200918304 九、發明說明 【發明所屬之技術領域】 本發明係關於家庭用電氣製品和汽車用車載構件等之 外板材和構造構材、及建材、屋頂材等所使用的預塗金屬 板（Pre-coated metal)及預塗金屬板之製造方法。 【先前技術】 以鋼板和鋁板或鋁合金板所代表的金屬薄板材（金屬 板）爲兼具高強度和成形性（formability )，經由施以各 式各樣的成形則可應用於家庭用電氣製品、汽車用車載構 件、及建材等各式各樣之用途。此等用途所使用的金屬板 成形品，於改善外觀和耐蝕性等爲目的而進行表面處理。 此表面處理，以往，將金屬板成形爲指定之形狀後進行後 塗（post-coat)方式爲主流，但最近，於改善職場環境和 令製造步驟簡單化和費用降低等爲目的，亦固定採用將金 屬板預先經表面處理之預塗金屬板成形爲指定形狀的預塗 方式。更且’近年，此類預塗金屬板爲了應付製品、機器 之多樣化和高級化’乃開發出賦予各種機能，例如，耐指 紋性（anti-fingerprint property )、防止刮傷性（anti scratch property )、接地性(ground connection property )、放熱性、遮熱性、抗菌性、潤滑性等之機能性預塗金 屬板，且已廣泛普及。 此類預塗金屬板，因爲以施行表面處理之狀態進行成 形’故對於皮膜不僅要求優良的成形性，且因成形後的外 -4- 200918304 觀就其原樣變成製品的外觀，故要求優良的表面外觀、性 狀等。 例如’於專利文獻1中，提案對鋁合金板材，以環氧 樹脂、胺基甲酸乙酯樹脂及丙烯酸樹脂單獨或其混合物作 爲基質樹脂、且含有粒徑0.1 μιη以下之Si02 5~40%、及 潤滑劑5〜60%之塗料，以〇.5〜10 μπι之厚度塗佈，將摩擦 係數控制成0.1 5以下之成形性和防止刮傷性優良的預塗 金屬板。 專利文獻1記載之預塗金屬板爲由鋁合金板材所構成 ’ 一般’以鋁作爲材料的預塗金屬板適於要求輕量的用途 ’例如’亦被使用於筆記型電腦搭載用之光碟驅動器的蓋 類’和液晶顯示裝置之框、背蓋類、車載用電裝品之ECU (Electronic Control Unit，電子控制元件）和車用音響、 車導航系統、光碟自動轉換器等之蓋類和構造構材。 圖3(a) 、 （b)爲示出先前之光碟驅動器及其所用 之光碟的斜視圖，（a )爲示出托盤方式的光碟驅動器， 又’ （M爲示出推入（si〇t_in)方式的光碟驅動器。 如圖3 ( a )所示般，於托盤方式的光碟驅動器20， 於托盤21中’安裝CD和DVD等之光碟10，並將托盤21 裝入蓋22中的方式，係爲目前許多製品所採用的方式。 又’如圖3(b)所示般，最近，開發出不會令安裝光碟 1 〇的托盤出入，僅將光碟1 〇以插進開口部3 1插入之推入 方式的光碟驅動器30。此類推入方式之光碟驅動器30中 ’光碟爲於光碟驅動器30之蓋32之逼近內面處出入 -5- 200918304 。因此’光碟10出入時，光碟10的表面與光碟驅動器30 的蓋3 2內面摩擦且有時產生褶動損傷，故爲了防止此情 事，必須於蓋3 2的內面側防止光碟1 0表面損傷的處理。 此類處理，自以往爲於推入方式的光碟驅動器3 0的 蓋3 2內面，一枚一枚施行防止部分刮傷的塗敷（後塗敷 )° 將此類後塗敷對蓋3 2 —枚一枚施行乃爲非常煩雜， 故期望開發出預先具備即使接觸光碟之情況，亦難令光碟 表面刮傷之特性（以下，稱爲「防止刮傷性」）的預塗金 屬板。 對於此類期望，本發明者爲開發出以氟系樹脂作爲基 質層，並對此基質層，令皮膜厚度與粒徑之比率爲指定範 圍內之各式各樣粒徑的胺基甲酸乙酯珠粒，以指定之配合 比率配合的樹脂皮膜於金屬板表面形成，則可對於成形所 使用之預塗金屬板而言，具有基本的，優良的成形性及外 觀，並且於倂用黏著物之用途中難附著黏著物，且，難附 著污染物和油，並且兼具光碟之防止刮傷性的預塗金屬板 ，且亦已實用化（參照特願2005 -294 1 09號）。 更且，本發明者開發出以環氧系樹脂作爲基質層，並 對此基質層，令皮膜厚度與粒徑之比率爲指定範圍內之各 式各樣粒徑的胺基甲酸乙酯珠粒，以指定之配合比率配合 的樹脂皮膜於金屬板表面形成，則可對於成形所使用之預 塗金屬板而言，具有基本的、優良的成形性及外觀，並且 與專利文獻2相反地，可強固貼附黏著物，且，兼具光碟 -6- 200918304 之防止刮傷性的預塗金屬板，並且已提案（參照特願 2006-85844 號）。 又’於專利文獻2中’揭示於聚酯系、環氧系、丙烯 酸系之任一者基質樹脂中’含有尼龍系、氟系、胺基甲酸 乙酯系之任一者樹脂珠粒和巴西棕櫚（carnauba )、聚乙 烯、微結晶（m i c r 〇 c r y s t a 11 i n e )任一者蠟，作爲設計成推 入先驅動器的預塗金屬板，且具備防止瑕疵損傷性的預塗 金屬板等。 〔專利文獻1〕專利第3 3 3 8 1 5 6號公報（段落編號 0008-0017) 〔專利文獻2〕特開2006-97127號公報 【發明內容】 (發明所欲解決之課題） 但是，專利文獻1記載之預塗金屬板雖可提高預塗金 屬板本身的成形性和耐刮性，但並無提高出入光碟表面之 耐刮性的效果，故如前述般，必須對成形終了的蓋3 2內 面一枚一枚施行後塗敷，但若進行此類處理，則其處理爲 非常煩雜，故生產性極低，且具有極昂貴的問題。 又，專利文獻2所記載之預塗金屬板的防止刮傷性， 根據使用者，不能稱爲必定具備可令人充分滿足的防止刮 傷性，而此些使用者更加強烈要求欲提高防止刮傷性。 本發明爲鑑於前述問題所完成者，以提供防止光碟損 傷，即，防止刮傷性比先前的預塗金屬板更加提高之預塗 200918304 金屬板及預塗金屬板之製造方、法。 (解決課題之手段） 本發明者爲了解決前述課題致力硏究之結果，爲了提 高光碟的防止刮傷性，在嚴格限制最支配防止刮傷性之軟 質珠粒的粒徑、添加量下’可提高基本的防止刮傷性。又 ’經由嚴格限制分散軟質珠粒之基質層的樹脂種類和玻璃 態化溫度’取得即使萬一於樹脂皮膜中產生軟質珠粒不均 勻分散的部位’且非以軟質珠粒而是以基質層本身接觸光 碟’亦可將光碟所造成的損傷抑制至最小限度之考慮風險 的樹脂皮膜。更且，發現於使用軟質珠粒之分散性變高之 作爲揮發成分的塗料下，可顯著減輕發生樹脂皮膜中產生 珠粒分散性不均勻部位且基質（母材）層露出的風險，並 且達到完成本發明。 解決前述課題之本發明的預塗金屬板爲具備於金屬板 表面所形成之樹脂皮膜（resinous coating film)的預塗金 屬板，該樹脂皮膜爲具備玻璃態化溫度（glass transition temperature)爲0°C以上50°C以下之聚醋樹脂與硬化劑交 聯反應（cross-linking reaction)而成之基質層（matrix) ，和在該基質層中分散，根據微小壓縮試驗（micro compression test)之單一珠粒 10%變形時之壓縮強度爲 lOMPa以下的軟質珠粒（soft beads)，且該軟質珠粒之 含有率相對於該基質層爲1 5質量％以上5〇質量％以下’ 該軟質珠粒之平均粒徑爲該基質層之平均厚度的1 · 1倍以 -8- 200918304 上5倍以下。 此處，本發明之預塗金屬板所用之軟質珠粒爲胺基甲 酸乙酯珠粒爲佳。 如此，本發明之預塗金屬板爲經由表面形成之基質層 和軟質珠粒所構成的樹脂皮膜，則可確保對於成形使用之 預塗金屬板而言，基本的、優良成形性、外觀。其次’經 由控制基質層中分散之胺基甲酸乙酯珠粒等之軟質珠粒含 有率及平均粒徑，即使預塗金屬板接觸光碟，亦因該軟質 珠粒可作用爲緩衝材，故可防止光碟表面刮傷。 此處，確保對於光碟之優良的防止刮傷性，並且亦考 慮與其他特性平衡之結果，軟質珠粒的平均粒徑爲基質層 之平均厚度1.1倍以上5倍以下。又，軟質珠粒之含有率 相對於基質層爲1 5質量％以上5 0質量％以下。 即’經由令胺基甲酸乙酯珠粒之平均粒徑爲基質層平 均厚度的1.1倍以上，則可抑制胺基甲酸乙酯珠粒埋沒 至基質層中’且經由今胺基甲酸乙酯珠粒之平均粒徑爲基 質層平均厚度的5倍以下，則可抑制胺基甲酸乙酯珠粒由 基質層脫落’故可以高程度誘導出胺基甲酸乙酯珠粒作爲 緩衝材的機能。又’經由令胺基甲酸乙酯之含有率相對於 基質層爲1 5質量％以上，則可確保胺基甲酸乙酯作爲緩衝 材之機能’又’經由令胺基甲酸乙酯珠粒之含有率爲5 〇 質量％以下’則可抑制塗料的黏度增加並且可確保適度的 塗佈性。 又’医1爲令樹脂皮膜主成分之基質層爲玻璃態化溫度 -9- 200918304 爲〇 °C以上5 0 °C以下之聚酯樹脂與硬化劑交聯反應而成 熱硬化性的聚酯樹脂，故交聯反應後之基質層被適度軟 化。因此，萬一於塗佈後之樹脂皮膜表面產生軟質珠粒 散不均勻的部位，則即使該部位接觸光碟，亦可經由露 的基質層減低光碟刮傷。 於本發明之預塗金屬板中，該金屬板期望爲鋁板或 合金板。若如此處理，則即使接觸光碟時不僅難造成刮 ，且在成形製作製品時可取得輕易的製品。 又，本發明之預塗金屬板的製造方法爲於金屬板表 具備樹脂皮膜之預塗金屬板的製造方法，係包含塗佈步 、加熱步驟而成。 塗佈步驟中，將包含玻璃能化溫度爲〇 °C以上5 0 °c 下之聚酯樹脂、和硬化劑、和根據微小壓縮試驗之單一 粒10%變形時之壓縮強度爲lOMPa以下的軟質珠粒、和 彼等均勻分散之揮發成分的塗料，於該金屬板上塗佈， 加熱步驟中，將該塗佈步驟中塗佈該塗料的金屬板以加 溫度爲2 0 0 °C以上3 0 0 °C以下，加熱時間爲2 0秒鐘以上 秒鐘以下之條件加熱。此處，該塗料中之成分比率，係 軟質珠粒的含有率預先調製至相對於聚酯樹脂與硬化劑 聯反應之基質層爲15質量％以上50質量％以下，又， 佈時的濕膜厚亦以成爲加熱步驟後之乾燥皮膜時，預先 算軟質珠粒之平均粒徑爲基質層之平均厚度1.1倍以上 倍以下的厚度塗佈。如此，令此類塗料交聯反應，則可 造具備相對於金屬板表面聚酯樹脂和硬化劑交聯反應向 之 質 分 出 鋁 傷 面 驟 以 珠 令 且 熱 60 將 交 塗 計 5 製 成 -10- 200918304 之基質層之軟質珠粒的含有率爲1 5質量％以上5 0質量％ 以下，軟質珠粒之平均粒徑爲基質層之平均厚度的1 . 1倍 以上5倍以下之樹脂皮膜的預塗金屬板。 於本發明之預塗金屬板的製造方法中，將揮發成分中 之芳香族烴系溶劑的含有比率規定爲3 0質量％以上。若如 此處理，則可大幅抑制塗料中分散的軟質珠粒爲於塗料中 沈降，且再凝集。因此，塗料中之軟質珠粒的分散狀態爲 依舊良好於金屬板上塗佈，故可大幅降低塗佈後之樹脂皮 膜中，產生軟質珠粒之分散爲不均勻的部位。其結果，軟 質珠粒爲部分少的部分，即，基質層露出之部分爲大幅減 少。如此，可減低光碟表面刮傷的或然率。 本發明之預塗金屬板之製造方法中所用的軟質珠粒以 胺基甲酸乙酯珠粒爲佳。若爲如此，則因該軟質珠粒可作 用爲緩衝材，故可確實取得能防止光碟表面刮傷的預塗金 屬板。 於本發明之預塗金屬板之製造方法中，該金屬板期望 爲鋁板或鋁合金板。若爲如此，則即使接觸光碟時不僅難 造成刮傷，且在成形製作製品時可取得輕量的製品。 (發明之效果） 若根據本發明之預塗金屬板，經由金屬板表面所形成 之包含基質層和軟質珠粒而成的樹脂皮膜，不僅可確保對 於成形所使用之預塗金屬板而言基本的、優良的成形性、 外觀，且經由令樹脂皮膜（基質層）中分散之軟質珠粒含 -11 - 200918304 有率和平均粒徑最適化，則亦可在樹脂皮膜表面與光碟表 面接觸時，令光碟之防止刮傷性比先前之預塗金屬板更加 提高。 若根據本發明之預塗金屬板的製造方法，經由金屬板 表面所形成之包含基質層和軟質珠粒而成的樹脂皮膜，可 製造確保對於成形所使用之預塗金屬板而言基本的、優良 的成形性、外觀之預塗金屬板。特別，經由適切規範作爲 揮發成分比率之芳香族烴系溶劑比率，則可製造比先前之 預塗金屬板的光碟防止刮傷性更加提高的預塗金屬板。 又，若根據具備此類樹脂皮膜之本發明的預塗金屬板 ，則可節省部分後塗時的塗料更換、塗佈設備及廢氣等之 環境設備更換、塗佈作業者的人事費、批量管理和輸送管 理等之步驟管理費等，故可大幅低費用化。 【實施方式】 以下，適當參照圖面詳細說明實施本發明之預塗金屬 板及預塗金屬板之製造方法的最佳形態。於參照之圖面中 ，圖1爲說明本發明之預塗金屬板之構成的部分剖面圖。 圖2爲說明本發明之預塗金屬板之製造方法之內容的流程 圖。另外，於各圖中，對於同一之構成要素附以同一符號 予以說明。 1 .預塗金屬板 如圖1所示般，本發明之預塗金屬板1爲具備於基質 -12- 200918304 素材之金屬板2表面所形成的樹脂皮膜3。其中 膜3爲包含聚酯樹脂與硬化劑交聯反應而成的基 和在此基質層4中分散的軟質珠粒5所構成，令 5之含有率及平均粒徑控制成指定値。 此處’所謂金屬板2之表面，係意指金屬板 一面。例如，如圖3 ( b )所示之推入方式的光 3 0之蓋3 2般，光碟1 0的接觸面僅限於蓋3 2的 時，將本發明之預塗金屬板1使用作爲蓋3 2時 爲蓋3 2內面之表面形成樹脂皮膜3即可。此時 接觸光碟10之成爲蓋32外面的表面並無特別限ί 又，雖未圖示，例如，如可同時搭載多數光 光碟自動更換器用光碟托盤般，於托盤兩面接角 之情形中，使用本發明之預塗金屬板1作爲托盤 屬板2之兩面形成本發明之樹脂皮膜3即可。其 各構成。 (金屬板） 本發明所用之金屬板2並無特別限制，除了 冷軋鋼板以外，可應用熔融鍍鋅鋼板、電鍍鋅鋼 化溶融鍍鋅鋼板和鍍銅鋼板、鍍錫鋼板等之各種 、及，不鏽鋼等之合金鋼板、和鋁或銘合金板、 金板等之非鐵金屬板等全部。 此處，對於筆記型個人電腦搭載用之光碟驅 類、和液晶顯示裝置之框類、車載用電裝品之蓋 ，樹脂皮 質層4、 軟質珠粒 2的至少 碟驅動器 內側表面 ，僅在成 ，不直接 郎。 碟10之 i光碟10 ，並於金 次，說明 最一般的 板、合金 鑛敷鋼板 銅或銅合 動器的蓋 等要求輕 -13- 200918304 度之用途，以鋁板或鋁合金板爲佳。此等用途不僅要求輕 度且亦要求強度，故特別以JI S規定之5 0 5 2和5 1 8 2所代 表之Al-Mg系合金爲更佳。 (樹脂皮膜） 樹脂皮膜3爲如前述，由基質層4、和此基質層4中 所分散的軟質珠粒5，並於前述金屬板2之表面形成。 (基質層） 基質層4所使用的聚酯樹脂爲使用玻璃態化溫度爲0 °C以上50°C以下，更佳爲5°C以上40°C以下之聚酯樹脂。 經由令玻璃態化溫度爲此範圍，則交聯反應後之基質層4 爲適度軟質化，故即使於預塗金屬板1表面所形成之樹脂 皮膜3產生軟質珠粒5不均勻分散的部位時，亦因露出的 基質層4較軟，故可抑制對光碟10造成損傷。又，製造 預塗金屬板1時以線圈型式捲取之情形中，面對面的樹脂 皮膜3難因接觸面彼此捲取時之線圈溫度而發生熱熔黏的 封黏現象(adhesion phenomenon) ° 此處，玻璃態化溫度之上限値規定爲5 0 °C，係考慮使 用光碟10之光碟驅動器裝置和音響機器，光碟自動更換 器、車用導航驅動器裝置等之使用光碟之電子機器運作時 的內部環境溫度。 即，將玻璃態化溫度爲超過5 0°C的聚酯樹脂使用於基 質層4之情形中，即使於此些裝置實際運作的50°C中，基 -14- 200918304 質層4爲以硬玻璃狀存在，故於具有軟質珠粒5爲不均句 分散的部位時，光碟1 0具有可與玻璃狀之基質層4接觸 的可能性，恐因此令光碟1 0損傷。 又，將玻璃態化溫度爲低於〇 °C之聚酯樹脂使用於基 質層4之情形中，因爲基質層4過軟且樹脂皮膜3的黏性 (tackiness ;黏著性）變大，故將已加熱塗佈煅燒的金屬 板2以線圈型式捲取時，樹脂皮膜3具有接觸之面彼此間 發生熱黏著之封黏現象的可能性。 此類玻璃態化溫度爲〇 °C以上5 0 °C以下之聚酯樹脂可 適當使用大日本油墨化學工業公司（Dainippon Ink and Chemicals, Incorporated)製、日本 Paint 公司（Nippon Paint Co., Ltd.)製者。另外，同樣之塗料亦可使用關西 Paint公司（Kansai Paint Co.，Ltd.)製、大日本塗料公司 (Dai Nippon Toryo Co.，Ltd.)製、川上塗料公司（ Kawakami Paint Mfg. Co., Ltd.)製者等。 此基質層4爲使用胺系之硬化劑，其中亦以使用蜜胺 系硬化劑作爲硬化劑爲佳。蜜胺系硬化劑不僅於有機溶劑 中溶解即可輕易塗料化，且在常溫下塗料壽命爲長壽命’ 故若加熱則可在短時間輕易進行交聯反應，且軟質珠粒5 的分散性亦良好’更且因具有優良的塗佈性’故塗料對於 金屬板2表面的塗佈容易。 又，聚酯樹脂與硬化劑經由熱的交聯反應，因分子彼 此間爲手連手形成三次元網孔構造，故可確保樹脂皮膜3 作爲膜的強度’並且具有更加強固樹脂皮膜3與金屬板2 -15- 200918304 之接黏力的作用。更且，如前述之玻璃態化溫度爲0 °c以 上5 0 °c以下之聚酯樹脂與硬化劑交聯反應的樹脂皮膜3， 即使交聯反應後亦保持適度的柔軟度，故萬一，於預塗金 屬板1之表面所形成之樹脂皮膜3產生軟質珠粒5分散不 均勻的部位且基質層4爲直接接觸光碟10之情形，亦難 令光碟1 〇損傷且維持防止刮傷性。 (軟質珠粒） 於推入方式之光碟驅動器30中出入光碟10時，爲了 防止光碟1 〇損傷，乃不可或缺如前述令樹脂皮膜3變軟 。如後所詳述般，本案中使用胺基甲酸乙酯珠粒所代表之 軟質珠粒5令樹脂皮膜3部分軟質化，但本來令樹脂皮膜 變軟的常規手段爲非令樹脂皮膜部分軟質化，而爲令樹脂 皮膜全體軟質化，即，並非依賴珠粒等之添加劑，而爲令 基質層本身所使用之樹脂的玻璃態化溫度下降的方法，和 抑制成爲基質層之樹脂與硬化劑之交聯反應的方法等。 此等方法，具有令樹脂皮膜非部分地，而爲全體性軟 質化之效果，故令樹脂皮膜軟質化之效果大’但副作用爲 樹脂皮膜之表面全體出現黏性。又，因爲未使用珠粒故表 面平滑。若此類平滑且具有黏性的樹脂皮膜表面接觸光碟 1 0之表面，則光碟1 〇變成貼至樹脂皮膜之狀態’產生損 害光碟10出入時之光碟10本身之活動和光碟驅動器30 等使用光碟1 〇之機器動作的問題。 相對地，本發明中，並非令樹脂皮膜3之基質層4軟 -16- 200918304 質化，而爲採用於樹脂皮膜3(基質層4)中添加軟質之 微粒子，即，軟質珠粒5令樹脂皮膜3部分軟質化之手法 。若根據此類手法，則如前述般，因爲並非必定令基質層 4軟質化，故不必降低玻璃態化溫度、抑制交聯反應以增 大基質層4的黏性。 本發明中所謂之軟質珠粒5的軟質，例如，係指經由 微小壓縮試驗之使用單一珠粒令其1 0%變形時（單一珠粒 10%變形時）的壓縮強度爲l〇MPa以下左右者。 進行微小壓縮試驗之試驗機，例如，島津製作所公司 (Shimadzu Corporation)製之微小壓縮試驗機 MCT-W500 等，經由使用此試驗機，則可對粒徑1 μιη至1 00 μηι左右 之單一珠粒進行壓縮試驗。更具體而言，將粒徑爲5〜1 0 μηι，期望爲8 μιη左右之單一珠粒安裝至試驗機的下方加 壓板（lower pressure plate)，一邊降低上方加壓壓子（ upper pressure indenter) —邊對單一珠粒加以壓縮變形且 同時測定荷重，於珠粒徑爲減少1 0 %之時刻的荷重視爲 1 〇%壓縮荷重値。若將此1 0%壓縮荷重値視爲P ( N ) '測 定之珠粒粒徑視爲d ( mm )，則可根據下式（1 )算出 10%變形時的壓縮強度St ( MPa)(參照日本礦業會誌（ Journal of MMIJ) 、81.10.24 ( 1965))。另外，此 10% 變形時之壓縮強度St ( MPa )愈小，則珠粒愈軟。本發明 ，此1 0%變形時之壓縮強度St ( MPa )必須爲1 OMPa以下 ，期望爲5 Μ P a以下。 -17- 200918304。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Coated metal) and the method of manufacturing precoated metal sheets. [Prior Art] A metal thin plate (metal plate) represented by a steel plate and an aluminum plate or an aluminum alloy plate has both high strength and formability, and can be applied to household electric appliances by applying various forms of forming. Various uses such as products, automotive components, and building materials. The metal sheet molded article used for these applications is subjected to surface treatment for the purpose of improving appearance and corrosion resistance. In the surface treatment, a post-coat method has been used to form a metal plate into a predetermined shape, but recently, it has been fixed for the purpose of improving the workplace environment, simplifying manufacturing steps, and reducing costs. The pre-coated metal sheet in which the metal sheet is previously surface-treated is formed into a pre-coating method of a specified shape. Moreover, in recent years, such pre-coated metal sheets have been developed to provide various functions, such as anti-fingerprint property and anti-scratch property, in order to cope with the diversification and advancement of products and machines. ), ground connection property, heat release, heat shield, antibacterial property, lubricity and other functional pre-coated metal sheets, and have been widely used. Since such a precoated metal sheet is formed by performing a surface treatment, it is required to have excellent moldability for the film, and it is required to be an appearance of the product as it is formed. Surface appearance, traits, etc. For example, in Patent Document 1, it is proposed that an aluminum alloy sheet is made of an epoxy resin, a urethane resin, and an acrylic resin alone or a mixture thereof as a matrix resin, and contains SiO 2 5 to 40% having a particle diameter of 0.1 μm or less. And the paint of 5 to 60% of the lubricant is applied at a thickness of 〇5 to 10 μm, and the friction coefficient is controlled to a formability of 0.15 or less and a precoated metal sheet excellent in scratch resistance. The precoated metal sheet described in Patent Document 1 is a pre-coated metal sheet made of an aluminum alloy sheet which is generally made of aluminum as a material, and is suitable for a lightweight application. For example, it is also used in a disc drive for notebook computers. Covers and constructions of liquid crystal display devices, ECUs (Electronic Control Units) for vehicle-mounted devices, automotive audio systems, car navigation systems, and optical disk autochangers Structure. Figures 3(a) and (b) are perspective views showing the prior optical disk drive and the optical disk used therein, (a) showing the optical disk drive of the tray mode, and '(M is shown pushing (si〇t_in) As shown in Fig. 3 (a), in the tray type optical disc drive 20, the optical disc 10 such as a CD and a DVD is mounted in the tray 21, and the tray 21 is loaded into the cover 22, It is a method used in many current products. Also, as shown in Fig. 3(b), recently, a tray that does not mount the optical disc 1 开发 has been developed, and only the optical disc 1 〇 is inserted into the opening 3 1 The push-in mode of the optical disc drive 30. In the push-in mode of the optical disc drive 30, the optical disc is in the vicinity of the inner surface of the cover 32 of the optical disc drive 30, and the surface of the optical disc 10 is in the range of -5 to 200918304. Since the inner surface of the cover 32 of the optical disc drive 30 is rubbed and creased damage may occur, it is necessary to prevent the surface of the optical disc 10 from being damaged on the inner surface side of the cover 32 in order to prevent this. Inside the cover 3 2 of the disc drive 30 of the push mode, one One application for preventing partial scratching (post-coating) ° It is very cumbersome to apply such a post-coating to the cover 32, so it is difficult to develop a pre-fitted case even if it is in contact with the optical disc. A precoated metal sheet which is characterized in that the surface of the optical disc is scratched (hereinafter referred to as "scratch prevention"). In view of such expectations, the inventors of the present invention have developed a fluorine-based resin as a substrate layer and the substrate layer. The ratio of the film thickness to the particle diameter is a range of urethane beads of various particle sizes within a specified range, and the resin film blended at a specified compounding ratio is formed on the surface of the metal sheet, which can be used for forming. Pre-coated metal sheets have basic, excellent formability and appearance, and are difficult to adhere to adhesives in the use of adhesives, and are difficult to adhere to contaminants and oils, and have the ability to prevent scratches on optical discs. The pre-coated metal sheet has also been put into practical use (see Japanese Patent Application No. 2005-294 1 09). Moreover, the inventors have developed an epoxy resin as a substrate layer, and the film layer is made to have a thickness of the film. Ratio of particle size A wide range of urethane beads of various particle sizes within a predetermined range are formed on the surface of the metal sheet by a resin compound film having a specified compounding ratio, which is essential for the precoated metal sheet used for forming. In addition to the patent document 2, it is possible to strongly adhere the adhesive, and it also has a scratch-preventing pre-coated metal plate of the optical disc-6-200918304, and has been proposed (see In the case of the polyester resin, the epoxy resin, or the acrylic resin, the resin is contained in the matrix resin of the polyester, the fluorine, or the urethane. One of the resin beads and any of the carnauba, polyethylene, and microcrystalline (micr 〇crysta 11 ine) waxes, as a pre-coated metal plate designed to be pushed into the first actuator, and having a pre-proofing property Coating metal plates, etc. [Patent Document 1] Patent No. 3 3 3 8 1 5 6 (paragraph No. 0008-0017) [Patent Document 2] JP-A-2006-97127 [Claim of the Invention] (Problems to be Solved by the Invention) However, the patent The precoated metal sheet described in Document 1 can improve the formability and scratch resistance of the precoated metal sheet itself, but does not improve the scratch resistance of the surface of the optical disc. Therefore, as described above, it is necessary to form the finished cover 3 2 The inner surface is applied one by one, but if such treatment is carried out, the treatment is very complicated, so the productivity is extremely low and the problem is extremely expensive. Further, the scratch-preventing property of the precoated metal sheet described in Patent Document 2 cannot be said to have a sufficiently satisfactory scratch prevention property according to the user, and these users are more strongly required to improve the scratch prevention. Injurious. SUMMARY OF THE INVENTION The present invention has been made in view of the foregoing problems, and provides a method and method for manufacturing a pre-coated 200918304 metal plate and a precoated metal sheet which prevent damage to the optical disk, i.e., prevent scratching more than that of the prior precoated metal sheet. (Means for Solving the Problem) In order to solve the above problems, the inventors of the present invention have made efforts to improve the scratch resistance of the optical disk, and to strictly limit the particle size and the amount of the soft beads which are the most dominant in preventing scratches. Improve basic scratch resistance. Further, 'the type of resin and the glass transition temperature of the matrix layer in which the soft beads are dispersed are strictly limited', and the portion where the soft beads are unevenly dispersed in the resin film is obtained, and the matrix layer is not used as the soft beads. The contact with the disc itself can also minimize the damage caused by the disc to the minimum risk of the resin film. Further, it has been found that under the use of a coating material as a volatile component in which the dispersibility of the soft beads is increased, the risk of occurrence of unevenness of the bead dispersion in the resin film and the exposure of the matrix (base metal) layer can be remarkably reduced. The present invention has been completed. The precoated metal sheet according to the present invention for solving the above problems is a precoated metal sheet having a resinous coating film formed on the surface of the metal sheet, the resin film having a glass transition temperature of 0°. a matrix of a cross-linking reaction of a polyacetal resin having a C content of 50 ° C or less and a hardener, and a dispersion in the matrix layer, according to a single micro compression test Soft beads having a compressive strength of 10% or less when the beads are deformed by 10% or less, and the content of the soft beads is 15% by mass or more and 5% by mass or less with respect to the matrix layer. The average particle diameter is 1.1 times the average thickness of the matrix layer and 5 times or less from -8 to 200918304. Here, it is preferred that the soft beads used in the precoated metal sheet of the present invention are amine urethane beads. As described above, the precoated metal sheet of the present invention is a resin film composed of a matrix layer formed on the surface and soft beads, thereby ensuring basic, excellent formability and appearance for the precoated metal sheet used for forming. Secondly, by controlling the soft bead content and the average particle diameter of the urethane beads dispersed in the matrix layer, even if the precoated metal plate contacts the optical disc, the soft bead can act as a cushioning material. Prevent scratches on the surface of the disc. Here, the excellent scratch resistance for the optical disk is ensured, and as a result of balancing with other characteristics, the average particle diameter of the soft beads is 1.1 times or more and 5 times or less the average thickness of the matrix layer. Further, the content of the soft beads is 15% by mass or more and 50% by mass or less based on the matrix layer. That is, 'By the average particle diameter of the urethane beads is 1.1 times or more the average thickness of the matrix layer, the urethane beads can be inhibited from being buried in the matrix layer' and the urethane beads are present. When the average particle diameter of the granules is 5 times or less of the average thickness of the matrix layer, the urethane beads can be prevented from falling off from the matrix layer, so that the function of the urethane beads as a buffer material can be induced to a high degree. In addition, when the content of the ethyl urethane is 15% by mass or more based on the matrix layer, the function of the ethyl urethane as a buffer material can be ensured to be 'containing' by the urethane beads. When the rate is 5 〇 mass% or less, the viscosity of the coating can be suppressed from increasing and the coating property can be ensured. Also, 'Doctor 1 is the matrix layer of the main component of the resin film. The glass transition temperature is -9- 200918304. The polyester resin which is 〇°C or more and 50 ° C or less is crosslinked with a hardener to form a thermosetting polyester. The resin, so the matrix layer after the crosslinking reaction is moderately softened. Therefore, if a soft bead uneven portion is formed on the surface of the resin film after coating, even if the portion contacts the optical disk, the scratch of the optical disk can be reduced via the exposed substrate layer. In the precoated metal sheet of the present invention, the metal sheet is desirably an aluminum sheet or an alloy sheet. If so treated, it is not only difficult to cause scratching even when the optical disk is touched, but an easy product can be obtained when forming the product. Further, the method for producing a precoated metal sheet according to the present invention is a method for producing a precoated metal sheet having a resin film on a metal sheet, and includes a coating step and a heating step. In the coating step, a polyester resin having a glass energyizing temperature of 〇 ° C or more and 50 ° C, and a hardener, and a soft strength at a 10% deformation of a single particle according to a micro compression test of 10 MPa or less are soft. The coating material of the beads and the uniformly dispersed volatile components is coated on the metal plate, and in the heating step, the metal plate coated with the coating material in the coating step is heated at a temperature of 200 ° C or higher. Below 0 0 °C, the heating time is heated for more than 20 seconds and less. Here, the ratio of the components in the coating material, the content of the soft beads, is adjusted in advance to 15% by mass or more and 50% by mass or less based on the matrix layer of the polyester resin and the curing agent, and the wet film at the time of cloth When the thickness is also a dry film after the heating step, the average particle diameter of the soft beads is preliminarily applied to a thickness of 1.1 times or more the average thickness of the matrix layer. In this way, the cross-linking reaction of such a coating can be carried out by making a cross-linking reaction of the polyester resin and the hardener on the surface of the metal sheet, and the aluminum-coated surface is separated into a bead and the heat is 60. -10- 200918304 The content of the soft bead of the matrix layer is 15% by mass or more and 50% by mass or less, and the average particle diameter of the soft bead is 1.1 times or more and 5 times or less the average thickness of the matrix layer. The precoated metal sheet of the film. In the method for producing a precoated metal sheet of the present invention, the content ratio of the aromatic hydrocarbon solvent in the volatile component is made 30% by mass or more. If so treated, it is possible to greatly suppress the soft beads dispersed in the coating from settling in the coating and re-aggregating. Therefore, the dispersion state of the soft beads in the coating material is still good on the metal plate, so that the resin film after coating can be greatly reduced, and the dispersion of the soft beads is uneven. As a result, the soft beads are a small portion, that is, the exposed portion of the matrix layer is drastically reduced. In this way, the probability of scratching the surface of the disc can be reduced. The soft beads used in the method for producing a precoated metal sheet of the present invention are preferably urethane beads. If this is the case, since the soft beads can be used as a cushioning material, it is possible to obtain a precoated metal plate which can prevent the surface of the optical disk from being scratched. In the method of producing a precoated metal sheet of the present invention, the metal sheet is desirably an aluminum sheet or an aluminum alloy sheet. If so, it is not only difficult to cause scratches even when the optical disk is touched, but a lightweight product can be obtained when the product is formed. (Effect of the Invention) According to the precoated metal sheet of the present invention, the resin film comprising the matrix layer and the soft beads formed on the surface of the metal sheet not only ensures the basicity of the precoated metal sheet used for forming. Excellent moldability and appearance, and by optimizing the yield and average particle diameter of the soft beads dispersed in the resin film (matrix layer), the resin film surface may be in contact with the surface of the optical disk. To make the disc's scratch resistance more improved than the previous pre-coated metal sheet. According to the method for producing a precoated metal sheet according to the present invention, the resin film comprising the matrix layer and the soft beads formed on the surface of the metal sheet can be manufactured to ensure the basicity of the precoated metal sheet used for forming. Pre-coated metal sheet with excellent formability and appearance. In particular, the ratio of the aromatic hydrocarbon-based solvent which is a ratio of the volatile component to the ratio of the volatile component can be used to produce a precoated metal sheet having a higher scratch-preventing property than the conventional precoated metal sheet. Further, according to the precoated metal sheet of the present invention having such a resin film, it is possible to save the replacement of the paint during the post-coating, the replacement of the environmental equipment such as the coating equipment and the exhaust gas, the personnel cost of the coating operator, and the batch management. With the management fee of the steps such as the transportation management, etc., it can be significantly reduced in cost. [Embodiment] Hereinafter, the best mode for carrying out the method for producing a precoated metal sheet and a precoated metal sheet according to the present invention will be described in detail with reference to the drawings. In the drawings, Fig. 1 is a partial cross-sectional view showing the configuration of a precoated metal sheet of the present invention. Fig. 2 is a flow chart for explaining the contents of the method for producing a precoated metal sheet of the present invention. In the drawings, the same components are denoted by the same reference numerals. 1. Precoated metal sheet As shown in Fig. 1, the precoated metal sheet 1 of the present invention is a resin film 3 formed on the surface of the metal sheet 2 of the substrate -12-200918304. The film 3 is composed of a base comprising a crosslinking reaction of a polyester resin and a curing agent, and a soft bead 5 dispersed in the matrix layer 4, and the content and average particle diameter of 5 are controlled to a specified enthalpy. Here, the surface of the metal plate 2 means one side of the metal plate. For example, as shown in FIG. 3(b), the push-on light of the push-type 3 is the cover 3, and when the contact surface of the optical disc 10 is limited to the cover 32, the pre-coated metal plate 1 of the present invention is used as a cover. At 3 o'clock, the resin film 3 may be formed on the surface of the inner surface of the lid 3 2 . At this time, the surface of the optical disk 10 that is the outer surface of the cover 32 is not particularly limited. For example, if not shown, for example, a plurality of optical disk trays for optical disc changers can be mounted at the same time, and the trays are used on both sides of the tray. The precoated metal sheet 1 of the present invention may be formed as the resin film 3 of the present invention on both sides of the tray member sheet 2. Each of its components. (Metal sheet) The metal sheet 2 used in the present invention is not particularly limited, and various types of hot-dip galvanized steel sheets, electrogalvanized steel galvannealed galvanized steel sheets, copper-plated steel sheets, tin-plated steel sheets, and the like can be applied, and , alloy steel plates such as stainless steel, and non-ferrous metal plates such as aluminum or alloy plates, gold plates, etc. Here, the disc drive type for the notebook type personal computer, the frame of the liquid crystal display device, the cover for the vehicle electric appliance, the resin cortex layer 4, and at least the inner surface of the disc drive 2 of the soft bead 2 are only formed. Not direct lang. The disc 10 of the i-disc 10, and in the gold, shows that the most common board, alloy ore plate, copper or copper clutch cover, etc., require light -13-200918304 degrees, preferably aluminum or aluminum alloy. These applications are not only required to be mild but also required to be strong, so that the Al-Mg alloy represented by 506 and 591 is particularly preferable. (Resin film) The resin film 3 is formed of the matrix layer 4 and the soft beads 5 dispersed in the matrix layer 4 as described above, and is formed on the surface of the metal plate 2. (Matrix Layer) The polyester resin used for the matrix layer 4 is a polyester resin having a glass transition temperature of from 0 ° C to 50 ° C, more preferably from 5 ° C to 40 ° C. When the glass transition temperature is in this range, the matrix layer 4 after the crosslinking reaction is moderately softened, so that even when the resin film 3 formed on the surface of the precoated metal sheet 1 produces a portion where the soft beads 5 are unevenly dispersed, Also, since the exposed substrate layer 4 is relatively soft, damage to the optical disc 10 can be suppressed. Further, in the case where the precoated metal sheet 1 is wound in a coil type, the face-to-face resin film 3 is hard to be thermally fused by the coil temperature when the contact faces are wound up each other. The upper limit of the glass transition temperature is specified to be 50 °C. It is the internal environment in which the optical drive using the optical disc, the optical disc changer, the car navigation drive device, etc. temperature. That is, in the case where a polyester resin having a glass transition temperature of more than 50 ° C is used for the substrate layer 4, even if the device is actually operated at 50 ° C, the base layer 14 - 200918304 is hard. When the soft bead 5 is a portion where the uneven beads are dispersed, the optical disk 10 has a possibility of coming into contact with the glassy substrate layer 4, which may cause the optical disk 10 to be damaged. Further, in the case where a polyester resin having a glass transition temperature lower than 〇 ° C is used for the matrix layer 4, since the matrix layer 4 is too soft and the tackiness (adhesiveness) of the resin film 3 becomes large, When the heat-coated and calcined metal sheet 2 is wound up in a coil form, the resin film 3 has a possibility that a heat-adhesive sealing phenomenon occurs between the surfaces in contact with each other. Such a polyester resin having a glass transition temperature of not more than 〇 ° C and 50 ° C or less can be suitably used by Dainippon Ink and Chemicals, Incorporated, and Japan Paint Company (Nippon Paint Co., Ltd.). ) Manufacturer. In addition, the same coating material can also be used by Kansai Paint Co., Ltd., manufactured by Dai Nippon Toryo Co., Ltd., Kawakami Paint Mfg. Co., Ltd. .) Manufacturers, etc. The base layer 4 is an amine-based hardener, and it is preferred to use a melamine-based hardener as a hardener. The melamine-based hardener can be easily coated not only by dissolving in an organic solvent, but also has a long life of the coating at normal temperature. Therefore, if heated, the crosslinking reaction can be easily carried out in a short time, and the dispersibility of the soft beads 5 is also It is good 'more and because of excellent coating properties', the coating is easy to apply to the surface of the metal plate 2. Further, the polyester resin and the curing agent undergo a thermal crosslinking reaction, and the ternary mesh structure is formed by hands of the molecules, so that the resin film 3 can be ensured as the strength of the film and the resin film 3 and the metal are more reinforced. The effect of the adhesion of the board 2 -15- 200918304. Further, the resin film 3 in which the polyester resin having a glass transition temperature of 0 ° C or more and 50 ° C or less is crosslinked and reacted with a curing agent maintains moderate softness even after the crosslinking reaction, so in case The resin film 3 formed on the surface of the precoated metal sheet 1 produces a portion where the soft beads 5 are unevenly dispersed, and the substrate layer 4 is in direct contact with the optical disc 10, and it is difficult to damage the optical disc 1 and maintain scratch resistance. . (Soft Bead) When the optical disc 10 is inserted into and removed from the optical disc drive 30 of the push type, it is indispensable to make the resin film 3 soft as described above in order to prevent damage to the optical disc 1 . As described in detail later, in the present case, the soft bead 5 represented by the urethane beads is used to soften the resin film 3, but the conventional means for softening the resin film is to soften the resin film portion. In order to soften the entire resin film, that is, it is not dependent on an additive such as a bead, but a method of lowering the glass transition temperature of the resin used for the substrate layer itself, and suppressing the resin and the hardener which become the matrix layer. The method of crosslinking reaction, and the like. These methods have the effect of softening the resin film in a non-partial manner, and the effect of softening the resin film is large. However, the side effect is that the entire surface of the resin film is sticky. Also, since the beads are not used, the surface is smooth. If such a smooth and viscous resin film surface contacts the surface of the optical disk 10, the optical disk 1 becomes a state of being attached to the resin film, which causes damage to the optical disk 10 itself when the optical disk 10 is taken in and out, and the optical disk drive 30 and the like use the optical disk. 1 The problem of machine movement. In contrast, in the present invention, the matrix layer 4 of the resin film 3 is not softened, but soft particles are added to the resin film 3 (substrate layer 4), that is, soft beads 5 The method of softening the 3 parts of the film. According to such a method, as described above, since the matrix layer 4 is not necessarily softened, it is not necessary to lower the glass transition temperature and suppress the crosslinking reaction to increase the viscosity of the matrix layer 4. The softness of the soft bead 5 in the present invention means, for example, a compression strength of 10 MPa or less when a single bead is deformed by a single compression test by a micro compression test (when a single bead is deformed by 10%). By. A test machine for performing a micro-compression test, for example, a micro-compression tester MCT-W500 manufactured by Shimadzu Corporation, and a single bead having a particle diameter of about 1 μm to about 100 μm by using the test machine. Perform a compression test. More specifically, a single bead having a particle diameter of 5 to 10 μm and desirably about 8 μηη is attached to a lower pressure plate of the testing machine while lowering the upper pressure indenter ) - while compressing and deforming a single bead and simultaneously measuring the load, the load at the time when the bead size is reduced by 10% is 1% by compression load 値. If the 10% compression load 値 is regarded as P ( N ) 'the measured bead size is regarded as d ( mm ), the compressive strength St (MPa) at 10% deformation can be calculated according to the following formula (1) ( Refer to the Journal of MMIJ, 81.10.24 (1965). In addition, the smaller the compressive strength St (MPa) at the 10% deformation, the softer the beads. In the present invention, the compressive strength St (MPa) at the time of 10% deformation must be 1 OMPa or less, and desirably 5 Μ P a or less. -17- 200918304
St = 2.8P/ ( Πά2 )......式（1 ) (但，於式（1)中，Π爲表示圚周率） 若根據使用此類軟質珠粒5的方法，則基質層4不會 產生黏性，故不會發生樹脂皮膜3與光碟1 0貼合之問題 ，且可提高對於光碟1〇的防止刮傷性。另外，此類軟質 珠粒5可適當使用例如，胺基甲酸乙酯珠粒、乙烯•甲基 丙烯酸甲酯共聚物（EMMA )珠粒、低密度聚乙烯（LDPE )珠粒等。另外，胺基甲酸乙酯珠粒可適當使用三洋化成 公司（Sanyo Chemical I n du s t r i e s , L t d .)製之 ME L T E X ( MELTEX ;註冊商標） '大日精化公司（Dainichiseika Color & Chemicals Mfg. Co.，Ltd.)製之 DAIMIC BEADS (DAIMIC BEADS ;註冊商標）、根上工業公司（N e g am i Chemical I n d u s t r i al C o ·，L t d ·)製之 A R T P E A R L ( A R T PEARL ;註冊商標）等。又，EMMA珠粒可適當使用住友 精化公司（Sumitomo Seika Chemicals Co., Ltd.)製之 SOFT BEADS ( SOFT BEADS) A、S OFT BE AD S B 等，且 LDPE珠粒可適當使用住友精化公司製之 FLO-BEADS ( FLO-BEADS ;註冊商標）等。 前述，說明即使未經由使用軟質珠粒5令基質層4軟 質化亦可確保對於光碟1 〇的防止刮傷性，但本發明中， 使用可產生此類效果的軟質珠粒5、和玻璃態化溫度爲〇 t以上5 (TC以下之聚酯樹脂。如此，經由與軟質的基質層 4併用，結果可令樹脂皮膜3全體更加軟質化。因此，比 -18- 200918304 僅部分軟質化的軟質珠粒5，可更加提高防止刮傷性。另 外，因樹脂皮膜3全體爲被軟質化，故擔心如前述之黏性 問題，但因具備軟質珠粒5，故即使光碟1 0出入亦不會因 黏性而產生妨礙動作。 即，並非僅單獨使用軟質之基質層4，而爲倂用軟質 珠粒5，並且控制基質層4之平均厚度與軟質珠粒5之粒 徑，故樹脂皮膜3之表面並非平滑而爲具有凹凸的表面狀 態。即，樹脂皮膜3中與光碟1 0表面接觸之幾乎所有部 分成爲軟質珠粒5的前端，大幅抑制光碟1 0與具有黏性 之基質層4爲直接接觸的機會。其結果，迴避光碟1〇與 樹脂皮膜3貼合之黏性問題。另外，因爲於軟質珠粒5中 具有如後說明之粒徑分佈，故雖未圖示，即使熱硬化性聚 酯樹脂薄薄覆被至較小之軟質珠粒5前端之情形，亦可經 由其鄰接之更大的軟質珠粒5確保防止刮傷性。 又，於本發明中，即使形成樹脂皮膜3後之預塗金屬 板1的表面軟質珠粒5爲不均句分散，產生基質層4露出 之部分，亦可與軟質珠粒5合倂，令基質層4亦適度軟質 化，使得即使光碟1 0與預塗金屬板1爲直接接觸之情形 ，亦可防止該光碟10的表面捐傷。 (軟質珠粒之含有率：1 5質量％以上5 0質量％以下） 爲了提局光碟10的防止刮傷性，令軟質珠粒5之含 有率，相對於基質層4較多者爲佳。軟質珠粒5之含有率 未滿1 5質量％，則於基質層4中所固定的軟質珠粒5份量 -19- 200918304 少’作爲緩衝材的機能降低，且防止刮傷性差。又’若提 高軟質珠粒5的含有率，則分散軟質珠粒5之塗料黏度增 黏’故以輥塗等將塗料塗佈至金屬板2之情形中，難將膜 厚控制成均勻（即，塗佈性惡化）。由上述理由，軟質珠 粒5的含有率相對於基質層4爲1 5質量％以上50質量％ 以下。爲了確保更加安定的塗佈性，令軟質珠粒5之含有 率爲40質量％以下爲佳。 (軟質珠粒之平均粒徑：基質層之平均厚度的1 . 1倍以上 5倍以下） 爲了以軟質珠粒5提高光碟1 0的防止刮傷性，其重 要爲令軟質珠粒5的平均粒徑大於基質層4的平均厚度。 經由令軟質珠粒5的平均粒徑大於基質層4的平均厚度， 則如圖1所示般，樹脂皮膜3的剖面形狀成爲軟質珠粒5 之存在部分爲凸出之具有微細凹凸形狀的樹脂皮膜3。因 此，光碟1 〇與樹脂皮膜3接觸時柔軟的軟質珠粒5不僅 作用爲緩衝材，且可大幅減低光碟10與基質層4直接接 觸，故不會產生光碟1〇的動作不良且可更加提高防止刮 傷性。 此處，軟質珠粒5之平均粒徑若相對於基質層4之平 均厚度爲超過5倍’則無法被固定於基質層4中並且發生 軟質珠粒5脫落’故降低可提高光碟1 0之防止刮傷性的 效果。即，經由避免使用比基質層4之平均厚度顯著大粒 徑的軟質珠粒5 ’則即使基質層4中之軟質珠粒含有率變 -20- 200918304 大亦可防止軟質珠粒脫落。又，軟質珠粒 相對於基質層4之平均厚度未滿1 . i倍， 珠粒5易埋沒至基質層4，故降低可提高$ 傷性的效果。因此，軟質珠粒5之平均粒 平均厚度的1 · 1倍以上5倍以下。另外， 厚度的1 · 5倍以上4倍以下爲更佳。 另外，若軟質珠粒5之平均粒徑與基 度爲保持此類關係，則可提高光碟1 〇的 若即使保持前述關係，使用超過必要大小 5，則必須亦增厚基質層4的平均厚度， 變厚至超過必要，爲不經濟的。另一方面 要之小軟質珠粒5之情形中，於工業上難 5之均粒徑與基質層4之平均厚度的關係 粒5之平均粒徑爲使用5〜30 μηι左右者爲 的平均厚度爲3 μιη以上1 5 μιη以下爲更 明中之基質層4的平均厚度爲測定每單位 3的重量，且以比重視爲1換算求出。 此處，如前述般，於軟質珠粒5的粒 如，積算體積50%粒徑（Cumulative 5 0% diameter)大約8 μιη左右之珠粒的粒徑分 1 μηι左右至最大20 μηι左右爲止分佈（ 精化工業（股）之主頁的DYMIC BEADS 粒度分佈（與粒徑分佈同義）。於是，本 粒5的粒徑指標爲採用平均粒徑。另外， 5之平均粒徑若 則粒徑小的軟質 ί碟1 0之防止刮 徑爲基質層4之 基質層4之平均 質層4之平均厚 防止刮傷性，但 粒徑的軟質珠粒 故令樹脂皮膜3 ，於使用超過必 以控制軟質珠粒 。因此，軟質珠 佳，且基質層4 佳。另外，本發 面積之樹脂皮膜 徑存在分佈。例 volume particle 佈已知爲由最小 例如，參照大曰 (註冊商標）的 發明中，軟質珠 本發明中所謂之 -21 - 200918304 平均粒徑，係指軟質珠粒5於水中分散之狀態下，以雷射 繞射式粒度分佈測定器等所測定之積算體積50%粒徑。 另外，本發明之預塗金屬板1爲於金屬板2、與含有 軟質珠粒5及基質層4之樹脂皮膜3之間，具備耐蝕性皮 膜（未予圖示）。 經由形成耐蝕性皮膜，則可對預塗金屬板1賦予耐鈾 性，並且提高金屬板2與樹脂皮膜3的接黏性。 此類耐蝕性皮膜的構成可使用含有C r或Zr作爲成分 之先前公知的耐蝕性皮膜。例如，可適當使用磷酸鉻酸酯 皮膜、磷酸鍩皮膜、氧化锆系皮膜、或塗佈型鉻皮膜等。 又，耐蝕性皮膜之附著量以 Cr或 Zr換算値爲 10〜5〇mg/m1爲佳。耐蝕性皮膜的附著量若少於1〇 mg/m1 ，則無法均勻覆被金屬板2全面，難以確保耐蝕性，無法 承受長期使用。又，耐蝕性皮膜的附著量若超過50 mg/m1 ’則於成形等，耐鈾性皮膜本身產生裂開（剝離），且難 長期維持高耐蝕性。 -22- 1 _預塗金屬板之製造方法 其次’參照圖2 ’詳細說明本發明之預塗金屬板的製 造方法。 如圖2所示般’本發明之預塗金屬板之製造方法爲包 含塗佈步驟S 1、和加熱步驟S 2。以下，說明各步驟。另 外於本發明之塗佈步驟S 1中，亦包含調整具有後述指定 組成之塗料的作業。 200918304 (塗佈步騾） 塗佈步驟S1爲將塗料之必須成分之玻璃態化溫度爲〇 °C以上5 (TC以下之聚酯樹脂、和硬化劑、和根據微小壓縮 試驗之單一珠粒10%變形時的壓縮強度爲l〇MPa以下之軟 質珠粒5、和令彼等均勻分散之揮發成分，充分混合並將 熱硬化性聚酯系塗料（以下，將其單稱爲「塗料」）於金 屬板2之表面塗佈的步驟。 另外，前述之必須成分中，軟質珠粒的含有率爲以經 過後述說明之加熱步驟S2，相對於聚酯樹脂與硬化劑交 聯反應之基質層4爲1 5質量％以上5 0質量％以下般預先 調整比率。 此處，前述之聚酯樹脂爲使用令多價醇與多元酸縮聚 所得的飽和聚酯樹脂。 其中，多價醇可使用例如，乙二醇、丙二醇、新戊二 醇、1，3-丁二醇、1,6-己二醇、二乙二醇等之二價醇、甘 油、三羥甲基乙烷、三羥甲基丙烷等之三價醇、及四價以 上之醇類等。 又’多元酸可使用例如，苯二甲酸酐、間苯二酸酐、 對苯二酸酐、己二酸、癸二酸等之二元酸、偏苯三酸酐等 之三元酸、及四價以上之多元酸等。 此等多價醇及多元酸可使用一種或同時使用二種以上 縮聚亦可，但以測定縮聚所製造之聚酯樹脂的玻璃態化溫 度，且爲0°C以上50。(：以下者，可使用於本發明之預塗金 -23- 200918304 屬板1之製造方法。 另外，玻璃態化溫度可根據差示掃描熱量測定（DSC ;differential scanning calorimetry)等之常法則可測定。 硬化劑可使用具有二個以上胺基之胺系硬化劑、和具 有二個以上異氰酸酯基之異氰酸酯系硬化劑等，由塗料安 定性等而言期望使用胺系硬化劑，且其中亦更期望爲蜜胺 系硬化劑。 揮發成分必須令硬化劑及軟質珠粒5於前述聚酯樹脂 中溶解或分散，又，必須確保塗佈上最適的塗料黏度。 軟質珠粒5爲以攪拌裝置充分攪拌，且可於塗料中均 勻分散，若停止拌且長時間放置，則因重力等而沈降、凝 集。 揮發成分爲以後述之加熱步驟S 2予以加熱，且於交 聯反應時揮發，不會以樹脂皮膜3之成分型式殘存，但此 成分爲何種物質均對塗料中之軟質珠粒5的分散性造成影 響，結果對於塗佈及交聯反應後之樹脂皮膜3的軟質珠粒 5的分佈造成大影響。 於本發明中，揮發成分中之芳香族烴系溶劑的含有比 率爲3 0質量％以上爲佳。若揮發成分之芳香族烴系溶劑的 含有比率爲3 0質量％以上，則可適當取得抑制塗料中分散 之軟質珠粒5之沈降（settling)和再凝集（reagregation )的效果。因此，因爲安定維持塗料的均勻性，故於塗佈 後之樹脂皮膜3中’可大幅降低發生軟質珠粒5分散不均 勻部位的可能性。如此，可更加確實防止光碟1 0表面損 -24- 200918304 害。此處，若考慮提高光碟1 0表面之防止刮傷性，則令 芳香族烴系溶劑之含有比率爲5 0質量％以上爲佳。另外， 即使揮發成分中之芳香族烴系溶劑的含有比率爲未滿5質 量％亦無妨，但難以有效取得前述效果。 具體的揮發成分例爲於水、異氟爾酮、環己酮、甲基 異丁基酮、甲醇、丁醇、雙丙酮醇、丁基溶纖劑、乙二醇 單丁醚、醋酸乙酯、醋酸丁酯等單獨或混合之溶劑中，將 乙基苯、二甲苯、甲苯、三甲基苯、萘、芳香族石油腦等 之芳香族烴系溶劑單獨或混合作成3 0質量％以上之含有比 率爲佳。 其次，將調整至含有率爲1 5質量％以上5 0質量％以 下之軟質珠粒5於塗料中均勻分散。於塗料中令軟質珠粒 5分散的處理方法可列舉超音波處理、磁鐵攪拌子（ magnet stirrer)和以渦輪攪拌機（impeller mixer)之攪 拌處理、使用均質器（homogenizer)、磨碎機（attritor )、球磨（ball mill)、珠粒磨（beads mill)等之攪拌處 理 方法。 此類 塗料之塗佈可依據刷子 (bru sh )、輥 塗器 (roll C 0 ater )、 幕流塗層器（curtain f 1 o w coater) 、輥幕塗層 器 (r ο 11 e r curtain coater ) 、靑爭 電塗 佈機（e 1e ctro static C 〇 ater ) 、刀塗器（blade coater ) •型板塗 層器 (die coater )等任一種手段進行，特別，以塗佈量爲均勻，且 作業簡便的輥塗器爲較佳使用。 另外，配合所使用之軟質珠粒5的粒徑調整塗料之塗 -25- 200918304 佈量’則可令軟質珠粒5的平均粒徑爲基質層4之平均厚 度的1 · 1倍以上5倍以下。本發明中，軟質珠粒5之平均 粒徑以使用5〜30 μπι左右者爲佳，故塗佈量爲以金屬板2 之表面形成平均厚度3〜15 4„!的基質層4般，適當調整金 屬板2的搬送速度、輥的迴轉方向和迴轉速度、輥間的押 壓（噴嘴壓）等即可。經由調整此等條件，則可變更轉印 至金屬板2之乾燥前的塗料厚度（即，溼膜厚）。其結果 ，可調整經後述加熱步驟S 2之交聯反應，並且乾燥之乾 燥皮膜之基質層4的平均厚度，且如前述般，可令軟質珠 粒5的平均粒徑爲基質層4之平均厚度的1 · 1倍以上5倍 以下。 另外’於此類塗料之塗佈前，亦可設置將金屬板2表 面予以脫脂的脫脂步驟（未予圖示）。脫脂步驟爲例如於 金屬板2之表面將酸和鹼水溶液噴霧，其後，水洗則可將 金屬板2之表面脫脂。 更且，如前述，於金屬板2與樹脂皮膜3之間具備耐 貪虫性皮膜之情形中，接著脫脂步驟，將含有鉻離子等之化 成處理液於金屬板2之表面噴霧並水洗，或者塗佈含有鉻 離子等之處理液並且乾燥，則可形成耐蝕性皮膜。 (加熱步驟） 加熱步驟S 2爲將具有塗佈步驟S 1所塗佈塗料之金屬 板2，以加熱溫度爲2 0 0 °C以上3 0 0 °C以下’加熱時間爲 20秒鐘以上60秒鐘以下之條件予以加熱的步驟°此加熱 -26- 200918304 步驟S2，令塗料中所含之揮發成分蒸發且乾燥，並且經 加熱的塗料爲進行交聯反應於金屬板2之表面形成樹脂皮 膜3(包含軟質珠粒5之基質層4)，並且強固接黏至該 金屬板2。另外，加熱步驟S 2所加熱的軟質珠粒5 ’當然 於基質層4中以適度分散之狀態被固定。 另外，經由加熱溫度，不會令樹脂皮膜3所造成之光 碟1 〇的防止刮傷性受到影響，但加熱溫度若未滿20(TC， 則塗料的交聯反應不夠充分，加熱溫度若超過3 00 °C，則 塗料（樹脂皮膜3 )熱惡化（分解），故以2 00°C以上300 °C以下爲佳。加熱時間爲20〜60秒鐘爲佳。加熱時間未滿 2〇秒鐘則易變成加熱不足，若超過60秒鐘則加熱時間爲 過長，故每時間的生產性降低，故爲不佳。 此加熱步驟S2爲例如可使用熱風爐、誘導加熱爐、 近紅外線爐、遠紅外線爐、能量線硬化爐進行。 〔實施例〕 其次，關於本發明之預塗金屬板及預塗金屬板之製造 方法，爲令滿足本發明要件之實施例、與未滿足本發明要 件之比較例對比且具體說明。 檢討之項目爲塗料中所用之樹脂種類及玻璃態化溫度 及樹脂皮膜之基質層的平均厚度、基質層中分散之軟質珠 粒的含有率、平均粒徑及塗料之揮發成分中之芳香族烴系 溶劑的含有比率。其次，評價對於光碟之防止刮傷性及塗 佈性、封黏性。以下詳述。 -27- 200918304 〔實施例1〜1 3〕 如表1所示般，實施例1〜1 3爲將含有玻璃態化溫度 爲〇 °C以上5 (TC以下之聚酯樹脂、和硬化劑、和具有本發 明所規定之1 0%變形時之壓縮強度的軟質珠粒、和令彼等 分散之揮發成分的塗料塗佈至金屬板，其次，將塗佈塗料 的金屬板以加熱溫度2 5 (TC、加熱時間3 0秒鐘加熱煅燒， 製造具備樹脂皮膜的預塗金屬板。此處，軟質珠粒爲使用 胺基甲酸乙酯珠粒。另外，實施例1〜1 3所用之金屬板爲 使用於其兩面，預先形成經磷酸鉻酸酯處理以提高耐蝕性 的耐蝕性皮膜者。磷酸鉻酸酯皮膜的附著量換算成Cr爲 2〇mg/m2。預塗金屬板之各構成爲如下。 (金屬板） 金屬板爲使用厚度0.5 mm，JIS規定之5052-H34的鋁 合金板。 (樹脂皮膜） 樹脂皮膜爲於磷酸鉻酸酯皮膜上令作爲軟質珠粒的胺 基甲酸乙酯珠粒分散，並且塗佈含有玻璃態化溫度爲0 °C 以上5 0 °C以下之聚酯樹脂的塗料，並以前述之加熱溫度及 加熱時間進行加熱處理則可形成。此處，金屬板的加熱方 式爲將已塗佈塗料的金屬板放置於輸送帶並由烤爐入口往 出口移動的連續锻燒（continuous backing)方式，並將金 -28- 200918304 屬板通過烤爐內的時間定義爲加熱時間’且其爲3 0秒鐘 。又，將確認貼附至金屬板之加熱程度之金屬板的最高到 達溫度定義爲加熱溫度，且其爲25 0 °c。 (玻璃態化溫度爲〇 °c以上5 0 °C以下之聚酯樹脂） 玻璃態化溫度爲〇 °C以上5 0t以下之聚酯樹.脂爲使用 大日本油墨化學工業公司製、日本Paint公司製者。 〔比較例1〜1 5〕 製造比較例1〜1 5之預塗金屬板’作爲實施例1 ~ 1 3的 對照。比較例1 ~ 1 5之預塗金屬板的製造’除了下列所述 之點以外，根據製造實施例1〜13之條件，構成。 比較例1及比較例2爲玻璃態化溫度未滿足本發明所 規定之數値範圍。比較例3至比較例6爲使用非本發明所 規定之聚酯樹脂種類的樹脂。比較例7及比較例8爲軟質 珠粒之平均粒徑，與基質層之平均厚度的關係’並不滿足 本發明所規定之數値範圍。又’比較例9至比較例1 3爲 軟質珠粒之添加量並不滿足本發明所規定之數値範圍。更 且，比較例14與比較例15爲使用不具有本發明所規疋之 1 0 %，變形時之壓縮強度的珠粒（即，非軟質珠粒）的比 較例。 分別對於如此處理所製造之實施例1〜1 3及比較例 1〜15之預塗金屬板’求出樹脂皮膜之基質層的平均厚度。 基質層的平均厚度爲測定每單位面積之樹脂皮膜的重量， -29 - 200918304 以比重爲1換算求出。 對於所製造之實施例1 ~ 1 3及比較例1〜1 5之預塗金屬 板，評價光碟之防止刮傷性、塗佈性及封黏性。光碟之防 止刮傷性、塗佈性及封黏性之評價爲如下處理進行。 (1 )光碟之防止刮傷性 光碟之防止刮傷性爲將市售的光碟記錄面，接觸預塗 金屬板之樹脂皮膜表面，一邊以指輕押一邊左右來回摩擦 1 〇次後，以目視觀察光碟表面之刮傷，未察見刮傷之情況 視爲「〇」，即使有少許刮傷之情況視爲「X」。另外， 試驗爲於加溫至50°C實施。 將其對一種實施例或比較例分別進行1 00次試驗，「 〇」之或然率爲9 5 %以上之情況視爲防止刮傷性良好（合 格），「〇」之或然率爲未滿95%之情況視爲防止刮傷性 不良（不合格）。 (2 )塗佈性 塗佈性爲經由測定塗料之黏度而加以確認。具體而言 ，使用測定塗料黏度所廣泛使用的Ford CuP#4 ’以塗料之 固形成分確保爲3 0%以上之狀態，即揮發成分之比率爲未 超過7 0 %之範圍下測定黏度’於黏度爲1 2 0秒以內之情況 判斷爲可塗佈，超過1 2 〇秒且爲1 8 0秒以內之情況判斷爲 塗佈性稍難（表1中以「塗佈性稍難」表示）’超過1 80 秒之情況判斷爲塗佈性不良（表1中以「塗佈性不良」。 -30- 200918304 (3 )封黏性 封黏性爲以經過塗料之塗佈步驟及加熱步驟之預塗金 屬板的塗膜（樹脂皮膜）面彼此間爲面對面之狀態，以加 熱至7 0 °C之熱加壓輕輕夾住保持1分鐘以上，若取出之預 塗金屬板的塗膜面彼此間未接黏則判斷爲良好，接黏之情 況則判斷爲不良（表1中以「封黏性不良」表示）。 表1中，示出實施例1~13、表2中示出比較例1〜15 之預塗金屬板的製造條件、構成，以及，光碟之防止刮傷 性、塗佈性及封黏性之評價。另外，表1、表2中之下線 爲表示未滿足本發明所規定之要件。 -31 - 200918304 冕 辑2 IK 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 Ο Ο ίΝ 1 ON 冕 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 Ο Ο CN Ο (Ν 未滿 1 5% 〇\ 習：: w 聚酯 Tg0〇c 胺基甲 酸乙酯 珠粒 ο ο (Ν Ο CN 未滿 5% ON m 習2 Ιϋ 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 «•η ο ιη in σν 實施例9 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο 〇\ 實施例8 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο 宕 ο CN 100% 塗佈性 稍難 實施例7 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ό ο ο (Ν Ο (Ν in ON 實施例ό 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο Ο (Ν Ο (Ν 卜 〇\ 實施例5 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 cn \〇 〇v 實施例4 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 in Ο (Ν Ο ：100% 1_ 實施例3 聚酯 Tg50°C 胺基甲 酸乙酯 珠粒 ο Ο CN 〇 m ON 實施例2 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο 宕 Ο (Ν 容 00 OS 實施例1 聚酯 Tg〇°c 胺基甲 酸乙酯 珠粒 ο Ο (Ν 〇 CO 式 OS OS 基質層之種類 -1 珠粒之種類 S 辁& m§； Ξ猓 -1\J S Μ 基質層平均厚度(Α: μηι) 珠粒平均粒徑(Β:μπι) CQ 珠粒含有率(質量％) 震 •fr蘅 Φ锲 賴 hm] K 光碟之防止刮傷性 塗佈性、封黏性 -32- 200918304 〔(N嗽〕 聚酯 Tg30°C 丙烯酸 珠粒 〇 in ^1 〇1 爆 聚酯 Tg30°C 齡 21 o ό CN ι〇 (Ν Ο CN \Τ) UJ 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 〇 m in ΞΙ ON \〇 鎰2 JJ 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 O in «ο 比較例 11 ! 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 o Ο (Ν ON 〇s 劁 K- 比較例 ίο 1 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 o Ο (Ν Ξ| 〇 ΓΟ 〇s 比較例 9 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 o Ο (Ν 容 5： 比較例 8 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 (N S| II 比較例 7 am。〇 mi ο 胺基甲 酸乙酯 珠粒 in 宕 SI II 比較例 6 m 胺基甲 酸乙酯 珠粒 o ο (Ν’ 1未滿 ,5% 容 比較例 5 &题 橄 胺基甲 酸乙酯 珠粒 o Ο (Ν !未滿 ,5% MD 〇〇 a If 比較例4 丙烯基 胺基甲酸 乙酯珠粒 o Ο (Ν 未滿 ,5% (N 比較例3 稍 祕 m 胺基甲 酸乙酯 珠粒 o Ο CN 未滿 5% CN 比較例2 ®ι ο 胺基甲 酸乙酯 珠粒 o Ο (Ν 比較例1 道。〇 ®H ΙΛ) ^ ώ Η 胺基甲 酸乙酯 珠粒 in o Ο (Ν 〇 〇\ 〇\ m 1¾ 基質層之種類 珠粒之種類 πα cd 辁& Μ δ ^ M 〇 m —nr> h) M 基質層平均厚度 (Α:μηι) 珠粒平均粒徑(Β·.μπι)Ι < 珠粒含有率(質量％) 鹊 Ν N B- g Φ锲 链味 鹩圈 戰 光碟之防止刮傷性 塗佈性、封黏性 -33- 200918304 如表1所示般’實施例1〜13之預塗金屬板均於光碟 之防止刮傷性取得優良之評價結果。又，實施例1〜1 3之 預塗金屬板爲於塗佈性及封黏性，在實用上無任何問題。 另一方面’比較例1~15之預塗金屬板因未滿足本發 明所規定的任一要件，故光碟之防止刮傷性、塗佈性及封 黏性之任一評價結果爲不佳。 具體而言，比較例1之預塗金屬板雖然光碟之防止刮 傷性爲良好，但因聚酯樹脂之玻璃態化溫度爲未滿本發明 所規定之數値範圍，故封黏性不良。因此，不能稱爲以線 圈材連續處理製造上可耐實用的預塗金屬板。 比較例2之預塗金屬板爲聚酯樹脂之玻璃態化溫度爲 超過本發明所規定之數値範圍，故光碟之防止刮傷性不良 〇 又，比較例3〜6之預塗金屬板因使用非聚酯樹脂的樹 脂，故光碟之防止刮傷性爲不良。 比較例7、8之預塗金屬板爲軟質珠粒之平均粒徑與 基質層之平均厚度之關係爲未滿足本發明所規定之要件， 故光碟之防止刮傷性均爲不良。 比較例9、10、12、13之預塗金屬板爲軟質珠粒之含 有率爲未滿足本發明所規定之數値範圍，故光碟之防止刮 傷性爲不良。 比較例Π之預塗金屬板爲軟質珠粒之含有率爲超過 本發明所規定之數値範圍，故雖然光碟之防止刮傷性爲良 好，但塗料之黏度爲顯著增加，且塗佈性不良。 -34- 200918304 比較例14、15之預塗金屬板爲所使用珠粒之10%變 形時的壓縮強度爲未滿足本發明所規定之數値範圍的珠粒 ，即，非軟質之珠粒，故均爲光碟的防止刮傷性不良。 以上，關於本發明之預塗金屬板及預塗金屬板之製造 方法，雖列舉最佳之實施形態及實施例予以詳細說明，但 本發明之內容並非被此些記載所限定，必須根據申請專利 範圍之記載予以廣泛解釋。又，本發明之內容可在不阻礙 本發明效果之範圍下作出各種變更、改變。 例如，爲了更加提高光碟的防止刮傷性，亦可令塗料 中含有指定量之一種或二種棕櫚油（palm oil )、巴西棕 櫚蠟、聚乙烯蠟及微晶狀蠟等之潤滑劑。 又，爲了確保塗料之塗佈性及作爲預塗金屬板的一般 性能’亦可含有通常所用之顏料、顏料分散劑、流動性調 卽劑、勻塗劑（leveling agent)、防沸劑（anti-popping agent )、防腐劑、安定化劑等。 更且，亦可將用以提高兩者密黏性之塗底層，設置於 樹脂皮膜、與金屬板及/或耐蝕性皮膜。如此，可更加提 高預塗金屬板的成形性。 【圖式簡單說明】 圖1爲模式性示出本發明之預塗金屬板之構成的剖面 圖。 圖2爲說明本發明之預塗金屬板之製造方法之內容的 流程圖。 -35- 200918304 圖3(a)及（b)爲示出先前之光碟驅動器及其所用 之光碟的斜視圖，（a)爲示出托盤方式之光碟驅動器， (b)爲表示推入方式之光碟驅動器。 【主要元件符號說明】 1 :預塗金屬板 2 :金屬板 3 :樹脂皮膜 4 :基質層 5 :軟質珠粒 S 1 :塗佈步驟 S2 :加熱步驟 10 :光碟 20:托盤方式之光碟驅動器 2 1 :托盤 22 :蓋 3 0 :推入方式之光碟驅動器 3 1 :開口部 32 :蓋 -36-St = 2.8P / ( Πά 2 ) (1) (However, in the formula (1), Π indicates the periorbital ratio) If the method is based on the use of such a soft bead 5, the substrate layer 4, no stickiness is generated, so that the problem that the resin film 3 is bonded to the optical disk 10 does not occur, and the scratch resistance to the optical disk 1 can be improved. Further, as the soft bead 5, for example, urethane beads, ethylene methyl methacrylate copolymer (EMMA) beads, low density polyethylene (LDPE) beads, or the like can be suitably used. Further, as the urethane beads, ME LTEX (MELTEX; registered trademark) manufactured by Sanyo Chemical I n du Stries, Ltd. (Dainichiseika Color & Chemicals Mfg.) can be suitably used. DAIMIC BEADS (DAIMIC BEADS; registered trademark) manufactured by Co., Ltd., ARTPEARL (ART PEARL; registered trademark) manufactured by Neg Am Chemical Industries, Inc., L td. Further, EMMA beads ( SOFT BEADS) A, S OFT BE AD SB, etc. manufactured by Sumitomo Seika Chemicals Co., Ltd. can be suitably used, and LDPE beads can be suitably used by Sumitomo Jinghua Co., Ltd. FLO-BEADS (FLO-BEADS; registered trademark) and so on. As described above, it is explained that the scratch prevention of the optical disk 1 can be ensured even without softening the matrix layer 4 by using the soft beads 5, but in the present invention, the soft beads 5 and the glassy state which can produce such effects are used. The polyester resin having a temperature of 〇t or more and 5 (TC or less) is used in combination with the soft matrix layer 4, and as a result, the entire resin film 3 can be softened. Therefore, only softer than -18-200918304 is partially softened. In addition, since the entire resin film 3 is softened, the resin film 3 is softened. However, since the soft bead 5 is provided, even if the disc 10 is in or out, it will not The barrier action is caused by the viscosity. That is, instead of using only the soft matrix layer 4 alone, the soft beads 5 are used, and the average thickness of the matrix layer 4 and the particle diameter of the soft beads 5 are controlled, so the resin film 3 The surface is not smooth and has a surface state having irregularities. That is, almost all portions of the resin film 3 that are in contact with the surface of the optical disk 10 become the front end of the soft beads 5, and the optical disk 10 and the viscous substrate layer 4 are greatly suppressed. As a result, the problem of adhesion between the optical disk 1 and the resin film 3 is avoided. Further, since the soft beads 5 have a particle size distribution as will be described later, even if not shown, even if it is thermally hardened, When the polyester resin is thinly coated to the front end of the smaller soft bead 5, scratch resistance can be ensured by the adjacent soft bead 5 which is adjacent thereto. Further, in the present invention, even if a resin film is formed After 3, the surface soft bead 5 of the precoated metal sheet 1 is dispersed in an uneven manner, and the exposed portion of the matrix layer 4 is generated, and the soft bead 5 can also be combined with the soft bead 5, so that the matrix layer 4 is also moderately softened, so that even the optical disc When the first coating is in direct contact with the precoated metal sheet 1, the surface of the optical disc 10 can be prevented from being damaged. (The content of the soft beads: 15% by mass or more and 50% by mass or less) In order to prevent scratching, the content of the soft beads 5 is preferably larger than that of the matrix layer 4. When the content of the soft beads 5 is less than 15% by mass, the soft beads fixed in the matrix layer 4 are used. 5 parts of granules -19- 200918304 Less 'function as a cushioning material, and prevent The scratch resistance is poor. In addition, if the content of the soft beads 5 is increased, the viscosity of the coating of the dispersed soft beads 5 is increased, so that the coating is applied to the metal plate 2 by roll coating or the like, and the film thickness is difficult. The content of the soft bead 5 is 15% by mass or more and 50% by mass or less based on the base layer 4, and the softness is ensured to ensure a more stable coating property. The content of the beads 5 is preferably 40% by mass or less. (Average particle diameter of the soft beads: 1.1 times or more and 5 times or less of the average thickness of the matrix layer) In order to improve the prevention of the optical disk 10 by the soft beads 5 The scratching property is important in that the average particle diameter of the soft beads 5 is larger than the average thickness of the matrix layer 4. By making the average particle diameter of the soft beads 5 larger than the average thickness of the matrix layer 4, as shown in Fig. 1, The cross-sectional shape of the resin film 3 is a resin film 3 having a fine uneven shape in which a portion where the soft beads 5 are present is protruded. Therefore, the soft soft bead 5 which is soft when the optical disc 1 is in contact with the resin film 3 functions not only as a cushioning material, but also can greatly reduce the direct contact between the optical disc 10 and the substrate layer 4, so that the malfunction of the optical disc 1〇 is not generated and can be further improved. Prevent scratching. Here, if the average particle diameter of the soft beads 5 is more than 5 times with respect to the average thickness of the matrix layer 4, it cannot be fixed in the matrix layer 4 and the soft beads 5 fall off, so that the reduction of the optical disk 10 can be improved. Prevent scratching effects. Namely, by avoiding the use of soft beads 5' having a significantly larger particle diameter than the average thickness of the matrix layer 4, the soft bead peeling can be prevented even if the soft bead content in the matrix layer 4 becomes large -20-200918304. Further, since the average thickness of the soft beads relative to the matrix layer 4 is less than 1. times, the beads 5 are easily buried in the matrix layer 4, so that the effect of improving the scratch resistance can be reduced. Therefore, the average particle thickness of the soft beads 5 is 1 · 1 time or more and 5 times or less. Further, it is more preferable that the thickness is 1 · 5 times or more and 4 times or less. Further, if the average particle diameter and the basicity of the soft beads 5 are maintained in such a relationship, the average thickness of the substrate layer 4 must be increased even if the above-mentioned relationship is maintained even if the above-mentioned relationship is maintained. , thicker than necessary, is uneconomical. On the other hand, in the case of the small soft beads 5, the industrial average is difficult to 5 the average particle size and the average thickness of the matrix layer 4, the average particle size of the particles 5 is the average thickness of 5 to 30 μηι or so. The average thickness of the matrix layer 4 which is 3 μm η or more and 15 μm η or less is measured as the weight per unit 3, and is calculated in terms of a specific gravity of 1 . Here, as described above, the particles of the soft beads 5 are distributed such that the particle size of the beads having a volume of 50% by volume (Cumulative 50% diameter) of about 8 μm is distributed from about 1 μηι to a maximum of 20 μηι. (The DYMIC BEADS particle size distribution of the homepage of Refined Chemicals Co., Ltd. is synonymous with the particle size distribution. Therefore, the particle size index of the grain 5 is the average particle diameter. In addition, if the average particle diameter of 5 is small, the particle diameter is small. The average thickness of the average layer 4 of the matrix layer 4 of the substrate layer 4 is prevented from being scratched, but the soft beads of the particle size are such that the resin film 3 is used to control the softness. Therefore, the soft beads are good and the matrix layer 4 is good. In addition, the resin film diameter of the hair area is distributed. The volume particle cloth is known to be the smallest, for example, in the invention of the big 曰 (registered trademark), soft In the present invention, the average particle diameter of the present invention refers to a 50% particle diameter of an integrated volume measured by a laser diffraction type particle size distribution measuring device in a state where the soft beads 5 are dispersed in water. Pre-preparation of the invention The metal plate 1 is provided with a corrosion-resistant film (not shown) between the metal plate 2 and the resin film 3 containing the soft beads 5 and the matrix layer 4. The pre-coated metal plate can be formed by forming the corrosion-resistant film. (1) The urethane resistance is imparted, and the adhesion between the metal plate 2 and the resin film 3 is improved. The corrosion-resistant film of this type may be a previously known corrosion-resistant film containing Cr or Zr as a component. For example, phosphoric acid may be suitably used. A chromate film, a strontium phosphate film, a zirconia film, or a coated chrome film, etc. Further, the adhesion amount of the corrosion-resistant film is preferably 10 to 5 〇 mg/m1 in terms of Cr or Zr. Corrosion-resistant film If the amount of adhesion is less than 1 〇mg/m1, the metal sheet 2 cannot be uniformly covered, and it is difficult to ensure corrosion resistance and cannot withstand long-term use. Further, if the adhesion amount of the corrosion-resistant film exceeds 50 mg/m1', it is formed. Etc., the uranium-resistant film itself is cracked (peeled), and it is difficult to maintain high corrosion resistance for a long period of time. -22- 1 _Pre-coated metal sheet manufacturing method Next, the pre-coated metal sheet of the present invention will be described in detail with reference to FIG. Manufacturing method. As shown in Figure 2' The method for producing a precoated metal sheet according to the invention includes a coating step S1 and a heating step S2. Hereinafter, each step will be described. In addition, in the coating step S1 of the present invention, the coating having the specified composition described later is also included. 200918304 (Coating step) The coating step S1 is to set the glass transition temperature of the essential components of the coating to 〇 ° C or higher 5 (polyester resin below TC, and hardener, and a single according to a small compression test) The soft bead 5 having a compressive strength of 10% or less at 10% deformation of the bead and the volatile component which is uniformly dispersed, and sufficiently mixed with the thermosetting polyester-based paint (hereinafter referred to as " The coating") is applied to the surface of the metal plate 2. In addition, among the above-mentioned essential components, the content of the soft beads is 15% by mass or more and 50% by mass or less based on the heating step S2 described later, and the matrix layer 4 which is crosslinked with the polyester resin and the curing agent. The ratio is adjusted in advance. Here, the aforementioned polyester resin is a saturated polyester resin obtained by polycondensation of a polyvalent alcohol and a polybasic acid. Among them, as the polyvalent alcohol, for example, divalent alcohol such as ethylene glycol, propylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol or diethylene glycol, glycerin or trihydroxyl can be used. A trivalent alcohol such as methylethane or trimethylolpropane, or an alcohol having a tetravalent or higher value. Further, as the polybasic acid, for example, a dibasic acid such as phthalic anhydride, isophthalic anhydride, terephthalic anhydride, adipic acid or sebacic acid, a tribasic acid such as trimellitic anhydride, or a polybasic acid having a tetravalent or higher value may be used. Wait. These polyvalent alcohols and polybasic acids may be used singly or in combination of two or more kinds, but the glass transition temperature of the polyester resin produced by the polycondensation is measured, and is 0 ° C or more. (The following method can be used for the method of manufacturing the precoated gold-23-200918304 of the present invention. Further, the glass transition temperature can be determined according to the usual rules such as differential scanning calorimetry (DSC). For the curing agent, an amine-based curing agent having two or more amine groups and an isocyanate-based curing agent having two or more isocyanate groups can be used, and an amine-based curing agent is desirably used for coating stability or the like, and among them, It is desirable to be a melamine-based hardener. The volatile component must be such that the hardener and the soft bead 5 are dissolved or dispersed in the aforementioned polyester resin, and it is necessary to ensure optimum coating viscosity on the coating. The soft bead 5 is sufficiently filled with a stirring device. Stirring, and evenly dispersing in the paint. If the mixture is stopped and left for a long time, it will settle and aggregate due to gravity. The volatile component is heated in the heating step S 2 described later, and volatilizes during the crosslinking reaction. The composition of the resin film 3 remains, but what kind of substance affects the dispersibility of the soft beads 5 in the coating, and as a result, coating and crosslinking In the present invention, the content of the aromatic hydrocarbon-based solvent in the volatile component is preferably 30% by mass or more. If the volatile component is aromatic hydrocarbon When the content ratio of the solvent is 30% by mass or more, the effect of suppressing settling and re-aggregation of the soft beads 5 dispersed in the coating material can be suitably obtained. Therefore, since the stability of the coating is maintained by stability, In the resin film 3 after coating, the possibility of uneven dispersion of the soft beads 5 can be greatly reduced. Thus, the surface loss of the optical disk 10 can be more reliably prevented. Here, if the optical disk is considered to be improved, The content of the aromatic hydrocarbon-based solvent is preferably 50% by mass or more, and the content ratio of the aromatic hydrocarbon-based solvent in the volatile component is less than 5% by mass. However, it is difficult to effectively achieve the aforementioned effects. Specific volatile components are water, isophorone, cyclohexanone, methyl isobutyl ketone, methanol, butanol, diacetone alcohol, butyl cellosolve An aromatic hydrocarbon system such as ethylbenzene, xylene, toluene, trimethylbenzene, naphthalene or aromatic petroleum brain in a solvent such as ethylene glycol monobutyl ether, ethyl acetate or butyl acetate alone or in combination. It is preferable that the solvent is used alone or in combination to form a content ratio of 30% by mass or more. Next, the soft beads 5 adjusted to have a content of 15% by mass or more and 50% by mass or less are uniformly dispersed in the coating material. The treatment method of the bead 5 dispersion may be an ultrasonic treatment, a magnet stirrer, a stirring treatment with an impeller mixer, a homogenizer, an attritor, or a ball mill. ), a stirring process such as a beads mill. Such coatings can be applied according to a brush (bru sh ), a roll coater (roll C 0 ater ), a curtain f 1 ow coater, a roll curtain coater (r ο 11 er curtain coater). E1e ctro static C 〇ater, blade coater, die coater, etc., in particular, the coating amount is uniform, and A roller applicator that is easy to handle is preferably used. In addition, by adjusting the particle size of the soft bead 5 to be used, the coating amount of the coating - 25 - 200918304 can make the average particle diameter of the soft bead 5 1 / 1 times or more and 5 times the average thickness of the substrate layer 4 the following. In the present invention, the average particle diameter of the soft beads 5 is preferably from about 5 to 30 μπι, so the coating amount is such that the surface of the metal plate 2 is formed to have an average thickness of 3 to 15 4 Å. The conveyance speed of the metal plate 2, the rotation direction and the rotation speed of the rolls, the pressing force between the rolls (nozzle pressure), and the like may be adjusted. By adjusting these conditions, the thickness of the paint before transfer to the metal plate 2 can be changed. (i.e., wet film thickness). As a result, the average thickness of the matrix layer 4 of the dried film which is subjected to the heating step S 2 described later and dried, and the average of the soft beads 5 can be adjusted as described above. The particle size is from 1. 1 time to 5 times the average thickness of the substrate layer 4. Further, a degreasing step (not shown) for degreasing the surface of the metal plate 2 may be provided before the coating of such a coating material. The degreasing step is, for example, spraying an aqueous acid and an aqueous alkali solution on the surface of the metal plate 2, and then, after washing with water, the surface of the metal plate 2 can be degreased. Further, as described above, the sorrel resistance between the metal plate 2 and the resin film 3 is provided. In the case of an insect film, followed by a degreasing step The chemical conversion treatment solution containing chromium ions or the like is sprayed on the surface of the metal plate 2 and washed with water, or a treatment liquid containing chromium ions or the like is applied and dried to form a corrosion-resistant film. (Heating step) The heating step S 2 is to have The metal plate 2 coated with the coating material of the step S1 is heated at a heating temperature of 200 ° C or more and 300 ° C or less, and the heating time is 20 seconds or more and 60 seconds or less. Heating -26- 200918304 Step S2, the volatile component contained in the coating is evaporated and dried, and the heated coating is subjected to a crosslinking reaction to form a resin film 3 on the surface of the metal plate 2 (the matrix layer 4 including the soft beads 5) And firmly bonded to the metal plate 2. Further, the soft beads 5' heated by the heating step S2 are of course fixed in a state of being moderately dispersed in the matrix layer 4. In addition, the resin is not allowed to be heated by the heating temperature. The scratch resistance of the disc 1 caused by the film 3 is affected, but if the heating temperature is less than 20 (TC, the crosslinking reaction of the coating is insufficient, and if the heating temperature exceeds 300 ° C, the coating (resin film 3) Hot (decomposition), so it is preferably 200 ° C or more and 300 ° C or less. The heating time is preferably 20 to 60 seconds. If the heating time is less than 2 seconds, it will become insufficient heating, and if it exceeds 60 seconds, it will be heated. Since the time is too long, the productivity per time is lowered, which is not preferable. This heating step S2 can be carried out, for example, using a hot air furnace, an induction heating furnace, a near infrared ray furnace, a far infrared ray furnace, and an energy ray hardening furnace. </ RTI> Next, the method for manufacturing the precoated metal sheet and the precoated metal sheet of the present invention is compared with and specifically described in the examples satisfying the requirements of the present invention and the comparative examples not satisfying the requirements of the present invention. The type of the resin to be used, the glass transition temperature, the average thickness of the matrix layer of the resin film, the content of the soft beads dispersed in the matrix layer, the average particle diameter, and the content ratio of the aromatic hydrocarbon solvent in the volatile component of the coating material. Next, the scratch resistance, the coating property, and the sealing property of the optical disk were evaluated. The details are as follows. -27- 200918304 [Examples 1 to 1 3] As shown in Table 1, Examples 1 to 13 contain a polyester resin having a glass transition temperature of 〇 ° C or higher and 5 (TC or less, and a curing agent, And a soft bead having a compressive strength at 10% deformation as defined in the present invention, and a coating material for dispersing the volatile components thereof are applied to the metal plate, and secondly, the metal plate to which the coating is applied is heated at a temperature of 2 5 (TC, heating time, heating and calcination for 30 seconds, to produce a precoated metal plate having a resin film. Here, the soft beads are made of urethane beads. In addition, the metal plates used in Examples 1 to 13 In order to use both surfaces, a corrosion-resistant film treated with phosphoric acid chromate to improve corrosion resistance is formed in advance. The amount of adhesion of the phosphoric acid chromate film is converted to 2 μg/m 2 of Cr. The composition of the precoated metal sheet is (Metal plate) The metal plate is an aluminum alloy plate with a thickness of 0.5 mm and a KMS-defined 5052-H34. (Resin film) The resin film is an ethyl urethane which is used as a soft bead on a phosphate chromate film. The beads are dispersed and coated with a glass transition temperature of 0 A coating of a polyester resin having a C content of 50 ° C or less and a heat treatment by the above-mentioned heating temperature and heating time may be formed. Here, the metal plate is heated by placing the metal plate to which the coating material has been applied for transportation. The continuous backing method with the inlet of the oven moving toward the exit, and the time when the gold-28-200918304 is passed through the oven is defined as the heating time 'and it is 30 seconds. Again, It is confirmed that the highest temperature of the metal plate attached to the heating degree of the metal plate is defined as the heating temperature, and it is 25 0 ° C. (The polyester resin having a glass transition temperature of 〇 °c or more and 50 ° C or less) The polyester resin having a temperature of 〇 ° C or more and 50 ° or less is used by a Japanese ink chemical company, and manufactured by Japan Paint Co., Ltd. [Comparative Examples 1 to 1 5] Preparation of Comparative Examples 1 to 1 5 The metallized plate was used as a control for Examples 1 to 13. The production of the precoated metal sheets of Comparative Examples 1 to 15 was carried out in accordance with the conditions of Production Examples 1 to 13 except for the points described below. 1 and Comparative Example 2 are glass transition temperatures not The range of the number specified in the present invention is Comparative Example 3 to Comparative Example 6 is a resin using a polyester resin type not specified in the present invention. Comparative Example 7 and Comparative Example 8 are average particle diameters of soft beads, and a matrix. The relationship of the average thickness of the layers does not satisfy the range of the number specified in the present invention. Further, the addition amount of the soft beads of Comparative Example 9 to Comparative Example 1 does not satisfy the range of the number specified in the present invention. Comparative Example 14 and Comparative Example 15 are comparative examples using beads (i.e., non-soft beads) having no compressive strength at the time of deformation of 10% of the present invention. The average thickness of the matrix layer of the resin film was determined for each of the precoated metal sheets of Examples 1 to 13 and Comparative Examples 1 to 15 thus produced. The average thickness of the matrix layer was determined by measuring the weight of the resin film per unit area, and -29 - 200918304 was calculated in terms of a specific gravity of 1. With respect to the precoated metal sheets of Examples 1 to 13 and Comparative Examples 1 to 15 which were produced, the scratch resistance, coatability and sealing property of the optical disk were evaluated. The evaluation of the scratch resistance, coatability, and sealability of the optical disk was carried out as follows. (1) The scratch-preventing property of the scratch-resistant optical disc of the optical disc is a commercially available optical disc recording surface which is in contact with the surface of the resin coating film of the pre-coated metal sheet, and is rubbed back and forth by the finger to the left and right sides for 1 time, and then visually observed. Observing the scratch on the surface of the disc, the scratch is not observed as "〇", even if there is a slight scratch, it is regarded as "X". In addition, the test was carried out by heating to 50 °C. It is tested in an example or a comparative example for 100 times. The probability of "〇" is more than 95%, which is considered to be good (satisfaction). The probability of "〇" is less than 95%. The situation is considered to prevent bad scratching (failed). (2) Coating property The coating property was confirmed by measuring the viscosity of the coating material. Specifically, Ford CuP #4 ', which is widely used for measuring the viscosity of the coating, is ensured to have a solid content of the coating of 30% or more, that is, the ratio of the volatile component is not more than 70%, and the viscosity is measured. It is judged that it is coatable within the range of 1 to 20 seconds, and it is judged that the coating property is slightly difficult when it is less than 12 seconds and is less than 180 seconds (in Table 1, "the coating property is slightly difficult") In the case of more than 180 seconds, it was judged that the coating property was poor (in Table 1, "the coating property was poor". -30- 200918304 (3) The sealing property was determined by the coating step and the heating step. The coating film (resin film) surface of the metal coated plate is in a face-to-face relationship with each other, and is gently held by heating under a heat of 70 ° C for 1 minute or more, and the coated film faces of the precoated metal sheets are taken out from each other. When it was not bonded, it was judged to be good, and when it was stuck, it was judged to be bad (in Table 1, it is indicated by "bad sealability"). Table 1 shows Comparative Examples in Examples 1 to 13 and Table 2. Manufacturing conditions and compositions of precoated metal sheets of 1 to 15 and scratch prevention and coating of optical discs And the evaluation of the sealability. In addition, the lower line in Tables 1 and 2 indicates that the requirements specified in the present invention are not satisfied. -31 - 200918304 冕 2 IK polyester Tg30 °C urethane beads Ο Ν 1 ON 冕 polyester Tg30°C urethane bead Ο Ο CN Ο (Ν less than 1 5% 〇 : 习:: w polyester Tg0〇c urethane beads ο ο (Ν Ο CN under 5% ON m 习2 聚酯 polyester Tg30°C urethane beads «•η ο ιη in σν Example 9 Polyester Tg30°C urethane beads ο 〇\ Example 8 Polyester Tg30°C urethane beads ο 宕ο CN 100% coatability slightly difficult Example 7 polyester Tg30°C urethane beads ο ο (Ν Ο (Ν in ON Example聚酯 Polyester Tg30°C urethane beads ο Ο (Ν Ο (Ν 〇 〇 实施 Example 5 polyester Tg30 °C urethane beads cn \〇〇v Example 4 polyester Tg30 ° C urethane beads in Ο (Ν Ο : 100% 1_ Example 3 polyester Tg50 °C urethane beads ο Ο CN 〇m ON Example 2 Polyester Tg30°C urethane beads 宕Ο 宕Ο (Ν容00 OS Example 1 Polyester Tg〇°c urethane beads ο Ο (Ν 〇CO type OS OS matrix Type of layer-1 Type of bead S 辁&m§; Ξ猓-1\JS 平均 Average thickness of matrix layer (Α: μηι) Average particle diameter of beads (Β: μπι) CQ Bead content (% by mass) ) 震•fr蘅Φ锲赖 hm] K-disc scratch-proof coating, sealability-32- 200918304 [(N嗽] polyester Tg30 °C acrylic beads 〇 in ^1 〇1 explosion polyester Tg30°C Age 21 o ό CN ι〇(Ν Ο CN \Τ) UJ Polyester Tg30°C Ethyl urethane bead 〇m in ΞΙ ON \〇镒2 JJ Polyester Tg30°C Ethyl urethane Beads O in «ο Comparative Example 11 ! Polyester Tg30°C urethane beads o Ο (Ν ON 〇s 劁K- Comparative Example ίο 1 Polyester Tg30°C Ethyl urethane beads o Ο (Ν Ξ| 〇ΓΟ 〇s Comparative Example 9 Polyester Tg30°C Ethyl urethane beads o Ο (Ν容5: Comparative Example 8 Polyester Tg30°C urethane beads (N S| II Comparative Example 7 am. 〇mi ο Ethyl urethane beads in 宕SI II Comparative Example 6 m Ethyl urethane beads o ο (Ν '1 less than 5% 容 Comparing 5 & Ethyl urethane beads Granule o Ο (Ν ! under full, 5% MD 〇〇a If Comparative Example 4 propylene urethane beads o Ο (Ν less than 5% (N Comparative Example 3 密密m carboxy carboxylate) Beads o Ο CN Less than 5% CN Comparative Example 2 ®ι ο Ethyl urethane beads o Ο (Ν Comparative Example 1 〇®H ΙΛ) ^ ώ Η Ethyl urethane beads in o Ο (Ν 〇〇\ 〇\ m 13⁄4 Type of substrate layer Bead type πα cd 辁& Μ δ ^ M 〇m —nr> h) M Average thickness of matrix layer (Α: μηι) Average particle size of beads (Β ··μπι)Ι < Bead content rate (% by mass) 鹊Ν N B- g Φ锲 Chain 鹩 鹩 战 之 之 防止 防止 涂布 涂布 - - 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 The precoated metal sheets of Examples 1 to 13 all achieved excellent evaluation results in the scratch resistance of the optical discs. Further, the precoated metal sheets of Examples 1 to 13 were used for coating properties and sealing. On the other hand, the precoated metal sheets of Comparative Examples 1 to 15 do not satisfy any of the requirements specified in the present invention, so the scratch resistance, coating properties and sealing properties of the optical discs are prevented. Specifically, the precoated metal sheet of Comparative Example 1 has a glass transition temperature of the polyester resin which is less than the number specified in the present invention, although the scratch resistance of the optical disc is good.値 , , 故 故 故 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In the range of the number of rims specified by the invention, the scratch resistance of the optical disk was poor, and the precoated metal sheets of Comparative Examples 3 to 6 were made of a non-polyester resin, so that the scratch resistance of the optical disk was poor. The pre-coated metal sheets of 7, 8 are the relationship between the average particle diameter of the soft beads and the average thickness of the matrix layer, which does not satisfy the requirements of the present invention, so the scratch resistance of the optical disc is poor. Comparative Examples 9 and 10. , 12, 13 pre-coated metal plates are soft Since the content ratio of the beads does not satisfy the range of the number specified in the present invention, the scratch resistance of the optical disk is poor. The content of the soft coated beads in the precoated metal sheet of Comparative Example is higher than the number specified in the present invention.値 range, so although the scratch resistance of the optical disc is good, the viscosity of the coating is significantly increased, and the coating property is poor. -34- 200918304 The precoated metal sheets of Comparative Examples 14 and 15 are 10% of the beads used. The compressive strength at the time of deformation is a bead which does not satisfy the range of the number of the present invention, that is, the beads which are not soft, and therefore the scratch resistance of the optical disc is poor. The method for producing the precoated metal sheet and the precoated metal sheet of the present invention will be described in detail with reference to the preferred embodiments and examples, but the contents of the present invention are not limited by the description, and must be applied according to the patent application. The description of the scope is widely explained. Further, the present invention can be variously changed and changed without departing from the scope of the invention. For example, in order to further improve the scratch resistance of the optical disc, the coating may contain a lubricant of a specified amount of one or two kinds of palm oil, Brazilian palm wax, polyethylene wax, and microcrystalline wax. Moreover, in order to ensure the coatability of the coating and the general performance as a precoated metal sheet, it is also possible to contain a pigment, a pigment dispersant, a fluidity agent, a leveling agent, and an anti-boiling agent (anti) which are usually used. -popping agent), preservatives, stabilizers, etc. Further, the undercoat layer for improving the adhesion between the two may be provided on the resin film, the metal plate, and/or the corrosion-resistant film. Thus, the formability of the precoated metal sheet can be further improved. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing the configuration of a precoated metal sheet of the present invention. Fig. 2 is a flow chart showing the content of the method for producing a precoated metal sheet of the present invention. -35- 200918304 Figures 3(a) and (b) are perspective views showing the prior optical disk drive and the optical disk used therein, (a) showing the optical disk drive in the tray mode, and (b) showing the push mode. Disc drive. [Description of main component symbols] 1 : Pre-coated metal plate 2 : Metal plate 3 : Resin film 4 : Substrate layer 5 : Soft bead S 1 : Coating step S2 : Heating step 10 : Disc 20 : Tray-type disc drive 2 1 : Pallet 22 : Cover 3 0 : Push-in mode disc drive 3 1 : Opening 32 : Cover - 36-