or more of the volume of the solid matter in the first coating layer, and preferably 〇9 or less. The film thickness of the first coating layer is preferably ΙΟμηι or more and 80 μηι or less. The film thickness of the second coating layer is preferably 5 μm or more and 30 μm or less. The layer to be coated may further include a third coating layer laminated between the metal material and the first coating layer. 7 201119847 The film thickness of the third coating layer is preferably 5 μηι or more and 3 μμίη or less. Further, according to the present invention, there is provided a method for producing the above-mentioned coated metal material, which is a method for producing the first coating layer by a plurality of simultaneous coating or wet-stacking methods. The coating material for forming the second coating layer is applied to part or all of the surface of the metal material. According to the present invention, a lighting fixture using the above-described coated metal material is used for the illumination reflector. According to the present invention, there is further provided an electronic device in which the above-described metal material is applied to a reflector for a light-emitting component or a reflector for an image display portion. Advantageous Effects of Invention According to the present invention, it is possible to provide a coated metal material having a higher total reflectance than that of the prior art and excellent in formability, and a method for producing the same. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional schematic view showing an example of a brightness measuring device used in the present embodiment. Fig. 2 is a view showing an example of a mode convex state of the brightness measuring device of Fig. 1 seen from the upper part. Fig. 3 is a view showing a concave surface of a coating film. [Embodiment] The embodiment for carrying out the invention is described in detail. A preferred embodiment of the invention. In addition, in the description of the Suifen Festival, in the book of the Moon and the _, the constituent elements of the same machine-monthly composition are explained. Hunting by attaching the same symbol to omit repeating 201119847 . <Configuration of Coating Metal Material> First, the configuration of the coated metal material according to an embodiment of the present invention will be described. The coated metal material of the present embodiment has at least two coating layers on a part or all of the surface of the metal material as the substrate. Specifically, the coating layer has at least a first coating layer containing rutile-type titanium oxide at a high concentration (hereinafter referred to as a "high-concentration pigment layer"), and a surface layer laminated on the first coating layer. The laminated structure of the second coating layer (hereinafter referred to as "upper coating"). Further, the coated metal material of the present embodiment may have a third coating layer (hereinafter referred to as "undercoat layer") on the inner layer side of the high-concentration pigment layer, that is, between the metal material and the high-concentration pigment layer. As the coating layer, it is also possible to have other coating layers (for example, a coating layer laminated on the more surface side of the upper coating layer). Hereinafter, the composition of each coating film-layer will be described in detail in the order of the high concentration pigment layer, the overcoat layer, and the undercoat layer. [High-concentration pigment layer] (Summary) The high-concentration pigment layer of the present embodiment contains rutile-type titanium oxide in an amount of 35% or more and 70% or less in terms of solid content volume concentration, and is a layer of a white pigment, and is a higher coating layer. Located on the inner layer side, that is, on the side of the metal material as the substrate. However, in the case where the coating layer is a three-layer structure composed of an undercoat layer, a high-concentration pigment layer, and an overcoat layer, the high-concentration pigment layer is a layer of a portion held by the undercoat layer after being in contact with the overcoat layer. Further, when the coating layer has a multi-layer structure including four or more layers other than the undercoat layer, the high-concentration pigment layer, and the overcoat layer, the coating layer is located on the upper coating layer and the lower coating layer. In the meantime, all the layers containing rutile-type titanium oxide of 35% or more and 70% or less are contained as a high-concentration pigment layer in terms of solid content volume concentration. Further, in the coating layer, in the case of Jinhong 201119847, the //titanium/thickness continuously changes, and the boundary of each layer is unclear, the volume concentration of the solid content of the rutile-type titanium oxide is set to be 35% or more, 7〇. All of the ranges below the % condition are used as the high concentration pigment layer. On the other hand, the term "the volume of solids of rutile-type titanium oxide is as follows, (4) the composition of the resin (10) in the coating film containing the high-concentration pigmented layer) and the solid matter of the pigment component. The volume of the rutile-type titanium oxide, that is, the ratio of the voids in the coating film to the product (the volume concentration of the solid content of the rutile-type titanium oxide of 5 hai) is slightly To be described later). In the high-concentration pigment layer of the present embodiment, the rutile-type titanium oxide is contained in a high concentration, and in the coating film after drying and curing, the rutile-type titanium oxide particles are present in the most densely packed portion, and the rutile-type oxidation is performed. The volume of the voids formed between the titanium particles will be larger than the volume of the binder resin. Therefore, in the high-concentration pigment layer of the conventional enamel form, unlike the coating film containing the pigment at a concentration less than the most densely packed, the portion where the binder resin is not present may be present as a void in the coating film. Here, in general, since the refractive index of air is lower than the refractive index of the resin used together with the binder, the difference in refractive index between the rutile-type titanium oxide and the void is larger than the difference in refractive index between the rutile-type titanium and the resin. Further, in the high-concentration pigment layer of the present fine form, the light received by the high-concentration pigment layer can be reflected on the interface between the binder resin and the void. As described above, in the concentration pigment layer of the present embodiment, the refractive index difference at the interface of the reflected light is larger than that of the pigment which is smaller than the concentration of the most densely packed pigment, and the area of the interface of the light reflection can be changed. Large, so you can get high total light reflectivity. Hereinafter, each component contained in the high-concentration pigment layer will be described in detail. 10 201119847 - (Rutile-type titanium oxide) In the present embodiment, the pigment contained in the high-concentration pigment layer is rutile-type titanium oxide. This is because the refractive index of the rutile-type titanium oxide is higher than that of other white pigments generally used, and the refractive index difference with the air existing in the voids in the resin or the coating film used as the binder can be increased, so that it can be further Improve the total light reflectance in the interface between the pigment and the resin, and at the interface between the pigment and the air. Further, although the anatase type titanium oxide has a high refractive index, the photocatalytic property is high. When light such as a fluorescent lamp is received, the possibility of decomposition of the binder resin is not preferable. Since the coated metal material of the present embodiment focuses on the reflection of visible light, it is important that the total light reflectance in the wavelength range of the human eye sensitivity is high. Although there are individual differences in the human eye, light of a wavelength of 380 nm to 780 nm can be felt, and the peak of the sensitivity is around 555 nm. Therefore, since the coated metal material of the present embodiment is also preferably light having a wavelength centered at 550 nm, the particle size of the pigment (rutile-type titanium oxide) used for the high-concentration pigment layer is also It is better to consider this point. When the average particle size of the rutile-type titanium oxide used as the pigment is small, the surface area per unit volume becomes large, and the area of the interface as the light-reflecting surface of the resin or the void and the pigment becomes large, so the total light reflectance is also It becomes higher, but when the average particle size of the pigment is too small, the total light reflectance 曰 decreases due to the transmission of long-wavelength light, and generally, there is a large light scattering in the particle size range of the same energy level as the wavelength. It is well known that the light scattering field is the highest in the field of scattering, and the particle diameter is about 1/2 of the wavelength. From this point of view, it is understood that the average particle diameter of the rutile-type titanium oxide used as the pigment is 200 nm or more and 4 nm or less, preferably 250 nm or more and 350 nm, which is about half of the visible light wavelength. The following is better. In addition, the golden red color in the form of (10); the flat particle size of the δ-type titanium oxide is observed by an electron microscope (SEM) at a magnification of 1 〇, 〇0〇, and is reflected in the field of view. In the rutile-type titanium oxide particles, the average of the particle diameters of the rutile-type titanium oxide particles remaining after the particle size of 20% is smaller than that of the particles having a large particle size of 5% is removed. <Measurement Conditions> A method for producing an observation sample was prepared by filling a sample with a sample and grinding a vertical cross section of the sample. Observation field of view: Any one of the high-concentration pigment layers is selected by an optical microscope or an electron microscope (SEM) of about 500 to 1000 times beforehand. A method of selecting the rutile-type titanium oxide particles having an average value: The image of the selected field of view was observed at a magnification of loooo using an electron microscope (SEM). A method for measuring the particle size of each rutile-type titanium oxide particle by measuring the particle diameter of the rutile-type titanium oxide particles in the imaged image: measuring the particle size of the rutile-type titanium oxide particle The rutile-type titanium oxide having a longest diameter and a shortest diameter '1 and having a particle diameter = (longest diameter + shortest diameter) / 2. The average of the sum averages (?): arbitrarily select the three "viewing fields of view" described above and arithmetically average the "added average values" obtained by the respective fields of view. The rutile-type titanium oxide particles used in the present embodiment are not particularly limited as long as they satisfy the above-mentioned conditions of 12 201119847. Further, the rutile-type titanium oxide particles used in the present embodiment may be a granule-type titanium oxide particle monomer, or may be coated with rutile-type titanium oxide, coated with sulphur dioxide, yttrium oxide S, or oxidized. False, oxidized words, oxidation records, various organic substances, etc. The organic substance to be applied to the rutile-type titanium oxide is not particularly limited, and examples thereof include a polyol compound such as pentaerythritol or trimethyl ketone; trishydroxyethylamine and trishydroxylamine; An alkanolamine compound such as an organic acid salt of (trimethyk)lamine; an anthracene compound such as a oxime resin or an alkane gas. σ In the present embodiment, the rutile-type titanium oxide is also commercially available, and for example, "TIPAQUE (registered trademark)" series manufactured by Ishihara Shoji Co., Ltd., "TA" series manufactured by Fuji Titanhmi Co., Ltd., and TAYCA 制" Trademarks) series, etc. Further, the solid concentration of the rutile-type titanium oxide as described above in the high-concentration pigment layer is 35% or more. When the volume concentration of the solid content of the rutile-type titanium oxide is 35°/〇 or more, as described above, the particles of the rutile-type titanium oxide in the coating film after drying and curing are present in the most densely packed state. A void in which no binder resin is present may be present in the coating film. Thereby, the total light reflectance of the south concentration pigment layer can be raised. When the coating metal material is required to have a more reflective property, the rutile-type titanium oxide having an average particle diameter of 200 nm to 400 nm is made 50% or more by volume of the solid matter. At this time, the interface between the rutile-type titanium oxide and the void in the coating film, the interface between the rutile-type oxidized resin and the resin, and the interface between the resin and the void will contribute to the total light reflectance efficiently, and the total height can be obtained. Reflectivity is better. 13 201119847 On the other hand, when the solid concentration of the rutile-type titanium oxide in the concentration pigment layer is more than 7 G%, the rutile-type oxide in the coating film and the void account for too many tt cases, so the chelating agent resin It is difficult to ensure that the continuity of the coating film (maintaining the state of the film) becomes 1S, and the high concentration pigment layer itself becomes weak. Therefore, the solid volume concentration of the rutile-type titanium oxide in the high-concentration pigment layer is set to 7 G% or less. The preferred range of the solid volume concentration of the rutile-type titanium oxide is 65 % or less from the viewpoint of ensuring a stable coating film strength. Here, a method of measuring the volume fraction of the solid matter in the coating layer in the present embodiment will be described. The method for measuring the solid volume concentration of the rutile-type titanium oxide in the three-layer structure in which the coating layer is composed of the upper coating layer, the high-concentration pigment layer, and the undercoat layer will be described as an example. (Method for Measuring Solid Content Volume Concentration of Rutile-Type Titanium Dioxide) First, a coating layer to be measured is cut into layers by a sample to form an overcoat layer, a still-concentrated pigment layer, and an undercoat layer, and the measurement is performed. Coating area A1 and mass Ml. Next, the film which was cut off was heated at 5 ° C for 1 hour using hydrazine to decompose the resin component. Since the portion remaining without being decomposed can be regarded as rutile-type titanium oxide, the mass M2 of the residual portion is measured. Since the density of the general rutile-type titanium oxide pigment is about 3,800 to 4,200 kg.m·3, the density of the rutile-type titanium oxide pigment is assumed to be 4000 kg.nT3, and the density of the general polyester resin is 1150 to 1250 kg. Approximately .m·3, it is assumed that the density of the polyester resin is 1200 kg·m·3, and the volume VI of the polyester resin is obtained by Vl=(Ml-M2)/1200 kg.m_3, and V2=M2/4000 kg.m_3 Find the volume V2 of rutile type Dunhua titanium. 14 201119847 The volume V1 of the poly-resin resin and the volume V2 of the rutile-type oxidation record obtained by the method can be 〇¥2/(¥1+¥2)><100 (% by volume) The volume concentration C1 of the rutile-type titanium oxide was determined. The above-described C1 is measured three times for one measurement target (for example, a high-concentration pigment layer), and the arithmetic mean thereof is obtained. (Addition of other particles) In the high-concentration pigment layer of the present embodiment, particles having a particle diameter lower than that of rutile strontium oxide and having a low refractive index (hereinafter referred to as "low-refractive-index particles") Case.) When used in combination with rutile plastic titanium oxide, it is better to increase the total light reflectance more efficiently. By adding particles larger than the rutile type titanium oxide to the high concentration pigment layer, the gap between the particles in the high concentration pigment layer can be increased, and more voids can be contained, thereby enhancing the total light reflection. rate. Further, since the particles having a large particle diameter in combination with the rutile-type titanium oxide are particles having a low refractive index, the contact interface between the low-refractive-index particles and the rutile-type titanium oxide particles may be oxidized by rutile type. The refractive index difference between the zirconia particles and the low refractive index particles reflects the total light reflectance. When the particle diameter of the low refractive index particles is too large with respect to the particle diameter of the rutile-type titanium oxide, it is difficult to efficiently form voids in the high-concentration pigment layer, and it is effective for the low refractive index particles and the titanium oxide. The contact interface gets the effect of light reflection. From such a viewpoint, the average particle diameter of the low refractive index particles is preferably Ιμηι or more and ΙΟμπι or less, and more preferably 3 μηι or more. The average particle size of the low-refractive-index particles and the rutile-type titanium oxide is 15 201119847, ie, (the average particle diameter of the low-refractive-index particles) / (the average particle diameter of the rutile-type titanium oxide), It is better to use 1/4 () or more, and it is better to use ~ (or especially 3/40 to 10/40). In addition, the average particle diameter of the low refractive index particles of the present embodiment is similar to the rutile type titanium oxide, and the portion of the coating film is observed by an electron microscope at a ratio of 10, plane, and magnification. In the case of the low refractive index 2, the average number of the particles having a small particle size of 20% and the low refractive index particle having a large particle diameter of 5% is added (that is, the average of the low-folding particles (four) is added. The value 1 can be measured in the same manner as in the case of the above-mentioned "rutile-type oxidized chin". The above (10) rate particles seem to be lower than the gold red ^ Weihua titanium low two 'not ❹ m fixed, but ^ rutile Wei Wei titanium refraction. ',, more than 1 is better than even to the light of the visible light field The absorption force is folded: it is preferably white in the powder state. Specifically, as the above-mentioned low-calorie particles, for example, oxidized #@矽, calcium carbonate, barium sulfate, or oxygen-inorganic particles can be used. In addition to the shape of X', the lyophile powder can also be used as a refractive index particle. The type of the crucible is not particularly limited, but 吏 2 is, for example, a propylene-based resin powder, a resin powder, a PTFE (polytetramer & olefin) powder, or the like. As described above, the low-refractive-index particles can efficiently have voids in the contact pigment layer and the reflected light of the low-refractive-index pigment and titanium oxide (4). Therefore, even if the amount of low refractive refraction / (10) is a small amount of effect that can still be emitted, the lower concentration of the low-mass particle is not particularly limited, but (low refractive 201119847 rate particle volume / gold The volume of red stone type titanium oxide is less than 0. At 05 o'clock, the effect of increasing the total light reflectance of the low refractive index particles is reduced. Therefore, the lower concentration of the low refractive index particles is (the volume of the low refractive index pigment / the volume of the rutile titanium oxide) is 0. The concentration above 05 is preferred. On the other hand, the upper limit concentration of the low refractive index particles is (the volume of the low refractive index pigment / the volume of the rutile titanium oxide) is 0. In the range of 2 or less, as the amount of addition of the low refractive index particles increases, the reflectance of the light increases, and the effect of adding the low refractive index particles can be found. However, when the value exceeds this value, it is found that there is a reflectance other than the light. The tendency of performance (processability, corrosion resistance, etc.) to decrease. Therefore, the upper limit concentration of the low refractive index particles is (the volume of the low refractive index pigment / the volume of the rutile type titanium oxide) is 0. The concentration below 2 is preferred. Further, the low-refractive-particle particles have an effect of controlling the roughness of the boundary surface between the high-concentration pigment layer and the overcoat layer in addition to the effect of improving the total light reflectance, and the details will be described later. (void in the coating film) The content of the voids in the high-concentration pigment layer is 0. More than 05 times, 0. 9 times or less is preferred. This is because when the content of the void is less than 0% of the solid volume. At 05 times, the effect of improving the reflectance of the total light by the voids is reduced, and when the content of the voids is greater than the volume of the solids. At 9 times, the high-concentration pigment layer becomes weak (the mechanical strength is lowered), and there is a possibility that the workability and the adhesion are poor. The "content ratio of the voids" can be measured by a method described later. The control of the content of the voids in the high-concentration pigment layer can be controlled by the concentration of the pigment such as rutile-type titanium oxide or low-refractive particles as described above, but otherwise, for example, : Controlling the dispersion state of the coating used to form the high concentration pigment layer. In other words, the better the dispersion state of the pigment in the coating material (the more uniform -) the binder layer 33 is efficiently absorbed in the gap between the pigment particles, so that the content of the voids is small. Therefore, in order to obtain a high total light reflectance, the minimum dispersion state is maintained within a range where the coating property or the stability of the coating is not problematic (the coating property or the stability of the coating is not problematic, as much as possible All -) is better. Further, the dispersion state of the pigment in the coating can be controlled by adjusting the type of the dispersing machine, the dispersion time, the kind of the dispersing agent, the amount of addition, and the like. The size of the voids in the high-concentration pigment layer is not particularly limited, but when it is an extremely large size, there is a problem that the coating film defects are caused, and the coating properties such as workability or corrosion resistance are lowered, which is not preferable, and The surface area per unit volume becomes small, and it is also poor from the viewpoint of the effect of improving the total light reflectance. On the other hand, when the size of the void is small, the surface area per unit volume of the void becomes large, and the area of the light reflection interface becomes large, so the total light reflectance is also good, but when the size of the void is extremely small, the length is long. Wavelength of light transmission 'has the concern that the total light reflectance decreases. Therefore, the size of the voids in the high-concentration pigment layer is preferably about half of the wavelength of visible light of from 200 〇 111 to 40011111, more preferably from 250 nm to 350 nm from the viewpoint of increasing the reflectance of light. However, due to the control of the gap size, especially the size of the void in the uniform coating film. It is difficult, so there is no particular problem in the size of the voids, such as the above-mentioned problems such as film defects or extreme effects on the reflectance. Further, in the present embodiment, the size of the void is an equivalent volume diameter (equivalent 18 201119847 volume diameter) having a diameter of a sphere having the same volume as the void. In fact, a scanning electron microscope (SEM) is used to take a vertical cross section of a high-concentration pigment layer at a magnification of 10,000 times, and any void observed by the captured image is selected, and a circle having the same surface area as the area is selected. The diameter 'is defined as the same diameter as the ball having the same volume as the void. The diameter of any of the 10 voids is calculated by the electron microscope in the gap where the image is perceived to be painful, and the arithmetic mean can be used as the diameter of the void. Here, the method of determining the volume % of the voids in the coating layer in the present embodiment will be described. With respect to the surface cut surface, or first, the coating layer to be measured is scraped off from the sample, and the coating surface (the surface parallel to the surface of the metal material) is vertically placed under the ** optical microscope, electron microscope, or the like. The thickness of the coating layer T1 was determined by observing the cross-section using the electromagnetic film thickness 氺*. Further, similarly to the volume concentration of the rutile-type titanium oxide, the coating film area A1 after the chipping, the volume V1 of the binder resin (for example, polyester resin), and the pigment (for example, rutile-type titanium oxide) are obtained. The volume V2. From the obtained A1, \^1, and 乂2, the film thickness T2 of the coating layer at the time of no void is obtained by T2 = (V1 + V2) / A1. In the case of VI, V2, Τ1 and Τ2, the volume V3 of the void can be obtained by V3=(V1+V2) χ(Τ1-Τ2)/(Τ1+Τ2). From the viewpoint of measurement accuracy, the method of measuring the film thickness T1 is preferably a method using an optical microscope or an electron microscope (SEM). Further, the above & gap volume was measured five times on the same sample (i.e., 'coating layer), and the arithmetic average (binder resin) was used as the binder resin used in the high-concentration pigment layer of the present embodiment, and 19 201119847 Particularly, a binder resin generally used, for example, a polyester resin, an amine phthalate resin, an epoxy resin, an acrylic resin, a fluorene resin, a fluororesin or the like can be used. However, in the high-concentration pigment layer of the present embodiment, the rutile-type titanium oxide particles having the highest amount of the above-described addition are added, so that the coating film is likely to be weak, and the bonding used in the high-concentration pigment layer is used. The resin is preferably a resin excellent in workability or adhesion. Specifically, as the binder resin, for example, a polyester resin A having a number average molecular weight of 19000 or more and 28,000 or less is preferably used. This is due to the following reasons. In the coated metal material of the present embodiment, since a high total light reflectance is obtained, it is necessary to set the rutile-type titanium oxide particles as a white pigment added to the high-concentration pigment layer to have a solid volume concentration. The system has a high concentration of 35% to 70%. Therefore, depending on the type of the binder resin used in the coating material, there is a problem that the binder property between the pigment particles is insufficient, so that the workability of the coated metal material is lowered. Then, the inventors of the present invention have been working to review the structure of a coating layer for ensuring workability with a small amount of a binder resin, and as a result, it has been found that the polyester resin having excellent adhesion to the pigment particles and the metal material as the substrate is the most In addition, by setting the number average molecular weight of the polyester resin to 19000 or more and 28,000 or less, it is possible to exhibit excellent balance between ductility and strength, and therefore, a polyester resin having a number average molecular weight of 19,000 or more and 28,000 or less is used. A, good processing is available. The number average molecular weight of the polyester resin can be determined by "GPC". When a commercially available resin is used, the value of the number average molecular weight disclosed by the manufacturer can be used. Here, in general, a coating using a high molecular weight polyester resin having a molecular weight of 19,000 or more as a binder tends to be too high in viscosity, so that the viscosity of the coating is lowered in order to ensure the viscosity of the coating in the coating of 2011 201119847. necessary. Therefore, in the use of the thick film coating as the main use of the present invention, it is easy to produce a coating defect called foaming, and it is considered that it is difficult to use a high molecular weight polyester resin. However, in the present embodiment, since the rutile-type oxidizing agent as a white pigment is added in a large amount, the concentration of the binder resin is relatively lowered, and the viscosity suitable for coating can be ensured even if the solid content concentration in the coating is not easily lowered. Therefore, even if the high-molecular-weight polyester resin A is used as the binder of the high-impact pigment layer of the present embodiment, the coating of the thick film can be performed without foaming, and the coating property and the workability can be achieved. In addition, when the number average molecular weight of the polyester resin A is less than 19 Å, it is difficult to ensure the moldability. Therefore, the polyester resin used as the binder resin used in the high-concentration pigment layer of the present embodiment is combined for the above reasons. A preferred range of the average molecular weight of A is set to be 19,000 or more. On the other hand, when the number average molecular weight of the polyester resin A is more than 28 ', the surface of the coating film is excessively soft, and there is a doubt that the smear resistance is not good, so it will be used as a high-concentration pigment layer. The preferred range of the average molecular weight of the polyvalent month A used in the binder used is set to be less than or equal to the coffee. When the concentration of the poly-resin A is more than 2 (% by mass) based on the total amount of the poly-resin of the binder resin, the coating can be carried out without foaming. Because of the coating property and the workability, it is preferable to set the concentration of the polyester resin A to the entire mass of the adhesive & Further, the present inventors have found that the binder resin in the high-concentration pigment layer contains a polyester having a number average molecular weight of 2,000 to 21 201119847, 6000 or less, and a valence of 20 or more, in addition to the above-mentioned poly(S) resin. Resin b, and the polyhedral resin A and the polyester resin B are 0 by mass ratio. 25 $ (polyester resin b) / (poly resin resin) $4, which gives better formability. As described above, the high-molecular-weight polyester resin A having a number average molecular weight of 19000 or more and 28,000 or less is excellent in workability, but the high-concentration pigment layer of the present embodiment contains a pigment such as rutile-type titanium oxide at a high concentration. It is considered to have a structure in which a binder resin is dispersed between pigments. In such a structure, even in the coating layer containing the high molecular weight polyester resin A, the workability is lower than that of the coating layer having a low pigment concentration, and further improved workability is sought. Then, the inventors of the present invention have conducted a review to further improve the workability, and as a result, it has been found that by combining the high molecular weight polyester resin A with the low molecular weight polyester resin B, it is possible to obtain a polyester having a higher molecular weight than the polyester alone. Resin A provides superior processing performance. In other words, when the high-molecular weight poly-polymer A is present in a gap between the pigments at a high concentration, the resin cannot sufficiently enter the resin, and the function as a binder is insufficient, and the workability is slightly lowered. On the other hand, by combining the high molecular weight polyester resin A and the low molecular weight polyester resin B, the low molecular weight polyester resin 8 can enter between the pigment and the pigment which the high molecular weight polyester resin A cannot enter. As a binder of a pigment, a pigment, or a pigment and a high-molecular-weight polyester resin A, it is considered to have excellent workability because it can increase the strength and adhesion of the entire coating layer. Further, the higher the hydroxyl group value of the low molecular weight polyester resin B, the more the parent point will be, and the higher film adhesion can be obtained. From the above viewpoints, the low molecular weight polyester resin B is preferably 2 or more and 6 GGG or less in the number average average of 22 201119847 - +, and the JMi base price is preferably 2 G or more. When the average molecular weight of the polysaccharide B is less than 2 _, the film strength is insufficient and the force of 1 ± decrease is considered. 'When the average molecular weight is greater than _, because the poly 曰曰曰 B is not easy to enter _ between And there is doubt that the effect of the adhesion is reduced. Further, when the base price of the binder resin B is less than 2 Å, the crosslinking point between the pigment and the pigment is small, and the effect of improving the adhesion is lowered. In addition, from the viewpoint of film properties, it is not necessary to specifically set the upper limit value of the base price of the polyfluorene I resin B, but from the viewpoint of easy availability of the resin and stability of the coating, the process of the polystyrene resin B The base price is preferably 2 〇〇 or less. Further, the mixing ratio of the polystyrene resin A and the polystyrene resin B is 0. When 25$ (polyacetate resin B) / (poly resin resin) ^ 4, excellent adhesion and processability can be obtained. When the mass ratio of polyacetal resin / (polyester resin Α) is less than 〇 _25, the function of poly _ age becomes insufficient, so there is a doubt that the adhesion is lowered, when (polyacetate resin ( When the poly-resin resin 大于) is more than 4, the function of the polyester resin enamel is insufficient, and there is a concern that the workability is lowered. (Thickness) The film thickness of the high-concentration pigment layer of the present embodiment is high. The total light reflectance is preferably ΙΟμηι or more, and is preferably 40 μπι or more when pursuing a higher total light reflectance. On the other hand, when the film thickness of the high-wavelength pigment layer is greater than 80 μm, the fg is coated with a film. The film thickness of the high-intensity pigment layer is preferably ΙΟΟμη or less, and is preferably 15 μη / or less in pursuit of high workability. Here, the height of the embodiment can be measured as follows The film thickness of the pigment layer is concentrated. In other words, the film thickness of the coating layer is obtained by cutting the coating surface with respect to each coating film on the vertical surface and observing the surface of the film by an optical microscope or an electron microscope. In the measurement of "film thickness", it is measured at any five places. The average thickness of the coating layer and the undercoat layer described later may be measured in the same manner as the film thickness of the high-concentration pigment layer. Further, a mixed layer is formed at the boundary portion of each coating layer. In the case of the above, the high-concentration pigment layer of the present embodiment will be described in detail, and the coating layer of the present embodiment will be described next. (Outline) It is a coating layer on the surface layer side of the high-concentration pigment layer, that is, a layer which is disposed on a side farther from the metal material of the substrate. Here, the coating layer is composed of a high-concentration pigment layer and an overcoat layer. In the case of a three-layer structure including a lower coat layer and a structure in which a plurality of layers of a high-concentration pigment layer are present in a plurality of layers at the time of construction, the upper coat layer is located at the outermost layer. However, the upper coat layer is only required to be When it is laminated directly on the surface side of the high-concentration pigment layer, it is not necessary to be located on the outermost layer, and other coating layers may be laminated on the more surface side of the upper coating layer. (Adhesive) The resin used as the adhesive for the upper coating layer is not Specially limited, but From the viewpoints of adhesion to a high-concentration pigment layer, formation of a mixed layer to be described later, and formation of a coating material, it is preferred to use a resin containing a pigment layer having a high concentration. Therefore, adhesion of a high-concentration pigment layer is preferable. The polyester resin A having a number average molecular weight of 19,000 or more and 28,000 or less is preferably used. Therefore, it is preferred to use the polyester resin A as a binder in the upper coating layer. 24 201119847 As an adhesive for the upper coating layer When the number average molecular weight of the polyester resin to be used is less than 19,000, there is a concern that the workability and the adhesion are lowered. When the number average molecular weight is more than 28,000, the surface of the coating film becomes too soft, and the scratch resistance and the anti-sticking property are deteriorated. In addition, the addition amount of the vinegar resin A of the upper coating layer can be improved by the processability or the adhesion property as long as the concentration of the vinegar resin VIII of the entire binder resin is 8 〇 mass% or more. Therefore, it is preferable to set the concentration of the resin A to be more than or equal to the total amount of the binder resin. (Pigment) The top coat is different from the high-concentration pigment layer, and it is not necessary to add a pigment 'visible use to adjust the presence or absence of the pigment, the concentration of the pigment to which the pigment is added, etc.' to provide the desired reflection or other characteristics. . First described in the upper coating, for example, adding rutile-type oxidized chin as a pigment, by adding rutile-type titanium oxide to the top coating, which can improve the light reflectance, and if the rutile thief-cutting titanium concentration is high, the reflective month is It is powerful, but the main function of the top coat is to protect the entire coating layer, so the coating of k is not good. Therefore, the concentration of the rutile-type titanium oxide in the coating layer which ensures the flexibility of the coating film is 35% or less in terms of solid volume/density. On the other hand, there is no need to specifically limit the above. The lower limit of the concentration of the work stone type Wei Qin also includes the case where there is no gold gas at all. In other words, in the coating layer of the present embodiment, the oxidation degree 'agronomic degree' is 0% or more and 3 5 % of the solid matter volume concentration, and in addition, when pursuing a higher total light reflectance, The concentration of rutile-type titanium oxide of d is set to 20% to 30% based on the solid volume concentration concentration of 25 201119847, and the protective function and high reflection performance of the coating layer obtained by the upper coating can be combined with high dimensionality. . In addition, the "volume concentration of solid content of rutile-type titanium oxide" referred to herein is a volume occupied by the entire solid matter of the resin (binder) component and the pigment component in the coating film in the overcoat layer. The proportion of the volume of rutile titanium oxide. When the rutile-type oxidized chin is used as the pigment, the average particle diameter of the rutile-type oxidized crystal is larger, and the surface area per unit volume becomes larger, and the area of the interface as the light-reflecting surface of the resin or the void and the pigment becomes larger. Therefore, the total light reflectance also becomes high, but when the average particle diameter of the pigment is too small, the total light reflectance is lowered due to the transmission of light of a long wavelength. Therefore, in the same manner as in the case of the high-concentration pigment layer, the average particle diameter of the rutile-type titanium oxide used as the pigment in the overcoat layer is preferably 2 〇〇 nm or more and 400 nm or less, and is preferably 250 nm or more. More preferably, it is below 350nm. (Additional component other than pigment) In the upper coating layer, in addition to rutile-type titanium oxide, for example, a matting agent may be added. By adding a matting agent to the upper coating layer at a solid volume concentration of 3% or more and 15% or less, it is possible to obtain a few non-reflective components at the same degree of total light reflectance as when the matting agent is not used. Reflection characteristics. When the coated metal material having such a reflection property is used as a reflector of a lighting fixture, since the distance and the angle of the light source are irrelevant, the reflected light can be obtained, so that the number of the light sources is small or the interval between the light sources is large. At the same time, uniform light can be obtained. However, by adding a matting agent, the surface of the upper coating layer will form fine concavities and convexities, and the contaminant is likely to accumulate in the fine concavities and convexities, and it is difficult to remove the contaminant by rubbing, so that it is resistant to pollution. Falling doubts. Therefore, the amount of the matting agent added is considered to have an effect on the uniformity of the reflected light and the deterioration of the stain resistance, and it is preferable to determine an appropriate amount. Further, the matting agent used in the present embodiment is not particularly limited, but for example, a silica dioxide having a particle diameter of 3 μm to 9 μm is preferably used. (Thickness) When rutile-type titanium oxide is added to the top coat layer, the thicker the film thickness of the top coat layer, the higher the workability, the adhesion, and the total light reflectance. However, when the film thickness of the top coat layer is more than 30 μm, the coating property is likely to be deteriorated at the time of coating, and the coating property is deteriorated, which is also inferior from the viewpoint of paint cost. On the other hand, when the film thickness of the upper coating layer is less than 5 μm, the effect of the coating on the basis of the workability, the posterior property, and the reflectance of the king light is small, so that the upper coating layer is used. It is preferable that the film thickness is set to be more than 30 μm. By ensuring stable processability, The film thickness of the overcoat layer is preferably 10 μm or more and 25 μm or less from the viewpoints of adhesion, total light reflectance, and paintability. When the top coat is added at a concentration of 3% or more and 15% or less of the matte agent, the film thickness of the top coat is the same as that of the rutile type ruthenium oxide added to the top coat, and is 5 μm or more. 3〇μηι is better. When the film thickness of the upper coating layer is more than 3 〇μηι, foaming is likely to occur during coating, so the cracking property is deteriorated, and the coating cost is also poor. On the other hand, when the film thickness of the overcoat layer is less than 5 Å, there is almost no fear of obtaining the effect of improving the workability of the overcoat layer, the adhesion, or the reflection property of a few non-reflective components. From the viewpoint of ensuring stable processability, adhesion, reflection characteristics, and coating growth, a preferred film thickness of the coating on the matte agent is 27 201119847 ΙΟμπι or more and 25 μmη or less. [Roughness of the interface between the high-concentration pigment layer and the overcoat layer] In the coated metal material of the present embodiment, the center line average roughness Ra of the boundary surface between the high-concentration pigment layer and the overcoat layer needs to be 〇. 8μηι or more. Thus, by increasing the Ra of the boundary surface between the high-concentration pigment layer and the upper coating layer, the boundary surface between the high-concentration pigment layer and the upper coating layer becomes thicker, so that the diffuse reflectance can be improved. When the Ra of the boundary surface between the south concentration pigment layer and the overcoat layer is less than μ 8 μm, the effect of improving the adhesion or improving the reflectance is not sufficiently obtained. When it is 〇·9 μm or more, it is preferable because it has a high reflectance. It is better when it is 2 〇μπ1 or more. The Ra system of the boundary surface between the intermediate coating layer and the upper coating layer is cut by the coating film of each embodiment, filled with a resin, and ground, and the cross section perpendicular to the surface of the coating film is smoothed, and then a scanning microscope (magnification) 1 〇〇〇 times) The photos taken are evaluated. Covering the transparent sheet used by the OHP from the top of the photo, and accurately drawing the unevenness of the boundary surface, as shown in Fig. 3, only 1 reference length is taken in the direction of the average line of the boundary surface curve, and the average of the taken portion is taken. The direction of the line is taken as the X-axis and the vertical magnification direction, and when the interface curve is represented by y=f(x), the value obtained by the number 1 is taken as the Ra of the boundary surface. Further, in the case of the invention, the $ of any of the coatings in the coating film is averaged by Ra measured by the aforementioned method. |dx (Control method of Ra of boundary surface): Ra of the boundary surface of the concentration pigment layer and the upper coating layer can be controlled by the following method of coating the pigment layer and the upper coating layer, and the high concentration pigment layer 28 201119847 The concentration of the pigment (rutile-type titanium oxide), the pigment type of the high-concentration pigment layer (such as rutile-type titanium oxide or ruthenium dioxide, low-refractive-index particles, etc.), and the low-concentration pigment layer and the coating for forming the overcoat layer are low. Viscosity or surface tension under shear. Further, in the present development, the boundary surface between the high-concentration pigment layer and the overcoat layer refers to a boundary surface (boundary line) visually observed when the cross section of the coating film is photographed by an optical microscope or an electron microscope. Specifically, the method for increasing Ra of the boundary surface between the high-concentration pigment layer and the upper coating layer has the following methods: (1) coating a coating material for forming a high-concentration pigment layer with a coating for forming an overcoat layer Laminating in an undried state, that is, using a so-called wet-stack wet method or a multi-layer simultaneous coating method; (2) raising a pigment (rutile-type titanium oxide, etc.) in a high-concentration pigment layer - to a pigment in the upper coating layer High concentration; (3) adding particles having a large particle size (cerium oxide, etc.) to the high-concentration pigment layer; (4) reducing the viscosity of the coating material for forming a high concentration pigment layer under low shear force; and (5) reducing the concentration of the pigment layer at a high concentration The surface tension of the coating for forming and the coating for forming an overcoat layer is poor. First, in the above method (1), the high-concentration pigment layer-forming coating material and the overcoat layer-forming coating material are laminated in an undried state, and the rutile-type titanium oxide particles are diffused from the high-concentration pigment layer toward the upper coating layer. With the action of the boundary surface, the Ra of the boundary surface of the coating layer becomes large. At this time, as in the method (2), the concentration of the rutile-type titanium oxide in the high-concentration pigment layer is raised to a high concentration, 29 201119847, in particular, 'the density is set to the most densely filled, thereby, with the upper coating film The difference in the degree of infiltration becomes large, and the force of diffusion of the rutile-type titanium oxide toward the upper coating layer strongly acts, so the Ra of the boundary surface becomes larger. Further, 'About the method (3)', a particle having a large particle size is added to the high-concentration pigment layer, and the large-sized particle is present in the vicinity of the boundary surface between the high-concentration pigment layer and the upper coating layer, thereby Since the interface has irregularities formed by particles having a large particle size, the Ra of the boundary surface becomes large. At this time, as in the method (1), the coating material for forming a high-concentration pigment layer and the coating material for forming an overcoat layer are laminated in an undried state, and since the particles having a large particle diameter are diffused from the high-concentration pigment layer to the overcoat layer, Particles having a large particle size tend to exist in the vicinity of the boundary surface between the high concentration pigment layer and the upper coating layer. Νανπ The straw is reduced from the low to the F concentration of the knife F. The viscosity of the paint is used. ‘Because of the rutile-type oxygen in the high-concentration pigment layer, the diffusion of the upper coating layer is increased, so the Ra of the boundary surface becomes larger. In other words, according to the knowledge of the person, etc., the coating which is added to the top 3 degrees with the addition of fine particles (in this case, rutile-type titanium oxide) after drying and hardening will become a high-concentration material. The non-Newtonian fluid becomes a coating that rotates when it has a viscosity, which has a high viscosity under low rotation and a high rotation = low, that is, shear thinning characteristics. In the thick dispersion coating, the distance between the pigment particles in the film is short, so that the intermolecular force is generated between the particles, and the shear force applied to the coating under the low rotation becomes small, so the viscosity of the molecule R is changed to: the lower viscosity is changed. high. On the other hand, application to the coating under high rotation is only large. When the shear force is greater than the intermolecular force, the viscosity becomes low. The coating workability when the material is applied to the substrate is greatly affected by the viscosity of the coating under the drying and sintering hardening steps after the coating, which is greatly affected by the viscosity of the high name 30 201119847. Viscosity effect under low rotation. Therefore, it is important to adjust the viscosity of the coating under low shear force in relation to controlling the Ra of the boundary layer between the high concentration pigment layer and the upper coating layer. Here, the viscosity of the paint under low rotation can be adjusted by changing the amount of the solvent in the paint and the storage conditions (storage temperature and storage period) of the paint. The storage conditions of the paint are such that the storage temperature is higher or the storage period is longer, and the thixotropy is lowered, so that the viscosity of the paint under low shear force is improved. This is because when the storage period is long, the wettability of the surface of the pigment and the coating material is high, and a large amount of the resin is adsorbed on the surface of the pigment, so that the intermolecular force between the pigments is weakened, and the thixotropy is lowered. In addition, by adding additives such as dispersants to the coating, the viscosity of the coating under low shear can be adjusted. Further, in the method (5), when the coating material for forming a high-concentration pigment layer and the coating material for forming an overcoat layer are reduced in surface tension, the coating material is laminated in an undried state, and dried and burned at the same time. When hardening is applied, the Ra of the boundary surface becomes large. However, the surface tension of the coating material for forming a high-concentration pigment layer and the coating material for forming an overcoat layer is inferior, and the appropriate values are different depending on the type of the resin or the type of the solvent in each layer. Therefore, it is not possible to generally specify the coating material beforehand. In order to determine the optimum value. Here, the surface tension of the coating can be adjusted by using an additive generally called a surfactant such as a leveling agent or an antifoaming agent, but it can also be adjusted by changing the kind of the solvent. Further, in the coated metal material of the present embodiment, the center line average roughness Ra of the boundary surface of the high-concentration pigment layer and the upper coating layer is set to be 0. 8μηι or more, a method which is more effective for this purpose, for example, adding 31 201119847 to a high-concentration pigment layer, and adding a rutile-type titanium oxide having a particle diameter of 200 nm to 4 〇〇 nm, so as to be a volume relative to the film after drying. A method in which the coating material for forming a high-concentration pigment layer and the coating material for forming an overcoat layer are laminated in an undried state, and dried and hardened simultaneously in a state of being laminated. By adding the rutile-type titanium oxide which is the most densely packed in the high-concentration pigment layer and laminating the upper coating layer in an undried state, a concentration gradient of the rutile-type titanium oxide particles is generated between the respective coating layers, and is generated. The effect of diffusing the rutile-type titanium oxide particles in the south concentration pigment layer toward the upper coating side, and applying heat to the drying and hardening steps, the heat becomes a driving force to diffuse the rutile-type titanium oxide. Significant. On the other hand, since the resin which forms the coating film generates a crosslinking reaction when it is heated by the drying and hardening steps, the effect of suppressing the interlayer diffusion operation of the rutile-type titanium oxide particles occurs. Therefore, the boundary surface between the high-concentration pigment layer and the upper coating layer becomes rough, and Ra becomes large. Further, by providing the high-concentration pigment layer of the present embodiment as the undercoat layer coating layer, Ra of the boundary surface between the high-concentration pigment layer and the overcoat layer can be made 0.8 or more, but as described above (4) The viscosity of the coating under low shear force greatly affects the control of the ruler 3 of the boundary surface between the high concentration pigment layer and the upper honey layer, and by increasing the viscosity of the paint under low shear force, the high concentration pigment layer and the upper layer can be further increased. Ra of the boundary surface of the coating. [Mixed layer] In the coated metal material of the present embodiment, a coating material for forming a high-concentration pigment layer and a coating material for forming an overcoat layer are applied by a wet-stacking method or a multi-layer simultaneous coating method, and a coating material for forming a pigment layer of a ruthenium concentration is formed. The rutile-type titanium oxide in the middle layer exceeds the interface between the layers and diffuses toward the coating for forming the upper coating layer, so that a concentration gradient layer of rutile-type titanium oxide can be formed in the vicinity of the interface between the pigment layer and the upper coating layer at a high concentration of 32 201119847. In the present invention, the concentration gradient layer of the present titanium oxide is referred to as a mixed layer. At this time, the adhesion between the high concentration pigment layer and the overcoat layer can be enhanced by the mixed layer present in the boundary portion between the high concentration pigment layer and the upper coating layer. Further, when the metal material is pre-coated, the total light reflectance of the coated metal material may be lowered due to the processing after the coating, but the mixed layer may be used to improve the adhesion, so that the processing may be inhibited. After that, the total light reflectance decreases. (Definition of Mixed Layer) Here, the "mixed layer" in the present embodiment means that the concentration of the rutile-type titanium oxide formed by the rutile-type titanium oxide having a high concentration of the pigment layer is diffused toward the upper coating layer. A layer of oblique construction. More specifically, in the present embodiment, when focusing on rutile-type titanium oxide, when the amount of Ti in the high pigment concentration layer is X and the amount of Ti in the overcoat layer is y, [χ+0·05 X (xy)]~[y-0. A part of 05x(x-y)] is used as a mixed layer. The amount of each Ti can be obtained by an analysis method described later, or can be calculated by using the measured intensity when Ti is measured by each analyzer. In addition, there is also a case where a mixed layer is formed between the undercoat layer and the high-concentration pigment layer, and in this case, the definition of the mixed layer or the definition of the boundary surface is also the mixed layer between the high-concentration pigment layer and the overcoat layer. the same. When the high-concentration pigment layer contains low-refractive-index particles, the volume ratio of the low-refractive-index particles to the rutile-type titanium oxide can be determined by the rutile type as long as the low-refractive-index particles are, for example, inorganic pigments. The operation of the same volume concentration of titanium oxide was obtained. The difference from the rutile-type titanium oxide is, for example, that the rutile-type titanium oxide is not used in the heat-retaining portion, and the chemical agent such as an acid which dissolves only the low-refractive-index particles is dissolved, and only the low-refractive-index particles are dissolved. The mass of the low refractive index particles can be determined from the difference in mass between the dissolved residual portion and the heated residual portion, and the volume of the low refractive index particles can be determined from the density of the mass and the low refractive index particles. On the other hand, when the transmittance of the electron beam is completely different from that of the rutile-type titanium oxide in the case of the low refractive index particles such as the resin particles, the cross section of the coating layer is observed by a scanning electron microscope, or thinly by a microtome or the like. The coating film layer was cut out, and the method was observed by a transmission electron microscope (magnification: 10,000 times). Specifically, it can be obtained by calculating the number of rutile-type titanium oxide and low-refractive-index particles seen in the field of view. However, when the amount is small, the difference is large, so it is preferable to calculate the number of particles in a range of at least one or more of the rutile-type titanium oxide. Moreover, the electron beam transmittance of the low refractive index particles is almost the same as that of the rutile type titanium oxide, and it is difficult to distinguish the difference between the low refractive index particles and the rutile type titanium oxide by a scanning electron microscope or a transmission electron microscope. The element composition in the cross section of the film layer can be determined from the composition of the rutile-type titanium oxide and other low-refractive-index particles. The elemental composition can be confirmed by using ΕΡΜΑ (electron probe microanalyzer) or GDS (glow discharge luminescence spectroscopic analyzer). (Thickness of mixed layer) In the present embodiment, when the mixed layer is present, the mixed layer preferably has a thickness of 3 μM or more and 12 cm or less. When the thickness of the mixed layer is less than 3 μηι, there is a fear that the adhesion improving effect between the high-concentration pigment layer and the overcoat layer produced by the mixed layer cannot be stably obtained. On the other hand, when the thickness of the layer 34 201119847 is more than 12 μm, it is difficult to sufficiently ensure the film thickness of the high-concentration pigment layer and the overcoat layer which share the necessary functions. Therefore, when the top coat layer is the outermost layer, appearance defects due to insufficient thickness of the outermost layer are likely to occur, and the performance of the high-concentration pigment layer and the overcoat layer itself is difficult to maintain, substantially due to mixing with The coating layer formed by the coating material for forming a high-concentration pigment layer and the coating material for forming an overcoat layer has the same performance, and thus the performance of the original high-concentration pigment layer and the overcoat layer cannot be obtained. In addition, it is substantially difficult to control the thickness of the mixed layer to a thickness greater than 12 μm. (Method for measuring the thickness of the mixed layer) The film thickness of the mixed layer can be determined by analyzing the distribution state of the component in the film thickness direction of only the component containing only the high concentration pigment layer or the upper coating layer. Analytical methods can use well-known analytical methods, such as: using * * Χ ray probe micro analyzer, electron probe micro analyzer (ΕΡΜΑ), X-ray photoelectron spectroscopy (XPS), Aojie electron spectroscopy (AES) Glow Discharge Luminescence Analysis (GDS)**, etc., to analyze the element concentration in the depth direction of the coating film, or to analyze the composition in the cross section of the coating film, the film thickness of the mixed layer can be determined from the concentration distribution of the target component. The type or method of the component analysis to be applied may be appropriately selected in accordance with the film thickness, the component amount, and the like. In addition to ΕΡΜΑ, XPS, AES, and GDS, as long as it is a method for component analysis in the depth direction, it can be appropriately selected. Further, the component for the analysis of the mixed layer may be other than Ti. In this analysis method, since the GDS system is analyzed by reducing the surface of the coating film toward the depth direction and argon ions which are inert to the mineral, the concentration in the depth direction of the measurement element can be accurately compared, which is preferable. In the invention of the present application, the film thickness of the mixed layer was measured at an average film thickness of any five points. 35 201119847 (Method for measuring the thickness of mixed layer) The thickness of this layer a can be mainly controlled by the coating method and the baking time. The coating method is carried out by using a wet-stack wet method or a multi-layer simultaneous coating method, and the valley is easy to form a mixed layer. Moreover, by extending the baking time, the time for forming the mixed layer can be sufficiently extended, so that the thickness of the mixed layer can be increased. Specifically, the burning time can be set to about 60 seconds to 180 seconds. The thickness of the mixed layer is 3 μm or more and less. Further, in order to form a stable mixed layer, the difference between the surface tension (σΐ) of the coating material for forming a high-concentration pigment layer forming the mixed layer and the surface tension (σ2) of the coating material for forming a coating layer on the mixed layer (Δσ = Σ2σ1) is controlled to be 0. 5 8 mN/m, and the difference between the viscosity (Φ 2) of the coating for forming a coating layer for forming a mixed layer and the viscosity (Φ 2) of the coating for forming a coating layer on the mixed layer (Δ) 2- φ 1) Control is -100~4000mPa. s is better. In this way, the type of coating or the coating conditions can be adjusted, and the appropriate value in the condition can be adjusted by appropriately adjusting the relationship between the surface tension and the viscosity of the high-concentration (4) and the coated material. The formation of the mixed layer and the film thickness can control the shape of the outermost surface. In other words, the interlayer adhesion can be further improved by forming a mixed layer having a sufficient thickness by & 8 or less, or Δ being 4 to 8 or less. On the other hand 'by Δσ is 〇. 5mN/m or more, or Λφ is. Upper, high concentration _ layer and upper (four) 1 thickness can be sufficient, and the shape of the outer surface is also suitable, which can ensure stable performance. In addition, the surface tension of the coating in the present embodiment can be determined by the platinum ring pull method (10) of the surface tension measurement (4), and can be carried out according to the dish (4) Factory Wheel 36 201119847. ). Further, the paint viscosity can be measured using a B-type viscometer at 20 ° C, * * 6 mpm * *. (The details of this viscosity measurement can be based on JIS. Z. 8803. 8 "Measurement method for viscosity by a single cylindrical rotary viscometer". Further, the surface tension of the coating is adjusted to utilize a surfactant (including an antifoaming agent or a leveling agent). As the surfactant, those skilled in the art can be used, and BYK-333, BYK-307, and EMULGEN of Kaosha, which are known from the market, are also available, and various other types can be appropriately added to the coating composition. Further, the surface tension of the coating material may be adjusted by diluting or mixing a surfactant other than a solvent. In addition, when the surface tension is too large, the surface tension of the coating material for the high-concentration pigment layer and the coating material for the top coating layer is preferably 40 mN/m or less. Further, it is preferable to adjust the viscosity of the coating to use a tackifier (including a rheology control agent and a viscosity modifier). The tackifier is known to be used, and many commercially available ones are known as BYK-411, BYK-425, etc. of BYK, and can be appropriately added in accordance with the coating composition. Further, the viscosity of the coating material may be adjusted by diluting, mixing other solvents, or by using a method other than an adhesion promoter such as increasing the ratio of the solid component. Further, the thickness of the mixed layer can also be controlled by adjusting the difference between the concentration of the pigment in the coating for the high concentration pigment layer and the concentration of the pigment in the coating for the top coating. In other words, when the difference in the concentration of the pigment is increased, the diffusion rate of the pigment which is coated with the high-concentration pigment layer is increased, so that the coating material for the high-concentration pigment layer and the coating for the top coating layer can be sufficiently formed before drying and hardening. A mixed layer of thickness. [About the undulation of the outer surface j 37 2 〇 1119847 In the coated metal material of the embodiment, it is preferable that the filter center line ripple WcA of the outermost surface of the coating layer is as follows. In this way, by narrowing the WCA of the outermost surface of the coating layer, the sharpness of the coated metal material can be improved, and a smooth surface having no minute four convexities can be obtained, so that the pollutants are less likely to accumulate on the surface of the coated metal material, so that the pollution is caused. Upgrade. When the WCA of the outermost surface of the coating layer is larger than 2 μm, there is a concern that the sharpness and the stain resistance are lowered. On the other hand, the preferred lower limit of the WCA of the outermost surface of the coating layer is not particularly limited, but it is difficult to control the WCA of the outermost surface of the coating layer to be substantially less than 0·2 μη, so from this point of view, 'The WCA of the outermost surface of the coating is 〇. 2μιη or less is preferred. Further, the WCA of the invention of the present application is measured at any five places and then averaged. Further, the term "the outermost surface of the coating layer" as used herein means the surface of the coating layer of the outermost layer of the coating layer. The "coat layer of the outermost layer" means the layer of the coating layer when the coating layer is further laminated on the surface layer side of the coating layer or the upper coating layer as in the above embodiment. (Control method of WCA at the outermost surface) The WCA system on the outermost surface of the coating layer is affected by the influence of Ra of the interface between the high-concentration pigment layer and the upper coating layer. Therefore, the WcA at the outermost surface of the coating layer can be mainly controlled by the coating method and the viscosity of the coating under low shear force. Specifically, by using a wet-stack wet method or a multi-layer simultaneous coating method as a coating method, since the rutile plastic titanium oxide is diffused from the high-concentration pigment layer toward the upper coating layer, the boundary layer between the high-concentration pigment layer and the upper coating layer is As Ra becomes larger, the Wca at the outermost surface of the coating layer also becomes larger. Further, by reducing the viscosity of the coating material for forming a high concentration pigment layer under low shear force, the rutile-type titanium oxide in the high-concentration pigment layer is easily diffused toward the upper coating layer, so that the Ra of the boundary surface becomes large, and the coating layer is the most The Wca of the surface also becomes larger. 38 201119847 As mentioned above, it is better to increase the Ra of the boundary surface of the high-concentration pigment layer and the upper coating layer, and to reduce the WCA of the outermost surface of the coating layer. Therefore, the balance between the two is considered to determine the low shear force. A suitable value of the viscosity of the coating for forming a high concentration pigment layer is preferred. [Improvement of water repellency and oil repellency of the outermost coating film] Further, in the coated metal material of the present embodiment, the coating layer of the outermost layer of the coating layer formed on the metal material may contain a fluorinated resin or fluorine. Resin. The term "coating layer of the outermost layer" as used herein refers to the coating layer when the upper coating layer is formed on the outermost layer, and when the coating layer is laminated on the surface layer side of the upper coating layer, it means the coating layer. Membrane layer. When the coated metal material of the present embodiment is used in a precoated metal sheet, it is considered that there is a possibility that the total light reflectance is lowered due to adhesion of contaminants during processing or the like. On the other hand, in some or all of the binders of the coating layer of the outermost layer of the coated metal material of the present embodiment, a silicone resin or a fluororesin is used, so that the oil repellency and water repellency of the surface of the coating film can be imparted. Therefore, by imparting oil repellency and water repellency to the surface of the coating layer of the outermost layer, it is preferable that the stain does not easily adhere to the surface of the coating film and suppresses a decrease in the total light reflectance. The method of including the oxime resin or the fluororesin in the coating layer of the outermost layer is a method of adding a oxime resin or a fluororesin to the coating layer of the outermost layer, or using a phthalocyanine resin or a fluororesin as a main resin. method. For example, "BYK (registered trademark) - 306", "BYK (registered trademark) - 378", etc., which are manufactured by BYK Corporation, are added to the most oxidized resin which is added to the coating layer of the outermost layer. The fluororesin of the coating layer of the surface layer is known, for example, "BYK (registered trademark)-340" manufactured by BYK Co., Ltd., and the like. Others 39 201119847 are also available in various forms, and can be appropriately added in accordance with the coating composition. In addition, the main resin containing a fluorinated resin or a fluororesin can be used as a SYMAC (registered trademark) series or a "RESEDA (registered trademark)" series manufactured by Toagosei Co., Ltd.矽 · 丙烯酸登录 TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO TO Or 矽 oxygen. Fluorine-Copolymerized Resins It is also possible to use generally known cross-linking agents, for example, cross-linking with an isogas oxime ester or a melamine resin. In this case, the isocyanate is used by a general supplier. For example, "Sumidur (registered trademark)" series by the Bayer Co., Ltd., "Desmodur (registered trademark)" series "TAKEN ATE" by Mitsui Takeda Chemica Co., Ltd. )" series. For the melamine resin, the "Cymel (registered trademark)" series, the "Mycoat (registered trademark)" series, and the "BECKAMINE (registered trademark)" series manufactured by Dainippon Ink Chemical Industry Co., Ltd. can be used. , "supER beckamine (registered trademark)" series, etc. For example, the coated metal material containing the stone oxide resin or the gas resin in the coating layer of the outermost layer is suitable for use in the inner layer of the naturalized sheet or the wall material, in addition to the use of the reflector for the lighting fixture. In addition, when the coated metal material containing ♦ oxygen resin or fluororesin in the coating layer of the outermost layer is used for ceilings or wall materials in indoors, the ceiling or wall material of the indoor towel also has the function of a reflecting plate. Therefore, the room can be made brighter with less light. [Improvement of hydrophilicity to the outermost coating film] Further, in the coated metal material of the present embodiment, the coating layer formed on the metal material may be formed on the surface of the coating layer. There is a -Si-0-Si-bond in the resin skeleton. The term "coating layer of the outermost layer" as used herein refers to the coating layer when the upper coating layer is formed on the outermost layer, and when the coating layer is laminated on the surface layer side of the upper coating layer, it means the coating layer. Membrane layer. Further, the Si in the -Si-0-Si-bond is derived from a hydrolysis condensate of alkoxysilane or alkoxysilane. When the coated metal material of the present embodiment is used in a precoated metal sheet, it is considered that there is a possibility that the total light reflectance is lowered due to adhesion of contaminants during processing or the like. On the other hand, in the coating film of the outermost layer of the coated metal material of the present embodiment, -Si-O-Si- is formed, in other words, Si containing a hydrolysis condensate derived from alkoxysilane or alkoxysilane is not The surface of the coating film can be rendered hydrophilic by impairing the surface gloss or processability. In this way, by making the surface of the coating layer on the outermost layer hydrophilic, it is preferable to easily remove the adhering matter adhering to the surface of the coating film by water wiping or the like and suppress the decrease in the total light reflectance. - The Si-0-Si-bonding is formed in the resin skeleton for forming a coating film, and a hydrolyzed condensate of alkoxysilane or alkoxysilane may be added to the coating material for forming the coating film of the outermost layer. The alkoxy oxane used at this time is generally known, and examples thereof include tetraoxane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy oxane, decyl trioxane decane, decyl triethoxy decane, Ethyltrimethoxysilane, ethyltriethoxysilane, dimethoxydiethoxysilane, dioxane dipropoxylate, etc. Further, the hydrolysis condensate of the calcined oxygen stone can be exemplified by the above-exemplified hydrolysis condensate of the calcined stone. As described above, the coated metal material in which -Si-0-Si- is formed in the coating film of the outermost layer is also suitable for use in ceilings or wall materials in indoors, in addition to the use of the reflector for lighting fixtures. In addition, it will be formed in the coating film of the outermost layer. 41 201119847 When the coated metal material with -Si-0-Si- is used for ceilings or wall materials in the room, the ceiling or the wall material itself has reflection. The role of the board makes it possible to brighten the room with less light. [Thickness of the coating layer of the outermost layer] Further, the coated metal material of the present embodiment has a coating layer of the outermost layer on the surface layer side of the overcoat layer (for example, a coating containing the above-described epoxy resin or fluororesin) When the film layer or the coating layer having a -Si-O-Si-bond in the resin skeleton forming the coating film), the film thickness of the coating layer of the outermost layer is such that the water repellency and the oil repellency are obtained. The film thickness of the coating layer of the outermost layer is preferably Ιμηι or more and 25 μηι or less, depending on characteristics such as hydrophilicity. When the film thickness of the coating layer of the outermost layer is less than Ιμιη, there is a possibility of water repellency, oil repellency, and hydrophilicity. When it is larger than 25 μm, there is a possibility of poor workability, and in terms of cost, Also not good. [Undercoat layer] (Summary) The coating layer having the coated metal material of the present embodiment may contain an undercoat layer in addition to the high-concentration pigment layer and the overcoat layer described above. The undercoat layer is formed on a coating layer between the metal material and the high concentration pigment layer, and when the coating layer is composed of three layers of an upper coating layer, a high concentration pigment layer and a lower coating layer, the coating layer is used as a substrate. The coating layer on the nearest side of the metal. However, at this time, even in the layer which is the closest to the metal material, the coating layer having a film thickness of less than Ιμηι for the purpose of improving the adhesion between the metal material and the coating film or improving the corrosion resistance is not the present embodiment. The coating layer is a coating layer on the surface side of the coating layer having a film thickness smaller than Ιμηη as an undercoat layer. (Binder) 42 201119847 The resin to be used as the binder for the undercoat layer is not particularly limited, but it is contained in a high concentration pigment, from the viewpoint of adhesion to a high concentration pigment layer or co-polymerization of a coating material. It is preferred to use the same layer of resin. Therefore, the binder of the south concentration pigment layer is preferably a polyester resin a having a number average molecular weight of 19,000 or more and 28,000 or less. It is preferred to use the resin A as the binder in the undercoat layer. When the number average molecular weight of the polymer resin used as the binder of the undercoat layer is less than 19 Å, there is a concern that the workability and the adhesion are lowered. When the number average molecular weight is more than 28 Å, the surface of the coating film becomes too soft, and there is a concern that the smear resistance and the anti-sticking property are deteriorated. In addition, when the amount of the polyester resin A to be used for the undercoat layer is 80% by mass or more based on the total amount of the polyester resin A in the binder resin, the effect of improving the workability or the adhesion can be exhibited. It is preferable that the concentration of the polyester resin A with respect to the entire binder resin is 80% by mass or more. (Pigment) In the undercoat layer, when the rutile-type oxidized phthalocene as a pigment is added in an amount of 20% or more and 35% or less as a pigment, the reflectance is preferably increased. The reason why the rutile-type titanium oxide is used as the pigment to be added to the undercoat layer is as follows. In the case of the high-concentration pigment layer, the refractive index of the rutile-type titanium oxide is higher than that of other commonly used pigments, and can be increased. The refractive index difference between the air and the void portion existing between the resin and the pigment particles used as the binder is large, whereby the light reflectance at the interface between the pigment and the resin and at the interface between the pigment and the air can be improved. When the rutile-type titanium oxide is used as the pigment, the average plate diameter of the rutile-type titanium oxide, when it is small, the surface area per unit volume becomes large, and the area of the interface of the resin or the void and the pigment of the light-reflecting surface of 43 201119847 becomes Large, the total light reflectance also becomes high, but when the average particle size of the pigment is too small, the total light reflectance will decrease due to the transmission of long-wavelength light. As in the case of &, as in the case of the high-concentration pigment layer, the average particle diameter ' of the rutile-type titanium oxide used as the pigment in the undercoat layer is preferably 20 〇 nm or more and 4 〇〇 n nm, and is 25 Above the surface, 350nm or less is better. (Thickness) Regarding the film thickness of the undercoat layer, the thicker the film thickness, the higher the workability or the adhesion, and the thicker film for the reflection property when the rutile-type titanium oxide is added as a pigment. The more advantageous, so from the performance point of view, it is not necessary to set the upper limit of the thickness of the undercoat film. However, when the film thickness of the undercoat layer is greater than 30μηι, it is different from the high concentration pigment layer in the coating. Since the pigment concentration is low, foaming and coating property are likely to occur during coating, and it is also poor from the viewpoint of coating cost. Therefore, the film thickness of the undercoat layer is preferably 3 Å or less. On the other hand, when the film thickness of the undercoat layer is less than 5 μΓΠ, the effect of improving the workability, the back property, and the reflection property of the undercoat layer becomes small, so that the film thickness of the undercoat layer is preferably 5 μm or less. From the viewpoint of ensuring stable processability, adhesion, reflection properties, and coating properties, it is preferable that the film thickness of the coating layer is 1 μmηηα or 25 μηι or less. [Substrate (Metal Material)] A metal material or an alloy material which is generally known can be used as the metal material used for the base material of the coated metal material of the present embodiment. Specific examples of the metal material include a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a Qin plate, and a copper plate. Electroplating may also be applied to the surface of such metal or alloy materials. The type of plating may be, for example, zinc plating, aluminum plating, copper plating, nickel plating or the like. Electroplating of these alloys is also possible. When using a steel plate as a metal material, it can be used: molten zinc-zinc steel plate, zinc-bonded steel plate, zinc-nickel alloy electric ore plate, dissolved fusion gold-zinc-zinc steel plate, Mingdian ore plate, Ming-word alloyed plated steel plate, etc. Well known steel plates and plated steel plates. When the chemical conversion treatment is applied to the surface of the metal material used in the present embodiment, the adhesion between the metal material and the coating layer or the corrosion resistance is improved, which is preferable. Such a chemical conversion treatment can be generally applied, and specific examples thereof include zinc phosphate chemical conversion treatment, non-chromic acid chemical conversion treatment, coated chromic acid treatment, electrolytic chromic acid treatment, and reactive chromic acid treatment. Wait. Among them, the coating type chromic acid treatment, the electrolytic chromic acid treatment, and the reaction chromic acid treatment are not preferable because they contain hexavalent chromium which is an environmentally-charged substance. Further, the zinc phosphate-based chemical conversion treatment has a problem that processing adhesion is poor compared to other treatments. Therefore, the chemical conversion treatment performed on the metal material of the present embodiment is preferably a non-chromic acid treatment. The non-chromic acid chemical conversion treatment may be carried out by using an inorganic chemical conversion treatment agent or an organic chemical conversion treatment agent. Specifically, the non-chromic acid-based chemical conversion treatment is known to be carried out by using an aqueous solution containing, for example, a sulphur coupling agent, a recorded compound, a titanium compound, tannin or tannic acid, a resin, cerium oxide, or the like. Japanese Patent Laid-Open Publication No. Sho 53-9238, Japanese Patent Laid-Open No. Hei 9-241576, Japanese Patent Laid-Open No. 2001-89868, Japanese Patent Laid-Open No. 2001-316845, and Japanese Patent Laid-Open A well-known technique described in Japanese Laid-Open Patent Publication No. 2002-253464, and the like. Further, for the chemical conversion treatment, a commercially available chemical conversion treatment agent can be used, for example, a chromic acid treatment agent "ZM-1300AN" manufactured by Japan PARKERIZING Co., Ltd., and a non-chromic acid chemical conversion treatment agent "CT" manufactured by Japan PARKERIZING Co., Ltd. -E: 300N", a trivalent chromium-based chemical conversion treatment agent "Surfcoat (registered trademark) NRC1000" manufactured by PAINT, Japan. [Regarding post-coating metal material] The above description is based on the example in which the present invention is mainly used for pre-coating a metal material, but the present invention is not limited to the pre-coating metal material, and Can be used for post-coating metal. When the metal material is applied later, it is different from the precoated metal material, and it is not necessary to require workability, adhesion, etc., but when used as a reflector, it is required to have a high total light reflectance. When the metal material is subsequently coated, 'low refractive index particles having a larger particle diameter than the rutile-type titanium oxide are added to the high-concentration pigment layer, and if the solid content of the low-refractive-index particles is high, the high concentration can be obtained. The Ra of the boundary surface between the pigment layer and the upper coating is taken as 〇. 8μηι or more. Further, after the processed metal material is formed with a high m-degree pigment, a physical enthalpy is added to the surface of the formed high-concentration pigment layer, so that the surface Ra becomes thicker than 〇, and then, even if the coating is applied In the coating material, Ra of the boundary surface between the high-concentration pigment layer and the upper coating layer may be set to 0·8 μm or more. <Manufacturing method of coated metal material> The structure of the coated metal material of the present embodiment will be described in detail. Next, the manufacturing method of the coated metal material having the above configuration will be described in detail. 46 201119847 The method for producing a coated metal material according to the present embodiment is to form a high pigment concentration layer containing at least two layers containing rutile-type titanium oxide at a solid volume concentration of 35% or more and 70% or less, and laminated to a high-concentration pigment. The coating layer of the upper coating layer on the surface layer side of the layer has a method in which the center line average roughness Ra of the boundary surface between the high concentration pigment layer and the upper coating layer is 0. 8 μm or more. Hereinafter, a case where the coated metal material is divided into a pre-coated metal material and a case where the metal material is post-coated will be described in detail, and a method of producing the coated metal material according to the present embodiment will be described in detail. [Case where pre-coated metal material] First, a method of manufacturing the coated metal material according to the embodiment in the case where the coated metal material is a pre-coated metal material will be described. The coated metal material of the present embodiment can be selected by a suitable continuous coating line (referred to as "CCL") or a coating line for a cutting board, and the selected one can be selected and implemented. Process to manufacture. Representative manufacturing steps for the coating line are "washing" - "drying" 4 "chemical conversion treatment" - > "drying" 4 "painting" 4 "drying, burning" 〇 "cooling" - > Although it is dry, the manufacturing process of the coated metal material in this embodiment is not limited to this. Further, the coated metal material of the present embodiment may be produced by repeatedly applying coating, drying, and baking to each coating layer, but forming a high-concentration pigment layer by using multiple layers of simultaneous coating or wet-stacking. It is preferable to apply a coating material and a coating material for forming an overcoat layer to a part or all of the surface of the metal material, and it is preferable from the viewpoint of the performance surface and the productivity of each layer. Similarly, when the coated metal material of the present embodiment further has a coating layer of the outermost layer on the surface layer side of the overcoat layer (for example, a coating layer containing the above-described oxime resin or fluororesin), 47 201119847 At the same time, it is preferable to apply a coating material for forming a high-concentration pigment layer, a coating for forming an overcoat layer, and a coating material for forming a coating layer on the outermost layer to a surface of a metal material by coating or wet-stacking. Further, in the case where the metal material of the present embodiment is a steel plated steel sheet, in the continuous electroplating steel sheet apparatus or the continuous molten zinc electroplating steel sheet apparatus, after the electroplating step, the wet lamination coating apparatus or the simultaneous multilayer coating is used. The production line of the equipment can be applied before the formation of the oxide film on the surface of the electroplated metal to prevent defects in appearance due to the oxide film. Here, the multi-layer simultaneous coating means that the coating material can be discharged by two or more parallel slits or the like by a slit die coater or a slide hopper type curtain coater. The apparatus is applied to a substrate in a state in which a plurality of coating liquids are simultaneously laminated, and the coating liquid after the lamination is simultaneously dried and baked. Further, the wet-stack wet coating means that after the coating liquid is applied onto the substrate, the coating liquid is dried, and the other coatings are applied to the coating layer, and the multilayer coating (four) is dried. method. Specifically, the method of wet-stack wet coating can be applied, for example, by a coating method such as a roll coater, a dip coating type, a curtain flow coater, or a roll curtain coater. After the first coating layer is applied, before the coating layer is dried and dried, the curtain coating applicator (Cunain ^ e_r), roller curtain curtain applicator, sliding funnel curtain applicator A method in which the coating layer is not in contact with the substrate, and the second layer is applied, and the method of drying and laminating the laminated coating film in a wet state is simultaneously dried. In the present embodiment, a method of simultaneously coating a plurality of layers or simultaneously baking a coating film by wet coating on 48 201119847 is to use a generally known coating baking furnace, for example, a hot air drying furnace or a direct heating type. Furnace, induction heating furnace, infrared heating furnace, or the like. In this manner, the coating liquid in the undried state is applied at the same time, and the coating liquid of each layer is mixed in a small amount at the boundary portion of the coating liquid to form a mixed layer in which the components of the respective layers are mixed, whereby the interlayer adhesion can be improved. Further, since the drying steps which have been carried out in the respective layers are carried out together, it is advantageous from the viewpoint of productivity or manufacturing cost, and there is also an advantage that the drying equipment can be completed. [Case of Post-Coating Metal Material] Next, a method of producing the coated metal material of the present embodiment will be described when the coated metal material is a post-coating metal material. - The coated metal material formed by post-coating in this embodiment is attached to . After the chemical conversion treatment or the like is performed as described above, the shape of the illumination reflector using the coated metal material of the embodiment, the reflector of the light-emitting component, or the reflector of the image display portion is formed, and then It is manufactured by post-coating. As the method of forming the metal material, a well-known method can be used. Further, as a method of post-coating, a well-known spray coating, dipping coating, coating by a curtain flow coater, brush coating, electrostatic coating or the like can be used. Further, when the metal material is applied later, wet wet coating may be carried out by spray coating or the like. (Summary) 'In an electronic device using the coated metal material according to the present embodiment as described above, since the coated metal material has a high total light reversed in a high degree, the radiation rate and formability are The same light source can be brighter than the current one, and the brightness can be ensured even if the number of light sources is reduced to less than before or the input power is reduced. Further, the coated metal material of the present embodiment has a special shape and can be formed into a more complicated shape, and it is also expected to expand the applicable electronic device object or to apply the component material lifting. The effect. An electronic machine in which such characteristics can be used is not particularly limited and can be used, for example. A specific example of the illumination reflector, the reflector of the light-emitting component, or the reflector of the image display unit, etc., may be, for example, a lighting fixture or an electric appliance, a mobile device, a mobile device, or the like, but used. It is better to use the reflector inside the interior reflector of the moon reflector and the backlight reflector of the liquid crystal display. [Examples]

接著’使用實施例更具體地說明本發明，但本發明並雙下述實施例所限定。首先’洋細說明本實施例中使用之塗料。本實施例中， χ金屬材係使用於作為基材之鍍鋅鋼板表面被覆有被覆預塗覆鋼板’該被覆層具有由該鋼板側依序積層有下曰、向濃度顏料層（中塗層）、上塗層之3層構造、或下塗層、塗層、2層上塗層之4層構造。以下，依下塗層用塗料（以 ’稱為「下塗塗料」）、高濃度顏料層（中塗層）用塗料（以「下，稱為「中塗塗料」）、上塗層用塗料（以下，稱為上塗塗料」）之順序，說明使用之塗料成分。 50 201119847 (下塗塗料）如下述表1所示，關於下塗塗料，係使用東洋紡社製之非晶性聚酯樹脂「VYLON(登錄商標）630」（數平均分子量 23000，羥基價5)作為黏合劑，使用平均粒徑為280nm之金紅石型氧化鈦的石原產業社製「TIPAQUE(登錄商標）CR95」 (折射率：2.5)作為顏料，並與黏合劑混合，使金紅石型氧化鈦之固形物體積濃度為25%，製作下塗塗料（下塗-1)。表1 塗料種類黏合劑顏料種類 Tg rc] 種類平均粒徑 (μηι) 固形物體積濃度 (%) 下塗-1 VYLON630 7 氧化鈦 TIPAQUECR95 0.28 25 (中塗塗料）如表1所示，關於中塗塗料，係使用東洋紡社製之非晶性聚酿樹脂「VYLON(登錄商標）」系列、及住化Bayer Urethan社製之非晶性聚醋樹脂「DESMOPHEN(登錄商標）」系列作為基礎樹脂。例如，中塗_1〜2〇中，將r vyl〇n(登錄商標）630」（數平均分子量23〇〇〇，羥基價5)與住化 Urethan社製之非晶性聚酯樹脂「DESMOPHEN(登錄商才示）690」（數平均分子量35〇〇，羥基價46)以質量比計1 : ! 溶解於有機溶劑（以質量比計1: 1混合有Solvessol5〇與環己酮者)者。交聯劑係將市售之六甲氧甲基化三聚氛胺的三井 Cytec杜製之「Cymel(登錄商標)3〇3」，相對於聚醋樹脂之固形物100質里份添加15質量份，並且，添加市售之酸性觸媒 51 201119847 的三井Cytec社製之「_iyst(登錄商標)_3b」g $質量份，而得到聚酯系透明塗料。金紅石型氧化鈦係使用平均粒徑280nm之石原產業社製「TIPAQUE(登錄商標)CR95」（折射率：2 5)。又，中塗層所含有之低折射率粒子係使用旭硝子枉製二氧化梦「SUnsphei*e(登錄商標)H_31」（平均粒徑3叫）。此外作為中塗層所含有之顏料的比較材，亦使用平均粒U〇nm之得化學工業社製硫酸鎖「b趣ace(登錄商 t)B 30」（折射率· 1.6)、平均粒徑2術爪之艰化學工業社製氧化鋅「微細氧化鋅」（折射率：2〇)。並且藉由隻更〉谷劑量及塗料之保管溫度、保管期間，調整中塗塗料於低剪力下之塗料黏度。另外，低剪力下之黏度係使用東京計器社製師黏度計（型式：隐)以旋轉數 6rpm測定之值。於下述表2顯示製作之中塗塗料的詳細内容。 52 n 9 11 (U1&1 i il 1^1Next, the present invention will be more specifically described by way of examples, but the invention is defined by the following examples. First, the coating used in the present embodiment will be described. In the present embodiment, the base metal material is used for coating the surface of the galvanized steel sheet as the base material with the coated pre-coated steel sheet. The coating layer has a lower layer and a concentration pigment layer (the middle coating layer) sequentially stacked from the side of the steel sheet. ), a three-layer structure of the upper coating layer, or a four-layer structure of the undercoat layer, the coating layer, and the two-layer coating layer. In the following, coatings for undercoating (referred to as 'undercoating coatings'), coatings for high-concentration pigment layers (intermediate coatings) (hereinafter referred to as "middle coatings"), coatings for coatings (below) The order of the coating, referred to as the top coating, describes the coating composition used. 50 201119847 (Undercoating) As shown in the following Table 1, the amorphous coating resin "VYLON (registered trademark) 630" (number average molecular weight 23,000, hydroxyl value 5) manufactured by Toyobo Co., Ltd. was used as the binder. "TIPAQUE (registered trademark) CR95" (refractive index: 2.5) manufactured by Ishihara Sangyo Co., Ltd., which has a rutile-type titanium oxide having an average particle diameter of 280 nm, is used as a pigment, and is mixed with a binder to form a solid of rutile-type titanium oxide. The volume concentration was 25%, and the undercoating coating (undercoat-1) was prepared. Table 1 Types of Coatings Adhesives Pigment Types Tg rc] Species Average Particle Size (μηι) Solids Volume Concentration (%) Undercoat-1 VYLON630 7 Titanium Dioxide TIPAQUECR95 0.28 25 (Middle Coating) As shown in Table 1, for medium coatings, As a base resin, the "VYLON (registered trademark)" series of amorphous polystyrene resin manufactured by Toyobo Co., Ltd. and the "DESMOPHEN (registered trademark)" series of amorphous polyester resin manufactured by Bayer Urethan Co., Ltd. are used. For example, in the intermediate coatings _1 to 2, r vyl〇n (registered trademark) 630" (number average molecular weight: 23 〇〇〇, hydroxyl number 5) and amorphous polyester resin "DESMOPHEN" manufactured by Urethan Co., Ltd. The quotient is 690" (number average molecular weight 35 〇〇, hydroxyl number 46) by mass ratio 1: ! Dissolved in an organic solvent (with a mass ratio of 1:1 mixed with Solvessol 5 〇 and cyclohexanone). The cross-linking agent is "Cymel (registered trademark) 3〇3" manufactured by Mitsui Cytec, which is a commercially available hexamethoxymethylated trimeric amine, and 15 parts by mass is added to the solid content of the polyester resin. In addition, "_iyst (registered trademark)_3b" g, which is manufactured by Mitsui Cytec Co., Ltd., commercially available as an acid catalyst 51 201119847, was added to obtain a polyester-based clear paint. As the rutile-type titanium oxide, "TIPAQUE (registered trademark) CR95" (refractive index: 25) manufactured by Ishihara Sangyo Co., Ltd. having an average particle diameter of 280 nm was used. In addition, the low-refractive-index particles contained in the intermediate coating layer are manufactured by Asahi Glass Co., Ltd., a dream of "O2, "Sensor's (registered trademark) H_31" (average particle size 3). In addition, as a comparative material of the pigment contained in the intermediate coating layer, the average particle size U〇nm is also obtained by the chemical industry company sulfuric acid lock "b interesting ace (registered trader t) B 30" (refractive index 1.6), average particle diameter 2 Zinc oxide "fine zinc oxide" (refractive index: 2 〇) manufactured by Dest Chemical Industry Co., Ltd. Moreover, the viscosity of the coating of the intermediate coating under low shear force is adjusted by merely changing the storage temperature and storage period of the dosage of the grain and the coating. In addition, the viscosity under low shear force was measured by a Tokyo Calibrator Viscometer (type: hidden) at a number of revolutions of 6 rpm. The details of the intermediate coating are shown in Table 2 below. 52 n 9 11 (U1&1 i il 1^1

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V jOQg. ^555^ 1^1 ^¾娜 0QQ01" OOQg^ 000la 01^ oews» 0£9§#> OSKSAA pewsAA— OSKSA^ loszcn^> °SKSAP s g'-KCHA^ -ςκοο r-Mg!A^ 91SN3» 03ΚΟΤΑΛ ί}-1λΛ ^¾¾^1^ os§dr> 15SNCnA>— loTAA οδζβ^κ. -SKOOi ^ι^μοίλλ r-lAp '-SKCnA^ 9§3αλ 91szcha> 9-t^y^- <N< ^-制安一丨制夺 $ £1"·夺 t1·1^1"- u1-1-0¾^ 61"1-— 10°.¾1^ L-^^ 9-斜午 zz-斜1^ 1-.1^— oz,^+ 61—制^ 10°一，制务卜一-物夺 9'制务 -"4> 寸一"务 tl-^-"--—物午 --糾 + ^.制夺 1--^1"-6¾1^ 1£—制夺寸'斜4* s 3 5 201119847 (上塗塗料）如下述表3所示，關於上塗塗料，係使用將東洋紡社製之非晶性聚酿樹脂「VYLON(登錄商標）63〇」（數平均分子量23000 ’羥基價5)溶解於有機溶劑（以質量比計1 : 1混合有 Solvesso 15〇與環己酮者)作為黏合劑。交聯劑係將市售之三井Cytec社製之完全烷基型甲基化三聚氰胺樹脂（以後，稱為甲基化三聚氰胺）的r Cy mel(登錄商標)3 〇3」，相脂之固形物灣量份添加晴份，並且，添加性觸媒的三井Cytee社製之「eatalyst(登錄商標)刪Β」Μ 質量份，而得到透明塗料。使用該透明塗料，並使用平均粒徑為2 8 〇nm之金紅石型氧化鈦的石原產举杜製「蘭QUE(登錄商標)CR95」（折射率：2·5)作為顏料，並與黏合劑混合，使金紅石型袅仆& 纟乳化鈦之固形物體積濃度為 25%，製作上塗塗料(上塗q)。又，使用與前述上塗-i相同之黏合劑樹脂與顏料，並且’亦製作相對於黏合賴脂_料之合計㈣㈣量份，添加有1質量份之BYK社之石夕氧系添加劑BYK-306的塗料 (上塗-2)、添加有0.5質量份之βγκ社之氟系添加劑 ΒΥΚ-340的塗料(上塗_3)。又，使用市售之石夕氧·丙稀酸共聚合樹脂之東亞合成社製的石夕改質丙稀酸樹脂「SYMAC(登錄商標⑽德」，作為黏合劑之基礎樹脂，並使用以質量比計為】：i混合有市售之大日本油墨化學工業社製之丁基化三聚氰胺樹脂之「SUPER BECKAMINE(登錄商標购〇」與三井以㈣社製 54 201119847 之甲基化二聚氰胺的「Cymel(登錄商標）303」者，作為交聯劑°以固形物質量比計為100: 30混合該等黏合劑樹脂與乂耳外mI付至）透明塗料（上塗-4)。此外’使用該透明塗料，與上塗_1同樣地，使用石原產業社製「TIPAQUE(登錄商標）CR95」作為顏料’並與黏合劑混合，使金紅石型氧化鈦之固形物體積濃度為25%，製作上塗塗料(上塗_5)。又除了使用住化Bayer Urethan社製之「DesmodurBL 3175(商品名）」（以後，稱為HDI)製作交聯劑以外，亦製作與上塗-4、5同樣地製作之塗料（上塗-6、7)。「 * 了使用昌士工業社製石夕氧·氟共聚合樹脂之〇01」作為黏合劑之基礎樹脂以外，亦製作盥上塗_4、 5同樣地製作之塗料(上塗-8、9)。 ” 、，使用與前述上塗-1相同之黏合劑樹脂與顏料，並且亦製作相對於黏合劑樹脂與顏料之合計量1〇〇質量份，添加有2〇質吾々、> ^ 貝里伤之四乙氧矽烷的塗料（上塗_1〇)。另外，刖述上塗-丨〜⑺中，均使用以質量比計丨：丨混合有環己與S〇lvessol50者作為稀釋溶劑。 55 201119847 ε< 添加劑添加量 [質量份] 1 — 〇 / / 1 / 〇 (N 種類 1 BYK-306 BYK-340 / / 1 / / 四乙氧矽烷固形物體積濃度（％) (N fN CN / ν-ί 1 CN / (N (N 平均粒徑 (μπι) 0.28 0.28 0.28 / 0.28 i 0.28 0.28 0.28 種類 TIPAQUECR95 TIPAQUECR95 TIPAQUECR95 / TIPAQUECR95 / TIPAQUECR95 / TIPAQUECR95 TIPAQUECR95 氧化鈦| 氧化鈦| |氧化鈦| 氧化鈦 / |氧化鈦| / 氧化鈦氧化鈦交聯劑種類曱基化三聚氰胺甲基化三聚氰胺曱基化三聚氱胺丁基化三聚氱胺與曱基化三聚氰胺之混合丁基化三聚氰胺與曱基化三聚氰胺之混合 HDI HDI 丁基化三聚氱胺與甲基化三聚氰胺之混合丁基化三聚氰胺與甲基化三聚氰胺之混合曱基化三聚氰胺黏合劑種類 VYLON630 VYLON630 VYLON630 SYMACUS-380 SYMACUS-380 SYMACUS-380 SYMACUS-380 ZX-001 ZX-001 VYLON630 聚酯聚酯聚酯矽氧·丙烯酸矽氧·丙烯酸石夕氧.丙烤酸矽氧·丙烯酸矽氧·氟矽氧·氟聚酯塗料種類上塗-1 上塗-2 上塗-3 上塗-4 上塗-5 上塗-6 上塗-7 上塗-8 上塗-9 上塗-10 56 201119847 - (預塗覆金屬板）接著，詳細說明本實施例中使用之預塗覆金屬板。準備新日本製鐵株式會社製之炼融鋅電鑛鋼板「siWerzinc (登錄商標）」（以後’稱為GI)作為原板。使用板厚為0.6mm者。使用電鍵附著量為單面6〇mg/m2者。之後’將準備好之原板以日本PARKERIZING社製的鹼脫脂液「FC-4336」以2質量％濃度、5〇°c水溶液喷霧脫脂，水洗、乾燥後’以輥塗布器塗布日本PARKERIZING社製之非鉻酸化學轉化處理的「CT-E300N」，再以熱風烘箱使其乾燥。以熱風烘箱之乾燥條件係鋼板之到達板溫（arrival sheet temperature)為60°C。非鉻酸處理之附著量係塗裝成以全固形物計附著200g/m2。 ' 接著，於經施行化學轉化處理之金屬板之一側的面以 - 輥塗布器塗裝製作好之下塗塗料，使乾燥後之膜厚為 20μιη，於另一面以輥塗布器塗裝日本Fine c〇atingS社製之裡面塗料「FL100HQ」的灰色，使乾燥後之膜厚為，再於吹入有熱風之感應加熱爐以金屬板之到達板溫為23〇 °C之條件乾燥燒附硬化。並且，於乾燥燒附後以噴霧器將水吹附至經塗裝之金屬板，進行水冷。然後’於下塗塗膜層之表面使用滑動漏斗式之簾幕式塗布器同時地積層塗裝中塗塗料與上塗塗料2層，於吹入有熱風之感應加熱爐以金屬板之到達板溫為220。(：之條件，同時地將經積層之塗膜乾燦燒附硬化。並且，於乾燥炉附後以喷霧器將水吹附至經塗裝之金屬板，進行水冷，以製作 57 201119847 具有3層構造之被覆層的預塗覆金屬板（以後，將本步驟之塗裝方法稱為「塗裝方法(i)」）。又，亦可視需要，使用輥塗布器於下塗塗膜層之表面僅塗裝1層中塗塗料，且以前述要領燒附後，於中塗塗膜層之表面再度使用輥塗布器塗裝1層上塗塗料，以製作具有以前述要領進行燒附之3層構造之被覆層的預塗覆金屬板（以後，將本步驟之塗裝方法稱為「塗裝方法(ii)」）。又，亦可視需要，使用滑動漏斗式之簾幕式塗布器同時地於下塗塗膜層上積層塗裝中塗塗料與上塗塗料、及該等上之上塗塗料3層，於吹入有熱風之感應加熱爐以金屬板之到達板溫為220°C之條件，同時地將經積層之塗膜乾燥燒附硬化。並且，於乾燥燒附後以喷霧器將水吹附至經塗裝之金屬板，進行水冷，以製作具有4層構造之被覆層的預塗覆金屬板（以後，將本步驟之塗裝方法稱為「塗裝方法 ⑽」）。 (評價方法）接著，說明如上述製作之預塗覆金屬板之評價方法的詳細内容。 1)預塗覆金屬板之全光線反射率測定使用於島津製作所社製之分光光度計「UV265」中安裝有積分球反射附屬裝置者，基準板則使用按壓固定有硫酸鋇粉末者。測定人眼感度最高之波長555nm中之全光線反射率，並以以下之基準進行評價。 ◎:全光線反射率為99%以上的情形 58 201119847 ◎〜〇：全光線反射率為97%以上、小於99%的情形〇：全光線反射率為95%以上、小於97%的情形〇〜△:全光線反射率為93%以上、小於95%的情形 △:全光線反射率為91%以上、小於93%的情形 △〜X :全光線反射率為89%以上、小於91%的情形 X:全光線反射率小於89%的情形 2)照明器具之亮度測定於第1圖及第2圖中顯示實驗裝置之概要。將被覆基材成形如第1圖及第2圖所示之長度方向兩端部朝上面側折彎的形狀，作為反射板1。將2根市售之螢光燈照明器具2並排於其中，並於其上安裝以毛玻璃所形成之外罩3。由測定點垂直地遠離50cm處設置亮度計6，測定由該外罩3之中央部分（以下，稱為「亮度測定部」）4與由中央部分4朝外側移動 1.5cm之部分（以下，稱為「亮度之均一性比較測定部」）5 的亮度。螢光燈照明器具2係使用16型燈管輸出16W之螢光燈。亮度評價係藉由測定外罩3之亮度測定部4來評價。測定時，係完全截斷螢光燈照明器具2以外之光，測定如以下製作之基準反射板的亮度，相對於此，測定使用安裝有由使用所製造之被覆基材所製作的反射板1時之亮度。並且，由於基準反射板測定時之亮度與於製作之被覆基材的反射板1測定時之亮度，定義出亮度變化率=([於已製作之被覆基材作成之反射板1的亮度]-[於基準反射板之亮度])χ100/[於基準反射板之亮度]，藉亮度變化率以以下基準進行評價。 59 201119847 ◎:亮度變化率為30¾以上的情形 ◎〜〇：亮度變化率為25%以上、小於30%的情形〇：亮度變化率為20%以上、小於25%的情形〇〜:亮度變化率為I5%以上、小於20%的情形 △:亮度變化率為10°/。以上、小於15°/°的情形 X :亮度變化率小於1 〇%的情形基準反射板係藉由塗裝用以提升以往之反射板表面之反射率的反射率高之白色系塗料的方法來製作。以與前述底塗塗裝板之製作相同的方法，將表4所示之塗料塗裝成乾燥後之膜厚為ΙΟμπι，並乾燥硬化。於其上’以輥塗布器再次將表4記載之塗料塗裝成乾燥後之膜厚為20μιη，再於吹入有熱風之感應加熱爐以金屬板之到達板溫為230°C之條件乾燥硬化。並且，於乾燥燒附後以喷霧器將水吹附至經塗裝之金屬板，進行水冷。又，亮度之均一性的評價係測定外罩之亮度測定部4 與由亮度測定部4移動1.5 c m的2處亮度之均一性比較測定部5的亮度’定義出亮度之均一度=刚_([亮度之均一性比較測定部5的亮度]•[亮度測定部4之亮度]V[亮度測定部4之亮度]xlOO，亮度之均__度以下基準進行評價。 ◎.冗度之均一度為90%以上的情形小於90%的情形小於85%的情形〇.冗度之均一度為85%以上、Λ △.冗度之岣—度為70%以上、Λ Χ·受度之均一度小於70%的情形 3)加工性及密著性 60 201119847 ^將製作好之懸覆金屬板夾持於任“數之試樣間的a下折t加工成⑽。（密料曲加卫），以目視觀察加工部之塗膜，調查有無《之破裂。另外，於進行⑽。折f 時，係折彎成預塗覆金屬板之表面成為料之外側，進行密者幫曲（-般而言’將未夾持試樣時視树彎曲、將夹持 1片試樣時視為1T彎曲）。之後，以目視觀察加工部，以以下基準進行評價。 : οτ彎曲無破裂或剝離 ◎ : 1Τ彎曲無破裂或剝離 ◎ Ο . 2Τ膏曲無破裂或剝離V jOQg. ^555^ 1^1 ^3⁄4娜0QQ01" OOQg^ 000la 01^ oews» 0£9§#> OSKSAA pewsAA— OSKSA^ loszcn^> °SKSAP s g'-KCHA^ -ςκοο r-Mg !A^ 91SN3» 03ΚΟΤΑΛ ί}-1λΛ ^3⁄43⁄4^1^ os§dr>15SNCnA>- loTAA οδζβ^κ. -SKOOi ^ι^μοίλλ r-lAp '-SKCnA^ 9§3αλ 91szcha> 9-t^y ^- <N< ^-System security to make a $1 quot;午 -- oblique 1^ 1-.1^— oz,^+ 61—manufacturing 10° one, the system of affairs, the first one, the material, the 9' system, the '4', the inch, the tl-^-";---material noon--correction ^ ^. systemion 1--^1"-63⁄41^ 1£- system wins the inch ' oblique 4* s 3 5 201119847 (top coating) as shown in Table 3 below, on the top coating In the coating, the amorphous polystyrene resin "VYLON (registered trademark) 63" (number average molecular weight 23000 'hydroxyl value 5) manufactured by Toyobo Co., Ltd. was dissolved in an organic solvent (1:1 by mass ratio of Solvesso 15) 〇 and cyclohexanone) as a binder. The cross-linking agent is a commercially available trimethyl melamine resin (hereinafter referred to as methylated melamine) manufactured by Mitsui Cytec Co., Ltd., r Cymel (registered trademark) 3 〇 3", solid matter of phase grease. In the case of the amount of the sensation, the "eatalyst (registered trademark) Μ" by the Mitsui Cytee Co., Ltd., which is a catalyst, was added to obtain a clear coating. Using this clear coating, and using a rutile-type titanium oxide having an average particle diameter of 28 nm, a lan QU (registered trademark) CR95 (refractive index: 2.5) is used as a pigment and bonded thereto. The mixture was mixed so that the solid concentration of the rutile type amp amp 纟 emulsified titanium was 25%, and the top coating was applied (top coating q). Further, the same binder resin and pigment as the above-mentioned top coating-i were used, and 'the total amount (4) (four) of the adhesive lyophile was also added, and 1 part by mass of the BYK-306 of the BYK-based additive was added. The coating (top coating-2) and the coating of 0.5 part by mass of the fluorine-based additive ΒΥΚ-340 of βγκ社 (top coating _3). In addition, SYMAC (registered trademark (10) De", which is a base resin of a binder, is used as a base resin of a binder, which is a synthetic resin manufactured by Toagosei Co., Ltd. The ratio is:: i mixed with the commercially available butyl melamine resin manufactured by Dainippon Ink Chemical Industry Co., Ltd. "SUPER BECKAMINE (registered trademark 〇) and Mitsui (4) company 54 201119847 methylated melamine "Cymel (registered trademark) 303", as a cross-linking agent, in a solid mass ratio of 100: 30, the binder resin and the mI are added to the transparent coating (upper coating-4). In the same manner as the top coating _1, "TIPAQUE (registered trademark) CR95" manufactured by Ishihara Sangyo Co., Ltd. was used as a pigment and mixed with a binder, and the solid concentration of the rutile-type titanium oxide was 25%. Top coating (Top coating _5). In addition to the use of "Desmodur BL 3175 (trade name)" (hereinafter referred to as HDI) manufactured by Bayer Urethan Co., Ltd., it is also produced in the same manner as the top coatings -4 and 5. Coating (top coating -6, 7). * In addition to the base resin of the binder used in Changshi Industrial Co., Ltd., as the base resin of the binder, the same coatings were applied to the top coatings _4 and 5 (upper coatings -8, 9). , using the same binder resin and pigment as the above-mentioned top coating-1, and also making 1 part by mass of the total amount of the binder resin and the pigment, adding 2 〇々々, > ^ 4 Ethoxy decane coating (top coating 〇). In addition, in the above-mentioned coating - 丨 ~ (7), the mass ratio is used: 丨 mixed with cyclohexene and S〇lvessol50 as a dilution solvent. 55 201119847 ε< Addition amount [parts by mass] 1 — 〇 / / 1 / 〇 (N type 1 BYK-306 BYK-340 / / 1 / / tetraethoxy decane solids volume concentration (%) (N fN CN / ν-ί 1 CN / (N (N average particle size (μπι) 0.28 0.28 0.28 / 0.28 i 0.28 0.28 0.28 type TIPAQUECR95 TIPAQUECR95 TIPAQUECR95 / TIPAQUECR95 / TIPAQUECR95 / TIPAQUECR95 TIPAQUECR95 Titanium oxide | Titanium oxide | | Titanium oxide | Titanium oxide / | Titanium oxide | / Oxidation Titanium titanium oxide crosslinker type Mixed melamine methylated melamine thiolated trimeric decylamine butylated melamine and thiolated melamine mixed butylated melamine mixed with guanidinated melamine HDI HDI Butylated melamine and A Mixed butylated melamine and methylated melamine mixed thiolated melamine adhesive type VYLON630 VYLON630 VYLON630 SYMACUS-380 SYMACUS-380 SYMACUS-380 SYMACUS-380 ZX-001 ZX-001 VYLON630 polyester polyester Ester 矽 · 矽矽矽矽丙烯酸丙烯酸丙烯酸 . . . . . . . . . . . . . -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 Top Coating-7 Top Coating-8 Top Coating-9 Top Coating-10 56 201119847 - (Pre-coated Metal Sheet) Next, the pre-coated metal sheet used in the present embodiment will be described in detail. A smelting zinc ore steel plate manufactured by Nippon Steel Co., Ltd. "siWerzinc (registered trademark)" (hereinafter referred to as GI) was prepared as the original plate. Use a plate thickness of 0.6 mm. The amount of bonding using the electric key is 6 〇 mg/m2 on one side. After that, the prepared raw plate was spray-degreased with an alkali degreasing liquid "FC-4336" manufactured by Japan PARKERIZING Co., Ltd. at a concentration of 2% by mass and 5 〇 °C, washed with water, and dried, and then coated with a roller coater by Japan PARKERIZING Co., Ltd. The non-chromic acid chemical conversion treatment "CT-E300N" was dried in a hot air oven. In the drying condition of the hot air oven, the arrival sheet temperature of the steel sheet was 60 °C. The adhesion amount of the non-chromic acid treatment was applied to adhere to 200 g/m 2 in terms of total solid content. ' Next, the surface of one side of the metal plate subjected to the chemical conversion treatment was coated with a roll coater to make a coating having a film thickness of 20 μm after drying, and the other side was coated with a Japanese coat by a roll coater. The gray color of the inner coating "FL100HQ" manufactured by c〇atingS Co., Ltd. makes the film thickness after drying, and then in the induction heating furnace which blows in hot air, and the plate temperature reaches 23 ° C. . Further, after drying and baking, water was sprayed to the coated metal plate by a sprayer to perform water cooling. Then, the surface of the undercoat layer is simultaneously coated with two layers of the intermediate coating and the upper coating using a sliding funnel curtain coater, and the induction heating furnace is blown into the induction furnace with a hot air to reach a plate temperature of 220. . (: The condition is that the laminated film is dried and hardened at the same time. Further, after the drying furnace is attached, water is sprayed to the coated metal plate by a sprayer, and water-cooled to produce 57 201119847 a precoated metal sheet of a coating layer having a three-layer structure (hereinafter, the coating method of this step is referred to as "coating method (i)"). Further, a coating coat layer may be applied to the lower coating layer as needed. The surface was coated with only one layer of the intermediate coating material, and after being baked in the above-mentioned manner, one layer of the top coating was applied to the surface of the intermediate coating layer by using a roll coater to prepare a three-layer structure having the above-described method of burning. The precoated metal sheet of the coating layer (hereinafter, the coating method of this step is referred to as "coating method (ii)"). Also, if necessary, a sliding funnel curtain coater may be used for simultaneous coating. On the coating layer, the intermediate coating and the upper coating, and the upper coating are applied in three layers, and the induction heating furnace is blown with hot air to reach a plate temperature of 220 ° C under the condition of the metal plate, and simultaneously The laminated film is dried and burned and hardened. After drying and baking, water is sprayed to the coated metal plate by a sprayer, and water-cooled to prepare a precoated metal plate having a coating layer of a 4-layer structure (hereinafter, the coating method of this step is referred to as "Coating method (10)") (Evaluation method) Next, the details of the evaluation method of the precoated metal sheet produced as described above will be described. 1) The total light reflectance measurement of the precoated metal sheet is used in Shimadzu Corporation. The integrating sphere reflection attachment is attached to the spectrophotometer "UV265", and the reference plate is fixed by pressing the barium sulfate powder. The total light reflectance at a wavelength of 555 nm having the highest sensitivity of the human eye was measured and evaluated based on the following criteria. ◎: The case where the total light reflectance is 99% or more 58 201119847 ◎~〇: The total light reflectance is 97% or more and less than 99% 〇: The total light reflectance is 95% or more and less than 97% 〇~ △: When the total light reflectance is 93% or more and less than 95% Δ: The total light reflectance is 91% or more and less than 93% Δ~X : The total light reflectance is 89% or more and less than 91%. X: Case where the total light reflectance is less than 89% 2) The brightness measurement of the lighting fixture shows the outline of the experimental apparatus in Figs. 1 and 2 . The coated base material is formed into a shape in which the longitudinal end portions are bent toward the upper surface side as shown in Figs. 1 and 2 as the reflecting plate 1. Two commercially available fluorescent lamp lighting fixtures 2 are arranged side by side, and an outer cover 3 formed of frosted glass is mounted thereon. The luminance meter 6 is disposed at a distance of 50 cm from the measurement point, and a central portion (hereinafter referred to as "luminance measuring portion") 4 of the outer cover 3 and a portion that is moved outward by 1.5 cm from the central portion 4 are measured (hereinafter referred to as The brightness of the "brightness uniformity comparison measuring unit") 5. Fluorescent lighting fixture 2 uses a 16-type lamp to output a 16W fluorescent lamp. The brightness evaluation is evaluated by measuring the brightness measuring unit 4 of the outer cover 3. In the measurement, the light other than the fluorescent lamp lighting device 2 was completely cut off, and the brightness of the reference reflecting plate produced as follows was measured. On the other hand, when the reflecting plate 1 produced by using the coated substrate produced by using the measurement was used, the measurement was performed. Brightness. Further, the luminance change rate = ([the brightness of the reflector 1 made of the coated substrate) is defined by the brightness of the reference reflector during measurement and the brightness of the reflector 1 of the coated substrate. [Brightness of the reference reflection plate] χ 100 / [luminance of the reference reflection plate] was evaluated by the following criteria based on the luminance change rate. 59 201119847 ◎: When the brightness change rate is 303⁄4 or more ◎~〇: The brightness change rate is 25% or more and less than 30% 〇: The brightness change rate is 20% or more and less than 25% 〇~: Brightness change rate In the case of I5% or more and less than 20%, Δ: the luminance change rate is 10°/. In the case of the above, less than 15°/°, the case where the brightness change rate is less than 1%%, the reference reflection plate is coated with a white paint having a high reflectance for improving the reflectance of the surface of the conventional reflector. Production. The coating material shown in Table 4 was applied to a dried film thickness of ΙΟμπι in the same manner as in the preparation of the above-mentioned primer coating sheet, and dried and hardened. On the above, the coating material described in Table 4 was again coated with a film thickness of 20 μm by a roll coater, and dried by an induction heating furnace blown with hot air at a sheet temperature of 230 ° C. hardening. Further, after drying and baking, water was sprayed to the coated metal plate by a sprayer to perform water cooling. In addition, the evaluation of the uniformity of the brightness is performed by measuring the brightness of the brightness measurement unit 4 of the cover and the brightness of the two portions of the brightness measurement unit 4 that are 1.5 cm apart. The brightness of the measurement unit 5 defines the uniformity of the brightness = just_([ The luminance uniformity comparison measurement unit 5 brightness] • [luminance of the luminance measurement unit 4 ] V [luminance of the luminance measurement unit 4 ] x 100 , and the luminance is equal to or less than the __ degree. ◎ The uniformity of redundancy is 90% or more of cases are less than 90% of cases less than 85%. 冗. The degree of redundancy is more than 85%, Λ △. The degree of redundancy is more than 70%, and the uniformity of Λ 受 is less than 70% of cases 3) Processability and adhesion 60 201119847 ^The prepared overhanging metal plate is clamped to any of the "numbers of samples" and then processed into (10). (The dense material is added) The film of the processed portion was visually observed to investigate whether or not the crack was formed. In addition, when (f) was folded, the surface of the precoated metal sheet was bent to the outside of the material, and the whistle was performed.言 'When the sample is not clamped, the tree is bent, and 1 piece of the sample is clamped as 1T bend.) After that, it is visually observed. Unit to perform the following evaluation standard:. Οτ bent without cracking or peeling ◎:. 1Τ bent without cracking or peeling ◎ Ο 2Τ paste curve without cracking or peeling

〇：2Τ彎曲有些微破裂或剝離，但3巧曲無破裂或剝〇〜△. 2T彎曲有到達下塗塗膜層或原板之破裂或制離，但3T彎曲無破裂或剝離 △:3Tf曲有些微破裂或剝離，但4T彎曲無破裂或剝 △〜X : 2 T彎曲有到達下塗塗膜層或原板之破裂或剝離，但3T彎曲無破裂或剝離 X : 4T彎曲有破裂或剝離此外’亦實施於加工部貼附膠帶後剝離之加工部密著性試驗’ U目視觀察膠帶剝離後之密著性，以以下基準進行評價。 ◎ ◎ : 0T彎曲無剝離 ◎ : 1T彎曲無剝離 61 201119847 ◎〜〇：2T彎曲無剝離〇：2Τ彎曲有相對於加工部之全長合計小於之長度的剝離，但3Τ彎曲無剝離〇〜Δ:2Τ彎曲有相對於加工部之全長合計小於一半之長度的剝離，但3Τ彎曲無剝離3Τ彎曲無剝離 △:3Τ彎曲有些微破裂或_，但㈣^破裂或剝離 △〜X : 2T彎曲有相對於全長合計小於—半之長度的剝離，但3T彎曲無剝離 X : 4T彎曲有剝離 4)綜合評價评分係以◎◎的情形為8分、◎的情形為7分、◎〜〇的情形為6分、〇的情形為5分、〇〜△的情形為4分、△的情形為3分、△〜x的情形為2分、χ的情形為丨分並加算全光線反射率與加工性之評分，算出該合計，以以下基準進行評價。 ◎:評分之合計為11分以上〇. 6平分之合计為9分以上、小於11分 △:評分之合計為7分以上、小於9分 X :評分之合計小於7分 5)邊界面Ra之測定中塗層與上塗層之邊界面的Ra係藉由將各實施例之塗膜切斷’填入樹脂後研磨，將垂直於塗膜表面的截面變得平滑’再以3500倍之掃描型顯微鏡拍攝的照片進行評價。 62 201119847 由照片上方覆蓋OHP所使用之透明片，精密地描繪邊界面之凹凸後，如第3圖所示，於邊界面曲線之平均線的方向上僅取出1基準長度，並將該取出部分之平均線的方向作為χ 軸、縱倍率方向作為Y轴，於以y=f(X)表示界面曲線時，將藉以下之式所求付之值以微米（μηι)表不。另，測定係於任意5處進行，求得其平均。〇: 2 Τ bending slightly broken or peeled off, but 3 cracks without cracking or peeling ~ △. 2T bending has reached the undercoat film layer or the original plate cracked or detached, but 3T bending without cracking or peeling △: 3Tf curved some Micro-cracking or peeling, but 4T bending without cracking or peeling △~X: 2 T bending has reached the lower coating film layer or the original plate cracked or peeled, but 3T bending without cracking or peeling X: 4T bending has cracking or peeling In the processed portion adhesion test which was performed after the tape was attached to the processed portion, the adhesion was measured by observing the peeling of the tape, and the evaluation was performed based on the following criteria. ◎ ◎ : 0T bending without peeling ◎ : 1T bending without peeling 61 201119847 ◎~〇: 2T bending without peeling 〇: 2Τ bending has a peeling of less than the total length of the processed portion, but 3Τ bending without peeling 〇~Δ: 2ΤBending has a length of less than half of the total length of the processed part, but 3Τ bends without peeling 3Τ bends without peeling △: 3Τ bends slightly broken or _, but (4)^ cracked or peeled △~X : 2T bending has relative The total length is less than - half the length of the peeling, but the 3T bending is not peeling X: 4T bending is peeling 4) The comprehensive evaluation score is 8 points for the case of ◎ ◎, 7 points for the case of ◎, and ◎ ~ 〇 for the case of ◎ 6 points, 〇 is 5 points, 〇~△ is 4 points, △ is 3 points, △~x is 2 points, and χ is 丨 and adding total light reflectance and processing The score was calculated, and the total was calculated and evaluated based on the following criteria. ◎: The total score is 11 points or more 〇. The total of 6 equal parts is 9 points or more and less than 11 points △: The total score is 7 points or more, less than 9 points X: the total score is less than 7 points 5) The boundary surface Ra The Ra system for measuring the boundary surface between the coating layer and the upper coating layer was cut by 3° times by cutting the coating film of each example by 'filling in the resin and grinding it, and smoothing the cross section perpendicular to the surface of the coating film'. The photos taken by the microscope were evaluated. 62 201119847 Covering the transparent sheet used by the OHP from the top of the photo, and accurately depicting the unevenness of the boundary surface, as shown in Fig. 3, only 1 reference length is taken in the direction of the average line of the boundary surface curve, and the taken portion is taken out. The direction of the average line is taken as the y-axis and the direction of the vertical magnification is the Y-axis. When the interface curve is expressed by y=f(X), the value obtained by the following formula is expressed in micrometers (μηι). In addition, the measurement was carried out at any five places, and the average was obtained.

Ra = i||f(x) |dx 6)最表面WCA之測定被覆層最表面之WCA係以明伸工業社製3次元表面形狀測定裝置計測。以測定時之評價長度40mm、截斷8mm之條件進行測定。詳細内容係依據jIS.B〇601進行測定。測定係於任意5處進行，求得其平均。 7)混合層厚度之測定藉由GDS(輝光放電發光分光分析裝置）分析中塗層與上塗層之邊界_近，測定深度方向mi更具體而言，係於將中塗層之Ti濃度作I、上塗層之Ti濃度作^ 時’將㈣叫列士舰x(x_y)]之料的厚度作為混合層厚度而敎。敎係練意5⑼行，求得其平均。 6)最表面WCA之測定被覆層最表面之貨以係以明伸工業社製3次元表面形狀測定裝置計測。 7)混合層厚度之測定藉由GDS(輝光放電發光分光μ裝置）分析上塗層之邊界_近，測定深度方_之分布。中塗層與更具體而 63 201119847 言，係於將中塗層之Ti濃度作為X、上塗層之Ti濃度作為y 時，將[x+〇.〇5x(x-y)]〜[y-0.05x(x-y)]之部分的厚度作為「混合層厚度」而測定。 8)耐汙染性又，將三菱化學社製塗料用碳「三菱carbon MA100」之10°/。懸浮液塗布於如上述般製作的預塗覆金屬板之塗膜表面，1小時後以日本waste社製之清潔白織物廢布拭取，並以藉分光測色計（SUGA試驗器製，型式MSC-45-2B)之ΔΕ 求得試驗前後之顏色變化，以以下基準進行評價。 ◎ : ΔΕ小於0.2 ◎〜〇：ΔΕ為0.2以上、小於0.5 〇：ΔΕ為0.5以上、小於1 △ : AE為1以上、小於2 X : ΔΕ為2以上 (評價結果）於表4〜6顯示本實施例中製作之預塗覆金屬板的構成與其評價結果。 64 201119847 較 ◎ΝΝ Η ◎ Ν Ν Νd—d— ττΜν Η Η Η Η Η Μ5!· οό οόηγ@ οτ@ οόV 〇 Μπ οό Γ^Γ ο@ οό οά οά ο@ οό ο@ οά 06 m οό οόηγ@ 06 06 〇 ~δ~~ 〇〇νό νόνόν-οκVVΜVvw〕 < Ν Ν Ν Ν Ν ^1 Ν Ν Ν Μ Ν Ν ◎ οό 06 οό οό οό ηγ® οί® οτ© οό οό οό οό 06 0X0 06 ηγ© ο® οό νό νό νό νόRa = i||f(x) | dx 6) Measurement of the outermost surface WCA The WCA system on the outermost surface of the coating layer was measured by a three-dimensional surface shape measuring apparatus manufactured by Mingshen Kogyo Co., Ltd. The measurement was carried out under the conditions of an evaluation length of 40 mm and a cut length of 8 mm. The details are measured in accordance with jIS.B〇601. The measurement was carried out at any five places, and the average was obtained. 7) Measurement of mixed layer thickness By GDS (Glow Discharge Emission Spectroscopic Analyzer), the boundary between the middle coating and the upper coating is analyzed, and the depth direction mi is measured. More specifically, the Ti concentration of the middle coating is used. I. The Ti concentration of the upper coating is used as the thickness of the material of the listed ship x (x_y) as the mixed layer thickness.敎练 5 5 (9), and find the average. 6) Measurement of the outermost surface WCA The outermost surface of the coating layer was measured by a three-dimensional surface shape measuring apparatus manufactured by Mingshen Industrial Co., Ltd. 7) Measurement of the thickness of the mixed layer The distribution of the depth _ was measured by analyzing the boundary of the upper coating layer by GDS (Glow Discharge Luminescence Spectrophotometer). The middle coating is more specific and 63 201119847, when the Ti concentration of the middle coating is taken as X and the Ti concentration of the upper coating is y, [x+〇.〇5x(xy)]~[y-0.05x The thickness of the portion of (xy)] was measured as "the thickness of the mixed layer". 8) Corrosion resistance In addition, 10°/ of the carbon “Mitsubishi carbon MA100” for coatings made by Mitsubishi Chemical Corporation. The suspension was applied to the surface of the coating film of the precoated metal sheet prepared as described above, and after 1 hour, it was wiped with a clean white fabric waste cloth manufactured by Japan Waste Co., Ltd., and was measured by a SUG tester. ΔΕ of MSC-45-2B) The color change before and after the test was obtained and evaluated on the basis of the following criteria. ◎ : ΔΕ is less than 0.2 ◎~〇: ΔΕ is 0.2 or more and less than 0.5 〇: ΔΕ is 0.5 or more and less than 1 △ : AE is 1 or more and less than 2 X : ΔΕ is 2 or more (evaluation result) Tables 4 to 6 show The composition of the precoated metal sheet produced in this example and its evaluation results. 64 2011 1984 1984 ΝΝ — — — — — — — — — ! ! ! ! ! ό γ γ ! ! ! ! ! ! ! γ ! ! ! ! Γ γ γ ! ! ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά ά 06 06 〇~δ~~ 〇〇νό νόνόν-οκVVΜVvw] < Ν Ν Ν Ν Ν ^1 Ν Ν Μ Ν Ν ◎ ◎ ό ό η η η η η η η η η η η η η η η ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό Ο® οό νό νό νό νό

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Li 8e 6£ 0寸 5 $ § b 65 201119847 擊♦ 4μ S? ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 耐汙染性 @~〇 @~〇 @~〇 @~〇 @~〇 @~〇 @~〇 @~〇 @~〇 1¾1 ◎ ◎ ◎ ◎ ◎ @~〇 @~〇 @~〇 @~〇加工性 ◎◎ | ◎◎ | ◎ ◎ ◎ 1 ©ο | @~〇 @~〇〇反射性能 ^ ίΓ ±1 Ηί v i 〇〇〇〇〇〇〇〇〇 < | ΟΔ | | ΟΔ 1 〇 @~〇 @~〇 ◎ ◎ ◎ 全光線反射率 < Ο-Δ ΟΔ 〇 @~〇 @~〇 ◎ ◎ ◎ *δ~ 糾® | 0.50 1 0.50 0.50 0.50 | 0.50 1 | 0.50 1 | 0.50 1 | 0.50 1 0.50 中塗與上塗之混合層厚度 (㈣ 0^ in in 最表層之 WCA (μηι) 寸〇寸〇寸〇寸〇寸〇寸〇寸〇寸· 寸· 铽W ν8百 •e- ^ ^ ί§ 〇 CN 〇 (Ν 〇〇 (N 〇 (N 〇 (N 〇 (N 〇 (N 〇 CN 塗裝燒附時間 (秒） § § § § § g g 乾燥後膜厚(μτη) 上塗層宕宕 5 〇〇〇下塗層 yn ϊ—Η yn in in iT) 上塗塗料種類 1上塗-ι I |上塗-ι I |上塗-ι I I上塗-ι | |上塗-ι | I上塗-ι | |上塗-ι I |上塗-ι I |上塗-ι | ψ n 料種類中塗-17 I |中塗-Π I 中塗-17 I 中塗-17 I 1中塗-Π I 丨中塗-17 | 1中塗-17 I |中塗-Π I 中塗-17 下塗塗料種類 |下塗-1 I 下塗-1 下塗-1 下塗、1 下塗-1 |下塗-ι I |下塗-ι I 下塗-1 |下塗“ | g In in in 66 201119847 ΌLi 8e 6 £ 0 inch 5 $ § b 65 201119847 ♦ ♦ 4μ S? ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Pollution resistance @~〇@~〇@~〇@~〇@~〇@~〇@~〇 @~〇@~〇13⁄41 ◎ ◎ ◎ ◎ ◎ @~〇@~〇@~〇@~〇Processability ◎◎ | ◎◎ | ◎ ◎ ◎ 1 ©ο | @~〇@~〇〇reflection performance ^ Γ ±1 Ηί vi 〇〇〇〇〇〇〇〇〇< | ΟΔ | | ΟΔ 1 〇@~〇@~〇◎ ◎ ◎ Total light reflectance < Ο-Δ ΟΔ 〇@~〇@~〇◎ ◎ ◎ *δ~ ®® | 0.50 1 0.50 0.50 0.50 | 0.50 1 | 0.50 1 | 0.50 1 | 0.50 1 0.50 Mixed layer thickness of medium and top coating ((4) 0^ in in WCA (μηι) inch of the outermost layer 〇 inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer layer surface layer Attached time (seconds) § § § § § gg film thickness after drying (μτη) top coat 宕宕5 undercoat yn ϊ—Η yn in in iT) top coat type 1 top coat - ι I | top coat - ι I |上涂- ι II上涂-ι | |上涂-ι | I上涂-ι | |上涂-ι I |上涂-ι I |上涂-ι | ψ n Material type 中涂-17 I |中涂-Π I 中涂-17 I 中涂- 17 I 1中涂-Π I 丨中涂-17 | 1中涂-17 I |中涂-Π I 中涂-17 Lower Coating Type|Undercoat-1 I Undercoat-1 Undercoat-1 Undercoat, 1 Undercoat-1 |Undercoat-ι I |下涂-ι I 下涂-1 |下涂" | g In in in 66 201119847 Ό

67 201119847 依本發明之實施例製作之預塗覆金屬板(No. 1〜42、 48〜62)的全光線反射率、亮度、塗膜加工性、耐汗染性均為良好之結果。如No. 1〜42、48~62所示，藉將中塗層中之金紅石型氧化鈦的體積濃度設為35%以上，中塗層與上塗層之邊界面的Ra將變成0.8μηι以上，因可反射之面積增加，可得高之全光線反射率。又，因中塗層與上塗層之接觸面積增加，故可得優異之密著性。中塗層中之顏料係非氧化鈦者(No.43、44)，因全光線反射率不佳’故不適合。中塗層中之金紅石型氧化鈦的體積濃度小於35%者(No.45) ’因全光線反射率不佳，故不適合。中塗層中之金紅石型氧化鈦的固形物體積濃度大於 70%者(No.46) ’因加工性及密著性不佳，故不適合。中塗層與上塗層之邊界面的尺3小於〇 8μιη者(N〇 47)，因加工性及密著性不佳，故不適合。如No.6〜42所示’藉使中塗層中含有金紅石型氧化鈦與粒徑大於金紅石型氧化鈦之低折射率顏料，可提升中塗層與上塗層之邊界面的Ra，可得較高之全光線反射率及優異之密著性。如No.13〜16所示，藉由降低中塗塗料之低剪力下的黏度’可提升中塗層與上塗層之邊界面的Ra ,可得較高之全光線反射率及優異之密著性。然而，當中塗塗料之低剪力下的黏度過低，最表面之WCA變成4μηι時(No.16)，有耐汙染性稍微不佳的傾向。因此，可知最表面之I為2μηι以下 68 201119847 較佳。 ,如No.17〜42所示，當延長塗裝燒附時間時，存在於中塗層與上塗層之邊界部的混合層將變厚，可得較高之全光線反射率及優異之密著性。可知存在於中塗層與上塗層之邊界部的混合層之厚度為3μηι以上較佳。所示’可知中塗層之膜厚越薄，全光線反 u率越低’而塗膜加工性提升。可知依本發明之實施例所製作之預塗覆金屬板的全級反射率與加工性之均衡皆優異。、如No.57〜80所示，可知於依本發明之實施例所製作之預塗覆金屬板之上塗層或最表層的黏合劑中，含有石夕氧樹脂或氟樹脂時(No.58〜62、64〜80) ’耐汙染性提升，而較佳。如Νο·81、82所示，可知於依本發明之實施例所製作之預塗覆金屬板的上塗層中，包含來自於烧氧雜或院氧石夕烷的水解縮合物Si時，耐汙染性提升，而較佳。又，可知於中塗層之膜厚為厚的版81中，全光線反射率或亮度係特別地優異，於中塗層之膜厚薄的Ν〇·82中，加工性或密著性係特別地優異。以上，一面參照附加圖式一面說明本發明之較佳實施形態，但本發明縣受鮮例所限定。只要為發明所屬技術領域中具通常知識者的話’於專利巾請範圍所記載之範可内，可想到之各種變更例或修正例係清楚可知，且理應了解該等亦當屬於本發明之技術範圍者。 69 201119847 【圖式簡單說明】第1圖係顯示本實施例中使用之亮度測定裝置之一例的截面模式圖。第2圖係由上部所見之第1圖之亮度測定裝置的模式圖。第3圖係顯示塗膜邊界面之凹凸狀態之一例的圖。【主要元件符號說明】 1.. .反射板 4...亮度測定部 2.. .螢光燈照明器具 5...亮度之均一性比較測定部 3···外罩 6...亮度計 7067 201119847 The total light reflectance, brightness, film processability, and sweat resistance of the precoated metal sheets (No. 1 to 42, 48 to 62) produced according to the examples of the present invention were all good results. As shown in No. 1 to 42, 48 to 62, by setting the volume concentration of the rutile-type titanium oxide in the intermediate coating to 35% or more, the Ra of the boundary surface between the intermediate coating and the upper coating layer becomes 0.8 μm. As described above, since the area of the reflectable surface is increased, a high total light reflectance can be obtained. Further, since the contact area between the intermediate coating layer and the upper coating layer is increased, excellent adhesion can be obtained. The pigment in the intermediate coating is non-titanium (No. 43, 44), which is not suitable because of the poor total light reflectance. The volume concentration of the rutile-type titanium oxide in the intermediate coating layer is less than 35% (No. 45) ′, which is unsuitable because the total light reflectance is not good. The rutile-type titanium oxide in the intermediate coating layer has a solid content concentration of more than 70% (No. 46). It is not suitable because of poor workability and adhesion. The ruler 3 of the boundary surface between the intermediate coating layer and the upper coating layer is smaller than 〇 8 μm (N〇 47), and is not suitable because of poor workability and adhesion. As shown in No. 6 to 42 'By the middle coating contains rutile-type titanium oxide and a low-refractive-index pigment having a particle diameter larger than that of rutile-type titanium oxide, the Ra of the boundary surface between the intermediate coating layer and the upper coating layer can be raised. It can achieve higher total light reflectivity and excellent adhesion. As shown in No. 13~16, by lowering the viscosity under the low shear force of the intermediate coating, the Ra of the boundary surface between the middle coating and the upper coating can be increased, and the total light reflectance and excellent density can be obtained. Sexuality. However, the viscosity of the intermediate coating under low shear force is too low, and when the WCA of the outermost surface becomes 4 μm (No. 16), the staining resistance tends to be slightly poor. Therefore, it can be seen that the I of the outermost surface is 2 μηι or less. 68 201119847 is preferred. As shown in No. 17 to 42, when the coating baking time is extended, the mixed layer existing at the boundary portion between the intermediate coating layer and the upper coating layer becomes thicker, and a higher total light reflectance and excellent result can be obtained. Adhesiveness. It is understood that the thickness of the mixed layer present at the boundary portion between the intermediate coat layer and the overcoat layer is preferably 3 μm or more. As shown in the figure, the thinner the film thickness of the intermediate coating layer is, the lower the total light retardation rate is, and the workability of the coating film is improved. It is understood that the pre-coated metal sheets produced in accordance with the embodiments of the present invention are excellent in the balance of full-scale reflectance and processability. As shown in Nos. 57 to 80, it can be seen that when the coating or the outermost layer of the precoated metal sheet produced according to the embodiment of the present invention contains the stone oxide resin or the fluororesin (No. 58~62, 64~80) 'The pollution resistance is improved, and it is better. As shown in FIG. 81 and 82, it is understood that when the supercoat layer of the precoated metal sheet produced according to the embodiment of the present invention contains the hydrolysis condensate Si derived from the burned oxygen or the oxazepine, The pollution resistance is improved, and it is better. Further, in the plate 81 having a thick film thickness of the intermediate coat layer, the total light reflectance or the brightness is particularly excellent, and in the case of the film thickness of the intermediate coat layer, the workability or the adhesion is particularly high. Excellent. The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is limited by the examples. It will be apparent that various modifications and changes can be made without departing from the scope of the invention as described in the appended claims. Range. 69 201119847 [Brief Description of the Drawings] Fig. 1 is a schematic cross-sectional view showing an example of a brightness measuring device used in the present embodiment. Fig. 2 is a schematic view of the brightness measuring device of Fig. 1 seen from the upper part. Fig. 3 is a view showing an example of the uneven state of the boundary surface of the coating film. [Description of main component symbols] 1. Reflector 4: Brightness measuring unit 2. Fluorescent lighting fixture 5: Brightness uniformity comparison measuring unit 3··· Cover 6... Luminance meter 70

Claims

201119847 VII. Patent application scope: 1. A coated metal material, characterized in that part or all of the surface of the metal material comprises 35% or more and 70% or less of rutile-type titanium oxide in a volume concentration of the solid material. a first coating layer and at least two coating layers of a second coating layer laminated on the surface layer side of the first coating layer, and a boundary surface between the first coating layer and the second coating layer The center line average roughness Ra is 0.8 μm or more. 2. The coated metal material according to the first aspect of the invention, wherein a component of the first coating layer is mixed with the second portion at a boundary portion between the first coating layer and the second coating layer A mixed layer of components in the coating layer, and the mixed layer has a thickness of 3 μm or more and 12 μm or less. 3. The coated metal material according to claim 1 or 2, wherein the filtered center line waviness WCA is 2 μm or less on the outermost surface of the coating layer. 4. The coated metal material according to any one of claims 1 to 3, wherein the coating layer of the outermost layer of the coating layer contains a silicone resin or a fluororesin. 5. The coated metal material according to any one of claims 1 to 3, wherein the coating layer of the outermost layer of the coating layer has a -Si-0-Si-bond in the resin skeleton forming the coating film. . 6. The coated metal material according to any one of claims 1 to 5, wherein the rutile-type titanium oxide has an average particle diameter of 200 nm or more and 400 nm or less. 7. The coated metal material according to any one of claims 1 to 6, wherein the first coating layer further contains a larger particle diameter than the rutile type titanium oxide, and 71 201119847 has a rutile type as described above. A particle having a low refractive index of titanium oxide. 8. The coated metal material according to any one of claims 1 to 7, wherein a void is present in the first coating layer, and the content of the void is a solid in the first coating layer. The volume of 〇·〇 is 5 times or more and 0.9 times or less. 9. The coated metal material according to any one of claims 1 to 8, wherein the film thickness of the first coating layer is ΙΟμπι or more and 80 μm or less. 10. The coated metal material according to any one of claims 1 to 9, wherein the film thickness of the second coating layer is 5 μm or more and 30 μm or less. The coated metal material according to any one of claims 1 to 10, wherein the coating layer further comprises a third coating layer laminated between the metal material and the first coating layer. 12. The coated metal material according to claim 11, wherein the film thickness of the third coating layer is 5 μm or more and 30 μm or less. A method for producing a coated metal material, which is a method for producing a coated metal material according to any one of claims 1 to 12, characterized in that it is applied by multiple layers simultaneously or wetly stacked. The coating material for forming the first coating layer and the coating material for forming the second coating layer are applied to part or all of the surface of the metal material. A lighting fixture for use in a lighting reflector, which is a coated metal material according to any one of claims 1 to 12. 15. An electronic device for use in a reflector for a light-emitting component or a reflector for an image display portion, which is a coated metal material according to any one of claims 1 to 12. 72