TWI335865B - Pre-coated metal plate and method for fabricating the same - Google Patents

Pre-coated metal plate and method for fabricating the same Download PDF

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Publication number
TWI335865B
TWI335865B TW096149945A TW96149945A TWI335865B TW I335865 B TWI335865 B TW I335865B TW 096149945 A TW096149945 A TW 096149945A TW 96149945 A TW96149945 A TW 96149945A TW I335865 B TWI335865 B TW I335865B
Authority
TW
Taiwan
Prior art keywords
metal sheet
beads
soft
coating
less
Prior art date
Application number
TW096149945A
Other languages
Chinese (zh)
Other versions
TW200918304A (en
Inventor
Nobuo Hattori
Original Assignee
Kobe Steel Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Publication of TW200918304A publication Critical patent/TW200918304A/en
Application granted granted Critical
Publication of TWI335865B publication Critical patent/TWI335865B/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2602/00—Organic fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Description

1335865 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-coatedmetal)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1335865 IX. EMBODIMENT OF THE INVENTION [Technical Fields of the Invention] The present invention relates to a pre-coated metal sheet for use in exterior sheets and structural members such as household electrical products and automotive vehicle-mounted members, and for building materials, roofing materials, and the like (pre- 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 impart 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 in a state in which surface treatment is performed, not only excellent formability is required for the film but also since it is formed.

S -4- 1335865 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Si〇2 5〜40%、及 潤滑劑5~60%之塗料，以0.5〜10 μηι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，（b)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 10的托盤出入，僅將光碟10以插進開口部31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1〇爲於光碟驅動器30之蓋32之逼近內面處出入 -5- 1335865 。因此，光碟10出入時，光碟10的表面與光碟驅動器30 的蓋32內面摩擦且有時產生摺動損傷，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30的 蓋32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32 —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2005-294109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- 1335865 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 乙醋系之任一者樹脂珠粒和巴西掠欄（carnauba)、聚乙 烯、微結晶（microcrystalline)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 56號公報（段落編號 0008〜00 1 7 ) 〔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 1335865 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)爲〇°C以上5(TC以下之聚酯樹脂與硬化劑交 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 1〇%變形時之壓縮強度爲 lOMPa以下的軟質珠粒（S0ft beads)，且該軟質珠粒之 含有率相對於該基質層爲15質量％以上50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- 1335865 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50 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’因爲令樹脂皮膜主成分之基質層爲玻璃態化溫度 -9- 1335865 爲0 °C以上50 °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50°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200°C以上3 00 °C以下，加熱時間爲20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- 1335865 之基質層之軟質珠粒的含有率爲15質量％以上50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30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，β卩，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 - 1335865 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 提局。 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 S ) -12- 1335865 素材之金屬板2表面所形成的樹脂皮膜3。其中，樹脂皮 膜3爲包含聚酯樹脂與硬化劑交聯反應而成的基質層4、 和在此基質層4中分散的軟質珠粒5所構成，令軟質珠粒 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2的至少 一面。例如，如圖3(b)所示之推入方式的光碟驅動器 30之蓋32般，光碟10的接觸面僅限於蓋32的內側表面 φ 時，將本發明之預塗金屬板1使用作爲蓋32時，僅在成 爲蓋32內面之表面形成樹脂皮膜3即可。此時，不直接 接觸光碟10之成爲蓋32外面的表面並無特別限制。 又’雖未圖不’例如’如可同時搭載多數光碟10之 光碟自動更換器用光碟托盤般，於托盤兩面接觸光碟10 -之情形中，使用本發明之預塗金屬板1作爲托盤，並於金 屬板2之兩面形成本發明之樹脂皮膜3即可。其次，說明 各構成。 (金屬板） 本發明所用之金屬板2並無特別限制，除了最一般的 冷軋鋼板以外，可應用熔融鍍鋅鋼板、電鍍鋅鋼板、合金 化溶融鍍鋅鋼板和鍍銅鋼板、鍵錫鋼板等之各種鑛敷鋼板 、及’不鏽鋼等之合金鋼板、和鋁或鋁合金板、銅或銅合 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動器的胃 類、和液晶顯不裝置之框類、車載用電裝品之蓋等要求輕 -13- 5 1335865 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JIS規定之5 052和5182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〇 °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 φ 預塗金屬板1時以線圏型式捲取之情形中，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50°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50°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- 1335865 質層4爲以硬玻璃狀存在，故於具有軟質珠粒5爲不均勻 分散的部位時，光碟10具有可與玻璃狀之基質層4接觸 的可能性，恐因此令光碟10損傷。 又，將玻璃態化溫度爲低於0 °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 φ 發生熱黏著之封黏現象的可能性。 此類玻璃態化溫度爲0 °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。 φ 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- 1335865 之接黏力的作用。更且，如前述之玻璃態化溫度爲〇 t：以 上50°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10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 〇之表面，則光碟1 0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10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-S -4- 1335865 Observes the appearance of the product as it is, so it requires excellent surface appearance and properties. For example, in Patent Document 1, it is proposed to use an epoxy resin, a urethane resin, and an acrylic resin alone or a mixture thereof as a matrix resin for an aluminum alloy sheet, and to contain Si〇2 5 to 40 having a particle diameter of 0.1 μm or less. %, and a lubricant of 5 to 60% of the coating material, coated with a thickness of 0.5 to 10 μηι, and a friction coefficient of 0.15 or less and a pre-coated metal sheet excellent in scratch resistance. The precoated metal sheet described in Patent Document 1 is formed of an aluminum alloy sheet. Generally, a precoated metal sheet made of aluminum 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 disc drive and the optical disc used therefor, (a) showing the disc drive of the tray mode, and (b) showing the push (si) T-in) mode of the disc drive. As shown in Fig. 3(a), in the tray-type optical disc drive 20, the optical disc 10 such as CDs and DVDs is mounted in the tray 21, and the tray 21 is loaded into the cover 22, which is a conventional product. The way it is adopted. Further, as shown in Fig. 3 (b), recently, an optical disk drive 30 has been developed which does not allow the tray for mounting the optical disk 10 to enter and exit, and only inserts the optical disk 10 into the opening 31. In the disc drive 30 of this type, the disc 1 is placed at -5 - 1335865 at the inner side of the cover 32 of the disc drive 30. Therefore, when the optical disc 10 is taken in and out, the surface of the optical disc 10 rubs against the inner surface of the cover 32 of the optical disc drive 30 and may cause snagging damage. Therefore, in order to prevent this, it is necessary to prevent the surface of the optical disc 10 from being damaged on the inner surface side of the cover 32. Processing. Such a treatment is applied to the inner surface of the cover 32 of the optical disc drive 30 which has been conventionally pushed in, and is applied one by one to prevent partial scratching (post-coating). It is very cumbersome to implement one, and it is expected to develop a pre-coated metal sheet which is characterized in that it is difficult to scratch the surface of the optical disc (hereinafter referred to as "scratch prevention") even if it is in contact with the optical disc. In view of such expectations, the inventors of the present invention have developed a urethane-based resin as a matrix layer, and the ratio of the film thickness to the particle diameter of the substrate layer is a range of urethanes of various sizes within a specified range. The beads, which are formed on the surface of the metal sheet by the specified blending ratio, have basic, excellent formability and appearance for the precoated metal sheet used for forming, and are used for the adhesive. It is difficult to adhere to the adhesive in the application, and it is difficult to adhere to the contaminant and the oil, and it has a pre-coated metal plate which is resistant to scratches of the optical disk, and has been put into practical use (refer to Japanese Patent Application No. 2005-294109). Furthermore, the present inventors have developed a urethane bead having an epoxy resin as a matrix layer and a ratio of a film thickness to a particle diameter of the substrate layer in a predetermined range. When the resin film which is blended at a predetermined blending ratio is formed on the surface of the metal sheet, it can have basic, excellent formability and appearance for the precoated metal sheet used for molding, and contrary to Patent Document 2, A pre-coated metal sheet with a scratch-proof property of the disc -6- 1335865, and has been proposed (see Japanese Patent Application No. 2006-85844). Further, in Patent Document 2, it is disclosed that any of a polyester resin, an epoxy resin, and an acrylic resin contains a resin bead of either a nylon-based or a fluorine-based urethane-based acetal copolymer and Brazil. Any of the waxes of carnauba, polyethylene, and microcrystalline is used as a pre-coated metal plate designed to be pushed into the first actuator, and is provided with a precoated metal plate for preventing ruthenium damage. [Patent Document 1] Patent No. 3 3 3 8 1 56 (Paragraph No. 0008 to 00 1 7) [Patent Document 2] JP-A-2006-97127 (Summary of the Invention) (The problem to be solved by the invention) The precoated metal sheet described in Patent 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 coated one by one, but if it is subjected to such treatment, 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 to provide a method of manufacturing a pre-coated 1335865 metal plate and a precoated metal sheet which prevents damage to the optical disk, i.e., which prevents scratching from being improved over the prior precoated metal sheet. (Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention have made efforts to improve the scratch resistance of the optical disc, and it is possible 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, by strictly restricting the resin type and the glass transition temperature of the matrix layer in which the soft beads are dispersed, it is possible to obtain a portion where the soft beads are unevenly dispersed in the resin film, and the matrix layer is not the soft beads but the matrix layer. The contact with the optical disc itself can also minimize the damage caused by the optical disc to a minimum risk-sensitive 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 has a glass transition temperature of 〇°. C above 5 (a matrix of a polyester resin and a hardener cross-linking reaction) and dispersed in the matrix layer, according to a single micro compression test Soft beads having a compressive strength of 1 MPa or less at a deformation of 1% by weight of the beads, and a content of the soft beads of 15% by mass or more and 50% by mass or less based on the matrix layer, the soft beads The average particle diameter is 1.1 times the average thickness of the matrix layer and 5 times or less on the range of -8 to 1335865. Here, the soft beads used for the precoated metal sheet of the present invention are preferably urethane beads. 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 and excellent forming for the precoated metal sheet used for forming. Second, 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 acts as a buffer. Material, so it can prevent the surface of the disc from being scratched. Here, to ensure excellent scratch resistance to the disc, and also to balance with other characteristics, the average particle size of the soft beads is 1.1 times or more the average thickness of the substrate layer. Further, the content of the soft beads is 15% by mass or more and 50% by mass or less based on the base layer. That is, the average particle diameter of the urethane beads is 1 of the average thickness of the matrix layer. When the content is more than 1 time, the urethane beads can be inhibited from being buried in the matrix layer, and the amino group can be inhibited by the average particle diameter of the urethane beads being less than 5 times the average thickness of the matrix layer. Since the ethyl formate beads are detached from the matrix layer, the function of the ethyl urethane beads as a buffer material can be induced to a high degree. Further, the content of the ethyl urethane is 15% by mass relative to the matrix layer. the above, The function of the ethyl urethane as a buffer material can be ensured, and the content of the urethane beads can be 50% by mass or less, thereby suppressing an increase in the viscosity of the coating material and ensuring proper coating properties. 'Because the matrix layer of the main component of the resin film is a glass transition temperature of -9- 1335865, the polyester resin of 0 ° C or more and 50 ° C or less is crosslinked with a hardener to form a thermosetting polyester resin, so cross-linking The matrix layer after the reaction is moderately softened. Therefore, if a soft bead unevenness is generated on the surface of the resin film after coating, even if the portion is in contact with 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 50 ° C or more and a hardener, and a soft bead having a compressive strength of 10 MPa or less when subjected to 10% deformation of a single particle according to a micro compression test are used. a coating of the particles and the uniformly dispersed volatile components, coated on the metal plate, and in the heating step, the metal plate coated with the coating in the coating step is heated at a temperature of 200 ° C or more and 300 ° C Hereinafter, the heating time is heated under the conditions of 20 seconds or more. 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- 1335865 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 precoated of the resin film of 1.1 times or more and 5 times or less the average thickness of the matrix layer. Metal plate. 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 set to 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 bead was a small portion, and the β 卩 was exposed, and the exposed portion of the matrix layer was greatly 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. It is excellent in formability and appearance, and by optimizing the yield and average particle diameter of the soft beads dispersed in the resin film (matrix layer), it is also possible to contact the surface of the resin film with the surface of the optical disk. To make the disc more scratch-resistant than previous pre-coated metal sheets. 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 S) -12-1335865. The resin film 3 is composed of a matrix layer 4 obtained by crosslinking and reacting a polyester resin and a curing agent, and a soft bead 5 dispersed in the matrix layer 4, so that the content and average particle size of the soft beads 5 are average. The path is controlled to the specified 値. Here, the surface of the metal plate 2 means at least one side of the metal plate 2. For example, when the contact surface of the optical disk 10 is limited to the inner surface φ of the cover 32 as shown by the cover 32 of the optical disk drive 30 of the push-in type as shown in FIG. 3(b), the precoated metal plate 1 of the present invention is used as a cover. At 32 o'clock, the resin film 3 may be formed only on the surface which becomes the inner surface of the cover 32. At this time, the surface which does not directly contact the optical disk 10 as the outer surface of the cover 32 is not particularly limited. In the case where the optical disc tray is mounted on both sides of the tray, the pre-coated metal sheet 1 of the present invention is used as a tray, and the same is not the case. The resin film 3 of the present invention may be formed on both sides of the metal plate 2. Next, each configuration will be described. (Metal Sheet) The metal sheet 2 used in the present invention is not particularly limited, and other than the most common cold-rolled steel sheet, a hot-dip galvanized steel sheet, an electrogalvanized steel sheet, an alloyed molten zinc-plated steel sheet, a copper-plated steel sheet, or a key tin-plated steel sheet can be applied. Various types of mineral-coated steel sheets, alloy steel sheets such as 'stainless steel, and non-ferrous metal sheets such as aluminum or aluminum alloy sheets, copper or copper alloy sheets. Here, 'the type of the stomach drive for the notebook-type personal computer, the frame for the liquid crystal display device, the cover for the vehicle-mounted electric appliance, etc., are required to be light -13 - 5 1335865 degrees, with aluminum or aluminum alloy. The board is better. These uses are not only required to be mild but also require strength, and therefore Al-Mg-based alloys represented by 5,052 and 5182 of JIS are 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. (Base layer) The polyester resin used for the matrix layer 4 is a polyester resin having a glass transition temperature of 〇 ° C or more and 50 ° C or less, more preferably 5 ° C or more and 40 ° C or less. By setting the glass transition temperature to this range, the matrix layer 4 after the crosslinking reaction is moderately softened, so that even the resin film 3 formed on the surface of the precoated metal sheet 1 produces a portion in which the soft beads 5 are unevenly dispersed. At the same time, since the exposed substrate layer 4 is soft, damage to the optical disk 10 can be suppressed. Further, in the case where the φ precoated metal sheet 1 is wound in the coil type, the face resin film 3 is hard to be thermally fused by the coil temperature when the contact faces are wound up. Here, the upper limit of the glass transition temperature is set to 50 ° C, and it is considered to be an internal operation of an optical device using an optical disk such as a disc drive device and an audio device using a compact disc 10, a disc automatic changer, and a car navigation drive device. Ambient 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 at 50 ° C in which the devices are actually operated, the base layer 14 - 1335865 is made of hard glass. In the case where the soft beads 5 are unevenly dispersed, the optical disk 10 has a possibility of coming into contact with the glassy substrate layer 4, and the optical disk 10 may be damaged. Further, in the case where a polyester resin having a glass transition temperature of less than 0 ° 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 in a coil type, 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 0 ° C or more 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 can also be used by Kansai Paint Co., Ltd., manufactured by Dai Nippon Toryo Co., Ltd., Kawakami Paint Mfg. Co., Ltd.) Manufacturers, etc. φ This 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, so if it is 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, and because of its excellent coating properties, the coating is easy to apply to the surface of the metal plate 2. Further, since the polyester resin and the curing agent undergo a thermal crosslinking reaction, the molecules form a three-dimensional mesh structure with each other, thereby ensuring the strength of the resin film 3 as a film, and having a stronger reinforcing resin film 3 and metal. The adhesion of the plate 2 -15- 1335865. Further, as described above, the resin film 3 having a glass transition temperature of 〇t: 50 ° C or less and a polyester resin cross-linked 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 disk 10. It is also difficult to damage the optical disk 1 and maintain scratch resistance. (Soft Bead) When the optical disc 10 is inserted into the optical disc drive 30 of the push-in mode, it is indispensable to make the resin film 3 soft as described above in order to prevent damage to the optical disc 10. 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. In the method of the cross-linking reaction, etc., the effect of softening the resin film is large, and the effect of softening the resin film is large, but 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 1 , the optical disk 10 becomes a state of being attached to the resin film, causing damage to the activity of the optical disk 10 itself when the optical disk 10 is taken in and out, and the use of the optical disk drive 30 and the like. 10 machine action problems. In contrast, in the present invention, the matrix layer 4 of the resin film 3 is not made soft -16-

1335865 質化，而爲採用於樹脂皮膜3(基質層4)中添加 微粒子，即，軟質珠粒5令樹脂皮膜3部分軟質化 。若根據此類手法，則如前述般，因爲並非必定令 4軟質化，故不必降低玻璃態化溫度、抑制交聯反 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 微小壓縮試驗之使用單一珠粒令其10%變形時（單 10%變形時）的壓縮強度爲lOMPa以下左右者。 進行微小壓縮試驗之試驗機，例如，島津製作所 (Shimadzu Corporation)製之微小壓縮試驗機MCT-等，經由使用此試驗機，則可對粒徑1 μιη至100 μιη 之單一珠粒進行壓縮試驗。更具體而言，將粒徑爲 μιη’期望爲8 μιη左右之單一珠粒安裝至試驗機的下 壓板（lower pressure plate)，一邊降低上方加壓壓 upper pressure indenter)—邊對單一珠粒加以壓縮變 同時測定荷重，於珠粒徑爲減少1 0%之時刻的荷重 10%壓縮荷重値。若將此10%壓縮荷重値視爲P ( N ) 定之珠粒粒徑視爲d ( mm )，則可根據下式（1 ) 10%變形時的壓縮強度St (MPa)(參照日本礦業會1335865 is tempered, and the microparticles are added to the resin film 3 (matrix layer 4), that is, the soft beads 5 partially soften the resin film 3. According to such a method, as described above, since it is not necessarily softened, it is not necessary to lower the glass transition temperature and suppress the viscosity of the crosslinked large matrix layer 4. The softness of the soft bead 5 in the present invention is, for example, a compression strength of 10 MPa or less when the single bead is deformed by 10% in a micro-compression test (in the case of single 10% deformation). A test machine for performing a micro-compression test, for example, a micro-compression tester MCT-, manufactured by Shimadzu Corporation, can perform a compression test on a single bead having a particle diameter of 1 μm to 100 μm by using this tester. More specifically, a single bead having a particle diameter of μ μ′ of about 8 μηη is attached to a lower pressure plate of a testing machine while lower pressure indenter is applied to the single bead. The compression was simultaneously measured for the load, and the load was 10% compression load 値 at the time when the bead size was reduced by 10%. If the 10% compression load is regarded as P ( N ) and the bead size is regarded as d ( mm ), the compressive strength St (MPa) at 10% deformation according to the following formula (1) can be used (refer to the Japan Mining Association).

Journal of MMIJ) ' 8 1.1 0.24 ( 1 965 ))。另外，此 變形時之壓縮強度St(MPa)愈小，則珠粒愈軟。本 ’此10 %變形時之壓縮強度St (MPa)必須爲l〇MPa ，期望爲5MPa以下。 :質之 :手法 丨質層 !以增 ί經由 珠粒 公司 W500 左右 5~1 0 方加 子（ 形且 視爲 、測 算出 誌（ 10% 發明 以下 -17- 1335865Journal of MMIJ) ' 8 1.1 0.24 ( 1 965 )). Further, the smaller the compressive strength St (MPa) at the time of this deformation, the softer the beads. The compressive strength St (MPa) at this 10% deformation must be 10 MPa and desirably 5 MPa or less. :Quality: Manipulative enamel layer! To increase ί via the bead company W500 about 5~1 0 square plus child (shaped and regarded as, measured and calculated (10% invention below -17- 1335865

St = 2.8P/ ( rid2)......式(1 ) (但，於式（1)中，Π爲表示圓周率）St = 2.8P / ( rid2) (1) (However, in the formula (1), Π is the pi)

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10貼合之問題 ’且可提高對於光碟10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 d u s t r i e s，L t d ·)製之 Μ E 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（Negami Chemical I n d u s t r i a 1 C ο .，L t d ·)製之 A RT P E A R L ( AR 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、SOFT BEADS 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10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 °C以上5 0°C以下之聚酯樹脂。如此，經由與軟質的基質層 4倂用’結果可令樹脂皮膜3全體更加軟質化。因此，比According to the method of using such a soft bead 5, the matrix layer 4 does not cause stickiness, 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 10 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, TEX ELTEX (MELTEX; registered trademark) and Dainichiseika Color & Chemicals Mfg. Co., manufactured by Sanyo Chemical Industries, Inc., may be suitably used. , Ltd., manufactured by DAIMIC BEADS (DAIMIC BEADS; registered trademark), APM PEARL (AR T PEARL; registered trademark) manufactured by Negami Chemical I ndustria 1 C ο., L td. Further, SOFT BEADS (SOFT BEADS) A, SOFT BEADS B, etc. manufactured by Sumitomo Seika Chemicals Co., Ltd. can be used as the EMMA beads, and LDPE beads can be suitably used by Sumitomo Seika Co., Ltd. FLO-BEADS (FLO-BEADS; registered trademark) and so on. The above description explains that the scratch prevention of the optical disk 10 can be ensured even if the softening of the substrate layer 4 is not performed by using the soft beads 5, but in the present invention, soft beads 5 which can produce such effects, and vitrification are used. The polyester resin has a temperature of 〇 ° C or more and 50 ° C or less. As a result, the entire resin film 3 can be softened by the use of the soft matrix layer. Therefore, than

S -18- 1335865 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10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 〇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1〇與具有黏性 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爲不均勻分散，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10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：15質量％以上50質量％以下） 爲了提高光碟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- !335865 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5 0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 φ 此，光碟10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10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10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- 1335865 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1.1倍， 珠粒5易埋沒至基質層4，故降低可提高今 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10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 μιη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 50% diameter)大約8 μιη左右之珠粒的粒徑分 1 μιη左右至最大20 μιη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 碟1 〇之防止刮 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 c S、 -21 - 1335865 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賦予耐蝕 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Cr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、磷酸鉻皮膜、氧化锆系皮膜、或塗佈型锆皮膜等。 又’耐蝕性皮膜之附著量以 Cr或 Zr換算値爲 10〜5 0mg/m2爲佳。耐蝕性皮膜的附著量若少於10 mg/m2 ’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/rn2 ’則於成形等，耐鈾性皮膜本身產生裂開（剝離），且難 長期維持高耐飽性。 2.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S1、和加熱步驟S2。以下，說明各步驟。另 外於本發明之塗佈步驟S1中，亦包含調整具有後述指定 組成之塗料的作業。 -22- 1335865 (塗佈步驟） 塗佈步驟s 1爲將塗料之必須成分之玻璃態化溫度 °C以上5 0 °c以下之聚酯樹脂、和硬化劑、和根據微小 試驗之單一珠粒10%變形時的壓縮強度爲lOMPa以下 質珠粒5、和令彼等均勻分散之揮發成分，充分混合 熱硬化性聚酯系塗料（以下，將其單稱爲「塗料」） 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 過後述說明之加熱步驟S 2，相對於聚酯樹脂與硬化 聯反應之基質層4爲1 5質量％以上5 0質量％以下般 調整比率。 此處，前述之聚酯樹脂爲使用令多價醇與多元酸 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 醇、1,3-丁二醇、1，6-己二醇、二乙二醇等之二價醇 油、三羥甲基乙烷、三羥甲基丙烷等之三價醇、及四 上之醇類等。 又，多元酸可使用例如，苯二甲酸酐、間苯二酸 對苯二酸酐、己二酸、癸二酸等之二元酸、偏苯三酸 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 縮聚亦可，但以測定縮聚所製造之聚酯樹脂的玻璃態 度，且爲0°C以上50°C以下者，可使用於本發明之預 :爲〇 壓縮 之軟 並將 於金 以經 劑交 預先 縮聚 戊二 、甘 價以 酐、 酐等 以上 化溫 塗金 -23- 1335865 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30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丨〇表面損 -24- 1335865 害。此處，若考慮提高光碟1〇表面之防止刮傷性，則令 芳香族烴系溶劑之含有比率爲50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15質量％以上50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 mil 1 )等之攪拌處 理方法。 此類塗料之塗佈可依據刷子（brush )、輥塗器（roll coater)、幕流塗層器（curtain flow coater)、輕幕塗層 器（roller curtain coater )、靜電塗佈機（electrostatic coater )、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- 1335865 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 μ™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 μιη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 φ ，可調整經後述加熱步驟S2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 蝕性皮膜之情形中，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S2爲將具有塗佈步驟S1所塗佈塗料之金屬 板2，以加熱溫度爲200°C以上300°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- 1335865 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S2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2 0 0 °C， 則塗料的交聯反應不夠充分，加熱溫度若超過3 〇 〇 »c，則 塗料（樹脂皮膜3)熱惡化（分解），故以200。(：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6 0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S 2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- 1335865 〔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50°C以下之聚酯樹脂、和硬化劑、和具有本發 明所規定之10%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25 0°C、加熱時間30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1〜13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 20mg/m2。預塗金屬板之各構成爲如下。 (金屬板） 金屬板爲使用厚度0.5mm，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50 °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 出口移動的連續烟燒（continuous backing)方式，並將金 -28- 1335865 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250°C。 (玻璃態化溫度爲0°C以上5(TC以下之聚酯樹脂） 玻璃態化溫度爲0°C以上50°C以下之聚酯樹.脂爲使用 大曰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1〜1 3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定之 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- 1335865 以比重爲1換算求出。 對於所製造之實施例及比較例1~15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 0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5 0 °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95 %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70%之範圍下測定黏度，於黏度爲120秒以內之情況 判斷爲可塗佈，超過1 2 0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180 秒之情況判斷爲塗佈性不良（表1中以「塗佈性不良」。 -30- 1335865 (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70°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。S -18- 1335865 Only partially softened soft beads 5 can improve scratch resistance. In addition, since the entire resin film 3 is softened, there is a concern that the viscosity is as described above. However, since the soft beads 5 are provided, the optical disk 10 does not interfere with the movement even if it enters and exits. That is, the soft film 5 is not used alone, but the soft beads 5 are used, and the average thickness of the substrate layer 4 and the particle diameter of the soft beads 5 are controlled, so that the surface of the resin film 3 is not smooth and has irregularities. Surface state. That is, almost all of the portion of the resin film 3 that is in contact with the surface of the optical disk 1 becomes the leading end of the soft beads 5, and the chance of the optical disk 1〇 being in direct contact with the viscous substrate layer 4 is greatly suppressed. As a result, the problem of adhesion of the optical disk 1 to the resin film 3 is avoided. In addition, since the soft bead 5 has a particle size distribution as described later, even if it is not shown, even if the thermosetting polyester resin is thinly coated to the front end of the soft bead 5, it can be passed through The larger soft beads 5 adjacent thereto ensure the prevention of scratching. Further, in the present invention, even if the surface soft beads 5 of the precoated metal sheet 1 after the formation of the resin film 3 are unevenly dispersed, the exposed portion of the matrix layer 4 is generated, and the soft beads 5 may be combined with the matrix. The layer 4 is also moderately softened so that even if the optical disc 10 is in direct contact with the precoated metal sheet 1, the surface of the optical disc 10 can be prevented from being damaged. (Content ratio of soft beads: 15% by mass or more and 50% by mass or less) In order to improve the scratch resistance of the optical disk 10, it is preferable that the content of the soft beads 5 is larger than that of the matrix layer 4. The content of the soft beads 5 is less than 15% by mass. The amount of the soft beads fixed in the matrix layer 4 is -19-!335865, and the function as a cushioning material is lowered, and the scratch resistance is poor. Further, if the content of the soft beads 5 is increased, the viscosity of the coating of the dispersed soft beads 5 is increased. Therefore, in the case where the coating is applied to the metal plate 2 by roll coating or the like, it is difficult to control the film thickness to be uniform (i.e., , coating properties deteriorated). For the above reasons, the content of the soft beads 5 is 15% by mass or more and 50% by mass or less based on the matrix layer 4. In order to ensure a more stable coating property, the content of the soft beads 5 is preferably 40% by mass or less. (Average particle diameter of 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 scratch resistance of the optical disk 10 with the soft beads 5, it is important to make the average particle diameter of the soft beads 5 It is larger than the average thickness of the substrate 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 such that the soft bead 5 is convex and has a fine uneven shape. Resin film 3. φ Therefore, the soft soft bead 5 which is soft when the optical disc 10 is in contact with the resin film 3 functions not only as a cushioning material, but also can directly reduce the direct contact between the optical disc 10 and the substrate layer 4, so that the malfunction of the optical disc 10 does not occur 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 prevented. Scratch effect. Namely, by avoiding the use of the soft beads 5' having a significantly larger particle diameter than the average thickness of the matrix layer 4, even if the soft bead content in the matrix layer 4 becomes -20 - 1335865, the soft beads can be prevented from falling off. Further, the average thickness of the soft beads relative to the matrix layer 4 is less than 1.1 times, and the beads 5 are easily buried in the matrix layer 4, so that the effect of improving the damage can be improved. 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 preferably 1.5 times or more and 4 times or less the thickness. Further, if the average particle diameter of the soft beads 5 and the basicity maintain such a relationship, it is possible to increase the average thickness of the substrate layer 4 by increasing the thickness of the substrate 10 even if the necessary size 5 is used even if the optical disk 10 is maintained. Thickening beyond necessary is uneconomical. On the other hand, in the case of the small soft bead 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 particle 5 is the average thickness of about 5 to 30 μηη. 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 diameter of the beads having a volume of 50% of the diameter of about 50 μm is about 1 μm to a maximum of about 20 μm. The DYMIC BEADS particle size distribution (synonymous with the particle size distribution) of the homepage of Jinghua Industrial Co., Ltd.. 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 size is small. The average thickness of the average layer 4 of the substrate 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 soft beads. Therefore, the soft beads are good, and the matrix layer 4 is preferable. 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), the soft bead In the invention, the average particle diameter of c S, -21 - 1335865 refers to an integrated volume of 50% particle diameter measured by a laser diffraction type particle size distribution measuring device in a state where the soft beads 5 are dispersed in water. , the invention The metal coated 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 can be formed by forming a corrosion-resistant film. The plate 1 imparts corrosion resistance and improves the adhesion of the metal plate 2 to the resin film 3. The corrosion-resistant film of this type may be a previously known corrosion-resistant film containing Cr or Zr as a component. For example, chromium phosphate may be suitably used. The acid ester film, the chromium phosphate film, the zirconia film, or the coated zirconium film. The amount of the corrosion-resistant film is preferably 10 to 50 mg/m 2 in terms of Cr or Zr. The adhesion of the corrosion-resistant film is preferable. If the amount is less than 10 mg/m2', it is impossible to uniformly cover the metal plate 2, and it is difficult to ensure corrosion resistance and cannot withstand long-term use. Moreover, if the adhesion amount of the corrosion-resistant film exceeds 50 mg/rn2', it is formed, etc. The uranium film itself is cracked (peeled), and it is difficult to maintain high saturability for a long period of time. 2. Manufacturing method of precoated metal sheet Next, the manufacturing method of the precoated metal sheet of the present invention will be described in detail with reference to FIG. As shown in Figure 2, this issue The method for producing the precoated metal sheet includes the coating step S1 and the heating step S2. Hereinafter, each step will be described. Further, in the coating step S1 of the present invention, the operation of adjusting the coating material having the specified composition described later is also included. 22- 1335865 (Coating step) The coating step s 1 is a polyester resin having a glass transition temperature of an essential component of the coating of ° C or more and 50 ° C or less, and a hardener, and a single bead 10 according to a micro test. The compressive strength at the time of % deformation is 10 MPa or less of the mass beads 5 and the volatile components uniformly dispersed, and the thermosetting polyester-based paint (hereinafter referred to simply as "coating") is sufficiently mixed. The step of coating. In addition, in the above-mentioned essential component, the content of the soft beads is adjusted in the heating step S 2 described later, and the matrix layer 4 of the polyester resin and the curing reaction is adjusted to be 15 mass% or more and 50 mass% or less. ratio. Here, the aforementioned polyester resin is a saturated polyester resin obtained by using a polyvalent alcohol and a polybasic acid. Among them, as the polyvalent alcohol, for example, a divalent alcohol oil such as ethylene glycol, propylene glycol, neoalcohol, 1,3-butanediol, 1,6-hexanediol or diethylene glycol, or trishydroxymethyl B may be used. a trivalent alcohol such as an alkane or a trimethylolpropane; and an alcohol of the above. Further, as the polybasic acid, for example, a dibasic acid such as phthalic anhydride, isophthalic acid terephthalic anhydride, adipic acid or sebacic acid, a tribasic acid of trimellitic acid, and a divalent or higher divalent group can be used. Acid, etc. These polyvalent alcohols and polybasic acids may be used alone or in combination with two types of polycondensation. However, in order to measure the glass attitude of the polyester resin produced by polycondensation, and it is 0 ° C or more and 50 ° C or less, it can be used in the present invention. Pre-invention of the invention: a method for producing a plate 1 which is softly compressed and which is pre-condensed with gold by a pre-condensation of ruthenium, a valence of an anhydride, an anhydride, or the like. Further, the glass transition temperature can be measured by a usual rule such as DSC 'differential scanning calorimetry. As 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 it is more desirable to use 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 beads 5 are sufficiently stirred by a stirring device and uniformly dispersed in the paint. When the mixture is stopped and left for a long time, it settles and aggregates due to gravity or the like. The volatile component is heated in the heating step S 2 described later, and volatilizes during the crosslinking reaction, and does not remain in the component form of the resin film 3, but which component is the dispersibility of the soft bead 5 in the coating. As a result, the distribution of the soft beads 5 of the resin film 3 after the coating and crosslinking reaction is greatly affected. In the present invention, the content ratio of the aromatic hydrocarbon solvent in the volatile component is preferably 30% by mass or more. When the content ratio of the aromatic hydrocarbon-based solvent of the volatile component 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 the stability, the possibility of occurrence of uneven dispersion of the soft beads 5 can be greatly reduced in the resin film 3 after application. In this way, it is more practical to prevent the surface damage of the disc from being damaged -24 to 1335865. Here, in order to improve the scratch resistance of the surface of the optical disk, it is preferable that the content ratio of the aromatic hydrocarbon-based solvent is 50% by mass or more. In addition, the content ratio of the aromatic hydrocarbon-based solvent in the volatile component may be less than 5% by mass, but it is difficult to effectively obtain the above effects. Specific volatile components are in water, isophorone, cyclohexanone, methyl isobutyl ketone 'methanol, butanol, diacetone alcohol, butyl cellosolve, ethylene glycol monobutyl ether, ethyl acetate, acetic acid In a solvent such as butyl ester, such as ethylbenzene, xylene, toluene, trimethylbenzene, naphthalene or aromatic petroleum brain, the aromatic hydrocarbon solvent is used alone or in combination to form a content ratio of 30% by mass or more. It is better. 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 for dispersing the soft beads 5 in the paint may be an ultrasonic treatment, a magnet stirrer, and a stirring treatment with an impeller mixer, using a homogenizer, an attritor. , a ball mill, a beads mill (beads mil 1 ) and the like. Such coatings can be applied according to a brush, a roll coater, a curtain flow coater, a roller curtain coater, an electrostatic coater. A blade coater, a die coater, or the like is used, and in particular, a roll coater having a uniform coating amount and a simple operation is preferably used. In addition, by adjusting the particle size of the soft bead 5 to be used to adjust the coating amount of the coating -25-13535, the average particle diameter of the soft bead 5 can be made more than 1 time to 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 about 5 to 30 μM, so the coating amount is such that the substrate layer 4 having an average thickness of 3 to 15 μm is formed on the surface of the metal plate 2, and is appropriately adjusted. The conveying 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 used. By adjusting these conditions, the thickness of the coating material (i.e., the wet film thickness) before the drying of the metal sheet 2 can be changed. As a result of φ, the crosslinking reaction by the heating step S2 described later can be adjusted, and the average thickness of the matrix layer 4 of the dried dry film can be adjusted, and as described above, the average particle diameter of the soft beads 5 can be made the average of the matrix layer 4. The thickness is 1.1 times or more and 5 times or less. 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 thereafter, washing with water to degrease the surface of the metal plate 2. Further, as described above, in the case where the corrosion-resistant film is provided between the metal plate 2 and the resin film 3, the degreasing step is followed by spraying the treatment liquid containing chromium ions or the like onto the surface of the metal plate 2, washing it, or coating it. When the cloth contains a treatment liquid such as chromium ions and is dried, a corrosion-resistant film can be formed. (heating step) The heating step S2 is a condition in which the metal sheet 2 having the coating material applied in the coating step S1 is heated at a temperature of 200 ° C to 300 ° C and a heating time of 20 seconds or longer and 60 seconds or shorter. The step of heating. This heating -26- 1335865 step S2' evaporates and dries the volatile components contained in the coating, 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 containing the soft beads 5) 4), and firmly bonded to the metal plate 2. Further, the soft beads 5 heated in the heating step S2 are of course fixed in the matrix layer 4 in a state of being appropriately dispersed. Further, the heating temperature 'does not affect the scratch resistance of the optical disk 1 caused by the resin film 3, but if the heating temperature is less than 200 ° C, the crosslinking reaction of the coating material is insufficient, and if the heating temperature is sufficient When the coating (resin film 3) deteriorates (decomposes) more than 3 〇〇»c, it is 200. (: Above 300 °C is preferred. Heating time is preferably 20~60 seconds. If the heating time is less than 2 〇 seconds, it will become insufficient heating. If it exceeds 60 seconds, the heating time is too long. The heating step S 2 can be performed, for example, using a hot air oven, an induction heating furnace, a near infrared ray furnace, a far infrared ray furnace, or an energy ray hardening furnace. [Embodiment] Next, the present invention The method for manufacturing the precoated metal sheet and the precoated metal sheet is to compare and specifically describe the embodiment satisfying the requirements of the present invention with the comparative example that does not satisfy the requirements of the present invention. The item to be reviewed is the type of resin used in the coating and the glass. The aging temperature and 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. Secondly, the evaluation is for the optical disc. Scratch resistance, applicability, and sealing property are described below. -27- 1335865 [Examples 1 to 1 3] As shown in Table 1, Examples 1 to 13 contain a glass transition temperature of 〇°C The polyester resin having a temperature of 50 ° C or less and a curing agent, and a soft bead having a compressive strength at a deformation of 10% as defined in the present invention, and a coating material which disperses the volatile components thereof are applied to the metal plate, followed by The metal plate coated with the coating material was heated and calcined at a heating temperature of 25 ° C for 30 seconds to produce a precoated metal plate having a resin film. Here, the soft beads were made of urethane beads. Further, the metal sheets used in Examples 1 to 13 were used for the corrosion-resistant coatings which were treated with phosphoric acid chromate to improve the corrosion resistance on both surfaces thereof. The adhesion amount of the phosphoric acid chromate film was converted to Cr of 20 mg/m2. The composition of the precoated metal sheet is as follows. (Metal sheet) The metal sheet is an aluminum alloy sheet having a thickness of 0.5 mm and a 5052-H34 prescribed by JIS. (Resin film) The resin film is applied to the phosphoric acid chromate film. The urethane beads of the soft beads are dispersed, and a coating containing a polyester resin having a glass transition temperature of 0 ° C or more and 50 ° C or less is applied, and heat treatment is performed at the aforementioned heating temperature and heating time. Can form Here, the metal plate is heated by a continuous backing method in which the coated metal plate is placed on the conveyor belt and moved from the oven inlet to the outlet, and the gold-28-1335865 is passed through the plate. The time in the oven was defined as the heating time, and it was 30 seconds. Further, it was confirmed that the highest temperature of the metal plate attached to the heating degree of the metal plate was defined as the heating temperature, and it was 250 °C. Glass transition temperature is 0 ° C or higher 5 (polyester resin below TC) Polyester tree having a glass transition temperature of 0 ° C or more and 50 ° C or less. The grease is used by Otsuka Ink Chemical Industry Co., Ltd., Japan Paint [Comparative Example 1 to 1 5] Precoated metal sheets of Comparative Examples 1 to 15 were produced as a control of 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. In Comparative Example 1 and Comparative Example 2, the glass transition temperature did not satisfy the range of the number specified in the present invention. Comparative Examples 3 to 6 are resins using a polyester resin type not specified in the present invention. Comparative Example 7 and Comparative Example 8 are the average particle diameter of the soft beads and the relationship with the average thickness of the matrix layer, which does not satisfy the range of the number specified in the present invention. Further, in Comparative Example 9 to Comparative Example 1, the amount of soft beads added did not satisfy the range of the number specified in the present invention. Further, 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, which is 10% as defined in the present invention. 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 of the resin film was determined. The average thickness of the matrix layer was determined by measuring the weight of the resin film per unit area, and -29 to 1335865 was calculated in terms of specific gravity of 1. With respect to the manufactured examples and the precoated metal sheets of Comparative Examples 1 to 15, the scratch resistance, coatability and sealing properties of the optical discs 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 for 10 times with a finger, 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, and the probability of "〇" being 95% or more is regarded as a good scratch resistance (qualified), and the probability of "〇" is less than 95%. It is considered to prevent scratching (unqualified). (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 a coating material, is used in a state in which the solid content of the coating is ensured to be 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 120 seconds, and it is judged that the coating property is slightly difficult in the case of more than 120 seconds and less than 180 seconds (in Table 1, "the coating property is slightly difficult"), and it is more than 180 seconds. In the case of the case, it was judged that the coating property was poor (in Table 1, "the coating property was poor". -30 - 1335865 (3) The sealing property was a precoated metal plate which was subjected to the coating step and the heating step of the coating. The coating film (resin film) faces are in a face-to-face relationship with each other, and are gently held by heat pressing at 70 ° C for 1 minute or more, and if the coated film faces of the precoated metal sheets are not bonded to each other, If it is judged to be good, it is judged to be defective in the case of adhesion (indicated by "blocking poorness" in Table 1). Table 1 shows the pre-preparations of Comparative Examples 1 to 15 shown in Examples 1 to 13 and Table 2. Manufacturing conditions and composition of coated metal sheets, and scratch prevention, coating properties and sealing of optical discs In addition, the lower line in Tables 1 and 2 indicates that the requirements specified in the present invention are not satisfied.

-31 - 1335865 m 習= 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο Ο (Ν 〇 1〇 S； 實施例 :12 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο o CN Ο (Ν Ο <Ν 未滿 5% v〇 Os 實施例 11 聚酯 Tg0〇c 胺基甲 酸乙酯 珠粒 ο S Ο CN 未滿 5% 容 v〇 〇\ 習2 m 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 κη ο «Ο *η yn Os 實施例9 1_ . 聚酯 Tg30°C 域IN3菜 ο yn 〇 名 ν〇 σ\ 實施例8 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο Ο (Ν 100% 塗佈性 稍難 實施例7 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 ο Ο <Ν 〇\ 實施例6 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 IT) ο 宕 Ο ίΝ 卜 VO σ\ 實施例5 聚酯 Tg30°C 「胺基甲 酸乙酯 珠粒 cn 式 ν〇 os 實施例4 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 «ο 宕 ο 七 宕 100% 實施例3 R酯 Tg50°C 胺基甲 酸乙酯 珠粒 ο ο oi 〇 1〇 VO 實施例2 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 Vi ο ο (Ν 〇 ir> oo Os 實施例1 聚酯 TgO°C 胺基甲 酸乙酯 珠粒 ο Ο CN 容 as 〇\ 基質層之種類 珠粒之種類 S $1 2 m n躍 s國 基質層平均厚度(A#m) 珠粒平均粒徑(Β:μη!) < 珠粒含有率(質量％) 搂 Μ 咏；Η i\!-N B~觀 Φ键 链味 辭翅 pSL 光碟之防止刮傷性 塗佈性、封黏性 s -32- 1335865-31 - 1335865 m 习 = polyester Tg30 °C urethane beads ο Ο (Ν 〇1〇S; Example: 12 polyester Tg30 °C urethane beads ο o CN Ο (Ν Ο <Ν less than 5% v〇Os Example 11 Polyester Tg0〇c Ammonium urethane beads ο S Ο CN Less than 5% 容 v〇〇\ 习 2 m Polyester Tg30°C Aminocarboxylic acid Ethyl bead κη ο «Ο *η yn Os Example 9 1_ . Polyester Tg30°C domain IN3菜ο yn 〇名ν〇σ\ Example 8 Polyester Tg30°C urethane beads ο Ο (Ν 100% coatability is slightly difficult. Example 7 Polyester Tg30°C urethane beads ο Ο <Ν 〇\ Example 6 Polyester Tg30°C urethane beads IT) ο 宕Ο ίΝ Bu VO σ\ Example 5 Polyester Tg30°C "Ethyl urethane beads cn ν〇os Example 4 Polyester Tg30 °C Ethyl urethane beads «ο 宕ο 宕 宕 100% Example 3 R ester Tg 50 ° C urethane beads ο ο oi 〇 1 〇 VO Example 2 Polyester Tg 30 ° C urethane beads Vi ο ο (Ν 〇ir& Gt oo Os Example 1 Polyester TgO °C urethane beads ο Ο CN 容 as 〇 \ Types of substrate layer Bead type S $1 2 mn 跃 s country substrate layer average thickness (A#m) Average particle diameter of beads (Β: μη!) < Bead content (% by mass) 搂Μ 咏; Η i\!-NB~ Φ bond chain flavored shark discs to prevent scratch coating, Sealing s -32- 1335865

比較例 15 sm ^ 阳。 Η 丙烯酸 珠粒 1 SI o m II ϋ 聚酯 |Tg30°C 21 o w-ί (Ν ri in jj 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 m o in 2| 〇\ v〇 比較例 12 聚酯 |Tg30°C 胺基甲 酸乙酯 珠粒 yn o »〇 IT) 求 比較例 11 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 κη o o (N A 隹 劍 3 比較例 10 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 o 〇 (N 2| 比較例 9 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 o 〇 (N 比較例 8 聚酯 Tg30°C 胺基甲 酸乙酯 珠粒 (N 宕 2| S II 比較例 7 聚酯 ! Tg30°C 胺基甲 酸乙酯 珠粒 S 21 II 比較例 6 m m 减 胺基甲 酸乙酯 珠粒 IT) o 〇 CN 宕 未滿 5% 丨比?例 m i a n3 ή 胺基甲 酸乙酯 珠粒 o o CN 张^ 求 v£> 00 »1 生 a 比較例4 m 缓 胺基甲酸 乙酯珠粒 o o <s S 堤彡 伥^ 容 CS u-> 比較例3 m m il 胺基甲 酸乙酯 珠粒 o 0 01 未滿 5% 系 CN 比較例2 >en 1 g 胺基甲 酸乙酯 珠粒 */> o o (S 另 比較例1 sm 1 P in il 胺基甲 酸乙酯 珠粒 o 0 01 式 Os ON a 兹 1 基質層之種類 珠粒之種類 m. cQ 边Cu 〇 m —Rr> N躍 im 慕s 基質層平均厚度 (Α:μΓη) 珠粒平均粒徑(Β:μηι) < ω 珠粒含有率(質置°/。） 搂 飽褂 •9·罷 链味 a 光碟之防止刮傷性 塗佈性、封黏性 -33- 1335865 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1〜13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 圏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11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- 1335865 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顔料、顏料分散劑、流動性調 節劑、勻塗劑（leveling agent )、防沸劑（an t i - p o pp i n g 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- 1335865 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 U :光碟 2〇:托盤方式之光碟驅動器 21 :托盤 22 :蓋 3〇:推入方式之光碟驅動器 3 1 :開口部 32 :蓋 < S ) -36-Comparative Example 15 sm ^ yang.丙烯酸 Acrylic beads 1 SI om II ϋ Polyester|Tg30°C 21 o w-ί (Ν ri in jj Polyester Tg30°C urethane beads mo in 2| 〇\ v〇Comparative Example 12 Polyester |Tg30°C urethane beads yn o »〇IT) Comparative Example 11 Polyester Tg30°C Ethyl carbamate beads κη oo (NA 隹剑 3 Comparative Example 10 Polyester Tg30°C Amino group Ethyl formate beads o 〇 (N 2 | Comparative Example 9 Polyester Tg 30 ° C urethane beads o 〇 (N Comparative Example 8 Polyester Tg 30 ° C urethane beads (N 宕 2| S II Comparative Example 7 Polyester! Tg30°C urethane beads S 21 II Comparative Example 6 mm Ethyl amide beads IT) o 〇CN 宕 less than 5% 丨 ratio? Example mia n3 ή Ethyl urethane beads oo CN 张 ^求v£> 00 »1 raw a Comparative Example 4 m urethane beads oo <s S 彡伥 ^容 CS u-> Comparative Example 3 mm il ethyl urethane beads o 0 01 less than 5% system CN Comparative Example 2 >en 1 g urethane beads*/> oo (S Comparative Example 1 sm 1 P in il Ethyl carbamate beads o 0 01 Formula Os ON a 1 Matrix type of bead type m. cQ side Cu 〇m —Rr> N hop im s stromal layer average Thickness (Α: μΓη) Average particle diameter of beads (Β: μηι) < ω Bead content (quality / °) 搂 搂 9 9 9 9 9 9 9 9 9 9 9 9 罢 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光Sealing property - 33 - 1335865 As shown in Table 1, the precoated metal sheets of Examples 1 to 13 all achieved excellent evaluation results in the scratch resistance of the optical disc. Further, the precoated metal sheets of Examples 1 to 13 In order to coatability and sealability, there is no problem in practical use. 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 prevention of the optical disc The evaluation results of any of the coating properties and the sealing properties are not good. Specifically, the precoated metal sheet of Comparative Example 1 has a glass transition temperature of the polyester resin because the scratch resistance of the optical disk is good. If the range of the number specified in the present invention is not exceeded, the sealing property is poor. Therefore, it cannot be said that the pre-coated metal sheet which is practical and practical in the manufacture of the wire coffin is continuously processed. The pre-coated metal sheet of Comparative Example 2 has a glass transition temperature of the polyester resin exceeding the range specified in the present invention, so that the scratch resistance of the optical disc is poor, and the precoated metal sheets of Comparative Examples 3 to 6 are Since the resin of the non-polyester resin is used, the scratch resistance of the optical disc is poor. The pre-coated metal sheets of Comparative Examples 7 and 8 were such that the relationship between the average particle diameter of the soft beads and the average thickness of the substrate layer did not satisfy the requirements specified in the present invention, so that the scratch resistance of the optical disk was poor. The pre-coated metal sheets of Comparative Examples 9, 10, 12, and 13 were soft beads having a content ratio which did not satisfy the range specified in the present invention, so that the scratch resistance of the optical disk was poor. The precoated metal sheet of Comparative Example 11 has a soft bead content exceeding the range specified in the present invention. Therefore, although the scratch resistance of the optical disc is good, the viscosity of the coating is remarkably increased, and the coating property is poor. -34- 1335865 The precoated metal sheets of Comparative Examples 14 and 15 have a compressive strength at 10% deformation of the beads used, which is a bead which does not satisfy the range of the number specified in the present invention, that is, a non-soft bead. Therefore, the discs are all scratch-resistant. 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 coating property of the coating material and the general performance as a precoated metal sheet, a pigment, a pigment dispersing agent, a fluidity adjusting agent, a leveling agent, and an anti-boiling agent (an ti) which are generally used may be contained. - po pp ing 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- 1335865 Figure 3 (a) and (b) are perspective views showing the prior optical disk drive and the optical disk used therein (a) is a disk drive showing a tray mode, and (b) is a push-in mode Disc drive. [Main component symbol description] 1 : Pre-coated metal plate 2 : Metal plate 3 : Resin film 4 : Substrate layer 5 = Soft bead s 1 : Coating step S2 : Heating step U : Disc 2 〇: Tray-type disc drive 21: tray 22: cover 3 〇: push-in mode optical disc drive 3 1 : opening portion 32: cover < S ) -36-

Claims (1)

1335865 十、申請專利範固 第096149945號專利申請案 中文申請專利範圍修正本 民國^^月 1· 一種預塗金屬板，其爲具備金屬板與於其表面所 形成之樹脂皮膜，經成形後使用的預塗金屬板，其特徵爲 該樹脂皮膜爲具備玻璃態化溫度爲0°C以上50°C以下 之聚酯樹脂與硬化劑交聯反應而成的基質層、和 於該基質層中分散的經由微小壓縮試驗之單一珠粒 10%變形時之壓縮強度爲lOMPa以下的軟質珠粒， 該軟質珠粒之含有率爲相對於該基質層爲15質量％以 上50質量％以下， 該軟質珠粒之平均粒徑爲該基質層之平均厚度之1.1 倍以上5倍以下。 2. 如申請專利範圍第1項之預塗章屬板，其中，該 軟質珠粒爲胺基甲酸乙酯珠粒。 3. 如申請專利範圍第1或第2項之預塗金屬板，其 中，該金屬板爲鋁板或鋁合金板。 4. 一種預塗金屬板之製造方法，其爲於金屬板表面 形成樹脂皮膜並經成形後使用之預塗金屬板之製造方法， 其特徵爲包含 將含有以玻璃態化溫度爲〇°C以上50°C以下之聚酯樹 脂、和硬化劑、和經由微小壓縮試驗之單一珠粒10%變形 1335865 時之壓縮強度爲lOMPa以下的軟質珠粒、和令彼等均勻分 散之揮發成分作爲必須成分之塗料以特定的濕膜厚塗佈在 該金屬板的表面之塗佈步驟，和 將該塗佈步驟塗佈該塗料之金屬板以加熱溫度爲200 °C以上30(TC以下，加熱時間爲20秒鐘以上60秒鐘以下 之條件加熱，令該聚酯樹脂與該硬化劑交聯反應生成基質 層，該塗料爲乾燥皮膜，於該金屬板表面形成該樹脂皮膜 的加熱步驟，而該樹脂皮膜具備該基質層與分散於其中的 該軟質珠粒， 該塗佈步驟中，該塗料係以該軟質珠粒之含有率爲相 對於該基質層調整比率至1 5質量％以上50質量％以下的 塗料，該塗料的濕膜厚，係以該樹脂皮膜中該軟質珠粒之 平均粒徑爲該基質層之平均厚度之1 . 1倍以上5倍以下計 算爲該平均厚度。 5. 如申請專利範圍第4項之預塗金屬板之製造方法 ，其中，該揮發成分爲含有芳香族烴系溶劑，且此揮發成 分中之該芳香族烴系溶劑的含有比率爲30質量％以上。 6. 如申請專利範圍第4項或第5項之預塗金屬板之 製造方法，其中，該軟質珠粒爲胺基甲酸乙酯珠粒》 7. 如申請專利範圍第4項或第5項之預塗金屬板之 製造方法，其中，該金屬板爲鋁板或鋁合金板》 -2 -1335865 X. Patent application Fan Gu No. 096149945 Patent application Chinese patent application scope revision Republic of China ^^月1· A pre-coated metal sheet which is provided with a metal plate and a resin film formed on the surface thereof, which is used after being formed. The precoated metal sheet is characterized in that the resin film is a matrix layer obtained by crosslinking a polyester resin having a glass transition temperature of 0 ° C or more and 50 ° C or less and a curing agent, and is dispersed in the matrix layer. The soft bead having a compressive strength of 10 MPa or less at a 10% deformation of a single bead in a micro compression test, and the content of the soft bead is 15% by mass or more and 50% by mass or less based on the matrix layer, and the soft bead is The average particle diameter of the particles is 1.1 times or more and 5 times or less the average thickness of the matrix layer. 2. The pre-coated plate according to item 1 of the patent application, wherein the soft beads are urethane beads. 3. The precoated metal sheet of claim 1 or 2, wherein the metal sheet is an aluminum sheet or an aluminum alloy sheet. A method for producing a precoated metal sheet, which is a method for producing a precoated metal sheet which is formed by forming a resin film on a surface of a metal sheet and is formed by molding, and is characterized in that it contains a glass transition temperature of 〇 ° C or higher. A polyester resin having a temperature of 50 ° C or less, a hardener, and a soft bead having a compressive strength of 10 MPa or less at a 10% deformation of 1335865 through a micro compression test, and a volatile component uniformly dispersed therein as an essential component a coating step of coating the surface of the metal plate with a specific wet film thickness, and coating the metal plate of the coating with the coating step at a heating temperature of 200 ° C or more and 30 (TC or less, heating time is Heating for 20 seconds or more and 60 seconds or less to crosslink the polyester resin with the hardener to form a matrix layer, the coating being a dry film, a heating step of forming the resin film on the surface of the metal sheet, and the resin The film comprises the substrate layer and the soft bead dispersed therein, wherein in the coating step, the coating has a ratio of the soft bead to the matrix layer adjusted to a ratio of 1 to 5 a coating material having a content of 50% by mass or more and 50% by mass or less, wherein the wet film thickness of the coating material is calculated by using the average particle diameter of the soft beads in the resin film as an average thickness of the matrix layer of 1 to 5 times or less. 5. The method of producing a precoated metal sheet according to the fourth aspect of the invention, wherein the volatile component is an aromatic hydrocarbon-based solvent, and the content of the aromatic hydrocarbon solvent in the volatile component is 30 6. The method of manufacturing a precoated metal sheet according to item 4 or item 5 of the patent application, wherein the soft bead is a urethane bead. 7. If the patent application is the fourth item Or the method of manufacturing the precoated metal sheet of item 5, wherein the metal sheet is an aluminum sheet or an aluminum alloy sheet - 2 -
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