201141623 六、發明說明： 【日月戶斤斗支冬餘々真3 技術領域 本發明係有關於一種成形係優異之預塗覆金屬板，係 於金屬板表層具備撥水性及撥油性之高硬度塗膜層者。 【先前技術3 背景技術 預塗覆金屬板（以下有時亦稱為rpCM」。）係將使用者 所需要的塗膜事先被覆再出貨之金屬板。由於只要選擇塗 料便可形成具備所需特性的塗膜，故在各種技術領域之利 用皆在擴大。近年，形成有具備美觀性與耐蝕性之塗膜的 PCM係作為野外構造物用之構造材而受到注目，被利用於 外壁、門扉、電柱、橋腳等。 然而，在構造物遭到噴漆、簽字筆(feh tippen)等塗鴉 時，由於會損害構造物的美觀，必須將塗鴉不留痕跡地除 去。又，將貼在構造物上的海報、廣告、傳單等的貼附物 剝除後的痕跡，由於將會顯著地損害構造物的美觀，因此 必須將貼附物不留痕跡地剥離。 因此，對構造用PCM的最表層塗膜，追求除了美觀性 及耐蝕性之外，還可不留痕跡地除去在塗鴉或對構造用 PCM的最表層塗膜，追求除了美觀性及耐蝕性之外，還可 不留痕跡地除去在塗鸦或貼附物的機能。貼附物的機能。 進步，對構在降雪處或寒冷處使用之pcm的最表層塗 膜，追求除了美觀性及耐钮性之外，還有防止附冰、附雪 201141623 的機能。 於是，至今提案有可形成具有該種機能之最表層塗膜 的塗膜用組成物（塗料)(參照專利文獻丨至”。 在專利文獻1中開示有難附雪性及耐候性優異之撥水 性塗料。在專利文獻2中開示有耐候性及财汙染性優異之塗 料。在專利文獻3中開示有可對塗膜賦予水滴滑動性、撥水 性及防汙性之塗料。 在專利文獻4中’開示有可簡單地除去塗鴉及貼附物’ 且可防止附冰、附雪之被覆組成物。在專利文獻5中，開示 有易於防止及除去塗鴉的樹脂塗料。 上記塗料及組成物基本上係具備有撥水性及/或撥油 性’而由該塗料或組成物在金屬板表面所形成之塗膜，係 作為機能塗膜而有效地發揮作用。 然而，在近年，隨著PCM用途的多樣化及擴大，成形 再使用的機會增加，就塗膜而言，除了上述特性及機能之 外’逐漸要求可追隨金屬板之成形的優異成形性。即，就 PCM而言’在上述的機能之外，逐漸要求兼備塗膜的加工 性、抗到性(硬度）、及塗覆外觀的美麗度。即便是具備以撥 水性及/或撥油性的塗料或組成物所形成之塗膜的PCM，也 被要求擴大適用範圍至抽油煙機等住宅設備機器或冰箱等 家電製品等，且兼備該等所有的性能。 有鑑於此，本發明者等就已知之具備以撥水性及/或撥 油性的塗料或組成物所形成之塗膜的p c Μ綜合性地調查了 塗膜的成形性、硬度、外觀之美麗度的結果，得知具備上 201141623 述所有特性者並不存在。 例如，使用高硬度塗料作為最表層之機能性塗料者， 雖然抗刮錄好，但卻是塗朗細彡，叫卫性)杨、亦或 外觀不錢。前者缝膜錢魏金屬㈣變形，而在塗 «本身產生龜裂、或自基底層剝離。後者雖塗膜加工性為 可實用之程度，但在塗絲面_定方向卻存在有條痕狀 的塗裝不平整。另-方面，使用柔軟的塗料作為最表層之 機能性塗料者，雖加讀充分，但塗膜的硬度不足故抗到 性不充分。 在最表層具備由已知的撥水性及/或撥油性塗料或組 成物所形成之魏的PCM巾，塗_成雜(加工性）、硬度 及外觀的美麗度難以兼備之理由係推測如下。 -般而s ’在PCM的製造係採用下述方法：以塗覆機 (塗布機)逐層塗布塗料，並逐次以加熱爐使其加熱硬化，反 覆進行該步驟以形成塗膜。作為塗覆機，—般使用輕塗覆 機’有時也使用簾式塗覆機。在任—種方法中，逐次塗裝 時’由於是在基底塗料經乾燥或烘烤後塗布最表層塗料之 故’產生最表層塗料無法對於基底塗料的表面良好地密著 而在加工時剝離等的問題。 在塗布最表層的機能性塗料時，若使用簾式塗覆機， 由於其為非接觸式的塗裝方式之&，可得到光滑而美麗的 塗裝外觀。,然而’就簾式塗覆機的特徵而言，無法以乾燥 時膜厚在1一以下程度之胃膜厚的方式塗裝 ，由於塗膜厚 度變厚則塗膜的成形性(加工性)低下之故，無法得到高度的 201141623 加工性。為了缓和此問題，若使用較柔軟的塗料，則硬度 變低而抗刮性變差。 接下來，在塗布最表層之機能性塗料時，若使用輥塗 覆機，則可有數μιη程度之較薄膜厚度的塗裝，雖因此而加 工性良好，但由於是接觸式的塗裝方式之故，容易產生塗 裝不平整而難以得到美麗的塗裝外觀。又，即便使用上述 任一種的塗料或塗裝方式，只要是進行逐次塗布烘烤，則 最表層塗料與其基底塗料間的界面密著性就有限。 另一方面，有以非逐次塗布烘烤方式，而是以將最表 層與基底層之2層以非接觸方式直接在濕潤狀態下同時塗 布並使其乾燥來製造PCM的方法。就該方法而言，因兩層 界面的密著性良好之故，若於最表層使用高硬度塗料，應 可較容易地實現塗膜之成形性(加工性）、硬度及外觀的美麗 度之兼備。然而，以撥水性及撥油性塗料作為最表層進行 非接觸式之多層同時塗布來製成製品在在現實上是困難 的。此係因為表現撥油及撥水性能的塗料在與一般塗料相 較之下，有塗料的表面張力極低之特徵，故最表層與基底 層用之2層將非常地不安定所造成。 如上所述，迄今，尚無法製得形成有下述塗膜層之預 塗覆金屬板；該塗膜層係由與一般的塗料相較之下塗料之 表面張力極低、表現撥油及撥水性能的塗料所形成之最表 層，與由具有普通表面張力之一般塗料所形成之基底層所 構成之塗膜層。因此，製造同時具有塗膜之成形性（加工 性）、硬度及外觀的美麗度，且具有撥水性及撥油性之塗膜 6 201141623 的PCM是困難的。 專利文獻 專利文獻1特開平10-036707號公報 專利文獻2特開平11-293180號公報 專利文獻3特開2000-119354號公報 專利文獻4特開2003-292870號公報 專利文獻5特開2004-216789號公報 C發明内容3 發明概要 發明欲解決之課題 本發明係有鏗於本發明者等之調查結果，為了謀求預 塗覆金屬板之用途的擴大，以在金屬板的表層形成高硬 度、塗膜之成形加工性優異、且美麗之撥水性及撥油性的 塗膜為課題，並以提供一種具備該塗膜之預塗覆金屬板為 目的。 用於解決課題之手段 本發明者等為了解決上述課題，發現藉由以表面張力 為19〜25mN/m之最表層塗料作為最表層塗料，並以表面張 力為25〜35mN/m之基底塗料作為基底塗料，且前述最表層 塗料與前記基底塗料之表面張力的差為6mN/m以上，將高 硬度之機能性塗料用於最表層塗料而形成最表層與基底 層，可在金屬板的表層形成加工性優異且美麗之撥水性及 撥油性的塗膜，及為此而使用多層塗覆機來塗布時的條件。 本發明之要旨係如下所示。 7 201141623 (1) 一種成形性優異之預塗覆金屬板，其特徵在於，金 屬板之表層係將最表層塗料及基底塗料烘烤所得之塗膜 層，該最表層塗料係形成最表層之表面張力為19〜25mN/m 者’該基底塗料係形成前述最表層下之基底層之表面張力 為25〜35mN/m者’且前述最表層塗料與前述基底塗料的表 面張力之差為6mN/m以上。 (2) 如（1)所§己載之成形性優異之預塗覆金屬板，其中 前述最表層與别述基底層係精由將前述最表層塗料與前述 基底塗料利用多層簾式塗覆機同時塗布所形成者。 (3) 如（1)或(2)之成形性優異之預塗覆金屬板，其中前 述最表層與前述基底層之界面的中心線平均粗度以為 Ο.ΐμπι以下。 (4) 如（1)〜(3)中任一項之成形性優異之預塗覆金屬 板，其中前述最表層塗料係撥水性且為撥油性。 (5) 如（1)〜(4)中任一項之成形性優異之預塗覆金屬 板，其中前述金屬板係鍍鋼板。 (6) 如（5)所記載之成形性優異之預塗覆金屬板，其中 前述金屬板係經被覆之鍍鋼板。 (7) 如（1)〜(6)中任一項之成形性優異之預塗覆金屬 板，其中刖述最表層塗料係矽氧•氟共聚樹脂或矽氧接枝 两稀酸系樹脂。 (8) 如（1)〜(7)中任一項之成形性優異之預塗覆金屬 板其中』这最表層之膜厚為0.5〜ΙΟμηι，前述基礎層的膜 厚為8〜30μηι，且前述最表層與前述基底層的膜厚之合計為 201141623 10〜30μηι 〇 (9) 如（1)〜(8)中任一項之成形性優異之預塗覆金屬板， 其中前述最表層之表面的中心線平均粗度Ra係0.2μιη以下。 (10) —種如（1)〜(9)中任一項之成形性優異之預塗覆金 屬板之製造方法，係藉由多層簾式塗覆機將形成最表層之 最表層塗料，與形成前述最表層下之基底層的基底塗料同 時塗布於金屬板的表面，並烘烤前述最表層塗料與前述基 底塗料以形成塗膜層者；其特徵在於：將前述最表層塗料 及前述基底塗料從多層簾式塗覆機脫離之脫離點與金屬板 表面之距離設為50〜150mm。 發明效果 依據本發明，可提供一種表層除了美麗性及耐蝕性之 外，還具備塗鴉•貼附物之防止/除去機能、及防止附冰· 附雪機能，且具備可追隨金屬板之變形之成形性優異的預 塗覆金屬板。 圖式簡單說明 第1圖係表示預塗覆金屬板之層結構之一態樣的圖。 第2圖係表示預塗覆金屬板經彎曲加工後所產生之龜 裂及剝離之態樣的圖。（a)係表示於最表層的表面產生了龜 裂之態樣，（b)係表示最表層與其下之基底層剝離之態樣。 第3圖係表示滑動漏斗(slide hopper)型簾式塗裝裝置的 態樣。 第4圖係表示調查了預塗覆鋼板(發明例）之表面的撥油 性的結果。 201141623 第5圖係表 圖。將比較例的 於第5(b)圖。 示對比在預塗覆鋼板之表面以墨水塗書之 圖案表示於第5(a)圖，將發明例的圖案表示 【實施冷式】 用以實施發明之形態 以下詳細地朗本發明。 先十對用於形成最表層之最表層塗料與用於形成 基底層之基底塗料的表面張力之限定理由進行說明。最表 層塗料的表面張力若超過25mN/m，則無法於賴後之塗膜 表現撥油·撥水性，最表層塗料的表面張力宜盡可能低， 就現貫上而§，即便是一般被認為是表面張力極低之樹脂 的氟樹脂，表面張力為19inN/m，因此將下限視為19mN/m。 另一方面’由於基底塗料係與最表層塗料之表面張力差為 6mN/m以上之故’被要求具有25mN/00m以上的表面張力。 又，基底塗料的表面張力若超過35mN/m，則難以形成多層 簾式而造成塗裝困難之故，將上限設為35mN/m。又，若最 表層塗料與基底塗料之表面張力的差未滿6mN/m，則最表 層與基底層之介面無法明白地區別而產生凹凸（一般認為 是兩層界面部分地混合者），對塗膜之表面粗度造成影響’ 而呈現外觀不良之故，將兩者的差定為6mN/m以上。 最表層塗料與基底塗料之表面張力差若大則兩層之界 面的表面粗度便降低之理由雖然並不明碟，但一般認為是 因為最表層塗料對基底塗料之表面澗溼性極高之故’最表 層塗料藉由潤濕擴散，兩層之界面的表面積變小(Ra變小） 201141623 而安定化之故。又，亦有認為是由於構成最表層塗料與基 底塗料之成分的極性迥異，超越層之分子間相互作用難以 發揮作用而造成明確的層分離之故。 本發明者等為了解決上述課題，認為使用高硬度之機 能性塗料作為最表層塗料，且提高與基底層之界面密著性 係有效的’又，藉著薄化最表層塗膜將進一步提高加工性， 針對其手法專心致力檢討的結果’發現若將形成最表層之 撥油性及撥水性的塗料，與形成最表層之基底層的基底塗 料同時塗布於金屬板面並烘烤，則可提高最表層與基底層 的密著性、形成既為高硬度兼又成形性優異之塗膜層。 在本發明中’最表層塗料與基底塗料之界面的中心線 平均粗度Ra以〇·ιμηι#下為佳。最表層與基底層之間的界面 之細微的凹凸，係藉由用來表示材料之表面粗度的中心線 平均粗度Ra(JISB〇6〇l)來規定。亦即，將以5〇〇〇倍觀測時 的界面曲線當作粗度曲線，求取Ra。例如，將經塗裝之鋼 板切斷並埋入樹脂中後進行研磨，使垂直於塗膜表面之斷 面平滑，再以5000倍的掃描型顯微鏡照相攝影後，可求得 其界面的Ra°具體而言’界面的Ra係在將用於之透明 薄片覆蓋在照片上，精密地描繪出界面的凹凸後如第5圖 所示’利用影像處理裳^來測定縱線的部分，可藉由下述 式來求得其平均值。201141623 VI. Description of the invention: [Japanese and Japanese households are supporting the winter and the future of the technology] The present invention relates to a pre-coated metal sheet excellent in the forming system, which is provided with a high hardness coating of water-repellent and oil-repellent properties on the surface of the metal sheet. Membrane layer. [Prior Art 3] A precoated metal sheet (hereinafter sometimes referred to as rpCM) is a metal sheet in which a coating film required by a user is previously re-coated. Since the coating film having the desired characteristics can be formed by selecting the coating material, the use in various technical fields is expanding. In recent years, the PCM which has a coating film having an aesthetic appearance and a corrosion resistance has been attracting attention as a structural material for a field structure, and is used for an outer wall, a door sill, an electric column, a bridge leg, and the like. However, when the structure is subjected to graffiti, a feh tippen, or the like, the graffiti must be removed without leaving a trace because it impairs the appearance of the structure. Further, since the traces of the posters, advertisements, flyers, and the like attached to the structure are peeled off, the appearance of the structure is significantly impaired, and the patch must be peeled off without leaving a mark. Therefore, in addition to the aesthetics and corrosion resistance, it is possible to remove the outermost coating film for graffiti or PCM for construction without leaving any traces, in addition to aesthetics and corrosion resistance. It can also remove the function of graffiti or attachment without leaving any traces. The function of the attachment. Advancement, the most superficial coating of the pcm used in snowfall or in the cold, in addition to the aesthetics and resistance to the button, as well as the function of preventing ice and snow 201141623. Then, a coating composition (coating material) capable of forming the outermost coating film having such a function has been proposed (see Patent Document 丨). Patent Document 1 discloses water repellency which is excellent in snow resistance and weather resistance. In the case of the coating material, a coating material having excellent weather resistance and chemical contamination is disclosed. Patent Document 3 discloses a coating material which can impart water slidability, water repellency and antifouling property to a coating film. In the case of the patent document 5, a resin coating which is easy to prevent and remove graffiti is disclosed in the patent document 5. The above-mentioned paint and composition are basically A coating film having a water repellency and/or oil repellency and having a coating or a composition formed on the surface of a metal sheet functions as a functional coating film. However, in recent years, with the diversification of PCM use In addition, as for the coating film, in addition to the above characteristics and functions, the coating film is required to have excellent formability which can follow the formation of the metal sheet. In addition to the above functions, it is required to have both the processability, the resistance (hardness) of the coating film, and the beauty of the coating appearance. Even if it has a coating or composition that is water-repellent and/or oil-repellent, it is formed. The PCM of the coating film is also required to be expanded to a range of applications such as a range hoist, a household appliance such as a range hood, and a home appliance such as a refrigerator, etc., and the present inventors are known to have water repellency and / The result of the film formability, the hardness, and the appearance of the appearance of the coating film of the coating film formed by the oil-repellent paint or the composition was comprehensively investigated, and it was found that all of the characteristics described in the above 201141623 did not exist. For example, the use of high-hardness paint as the most functional coating of the surface layer, although scratch-resistant, but it is smeared, called Wei) Yang, or the appearance is not money. The former film Qian Wei metal (four) deformation, However, the coating «is itself cracked or peeled off from the base layer. Although the latter is practical, the coating film has a streaky coating unevenness in the direction of the coating surface. Use soft As the most functional coating of the surface layer, the coating has sufficient hardness, but the hardness of the coating film is insufficient, so the resistance is insufficient. The surface layer is formed by a known water-repellent and/or oil-repellent coating or composition. Wei's PCM towel, the reason why it is difficult to combine the beauty of the coating, the hardness and the appearance is presumably as follows. - Generally, the manufacturing method of the PCM adopts the following method: a coating machine (coating machine) The coating is applied layer by layer, and it is heat-hardened successively in a heating furnace, and the step is repeated to form a coating film. As a coating machine, a light coating machine is generally used, and a curtain coating machine is sometimes used. In the method, when the coating is applied one by one, 'because the top coating is applied after the base coating is dried or baked, the problem arises that the outermost coating does not adhere well to the surface of the base coating and peels off during processing. When the top layer of the functional coating is applied, if a curtain coater is used, since it is a non-contact type of coating, a smooth and beautiful coating appearance can be obtained. However, in the case of the characteristics of the curtain coating machine, it is not possible to apply the film thickness of the film thickness at a thickness of 1 or less during drying, and the formability (processability) of the coating film is increased due to the thickness of the coating film. Due to the low level, the high 201141623 processability cannot be obtained. In order to alleviate this problem, if a softer coating is used, the hardness is lowered and the scratch resistance is deteriorated. Next, when the top coat functional coating is applied, if a roll coater is used, it can be coated with a film thickness of several μm, and the workability is good, but it is a contact type coating method. Therefore, it is easy to produce uneven coating and it is difficult to obtain a beautiful appearance of painting. Further, even if the coating material or the coating method of any of the above is used, the interface adhesion between the outermost layer coating material and the base coating material is limited as long as the coating baking is performed successively. On the other hand, there is a method in which the PCM is produced by a non-sequential coating baking method, in which two layers of the outermost layer and the base layer are simultaneously coated in a wet state in a non-contact manner and dried. In this method, since the adhesion of the two-layer interface is good, if a high-hardness coating is used on the outermost layer, the formability (workability), hardness, and appearance of the coating film can be easily achieved. Both. However, it is practically difficult to make a non-contact multi-layer simultaneous coating with a water-repellent and oil-repellent coating as the outermost layer. This is because the paint exhibiting oil-repellent and water-repellent properties is characterized by a very low surface tension of the paint compared to the general paint, so that the two layers of the outermost layer and the base layer are extremely unstable. As described above, it has heretofore not been possible to obtain a precoated metal sheet having the following coating layer formed; the coating layer is made of a coating having a surface tension which is extremely low compared to a general coating, and exhibits oil repellency and dialing. A coating layer composed of a water-based coating formed on the outermost layer and a base layer formed of a general coating having a common surface tension. Therefore, it is difficult to manufacture a PCM which has both the formability (processability) of the coating film, the hardness and the appearance, and the coating film 6 201141623 which has water repellency and oil repellency. Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention is based on the findings of the present inventors, and in order to expand the use of a precoated metal sheet, high hardness and coating are formed on the surface layer of the metal sheet. It is an object of providing a coating film having excellent film forming workability and a beautiful water repellency and oil repellency, and providing a precoated metal plate having the coating film. Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have found that a top coat having a surface tension of 19 to 25 mN/m is used as a top coat, and a base paint having a surface tension of 25 to 35 mN/m is used as a base paint. The base paint, and the difference between the surface tension of the above-mentioned outermost layer coating and the pre-recording base coating is 6 mN/m or more, and the high-hardness functional coating is applied to the outermost layer coating to form the outermost layer and the base layer, which can be formed on the surface layer of the metal sheet. A coating film which is excellent in workability and beautiful in water repellency and oil repellency, and conditions for coating with a multilayer coater for this purpose. The gist of the present invention is as follows. 7 201141623 (1) A precoated metal sheet excellent in formability, characterized in that the surface layer of the metal sheet is a coating layer obtained by baking the outermost layer coating and the base coating, and the outermost layer coating forms the surface of the outermost layer. When the tension is 19 to 25 mN/m, the surface tension of the base layer formed under the outermost layer is 25 to 35 mN/m, and the difference between the surface tension of the outermost coating and the base coating is 6 mN/m. the above. (2) A pre-coated metal sheet excellent in formability as contained in (1), wherein the outermost layer and the other base layer are formed by using the multi-layer curtain coater from the outermost layer coating material and the base paint layer At the same time, the formed person is coated. (3) A precoated metal sheet having excellent formability as in (1) or (2), wherein the center line average thickness of the interface between the outermost layer and the base layer is Ο.ΐμπι or less. (4) A precoated metal sheet excellent in formability according to any one of (1) to (3), wherein the outermost layer coating material is water-repellent and oil-repellent. (5) A precoated metal sheet excellent in formability according to any one of (1) to (4), wherein the metal sheet is a plated steel sheet. (6) A precoated metal sheet excellent in moldability as described in (5), wherein the metal sheet is a coated steel sheet. (7) A precoated metal sheet excellent in formability according to any one of (1) to (6), wherein the outermost coating layer is a fluorinated/fluorinated copolymer resin or a bismuthoxygen grafted dilute acid resin. (8) The precoated metal sheet having excellent formability according to any one of (1) to (7), wherein the film thickness of the outermost layer is 0.5 to ΙΟμηι, and the thickness of the base layer is 8 to 30 μm, and The total thickness of the outermost layer and the base layer is 201141623 10 to 30 μηι 〇 (9) The precoated metal sheet excellent in formability according to any one of (1) to (8), wherein the surface of the outermost layer is The center line average roughness Ra is 0.2 μm or less. (10) A method for producing a precoated metal sheet excellent in moldability according to any one of (1) to (9), wherein the outermost layer of the outermost layer is formed by a multi-layer curtain coater, a base coating layer forming the underlying skin layer of the outermost layer is simultaneously coated on the surface of the metal plate, and baking the outermost layer coating material and the base material coating layer to form a coating film layer; wherein the outermost layer coating material and the foregoing base coating layer are The distance from the point of separation of the multi-layer curtain coater to the surface of the metal plate was set to 50 to 150 mm. Advantageous Effects of Invention According to the present invention, in addition to the beauty and corrosion resistance, the surface layer can be provided with an anti-icing/removal function of graffiti/adhesives, an anti-icing and snow-attaching function, and a deformation capable of following a metal plate. A precoated metal sheet excellent in formability. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an aspect of a layer structure of a precoated metal sheet. Fig. 2 is a view showing a state of cracking and peeling of a precoated metal sheet after bending. (a) indicates a state in which a crack is formed on the surface of the outermost layer, and (b) indicates a state in which the outermost layer is peeled off from the underlying layer. Fig. 3 is a view showing a state of a slide hopper type curtain coating device. Fig. 4 shows the results of investigating the oil repellency of the surface of the precoated steel sheet (invention example). 201141623 Figure 5 is a diagram. The comparative example is shown in Fig. 5(b). The contrast is shown in Fig. 5(a) on the surface of the precoated steel sheet by the ink coating pattern, and the pattern of the invention example is shown. [Implementation of the cold type] The form for carrying out the invention is described in detail below. First, the reasons for limiting the surface tension of the outermost layer coating for forming the outermost layer and the base coating for forming the base layer will be described. If the surface tension of the outermost coating exceeds 25 mN/m, it is impossible to exhibit oil and water repellency after the coating is applied. The surface tension of the outermost coating should be as low as possible, and it is now §, even if it is generally considered The fluororesin of a resin having an extremely low surface tension has a surface tension of 19 inN/m, so the lower limit is regarded as 19 mN/m. On the other hand, since the difference in surface tension between the base coating system and the outermost coating material is 6 mN/m or more, it is required to have a surface tension of 25 mN/00 m or more. Further, when the surface tension of the base paint exceeds 35 mN/m, it is difficult to form a multilayer curtain type and the coating is difficult, and the upper limit is made 35 mN/m. Moreover, if the difference in surface tension between the outermost surface coating material and the base coating material is less than 6 mN/m, the interface between the outermost layer and the base layer is indistinctly distinguishable to cause unevenness (generally considered to be a partial mixing of the two layers), and the coating is applied. The surface roughness of the film causes an influence, and the appearance is poor, and the difference between the two is set to be 6 mN/m or more. If the difference in surface tension between the top coat and the base paint is large, the reason why the surface roughness of the interface between the two layers is lowered is not clear, but it is generally considered that the surface of the base paint is extremely wet due to the extreme surface coating. 'The surface coating of the outermost layer is wetted and diffused, and the surface area of the interface between the two layers becomes smaller (Ra becomes smaller) 201141623 and it is stabilized. Further, it is considered that the polarities of the components constituting the outermost layer coating and the base coating are different, and the intermolecular interaction of the transmissive layer is hard to function to cause a clear layer separation. In order to solve the above problems, the inventors of the present invention have considered that it is effective to use a high-hardness functional coating as the outermost coating material and to improve the interface adhesion to the undercoat layer, and further improve the processing by thinning the outermost coating film. Sexuality, the results of the review focused on its tactics, 'I found that if the oil-repellent and water-repellent coatings that form the outermost layer are applied to the surface of the metal sheet and baked at the same time as the base coating forming the outermost base layer, the most The adhesion between the surface layer and the underlying layer forms a coating layer which is excellent in both high hardness and formability. In the present invention, the center line average roughness Ra of the interface between the topmost layer coating and the base coating is preferably 〇·ιμηι#. The fine unevenness of the interface between the outermost layer and the base layer is defined by the center line average roughness Ra (JISB〇6〇l) for indicating the surface roughness of the material. That is, the interface curve at 5 〇〇〇 times is taken as a roughness curve to obtain Ra. For example, after the coated steel sheet is cut and embedded in the resin, it is ground to make the cross section perpendicular to the surface of the coating film smooth, and then photographed by a scanning microscope of 5000 times, the Ra° of the interface can be obtained. Specifically, the Ra of the interface is covered with a transparent sheet for the photo, and the unevenness of the interface is accurately drawn, and as shown in FIG. 5, the portion of the vertical line is measured by the image processing. The average value is obtained by the following formula.
Ra=(J〇l|f(x)|dx)/l 式中的1係第5圖所示之中心線方向的測定長度。 就更簡便地測定界面2Ra而言，亦可將用於〇Hp之透 201141623 明薄片覆蓋在照片上，精密地描繪出界面的凹凸後，拉出 相當於第5圖之中心線的平均線，延著凹凸切取透明薄片， 測量平均線上下之山的部分及谷的部分之重量，再將其重 量換算成平均長度而求得Ra。 文到上述之與基底層的界面粗度之影響，為了得到良 好的水滴滾落性，最表層的表面粗度宜為0.2μηι以下。又， 表面層的表面粗度R a之測定方法可依據上述之界面R a的測 疋方法來進行。最表層塗膜為透明塗膜時，為了使與埋入 樹脂間的界面明瞭可見，期望在塗膜表面進行金屬蒸鍍後 才埋入樹脂，或使用經著色顏料著色之埋入樹脂。在切斷 經塗裝之鋼板並埋入樹脂後進行研磨，使垂直於塗膜表面 之斷面平滑，以掃描型顯微鏡照相攝影後，以與上述界面 中心線平均粗度相同的方式來求取塗膜最表面的Ra。又， 亦可同樣地在照片上被覆透明薄片，精密地描繪出界面的 凹凸來簡便地進行。 就塗膜的膜厚而言，並無特別限定，但宜將基底層設 為8〜30μηι、最表層〇5〜1〇μηι，且兩層之合計膜厚設為 〜30μηι。基底層若較8μηι薄則無法隱蔽原板而多有外觀不 美麗的If形。基底層若超過，則經濟性降低且容易產 生針孔(pinhole)。最表層若薄於〇 5μηι則多有撥油撥水性能 不充分的情形。最表層若超過ΙΟμηι則加工性低下。又，合 計膜厚未滿ΙΟμηι則無法形成塗料簾，而難以塗裝。合計膜 厚超過30μη!則多有在烘烤時產生針孔的情形。 又，就同時塗布兩層的方法而言，藉由使用多層多層 12 201141623 簾式塗覆機可將最表層塗膜_厚㈣㈣至未滿_， 而成功地進-步提高成形性(加工性）。再者，雖然以7字模 方法亦可多制時塗布，但由於難以將金屬板在塗出口附 近高速搬送之故，以多層簾式塗覆機為宜。 又’表現撥油及撥水性能之塗料的表面張力較基底層 塗料低極多，故若將該塗料作為最表層而與—般的基底層 同時以多層簾式塗覆機進行塗裝，則有塗料簾將自簾引導 4(llb)下方脫離而無法形成簾式臈、或基底層塗料的膜厚 在簾幅内無法m定而形成不平整等塗裝上的問題。關於此 問題，發現可藉由下述方式來解決：在多層簾式膜形成後， 賴後立即地進行塗裝，亦即，在第3圖中，充分地縮短塗料 從多層簾—錢麟找__紅唇卵a)與金屬 板⑻之_距離(L)，且，相對於最表層膜厚，不過度薄化 基底層的膜厚》 之 曰從簾_覆機麟之麟點所形成 唇部㈣與金屬板⑻間之距離（L)設為5〇麵以上且 150mnm下，可實現無^平整之线的塗裝。該距離若未滿 版爪，則塗料簾膜衝突到金屬板上時的運動動能不充足， 將產生將空氣捲入塗料與金屬板之間被稱為「空氣同伴之 塗裝缺陷。該距離若超過15Gmm，則如前所述將產生練 將自簾引導部脫離而無法形成簾式膜、或基底層塗料的膜尸 在簾幅内無法固定而形成不平整等塗裝上的問題。 予 接著，依據圖面來針對本發明進行說明。 在第1圖中顯示預塗覆金屬板之層結構的—態樣。在第 13 201141623 1圖所示之層結構中，於金屬板1的表面形成有鐘層2，例如 鋅鍍層，並於其上依序形成化成處理層3及底漆層4，再於 底漆層4上隔著基底層5形成最表層6。 通常，各層雖為逐層形成，但在預塗覆金屬板之成形 時，在各層若拉伸應力或壓縮應力作用，則將在層間發生 剝離或於層内產生龜裂。特別是，在最表層因拉伸應力或 壓縮應力強烈作用，將在最表層產生龜裂或使最表層從基 底層剝離。 在第2圖中，顯示預塗覆金屬板經彎曲加工時所產生之 龜裂及玻璃的態樣。在第2(a)圖中，顯示於最表層6的表面 產生了龜裂的態樣，在第2(b)圖中，顯示最表層6與其下之 基底層5剝離的態樣。再者，圖中，S係指鍍金屬板或具有 被膜之鍍金屬板。 由於在最表層即使僅有非常少的龜裂或剝離產生，預 塗覆金屬板之商品價值仍會消失之故，必須找到不產生龜 裂或剝離之層結構。 最表層中龜裂的產生雖可藉由形成變形能大之塗膜而 在某種程度上抑制之，然而，最表層的剝離則必須以某種 手法來提高最表層與基底層之層間密著性來進行抑制。再 者，此處所說的層間密著性，並非僅指兩層界面單純的密 著性，而是還包含了拉伸應力或壓縮應力作用於塗膜時的 密著性。 本發明係為了謀求與塗覆金屬板之用途的擴大，以在 金屬板的表層形成成形性優異之撥水性及撥油性的塗膜為 14 201141623 課題’本發明者致力研究了關於在成形時，即使拉伸應力 或壓縮應力作用於塗膜’也不會產生龜裂或剝離，提高最 表層與基底層之層間密著性的手法。 其結果’本發明者等，發現了將形成最表層之塗料與 形成基底層之基底塗料以多層簾式塗覆機重疊地在金屬板 表面同時塗布並烘烤，便可形成最表層與基底層之層間密 著性（以下亦僅稱為「密著性」）極為良好之塗膜層作為預塗 覆金屬板的表層。 形成最表層的塗料與形成基底層之基底塗料之2層同 時塗布，例如可使用第3圖所示公知的滑動漏斗（sude hopper)型簾式塗裝裝置（多層簾式塗覆機的一種）來進行。 再者，第3圖所示之塗裝裝置為可同時塗布3層者，但亦可 使用於2層同時塗布的情況。 上述塗裝裝置係備有具傾斜面8之滑動漏斗7，在傾斜 面8形成有3列溝槽9a、9b及9c。3列溝槽9a、9b及9c係各別 連接於塗料供給部l〇a、10b及10c。 塗料供給部10a、10b及10c係連接於齒輪泵（圖未示） 4，塗料係自塗料供給部10a、10b及10c，經過溝槽9a、9b 及9c，定量地進料至傾斜面8，形成重疊塗料膜12。 在傾斜面8的兩側，設有引導重疊塗料膜12之廉引導部 11a ’進一步，設有鏈狀的簾引導部lib，其係從傾斜面8之 唇部8a的兩端部到達設置於唇部8a下方之塗料盤13底部。 形成2層重疊塗料膜12時，使用溝槽9a及9b。從溝槽 9a’在寬方向上均勻地供給至傾斜面8之塗料，係積層於同 15 201141623 ，幕槽9a在寬方向上均勻地供給至傾斜面 膜，：在傾斜面8上形成在寬方向上均勾的重叠塗料二枓 重疊塗料膜12係由簾引導部lla及Ub所弓|導、。 ^之唇部8a脫離’落下至圖中_上朝箭頭方向移動^ ’’板或具有被膜之鍍金屬板S上，以形成重疊塗 1 再去，*丨从 且i腸層13 〇 剩餘的重疊塗料膜12係經過塗料盤15，回 未示）。 主槽（圖 :若從溝槽9b供給基底塗料 '從溝槽9a供給最表層塗 料’則可在金屬板或具有被膜之鍍金屬板S的表面形成最手 層塗料膜重疊於基底塗料膜之上的重疊塗膜層13。塗布 後’將重疊塗膜層13乾燥、烘烤，形成塗膜層。供烤冰户 係—般的烘烤溫度即可。 如此，可在金屬板或具有被膜的鍍金屬板S表面同時的 塗布基底塗料與最表層塗料。塗布後，將重疊塗膜層u乾 燥、烘烤而形成塗膜層。烘烤溫度係以一般的烘烤溫度即可。 若使用滑動漏斗(slide hopper)^簾式塗裝裝置，由於可 用不接觸金屬板表面的方式進行複數塗料之同時塗布，所 以可回避在使用輥塗覆機時不可避之條痕的產生。又，由 於即便一層的膜厚為數μπι左右，仍可在金屬板表面形成膜 厚安定之重疊塗膜層，故可得到外觀美麗之預塗覆金屬板。 本發明者等，藉由各種的試驗確認了，將基底塗料與 最表層塗料同時地塗布所形成之·塗膜層，係基底層與最表 層之密著性優異，且具有會隨著金屬板之變形而變形之優 異成形性。確認試驗的態樣係如下所述。 16 201141623 以每一面60g/m2之附著量，將兩面經鍍覆之厚度 0.8mm的熔融辞鍍鋼板浸潰於脫月旨處理劑（日本 PARKERIZING社製）中進行脫脂，水洗後乾燥。接著，在 經脫脂之熔融鋅鍍鋼板上，以輥塗覆機塗布無鉻化成處理 劑(CT-300N，日本PARKERIZING社製）10〇mg/m2，在最高 到達板溫為60°C條件下熱風乾燥。 在無鉻化成處理後，將非鉻系底漆之可撓性塗料69〇 底漆（日本FINE COATINGS社製）以桿塗覆機塗布以使乾燥 膜厚成為5μηι，並在最高到達板溫為215°c之條件下，以熱 風爐烘烤，形成底漆層。其後，使用滑動漏斗(snde h〇pper) 型簾式塗裝裝置（第3圖）將基底塗料與最表層塗料同時地塗 布於底漆層上。 作為基底塗料’係使用常用的高分子聚醋/三聚氛胺樹 脂硬化系塗料可撓性塗料71 〇〇白（日本FINEC〇ATINGS社 製作為最表層塗料’使用1/三聚氰胺樹脂硬化系撥油撥 水m塗料（大日本塗料社製）。將該等層藉由熱風爐在45 秒、最高到達板溫達到230X：的條件下，進行同時烘烤，形 成基底層（厚度15μηι)與最表層（厚度3gm)。 使用依此而製作之預塗覆鋼板，進行了 Tf曲試驗及歐 森(Erichsen)加工試驗。 τ彎曲試驗係使塗膜層位於外側，並在抓下進行3τ 彎曲。錢倍放大賴⑽曲加工料，並沒有產生龜裂 及剝離(參照第2⑷及(b)圖）。又，在彎曲加工部分的塗膜層 以市售的油性墨水(紅及黑)描畫著色圖案，其後以紗布擦 17 201141623 拭’則可完全栻除著色圖案。從這點也確認了，在τ彎曲加 工部分之最表層塗膜是健全的。 歐森(Erichsen)加工試驗係使塗膜層位於外側’並在 2〇C下進行8mm歐森(Erichsen)擠製加工。以10倍放大鏡觀 察歐森(Erichsen)加工部時，並沒有產生龜裂及剝離（參照第 2(a)及(b)圖）。 又，於歐森(Erichsen)加工部分的塗膜上，以市售的油 性墨水(紅及黑)描畫著色圖案，其後，以紗布擦拭，則可完 全拭除著色圖案。從這點也確認了，在歐森(Erichsen)加工 部分之最表層塗膜是健全的。 本發明者等進一步測定了塗膜層的硬度。塗膜層的硬 度以錯筆硬度計為H，與單獨塗布最表層塗料所形成之塗膜 的硬度無異。 將最表層塗料在前述化成處理鋼板上單獨地塗布.烘 烤，而形成了厚度3μιη之塗膜時，藉由3T彎曲或歐森 (EriChSen)8mm擠製加工，會在塗膜產生多數的龜裂。 又，在前述的底漆塗裝上，逐次將15μηι基底塗料、3μΙΏ 最表層塗料進行塗裝.烘烤而形成了塗膜時， 藉由3Τ彎曲 炉歐森(Erichsen)8mm擠製加工，在基底塗料與最表層塗料 塗膜間的界面’會發生塗膜剝離。 如此，確s忍了將基底塗料與最表層塗料同時塗布所形 成之塗膜層，相較於藉由該等之習知方法所形成的塗膜， 係加工性與硬度兼備。 本發明者等5忍為在將基底塗料與最表層塗料同時塗布 201141623 所形成的塗膜層中，加工性與硬度可兼備之理由係如下所 述。 使用於最表層之塗料單獨地形成塗膜，且該塗膜具有技 級硬度時，一般而言，譚塗膜的加工性低，無法承受3丁彎 曲或歐森(ErichSen)8mm擠製加工程度之嚴苛的加工。緣此 之故，若將最表層塗料在化成處理鋼板上單獨地塗布.烘 烤而形成塗膜並加工，則在塗膜上會產生多述的龜裂。 又，依照一般的預塗覆金屬板之製造方法，將基底塗 料與最表層塗料逐次地進行塗裝•烘烤，縣在基底層與 最表層之界面產生急劇的硬度變化，加工時，應力集中於 兩層界面，而產生塗膜剝離。 然而，若同時地塗布基底塗料與最表層塗料來形成堂 膜’則未反狀濕塗此會同時崎硬化反應之故，在 兩層間形成強而堅固的化學鍵，而提高層間密著性。進— 步’在兩層的界面附近’會產生兩層的相互擴散而使在兩 層界面之硬度變化相較下變得比較緩和。 在兩層的界面中，產生以上的現象，加工時，應力不 會集中於界面而將分散，又，柔軟的下層塗膜呈緩衝材的 形式而吸收應力，般認為騎便承受了 3Tf曲或歐 森(EdChSen)8mm擠製加工程度之嚴苛的加工，也不至於龜 裂或剝離。 作為使用於本發明之預塗覆金屬板的金屬板，可使用 鐵系金屬板、非鐵系金屬板等。作為鐵系金属板，係可舉 例如冷延鋼板、熱延鋼板、鋅鍍鋼板、合金化鋅鍍鋼板、 201141623 鋅-鐵合金錢鋼板、鋅-鋁合金鐘鋼板、鋁鍵鋼板、鉻鍵鋼板、 錄錢鋼板、鋅-鎳合金艘鋼板、錫鍍鋼板等的鋼板，而從耐 触性的觀點看來，制以使諸鋼板為佳。 尤非鐵系金屬板而言，可舉例如銘板、欽版及非 鐵合金板’及進—步將該等施予鍍覆所成之各種鍍覆板， 然本發明所使用之金屬板並不限於該等金屬板。 對金屬板宜視需要施予化成處理（塗裝前處理）。作為 可使用之處理，有水洗、熱水洗、酸洗、鹼脫脂、研磨、 拋光、絡處理、磷酸鋅處理、複合氧化膜處理、其他無鉻 型處理等。可以將該等處理單獨或組合來進行金屬板的塗 裝前處理。 在同時將底漆塗料與最表層塗料塗布於金屬板之前， 可進行基底塗裝。底漆亦可含有各種防鏽顏料。 作為形成基底層之基底塗料，若為表面張力 25〜35mN/m、表面張力較最表層塗料高出6mN/ma上者， 可使用任意之一般塗料。表面張力的差若小於6mN/m，在 同時塗布時無法明白區別界面而會產生凹凸，無法產生作 為目標的塗膜構造。 作為基底塗料’例如作為形成塗膜的樹脂成分，可適 宜地使用含有聚酯系樹脂者。基底塗料除此之外，可以塗 料組成物形式包含一般所使用之各種成分。例如三聚氰胺 樹脂糸、異氰酸醋系等公知的硬化劑。基底塗料亦可視需 要含有含有硬質顏料、骨材等。 就塗料的溶劑而言，可使用碳氫系、環己酮 20 201141623 (anone)/Solvesso(環己酮（cyclohexanone)(通稱環己酮 (anone))與Solvesso 15〇之混和比1:1之混合溶劑）等。 在基底塗料中，可使用從已知的著色顏料中選出之任 意著色顏料來作為著色顏料。代表性的著色顏料係由偶氮 系黄色、異吲哚啉酮系黄色 '偶氮系紅色、酞花青系藍色、 陰丹士林系藍色、喹吖酮系紅色等所代表的有機顏料，或 由碳黑、紅丹、絡黃、翻撥、鈦白、群青（ultramarine blue ).. 藏月（普魯士藍）、欽黃、石墨（graphite)、鋅白等所代表的無 機顏料。 添加於基底塗料之著色顏料的添加量係以相對於樹脂 1 〇〇重里份為重量份以上為佳。若未滿20重量份，則線速 加速至80m以上為止時，容易發生屬塗裝缺陷的針孔 (pinhole) 〇 本發明中’作為形成最表層的塗料，係使用表面張力 19〜25mN/m之塗料。較佳係使用撥水性且為撥油性的塗 料。只要具有可承受實際使用之硬度，且具有撥水性及撥 油性’可使用任意的塗料，但具有良好撥油性及撥水性之 塗料大多表面張力較低。 例如’亦可使用以矽氧樹脂、氟樹脂、矽氧接枝丙缚 酸系樹脂、矽氧•氟共聚樹脂等表面能低的樹脂作為主樹 脂’並以三聚氰胺衍生物或異氰酸酯等進行了交聯之塗 料。又’亦可使用在一般的聚酯/三聚氰胺硬化系等的底塗 料中添加有矽氧樹脂、氟樹脂等的塗料。 就含有矽氧樹脂或氟樹脂之主樹脂而言，可使用市售 21 201141623Ra=(J〇l|f(x)|dx)/l The length of the measurement in the center line direction shown in Fig. 5 of the equation. For the measurement of the interface 2Ra more easily, the 201141623 thin sheet for 〇Hp can also be covered on the photograph, and the unevenness of the interface can be accurately drawn, and the average line corresponding to the center line of FIG. 5 can be pulled out. The transparent sheet was cut out by the unevenness, and the weight of the portion of the mountain below the average line and the portion of the valley was measured, and the weight was converted into an average length to obtain Ra. In order to obtain a good water droplet rolling property, the surface roughness of the outermost layer is preferably 0.2 μm or less. Further, the method of measuring the surface roughness Ra of the surface layer can be carried out in accordance with the above-described method of measuring the interface R a . When the outermost coating film is a clear coating film, in order to make the interface with the embedded resin visible, it is desirable to embed the resin after metal deposition on the surface of the coating film, or to use a buried resin colored by the coloring pigment. After cutting the coated steel sheet and embedding the resin, polishing is performed to smooth the cross section perpendicular to the surface of the coating film, and after scanning with a scanning microscope, the same is obtained in the same manner as the average thickness of the interface center line. Ra on the outermost surface of the coating film. Further, in the same manner, the transparent sheet can be coated on the photograph, and the unevenness of the interface can be accurately drawn and easily performed. The film thickness of the coating film is not particularly limited, but the base layer is preferably 8 to 30 μm, and the outermost layer is 5 to 1 μm, and the total thickness of the two layers is -30 μm. If the base layer is thinner than 8μηι, the original plate cannot be concealed and the If shape is not beautiful. If the base layer is exceeded, the economy is lowered and pinholes are easily generated. If the outermost layer is thinner than 〇 5μηι, there is a case where the oil-repellent performance is insufficient. If the outermost layer exceeds ΙΟμηι, the workability is low. Further, if the total film thickness is less than ημηι, the paint curtain cannot be formed, and it is difficult to apply. When the total film thickness exceeds 30 μm, there are many cases where pinholes are generated during baking. Further, in the method of simultaneously coating two layers, the outermost coating film _thickness (four) (four) to less than _ can be used to improve the formability by using the multilayer multilayer 12 201141623 curtain coater (processability) ). Further, although the 7-mold method can be applied at a multi-time, it is difficult to transport the metal sheet at a high speed near the coating outlet, and a multi-layer curtain coating machine is preferred. Moreover, the surface tension of the paint exhibiting oil-repellent and water-repellent properties is much lower than that of the base paint, so if the paint is used as the outermost layer and the base layer is coated with a multi-layer curtain coater at the same time, There is a problem that the paint curtain is detached from the lower side of the curtain guide 4 (llb), and the film thickness of the curtain layer or the base layer paint cannot be fixed in the curtain web to form unevenness. Regarding this problem, it was found that it can be solved by the following method: after the formation of the multilayer curtain film, the coating is immediately performed, that is, in the third figure, the coating is sufficiently shortened from the multi-layer curtain - Qian Lin __Red lip egg a) and the metal plate (8) _ distance (L), and relative to the outermost film thickness, do not excessively thin the film thickness of the base layer 》 曰 帘 帘 帘 覆 覆 覆 覆 覆The distance (L) between the lip (4) and the metal plate (8) is set to be 5 〇 or more and 150 mnm, and the coating without the flat line can be realized. If the distance is not full of the claws, the kinetic energy of the paint curtain colliding with the metal plate is insufficient, and a coating defect called "air companion" between the paint and the metal plate will be generated. When it exceeds 15 Gmm, as described above, there is a problem in that the film which is detached from the curtain guide portion and which cannot form the curtain film or the undercoat layer cannot be fixed in the curtain frame to form unevenness or the like. The present invention will be described with reference to the drawings. In Fig. 1, the layer structure of the precoated metal sheet is shown. In the layer structure shown in Fig. 13 201141623, the surface of the metal sheet 1 is formed. A clock layer 2, such as a zinc plating layer, is formed thereon, and the chemical conversion treatment layer 3 and the primer layer 4 are sequentially formed thereon, and the outermost layer 6 is formed on the primer layer 4 via the base layer 5. Usually, the layers are layer by layer. Formed, but in the formation of pre-coated metal sheets, if tensile stress or compressive stress acts on each layer, peeling occurs between layers or cracks occur in the layers. In particular, at the outermost layer due to tensile stress or compression Strong stress, will be produced at the most surface Cracking or peeling off the outermost layer from the base layer. In Fig. 2, the crack and glass of the precoated metal sheet are shown in the bending process. In the second (a), it is shown on the outermost layer. The surface of 6 has a cracked appearance, and in the second (b) diagram, the state in which the outermost layer 6 is peeled off from the underlying base layer 5 is shown. Further, in the figure, S means a plated metal plate or has a film. The metal plate is plated. Since there is only very little cracking or peeling on the outermost layer, the commercial value of the precoated metal plate will disappear, and it is necessary to find a layer structure that does not cause cracking or peeling. The occurrence of cracks can be suppressed to some extent by the formation of a coating film having a large deformation energy. However, the peeling of the outermost layer must be carried out by some means to improve the adhesion between the outermost layer and the base layer. Further, the term "interlayer adhesion" as used herein does not mean only the adhesion of the two layers of the interface, but also the adhesion of the tensile stress or the compressive stress to the coating film. In order to seek for the expansion of the use of coated metal sheets, in gold The water-repellent and oil-repellent coating film which is excellent in formability of the surface layer of the sheet is 14 201141623. The present inventors have made an effort to study that even if tensile stress or compressive stress acts on the coating film during molding, cracking does not occur. Or peeling, a method of improving the adhesion between the outermost layer and the base layer. As a result, the inventors have found that the coating material forming the outermost layer and the base coating forming the base layer are overlapped by a multi-layer curtain coater. When the surface of the metal plate is simultaneously coated and baked, a coating layer having excellent interlayer adhesion (hereinafter also referred to simply as "adhesiveness") of the outermost layer and the underlying layer can be formed as a surface layer of the precoated metal sheet. The coating layer forming the outermost layer is applied at the same time as the two layers of the base coating layer forming the base layer. For example, a known sude hopper type curtain coating device (one of the multilayer curtain coating machines) shown in Fig. 3 can be used. Come on. Further, the coating apparatus shown in Fig. 3 may be applied to three layers at the same time, but it may be used in the case where two layers are simultaneously coated. The coating apparatus is provided with a sliding funnel 7 having an inclined surface 8, and three rows of grooves 9a, 9b, and 9c are formed on the inclined surface 8. The three rows of grooves 9a, 9b, and 9c are connected to the paint supply portions 10a, 10b, and 10c, respectively. The paint supply portions 10a, 10b, and 10c are connected to a gear pump (not shown) 4, and the paint is supplied from the paint supply portions 10a, 10b, and 10c through the grooves 9a, 9b, and 9c, and is quantitatively fed to the inclined surface 8, The overlapping coating film 12 is formed. Further, on both sides of the inclined surface 8, a guide portion 11a' for guiding the superimposed paint film 12 is provided. Further, a chain-shaped curtain guide portion lib is provided, which is provided from both end portions of the lip portion 8a of the inclined surface 8 The bottom of the coating pan 13 below the lip 8a. When two layers of the overcoat film 12 are formed, the grooves 9a and 9b are used. The coating material uniformly supplied from the groove 9a' to the inclined surface 8 in the width direction is laminated on the same 15 201141623, and the curtain groove 9a is uniformly supplied to the inclined mask in the width direction: formed in the width direction on the inclined surface 8 The superimposed paint coating layer 12 of the upper hook is guided by the curtain guiding portions 11a and Ub. ^The lip 8a is detached from the 'falling to the figure'. The upper side moves in the direction of the arrow ^'' plate or the plated metal plate S with the film to form the overlap coating 1 and then the remaining layer of the intestinal layer 13 The overlapping coating film 12 passes through the coating pan 15, not shown). Main groove (figure: if the base coating material is supplied from the groove 9b to the outermost layer coating from the groove 9a), the most hand coating film may be formed on the surface of the metal plate or the metal plate S having the film to overlap the base coating film. The superimposed coating layer 13 is applied. After coating, the overlapping coating film layer 13 is dried and baked to form a coating film layer. The baking temperature can be used for the baking ice-based system. Thus, it can be on a metal plate or have a film. The surface of the metal plate S is coated with the base coating and the outermost coating at the same time. After coating, the overlapping coating layer u is dried and baked to form a coating layer. The baking temperature is generally at a baking temperature. The slide hopper curtain coating device can avoid the occurrence of streaks when using the roll coater because the coating can be applied at the same time without contacting the surface of the metal sheet. The film thickness of one layer is about several μm, and a superposed coating film layer having a stable film thickness can be formed on the surface of the metal plate, so that a pre-coated metal plate having a beautiful appearance can be obtained. The inventors confirmed by various tests that Base When the coating material is applied to the coating layer at the same time as the coating material, the coating layer is excellent in adhesion to the outermost layer, and has excellent moldability which is deformed by deformation of the metal sheet. 16 201141623 A molten steel plated steel plate having a thickness of 0.8 mm coated on both sides was immersed in a de-moisture treatment agent (manufactured by Japan PARKERIZING Co., Ltd.) for degreasing after washing with water at a rate of 60 g/m 2 per surface. Then, on a degreased molten zinc-plated steel sheet, a chromium-free chemical conversion treatment agent (CT-300N, manufactured by Japan PARKERIZING Co., Ltd.) was applied by a roll coater at 10 〇 mg/m 2 , and the maximum plate temperature was 60 ° C. After the chrome-free chemical conversion treatment, a non-chromic primer flexible coating 69 〇 primer (manufactured by Nippon FINE COATINGS Co., Ltd.) was applied by a bar coater to make the dry film thickness 5 μm, and Under the condition that the maximum plate temperature is 215 ° C, it is baked in a hot air oven to form a primer layer. Thereafter, the base paint is applied using a sliding funnel (snde h〇pper) type curtain coating device (Fig. 3). The topmost coating is applied to the primer layer simultaneously As a base coating, it is a commonly used polymer polyester/trisamine resin hardening coating. Flexible coating 71 〇〇 White (Japan's FINEC 〇ATINGS Co., Ltd. is the most surface coating material' using 1/melamine resin hardening system Oil-repellent water m coating (manufactured by Dainippon Coatings Co., Ltd.). The layers are simultaneously baked by a hot air oven at 45 seconds and the highest reaching plate temperature reaches 230X: to form a base layer (thickness 15 μm) and most Surface layer (thickness: 3 gm) The Tf curve test and the Erichsen process test were carried out using the precoated steel sheet produced in this manner. The τ bending test was performed by placing the coating layer on the outside and performing 3τ bending under grasping. The money is magnified by Lai (10), and there is no cracking or peeling (see Figures 2(4) and (b)). Further, the coloring pattern is drawn on the coating layer of the bent portion by a commercially available oil-based ink (red and black), and then the coloring pattern is completely removed by gauze rubbing 17 201141623. From this point, it was confirmed that the outermost coating film in the τ bending processing portion was sound. The Erichsen processing test unit placed the coating layer on the outside side and performed an 8 mm Erichsen extrusion process at 2 °C. When the Erichsen processing section was observed with a magnifying glass of 10 times, cracking and peeling did not occur (see Figures 2(a) and (b)). Further, on the coating film of the processed portion of Erichsen, a colored pattern was drawn with a commercially available oil-based ink (red and black), and then, by wiping with a gauze, the colored pattern was completely erased. From this point, it was confirmed that the outermost coating film in the processing part of Erichsen was sound. The inventors further measured the hardness of the coating layer. The hardness of the coating layer is H in terms of the pen hardness, which is the same as the hardness of the coating film formed by coating the outermost coating alone. The outermost coating layer is separately coated and baked on the chemical conversion treated steel sheet to form a coating film having a thickness of 3 μm, and a majority of the turtles are produced in the coating film by 3T bending or EriChSen 8 mm extrusion processing. crack. Further, in the above-mentioned primer coating, 15 μm of the base paint and 3 μ of the top coat were successively coated and baked to form a coat film, which was extruded by a 3 inch bending furnace Erichsen 8 mm. The interface between the base coating and the coating film of the top coating is peeled off. Thus, it is true that the coating layer formed by coating the base coating with the outermost coating at the same time is compatible with both the workability and the hardness as compared with the coating film formed by the conventional methods. The inventors of the present invention have endured the coating layer formed by applying the base coating material to the outermost coating layer at the same time as 201141623, and the reason why both workability and hardness can be combined is as follows. When the coating film is formed separately on the coating of the outermost layer, and the coating film has a skill level, in general, the tan coating film has low processability, and cannot withstand the 3 inch bending or the ErichSen 8 mm extrusion processing degree. Harsh processing. For this reason, when the outermost layer coating material is separately coated and baked on the chemical conversion treated steel sheet to form a coating film and processed, a crack described above is generated on the coating film. Moreover, according to the general method for manufacturing a pre-coated metal sheet, the base paint and the top coat are successively coated and baked, and the county has a sharp hardness change at the interface between the base layer and the outermost layer, and stress concentration during processing. At the two-layer interface, peeling of the coating film occurs. However, if the base paint and the top coat are applied simultaneously to form the film, the wet coating will not form a strong and strong chemical bond between the two layers, thereby improving the interlayer adhesion. The advancement - in the vicinity of the interface between the two layers will cause two layers of interdiffusion to make the hardness change at the interface between the two layers relatively milder. In the interface between the two layers, the above phenomenon occurs. During processing, the stress does not concentrate on the interface and is dispersed. Moreover, the soft undercoat film absorbs the stress in the form of a cushioning material. It is considered that the ride is subjected to 3Tf or EdChSen's 8mm extrusion processing is not as severe as cracking or peeling. As the metal plate used for the precoated metal sheet of the present invention, an iron-based metal plate, a non-ferrous metal plate or the like can be used. Examples of the iron-based metal plate include a cold-rolled steel plate, a heat-expanded steel plate, a zinc-plated steel plate, an alloyed zinc-plated steel plate, a 201141623 zinc-iron alloy money plate, a zinc-aluminum alloy steel plate, an aluminum bond steel plate, and a chrome-bonded steel plate. A steel plate such as a steel plate, a zinc-nickel alloy steel plate, or a tin-plated steel plate is used, and from the viewpoint of the touch resistance, it is preferable to make the steel plates. In particular, for iron-based metal sheets, for example, nameplates, stencils, and non-ferrous alloy sheets, and various types of plated sheets which are applied by plating, and the metal sheets used in the present invention are not Limited to these metal plates. The metal plate should be subjected to chemical conversion treatment (pre-painting treatment) as needed. As the treatment which can be used, there are washing, hot water washing, pickling, alkali degreasing, grinding, polishing, complex treatment, zinc phosphate treatment, composite oxide film treatment, and other chromium-free treatment. These treatments may be performed separately or in combination for pre-coating treatment of the metal sheets. The substrate coating can be performed before the primer coating and the top coating are applied to the metal sheet at the same time. The primer may also contain various anti-rust pigments. As the base coating for forming the underlayer, if the surface tension is 25 to 35 mN/m and the surface tension is 6 mN/ma higher than the outermost coating, any general coating can be used. When the difference in surface tension is less than 6 mN/m, it is impossible to understand the difference in the interface at the time of coating, and unevenness is generated, and the coating film structure which is the target cannot be produced. As the base paint, for example, as the resin component for forming a coating film, those containing a polyester resin can be suitably used. In addition to the base coating, various components which are generally used may be contained in the form of a coating composition. For example, a known hardener such as melamine resin or isocyanate is used. The base paint may also contain hard pigments, aggregates, etc. as needed. For the solvent of the coating, a hydrocarbon-based, cyclohexanone 20 201141623 (anone) / Solvesso (cyclohexanone (commonly known as cyclohexanone (anone)) and Solvesso 15 〇 can be used in a ratio of 1:1. Mixed solvent) and the like. In the base paint, any coloring pigment selected from known coloring pigments can be used as the coloring pigment. Representative colored pigments are organic represented by azo yellow, isoindolinone yellow 'azo red, phthalocyanine blue, indanthrene blue, quinactone red, etc. Pigment, or inorganic pigments represented by carbon black, red dan, complex yellow, plucking, titanium white, ultramarine blue.. Tibetan moon (Prussian blue), yellow, graphite, zinc white, etc. The amount of the coloring pigment added to the base paint is preferably at least the weight of the resin relative to the weight of the resin. When it is less than 20 parts by weight, when the linear velocity is accelerated to 80 m or more, pinholes which are coating defects are likely to occur. In the present invention, the surface tension is 19 to 25 mN/m as the coating for forming the outermost layer. Coatings. It is preferred to use a water-repellent and oil-repellent coating. As long as it has a hardness that can withstand practical use, and has water repellency and oil repellency, any coating material can be used, but a coating having good oil repellency and water repellency has a low surface tension. For example, 'a resin having a low surface energy such as a phthalocyanine resin, a fluororesin, a ruthenium-oxygen-grafted acid-based resin, a ruthenium-oxygen/fluoropolymer resin, or the like can be used as the main resin', and a melamine derivative or an isocyanate is used. Lianzhi paint. Further, a coating material such as a fluorinated resin or a fluororesin may be added to a primer such as a general polyester/melamine curing system. For the main resin containing a silicone resin or a fluororesin, commercially available 21 201141623
的石夕氧.丙稀酸共聚樹脂(例如，東亞合成社製「symac(註 冊商標列、「reseda(註㈣標)」㈣、及TQKUSHIKI 社製「SQ(註冊__等)及市㈣錢·以聚樹脂(例 如，富士化成工業社製[^'-(^^等）。 就添加的石夕氧樹脂而言，在市售者中，例如有BYK社 製的ΓΒΥΚ(註冊商標)_」、「Βγκ(註冊商標)_378」等就 添加之氟樹脂而言，在市售者中，例如有Βγκ社製的「 BYK(註冊商標)_34〇」等’其他還有很多，只要視塗料成分 適當選擇添加即可。 將上述矽氧•丙烯酸共聚樹脂或矽氧·氟共聚樹脂交 聯之父聯劑，就異氰酸酯而言，例如可使用住化BAYER社 製「Sumidur( S主冊商標）」系列、「Desm〇dur(註冊商標）」系 列、三井武田化學社製ΓΤΑΚΕΝΑΤΕ(註冊商標)」系列等。 就二聚氰胺樹脂而言，可使用例如三井Sai-Tech社製厂 CYMEL(註冊商標)」系列、「MYCOAT(註冊商標)」系列、大 曰本墨水化學工業社製「BECKAMINE(註冊商標)」系列、「 SUPER BECKAMINE(註冊商標)」系列等。 形成最表層的塗料可為非著色的透明塗料，亦可為藉 由顏料或染料著色之塗料。又，為了提高設計性或提高非 黏著性能’亦可含有光輝材或骨材。又，視需要亦在不會 影響到其他性能的範圍内可含有體質顏料、消泡劑、蠟等。 在本發明中，各塗膜層的厚度不限定於特定厚度，但 般底漆層為1〜lOpm左右。底漆層若過薄，則無法得到充 分的财触性’若太厚，則加工性低下。基底層與最表層的 22 201141623 膜厚均衡雖應依據所期望之色調、 n加工性、最表層之撥油 性及撥水性來決定，最表錢厚 $輯—’則加工'14低 下，最表層的膜厚若過薄(0.5_未满），則無法得到充分的 撥油性及撥水性。 又’基底層與最表層之合計膜厚若過薄，則無法形成 塗科廉，無法塗裝，另—方面，若過厚，則在塗料的_ 時’容易發生屬塗裝缺_「針孔(pinhQle)」。為了形成可 多層同時塗布，可在以LS7Gm無針孔條件τ烘烤且性能、 外觀皆良好的塗膜之膜厚結構，在撥油撥水型的情況下， 基底層宜為8〜3_、最表層宜為〇.5〜1()帅、兩層之合計膜 厚宜為10〜30卿’且，基底層膜厚/(最表層膜厚+基底層獏 厚）的比宜超過0.3’更宜超過0.6。基底層若薄於—則無法 隱蔽原板而大？外觀衫麗。基底層若超過鄉_經濟性 低下且容易產生針I最表層若薄於則多有撥油撥水 性能不充足的情形。最表層若超過1()卿則加卫性低下。 又，合計膜厚未滿1〇μίη則無法形成塗料簾難以塗裝。合 計膜厚超過3_則烘烤時常會產生針孔。基底層膜厚/(最 表層膜厚+基底層膜厚)之比在0.3以下則無法形成塗料簾， 或即使形成塗料簾也無法在塗布於鋼板時使基底層塗膜呈 均勻的膜厚，而有呈外觀不良（不平整)之傾向。 同時塗布之基底層及最表層塗料的乾燥•烘烤係可使 用例如熱風爐、料加熱爐、近紅外線爐、遠紅外線爐、 能量線硬化絲進行。從從藉加熱進行之溶綱蒸發或塗 料的硬化與塗料中樹脂成分劣化之平衡的觀點看來，塗料 23 201141623 的烘烤溫度一般期望為180°C以上且未滿300°C。 實施例 接著，針對本發明之實施例進行說明，在實施例中的 條件係用於確認本發明之可實施性及效果而採用之一條件 例，本發明並非受該條件例所限定者。本發明只要在不脫 離本發明之要旨且可達成本發明之目的的條件下，係可採 用各種條件。 (實施例） 使用滑動漏斗(slide hopper)型簾式塗裝裝置（參照第3 圖），以表1所示條件，將具有撥水性及撥油性之最表層塗料 與一般的基底形成塗料，在已施予底漆被膜之Zn鍍鋼板的 表面，同時塗布並烘烤，形成了塗膜層（最表層+基底層）。 24 201141623 甸p 〇 (N o CO (N o CN o m (N o m (N ο ΓΟ (Ν Ο m (Ν o m CN o CN 〇 ΓΛ CN ο m (Ν g 1—^ Ο o On CN o o m CN o m (N Ο m (Ν ο m (Ν 〇 (N 1 o ro CN o c^i CN 塗裝方法 多層簾(2層同時） * CN, Dgm Cl s οσ 肊 α|π 藏 t^ni 咖 Q|CD Ci 藏 α|αι 咖 亟 議 /·—Ν 价 03 CN, 0 Q|ra 咖 * ίϋ： Cl D|Kt 咖 * Dim 峰 /*—V 伽 CD t!E 亟 D|n 咖 dn /—N •Φ m 呢 D|m 采 咖 ίϋ 溪 Q|m 吻 * CN^ 溪 α|π 妙\ * ϋ? t^t * <N, πι: CS * tgm 咖 /«—s * ii： 上下表面 張力差 (下-上） yn un Ο in ο m o ο Ο 〇 in m o 〇 Ο in ο IT) ο in o ο 卜 σί 卜 G\ ON 〇〇 ΓΛ 〇 Ο (Ν 寸 vo IT) iT) 膜厚比 下/(下+上） 〇 as ο Ο cn oo C) jo o s ο ν〇 νη Ο o o o Os 00 o 〇 Os (Ν Ο m 00 ο m 00 ο ΓΛ 00 o m 00 ο m oo o m 00 ο m 00 ο m 00 ο S Ο ΓΛ 00 Ο cn 00 o m 00 o 合計 膜厚 /μτη in oo 宕 (Ν o 00 (N ΓΛ 00 (Ν oo oo oo oo oo oo oo oo οο OO oo oo /—V 膜厚/μτη 寸 〇 in n m Ο (Ν m cn m r~i 宕 m m m m ΓΛ ΟΊ m ΓΛ ΓΛ ΓΛ 表面張力 /mN/m <N trt in υ-ϊ ?ΐ U^i ή ir> ΓΛ ri (Ν m (Ν (Ν m <N (N in <N m 塗料 r— H i 1 i H »™Η >1 i i 1 * Η ρ Η P P > i p Ρ Η P P 基礎層(下） 膜厚/μπι ίη <-n IT) κη 卜 OO IT) (N 00 04 00 κη 的 to vr> »-— 表面張力 /mN/m 〇 (N ο <N cn O (N o (N m o CN ο (Ν m ο (Ν ΓΛ o (N m o (N CO 〇 (N m 〇 oi m ο (Ν m Ο <N m 〇 <N o (N ΓΛ 〇 <N 04 Ο (Ν m (Ν m 〇 <N (N i〇 (Ν o VO m 0 01 o 幻 塗料 5 s CO 5 DQ 5 S 5 5 5 S δ 5 CQ 5 5 <N OQ CQ (Ν PQ m CQ S OQ 5 Ό CQ 底漆 1 1 非鉻 (5㈣ 化成 處理 1 i CT- E300N 原板 1 GI (0.6 mmt) 1 實施例1 實施例2 實施例3 I |實施例4 1 實施例5 1實施例6 1 實施例7 實施例8 實施例9 實施例10 實施例11 1實施例12| |實施例13 1 實施例14 |實施例15| |實施例16| 實施例17 實施例18 實施例19 |比較例1 | 比較例2 I比較例3 | I比較例4 | 比較例5 25 201141623 在形成有塗膜層之鋼板，調查最表層與基底層之界面 的中新線平均粗度Ra(pm)、最表層之表面粗度Ra(pm)、鋼 板的撥油性及撥水性，及加工性。將其結果表示於表2。 26 201141623 <N< 備註 1 稍微色調不良 1 針孔產生 1 1 稍微不平整外観 I | 稍微硬化不足 | 稍微黃變 1 因混層而明顯外觀不良(斑紋） 不形成簾而無法塗裝 1 加工性 丨歐森試驗(8mm) 永久墨水 拭除性 〇 〇 〇 〇 〇 〇 < 〇 〇 〇 < 〇 〇 〇 〇 〇 〇 〇 X X 1 X 〇 剝離 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 < < 1 〇 〇 〇 〇 〇 〇 〇 〇 < 〇 〇 〇 〇 <] 〇 〇 〇 〇 〇 〇 〇 <1 < 1 〇 〇 | 3T彎曲 永久墨水 拭除性 〇 〇 〇 〇 〇 < 〇 〇 < < <] 〇 〇 〇 〇 〇 〇 〇 X X 1 X <3 剝離 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X 1 〇 〇 〇 〇 〇 〇 〇 〇 < 〇 〇 < 〇 〇 〇 〇 〇 〇 〇 X X 1 〇 <] 鉛筆 硬度 X X X X X X X X X X X X X X X X X X X 1 X 1 撥油•撥水性能 水滴 滾落性 <1 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X 1 X X I耐永久墨水性(紅黑） 拭除性 < 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 1 X 〇 反彈性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 <] 〇 X 〇 最表層 Ra/μηι I 0.19 I 0.19 | 0.15 丨 0.17 丨 0.15 | 0.18 I I 0.18 I I 0.15 I | 0.15 I I 0.15 I | 0.15 I | 0.13 I I 0.15 I | 0.16 I 0.15 I 0.16 I 0.15 I 0.15 I 0.15 I 1 0.33 I 1 0.25 I 0.28 上下層 界面 Ra/μιτι | <0.1 i I <0.1 <0.1 I <0-1 〇 | <0.1 i 〇 〇 〇 <0.1 I <0.1 1 <0.1 1 ! <0.1 I 〇 〇 〇 <0.1 I 無法測定 (混層） 0.36 I 無法測定 (無法塗裝） 0.15 I 0.23 丨烘烤溫度 (PMT) rc 下/上 | 230 230 | 230 230 | I 230 I I 230 I I 230 I 230 230 I 230 I 230 I 230 I 〇 290 1 300 I 230 230 I 230 I 230 230 1 1 230 I 230 No, 實施例1 實施例2 |實施例3 實施例4 |實施例5 實施例6 , 丨實施例7 i 實施例8 I 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 實施例17 實施例18 |實施例19| 比較例1 |比較例2 I 比較例3 |比較例4 I 比較例5 27 201141623 最表層與基底層之間的界面粗度，係藉由用於表示材 料表面粗度之心線平均粗度Ra(JIS B 0601)，在以5000倍觀 測時的界面曲線當作粗度曲線，來求得Ra(pm)。最表層之 粗度Ra，係將以5000倍觀測時的最表層的表面曲線當作粗 度曲線，來求得Ra(pm)。 撥油性及撥水性係調查耐油性墨水性（反彈性與拭除 性)及水滴的滾落性而進行了評價。 (耐油性墨水性） 在塗膜表面以市售的油性墨水（紅及黑）描畫圖案而汙 染之，將塗膜表面反彈該墨水的態樣（反彈性）評價如下。 〇：反彈而使墨水成滴狀，無法描晝圖案。 △:反彈遲緩，且不充足。 X:完全不反彈，可清楚的描晝圖案。 接著，將以市售的油性墨水汙染的塗膜表面，以乾紗 布擦拭，是否可以拭除係評價如下。 〇：乾淨地拭除，完全不留痕跡。 △:大致拭除，但殘留一些痕跡。 X :完全無法拭除。 (水滴滚落性） 在塗膜表面以注射器將蒸餾水一滴滴滴下，從水平狀 態至傾斜10度時的水滴滾落性，係評價如下。 〇：立刻滾落流下來。 △:緩慢地流動。 X:幾乎不動。 28 201141623 塗膜硬度係剛定錯筆硬度。 加工14係進行了彎曲試驗及歐森(Erichsen)試驗來評價= (3T彎曲試驗） 在20C下進行3T彎曲以1〇倍放大鏡觀察加工部的龜 裂與剝離狀態，並評價如下。 〇：完全看不見龜裂（或剝離）。 △:可看見細微的龜裂（或剝離）。 Χ:可看見重度的龜裂（或剝離）。 (歐森(EHChSen)8mm擠製成形試驗） 在20C下進行歐森(Erichsen)8mm擠製加工以倍放 大鏡觀察加工部的龜裂與剝離狀態，並評價如下。 〇：完全看不見龜裂（或剝離）。 △:可看見細微的龜裂（或剝離）。 X:可看見重度的龜裂（或剝離）。 進一步，在經T彎曲及歐森(Erichsen)加工之部分的塗 膜上，以紅及黑的油性墨水（市售物）描畫圖案而汙染之，其 後，以乾紗布擦拭，是否可以拭除，係評價如下。 〇:乾淨地拭除，完全不留痕跡。 △:大致拭除，但殘留一些痕跡。 X:完全無法拭除。 藉由此評價’可藉由放大鏡確認以目視觀察無法確認 程度之細微的龜裂是否有進入最表層塗膜。細微的龜裂存 在時，油性墨水將自龜裂處侵入塗膜的基礎層，拭除性孽 化。該評價係藉由放大鏡而較目視判定更為嚴袼的評價二 29 201141623 表2中，在實施例4之預塗覆鋼板(發明例）的表面，以紅 與黑的油性墨水(市售物)描畫圖案，其後，將乾拭後的結果 表示於第4圖。得到在預塗覆鋼板(發明例）表面遭反彈之油 性墨水(市售物）係可被乾淨地拭除。 在實施例4之預塗覆鋼板(發明例）與比較例1之預塗覆 鋼板（比較例）的表面’以油性墨水(市售物)描畫圖案進行對 比。將其結果表示於第5圖。在第5(a)圖中表示比較例的圖 案，在第5(b)圖中表示發明例的圖案。得知在發明例中，墨 水反彈成點狀，無法描畫所要的圖案。 實施例1〜19中任一者皆滿足了本發明之要件，且撥油 性、撥水性、硬度及加工性大致良好。特別是，實施例1〜7、 9、10、13、15、17~ 19為良好。惟’若仔細觀察，則在實 施例8中由於基礎層的膜厚較薄之故，稍微色調不良。在實 施例11中，因塗膜的合計厚度厚而有針孔產生。在實施例 12中，因基礎層膜厚/(最表層膜厚+基礎層膜厚）的比在〇3〇 以下而稍微有不平整發生。在實施例14中，由於供烤溫卢 低之故，稍微硬化不足。又，在實施例16中，由於供烤严 度高之故，呈加熱過多，稍微產生了黃變。 相對於此，在比較例1中，基底塗料的表面張力未滿 25mN/m ’最表面層形成塗料與基底塗料之表面張力差未、、高 6mN/m之外，由於其值為負，在兩層間產生混層，形成斑 紋狀之明顯的外觀不良。在比較例2中，表面張力差，丨至 2.0mN/m，因表面張力差未滿6mN/m而使最表層_ & 之界面的Ra高達0·36μηι。此係推測為塗膜最表面之^^增 30 201141623 大，平滑性降低之故。在比較例3中，基底塗料的表面張力 超過35，無法形成多層簾而無法塗裝。在比較例4中，最表 層塗料的表面張力超過25，在成膜後的塗膜無法表現撥油/ 撥水性。在比較例5中，最表面層形成塗料與基底塗料的表 面張力差未滿6mN/m ’界面的Ra變大，因其影塑而使最表 層之平滑性低下，水滴滾落性低下。 接下來’改變多層簾式塗布的塗布條件來形成塗膜。 使用與實施例1相同的最表層塗料與基底塗料，在將唇部 (8a)與金屬板(s)間的距離(L)設為45mrn時，在塗膜與金屬板 間產生了塗裝缺陷，其中該唇部(8a)係從多層簾式塗布之塗 料的脫離點。又，同樣地使用與實施例丨相同的塗料，在將 夕層簾式塗覆機之該距離設為18〇mm時，塗料簾係自簾引 導部脫離而無法形成簾式膜。 進一步，以與實施例4相同的塗料及塗膜結構，藉由2 塗覆2供烤的方式，輥塗覆機塗布基底塗料，並以PMT215°C 洪烤後’以輥塗覆機於其上層塗覆最表層塗料，再以 PMTUOC供烤’製作塗裝鋼板並進行評價時 ，加工性試驗 皆呈X的結果。 產業上之可利用性 如前所述，根據本發明，可提供一種預塗覆金屬板， /、表s除了具備美麗性及财餘性之外，還具有防止.除去 塗鴉貼附物的機能’及防止附冰.附雪的機能，且具備 可追隨金屬板之變形之優異成形性。 又’根據本發明，藉由提高最表層之成形性，預塗覆 31 201141623 金屬板的用途可擴大至油汙嚴重的器具(吸油煙機等）、暴露 於雨水之器具(排水溝等），本發明在預塗覆金屬板製造•利 用産業係可利用性高者。 【圆式簡單說明3 第1圖係表示預塗覆金屬板之層結構之一態樣的圖。 第2圖係表示預塗覆金屬板經彎曲加工後所產生之龜 裂及剝離之態樣的圖。（a)係表示於最表層的表面產生了龜 裂之態樣，（b)係表示最表層與其下之基底層剝離之態樣。 第3圖係表示滑動漏斗(slide hopper)型簾式塗裝裝置的 態樣。 第4圖係表示調查了預塗覆鋼板(發明例）之表面的撥油 性的結果。 第5圖係表示對比在預塗覆鋼板之表面以墨水塗畫之 圖。將比較例的圖案表示於第5(a)圖，將發明例的圖案表示 於第5(b)圖。 【主要元件符號說明】 1…金屬板 2…鍍層 3…化成處理層 4…底漆層 5…基底層 6…最表層 7…滑動漏斗 8···傾斜面 8a…唇部(塗料的脫離點) 9a、9b、9c…溝槽 10a、10b、10c…塗料供給部 11a、lib…簾引導部 12…重疊塗料膜 13…重疊塗膜層 14…幸昆 15…塗料盤 S···鍍金屬板或具有被膜的鍍 金屬板 32Shiki Oxygen. Acrylic Copolymer Resin (for example, symac (registered trademark, "reseda") (4), and TQKUSHIKI" "SQ (Registration__, etc.) and City (4) - Poly resin (for example, Fuji Chemical Industry Co., Ltd. [^'-(^^, etc.). For the addition of the Shiki Oxygen Resin, for example, there is a ΓΒΥΚ (registered trademark) manufactured by BYK Co., Ltd. For example, "BYK (registered trademark) _34" manufactured by Β γ κ 社 ' ' BY κ κ κ κ 添加 添加 BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY For the isocyanate, for example, Sumidur (S main volume trademark) manufactured by BAYER Co., Ltd. can be used as the isocyanate for crosslinking the above-mentioned oxime/acrylic copolymer resin or oxime/fluoro copolymer resin. Series, "Desm〇dur (registered trademark)" series, Mitsui Takeda Chemical Co., Ltd. (registered trademark) series, etc. For melamine resin, for example, CYMEL (registered by Mitsui Sai-Tech Co., Ltd.) can be used. Trademark) series, "MYCOAT (registered trademark)" series, Otsukamoto ink "BECKAMINE (registered trademark)" series and "Super BECKAMINE (registered trademark)" series manufactured by Chemical Industry Co., Ltd. The coating that forms the outermost layer can be a non-colored clear coating or a pigment colored by pigment or dye. In order to improve design or improve non-adhesive performance, it may also contain a bright material or an aggregate. Further, an extender pigment, an antifoaming agent, a wax, etc. may be contained in a range that does not affect other properties as needed. In the meantime, the thickness of each coating layer is not limited to a specific thickness, but the primer layer is about 1 to 10 μm. If the primer layer is too thin, sufficient chemical properties cannot be obtained. If it is too thick, the workability is lowered. The base layer and the outermost layer 22 201141623 The film thickness balance should be determined according to the desired color tone, n processability, oiliness of the outermost layer and water repellency. The most expensive one is $--the processing is lower than the 14th level. If the film thickness is too thin (0.5_underfill), sufficient oil repellency and water repellency cannot be obtained. Further, if the total thickness of the base layer and the outermost layer is too thin, it cannot form a coating, and it cannot be coated. Another aspect, if ever Thick, it is easy to occur in the coating _ when the coating is missing _ "pinhQle". In order to form a multi-layer coating at the same time, can be baked in LS7Gm pin-free conditions τ and good performance and appearance The film thickness structure of the film, in the case of oil-repellent type, the base layer should be 8~3_, and the outermost layer should be 〇.5~1 () handsome, the total thickness of the two layers should be 10~30 qing' Further, the ratio of the thickness of the base layer / (the thickness of the outermost layer + the thickness of the base layer) is preferably more than 0.3', more preferably more than 0.6. If the base layer is thinner than - the original layer cannot be concealed and the appearance is large. If the base layer is more than the township, the economy is low and it is easy to produce the case where the outermost layer of the needle I is thinner, and the oil-repellent performance is insufficient. If the outermost layer exceeds 1 (), the defender is low. Further, when the total film thickness is less than 1 μm, the coating curtain cannot be formed to be difficult to apply. When the film thickness exceeds 3 mm, pinholes are often generated during baking. When the ratio of the base layer film thickness / (the outermost layer film thickness + the base layer film thickness) is 0.3 or less, the paint curtain cannot be formed, or even if the paint curtain is formed, the base layer coating film cannot have a uniform film thickness when applied to the steel sheet. There is a tendency to look bad (uneven). The drying and baking of the base layer and the outermost coating which are simultaneously applied can be carried out, for example, by using a hot air furnace, a material heating furnace, a near infrared ray furnace, a far infrared ray furnace, and an energy ray hardening yarn. The baking temperature of the coating material 23 201141623 is generally desirably 180 ° C or more and less than 300 ° C from the viewpoint of the evaporation of the solvent by heating or the hardening of the coating material and the deterioration of the resin component in the coating. EXAMPLES Next, examples of the present invention will be described. The conditions in the examples are examples for confirming the workability and effects of the present invention, and the present invention is not limited by the conditions. The present invention can be applied to various conditions without departing from the gist of the present invention and up to the purpose of the invention. (Example) Using a slide hopper type curtain coating apparatus (refer to Fig. 3), a surface coating material having water repellency and oil repellency was formed into a coating material on a general substrate under the conditions shown in Table 1. The surface of the Zn-plated steel sheet to which the primer film has been applied is simultaneously coated and baked to form a coating layer (the outermost layer + the base layer). 24 201141623 甸 p 〇 (N o CO (N o CN om (N om (N ο ΓΟ (Ν Ο m (Ν om CN o CN 〇ΓΛ CN ο m (Ν g 1—^ Ο o On CN oom CN om ( N Ο m (Ν ο m (Ν 〇 (N 1 o ro CN oc^i CN coating method multilayer curtain (2 layers simultaneously) * CN, Dgm Cl s οσ 肊α|π 藏 t^ni 咖 Q|CD Ci藏α|αι 咖亟议/·—Ν Price 03 CN, 0 Q|ra 咖* ϋ Cl: Cl D|Kt 咖* Dim peak/*—V gamma CD t!E 亟D|n dn /—N • Φ m D|m 采咖ίϋ 溪Q|m kiss* CN^ 溪α|π 妙@ * ϋ? t^t * <N, πι: CS * tgm 咖/«-s * ii: upper and lower surface tension差 (下下上) yn un Ο in ο mo ο Ο mo in mo 〇Ο in ο IT) ο in o ο 卜σί 卜 G\ ON 〇〇ΓΛ 〇Ο (Ν inch vo IT) iT) film thickness ratio /(下+上) 〇as ο Ο cn oo C) jo os ο ν〇νη Ο ooo Os 00 o 〇Os (Ν Ο m 00 ο m 00 ο ΓΛ 00 om 00 ο m oo om 00 ο m 00 ο m 00 ο S Ο ΓΛ 00 Ο cn 00 om 00 o Total film thickness / μτη in oo 宕 (Ν 00 00 (N ΓΛ 00 (Ν oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo 〇in nm Ο (Ν m cn mr~i 宕mmmm ΓΛ ΟΊ m ΓΛ ΓΛ ΓΛ Surface tension/mN/m <N trt in υ-ϊ ?ΐ U^i ή ir> ΓΛ ri (Ν m (Ν (Ν m <N (N in <N m coating r-H i 1 i H »TMΗ >1 ii 1 * Η ρ Η PP > ip Ρ Η PP base layer (bottom) film thickness / μπι ίη < -n IT) κη 卜 OO IT) (N 00 04 00 κη to vr> »-- Surface tension/mN/m 〇(N ο <N cn O (N o (N mo CN ο (Ν m ο ( Mo ΓΛ o (N mo (N CO 〇(N m 〇oi m ο (Ν m Ο <N m 〇<N o (N ΓΛ 〇<N 04 Ο (Ν m (Ν m 〇<N ( N i〇(Ν o VO m 0 01 o Magic paint 5 s CO 5 DQ 5 S 5 5 5 S δ 5 CQ 5 5 <N OQ CQ (Ν PQ m CQ S OQ 5 Ό CQ primer 1 1 non-chromium (5 (4) Chemical Processing 1 i CT- E300N Original Board 1 GI (0.6 mmt) 1 Example 1 Example 2 Example 3 I | Example 4 1 Example 5 1 Example 6 1 Example 7 Example 8 Example 9 Implementation Example 10 Example 11 1 Example 12| | Example 13 1 Example 14 | Example 15 | | Example 16 | Example 17 Example 18 Implementation 19 |Comparative Example 1 | Comparative Example 2 I Comparative Example 3 | I Comparative Example 4 | Comparative Example 5 25 201141623 In the steel sheet on which the coating layer was formed, the average thickness Ra of the neutral line at the interface between the outermost layer and the base layer was investigated ( Pm), surface roughness Ra (pm) of the outermost layer, oil repellency and water repellency of the steel sheet, and processability. The results are shown in Table 2. 26 201141623 <N< Remarks 1 Slightly poor color tone 1 Pinhole generation 1 1 Slightly uneven outer 観I | Slightly hardened insufficient | Slightly yellowed 1 Poor appearance due to mixed layer (plaque) Cannot be coated without forming a curtain 1 Processability丨Ou Sen test (8mm) permanent ink erasing 〇〇〇〇〇〇<〇〇〇< 〇〇〇〇〇〇〇XX 1 X 〇 peeling 〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇<< 1 〇〇〇〇〇〇〇〇<〇〇〇〇<]〇〇〇〇〇〇〇<1< 1 〇〇| 3T bending permanent ink erasing Sex 〇〇〇〇〇<〇〇<<<> 〇〇〇〇〇〇〇XX 1 X <3 stripping 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 XX 1 〇〇〇〇〇〇〇〇<〇〇< 〇〇〇〇〇〇〇XX 1 〇<] pencil hardness XXXXXXXXXXXXXXXXXXX 1 X 1 oil-repellent water-repellent water drop-off property< 1 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇XX 1 XXI permanent ink resistance (red and black) Erasing < 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇1 X 〇 Rebound 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇<] 〇X 〇The most surface layer Ra/μηι I 0.19 I 0.19 | 0.15 丨0.17 丨0.15 0.18 II 0.18 II 0.15 I | 0.15 II 0.15 I | 0.15 I | 0.13 II 0.15 I | 0.16 I 0.15 I 0.16 I 0.15 I 0.15 I 0.15 I 1 0.33 I 1 0.25 I 0.28 Upper and lower interface Ra/μιτι | <0.1 i I <0.1 <0.1 I <0-1 〇| <0.1 i 〇〇〇<0.1 I <0.1 1 <0.1 1 ! <0.1 I 〇〇〇<0.1 I cannot be measured ( Mixed layer) 0.36 I Cannot be measured (cannot be coated) 0.15 I 0.23 丨 Baking temperature (PMT) rc Lower / upper | 230 230 | 230 230 | I 230 II 230 II 230 I 230 230 I 230 I 230 I 230 I 〇 290 1 300 I 230 230 I 230 I 230 230 1 1 230 I 230 No, Example 1 Example 2 | Example 3 Example 4 | Example 5 Example 6丨Example 7 i Example 8 I Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 1 Comparison Example 2 I Comparative Example 3 | Comparative Example 4 I Comparative Example 5 27 201141623 The interface thickness between the outermost layer and the base layer is expressed by the average roughness Ra (JIS B 0601) for indicating the surface roughness of the material. Ra (pm) is obtained by taking the interface curve at 5000 times as a roughness curve. The roughness Ra of the outermost layer is obtained by taking the surface curve of the outermost layer when viewed at 5000 times as a roughness curve to obtain Ra (pm). The oil repellency and water repellency were evaluated by investigating the oil resistance ink properties (rebound and repellency) and the roll-off property of water droplets. (Oil resistance ink property) The surface of the coating film was stained with a commercially available oil-based ink (red and black), and the state in which the surface of the coating film rebounded (rebound property) was evaluated as follows. 〇: Bounce and make the ink drop, unable to trace the pattern. △: The rebound is sluggish and not sufficient. X: No rebound at all, it can clearly trace the pattern. Next, the surface of the coating film contaminated with a commercially available oil-based ink was wiped with a dry gauze, and whether or not the wiping off was evaluated was as follows. 〇: Cleanly wiped away, leaving no trace at all. △: It is roughly wiped off, but some traces remain. X: Can't be erased at all. (Water Drop Rolling Property) The distilled water was dropped by a syringe on the surface of the coating film, and the water drop property from the horizontal state to the inclination of 10 degrees was evaluated as follows. 〇: I immediately rolled down and ran down. △: Flows slowly. X: Almost no movement. 28 201141623 The film hardness is just the wrong pen hardness. The 14-process was subjected to a bending test and an Erichsen test to evaluate = (3T bending test) 3T bending was performed at 20 C. The cracked and peeled state of the processed portion was observed with a 1× magnification magnifying glass, and evaluated as follows. 〇: Cracks (or peeling) are not visible at all. △: Fine cracks (or peeling) can be seen. Χ: Severe cracks (or peeling) can be seen. (EH ChSen 8 mm extrusion molding test) An Erichsen 8 mm extrusion process was carried out at 20 C to observe the cracked and peeled state of the processed portion by a double magnification mirror, and the evaluation was as follows. 〇: Cracks (or peeling) are not visible at all. △: Fine cracks (or peeling) can be seen. X: Severe cracks (or peeling) can be seen. Further, on the coating film which is processed by T-bending and Erichsen, the pattern is stained with red and black oily ink (commercially available), and then wiped with a dry gauze, whether it can be erased. The system is evaluated as follows. 〇: Cleanly wiped away, leaving no trace at all. △: It is roughly wiped off, but some traces remain. X: It cannot be erased at all. By this evaluation, it is confirmed by a magnifying glass whether or not the fine crack which cannot be confirmed by visual observation is entered into the outermost coating film. When a fine crack occurs, the oily ink will invade the base layer of the coating film from the crack and wipe off the smear. This evaluation is a more severe evaluation by visual observation by a magnifying glass. No. 29 201141623 Table 2, in the surface of the precoated steel sheet (invention example) of Example 4, with red and black oily ink (commercially available) The drawing pattern is followed, and the result of the dry wiping is shown in Fig. 4. An oily ink (commercially available) which was rebounded on the surface of the precoated steel sheet (invention example) was cleaned off. The surface of the precoated steel sheet (invention example) of Example 4 and the precoated steel sheet (comparative example) of Comparative Example 1 were compared with a pattern drawn by an oily ink (commercial product). The result is shown in Fig. 5. The pattern of the comparative example is shown in Fig. 5(a), and the pattern of the invention example is shown in Fig. 5(b). It was found that in the inventive example, the ink rebounded into a dot shape, and the desired pattern could not be drawn. Any of Examples 1 to 19 satisfies the requirements of the present invention, and has excellent oil repellency, water repellency, hardness and workability. In particular, Examples 1 to 7, 9, 10, 13, 15, and 17 to 19 were good. However, if observed carefully, in Example 8, since the film thickness of the base layer was thin, the color tone was slightly poor. In Example 11, pinholes were generated due to the thick total thickness of the coating film. In Example 12, the ratio of the base layer film thickness / (the outermost layer film thickness + the base layer film thickness) was slightly uneven due to the ratio of 〇3 〇 or less. In Example 14, since the baking temperature was low, the hardening was slightly insufficient. Further, in Example 16, since the baking severity was high, the heating was excessive and yellowing was slightly caused. On the other hand, in Comparative Example 1, the surface tension of the base paint was less than 25 mN/m. The difference in surface tension between the outermost layer forming paint and the base paint was not higher than 6 mN/m, and the value was negative. A mixed layer is formed between the two layers to form a streak-like appearance with poor appearance. In Comparative Example 2, the surface tension was poor, 丨 was 2.0 mN/m, and the surface tension was less than 6 mN/m, and the Ra of the interface of the outermost layer _ & was as high as 0·36 μη. This is presumed to be the largest surface of the coating film, and the smoothness is lowered. In Comparative Example 3, the surface tension of the base paint exceeded 35, and the multilayer curtain could not be formed and could not be coated. In Comparative Example 4, the surface tension of the outermost coating material exceeded 25, and the coating film after film formation could not exhibit oil repellency/water repellency. In Comparative Example 5, the surface tension of the outermost layer forming paint and the base paint was less than 6 mN/m', and the Ra of the interface became large, and the smoothness of the outermost layer was lowered due to the shadow formation, and the water drop rolling property was lowered. Next, the coating conditions of the multilayer curtain coating were changed to form a coating film. Using the same top coat and base paint as in Example 1, when the distance (L) between the lip portion (8a) and the metal plate (s) was set to 45 mrn, a coating defect occurred between the coating film and the metal plate. Where the lip (8a) is the point of departure from the multi-layer curtain coated coating. Further, in the same manner as in Example 丨, when the distance of the curtain coating machine was set to 18 〇 mm, the coating curtain was detached from the curtain guiding portion, and the curtain film could not be formed. Further, in the same coating and coating structure as in Example 4, the base coating was applied by a roll coating machine by means of 2 coating 2, and was baked at PMT 215 ° C, followed by a roll coating machine. When the upper layer was coated with the top coat and then baked with PMTUOC' to make a coated steel sheet and evaluated, the processability test showed the result of X. INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to provide a pre-coated metal sheet, and in addition to the beauty and the plethora, the watch s has the function of preventing the removal of the graffiti stick. 'And prevent ice. It has the function of snow, and has excellent formability that can follow the deformation of the metal plate. Further, according to the present invention, by increasing the formability of the outermost layer, the use of the pre-coated 31 201141623 metal plate can be extended to appliances with severe oil stains (such as range hoods) and appliances exposed to rain (drains, etc.). Invented in the pre-coated metal sheet manufacturing and utilization industry is highly available. [Circular Simple Description 3 Fig. 1 is a view showing one aspect of the layer structure of the precoated metal sheet. Fig. 2 is a view showing a state of cracking and peeling of a precoated metal sheet after bending. (a) indicates a state in which a crack is formed on the surface of the outermost layer, and (b) indicates a state in which the outermost layer is peeled off from the underlying layer. Fig. 3 is a view showing a state of a slide hopper type curtain coating device. Fig. 4 shows the results of investigating the oil repellency of the surface of the precoated steel sheet (invention example). Fig. 5 is a view showing a comparison of ink painting on the surface of a precoated steel sheet. The pattern of the comparative example is shown in Fig. 5(a), and the pattern of the invention example is shown in Fig. 5(b). [Description of main component symbols] 1...metal plate 2...plating layer 3...formation processing layer 4...primer layer 5...base layer 6...most surface layer 7...sliding funnel 8···inclined surface 8a...lips (coating point of separation) 9a, 9b, 9c...grooves 10a, 10b, 10c... paint supply unit 11a, lib... curtain guide 12...overcoat film 13...overcoat layer 14...Kyo Kun 15...Paint plate S···metal plating Plate or metal plate 32 with film