201105497 六、發明說明： 【發明所屬之^技^軒領与^】 發明領域 本發明係有關於—種耐損傷性優異之表面處理金屬 板。本發明之預塗覆金屬板係特別適用於以塗裝後進行成 形加工為前提之用途之已喊塗I有塗料之預塗覆金屬 板。 本發明之預塗覆金屬板可適用於諸如家電、建材、土 木、機械、汽車、家具、容器等用途。 L前才支制牙】 發明背景 塗覆有已著色之塗膜之預塗覆金屬板已逐漸取代習知 之加工後塗裝之後塗裝產品而使用於家電、建材、汽車等 用途。上述金屬板一般而言，係對金屬板施予化成處理再 塗覆塗料而成者，一般均在塗裝塗料後進行裁切並經加壓 成形而供作使用。 由於預塗覆金屬板之塗膜將在塗膜形成後進行成形加 工，故要求其加工性。為提昇塗膜之加工性，一般係採用 使用破璃轉化溫度較低、分子量較高之樹脂而使塗膜具備 柔軟性之技術，但上述塗膜在加工性優良之外相反地則 有硬度較低而易受損傷之問題。又’近年因設計觀點而要 求具備較佳光澤之塗裝鋼板 ，但高光澤塗膜之損傷較為明 顯，尚光澤度之耐損傷性便成一大問題。 解決上述問題之方法 ，已有專利文獻1所揭露之對金屬 201105497 板塗裝已對混合有玻璃轉化溫度5〜40〇c之聚酯樹脂與六甲 氧甲基三聚氰胺樹脂之聚酯.蜜胺塗膜混合十二烷基苯磺 酸之胺塊體而成之塗料塑性物，而使其乾燥以兼顧加工性 與高硬度之技術，又，專利文獻2已揭露對金屬板塗裝以具 有特定組成之化合物與聚醇、固化劑為主成分之預塗覆鋼 板用塗料，而兼顧加工性與高硬度之技術。又，專利文獻 3〜5中，則已揭露於塗膜中添加微粒子而提昇耐損傷性之技 術。 先行技術文獻 專利文獻 [專利文獻丨]特開平2-269168號公報 [專利文獻2]特開平7-31649 8號公報 [專利文獻3]特開平9-111183號公報 [專利文獻4]特開平1〇_219188號公報 [專利文獻5]特開平11-90322號公報 L 明内^^ 3 發明揭示 發明欲解決之課題 如上所述’近年雖已開發加工性優良且具而硬度之預 塗覆鋼板之塗膜，且均具備高硬度而不易受損傷，但無法 避免預塗覆鋼板與較塗膜堅硬之物磨擦及碰撞所導致塗膜 之損傷’ 一旦受損將永久殘留痕跡即成問題。因此，具備 尚加工性之預塗覆金屬板用塗膜之進一步改善耐損傷性已 備又期待’但由塗膜之硬度著眼而更為提昇硬度將使加工 4 201105497 性降低’故必要之喊傷性與加工性之高度兼顧咸認甚為 困難此外’於塗膜中添加微粒子而提昇耐損傷性之技術， 則除藉添加微粒子而提昇耐損傷性，相反地亦使光澤不 佳’而有影響色調之問題。 本發明係解決習知技術之上述問題之方法，並非單純 使塗膜高硬度化，而係著眼於使塗膜即便受損亦可隨時間 回復損傷部之塗膜變料使損傷消失，或使損傷部之塗膜 變形回復至目視日林甚賴讀度，目的在提供藉此功能 而兼顧耐損傷性與高加工性之預塗覆金屬板及其製造方 法0 本發明進而以藉本功能而完全不添加微粒子仍在光 澤佳、維持色調之狀態下賦與耐損傷性為目栌。 用以欲解決課題之手段 本發明人為解決上述問題而鑽研檢討之結果，發現不 僅塗膜具備樹脂彈性，且使該樹脂彈性具備特定之回復特 性，則即便該塗膜上產生凹陷或損傷（非塑性變形），亦可隨 時間經過而適當藉彈性回復。 結果，進而發現 柔軟性，加工性 本發明人基於上述發現而進而研究之 具備上述之特定之回復特性之塗膜亦具備 亦甚為優良。 具備上述各種特定之回復特性之塗膜可藉諸如就塗膜 树毅用麵轉化溫度為極低溫之以樹脂或料彈性體 而適當 祕月曰，並予以混合固化劑而構成熱固性塗膜樹脂， 實現。 、.曰， L S }. 5 201105497 本案發明係基於上述發現而完成者，本發明之要旨則 諸如以下所述。 (1) 一種耐損傷性優異之預塗覆金屬板，係於金屬板上 具有至少一層塗膜預塗覆金屬板，並於最表層具有一高彈 性塗膜，該高彈性塗膜係使用微小硬度計而在25°C之溫度 下對塗膜施予5mN之負載而壓入壓頭後除去該負載，測量 此時對壓頭施加之負載與壓入深度而求出之壓入深度回復 率α(α (DM —DE)xl〇〇/(DM —D0)，但D0 :剛對壓頭施予負 載後之壓人*度，Dm .對壓頭施加之負載已達時之壓 冰度DE. ^全除去壓頭之負载之前之壓人深度）為 乂上之回彈性塗膜’即便塗膜受損傷，塗膜亦將彈性回復 而使損傷消失或不甚明顯。 (2) 種耐損傷性優異之預塗覆金屬板，於最表層具有 前述損傷回復率：_85%以上之高彈性塗膜層。 (3) 如w述⑴及(2)之耐損傷性優異之預塗覆金屬板，前 述高彈性塗狀依據爆Κ5_·4领記載之鏡面光澤度在 幾何學條件60度下為9〇%以上。 一⑷如刖述⑴〜(3)之耐損傷性優異之預塗覆金屬板，前 述门彈H塗則目對於塗膜之主樹脂與固化劑之總和樹脂 100質量份而包含4質量份以下之微粒子。 如前述⑴〜(4)之耐損傷性優異之預塗覆金屬板，前 述ΓΪ彈f生塗膜之主;^脂係、對聚自旨樹脂或聚自旨彈性體樹脂之 任一種混合有固化劑而成之熱固性樹脂，且，主樹脂之玻 璃轉化溫度為一 1 〇°C以下。 201105497 。⑹如前述(5)之耐損傷性優異之預塗覆金屬板，前述高 彈性塗膜之主樹脂之玻璃轉化溫度為_3叱以下。 一⑺如刚述(5)〜⑹之财損傷性優異之預塗覆金屬板，前 述问彈性塗膜之主樹脂所混合之固化劑係蜜胺樹脂。 (8) 如4述（1)至（7)中任一項之耐損傷性優異之預塗覆 金屬板，前述預塗覆金屬板係於前述高彈性塗膜之下層設 有塗膜之2層以上之塗膜構造者。 (9) 如前述（1)至（8)中任一項之耐損傷性優異之預塗覆 金屬板’前述預塗覆金屬板中，最表層之高彈性塗膜係不 含顏料之透明型塗膜，且，該高彈性塗膜之下層設有著色 塗膜。 (10) 如前述(9)之耐損傷性優異之預塗覆金屬板，前述 著色膜之主樹脂係對聚酯樹脂或聚酯彈性體樹脂之任一者 混合有固化劑而成之熱固性樹脂，且，該主樹脂之玻璃轉 化溫度為一1〇。〇以下。 (11) 如前述（8)至（10)之耐損傷性優異之預塗覆金屬 板，前述高彈性塗膜層與位於其下層之塗膜層之界面之 Ra(中心線平均粗度）為〇 3〜〇 8。 (12) —種耐損傷性優異之預塗覆金屬板之製造方法，係 前述（8)至（丨^項之預塗覆金屬板之製造方法，於金屬板 上，將用以形成最上層之高彈性塗膜層之塗料與用以形成 其下之塗膜層之塗料在未乾燥狀態下加以積層，並使上述 未乾細狀態之多層塗裝獏同時乾燥固化。 發明效果 201105497 依據本發明，可提供較以往具備更優異耐損傷性之預 塗覆金屬板，在製造、組裝使用預塗覆金屬板而製造之家 電用、建材用、土木用、機械用、汽車用'家具用、容器 用之零件時，將不易發生加工損傷等，而提昇製造良率， 較習知材料容易加工卻不易發生加工損傷，因此可獲致提 昇作業效率等效果。又，使用本案發明之預塗覆金屬板， 與習知技術相較，加以使用之各產品之而ΐ損傷性已大幅提 昇，故產品之品質已獲提昇。故而，本發明可謂產業上之 價值極高之發明。 圖式簡單說明 第1圖係使用微小硬度計測得之對壓頭施加負載至 5mN而壓入塗膜，然後除去負載而至負載完全除去為止之 時間與壓入負載之關係。 第2圖係微小硬度計所測得之壓頭壓入深度與負載之 關係。 第3圖係就第2圖之資料進行零點修正後之壓頭壓入深 度與負載之關係。 第4圖係顯示塗膜界面之凹凸者。 【實施方式J 用以實施發明之形態 本發明係藉於金屬板上塗覆使用微小硬度計而在25°C 之溫度下對塗膜施予5mN之負載而壓入壓頭後除去該負 載，測量此時對壓頭施加之負載與壓入深度而求出之壓入 深度回復率：a(a=(DM —De)x100/(Dm — D〇) ’ 但D〇 :剛對壓 201105497 頭施予負載後之壓入深度，DM:對壓頭施加之負載已達5mN 時之壓入深度，DE :完全除去對壓頭施加之預定負載之前 之壓入深度）為70%以上之樹脂彈性塗膜，而使塗膜即便有 損傷亦可藉彈性回復而使損傷消失或不明顯。前述壓入深 度回復率若在70%以下，則實際上產生損傷之後該損傷減 至目視不明顯之私度之A將不回復，故不適用。前述壓入 深度回復率若為85%以上則更為適用。 本發明之預塗覆金屬板以微小硬度計測定塗膜物性 時，在（25+l)°C下測定所得之壓入深度回復率：以為川％以 上。 本發明之用以求出壓入深度回復率：微小硬度計可 使用一般可測定公知之塗膜等樹脂之硬度之微小硬度計。 Τ使用市售之測疋裝置諸如Fischer instruments出品之 FISCHERSCOPE H100V等。可使用德國0^503594所揭露 之方法。壓頭之形狀並無特別之限制，但可使用韋克斯四 角錐鑽石壓頭或Berkovich三角錐鑽石㈣、羅普鑽石壓 頭、碳化鎢製球壓頭等-般公知之壓頭。對壓頭施加負載 之方法及除去之方法亦可連續進行，或時而施加階段負載 時而加以除去。 本案發明中，用以求出壓入深度回復率：α之參數已定 義剛對壓祕加負倾之壓人深度為D。，而完全除去壓頭 之？载刖之壓入洙度為DE。D〇代表對壓頭施加負載前之塗 膜最=面之壓頭位置，即零點。實際之測定裝置難以精痛 檢出零點’故以藉測定裝置對壓頭施加負載而開始測定時 201105497 之初始檢出負載與壓入深度之壓頭位置為零點而設為D〇。 又代表除去壓頭之負載之過程中，完全除去負載之時 之壓頭位置（測試之終點）。由於測定裝置可能難以檢出壓頭 負載完全除去後之位置，故可將負載完全除去前之測定裝 置所檢出之位置設為DE。D0、DE雖可能因測定裝置而隨機 械精度之不同而不同，但可應用各個測定裝置之指示零點 或與其相當之點，以及測試之終點及與其相當之點。 貫際上，使用微小硬度計而測得之對壓頭施加負載至 5mN而壓入塗膜，然後除去負載而完全除去負載為止之時 間與壓入負載之關係顯示於第1圖，壓頭壓入深度與負載之 關係與D〇、DE、Dm之點顯示於第2及第3圖。第2圖係市售 之測定裝置之Fischer Instruments 出品之 FISCHERSCOPE H100V所測得之資料上之壓頭壓入深度與負載之關係及 D〇、DE、DM之點之例示。第3圖係顯示就第2圖之資料予以 零點修正後之壓頭壓入深度與負載之關係及D()、de、DM之 點者。 本案發明之預塗覆金屬板中，前述高彈性塗膜之主樹 脂係對聚酯樹脂或聚酯彈性體樹脂之任一種混合有固化劑 之熱固性樹脂，且，主樹脂之玻璃轉化溫度在— 1(rc以下， 則更佳。藉此’即可使高彈性塗膜之壓入深度回復率α為 700/。以上’且，塗膜之加工性亦可得確保之故。玻璃轉化 溫度若在一 1 〇°C以上’則塗膜之壓入深度回復率可能在 70%以下，故不適用^ —3〇。〇以下則更佳。主樹脂之玻璃 轉化溫度之下限雖未特別限定，由於玻璃轉化溫度過低 10 201105497 時，塗膜將過於柔軟而容易受破壞產生不易藉彈性回復之 損傷’故宜為一40°C以上。又，若使用聚酯樹脂或聚酯彈 性體以外之主樹脂，塗膜之加工性可能降低，故不適用。 又’若未於主樹脂混合固化劑，則成膜不充分而可能具有 黏著性，故不適用。 適合使用於本案發明之高彈性塗膜之主樹脂之聚酯樹 脂可使用一般公知者。市售者可使用諸如東洋紡公司出品 之聚酯樹脂「VYLON®」系列及住化Bayer Urethane出品之 聚S旨樹脂「Desmophen」系列等。聚酯彈性體亦可使用一般 公知者，諸如聚對苯二曱酸二丁酯等。 本案發明之高彈性塗膜之主樹脂所混合之固化劑可添 加一般公知之塗料用固化劑，諸如蜜胺樹脂及異氰酸酯等 之固化劑。市售者可使用諸如三井Cytec出品之蜜胺樹脂 「Cymel®」系列、「MYCOAT®」系列、DIC公司出品之蜜 胺樹脂「SUPER BECKAMINE®」系列、住化Bayer Urethane 出品之異氰酸酯「Sumidur®」系列、「Desmodur®」系列等。 前述固化劑若為蜜胺樹脂，塗膜之壓入深度回復率將 大於使用其它固化劑者，故較為適用。固化劑之添加量可 視需要而適當加以選定。若使用蜜胺樹脂，則宜相對主樹 脂100質量份而為1〇〜1〇〇質量份。若為1〇質量份以下，則塗 膜可能未固化，若為100質量份以上，膜體可能變脆而降低 加工性。固化劑添加有異氰酸酯時，宜添加至可使混合之 聚酯樹脂之OH基價與異氰酸酯之NCO基價之當量比為 OH/NC00.8〜HOH/NCO若在0.8以下或1<2以上，塗膜中 201105497 之主樹脂或固化劑中將殘留未反應之官能基，而可能導致 未固化。若添加而使OH/NCO為1.0，則塗膜中之主樹脂或 固化劑之未反應官能基不易殘留，膜體之硬度與加工性可 與硬度取得平衡，故較為適用。 本案發明之預塗覆金屬板若為積層2層以上之塗膜而 成之預塗覆金屬板，則若最上層之塗膜係前述高彈性塗 膜，除下層之塗膜所具備之功能外，亦可具備優良之财損 傷性，故較為適用。舉例言之，若為於金屬板上塗裝含有 防鏽顏料之底漆塗膜，並於其上塗裝有已著色之高彈性塗 膜之2層預塗覆金屬板，則除優良之耐蝕性以外，亦可具備 優良之耐損傷性。 本案發明之高彈性塗膜亦可著色。著色顏料中尤以添 加碳黑為佳，因其可提昇損傷回復性。此可推論係因樹脂 中添加碳黑，碳黑與樹脂之親和性甚強，故可提高塗膜之 彈性率而亦提昇損傷回復率之故。又，本案發明之高彈性 塗膜若完全不含微粒，或相對主樹脂與固化劑之總和全部 樹脂100質量份而為4質量份以下，則可在保持優良之耐損 傷性之狀態下提高光澤度，故較為適用。 又，若為於金屬板上塗裝已著色之底塗塗膜，並於其 上塗裝有透明之高彈性塗膜之2層預塗覆金屬板，則不僅具 備耐損傷性，亦可調色成各種顏色，且，可具備高光澤度。 又，於金屬板上塗裝含有防鏽顏料之底漆塗膜，並於其上 塗裝已著色之中塗塗膜，進而於其上塗裝高彈性塗膜，即 可具備耐蝕性、高光澤度及耐損傷性。最表層之高彈性塗 12 201105497 膜若為透明塗膜，則藉於習知之預塗覆金屬板上加以塗 裝，即可在習知之預塗覆金屬板所具備之塗膜性能之外， 亦具備耐損傷性，故較為適用。 最上層以外之塗膜可使用一般公知之預塗覆金屬板用 塗膜，諸如聚酯系塗膜、丙烯系塗膜、胺曱酸乙酯系塗膜、 環氧系塗膜等。亦可使用市售之預塗覆金屬板用塗膜。又， 最表層以外之塗膜亦可使用本案發明之高彈性塗膜。 本案發明之預塗覆金屬板之最上層之高彈性塗膜及其 它層之塗膜亦可視需要而添加著色顏料、防鏽顏料等顏 料。著色顏料則可使用氧化鈦、碳黑、鉻黃等一般公知之 無機系著色顏料或有機系著色顏料。 防鏽顏料則可使用鉻酸锶、鉻酸鉀、鉻酸鈣、三聚磷 酸二氫鋁、鈣吸附氧化矽、磷酸辞、亞磷酸辞等一般公知 之防鏽顏料。但，近年鉻酸锶、鉻酸鉀、鉻酸鈣等含有六 價鉻之防鏽顏料被視為環境負荷物質，故更宜使用不含此 類成分者。 又，本案發明之塗膜亦可視需要而添加消光劑、平滑 劑、消泡劑、光滑劑、壞等各種添加劑。 本案發明之預塗覆金屬板若為2層以上之塗膜積層而 成之預塗覆金屬板，予以加工，則加工後之高彈性塗膜内 容易殘留彈性之變形能量，故加工附著性可能降低。然而， 製造積層2層以上之塗膜而成之本案發明之預塗覆金屬板 時，若將用以形成最上層之高彈性塗膜層之塗料與用以形 成其下之塗膜層之塗料在未乾燥狀態下加以積層，並使上 13 201105497 述未乾燥狀態之多層塗裝膜同時乾燥固化，即藉所謂濕對 濕方法進行製造，則可提昇加工部位之塗膜附著性，而較 為適用》 採用多層同時塗佈或濕對濕塗裝，即可更適當地將界 面之Ra(中心線平均粗度)控制在〇·3〜。界面之Ra若在 0.3μιη以下，加工後之附著性不佳，〇·以上則可能發生 外觀瑕疵。界面之Ra可藉控制多層同時塗佈時或濕對濕塗 裝時已積層之各塗料之表面張力而實現。若〇 3mN/m$ [下 層側之塗料之表面張力]一[上層側之塗料之表面張 力]$5mN/m，則易使界面之Ra為0.3〜0.8μηι ’故較為適用。 [下層側之塗料之表面張力]一[上層側之塗料之表面張力] 若在0.3mN/m以下，界面之Ra可能在〇8gm以上，若為 5mN/m以上，則界面之Ra可能在〇 3μηι以下。另，本發明中， 上述界面之Ra可藉以下之方法（即，基本上遵循 JIS-B-0601-1982之方法）加以測定。亦即，為測定表面粗度 Ra，可以顯微鏡相片拍攝界面之垂直截面後，描繪界面之 凹凸（粗度曲線），再依循JIS_B_〇6〇1_1982所定之數式而求出 上述界面之中心線平均粗度Ra。 上述之濕對濕塗裝方法可採用藉輥塗機或淋幕塗佈機 塗層下層塗膜，並藉淋幕塗佈機塗裝最上層之高彈性塗膜 之方法，或使用滑動料斗式多層同時塗佈型淋幕塗佈機等 塗裝高彈性塗膜與其下之下層塗膜之方法等。又，該等已 塗裝之塗膜可藉熱風烘爐、紅外線爐、近紅外線爐、感應 加熱爐等而進行乾燥固化。 14 201105497 本案發明之高彈性塗膜層之膜厚並無特別之限制，可 視需要而適當加以選定，但宜為3〜25μιη。此因若在3μιη以 下，則而ί損傷性之效果可能無法充分發揮，若在25 μιη以 上，則烘乾塗膜時可能產生稱為起泡之塗裝瑕疵之故。本 案發明之預塗覆金屬板具有2層以上之塗膜層時，高彈性塗 膜層以外之塗膜層之膜厚亦宜為3〜25μηι。此因若在3μιη以 下，則可能無法發揮塗裝該塗膜層之效果，若在25μιη以 上，則烘乾塗膜時可能產生稱為起泡之塗裝瑕疵之故。 本案發明之預塗覆金屬板在金屬板上業經化成處理後 若塗覆塗膜，即可提昇塗膜附著性，故更為適用。化成處 理可採用一般公知之鉻酸處理、電解鉻酸處理、三價鉻處 理、磷酸鋅處理、氧化鍅系處理、市售之無鉻化成處理、 使用矽烷耦合劑之處理、包含矽烷耦合劑與水溶性樹脂之 化成處理等。鉻酸處理由於包含環境負荷物質之六價鉻， 故更宜採用不含此類物質之無鉻化成處理。該等化成處理 之處理方法雖可藉一般公知之塗佈方法進行塗佈，但使用 輥塗機進行塗佈，並藉乾燥器或烘爐進行乾燥，則可提昇 作業效率，故較為適用。 本案發明之預塗覆金屬板亦可於塗裝高彈性塗膜層之 面之背面上進行塗裝。背面塗裝可塗裝一般公知之預塗覆 金屬板用背面塗料，諸如聚酯系塗料、環氧系塗料、胺曱 酸乙酯系塗料、丙烯系塗料等。塗裝可僅為1層，亦可為2 層以上之塗裝。又，亦可塗裝本案發明之高彈性塗膜層。 本案發明之預塗覆金屬板所使用之金屬板可使用一般 15 201105497 公知之金屬板，諸如鋁板、銅版、鋼板、鍍敷鋼板、不鑛 鋼板等。採用鍍敷鋼板時，可使用熔融鋅鍍敷鋼板、鋅電 鍍鋼板 '鋅·鐵合金鍍敷鋼板、鋅-鎳合金鍍敷鋼板、鋅-55% 鋁合金鍍敷鋼板、鋅-13%鋁-3%鎂合金鍍敷鋼板、鋁鍍敷 鋼板等一般公知之鍍敷鋼板。該等金屬板可視需要而適當 選用。 [實施例] 以下，詳細說明實施例。 1. 金屬板 使用板厚〇.5mm之熔融鋅鍍敷鋼板。使用鋅附著量為 單面45g/m2者。 2. 化成處理液 製作含矽烷耦合劑5g/l、水分散型氧化矽i.〇g/i、水性 丙烯樹脂25g/l之水溶液’作為化成處理液。另，矽烷耦合 劑則使用γ-甘油酸丙基三甲氧基矽烧，微粒氧化矽使用日 產化學公司出品之「Snowtex-N」，水性丙浠樹脂則使用聚 丙稀酸。 3. 底漆塗料 對東洋紡公司出品之聚酯樹脂之「VYLON®290」（玻 璃轉化溫度72 C)按樹脂固悲部之質量份，相對聚醋樹脂固 態部100質量份而添加10質量份之三井Cytec出品之蜜胺樹 脂「Cymel®303」。進而，對該聚酯樹脂與蜜胺樹脂之混合 溶液添加0.5質量百分比之三井Cytec出品之酸性觸媒 「CatalystTM600」而製成透明塗料。再者，於該透明塗料 16 201105497 中相對聚酯樹脂與蜜胺樹脂之總和之樹脂固態部1 〇 〇質量 份而添加30質量份之TAYCA公司出品之三聚填酸二氫鋁 「K-WHITE®#105」，而製成底漆塗料。 4.中塗塗料 對東洋紡公司出品之聚酯樹脂之「VYLON®200」（玻璃 轉化溫度67 C)按樹脂固態部之質量比相對聚g旨樹脂固態 部1〇〇質量份而添加10質量份之三井Cytec出品之蜜胺樹脂 「Cymel®303」。進而，對該聚酯樹脂與蜜胺樹脂之混合溶 液添加0.5質量百分比之三井Cytec出品之酸性觸媒 「CatalystTM 600」而製成透明塗料。再者，於該透明塗料 中相對聚酯樹脂與蜜胺樹脂之總和之樹脂固態部1 〇 0質量 份而添加5質量份之東海CARBON公司出品之碳黑 「TOKABLACK#7300」而製成中塗塗膜（以下稱為「一般 中塗」）。又，對以聚對苯二曱酸二丁酯為主成分之Tg為 36°C之聚酯彈性體之環己酮溶解物，按樹脂固態部之質量 比而相對聚酯樹脂固態部100質量份添加20質量份之三井 Cytec出品之蜜胺樹脂「Cymel®303」，進而，對該聚酯樹脂 與蜜胺樹脂之混合溶液添加0.5質量百分比之三井Cytec出 品之酸性觸媒「Catalyst™ 600」並相對聚酯樹脂與蜜胺樹 脂之總和之樹脂固態部100質量份添加5質量份之東海 CARBON公司出品之碳黑「TOKABLACK#7300」，而製成 高彈性中塗塗料（以下稱為「高彈性中塗」）。 5.表塗塗料（高彈性塗料） 按固態部質量比率1 : 1之比例混合東洋紡公司出品之201105497 VI. Description of the Invention: [Technical Field] The present invention relates to a surface-treated metal sheet excellent in damage resistance. The precoated metal sheet of the present invention is particularly suitable for use in pre-coated metal sheets which have been coated with coatings for the purpose of forming after painting. The precoated metal sheet of the present invention can be suitably used for applications such as home appliances, building materials, civil engineering, machinery, automobiles, furniture, containers, and the like. BACKGROUND OF THE INVENTION Precoated metal sheets coated with a colored coating film have been gradually replaced by conventionally coated products after processing and used for home appliances, building materials, automobiles, and the like. Generally, the above-mentioned metal plate is obtained by subjecting a metal plate to a chemical conversion treatment and then coating the coating material, and generally, after coating the coating material, it is cut and press-formed for use. Since the coating film of the precoated metal sheet is subjected to forming processing after the coating film is formed, workability is required. In order to improve the processability of the coating film, a technique of using a resin having a low glass transition temperature and a high molecular weight to impart flexibility to the coating film is generally employed. However, the coating film is superior in workability, and vice versa. Low and vulnerable to damage. In addition, in recent years, coated steel sheets having a better gloss have been demanded from the viewpoint of design, but the damage of the high-gloss coating film is conspicuous, and the damage resistance of the glossiness is a major problem. In order to solve the above problems, the metal 201105497 plate coated with the polyester resin and the hexamethoxymethyl melamine resin mixed with the glass transition temperature of 5 to 40 〇c has been coated with the polyester. A technique in which a film is mixed with an amine block of dodecylbenzenesulfonic acid to form a plastic, and the film is dried to achieve both workability and high hardness. Further, Patent Document 2 discloses that a metal plate is coated to have a specific composition. The compound is a coating material for pre-coated steel sheets containing a polyalcohol or a curing agent as a main component, and a process which combines workability and high hardness. Further, in Patent Documents 3 to 5, a technique of adding fine particles to a coating film to improve the scratch resistance has been disclosed. [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei 9-111183 (Patent Document 3) Japanese Patent Publication No. Hei 9-111183 (Patent Document 4) [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei No. Hei 11-90322. The present invention discloses a problem to be solved by the invention. As described above, in recent years, pre-coated steel sheets having excellent workability and hardness have been developed. The coating film has high hardness and is not easily damaged, but it is impossible to avoid the damage of the coating film caused by the friction and collision between the pre-coated steel sheet and the hard coating of the coating film. Therefore, it is necessary to further improve the damage resistance of the coating film for pre-coated metal sheets which are still workable. However, it is necessary to increase the hardness by the hardness of the coating film and to reduce the hardness of the processing. The high degree of damage and workability is difficult to understand. In addition, the technique of adding fine particles to the coating film to improve the damage resistance improves the damage resistance by adding microparticles, and vice versa. Affect the problem of hue. The present invention is a method for solving the above-mentioned problems of the prior art, and does not simply increase the hardness of the coating film, but pays attention to the fact that even if the coating film is damaged, the coating film of the damaged portion can be recovered over time to cause the damage to disappear, or The coating film deformation of the damaged portion is restored to the visual degree, and the purpose is to provide a pre-coated metal sheet having the function of both the damage resistance and the high workability, and the manufacturing method thereof. It is a goal to impart damage resistance even in the state where the gloss is good and the color tone is maintained without adding the fine particles at all. Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that not only the coating film has resin elasticity, but also the resin has elasticity with specific recovery characteristics, even if there is a depression or damage on the coating film (non- Plastic deformation), and can also be elastically recovered by time. As a result, it has been found that the coating film having the specific recovery characteristics described above, which has been further studied by the present inventors based on the above findings, is also excellent. The coating film having the above various specific recovery characteristics can be formed into a thermosetting coating resin by, for example, applying a resin or a material elastomer to a coating film having a surface temperature of a very low temperature, and mixing the curing agent. achieve. , 曰, L S }. 5 201105497 The invention of the present invention has been completed based on the above findings, and the gist of the present invention is as follows. (1) A pre-coated metal sheet excellent in damage resistance, comprising at least one coating film precoated metal sheet on a metal sheet, and having a high elastic coating film on the outermost layer, the high elastic coating film being used in a small amount The hardness tester applied a load of 5 mN to the coating film at a temperature of 25 ° C, and the load was removed by pressing the indenter, and the depth of penetration of the indentation depth obtained by applying the load to the indenter and the depth of the indentation at this time was measured. α(α (DM —DE)xl〇〇/(DM —D0), but D0: the pressure of the pressure applied to the indenter, Dm. The load applied to the indenter has reached the degree of crushing. DE. ^Before removing the load of the indenter, the depth of the pressing is the elastic coating film on the crucible. Even if the coating is damaged, the coating will elastically recover and the damage will disappear or be less noticeable. (2) A precoated metal sheet excellent in damage resistance has a high elastic coating layer having a damage recovery rate of _85% or more in the outermost layer. (3) If the pre-coated metal sheet with excellent damage resistance is described in (1) and (2), the high-elastic coating shape according to the bursting 5_·4 has a specular gloss of 9〇% at a geometric condition of 60 degrees. the above. (4) The pre-coated metal sheet having excellent damage resistance as described in (1) to (3), wherein the door shot H coating is contained in an amount of 4 parts by mass or less based on 100 parts by mass of the total resin of the main resin and the curing agent of the coating film. Microparticles. The pre-coated metal sheet excellent in damage resistance as described in the above (1) to (4) is mainly composed of the above-mentioned sputum-foil coating film, and is a mixture of any of the resin or the self-adhesive resin. A thermosetting resin made of a curing agent, and the glass transition temperature of the main resin is 1 〇 ° C or less. 201105497. (6) The pre-coated metal sheet excellent in damage resistance according to the above (5), wherein the glass transition temperature of the main resin of the high elastic coating film is _3 Å or less. (7) A pre-coated metal sheet having excellent damage properties as described in (5) to (6), wherein the curing agent mixed with the main resin of the elastic coating film is a melamine resin. (8) The precoated metal sheet excellent in damage resistance according to any one of (1) to (7), wherein the precoated metal sheet is provided with a coating film under the high elastic coating film. The coating film structure above the layer. (9) The precoated metal sheet excellent in damage resistance according to any one of the above (1) to (8), wherein the outermost layer of the highly elastic coating film is a pigment-free transparent type The film is coated, and a layer of a color coating film is provided under the high elastic coating film. (10) The precoated metal sheet excellent in damage resistance according to the above (9), wherein the main resin of the colored film is a thermosetting resin obtained by mixing a curing agent with any of a polyester resin or a polyester elastomer resin. And, the main resin has a glass transition temperature of one 〇. 〇The following. (11) The pre-coated metal sheet excellent in damage resistance according to the above (8) to (10), wherein the Ra (center line average thickness) of the interface between the high elastic coating layer and the coating layer at the lower layer is 〇3~〇8. (12) A method for producing a precoated metal sheet excellent in damage resistance, which is the method for producing a precoated metal sheet according to the above (8) to (a), which is used for forming an uppermost layer on a metal plate The coating of the high elastic coating layer and the coating for forming the coating layer thereunder are laminated in an undried state, and the multi-layer coating of the above-mentioned undried state is simultaneously dried and solidified. Effect of the invention 201105497 According to the present invention It can provide pre-coated metal sheets with better damage resistance than conventional ones, and can be used for home appliances, building materials, civil engineering, machinery, automotive, furniture, and containers manufactured by using pre-coated metal sheets. When the parts are used, it is less likely to cause processing damage, etc., and the manufacturing yield is improved, and the processing material is easier to process than the conventional materials, but the processing damage is less likely to occur, so that the effect of improving the work efficiency can be obtained. Further, the precoated metal sheet of the present invention is used. Compared with the prior art, the damage of each product has been greatly improved, so the quality of the product has been improved. Therefore, the present invention is an industry of high value. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a relationship between the time when a load is applied to a head by a micro hardness tester and the load is applied to a film of 5 mN, and then the load is removed until the load is completely removed, and the load is applied. The relationship between the indentation depth and the load measured by the micro hardness tester. Fig. 3 is the relationship between the indenter depth and the load after the zero point correction is performed on the data in Fig. 2. Fig. 4 shows the coating film interface. [Embodiment J] The present invention is a method for carrying out the invention. The present invention is applied by applying a microhardness tester to a metal plate and applying a load of 5 mN to the coating film at a temperature of 25 ° C to be pressed into the indenter. The load is measured by the load applied to the indenter at this time and the depth of penetration of the indentation depth: a (a = (DM - De) x 100 / (Dm - D〇) ' But D〇: just right Pressure 201105497 The depth of penetration after the head is applied to the load, DM: the depth of penetration when the load applied to the indenter has reached 5 mN, and DE: the depth of penetration before the predetermined load applied to the indenter is completely 70% or more. The resin elastic coating film, so that the coating film can be elastic even if it is damaged If the recovery depth recovery rate is less than 70%, the A which is actually reduced to visually inconspicuous after the damage is actually generated will not be recovered, so it is not applicable. When the depth recovery rate is 85% or more, it is more suitable. When the precoated metal sheet of the present invention is used to measure the physical properties of the coating film by a micro hardness tester, the indentation depth recovery rate measured at (25 + 1) ° C is considered: In the present invention, the indentation depth recovery rate can be obtained: a micro hardness tester can be used as a micro hardness tester which can generally measure the hardness of a resin such as a known coating film. Τ Use a commercially available measuring device such as Fischer instruments. FISCHERSCOPE H100V, etc. The method disclosed in German 0^503594 can be used. The shape of the indenter is not particularly limited, but a well-known indenter such as a Wexs quadrangle diamond indenter or a Berkovich triangular pyramid diamond (four), a Ropp diamond indenter, and a tungsten carbide ball indenter may be used. The method of applying a load to the indenter and the method of removing it may be carried out continuously or when a stage load is applied from time to time. In the invention of the present invention, the parameter for determining the indentation depth recovery rate: α has been defined as the pressure depth of the pressurization plus the negative pressure. And completely remove the indenter? The pressing force of the load is DE. D〇 represents the position of the head of the coating film before the load is applied to the indenter, ie, the zero point. In actual measurement equipment, it is difficult to detect the zero point. Therefore, when the measurement is started by applying a load to the indenter by the measuring device, the head position of the initial detection load and the indentation depth of 201105497 is zero, and is set to D〇. It also represents the position of the indenter at the time of the load removal (end of the test) during the removal of the load of the indenter. Since it is difficult for the measuring device to detect the position after the indenter load is completely removed, the position detected by the measuring device before the load is completely removed can be set to DE. Although D0 and DE may differ depending on the randomness of the measuring device, the indication zero of each measuring device or a point corresponding thereto, and the end point of the test and the point corresponding thereto may be applied. The relationship between the time when the load is applied to the indenter and the load is applied to the indenter and the load is completely removed, and the relationship between the time and the indentation load is shown in Fig. 1, the indenter pressure is shown in Fig. 1 . The relationship between the depth of entry and the load and the points of D〇, DE, and Dm are shown in the second and third figures. Fig. 2 is an illustration of the relationship between the indentation depth of the indenter and the load and the points of D〇, DE, and DM on the data measured by FISCHERSCOPE H100V by Fischer Instruments, which is a commercially available measuring device. Fig. 3 shows the relationship between the indentation depth of the indenter and the load and the points of D(), de, and DM after zero correction of the data in Fig. 2. In the precoated metal sheet of the present invention, the main resin of the high elastic coating film is a thermosetting resin in which a curing agent is mixed with any one of a polyester resin or a polyester elastomer resin, and the glass transition temperature of the main resin is - 1 (more preferably rc or less. By this, the depth-recovery rate α of the high-elasticity coating film can be made 700/. or more), and the workability of the coating film can be ensured. In the case of more than 1 〇 ° C, the depth of penetration of the coating film may be less than 70%, so it is not applicable to ^ 3 〇. The following is more preferable. The lower limit of the glass transition temperature of the main resin is not particularly limited. Since the glass transition temperature is too low at 10 201105497, the coating film will be too soft and easily damaged, resulting in damage that is not easily recovered by elastic recovery. Therefore, it is preferably 40 ° C or more. Also, if polyester resin or polyester elastomer is used. The main resin and the coating film may have reduced workability, so it is not suitable. If the curing agent is not mixed with the main resin, the film formation may be insufficient and the adhesiveness may be applied. Therefore, it is not suitable for use in the high elastic coating of the present invention. Membrane tree The polyester resin can be used by a general public, and a commercially available one can use a polyester resin "VYLON®" series produced by Toyobo Co., Ltd., and a "S Desmophen" series of a resin which is produced by Bayer Urethane. A generally known one may be used, such as dibutyl terephthalate or the like. The curing agent mixed with the main resin of the high elastic coating film of the present invention may be added with a generally known curing agent for coatings such as melamine resin and isocyanate. Curing agent. Commercially available melamine resin "Cymel®" series from Mitsui Cytec, "MYCOAT®" series, DIC's melamine resin "SUPER BECKAMINE®" series, and Isochemical Bayer Urethane isocyanate "Sumidur®" series, "Desmodur®" series, etc. If the curing agent is melamine resin, the depth of penetration of the coating film will be greater than that of other curing agents, so it is suitable. The amount of curing agent can be added as needed. When melamine resin is used, it is preferably 1 part by mass to 1 part by mass based on 100 parts by mass of the main resin. The coating film may be uncured, and if it is 100 parts by mass or more, the film may become brittle and the workability may be lowered. When the curing agent is added with an isocyanate, it is preferably added to the NCO group of the OH group and the isocyanate of the mixed polyester resin. When the equivalent ratio of the valence is OH/NC00.8 to HOH/NCO, if it is 0.8 or less or 1 < 2 or more, unreacted functional groups remain in the main resin or curing agent of 201105497 in the coating film, which may cause uncured. When the OH/NCO is 1.0, the unreacted functional groups of the main resin or the curing agent in the coating film are not easily left, and the hardness and workability of the film are balanced with the hardness, which is suitable. In the case where the precoated metal sheet of the present invention is a precoated metal sheet in which a coating film of two or more layers is laminated, if the coating film of the uppermost layer is the high elastic coating film, the function of the coating film of the lower layer is excluded. It can also have good financial damage, so it is more suitable. For example, if a primer coating film containing an anti-rust pigment is applied to a metal plate and a 2-layer pre-coated metal plate coated with a highly colored elastic coating film is applied thereon, in addition to excellent corrosion resistance, In addition to sex, it can also have excellent damage resistance. The highly elastic coating film of the present invention can also be colored. It is preferable to add carbon black to the coloring pigment because it can improve the recovery of damage. It can be inferred that the carbon black is added to the resin, and the affinity between the carbon black and the resin is strong, so that the elastic modulus of the coating film can be improved and the damage recovery rate can be improved. In addition, if the high-elasticity coating film of the present invention contains no fine particles or is contained in an amount of 4 parts by mass or less based on 100 parts by mass of the total of the total resin and the curing agent, the gloss can be improved while maintaining excellent damage resistance. Degree, so it is more suitable. Moreover, if a colored primer coating film is applied to a metal plate and a two-layer precoated metal plate coated with a transparent high elastic coating film is applied thereon, not only damage resistance but also adjustment can be adjusted. The color is various colors and can have high gloss. In addition, a primer coating film containing an anti-rust pigment is applied to a metal plate, and a colored coating film is applied thereon, and a high-elastic coating film is coated thereon to provide corrosion resistance and high gloss. Degree and damage resistance. The highest surface elastic coating 12 201105497 If the film is a transparent coating film, it can be coated on a conventional pre-coated metal plate, which can be used in the coating properties of the conventional pre-coated metal plate. It is resistant to damage and is therefore suitable. As the coating film other than the uppermost layer, a generally known coating film for precoated metal sheets such as a polyester coating film, a propylene coating film, an amine phthalate coating film, an epoxy coating film, or the like can be used. A commercially available coating film for precoated metal sheets can also be used. Further, the highly elastic coating film of the present invention can also be used for the coating film other than the outermost layer. The uppermost layer of the highly elastic coating film of the precoated metal sheet of the present invention and the coating film of the other layer may be added with a pigment such as a coloring pigment or an antirust pigment as needed. As the coloring pigment, a generally known inorganic coloring pigment such as titanium oxide, carbon black or chrome yellow or an organic coloring pigment can be used. As the rust preventive pigment, generally known rust preventive pigments such as strontium chromate, potassium chromate, calcium chromate, aluminum dihydrogen phosphate, calcium absorbing cerium oxide, phosphoric acid, and phosphorous acid can be used. However, in recent years, anti-rust pigments containing hexavalent chromium such as strontium chromate, potassium chromate, and calcium chromate are considered as environmentally hazardous substances, so those containing no such components are more suitable. Further, the coating film of the present invention may be added with various additives such as a matting agent, a smoothing agent, an antifoaming agent, a smoothing agent, and a bad one as needed. In the case where the precoated metal sheet of the present invention is a precoated metal sheet formed by laminating two or more layers of coating film, the elastic deformation energy is likely to remain in the highly elastic coating film after processing, so that the processing adhesion may be reduce. However, when a precoated metal sheet of the present invention is formed by laminating a coating film of two or more layers, the coating for forming the uppermost highly elastic coating layer and the coating for forming the coating layer thereunder are formed. Lamination is carried out in an undried state, and the multi-layer coating film of the above-mentioned 13 201105497 undried state is simultaneously dried and solidified, that is, by the so-called wet-to-wet method, the coating adhesion of the processed portion can be improved, and is more suitable. 》 With multi-layer simultaneous coating or wet-on-wet coating, the Ra of the interface (center line average roughness) can be more appropriately controlled at 〇·3~. If the Ra of the interface is 0.3 μm or less, the adhesion after processing is not good, and the appearance may be 〇. The Ra of the interface can be achieved by controlling the surface tension of each of the coatings which have been laminated at the time of simultaneous coating or wet-on-wet coating. If 〇 3mN/m$ [surface tension of the coating on the lower layer] - [surface tension of the coating on the upper layer] is $5mN/m, it is easy to make the Ra of the interface 0.3 to 0.8μηι ‘. [Surface tension of the coating on the lower layer] - [surface tension of the coating on the upper layer] When the thickness is 0.3 mN/m or less, the Ra of the interface may be 〇8 gm or more, and if it is 5 mN/m or more, the Ra of the interface may be 〇 3μηι or less. Further, in the present invention, Ra of the above interface can be measured by the following method (i.e., substantially following the method of JIS-B-0601-1982). That is, in order to measure the surface roughness Ra, the vertical section of the interface can be photographed by a microscope photograph, and the unevenness (thickness curve) of the interface can be drawn, and the center line of the interface can be obtained according to the number formula determined by JIS_B_〇6〇1_1982. Average roughness Ra. The wet-on-wet coating method described above may be a method of coating a lower layer coating film by a roll coater or a curtain coater, and coating the uppermost layer of the high elastic coating film by a curtain coater, or using a sliding hopper type. A multi-layer simultaneous coating type curtain coater or the like for coating a high-elasticity coating film and a lower-layer coating film thereof. Further, the coated coating film can be dried and solidified by a hot air oven, an infrared furnace, a near infrared furnace, an induction heating furnace or the like. 14 201105497 The film thickness of the highly elastic coating layer of the present invention is not particularly limited, and may be appropriately selected as needed, but is preferably 3 to 25 μm. If the reason is below 3 μm, the effect of 损伤 damage may not be fully exerted. If it is 25 μm or more, a coating called blistering may occur when the film is dried. When the precoated metal sheet of the present invention has a coating layer of two or more layers, the film thickness of the coating layer other than the high elastic coating layer is preferably from 3 to 25 μm. If the reason is 3 μm or less, the effect of coating the coating layer may not be exhibited, and if it is 25 μm or more, a coating film called foaming may occur when the coating film is dried. The pre-coated metal sheet of the invention of the present invention is more suitable for use in a metal sheet after being chemically processed, and if the coating film is applied, the adhesion of the coating film can be improved. The chemical conversion treatment can be generally known as chromic acid treatment, electrolytic chromic acid treatment, trivalent chromium treatment, zinc phosphate treatment, lanthanum oxide treatment, commercially available chromium-free chemical conversion treatment, treatment with decane coupling agent, and decane coupling agent. Chemical treatment of water-soluble resin. Since chromic acid treatment contains hexavalent chromium which is an environmentally hazardous substance, it is more preferable to use a chromium-free chemical conversion treatment which does not contain such a substance. Although the treatment method of the chemical conversion treatment can be carried out by a generally known coating method, it is preferably applied by coating with a roll coater and drying it by a dryer or an oven to improve work efficiency. The precoated metal sheet of the present invention may also be coated on the back side of the surface on which the highly elastic coating layer is applied. The backside coating can be applied to a commonly known back coating for precoated metal sheets, such as a polyester coating, an epoxy coating, an amine phthalate coating, an acrylic coating, and the like. The coating can be applied to only one layer or two or more layers. Further, the highly elastic coating layer of the invention of the present invention can also be applied. The metal plate used for the precoated metal sheet of the present invention can be a metal plate generally known as 15 201105497, such as an aluminum plate, a copper plate, a steel plate, a plated steel plate, a non-mineral steel plate or the like. When using a plated steel plate, a molten zinc plated steel plate, a zinc plated steel plate, a zinc-iron alloy plated steel plate, a zinc-nickel alloy plated steel plate, a zinc-55% aluminum alloy plated steel plate, or a zinc-13% aluminum-3 can be used. A commonly known plated steel sheet such as a % magnesium alloy plated steel sheet or an aluminum plated steel sheet. These metal plates can be suitably selected as needed. [Examples] Hereinafter, examples will be described in detail. 1. Metal plate A molten zinc plated steel plate having a thickness of 55 mm is used. The amount of zinc adhered was 45 g/m2 on one side. 2. Chemical treatment liquid A 5 g/l of a decane coupling agent, a water-dispersed cerium oxide i.〇g/i, and an aqueous propylene resin 25 g/l aqueous solution were prepared as a chemical conversion treatment liquid. Further, the decane coupling agent is gamma-glyceric acid propyltrimethoxy fluorene, the particulate cerium oxide is "Snowtex-N" produced by Nissan Chemical Co., Ltd., and the aqueous acryl resin is polyacrylic acid. 3. Primer coating "VYLON® 290" (glass transition temperature 72 C) of the polyester resin produced by Toyobo Co., Ltd. is added in an amount of 10 parts by mass based on 100 parts by mass of the solid portion of the polyester resin in terms of the mass portion of the resin solid portion. The melamine resin "Cymel® 303" produced by Mitsui Cytec. Further, a 0.5% by mass of an acid catalyst "CatalystTM 600" produced by Mitsui Cytec was added to the mixed solution of the polyester resin and the melamine resin to prepare a clear coating. Further, in the transparent coating material 16 201105497, 30 parts by mass of the trimeric acid-filled dihydrogen aluminum "K-WHITE" produced by TAYCA Co., Ltd. is added to the resin solid portion of the sum of the polyester resin and the melamine resin. ®#105", which is made into a primer coating. 4. In the intermediate coating, the "VYLON® 200" (glass transition temperature: 67 C) of the polyester resin produced by Toyobo Co., Ltd. is added in an amount of 10 parts by mass based on the mass ratio of the solid portion of the resin to the solid portion of the resin. The melamine resin "Cymel® 303" produced by Mitsui Cytec. Further, a 0.5% by mass of an acid catalyst "CatalystTM 600" produced by Mitsui Cytec was added to the mixed solution of the polyester resin and the melamine resin to prepare a clear coating. In addition, 5 parts by mass of carbon black "TOKABLACK #7300" produced by Tokai CARBON Co., Ltd. was added to the resin solid portion of the total of the polyester resin and the melamine resin in the clear coating to prepare a medium coating. Membrane (hereinafter referred to as "general intermediate coating"). Further, the cyclohexanone solute of the polyester elastomer having a Tg of 36 ° C which is mainly composed of dibutyl terephthalate as a main component is 100 parts by mass of the solid portion of the polyester resin in terms of the mass ratio of the solid portion of the resin. 20 parts by mass of the melamine resin "Cymel® 303" produced by Mitsui Cytec was added, and 0.5% by mass of the acid catalyst "CatalystTM 600" produced by Mitsui Cytec was added to the mixed solution of the polyester resin and the melamine resin. And adding 5 parts by mass of carbon black "TOKABLACK #7300" produced by Tokai CARBON Co., Ltd. to 100 parts by mass of the resin solid portion of the sum of the polyester resin and the melamine resin, and producing a highly elastic intermediate coating (hereinafter referred to as "high elasticity"中涂"). 5. Surface coating (highly elastic coating) Mixed by Toyobo Co., Ltd. according to the mass ratio of solid part 1: 1
I 17 201105497 聚酯樹脂「VYLON®290」（玻璃轉化溫度5。〇)與 「VYLON®550」（玻璃轉化溫度〜15t)，加以溶解於環己 酮：SOLVESSO150=l : 1而混合之溶劑（質量比）並予以搜掉 製成玻璃轉化溫度（以下稱為Tg)—1〇<t之聚酯樹脂之溶劑 溶解物。3，本樹脂係使已製成之溶劑溶解物之溶劑部^ 揮發後再藉熱分析法調查玻璃轉化溫度，而確認乃—1〇七 又，亦已製成僅將東洋紡公司出品之聚酯樹脂 「VYLON®55G」（玻璃轉化溫度—15。〇溶解於環已網： SOLVESSO150=l: 1而混合之溶劑（質量比）之丁§為—15它之 聚酯樹脂之溶劑溶解物。 進而，亦製成以聚對笨二曱酸二丁酯為主成分之丁§為 — 36°C之聚酯彈性體之環己酮溶解物。 另，亦製成僅將東洋紡公司出品之聚酯樹脂 「VYLON®290」（玻璃轉化溫度5<5(：)溶解於環己鲖： SOLVESSO150=l : 1而混合之溶劑（質量比）之Tg為5。匸之聚 酯樹脂之溶劑溶解物，以供比較之用。 其次，對製成之各聚酯或聚酯彈性體之溶解物按樹脂 固態部之質量比而相對聚酯樹脂固態部100質量份添加 5〜120質重份之二井Cytec出品之蜜胺樹脂「Cymel⑧3〇3」， 而製成蜜胺樹脂添加量不同之聚㈣脂/蜜胺樹脂之混合 用液。進而’對该聚酿樹脂與蜜胺樹脂之混合溶液添加〇5 質莖百分比之二井Cytec出品之酸性觸媒「CatalystTM6〇〇」 而製成蜜胺固化型之透明塗料。χ，對已製成之各聚醋或 聚醋彈性體之溶解物按聚顆樹脂之ΟΗ基價與異氰酸酷樹 201105497 脂之NCO基價之當量比為〇H/NCO=l .〇之條件混合住化 Bayer Urethane出品之異氰酸酯樹脂「Sumidur®BL3175」。 進而’視需要而於上述透明塗料中添加了東海carbon公 司出品之碳黑「TOKABLACK#7300」、日本AEROSIL公司 出品之氧化矽「AEROSILTM200」、ATOChimie公司出品之 尼龍微粒子「〇rgas〇12002EX-D」、鐘紡公司出品之酚樹脂 微粒子「BELLPEARLR800」。 6. 背面塗料 已準備曰本ΠΝΕ COATINGS公司出品之背面塗料， OrgalOO之米黃色。 7. 預塗覆鋼板之製作 將金屬板浸潰於FC_4366(曰本Parkedzing出品）之2質 量百分比濃度、6〇t：溫度之水溶液中1〇秒而進行脫脂，水 洗後再進行乾燥。其次，藉輥塗機於金屬板之兩面上塗佈 化成處理液，並藉熱風乾燥爐進行乾燥作業而製得化成處 理膜層。塗裝係使化成處理液之附著量達到乾燥膜整體之 附著量為lGGmg/m2者。化成處理乾燥時之到達板溫為6〇t> 其次，於業經化成處理之金屬板表面上藉輥塗機塗裴 底漆塗料以使乾燥膜厚為5μιη，進而於另—面上藉輥塗機 塗裝背面塗料以使塗裝膜厚為一，再藉吹入熱風之感應 加熱爐在金屬板之到達板溫為2nrc之條件下進行乾燥固 化而製得塗膜層。乾燥烘乾後則對已塗裝之金屬板噴水而 進行擦沖、水冷。進而，於底漆塗膜上藉滑動料斗式淋幕 塗佈機進行中塗塗料與面塗塗料之多層同時積層塗佈，再 19 201105497 藉人入熱風之感應加熱爐按金屬板之到達板溫為23〇乞之 條件同時乾燥洪乾已積層之塗料，再予水冷而製得試樣之 預塗覆金屬板(本方法所製作之預塗覆鋼板以下稱為「3塗2 烘」或「3C2B」）。另，藉滑動料斗式淋幕塗佈機進行塗裝 時，於面塗塗料中適量添加ΒΥΚ公司出品之添加材 「ΒΥΚ-333」而逐次調整使面塗塗膜之表面張力較共同積 層之中塗塗料之表面張力高3mN/m。 又，亦視需要而於底塗塗膜上藉輥塗機塗裝中塗塗 料，並藉吹入熱風之感應加熱爐在金屬板之到達板溫為 230 C之條件下同時進行乾燥烘乾，再於水冷後於其上藉幸昆 塗機塗裝表塗塗料，然後藉吹入熱風之感應加熱爐在鋼板 之到達板溫為230°C之條件下同時進行乾燥烘乾、水冷，而 製得試樣之預塗覆鋼板（本方法製作之預塗覆金屬板以下 稱為「3塗3烘」或「3C3B」）。 又’本發明之預塗覆金屬板樣本之生產線係僅包含2個 烘爐之2烘爐線，故製作3C3B之樣本時，係經2次生產線之 處理而製作樣本。又，亦視需要而製作了不含底漆塗膜層、 中塗塗膜層之1塗1烘（1C1B)及2塗2烘(2C2B)之樣本。另， 已製作了中塗塗膜塗裝成乾燥膜厚15μηι，且表塗塗膜之膜 厚已改變者。 已製作之預塗覆鋼板之詳情整理於表1。 ‘ 20 201105497 表1I 17 201105497 Polyester resin "VYLON® 290" (glass transition temperature 5. 〇) and "VYLON® 550" (glass transition temperature ~ 15t), dissolved in cyclohexanone: SOLVESSO150 = l: 1 mixed solvent ( The mass ratio) was searched for a solvent solute of a polyester resin having a glass transition temperature (hereinafter referred to as Tg) - 1 〇 < t. 3. The resin is obtained by volatilizing the solvent portion of the prepared solvent solution, and then investigating the glass transition temperature by thermal analysis, and confirming that it is -1〇7, and has also made polyester which only produces Toyobo Co., Ltd. Resin "VYLON® 55G" (glass transition temperature - 15. 〇 dissolved in the ring network: SOLVESSO150 = l: 1 and the mixed solvent (mass ratio) is § § 15 its solvent solution of polyester resin. It is also made into a cyclohexanone solute of a polyester elastomer which is mainly composed of poly(p-butyl phthalate) and is a polyester elastomer of 36 ° C. In addition, it is also made into a polyester which only produces from Toyobo Co., Ltd. Resin "VYLON® 290" (glass transition temperature 5 < 5 (:) dissolved in cyclohexane: SOLVESSO 150 = 1: 1 and the solvent (mass ratio) of Tg is 5. The solvent solution of the polyester resin of 匸, For comparison, the second solution of the polyester or polyester elastomer prepared is added in an amount of 5 to 120 parts by weight based on the mass ratio of the solid portion of the resin to 100 parts by mass of the solid portion of the polyester resin. The melamine resin "Cymel83〇3" is produced, and the amount of melamine resin added is different. a mixture of poly(iv) fat/melamine resin. Further, 'the mixture of the blended resin and the melamine resin is added to the acid catalyst "CatalystTM 6" produced by the second well Cytec, which is a percentage of the sputum resin and the melamine resin. Amine-curable clear coating. χ, the ratio of the valence of the phenolic base of the poly-resin to the NCO base of the isocyanate 201105497 grease is 溶解In the case of H/NCO=l., the isocyanate resin "Sumidur® BL3175" produced by Bayer Urethane was mixed with the carbon black "TOKABLACK #7300" produced by Tokai Carbon Co., Ltd., Japan. The AEROSILTM 200 produced by AEROSIL, the nylon granules “〇rgas〇12002EX-D” produced by ATOChimie, and the phenol resin granule “BELLPEARLR800” produced by the company. 6. The back coating is ready for this product. The back of COATINGS Coating, beige of OrgalOO 7. Preparation of pre-coated steel sheet The metal sheet was immersed in 2% by mass concentration of FC_4366 (produced by Sakamoto Parkedzing), 6〇t: Degreasing is carried out in an aqueous solution for 1 sec., and then dried after washing with water. Secondly, a treatment liquid is applied to both sides of the metal plate by a roll coater, and dried by a hot air drying oven to obtain a chemical conversion treatment layer. The coating system is such that the adhesion amount of the chemical conversion treatment liquid reaches the total amount of the dried film of 1 GGmg/m 2 , and the plate temperature reaches 6 〇t when the chemical conversion treatment is dried. Secondly, the surface of the metal plate which has been chemically processed is used as a roller. The coater coats the primer paint so that the dry film thickness is 5 μm, and then the back coat is applied on the other surface by a roll coater to make the coat film thickness one, and then the hot air is used to heat the induction furnace in the metal plate. The coating layer was obtained by drying and solidifying under the condition that the sheet temperature was 2 nrc. After drying and drying, the coated metal plate is sprayed with water and rubbed and water cooled. Further, on the primer coating film, a multi-layer simultaneous coating of the intermediate coating and the top coating is carried out by a sliding hopper type curtain coating machine, and then 19 201105497 is introduced into the hot air induction heating furnace to reach the panel temperature according to the metal plate. Under the condition of 23 同时, the pre-coated metal sheet of the sample is prepared by drying the dried coating and then water-cooling (the pre-coated steel sheet produced by the method is hereinafter referred to as “3 coating 2 baking” or “3C2B”. "). In addition, when the coating is applied by a sliding hopper-type curtain coating machine, the additive material "ΒΥΚ-333" produced by the company is added to the top coating material, and the surface tension of the top coating film is adjusted successively. The surface tension of the coating is 3 mN/m. Further, the intermediate coating film is also coated on the primer coating film by a roll coater as needed, and simultaneously dried and dried by the induction heating furnace blown into the hot air at a sheet temperature of 230 C. After water cooling, the surface coating paint is coated on the Kunming coating machine, and then dried and dried by water in an induction heating furnace blown into the hot air at a plate temperature of 230 ° C. The precoated steel sheet of the sample (the precoated metal sheet produced by the method is hereinafter referred to as "3 coating 3 baking" or "3C3B"). Further, the production line of the precoated metal sheet sample of the present invention contains only two oven lines of two ovens. Therefore, when a sample of 3C3B is produced, a sample is produced by processing twice. Further, a sample of 1 coat 1 baking (1C1B) and 2 coating 2 baking (2C2B) containing no primer coating layer and intermediate coating layer was prepared as needed. Further, the intermediate coating film was applied to have a dry film thickness of 15 μm, and the film thickness of the surface coating film was changed. Details of the precoated steel sheets that have been produced are summarized in Table 1. ‘ 20 201105497 Table 1
標準 底漆 塗膜 中塗塗膜 表塗塗膜 塗裝 方法 樹脂種類 樹脂 Tg CC) 固化劑 種類 固化劑添加量 (相對於聚酯固態 部100質量份之 固態部質量份） 微粒子之種類/ 添加量(相對於 全部樹脂丨00質 量份之質量份） 膜厚 (μιη) PCM-1 有 無 聚酯 -10 蜜胺 20 碳黑/5 10 2C2B PCM-2 有 無 聚酯 -15 蜜胺 20 碳黑/5 10 2C2B PCM-3 有 無 聚酯彈性體 -36 蜜胺 20 碳黑/5 10 2C2B PCM-4 有 一般中塗 聚酯 -10 蜜胺 20 碳黑/5 10 3C2B PCM-5 有 一般中塗 聚酯 -15 蜜胺 20 碳黑/5 10 3C2B PCM-6 有 一般中塗 聚酯彈性體 -36 蜜胺 20 碳黑/5 10 3C2B PCM-7 有 一般中塗 聚酯 -10 蜜胺 20 未添加/0 10 3C2B PCM-8 有 一般中塗 聚酯 -15 蜜胺 20 未添加/0 10 3C2B PCM-9 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-10 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-11 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-12 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-13 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-14 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-15 有 一般中塗 聚酯彈性體 -36 異氰 酸酯 ※OH/NCO=1.0 (當臺比） 未添加/0 10 3C2B PCM-16 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 3 3C2B PCM-17 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 25 3C2B PCM-18 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0 30 3C2B PCM-19 有 一般中塗 聚酯彈性體 -36 蜜胺 20 未添加/0無 20 3C3B PCM-20 無 無 聚酯彈性體 -36 蜜胺 20 碳黑/5 10 1C1B PCM-21 有 高彈性中 塗 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-22 有 無 聚酯 5 蜜胺 20 碳黑/5 10 2C2B PCM-23 有 有 聚酯 5 蜜胺 20 未添加/0 10 3C2B PCM-24 有 有 聚酯彈性體 -36 蜜胺 20 未添加/0 10 3C2B PCM-25 有 有 聚酯彈性體 -36 蜜胺 20 未添加/0 3C2B PCM-26 有 一般中塗 聚酯彈性體 -36 蜜胺 20 碳黑/4 10 3C2B PCM-27 有 一般中塗 聚酷彈性體 -36 蜜胺 20 碳黑/2 10 3C2B PCM-28 有 一般中塗 聚酯彈性體 -36 蜜胺 20 氧化矽/5 10 3C2B PCM-29 有 一般中塗 聚酯彈性體 -36 蜜胺 20 尼龍微粒子/5 3C2B PCM-30 有 一般中塗 聚酯彈性體 -36 蜜胺 20 聚丙烯微粒子/5 10 3C2B PCM-31 有 一般中塗 聚酯彈性體 -36 蜜胺 20 酚微粒子/5 10 3C2B PCM-32 有 一般中塗 聚酯 -15 蜜胺 20 氧化矽/5 10 3C2B PCM-33 有 一般中塗 聚酯 -15 蜜胺 20 尼龍微粒子/5 10 3C2B PCM-34 有 一般中塗 聚酯 -15 蜜胺 20 聚丙烯微粒子/5 10 3C2B PCM-35 有 一般中塗 聚酯 -15 蜜胺 20 酚微粒子/5 10 3C2B PCM-36 有 一般中塗 聚酯彈性體 -36 蜜胺 20 氧化矽/1 10 3C2B PCM-37 有 一般中塗 聚酯彈性體 -36 蜜胺 20 尼龍微粒子/3 10 3C2B PCM-38 有 一般中塗 聚酯彈性體 -36 蜜胺 20 聚丙烯微粒子/2 10 3C2B PCM-39 有 一般中塗 聚酯彈性體 -36 蜜胺 20 酚微粒子/4 10 3C2B 21 201105497 就如上所製作之預塗覆鋼板已實施以下之評價測試。 另，所有測試均係以塗裝有表塗塗膜之面為評價面而實施 測試。 1. 塗裝外觀觀察 藉目視觀察已製作之預塗覆金屬板之塗裝外觀，並觀 察起泡瑕疵之產生狀況。 2. 表塗塗膜之機械特性 使用Fischer Instruments出品之微小硬度計 「FISCHERSCOPE H100V」，就已製作之預塗覆鋼板之塗 膜表面測定了壓入負載與壓入深度之關係。該測定係在 25°C之溫度下進行。壓頭形狀係使用韋克斯四角錐鑽石壓 頭，藉60次之階段負載達到最大負載5mN而緩緩增加階段 負載，以對塗膜壓入壓頭。階段間隔為Is，各階段負載則 依比例增加之條件而增加。又，負載達5mN後，則依與負 載增加時之相同條件減少負載，並測定了壓入負載減至零 為止之壓頭之壓入深度。本條件之時間與負載之關係顯示 於第1圖。 其次，求出第2圖所示之壓入深度-壓入負載線圖所示 之D〇、De、Dm，並算出壓入深度回復率a=(DM — De)X1 00/(Dm 一 D〇) 0 3. 加工性測試 就已製作之預塗覆鋼板將相同厚度之間隔件夾置其 中，而實施180。彎曲加工（一般稱為1T彎曲之加工），並以20 倍放大鏡目視觀察加工部之塗膜，調查塗膜有無裂痕。彎 22 201105497 曲加工則在20 C環境中進行加工。 塗膜裂痕之評價係於20倍放大鏡觀察下亦完全無塗膜 裂痕時評為◎，而在20倍放大鏡下塗膜雖有極小之裂痕但 目視觀察下未見裂痕時評為〇，目視時亦見微細裂痕時評 為△，目視時亦可見明確之大裂痕存在加工部全面上時評 4. 加工附著性測試 於業經前述3.之加工性測試之樣本之加工部之塗膜上 貼附膠帶，並藉20倍放大鏡與目視觀察剝離該膠帶時之塗 膜剝離狀態，而調查塗膜之剝離程度。 塗膜剝離之評價，係於20倍放大鏡觀察下亦全無塗膜 剝離時評為◎’ 20倍放大鏡下塗膜雖有極小之剝離但目視 觀察下未見剝離時評為◦，目視時亦可見微細之剝離時評 為△’目視時已存在明確之大幅剝離於加工部全面上時評 為X。 5. 損傷回復性測試Standard primer coating film coating film coating film coating method Resin type resin Tg CC) Curing agent type curing agent addition amount (100 parts by mass of solid portion in the solid portion of polyester) Type of microparticle / Adding amount (parts by mass of 00 parts by mass relative to total resin) Film thickness (μιη) PCM-1 with or without polyester-10 melamine 20 carbon black/5 10 2C2B PCM-2 with or without polyester-15 melamine 20 carbon black/5 10 2C2B PCM-3 with or without polyester elastomer -36 melamine 20 carbon black/5 10 2C2B PCM-4 with general medium coating polyester-10 melamine 20 carbon black/5 10 3C2B PCM-5 with general medium coating polyester-15 Melamine 20 Carbon Black/5 10 3C2B PCM-6 General Medium Coating Polyester Elastomer -36 Melamine 20 Carbon Black/5 10 3C2B PCM-7 General Medium Coating Polyester-10 Melamine 20 Not Added /0 10 3C2B PCM -8 There are general intermediate coating polyester-15 melamine 20 not added /0 10 3C2B PCM-9 has a general medium coated polyester elastomer -36 melamine 20 not added /0 10 3C2B PCM-10 has a general medium coated polyester elastomer - 36 melamine 20 not added /0 10 3C2B PCM-11 has a general medium coated polyester elastomer -36 melamine 20 not added /0 10 3C2B PCM-12 has a general medium coated polyester elastomer -36 melamine 20 not added /0 10 3C2B PCM-13 has a general medium coated polyester elastomer -36 melamine 20 not added /0 10 3C2B PCM-14 has a general medium coating Ester Elastomer-36 Melamine 20 Not added /0 10 3C2B PCM-15 General medium-coated polyester elastomer -36 Isocyanate ※OH/NCO=1.0 (When bench ratio) Not added /0 10 3C2B PCM-16 General coating Polyester Elastomer -36 Melamine 20 Not Added /0 3 3C2B PCM-17 General Medium Coated Polyester Elastomer -36 Melamine 20 Not Added /0 25 3C2B PCM-18 General Medium Coated Polyester Elastomer -36 Melamine 20 Not added /0 30 3C2B PCM-19 General medium polyester elastomer -36 Melamine 20 Not added /0 No 20 3C3B PCM-20 No polyester elastomer -36 Melamine 20 Carbon black/5 10 1C1B PCM -21 Highly elastic medium-coated polyester elastomer -36 melamine 20 not added /0 10 3C2B PCM-22 with or without polyester 5 melamine 20 carbon black/5 10 2C2B PCM-23 with polyester 5 melamine 20 not added /0 10 3C2B PCM-24 with polyester elastomer -36 melamine 20 not added /0 10 3C2B PCM-25 with polyester elastomer -36 melamine 20 Not added /0 3C2B PCM-26 has a general medium coated polyester elastomer -36 melamine 20 carbon black / 4 10 3C2B PCM-27 has a general medium coated poly elastomer -36 melamine 20 carbon black / 2 10 3C2B PCM-28 There are general medium-coated polyester elastomer-36 melamine 20 yttrium oxide/5 10 3C2B PCM-29 has general medium-coated polyester elastomer-36 melamine 20 nylon micro-particles/5 3C2B PCM-30 has general medium-coated polyester elastomer-36 Melamine 20 polypropylene microparticles/5 10 3C2B PCM-31 have general medium coated polyester elastomer -36 melamine 20 phenol microparticles/5 10 3C2B PCM-32 have general medium coating polyester-15 melamine 20 cerium oxide /5 10 3C2B PCM-33 has general medium coating polyester-15 melamine 20 nylon micron particles/5 10 3C2B PCM-34 has general medium coating polyester-15 melamine 20 polypropylene micro particles/5 10 3C2B PCM-35 has general medium coating polyester-15 honey Amine 20 Phenol Microparticles/5 10 3C2B PCM-36 General Typified Polyester Elastomer -36 Melamine 20 Oxide Oxide / 1 10 3C2B PCM-37 General Typified Polyester Elastomer -36 Melamine 20 Nylon Microparticles / 3 10 3C2B PCM-38 has a general medium coated polyester elastomer -36 melamine 20 polypropylene micro particles / 2 10 3C2B PCM-39 has a general intermediate coating polyester elastomer -36 melamine 20 phenol fine particles / 4 10 3C2B 21 201105497 The following evaluation test has been carried out on the precoated steel sheet produced as above. In addition, all the tests were carried out by using the surface coated with the surface coating film as the evaluation surface. 1. Appearance of Painting Appearance Observe the appearance of the painted pre-coated metal sheet by visual inspection and observe the occurrence of foaming. 2. Mechanical properties of the surface coating film The relationship between the press-in load and the press-in depth was measured on the surface of the coated film of the prepared precoated steel sheet by using the "FISCHERSCOPE H100V", a micro hardness tester manufactured by Fischer Instruments. The measurement was carried out at a temperature of 25 °C. The shape of the indenter was made using a Wex square quadrangular diamond indenter, and the load was increased by 5 mN in a period of 60 times, and the stage load was gradually increased to press the film into the indenter. The phase interval is Is, and the load of each phase increases according to the condition of proportional increase. Further, after the load reached 5 mN, the load was reduced in accordance with the same conditions as when the load was increased, and the indentation depth of the indenter until the press-in load was reduced to zero was measured. The relationship between time and load for this condition is shown in Figure 1. Next, the indentation depth shown in Fig. 2 is obtained - D〇, De, Dm shown in the load line diagram, and the indentation depth recovery rate a = (DM - De) X1 00 / (Dm - D) is calculated. 〇) 0 3. Processability test The pre-coated steel sheet which has been produced is sandwiched between spacers of the same thickness and 180 is carried out. Bending processing (generally referred to as 1T bending processing), and observing the coating film of the processed portion with a 20-fold magnifying glass, and investigating whether or not the coating film is cracked. Bend 22 201105497 The curved machining is processed in a 20 C environment. The evaluation of the coating film crack was evaluated as ◎ when there was no coating crack under the observation of 20 times magnifying glass, and the film was slightly cracked under the 20 times magnifying glass, but it was evaluated as 〇 when no crack was observed under visual observation, and also when visually observed. When the micro-crack is evaluated as △, it can be seen that there is a clear large crack in the visual inspection. The processing adhesion test is carried out on the coating film of the processing part of the sample of the above-mentioned 3. The peeling state of the coating film when the tape was peeled off was visually observed by a 20-times magnifying glass, and the peeling degree of the coating film was investigated. The evaluation of the peeling of the coating film was evaluated as ◎ when the film peeling was not observed under a 20-fold magnifying glass. Although the coating film under the magnifying glass had a very small peeling, it was evaluated as ◦ when no peeling was observed under visual observation, and fine was observed when visually observed. When peeled off, it was rated as △'. When there was a clear discretion, it was rated as X when it was comprehensively processed. 5. Damage recovery test
依據JIS.K.5600.5.4之刻劃硬度(錯筆法），藉η、2H、3H 之硬度之錯筆在塗膜表面上劃上刻痕。其次，加以浸潰於 彿水中1分鐘後，再藉目視觀察損傷之回復狀況而進行評 價。 評價係於3 Η之鉛筆所刻劃之部位未見刻痕時評為◎， 而於3Η之鉛筆所刻劃之部位雖已見刻痕但2Η之部位則未 見刻痕時評為〇，2Η之鉛筆所刻劃之部位雖已見刻痕但Η 之部位則未見刻痕時評為△，Η之鉛筆所刻劃之部位亦見刻 23 201105497 痕時評為X。 6. 高彈性塗膜與位於其下層之塗膜之界面之Ra測定 垂直裁切預塗覆金屬板以觀察塗膜截面，並將裁切後 之預塗覆金屬板嵌入樹脂後再研磨截面部，而藉3500倍之 掃描型電子顯微鏡拍攝塗膜之截面相片。其次，於相片上 覆蓋透明之樹脂片（使用市售之OHP片），而正確地描繪塗膜 界面之凹凸。接著，如第4圖所示，以影像處理裝置測定縱 線部分之面積，而由式（I )算出Ra作為其平均值。 [數式1]According to the hardness of JIS.K.5600.5.4 (wrong pen method), the surface of the coating film is scored by the wrong pen of η, 2H, 3H hardness. Next, after being immersed in the water for 1 minute, the evaluation was made by visually observing the recovery of the damage. The evaluation was rated as ◎ when the scratched part of the pencil of 3 Η was not seen, and the nicked part of the pencil of 3 已 was found to have a nick, but the part of the 2 Η was rated as 〇, 2Η Although the part marked by the pencil has been scored, the part of the enamel is rated as △ when no nick is found, and the part marked by the pencil of Η is also seen at 23 201105497 when it is marked as X. 6. The Ra coating of the interface between the highly elastic coating film and the coating film located at the lower layer thereof is vertically cut to pre-coat the metal sheet to observe the cross section of the coating film, and the cut pre-coated metal sheet is embedded in the resin and then the section is polished. A cross-sectional photograph of the coating film was taken by a scanning electron microscope of 3500 times. Next, the transparent resin sheet (using a commercially available OHP sheet) was overlaid on the photograph to accurately describe the unevenness of the coating film interface. Next, as shown in Fig. 4, the area of the vertical line portion was measured by the image processing apparatus, and Ra was calculated from the formula (I) as the average value. [Expression 1]
Ra=-|- J ^ lf<x> |dx …⑴ 然後，將算出之Ra在0.3〜0.8μιη之範圍内者評為ο，在 0.3〜0·8μηι之範圍外者評為△。 7. 光澤測定 已測定所製作之預塗覆金屬板之鏡面光澤度。測定方 法係依據HS-K5600-4-7而在幾何學條件60度之條件下進行 測定。其次，依以下之標準進行評價。 鏡面光澤度為95以上時：〇 鏡面光澤度為90以上95以下時：△Ra = - | - J ^ lf < x > | dx (1) Then, the calculated Ra is in the range of 0.3 to 0.8 μm, and is evaluated as Δ in the range of 0.3 to 0.8 μm. 7. Gloss measurement The specular gloss of the precoated metal sheets produced was determined. The measurement method was carried out in accordance with HS-K5600-4-7 under the geometric condition of 60 degrees. Second, the evaluation was carried out according to the following criteria. When the specular gloss is 95 or more: 〇 When the specular gloss is 90 or more and 95 or less: △
鏡面光澤度為90以下時：X 以下，已就評價結果加以詳細揭露。表2即顯示所製作 之預塗覆金屬鋼板之評價結果。表2所揭露之壓入回復率係 全部在「25°C」下測定所得者。 24 201105497 表2When the specular gloss is 90 or less: X or less, the evaluation results are disclosed in detail. Table 2 shows the evaluation results of the precoated metal sheets produced. The indentation recovery rates disclosed in Table 2 were all measured at "25 ° C". 24 201105497 Table 2
No. 樣本 種類 塗裝 外觀 壓入 深度 回復率 (%) 加工性 加工 附著性 損傷 回復性 表塗膜與 位於其下 之塗膜之 界面Ra 鏡面 光澤度 備考 1 PCM-1 良好 73 ◎ 〇 Δ Δ Δ 本發明例 2 PCM-2 良好 86 ◎ 〇 〇 Δ Δ 本發明例 3 PCM-3 良好 89 ◎ 〇 ◎ Δ Δ 本發明例 4 PCM-4 良好 73 ◎ ◎ Δ 〇 Δ 本發明例 5 PCM-5 良好 86 ◎ ◎ 〇 〇 Δ 本發明例 6 PCM-6 良好 89 ◎ ◎ ◎ 〇 Δ 本發明例 7 PCM-7 良好 70 ◎ ◎ Δ 〇 〇 本發明例 δ PCM-8 良好 83 ◎ ◎ Δ 〇 〇 本發明例 9 PCM-9 良好 86 ◎ ◎ 〇 〇 〇 本發明例 10 PCM-10 良好 77 ◎ ◎ Δ 〇 〇 本發明例 11 PCM-11 良好 88 ◎ ◎ 〇 〇 〇 本發明例 12 PCM-12 良好 88 ◎ ◎ 〇 〇 〇 本發明例 13 PCM-13 良好 91 〇 ◎ 〇 〇 〇 本發明例 14 PCM-14 良好 93 Δ ◎ 〇 〇 〇 本發明例 15 PCM-15 良好 73 ◎ ◎ Δ 〇 〇 本發明例 16 PCM-16 良好 75 ◎ ◎ 〇 〇 〇 本發明例 17 PCM-17 良好 86 ◎ ◎ 〇 〇 〇 本發明例 18 PCM-18 部分 不佳 86 ◎ ◎ 〇 〇 〇 本發明例 19 PCM-19 良好 86 ◎ Δ 〇 Δ 〇 本發明例 20 PCM-20 良好 89 ◎ Δ ◎ — Δ 本發明例 21 PCM-21 良好 89 ◎ ◎ ◎ 〇 〇 本發明例 22 PCM-22 良好 65 ◎ 〇 X Δ Δ 比較例 23 PCM-23 良好 63 ◎ ◎ X 〇 〇 比較例 24 PCM-24 良好 61 ◎ ◎ X 〇 〇 比較例 25 PCM-25 良好 64 ◎ ◎ X 〇 〇 比較例 26 PCM-26 良好 89 ◎ ◎ ◎ 〇 〇 本發明例 27 PCM-27 良好 89 ◎ ◎ ◎ 〇 〇 本發明例 28 PCM-28 良好 86 ◎ ◎ 〇 〇 Δ 本發明例 29 PCM-29 良好 86 ◎ ◎ 〇 〇 Δ 本發明例 30 PCM-30 良好 86 ◎ ◎ 〇 〇 Δ 本發明例 31 PCM-31 良好 86 ◎ ◎ 〇 〇 Δ 本發明例 32 PCM-32 良好 83 ◎ ◎ Δ 〇 Δ 本發明例 33 PCM-33 良好 83 ◎ ◎ Δ 〇 Δ 本發明例 34 PCM-34 良好 83 ◎ ◎ Δ 〇 Δ 本發明例 35 PCM-35 良好 83 ◎ ◎ Δ 〇 Δ 本發明例 36 PCM-36 良好 86 ◎ ◎ 〇 〇 〇 本發明例 37 PCM-37 良好 86 ◎ ◎ 〇 〇 〇 本發明例 38 PCM-38 良好 86 ◎ ◎ 〇 〇 〇 本發明例 39 PCM-39 良好 86 ◎ ◎ 〇 〇 〇 本發明例 25 201105497 本發明之壓入深度回復率為70%以上之預塗覆金屬板 (本發明例-1〜21)因損傷回復性優良，故即便受損傷亦可回 復而使損傷不明顯，較為適用。而，壓入深度回復率在7〇0/〇 以下者（比較例-2〜25)之損傷回復性較差，若受損傷將殘留 永久之痕跡，故不適用。 最表層之表塗塗膜使用玻璃轉化溫度在一 1〇t»c以上之 樹脂者（比較例-22、23)之壓入深度回復率容易在7〇%以 下，損傷回復性亦呈優良傾向，故塗膜樹脂宜使用具有— 10 C以下之玻璃轉化溫度之聚酯樹脂或聚酯彈性體樹脂 (本案發明例-1〜21)。玻璃轉化溫度為—30〇c以下者(本發明 例-3、6、9~21等）之壓入深度回復率容易在85〇/。以上，損傷 回復性亦優良，故更為適用。 高彈性塗膜所使用之固化劑若比較使用異氰酸酯者 (本案發明例-15)與使用蜜胺樹脂者(本發明例_7〜14)，則使 用蜜胺樹脂者之壓入深度回復率較高，損傷復原性亦優 良，故較為適用。 蜜胺樹脂之添加量宜相對聚酯樹脂或聚酯彈性體樹脂 100質1份而為10〜100質量份。1〇質量份以下者（比較例_24) 之壓入深度回復率較低，損傷回復性亦呈劣化之傾向，而 100貝1伤以上者（本發明例_14)之加工性則有劣化之傾向。 南彈性塗膜之膜厚宜為3〜25μηι，若在3μιη以下（比較例 -25)則壓入深度回復率較低，損傷回復性亦呈劣化之傾向， 右在25μιη以上（本發明例_18)，則在烘乾步驟中已發現局部 發生起泡瑕疵。 26 201105497 又，在未乾燥狀態下積層用以形成最上層之高彈性塗 膜層之塗料與用以开>成其下之塗臈層之塗料，並同時乾燥 該未乾燥狀態之多層膜之方法所製造者(本發明例_4〜18)之 加工附著性可較就該等塗膜逐層反覆進行塗裝烘乾而製造 者(本發明例―1〜3、19)更為提昇，故較為適用。 又於尚彈性塗膜下塗佈有底漆者（本發明例1〜19)與於 至屬板上僅塗裝有！層尚彈性塗膜者(本發明例.Μ)相較，加 工附著性較為優良，故較為適用。 本案發明之預塗覆金屬板中，於高彈性塗膜層中微粒 子添加里相對主樹脂與固化劑之總和丨〇 〇質量份而為4質量 份以上者(本發明例卜6、28〜35)已呈現塗膜光澤降低之傾 向，故微粒子添加量宜在4質量份以下。然而，高彈性塗膜 中添加有&黑者(諸如本發日月例_6)與未添加者(諸如本發明 例-9)相較’壓入深度回復率較高，損傷回復性亦呈優良之 傾向’故添加有碳黑者更為適用。 【圖式簡單説明】 第1圖係使用微小硬度計测得之對壓頭施加負載至 5mN而壓人塗膜，然後除去負載而至負載完全除去為止之 時間與壓入負載之關係。 第2圖係微小硬度計所測得之壓頭壓入深度與負載之 關係。 第3圖係就第2圖之資料進行零點修正後之壓頭墨 度與負載之關係。 第4圖係顯示塗膜界面之凹凸者。 27 201105497 【主要元件符號說明】 (無） 28No. Sample type Applicator appearance Indentation depth recovery rate (%) Processability Adhesive damage Resilience coating film interface with coating film underneath Ra Specular gloss test 1 PCM-1 Good 73 ◎ 〇Δ Δ Δ Inventive Example 2 PCM-2 Good 86 ◎ 〇〇Δ Δ Inventive Example 3 PCM-3 Good 89 ◎ 〇 ◎ Δ Δ Inventive Example 4 PCM-4 Good 73 ◎ ◎ Δ 〇 Δ Inventive Example 5 PCM-5 Good 86 ◎ ◎ 〇〇 Δ Inventive Example 6 PCM-6 Good 89 ◎ ◎ ◎ 〇 Δ Inventive Example 7 PCM-7 Good 70 ◎ ◎ Δ 〇〇 Inventive Example δ PCM-8 Good 83 ◎ ◎ Δ 〇〇 Inventive Example 9 PCM-9 Good 86 ◎ ◎ 〇〇〇 Inventive Example 10 PCM-10 Good 77 ◎ ◎ Δ 〇〇 Inventive Example 11 PCM-11 Good 88 ◎ ◎ 〇〇〇 Inventive Example 12 PCM-12 Good 88 ◎ ◎ 〇〇〇 Inventive Example 13 PCM-13 Good 91 〇 ◎ 〇〇〇 Inventive Example 14 PCM-14 Good 93 Δ ◎ 〇〇〇 Inventive Example 15 PCM-15 Good 73 ◎ ◎ Δ 〇〇 The present invention example 16 PCM-16 Good 75 ◎ ◎ 〇〇〇本发EXAMPLE 17 PCM-17 Good 86 ◎ ◎ 〇〇〇 Inventive Example 18 PCM-18 Partially poor 86 ◎ ◎ 〇〇〇 Inventive Example 19 PCM-19 Good 86 ◎ Δ 〇 Δ 〇 Inventive Example 20 PCM-20 Good 89 ◎ Δ ◎ - Δ Inventive Example 21 PCM-21 Good 89 ◎ ◎ ◎ 〇〇 Inventive Example 22 PCM-22 Good 65 ◎ 〇X Δ Δ Comparative Example 23 PCM-23 Good 63 ◎ ◎ X 〇〇 Comparative Example 24 PCM-24 Good 61 ◎ ◎ X 〇〇 Comparative Example 25 PCM-25 Good 64 ◎ ◎ X 〇〇 Comparative Example 26 PCM-26 Good 89 ◎ ◎ ◎ 〇〇 Inventive Example 27 PCM-27 Good 89 ◎ ◎ ◎ 〇发明 Inventive Example 28 PCM-28 Good 86 ◎ ◎ 〇〇 Δ Inventive Example 29 PCM-29 Good 86 ◎ ◎ 〇〇 Δ Inventive Example 30 PCM-30 Good 86 ◎ ◎ 〇〇 Δ Inventive Example 31 PCM-31 Good 86 ◎ ◎ 〇〇 Δ Inventive Example 32 PCM-32 Good 83 ◎ ◎ Δ 〇 Δ Inventive Example 33 PCM-33 Good 83 ◎ ◎ Δ 〇 Δ Inventive Example 34 PCM-34 Good 83 ◎ ◎ Δ 〇 Δ Inventive Example 35 PCM-35 Good 83 ◎ ◎ Δ 〇 Δ The present invention 36 PCM-36 Good 86 ◎ ◎ 〇〇〇 Inventive Example 37 PCM-37 Good 86 ◎ ◎ 〇〇〇 Inventive Example 38 PCM-38 Good 86 ◎ ◎ 〇〇〇 Inventive Example 39 PCM-39 Good 86 ◎ ◎ Inventive Example 25 201105497 The precoated metal sheet (Inventive Examples-1 to 21) having a press-in depth recovery ratio of 70% or more of the present invention is excellent in damage recovery property, so that it can be recovered even if it is damaged. The damage is not obvious and is more suitable. On the other hand, those having a deep penetration recovery ratio of 7 〇 0 / 〇 or less (Comparative Example - 2 to 25) have poor damage recovery property, and if they are damaged, permanent traces remain, which is not applicable. When the surface coating film of the outermost layer is a resin having a glass transition temperature of 1 〇t»c or more (Comparative Example -22, 23), the indentation depth recovery rate is easily 7 % or less, and the damage recovery property is also excellent. Therefore, a polyester resin or a polyester elastomer resin having a glass transition temperature of -10 C or less (inventive Examples-1 to 21) is preferably used as the coating film resin. The indentation depth recovery rate of the glass transition temperature of -30 〇c or less (inventive examples -3, 6, 9 to 21, etc.) is easily 85 Å/. Above, the damage recovery is also excellent, so it is more suitable. When the curing agent used for the highly elastic coating film is used in comparison with those using isocyanate (Inventive Example -15) and those using melamine resin (Inventive Examples _7 to 14), the depth of penetration of the melamine resin is higher. High, damage is also excellent, so it is more suitable. The amount of the melamine resin to be added is preferably 10 to 100 parts by mass based on 1 part by mass of the polyester resin or the polyester elastomer resin. In the case of 1 part by mass or less (Comparative Example _24), the indentation depth recovery rate is low, and the damage recovery property tends to deteriorate, and the workability of 100 Å or more (Inventive Example _14) is deteriorated. The tendency. The film thickness of the south elastic coating film is preferably 3 to 25 μm, and if it is 3 μm or less (Comparative Example-25), the depth of penetration of the press-in is low, and the damage recovery property tends to be deteriorated, and the right is 25 μm or more (inventive example _ 18), a localized foaming enthalpy has been found in the drying step. 26 201105497 In addition, in the undried state, a coating for forming the uppermost high elastic coating layer and a coating for opening the underlying coating layer are laminated, and at the same time, the undried state of the multilayer film is dried. The process adhesion of the manufacturer of the method (Inventive Example _4 to 18) can be further improved by coating and drying the coating film layer by layer, and the manufacturer (Examples 1-3 to 19 of the present invention) is further improved. Therefore, it is more suitable. Further, those who have been coated with a primer under the elastic coating film (Inventive Examples 1 to 19) are only coated on the slab! The layer is also an elastic coating film (inventive example. Μ), and the processing adhesion is relatively excellent, so it is suitable. In the precoated metal sheet of the present invention, the amount of fine particles added to the high elastic coating layer is 4 parts by mass or more based on the total mass of the main resin and the curing agent (Examples of the present invention, 6, 28 to 35) The coating film has a tendency to lower the gloss, and the amount of the fine particles added is preferably 4 parts by mass or less. However, the addition of & black in the highly elastic coating film (such as the present invention _6) is higher than the indentation depth (such as the inventive example-9), and the damage recovery is also high. Good tendencies' so it is more suitable to add carbon black. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a relationship between the time when a load is applied to a head by a micro hardness tester and the load is applied to 5 mN to press a film, and then the load is removed until the load is completely removed, and the load is pressed. Figure 2 shows the relationship between the indenter depth and the load measured by the micro hardness tester. Figure 3 is the relationship between the indenter ink and the load after zero correction for the data in Figure 2. Figure 4 shows the bumps at the interface of the coating film. 27 201105497 [Explanation of main component symbols] (none) 28