TW201043457A - Precoated metal sheet and process for producing same - Google Patents

Precoated metal sheet and process for producing same Download PDF

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Publication number
TW201043457A
TW201043457A TW099109623A TW99109623A TW201043457A TW 201043457 A TW201043457 A TW 201043457A TW 099109623 A TW099109623 A TW 099109623A TW 99109623 A TW99109623 A TW 99109623A TW 201043457 A TW201043457 A TW 201043457A
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Taiwan
Prior art keywords
coating layer
coating
layer
metal sheet
coating film
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TW099109623A
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Chinese (zh)
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TWI409168B (en
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Tomoaki Hosokawa
Kohei Ueda
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Nippon Steel Corp
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    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • 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
    • 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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • 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
    • B05D2202/00—Metallic substrate
    • 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
    • B05D2502/00—Acrylic polymers
    • 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
    • B05D2508/00—Polyesters

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

Abstract

A precoated metal sheet having at least a topcoat layer that is a coating film formed as the uppermost layer and an intercoat layer that is a coating film underlying and adjoining the topcoat layer. The topcoat layer is a clear coating film comprising a silicone-grafted acrylic resin but containing no pigment. The intercoat layer comprises a melamine-cured or isocyanate-cured polyester resin and contains a coloring pigment. The coating film surface has an average coefficient of friction of 0.08 or lower, a hardness at 23 C of 75-200 N/mm2 in terms of universal hardness measured under a load of 5 mN, and a specular gloss of 50% or more when measured at an incidence angle of 20 and a receiving angle of 20 . The precoated metal sheet has appearance properties including gloss and clearly reflecting properties and has excellent mar resistance.

Description

201043457 六、發明說明： 【明戶斤支名好冷貝u 發明領域 本發明係有關於一種預塗佈金屬板及其製造方法，特 別是有關於一種在家電用、建材用、土木用、機機用、汽 車用、家具用、容器用等的各種用途之具有光澤等的圖案 設計性及優良的耐負傷性之預塗佈金屬板及其製造方法。 I：先前技術3 發明背景 例如’在家電領域、建材領域、汽車領域等的外板’ 逐漸使用以預先被覆著色塗膜的狀態加工而成之預塗佈金 屬板來代替先前將金屬板加工後進行塗裝而成之後塗裝製 品。另一方面’在該等用途，從圖案、設計性的觀點，對 塗裝之高光澤的塗裝外觀的要求逐漸增高。 作為提高塗膜光澤之技術，例如在專利文獻1所記載， 公開一種將母材亦即金屬板的表面粗糙度降低之技術；例 如在專利文獻2所記載’公開一種塗裝使用低分子量樹脂而 成的塗膜之技術；例如在專利文獻3所記載，公開一種在著 色塗膜層上被覆透明塗膜之技術。 在工業上生產預塗佈金屬板時，通常，例如非專利文 獻1所δ己載，係藉由稱為卷材塗佈線(c〇ii coating iine)之連 續塗裝線製造。在通常的卷材塗佈機，一般是藉由稱為輥 塗佈機(roll coater)或簾流塗佈機（curtain coater)之塗裝裝 置，將具有防鏽功能的底漆塗料塗裝在金屬板上並使用熱 201043457 風洪箱等洪烤後，再次错由塗裝裝置塗裝著色塗料並供烤 之2次塗裝2次烘烤(通常稱為2塗2烤方式）。因此，欲在著色 層上塗裝透明塗料等鮮映性優良的塗膜時，因為塗裝次數 為3次以上，進行巨額的設備投資來增設塗佈裝置及烘箱， 或是使板通過卷材蜜佈機2次來進行塗裝等之因應係必要 的。但是，作為解決此問題之手段，如專利文獻4〜12所記 載，已知有一種以未乾燥狀態重複塗佈塗料之濕上濕式 (wet on wet)式的塗裝方法。 另一方面，因為預塗佈金屬板係在塗裝後進行成形加 工而使用，要求成形加工時的而寸負傷性。又，防止因輸送 時或手工操作的組裝時所產生的傷痕亦是重要的。例如， 在專利文獻13揭示一種塗膜硬度高、耐負傷性優良且加工 性亦優良之塗裝金屬板用塗料組成物，其係使用相斜於1〇〇 質量份將玻璃轉移溫度5〜40°C、數量平均分子量15,〇〇()〜 30,000的聚醋樹脂及六甲氧基經甲基化三聚氰胺樹月旨以巧 量比為75/25〜55/45調配而成之聚酯-三聚氰胺樹脂，調配】 〜2質量份十二烷基苯磺酸的胺封端物而構成之塗料。在專 利文獻14、15揭示一種藉由在塗膜添加玻璃纖維或破璃珠 而提高其硬度並使耐負傷性提升之技術。在專利文獻16、 17，係揭示一種藉由在塗膜添加樹脂珠或蠟而提高其;間滑 性並使耐負傷性提升之技術。 先前技術文獻 專利文獻 [專利文獻1]特開平7-150236號公報 201043457 Ο201043457 VI. Description of the Invention: [Description of the invention] The present invention relates to a precoated metal sheet and a method for manufacturing the same, and more particularly to a household appliance, building materials, civil engineering, machine A precoated metal sheet having a pattern design property such as gloss, such as a machine, an automobile, a furniture, a container, or the like, and an excellent damage resistance, and a method for producing the same. I: Prior Art 3 Background of the Invention For example, 'the outer panel of the home appliance field, the building materials field, the automobile field, and the like' is gradually used by pre-coated metal sheets processed in a state in which the colored coating film is applied in advance, instead of previously processing the metal sheets. After painting, the product is coated. On the other hand, in such applications, the requirements for the high-gloss coating appearance of the coating are gradually increasing from the viewpoint of pattern and design. As a technique for improving the gloss of a coating film, for example, Patent Document 1 discloses a technique for reducing the surface roughness of a metal plate which is a base material. For example, Patent Document 2 discloses a coating using a low molecular weight resin. A technique for forming a coating film; for example, Patent Document 3 discloses a technique of coating a transparent coating film on a colored coating film layer. In the industrial production of precoated metal sheets, for example, the δ loading of Non-Patent Document 1 is usually made by a continuous coating line called a coil coating line. In a conventional coil coater, a primer coating having a rust preventive function is generally applied by a coating device called a roll coater or a curtain coater. After hot-rolling on the metal plate and using hot 201043457 air-harvesting box, it is again wrong to apply the coloring coating by the coating device and bake twice for 2 times (usually called 2 coating 2 baking method). Therefore, when a coating film having excellent image quality such as a clear paint is applied to the colored layer, the number of coatings is three or more, and a large amount of equipment investment is required to add a coating device and an oven, or to pass the sheet through the coil. It is necessary to apply the honey cloth machine twice for painting. However, as a means for solving this problem, as described in Patent Documents 4 to 12, a wet-on-wet coating method in which a coating material is repeatedly applied in an undried state is known. On the other hand, since the precoated metal sheet is used for forming and processing after coating, it is required to be inferior in the forming process. Further, it is also important to prevent the occurrence of scratches caused by the assembly or the manual operation. For example, Patent Document 13 discloses a coating composition for a coated metal sheet having a high hardness of a coating film and excellent damage resistance and excellent workability, and the glass transition temperature is 5 to 40 by using a gradient of 1 part by mass. °C, a number average molecular weight of 15, 〇〇 () ~ 30,000 of polyester resin and hexamethoxy methylated melamine tree made of polyester / melamine formulated by a ratio of 75 / 25 ~ 55 / 45 Resin, formulation] ~2 parts by mass of a coating of amine terminated with dodecylbenzenesulfonic acid. Patent Literatures 14, 15 disclose a technique for increasing the hardness and improving the resistance to damage by adding glass fibers or glass beads to a coating film. Patent Documents 16 and 17 disclose a technique for improving the slip resistance and improving the damage resistance by adding resin beads or wax to a coating film. PRIOR ART DOCUMENT Patent Document [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-150236 201043457 Ο

[專利文獻2]特開平1-304934號公報 [專利文獻3]特開平10-66931號公報 [專利文獻4]特開平11-19581號公報 [專利文獻5]特開平11-19582號公報 [專利文獻6]特開平11-19583號公報 [專利文獻7]特開平11-19584號公報 [專利文獻8]特開平11-19585號公報 [專利文獻9]特開平11-19586號公報 [專利文獻10]特開平11-57608號公報 [專利文獻11]特開平11-76932號公報 [專利文獻12]特開平11-76933號公報 [專利文獻13]特開平2-269168號公報 [專利文獻14]特開昭63-5938號公報 [專利文獻15]特開平4-11671號公報 [專利文獻16]特開2004-98624號公報 [專利文獻17]特開2004-34591號公報 非專利文獻 [非專利文獻1]植田等、色材、72(8)、第525-531頁(1999年) C 明内容】 發明概要 發明欲解決之課題 但是藉由將預塗佈金屬板的母材之表面粗糙度控制為 較低來得到高光澤及高鮮映性之方法，若能夠控制母材亦 即金屬板的表面粗糙度時，使用任何塗膜均能夠得到較高光 201043457 澤之反面，必須藉由調整表面粗糙度後的壓延輥等壓延金 屬，或是藉由研磨機等研磨，來控制母材亦即金屬板的表面 粗糙度。因此，利用該方法來製造高光澤的預塗佈金屬板 時，因為花費許多勞力或成本，工業上大量生產係困難的。 另一方面，藉由塗裝低分子量樹脂而成的塗料來得到 高光澤的預塗佈金屬板之方法，雖然相較於控制母材亦即 金屬板的表面粗糖度而得到之方法，能夠較簡單地製造’ 但是因為必須在塗料使用特定樹脂，賦予其他塗膜性能、 例如加工性等係困難的。 作為得到一種不使用性能上受到限制的樹脂而較容易 地得到高光澤的預塗佈金屬板之方法，有專利文獻13之方 法，其係在著色塗膜層上塗裝透明的透明塗膜。對於將該 方法應用在原有的2塗2烤方式之卷材塗佈線時在製造上的 課題，雖然能夠藉由如上述應用濕對濕塗裝的方法來解 決，但是在性能方面（例如專利文獻13)，雖然能夠得到優良 的光澤，但是無法得到充分的对負傷性。 又，關於在專利文獻14、15所揭示之在著色塗膜上的 透明塗膜中添加玻璃珠之技術，雖然具有提升塗膜硬度之 效果，但是未達到可滿足耐負傷性。又，在專利文獻16、 17所揭示之在著色塗膜上的透明塗膜中添加蠟，雖然潤滑 性提升，但是無法得到充分的耐負傷性。又，該等在皮膜 添加玻璃珠、蠟，因為會使塗膜的光澤下降，必須光澤外 觀之用途係不適合的。 如以上，雖然關於光澤、鮮映性等的圖案設計性優良 201043457 =塗佈金屬板，在先前技雜夠查相，但是關於光澤、 鮮映性等的μ設計性優良並且耐負傷性亦優良之預塗佈 金屬板’目前尚未揭示。 因此，本發明係蓥於如此的課題而進行，係以提供一 種光澤、鮮映性高且耐負傷性亦優良 ’、 製造方法作為目的。 良之預㈣金屬板及其 用以解決課題之手段 Ο ο 為了得到光澤、鮮映性高且充分的耐負傷性本發明 者等基於錄的知識而專叫料，發現如先前技術只有 提高硬度m提高潤滑㈣不充㈣，有兼具高塗 膜硬度及高潤滑性之必要，因此，藉由使在頂_含_ 酮接枝丙烯_脂作為透明層且使中塗_層含有三聚氛 胺硬化型«氰義硬化型的料樹脂之構造在確保高 =澤度之同時’能夠達成提升塗膜的硬度及降低摩擦係 數’而且發現能夠得到光澤、鮮映性等的圖案設計性及财 負傷性的雙方均優良，且加讀亦優良之預塗佈金屬板。 本發明係基於此種知識而完成者，本發明之魏如以下。 π]種預塗佈金屬板，該預塗佈金屬板係在金屬板的 一面或兩面具有塗膜層，其特徵在於： 前述塗臈層係至少具有：頂塗膜層，其係形成於最表 面之塗膜；及’中塗塗膜層’其係與該頂塗膜層連接之下 層塗膜； 别述頂塗膜層係含有矽酮接枝丙烯酸樹脂且不未含顏 料之透明塗臈’前述中塗塗膜層係含有三聚氰胺硬化型或 201043457 異氰酸酯硬化型的聚酯樹脂且含有著色顏料之塗膜， 而且，前述塗膜層之塗膜層表面的平均摩擦係數為 0.08以下；且塗膜層表面在23°C下之硬度以5mN負荷下的通 用硬度計係75〜200 N/mm2 ;且塗膜層表面之鏡面光澤度在 入射角及受光角各自為20°的條件下測定時，為50%以上。 [2] —種預塗佈金屬板，該預塗佈金屬板係在金屬板的 一面或兩面具有塗膜層，其特徵在於： 前述塗膜層係至少具有：頂塗膜層，其係形成於最表 面之塗膜；及，中塗塗膜層，其係與該頂塗膜層連接之下 層塗膜； 前述頂塗膜層係含有矽酮接枝丙烯酸樹脂且含有顏料 之透明塗膜，而前述中塗塗膜層係含有三聚氰胺硬化型或 異氰酸酯硬化型的聚酯樹脂且含有著色顏料之塗膜； 此外，前述塗膜層之塗膜層表面的平均摩擦係數為 0.08以下；且塗膜層表面在23°C下的硬度以5mN負荷下的通 用硬度計係75〜200 N/mm2 ;且塗膜層表面之鏡面光澤度在 入射角及受光角各自為20°的條件下測定時，為50%以上。 [3] 如[2]之預塗佈金屬板，其中前述頂塗膜層係含有 光亮顏料之透明塗膜。 [4] 如[1]或[2]之預塗佈金屬板，其中前述頂塗膜層係 三聚氰胺硬化型。 [5] 如[1]或[2]之預塗佈金屬板，其中前述頂塗膜層係 異氰酸酯硬化型。 [6] 如[5]之預塗佈金屬板，其中前述異氰酸酯硬化型 201043457 之頂塗膜層中，NCO/OH的比為0.05〜0.5。 [7] 如[1]至[6]項中任一項之預塗佈金屬板，其中前述 頂塗膜層與中塗塗膜層之界面的Ra(中心線平均粗糙度）為 0.3〜0.8 〇 [8] 如[1]至[7]項中任一項之預塗佈金屬板，其中前述 頂塗膜中的砍酮接枝丙稀酸樹脂（silicone grafted acrylic resin)之含量換算成矽樹脂（silicone resin)為2〜18質量〇/〇。 [9] 如[1]至[8]項中任一項之預塗佈金屬板，其中前述 頂塗膜的玻璃轉移溫度為30〜67°C，前述頂塗膜中所含石夕 酮接枝丙烯酸樹脂中之矽樹脂比率為3〜20質量％，且前述 中塗塗膜層的玻璃轉移溫度為25〜50。(：。 [10] 如[1]至[8]項中任一項之預塗佈金屬板，其中塗膜 層表面在23°C下的硬度以5mN負荷下的通用硬度計係15〇 〜200 N/mm2。 [11] 如[10]或[11]之預塗佈金屬板，其中前述頂塗膜層 係異氰酸醋硬化型。 [12] 如[11]之預塗佈金屬板，其中前述頂塗膜層中之 硬化劑為異佛爾酮二異氰酸酯(IPDi)。 [13] 如[11]或[12]之預塗佈金屬板，其中在前述頂塗膜 層之硬化劑的比率0.1〜0.5。 [14] 一種預塗佈金屬板，該預塗佈金屬板係在金屬板 的一面或兩面具有塗膜層，其特徵在於： 前述塗膜層至少具有：頂塗膜層，其係形成於最表面 之塗膜；中間層，其係與該頂塗膜層連接；及，中塗塗膜 201043457 層，其係與該中間塗膜層連接之下層塗膜； 前述頂塗膜層係含有矽酮接枝丙烯酸樹脂且不含顏料 之透明塗膜，前述中塗塗膜層係含有三聚氰胺硬化型或異 氰酸酯硬化型的聚酯樹脂且含有著色顏料之塗膜， 而且，前述塗膜層之塗膜層表面的平均摩擦係數為 0.08以下；且塗膜層表面在23°C下的硬度以5mN負荷下的通 用硬度計係75〜200 N/mm2 ;且塗膜層表面之鏡面光澤度在 入射角及受光角各自為20°的條件下測定時，為50%以上。 [15] 如[14]之預塗佈金屬板，其中前述中間層含有顏 料。 [16] 如[15]之預塗佈金屬板，其中前述中間層含有光 亮顏料。 [17] 如[14]至[16]中任一項之預塗佈金屬板，其中前述頂 塗膜層與中間層之界面的Ra(中心線平均粗糙度)為0.3〜0.8。 [18] —種預塗佈金屬板之製造方法，係如[1]至[17]中 任一項之預塗佈金屬板之製造方法，其特徵在於： 藉由多層同時塗佈或濕對濕式方式，分別將會成為中 塗塗膜層及前述頂塗膜層的塗料予以塗佈後，進行烘烤。 發明效果 依照本發明，能夠提供一種光澤、鮮映性高且耐負傷 性、加工性優良之預塗佈金屬板及其製造方法及塗裝金屬 成形物。 圖式簡單說明 第1圖係用以說明中心線粗糙度Ra的測定方法之模式 10 201043457 剖面圖。 【實施冷式】 用以實施發明之形態 乂下詳、、田地說明本發明之較佳實施形態。 本發月的預塗佈金屬板係具有2層以上的塗膜層，藉由 • H塗膜層為透明塗膜’表面變為平滑，能夠得到在入射角 及文光角各自為2〇。的條件測定的鏡面光澤度為5〇%以上 0 之光澤度在此，所謂透明塗膜係指塗膜中的顏料濃度低、 基底的掩蔽力低而具有透明感之塗臈。 而且，藉由使前述頂塗膜層含有規定量的矽嗣接枝丙 稀酸樹脂，而能夠得到高潤雜及高硬度(平均摩擦係數為 0,08以下’在23。(：下的硬度以5mN負荷下的通用硬度計係75 〜200 ΝΑηηή，，且能夠兼具耐負傷性及高光澤度。 為了確保本發明之預塗佈金屬板的耐負傷性，必須將 平均摩擦係數設為〇.〇8以下。在此，所謂平均摩擦係數係 〇 敎使不鏽鋼製的鋼球(1()_Φ)以lGGg負荷、15Gmm/min 的條件在預塗佈金屬板上平行移動11〇mm時所施加的力 F’算出將除去最初的10職後，在剩餘1〇〇咖的範圍的複 數位置的力F的測定值之平均而成者。 平均摩擦係數大於〇〇8時，在成形加工時的模具，異 物與預塗佈金屬板表面接觸且摩擦時之摩擦力變大，因為 皮膜表面被破壞’致使耐負傷性變差。藉由平均摩擦係數 為0.08以下，預塗佈金屬板表面與模具或異物摩擦時之摩 擦力變小’耐負傷性提升。為了得到安定的财負傷性，平 201043457 均摩擦係數以0.05以下為較佳。 又’為了破保本發明之預塗佈金屬板的财負傷性，表 面的通用硬度必要為75〜200 N/mm2。在此，所謂通用硬度 係指依在德國的DIN 50359-1所記載之塗膜硬度測定方 法’將以鑽石製造之對面角度為136。(：的四角錐（與在 JIS-Z-2244所記載的維氏硬度(vickers hardness)試驗所使用 的壓頭相同者)壓住材料表面，並從在作用的負荷條件下的 壓入深度算出硬度者。而且，在本發明之所謂通用硬度係 指在溫度23°C、壓入負荷5mN的條件下且使用該DIN規格所 記載的微小硬度計所測得者。通用硬度小於75 N/mm2時， 即便平均摩擦係數為〇.〇8以下，仍因塗膜硬度低而致耐負 傷性差。通用硬度大於200 N/mm2時，塗膜變得太硬，難以 擔保加工性’乃是不佳。通用硬度以75〜200 N/mm2為佳。 耐磨耗性亦屬必要時，以將通用硬度控制為15〇〜2〇〇 N/mm2為佳。 又，本發明之預塗佈金屬板的鏡面光澤度可依照z 8741測定，在入射角及受光角各自為2〇。的條件下測定 時’必須為50%以上。小於50%時，則外觀品質差。 本發明之預塗佈金屬板的頂塗膜層係如前述，以含有 矽酮接枝丙烯酸樹脂作為特徵。所謂矽酮接枝丙烯酸樹脂 係矽樹脂在丙烯酸樹脂主鏈接枝聚合而成者。藉由主鏈的 丙烯酸樹脂所具有之優良的強度或透明度及從該主鏈枝狀 地懸吊之矽樹脂容易配位於塗佈表面之特性，能夠有效地 待到優良的潤滑性。又，因為石夕樹脂係高潤滑性而且強度 12 201043457 亦比較優良’藉由在頂塗膜層含有矽酮接枝丙烯酸樹脂， 能夠形成光澤、硬度、潤滑性優良之塗膜。 藉由將本發明之預塗佈金屬板的頂塗膜層設為含有顏 料之透明塗膜’能夠進一步提升圖案設計性。 藉由將本發明之預塗佈金屬板的頂塗膜層設為含有光 免顏料之透明塗膜，圖案設計性提升，並且由於傷痕變為 不明顯’亦能夠提升耐負傷性。 頂塗膜中的矽酮接枝丙烯酸樹脂之含量以換算成矽樹 脂為2〜20質量％為佳。塗膜中的矽酮接枝丙烯酸樹脂之含 量小於2質量％時’潤滑性不充分，難以確保耐負傷性。大 於20質量％時，塗料的儲存安定性有低落之可能性，變得 難以安定製造。又，在此所謂「換算為矽樹脂」係意味著： 使用在頂塗膜中所含石夕酮單體(silicone monomer)總量之含 量’來表示矽酮接枝丙烯酸樹脂的含量。 頂塗膜中所含矽酮接枝丙烯酸樹脂以外的樹脂，只要 是可與矽酮接枝丙烯酸樹脂相溶，則可無問題地使用，但 仍以與矽酮接枝丙烯酸樹脂的相溶性優良且具有優良強度 及透明度之丙烯酸樹脂為最佳。 頂塗膜的交聯劑以三聚氰胺樹脂或異氰酸酯化合物為 佳。相較於異氰酸酯化合物，三聚氰胺樹脂係硬度較高， 容易得到規定的塗膜硬度。但是使用十二烷基苯績酸的胺 封端物等而使三聚氰胺樹脂在塗膜表面增稠時，矽樹脂變 為不容易配位於塗膜表面，潤滑性有低落之可能性。 將三聚氰胺樹脂作為交聯劑使用時之調配量，從確保 13 201043457 頂塗膜層的硬度或潤滑性之觀點’相對於100質量份砂綱接 枝丙烯酸樹脂，以5〜30質量份為佳。 另一方面，將三聚氰胺樹脂使用作為交聯劑並在高溫 放置時’與矽酮接枝丙烯酸樹脂反應容易進行，有塗料的 儲存安定性差之可能性，從塗料的儲存安定性之觀點，異 氰酸酯化合物比三聚氰胺樹脂佳。 通常’使用異氰酸酯化合物時，NCO/OH的莫耳比為 0.9/1.0以上。這是因為，可以想見NCO/OH的莫耳比若比 0.9/1.0低時將會交聯不足，致使塗膜變為太柔軟。 但是，經本案發明人詳細調查NCO/OH的莫耳比與性能 之關係的結果，發現使用矽酮接枝丙烯酸樹脂作為主樹脂 時，NCO/OH的莫耳比與一般認為最佳之值更低，且藉由使 NCO/OH的莫耳比為0.05/1.0〜0.5/1.0 ’將能夠使硬度與加 工性取得高位平衡。推測這是因為矽酮接枝丙烯酸樹脂比 異氰酸酯化合物硬度高，NCO/OH的莫耳比較低，亦即，異 氰酸酯化合物的量較少，因此能夠得到較硬的塗膜，且因 為交聯密度低，能夠得到高加工性。但是NCO/OH的莫耳比 小於0.05/1.0時，交聯密度太低，有無法得到塗膜硬度之可 能性。 使用異佛爾酮二異氰酸酯化合物作為異氰酸酯化合物 時，容易得到高塗膜硬度。因為異佛爾酮二異氰酸酯具有 較硬之骨架。 使用異氰酸酯化合物作為塗膜的硬化劑時，通常有將 NCO/OH的莫耳比設為0.9/1.0以上之必要。認為這是因為 14 201043457 NCO/OH的莫耳比小於〇·9/：ι ·〇時有助於交聯反應之異氰酸 醋基的量太少’藉由交聯反應之皮膜硬度提升效果不足， 致使塗膜變為太柔軟。 但是得知使用矽酮接枝丙烯酸樹脂作為主樹脂之本發 明時，將NCO/OH的莫耳比設為0.9/lo以上時，塗膜硬度比 將NCΟ/ΟΗ的莫耳比設為小於〇 9/丨〇者低。本發明者等詳細 地調查使用矽酮接枝丙烯酸樹脂作為主樹脂時NCO/OH的 莫耳比與性能的關係之結果，發現藉由將NCO/OH的莫耳比 6又為比通常被s忍為最佳的值低之0.05/1.0〜0.5/1.0時，能夠 南度地使硬度與加工性平衡。 推測這是因為矽酮接枝丙烯酸樹脂比異氰酸酯化合物 硬度高、更硬之緣故，NCO/OH的莫耳比低亦即異氰酸酯化 合物的量少’能夠得到較硬的塗膜，且因為交聯密度低而 延展性優良，能夠得到高加工性。但是NCO/OH的莫耳比小 於0.05/1.0時’交聯密度太低，無法充分地成膜，致使皮膜 強度本身有低落的可能性，乃是不佳。 使用異佛爾酮二異氰酸酯作為異氰酸酯化合物時，容 易得到高塗膜硬度。因為異佛爾酮二異氰酸酯具有硬骨架。 頂塗膜層的玻璃轉移溫度以30〜67°C為佳。玻璃轉移 溫度小於30°C時，塗膜硬度變低，有耐負傷性差之可能性。 玻璃轉移溫度比67°C高時，塗膜硬度太高’有變脆致使加 工性低落之可能性。 矽酮接枝丙烯酸樹脂中的矽樹脂之比率以3〜2〇質量 %為較佳。矽酮接枝丙烯酸樹脂中的矽樹脂之比率小於3質量 15 201043457 %時，賴脂對頂塗膜層表面之配位變為不充分、潤滑性降 低有而f負傷性差之可能性。石夕酮接枝丙稀酸樹脂中的石夕樹 脂之比料20質量％高時，有塗料的儲存安定性低落之可能 性。 頂塗膜層的膜厚度以卜⑺师為佳。頂塗膜層的膜厚 度小於Ιμιη時法將+塗塗膜層完全地覆蓋，有光澤或 润滑性低落之可驗。職膜層的轉度大於1_時，有 加工性低落之可能性。又，成本面亦是不佳。 中塗塗膜層係含有三聚氰胺硬化型或異氰酸酯硬化型 的聚自曰樹爿曰且含有著色顏料。而且，中塗塗膜層的玻璃轉 移狐度以25〜50 C為佳。將中塗塗膜層的主樹脂限定為聚 酉曰樹月曰之理由，係藉由將延展性及黏附性優良的聚醋樹脂 »又為中塗塗膜層，能夠確保加工性。而且，限定中塗塗膜 層的玻璃轉移溫度之理由，係用以兼具硬度及加工性之中 塗塗膜層的玻璃轉移溫度小於乃^時，有硬度不足之可能 性，大於50。(：時，有加工性不足之可能性，所以中塗塗膜 層的玻璃轉移溫度為25〜50。(：。 又，在中塗塗膜能夠組合主樹脂之聚酯樹脂以外的樹 脂而使用，為了確保前述聚酯樹脂的特性之延展性或黏附 性，在中塗塗膜所含有的聚酯樹脂之濃度以7〇質量％以上 為佳。在中塗塗膜能夠使用之聚酯樹脂以外的樹脂之種類 係無特別限定之必要，能夠按照必要適當地選擇對塗膜的 性能或塗裝性無不良影響者。 中塗塗膜層的膜厚度以5〜2〇μπι為佳。因為本發明之 201043457 預塗佈金屬板係頂塗膜層比中塗塗膜層硬之構造，中塗塗 膜層的膜厚度越厚，中塗塗膜層對塗膜整體的硬度之影響 變大，為中塗塗膜層的膜厚度大於20μιη時，因通用硬度有 變成75N/mm2以下之可能性，以2〇μηι以下為佳。又，中塗 塗膜層的膜厚度小於5μπι時，因顏料之掩蔽率降低，有難 - 以顯現顏色之可能性，中塗塗臈的膜厚度以5μιη以上為 佳。又，從確保皮膜的延展性之觀點，中塗塗膜的膜厚度 亦以5μιη以上為佳。 〇 而且，所謂在本發明之預塗佈金屬板的塗膜之玻璃轉 移溫度，含有顏料或硬化劑之塗膜時，係設作添加該等後 的塗膜整體之玻璃轉移溫度。塗膜的玻璃轉移溫度可以藉 由將在預塗佈金屬板所塗裝的塗膜剝離並使用差示掃描熱 量分析裝置(通常稱為DSC)來測定；亦可藉由在被塗裝作為 預塗佈金屬板的狀態使賴機械分析裝置(通常稱為谓八) 來測定。X，亦可藉由其他通常已知的方法來測定。而且， 〇 &知塗膜的玻璃轉移溫度會因測定機H或測定條件而產生 多少的誤差。因此，本發明係在複數通知眾所周知的玻璃 轉移溫度測定方法之中，使用任一方法亦即使用DSC之方 法或使用TMA之綠測料，只要塗朗玻_移溫度為 在本發明的範圍，係被本發明包含。因為塗膜的玻璃轉移 溫度，主要是基質樹脂的玻璃轉移溫度具有支配性，藉由 控制基質樹脂的《轉移溫度，能難塗_朗轉移溫度。 本發明的頂塗膜層與中塗塗膜層的界面之如(中心線 平均粗糙度）以0.3〜0.8师為較佳。塗膜的界面後小於 17 201043457 肩3卿時，該塗膜界面的黏附性有低落的可能性。通常，積 =模時’塗膜的黏附性係藉由塗膜間的化學鍵或氯鍵、 认瓦耳力等的物理鍵來保持，藉由使塗膜層間之Ra為〇 3 _卜 ， 除了该等的黏附力以外並加上能夠賦予錨固效果之 黏附力。但是，各塗膜的界面之Ra大於〇.8μπι時，會影響外 觀’有光澤低落之可能性。 在此，在本發明，上述界面Ra能夠藉由以下的方法(基 本上係依照JIS-B_060M982之方法）來測定。 將應測定表面粗糙度Ra之界面的垂直剖面拍攝在顯微 鏡照片後，描畫界面的凹凸，並依照JIS-B-0601-1982規定 之規定式（參照後述的實施例），能夠求取該界面的中心線平 均粗糙度。 因為本申請發明之預塗佈金屬板係在著色塗膜層上更 塗裝透明的透明塗膜，在使用原有的2塗2烤方法的設備來 製造時’增設塗佈裝置及烘箱，或是使板通過卷材塗佈機2 次來進行塗裝等之因應係必要的。但是藉由利用多層同時 塗佈或濕對濕式來塗裝塗膜及中塗塗膜，能夠使用原有的2 塗2烤方法之設備來製造本發明之預塗佈金屬板。又，賦予 上述界面的Ra，能藉由多層同時塗佈或濕對濕式來達成， 又’如後述，因為利用多層同時塗佈或濕對濕式來塗裝， 能夠得到良好的加工部外觀，就該等而言亦是較佳。 在本申請發明之所謂多層同時塗佈，有將縫模塗佈器 或滑動料斗式的簾流塗佈器等的複數層的塗液以同時積層 的狀態塗佈在基材上，隨後使多層同時乾燥烘烤之方法。 201043457 又，所謂濕對濕式塗裝係一次在基材上塗裝塗液後， 在該塗液乾燥前的濕狀態中，在其上面更塗佈其他塗液， 並將該被積層後的多層塗液同時乾燥烘烤之方法，例如藉 由輥塗佈器或簾流塗佈器等塗裝下層塗膜，並在將其烘烤 之前藉由簾流塗佈器等的塗裝方法塗裝上層塗膜後，將下 層塗膜及上層塗膜之複數塗膜同時烘烤之方法。 利用該等方法，藉由將未乾燥狀態的塗液積層並同時 塗佈，能夠以在界面各層的塗液稍微互相摻混的狀態在界 面形成濃度傾斜層。在本申請發明之濃度傾斜層係成為在 頂塗膜側為硬質而朝向中塗塗膜層側慢慢地變為柔軟之構 造。因此，即便在折曲加工等在硬質的頂塗膜層產生龜裂， 藉由位於界面之濃度傾斜層，龜裂的進展被抑制而不會達 到中塗塗膜層。因為頂塗膜層係透明的，龜裂只有停留在 頂塗膜層時，對外觀的影響微少而不會成為問題。又，藉 由將未乾無狀態的塗液積層並同時塗佈*並精由在界面各 層的塗液稍微互相摻混，在中塗塗膜層與頂塗膜層之間能 〇 夠得到優良的黏附性。 將本發明的多層同時塗佈或是濕對濕式塗裝後的塗膜 同時烘烤之方法，能夠使用通常眾所周知的塗料用烘烤爐 例如熱風乾燥爐、感應加熱爐、紅外線加熱爐或並用該等 之爐等。 在本發明之預塗佈金屬板的中塗塗膜層添加之著色顏 料係能夠使用通常眾所周知的無機系顏料、有機系顏料、 金屬顏料。作為具體例，可舉出碳黑、氧化鈦、鋅白、萘 19 201043457 酚紅、二重氮黃、二重氮吡唑橙、鋁顏料、鎳顏料等。通 常，黑系、濃色系的顏色時，傷痕容易明顯而難以確保耐 負傷性，但是本發明係即便是黑系或濃色系亦無問題而能 夠發揮效果並顯現良好的耐負傷性。 在本發明所使用的金屬板能夠使用通常眾所周知的金 屬材料。金屬材料亦可以是合金材料。可舉出例如鋼板、 不鏽鋼板、鋁板、鋁合金板、鈦板、銅板等。該等材料的 表面亦可施加鍍覆。鍍覆的種類可舉出鍍鋅、鍍鋁、鑛銅、 鍍鎳等。亦可以鍍覆該等的合金。鋼板時’能夠應用炫融 鍍鋅鋼板、電鍍鋅鋼板、鍍鋅-錄合金鋼板、、熔融鑛合金化 辞鋼板、鍍鋁鋼板及鍍鋁-鋅合金化鋼板等通常眾所周知的 鋼板及鍍覆鋼板。 在本發明所使用的金屬板之表面，因為施加通常眾所 周知的化成處理時，金屬板與塗膜層之黏附性提升，乃是 較佳。化成處理能夠使用碟酸辞系化成處理、塗佈鉻酸鹽 處理、電解鉻酸處理、反應鉻酸鹽處理、無鉻酸鹽系化成 處理等。作為無鉻酸鹽系化成處理，已知使用含有矽烷偶 合劑、錯·化合物、鈦化合物 '组或丹寧酸、樹脂、二氧化 矽等之水溶液處理而成者等，亦可使用在特開昭53-9238號 公報、特開平9-241576號公報、特開2001-89868號公報、特 開2001-316845號公報、特開2002-60959號公報、特開 2002- 38280號公報、特開2002-266081號公報、特開 2003- 253464號公報等所記載之眾所周知的技術。該等化成 處理能夠使用市售者，例如日本PARKERIZING公司製的鉻 20 201043457 酸鹽處理「ΖΜ-13〇〇ΑΝ」、日本PARKERIZING公司製的無 鉻酸鹽化成處理「CT-E300N」、日本PAINT公司製的三價鉻 系化成處理「SURFCOAT(註冊商標)NRC1000」等。[Patent Document 3] Japanese Laid-Open Patent Publication No. Hei No. Hei 11-19581 (Patent Document 5) Japanese Patent Publication No. Hei 11-19581 (Patent Document 5) Japanese Laid-Open Patent Publication No. Hei 11-19585 (Patent Document No. 11) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 15] JP-A-2004-98624 [Patent Document 17] JP-A-2004-34591 (Non-Patent Document) 1] Ueda et al., Color Materials, 72(8), pp. 525-531 (1999) C. Contents of the Invention Summary of the Invention The problem to be solved by the invention is to control the surface roughness of the base material of the precoated metal sheet. For lowering the method of obtaining high gloss and high vividness, if the surface roughness of the base metal, that is, the metal plate, can be controlled, The surface of the base material, that is, the surface roughness of the metal plate, can be obtained by rolling the metal with a calender roll after adjusting the surface roughness or by grinding with a grinder or the like. . Therefore, when this method is used to manufacture a high-gloss precoated metal sheet, industrial mass production is difficult because it requires a lot of labor or cost. On the other hand, a method of obtaining a high-gloss precoated metal sheet by coating a coating material of a low molecular weight resin can be obtained by a method of controlling the surface roughness of the metal sheet, that is, the surface of the metal sheet. It is simple to manufacture 'But it is difficult to impart other coating properties, such as processability, because it is necessary to use a specific resin in the coating. As a method of obtaining a precoated metal sheet which is easy to obtain a high gloss without using a resin which is limited in performance, there is a method of Patent Document 13, which is to apply a transparent clear coating film to a colored coating film layer. The problem of manufacturing this method when applied to the original 2 coat 2 baking type coil coating line can be solved by the wet-on-wet method as described above, but in terms of performance (for example, patent) In the case of the document 13), although excellent gloss can be obtained, sufficient damage to the skin cannot be obtained. Further, the technique of adding glass beads to the clear coating film on the colored coating film disclosed in Patent Documents 14 and 15 has an effect of improving the hardness of the coating film, but does not satisfy the resistance to scratch. Further, the addition of the wax to the clear coating film on the colored coating film disclosed in Patent Documents 16 and 17 improves the lubricity, but does not provide sufficient damage resistance. Moreover, the addition of glass beads and waxes to the film causes the gloss of the coating film to be lowered, and the use of the gloss appearance is not suitable. As described above, the pattern design is excellent in terms of gloss, vividness, and the like. 201043457 = coated metal sheet, which has been sufficiently correlated with the prior art, but has excellent designability for gloss, vividness, and the like, and is excellent in damage resistance. The pre-coated metal sheet ' has not been disclosed yet. Therefore, the present invention has been made in view of such a problem, and it is an object of the production method to provide a gloss, a high image, and a high impact resistance. The pre- (4) metal plate and the means for solving the problem ο ο In order to obtain gloss, high image clarity and sufficient resistance to injury, the inventors of the present invention have written materials based on the knowledge of the recording, and found that the prior art only improves the hardness m. Improve lubrication (4) without filling (4), it is necessary to have both high film hardness and high lubricity. Therefore, by using the top-containing ketone-grafted propylene-lip as a transparent layer and the intermediate coating layer containing trimeric amine The structure of the hardening type "cyanide-hardening type resin" can achieve the improvement of the hardness of the coating film and the reduction of the friction coefficient while ensuring the height = the degree of the film, and it is found that the design and the damage of the gloss and the vividness can be obtained. Both sides of the sex are excellent, and the pre-coated metal sheets are also excellent. The present invention has been completed based on such knowledge, and the present invention is as follows. a pre-coated metal sheet having a coating layer on one or both sides of the metal sheet, wherein the coating layer has at least a top coating layer formed on the most a coating film on the surface; and a 'middle coating layer' which is a layer coating film attached to the top coating layer; the top coating layer is a transparent coating layer containing an anthrone-grafted acrylic resin and not containing a pigment. The intermediate coating layer contains a melamine-cured or 201043457 isocyanate-curable polyester resin and contains a coating film of a coloring pigment, and the coating layer of the coating layer has an average coefficient of friction of 0.08 or less; and a coating layer The hardness of the surface at 23 ° C is 75 to 200 N/mm 2 in a universal hardness of 5 mN load; and the specular gloss of the surface of the coating layer is measured under the conditions of an incident angle and a light receiving angle of 20°, respectively. above 50. [2] A precoated metal sheet having a coating layer on one or both sides of the metal sheet, wherein: the coating layer has at least: a top coating layer, which is formed a coating film on the outermost surface; and an intermediate coating layer which is a layer coating film connected to the top coating film layer; the top coating film layer is a transparent coating film containing an anthrone-grafted acrylic resin and containing a pigment, and The intermediate coating layer is a coating film containing a melamine hardening type or an isocyanate curing type polyester resin and containing a coloring pigment; and the average coating coefficient of the surface of the coating layer of the coating layer is 0.08 or less; and the surface of the coating layer The hardness at 23 ° C is 75 to 200 N/mm 2 in a universal hardness test under a load of 5 mN; and the specular gloss of the surface of the coating layer is measured under the conditions of an incident angle and a light receiving angle of 20°, respectively. %the above. [3] The precoated metal sheet according to [2], wherein the top coating film layer is a clear coating film containing a bright pigment. [4] The precoated metal sheet according to [1] or [2], wherein the top coating film layer is a melamine hardening type. [5] The precoated metal sheet according to [1] or [2], wherein the top coating film layer is an isocyanate curing type. [6] The precoated metal sheet according to [5], wherein the ratio of NCO/OH in the top coating layer of the aforementioned isocyanate curing type 201043457 is 0.05 to 0.5. [7] The precoated metal sheet according to any one of [1] to [6], wherein an Ra (center line average roughness) of the interface between the top coating layer and the intermediate coating layer is 0.3 to 0.8 〇 [8] The precoated metal sheet according to any one of [1] to [7], wherein the content of the silicone grafted acrylic resin in the above top coating film is converted into an anthracene resin (silicone resin) is 2 to 18 mass 〇 / 〇. [9] The precoated metal sheet according to any one of [1] to [8], wherein the glass transition temperature of the top coating film is 30 to 67 ° C, and the axene sulphonate contained in the top coating film The ratio of the bismuth resin in the acrylic resin is 3 to 20% by mass, and the glass transition temperature of the above-mentioned intermediate coating layer is 25 to 50. [10] [10] The precoated metal sheet according to any one of [1] to [8], wherein the hardness of the surface of the coating layer at 23 ° C is 15 μm under a load of 5 mN. 200 N/mm2 [11] The precoated metal sheet of [10] or [11], wherein the above top coating layer is made of isocyanate hardened type. [12] Precoated metal sheet as in [11] The hardener in the above-mentioned top coat layer is isophorone diisocyanate (IPDi). [13] The precoated metal sheet according to [11] or [12], wherein the hard coater in the above top coat layer The ratio of 0.1 to 0.5. [14] A precoated metal sheet having a coating layer on one or both sides of the metal sheet, wherein: the coating layer has at least: a top coating layer a film formed on the outermost surface; an intermediate layer connected to the top coating layer; and an intermediate coating film 201043457 layer, which is a layer coating film connected to the intermediate coating layer; the top coating film The layer is a transparent coating film containing an anthrone-grafted acrylic resin and containing no pigment, and the intermediate coating layer contains a melamine-hardened or isocyanate-cured polyester resin. a coating film containing a coloring pigment, wherein an average coefficient of friction of the surface of the coating layer of the coating layer is 0.08 or less; and a hardness of the surface of the coating layer at 23 ° C is a general hardness of 75 to 200 under a load of 5 mN. N/mm2; and the specular gloss of the surface of the coating layer is 50% or more when the incident angle and the light receiving angle are each measured at 20°. [15] The precoated metal sheet of [14], wherein the foregoing The intermediate layer contains a pigment. [16] The precoated metal sheet according to [15], wherein the intermediate layer contains a bright pigment. [17] The precoated metal sheet according to any one of [14] to [16], wherein The Ra (center line average roughness) of the interface between the top coating film layer and the intermediate layer is 0.3 to 0.8. [18] A method for producing a precoated metal sheet, such as any one of [1] to [17] The method for producing a precoated metal sheet according to the invention, characterized in that: the coating which is to be the intermediate coating layer and the top coating layer is applied by multiple simultaneous coating or wet-on-wet method Bake. Effect of the Invention According to the present invention, it is possible to provide a gloss, high vividness, and resistance to injury and excellent workability. A pre-coated metal sheet, a method for producing the same, and a coated metal molded article. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram for explaining a method for measuring the center line roughness Ra. 10 201043457 Cross-sectional view. BEST MODE FOR CARRYING OUT THE INVENTION A preferred embodiment of the present invention will be described in detail below. The precoated metal sheet of the present month has two or more coating layers, and the coating layer of the H coating is a transparent coating film. The surface becomes smooth, and the specular gloss measured at the incident angle and the illuminating angle of 2 〇 can be obtained. The gloss of the specular gloss is 5〇% or more. Here, the transparent coating refers to the pigment concentration in the coating film. Low, the substrate has a low masking power and a transparent coating. Further, by allowing the top coat film layer to contain a predetermined amount of ruthenium grafted acrylic resin, high wetting and high hardness (average friction coefficient of 0,08 or less) can be obtained at 23%. With a universal hardness tester of 75 to 200 ΝΑηηή under a load of 5 mN, it is possible to have both impact resistance and high gloss. In order to ensure the damage resistance of the precoated metal sheet of the present invention, the average friction coefficient must be set to 〇. 〇8 or less. Here, the average coefficient of friction is such that the steel ball (1()_Φ) made of stainless steel is moved by 11 〇mm on the precoated metal plate under the condition of 1 GGg load and 15 Gmm/min. The applied force F' is calculated by averaging the measured values of the force F at the plural positions in the range of the remaining ones after the first ten jobs are removed. When the average friction coefficient is larger than 〇〇8, during the forming process The mold, the foreign matter is in contact with the surface of the precoated metal plate and the frictional force when rubbing becomes large, because the surface of the film is broken, which causes the damage resistance to be deteriorated. By the average friction coefficient of 0.08 or less, the surface of the precoated metal plate is Friction when the mold or foreign object rubs It is smaller and less resistant to injury. In order to obtain stable financial damage, the average coefficient of friction of flat 201043457 is preferably 0.05 or less. In order to break the financial damage of the precoated metal sheet of the present invention, the universal hardness of the surface is necessary. It is 75 to 200 N/mm2. Here, the term "universal hardness" refers to the method for measuring the hardness of a coating film described in DIN 50359-1 of Germany. The angle of the opposite side made of diamond is 136. (: the quadrangular pyramid (with In the same manner as the indenter used in the Vickers hardness test described in JIS-Z-2244, the surface of the material is pressed, and the hardness is calculated from the penetration depth under the applied load conditions. The term "universal hardness" as used in the invention is measured by using a micro hardness tester described in the DIN standard under the conditions of a temperature of 23 ° C and a press load of 5 mN. When the universal hardness is less than 75 N/mm 2 , even if the average friction coefficient is 〇.〇8 or less, due to the low hardness of the coating film, the damage resistance is poor. When the general hardness is more than 200 N/mm2, the coating film becomes too hard, and it is difficult to guarantee the processability' is not good. The universal hardness is 75~200. N/mm2 is preferred. When it is necessary, it is preferable to control the universal hardness to 15 〇 2 2 N/mm 2 . Further, the specular gloss of the precoated metal sheet of the present invention can be measured according to z 8741 at an incident angle and a light receiving angle. When measured under the conditions of 2 Å, it must be 50% or more. When the temperature is less than 50%, the appearance quality is poor. The top coating film layer of the precoated metal sheet of the present invention is as described above, and is grafted with an anthrone. Acrylic resin is characterized by the fact that the fluorenone-grafted acrylic resin-based oxime resin is polymerized in the main chain of the acrylic resin, and has excellent strength or transparency by the acrylic resin of the main chain and branches from the main chain. The hanging resin is easy to match the characteristics of the coated surface, and can effectively maintain excellent lubricity. In addition, because of the high lubricity and the strength 12 201043457, Shih-Hui resin is excellent in its ability. By containing an anthrone-grafted acrylic resin in the top coating layer, it is possible to form a coating film having excellent gloss, hardness and lubricity. The pattern design property can be further improved by using the top coat film layer of the precoated metal sheet of the present invention as a transparent coating film containing a pigment. By setting the top coat film layer of the precoated metal sheet of the present invention to a clear paint film containing a light-free pigment, the design of the pattern is improved, and the scratch resistance becomes inconspicuous, and the damage resistance can be improved. The content of the anthrone-grafted acrylic resin in the top coating film is preferably 2 to 20% by mass in terms of eucalyptus resin. When the content of the fluorenone-grafted acrylic resin in the coating film is less than 2% by mass, the lubricity is insufficient, and it is difficult to ensure the damage resistance. When it is more than 20% by mass, the storage stability of the coating material may be lowered, and it becomes difficult to manufacture stably. Here, "converted to oxime resin" means that the content of the fluorenone graft acrylic resin is represented by the content "the total amount of the silicone monomer contained in the top coat film". The resin other than the anthrone-grafted acrylic resin contained in the top coat film can be used without any problem as long as it can be compatible with the anthrone-grafted acrylic resin, but is excellent in compatibility with the anthrone-grafted acrylic resin. An acrylic resin having excellent strength and transparency is preferred. The crosslinking agent of the top coating film is preferably a melamine resin or an isocyanate compound. The melamine resin has a higher hardness than the isocyanate compound, and it is easy to obtain a predetermined coating film hardness. However, when the melamine resin is thickened on the surface of the coating film by using an amine-terminated material such as dodecylbenzene acid, the oxime resin may not be easily disposed on the surface of the coating film, and the lubricity may be lowered. The blending amount when the melamine resin is used as a crosslinking agent is preferably from 5 to 30 parts by mass based on 100 parts by mass of the sand-bonding acrylic resin from the viewpoint of ensuring the hardness or lubricity of the top coating layer of 13 201043457. On the other hand, when the melamine resin is used as a crosslinking agent and is placed at a high temperature, the reaction with the fluorenone-grafted acrylic resin is easy, and the storage stability of the coating is poor. From the viewpoint of storage stability of the coating, the isocyanate compound Better than melamine resin. Generally, when an isocyanate compound is used, the molar ratio of NCO/OH is 0.9/1.0 or more. This is because it is conceivable that if the molar ratio of NCO/OH is lower than 0.9/1.0, the crosslinking will be insufficient, resulting in the coating film becoming too soft. However, the inventors of the present invention investigated in detail the relationship between the molar ratio of NCO/OH and the performance, and found that when an anthrone-grafted acrylic resin is used as the main resin, the molar ratio of NCO/OH is generally considered to be the optimum value. It is low, and by setting the molar ratio of NCO/OH to 0.05/1.0 to 0.5/1.0', it is possible to achieve a high balance between hardness and workability. It is presumed that this is because the anthrone-grafted acrylic resin has a higher hardness than the isocyanate compound, and the NCO/OH has a relatively low molar content, that is, the amount of the isocyanate compound is small, so that a hard coating film can be obtained and the crosslinking density is low. , can obtain high processability. However, when the molar ratio of NCO/OH is less than 0.05/1.0, the crosslinking density is too low, and there is a possibility that the hardness of the coating film cannot be obtained. When an isophorone diisocyanate compound is used as the isocyanate compound, high coating film hardness is easily obtained. Because isophorone diisocyanate has a harder backbone. When an isocyanate compound is used as a curing agent for a coating film, it is usually necessary to set the molar ratio of NCO/OH to 0.9/1.0 or more. It is considered that this is because the molar ratio of the isocyanate group which contributes to the cross-linking reaction when the molar ratio of 14 201043457 NCO/OH is less than 〇·9/:ι·〇 is too small. Insufficient, causing the film to become too soft. However, when the present invention using an anthrone-grafted acrylic resin as a main resin is known, when the molar ratio of NCO/OH is 0.9/lo or more, the hardness ratio of the coating film is set to be smaller than the molar ratio of NCΟ/ΟΗ. 9/ The leader is low. The inventors of the present invention investigated in detail the relationship between the molar ratio of NCO/OH and the performance when using an anthrone-grafted acrylic resin as a main resin, and found that by making the molar ratio of NCO/OH 6 more than usual When the optimum value is 0.05/1.0 to 0.5/1.0, the hardness and workability can be balanced in the south. It is presumed that this is because the anthrone-grafted acrylic resin is harder and harder than the isocyanate compound, and the molar ratio of NCO/OH is low, that is, the amount of the isocyanate compound is small, a hard coating film can be obtained, and the crosslinking density is obtained. It is low in ductility and can be highly processed. However, when the molar ratio of NCO/OH is less than 0.05/1.0, the crosslink density is too low to form a film sufficiently, so that the film strength itself is low, which is not preferable. When isophorone diisocyanate is used as the isocyanate compound, high coating film hardness is easily obtained. Because isophorone diisocyanate has a hard backbone. The glass transition temperature of the top coat layer is preferably from 30 to 67 °C. When the glass transition temperature is less than 30 ° C, the hardness of the coating film becomes low, and there is a possibility that the abrasion resistance is poor. When the glass transition temperature is higher than 67 ° C, the hardness of the coating film is too high, and there is a possibility that the product becomes brittle and the workability is lowered. The ratio of the oxime resin in the fluorenone-grafted acrylic resin is preferably 3 to 2 % by mass. When the ratio of the oxime resin in the fluorenone-grafted acrylic resin is less than 3 masses 15 201043457%, the coordination of the lysine to the surface of the top coat layer is insufficient, the lubricity is lowered, and the damage to f is poor. When the ratio of the stone material of the Shixishu grafted acrylic resin is 20% by mass, there is a possibility that the storage stability of the paint is low. The film thickness of the top coat layer is preferably as good as (7). When the film thickness of the top coat layer is less than Ιμιη, the + coat layer is completely covered, and the gloss or lubricity is low. When the rotation of the film layer is greater than 1 mm, there is a possibility that the workability is low. Also, the cost side is not good. The intermediate coating layer contains a melamine hardening type or an isocyanate curing type poly eucalyptus and contains a coloring pigment. Moreover, the glass transition of the intermediate coating layer is preferably 25 to 50 C. The reason why the main resin of the intermediate coating layer is limited to the eucalyptus eucalyptus is to ensure the processability by using a polyester resin which is excellent in ductility and adhesion, and is also an intermediate coating layer. Further, the reason for limiting the glass transition temperature of the intermediate coating layer is that the glass transition temperature of the coating layer is less than or equal to the hardness and workability, and the possibility of insufficient hardness is more than 50. (There is a possibility that the processability is insufficient, so the glass transition temperature of the intermediate coating layer is 25 to 50. (:: Further, the intermediate coating film can be used in combination with a resin other than the polyester resin of the main resin, in order to use The concentration of the polyester resin contained in the intermediate coating film is preferably 7% by mass or more, and the type of the resin other than the polyester resin which can be used for the intermediate coating film. It is not necessary to be particularly limited, and it is possible to appropriately select the one which does not adversely affect the performance or the coating property of the coating film as necessary. The film thickness of the intermediate coating layer is preferably 5 to 2 〇μπι. Because of the 201043457 precoating of the present invention The structure of the top coating layer of the cloth metal plate is harder than that of the middle coating layer, and the thicker the film thickness of the middle coating layer, the influence of the intermediate coating layer on the hardness of the entire coating film becomes larger, and the film thickness of the intermediate coating layer is When the thickness is more than 20 μm, the general hardness may be 75 N/mm 2 or less, preferably 2 〇 μηι or less. Further, when the film thickness of the intermediate coating layer is less than 5 μm, the masking rate of the pigment is lowered, and it is difficult to In the case of color, the film thickness of the intermediate coating is preferably 5 μm or more. Further, from the viewpoint of ensuring the ductility of the film, the film thickness of the intermediate coating film is preferably 5 μm or more. The glass transition temperature of the coating film of the coated metal sheet, and the coating film containing the pigment or the curing agent, is set as the glass transition temperature of the entire coating film after the addition. The glass transition temperature of the coating film can be obtained by The coating film coated on the coated metal sheet is peeled off and measured using a differential scanning calorimeter (commonly referred to as DSC); or the mechanical analysis device can be made by being coated as a precoated metal sheet ( It is usually referred to as the measurement of X. It can also be measured by other commonly known methods. Moreover, the glass transition temperature of the coating film is determined by the measurement machine H or the measurement conditions. Therefore, the present invention is among the well-known methods for measuring the glass transition temperature of a plurality of notifications, using either the DSC method or the TMA green material, as long as the coating temperature is in the scope of the present invention. The present invention is included in the present invention because the glass transition temperature of the coating film is mainly dominant in the glass transition temperature of the matrix resin, and by controlling the "transfer temperature of the matrix resin, it is difficult to apply the temperature. The interface between the film layer and the intermediate coating layer (center line average roughness) is preferably 0.3 to 0.8. The interface of the coating film is less than 17 201043457. When the shoulder is 3, the adhesion of the coating interface is low. Possibility. Generally, when the product is a mold, the adhesion of the coating film is maintained by a chemical bond between the coating film or a physical bond such as a chlorine bond or a wattage, by Ra such that the Ra between the coating layers is 〇3. In addition to the adhesion, the adhesion force capable of imparting an anchoring effect is added. However, when the Ra of the interface of each coating film is larger than 〇.8 μm, the appearance of the glossiness of the appearance is affected. Here, in the present invention, the interface Ra can be measured by the following method (basically in accordance with the method of JIS-B_060M982). The vertical cross section of the interface at which the surface roughness Ra is to be measured is taken after a microscope photograph, and the unevenness of the interface is drawn, and the interface can be obtained according to the predetermined formula defined in JIS-B-0601-1982 (see the example described later). Centerline average roughness. Since the precoated metal sheet of the invention of the present application is further coated with a transparent transparent coating film on the colored coating film layer, the coating device and the oven are added when the original 2 coating 2 baking method is used, or It is necessary to apply the plate to the coil coater twice for coating. However, by coating the coating film and the intermediate coating film with a plurality of simultaneous coating or wet-on-wet coating, the precoated metal sheet of the present invention can be produced by using the apparatus of the conventional two-coating method. Moreover, Ra which is provided to the above-mentioned interface can be achieved by simultaneous application of a plurality of layers or wet-on-wet type, and as will be described later, since a plurality of simultaneous coatings or wet-on-wet coatings are used, a good processed portion appearance can be obtained. It is also better in this regard. In the so-called multi-layer simultaneous coating of the invention of the present application, a coating liquid of a plurality of layers such as a slit die coater or a slide hopper type curtain coater is applied to the substrate in a state of being laminated at the same time, and then the multilayer is applied. The method of drying and baking at the same time. 201043457 In addition, the wet-on-wet coating system applies a coating liquid to a substrate once, and further applies a coating liquid on the surface of the coating liquid in a wet state before drying, and the laminated layer is coated. The method of simultaneously drying and baking the multi-layer coating liquid, for example, coating the undercoat film by a roll coater or a curtain coater, and coating it by a coating method such as a curtain coater before baking it. After the upper layer coating film is applied, the plurality of coating films of the lower layer coating film and the upper layer coating film are simultaneously baked. By these methods, by laminating and coating the coating liquid in an undried state, it is possible to form a concentration inclined layer on the interface in a state in which the coating liquids of the respective layers at the interface are slightly blended with each other. In the concentration inclined layer of the present invention, the structure is hard on the top coating film side and gradually becomes soft toward the intermediate coating layer side. Therefore, even if cracks occur in the hard top coat layer such as the bending process, the progress of the crack is suppressed by the concentration of the layer located at the interface, and the intermediate coat layer is not obtained. Since the top coat layer is transparent, the crack only stays on the top coat layer, and the influence on the appearance is small and does not become a problem. Moreover, by laminating the undryed stateless coating liquid and simultaneously coating and finely blending the coating liquids on the respective layers of the interface, excellent adhesion between the intermediate coating layer and the top coating layer can be obtained. Adhesion. The simultaneous coating of the multilayer of the present invention or the simultaneous drying of the coating film after wet-on-wet coating can be carried out using a commonly known baking furnace for coatings such as a hot air drying furnace, an induction heating furnace, an infrared heating furnace or a combination thereof. Such furnaces, etc. In the colored pigment to which the intermediate coating layer of the precoated metal sheet of the present invention is added, an inorganic pigment, an organic pigment, or a metallic pigment which is generally known can be used. Specific examples thereof include carbon black, titanium oxide, zinc white, and naphthalene 19 201043457 phenol red, disazo yellow, diazopyrazole orange, aluminum pigment, and nickel pigment. In general, in the case of black or dark color, the scar is likely to be noticeable, and it is difficult to ensure the damage resistance. However, the present invention has no problem even in the case of black or dark color, and can exhibit an effect and exhibit good damage resistance. The metal plate used in the present invention can use a metal material which is generally known. The metal material can also be an alloy material. For example, a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a titanium plate, a copper plate, etc. are mentioned. The surface of the materials may also be plated. The type of plating may be galvanized, aluminized, copper or nickel plating. These alloys can also be plated. Steel plate can be applied to commonly known steel plates and plated steel plates such as glazed galvanized steel sheets, electrogalvanized steel sheets, galvanized-alloyed steel sheets, molten ore alloyed steel sheets, aluminized steel sheets, and aluminized-zinc alloyed steel sheets. . In the surface of the metal plate used in the present invention, it is preferable that the adhesion between the metal plate and the coating layer is improved when a chemical treatment which is generally known is applied. The chemical conversion treatment can be carried out by using a dish acidification treatment, a coating chromate treatment, an electrolytic chromic acid treatment, a reaction chromate treatment, a chromate-free chemical conversion treatment, or the like. The chromate-free chemical conversion treatment is known to be carried out using an aqueous solution containing a decane coupling agent, a wrong compound, a titanium compound 'group, or a tannic acid, a resin, or a cerium oxide, and the like. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A well-known technique described in, for example, JP-A-2003-253464. For the chemical conversion treatment, for example, chromium 20 201043457 acid salt produced by Japan PARKERIZING Co., Ltd., "ΖΜ-13〇〇ΑΝ", and non-chromate chemical conversion treatment "CT-E300N" manufactured by Japan PARKERIZING Co., Ltd., Japan PAINT can be used. The company's trivalent chromium system is processed into "SURFCOAT (registered trademark) NRC1000".

本發明的預塗佈金屬板係按照必要能夠塗裝具有防鏽 塗料功能之底漆塗膜。塗裝底漆塗膜時，因為金屬板的耐 蝕性提升，乃是較佳。在本發明的預塗佈金屬板塗裝之底 漆塗膜能夠使用通常眾所周知的預塗佈金屬板用底漆塗 膜，例如能夠使用聚酯系底漆、環氧系底漆、胺基甲酸乙 醋系底漆等。底漆塗膜的硬化劑係三聚氰胺系、異氰酸醋 系的任-者均可。在底漆塗膜添加之防鏞㈣能夠使用絡 酸鹽系、磷酸系、二氧化矽系等通常眾所周知者，因為對 環境友善，以鉻酸㈣以外者為較佳。在本發明的預塗佈 金屬板塗裝之底漆塗膜能夠藉由通常眾所周知的方法，例 如輥塗佈器、捲軸帶塗佈器_ e_in _㈣ 布器(wdngerrollcoater)、噴霧塗裝等進行塗裝，隨後，利 用通常眾所周知的塗料㈣烤爐例如熱風乾燥爐、感應加 熱爐、紅外線加熱爐或並用該等的爐等來烘烤。 實施例 但是本發 隨後，使用實施例纟更詳細地說明本發明 明不被下述的實施例限定。 以下，對實驗詳細說明。 首先，詳細地說明實驗所使用的表面塗料 在具備機械式攪拌裝置、 導入口之破璃製反應機，添加 溫度計、冷卻器、乾燥氮氣 100質量份異丙醇，並在· 21 201043457 氮氣下加熱至8G c，使用滴人漏斗以2小時滴入如表 1所不之<雜的,¾合液’隨後在同溫度保持4小時後結束反 應。如此進行而得到接枝共聚物溶液 。將由混合液1〜12所 得到的接枝絲物溶液作為接枝共聚物溶液1〜12。 亦吏用了市售品之砂酮接枝丙稀酸樹脂。使用了 東亞合成公司製的「REZEDA(註冊商標)GS-1015」（玻璃轉 移溫度為54°C)。 又’亦使用了日本觸媒公司製的丙烯酸樹脂亦即 「U-DOUBLE(註冊商標)s_27丨〇」（玻璃轉移溫度為4〇。〇卜 「ACRYSET(註冊商標）AST_5892」（玻帛轉移溫度為7〇 °C)(表 2 的 Τ0Ρ-16〜18)。 而且’使用了東洋紡公司製的非晶性聚酯樹脂亦即 「VYLON(註冊商標)GK8丨〇」(玻璃轉移溫度為46。〇 )作為未 使用矽酮接枝丙烯酸樹脂之比較用水準。 作為交聯劑’係使用了大曰本INK化學工業公司製的丁 基化三聚氰胺樹脂（以下，稱為丁基化三聚氰胺）亦即 「SUPER-BECKAMINE(註冊商標）J830」、三井CYTEC公 司製的完全烷基型曱基化三聚氰胺樹脂（以下，稱為曱基化 三聚氰胺）亦即「CYMEL(註冊商標）303」、住化BAYER URETHANE公司製的異氰酸酯化合物亦即「DESMODUR BL3175(註冊商標）」（以下，稱為HDI)、「DESMODUR BL4265SN(註冊商標）」（以下，稱為IPDI)、「DESMODUR BL1265MPA/X(註冊商標）」（以下，稱為TDI)、旭化成 CHEMICALS公司製「DURANETEE402-B80T」（以下，稱 22 201043457 為HDI②）。 作為光亮顏料，使用了旭化成METALS公司製的鋁碎 片「ALUMIPASTE CR-9800RM(商品名）」（平均粒徑為8// m)、東洋ALUMINUM公司製鋁碎片「LUPASTE 7220NS(商 品名）」（平均粒徑為25/im)。 作為比較材所使用的蠟，係使用了市售的 MICROCRYSTALINE。 而且，稀釋溶劑係使用了以質量比為環己烷： 〇 SOLVESSO150=l : 1 混合而成者。 隨後，詳細地說明在實驗所使用的中塗塗料。 使用東洋纺公司製的非晶性聚酯樹脂作為基質樹脂， 「VYLON(註冊商標）GK140」（坡螭轉移溫度為2〇。〇、 「VYLON(註冊商標）GK360」（破璃轉移溫度為36〇c )、 「VYLON(註冊商標）GK110」（破璃轉移溫度為5〇〇c)、 「VYLON(註冊商標)GK660」（破螭轉移溫度為55。〇。並按 〇 照必要混合而調整樹脂的玻璃轉移溫度來使用。作為交聯 劑’係使用了大曰本INK化學工業公司製的丁基化三聚氰胺 (以下稱為丁基化二聚氰胺）亦即「SUpERBECKAMINE(註 冊商標)卿。作為著色顏料’銀系的顏料係使用了市售的 銘碎片，黑系的顏料係使用了市售的碳黑，白系的顏料係 使用了市售的氧化鈦，紅系的顏料係使用了市售的氧化鐵 、工。又’溶劑係使用了以質量比為環己烧：S〇LVESS〇15〇= 1 · 1混合而成者。 在表2、表2_3、表3係各自記栽所製造的表面塗料、中 23 201043457 塗塗料之詳細。又，塗膜的玻璃轉移溫度係藉由SEIKO電 子公司製的熱機械分析裝置「SSC5200系列TMA/SS120C」， 測定時的探測器係使用具備針之探測器來測定。 24 201043457 表1The precoated metal sheet of the present invention can be coated with a primer coating film having a function of an rust preventive coating as necessary. When the primer coating film is applied, it is preferable because the corrosion resistance of the metal plate is improved. The primer coating film for precoated metal sheet coating of the present invention can be coated with a primer which is generally known as a precoated metal sheet, and for example, a polyester primer, an epoxy primer, an amide can be used. Ethyl vinegar primer, etc. The curing agent for the primer coating film may be any of melamine-based or isocyanuric acid-based. The anti-mite (4) to be added to the primer coating film can be generally known as a complex acid system, a phosphoric acid system or a cerium oxide system, and it is preferable to use it other than chromic acid (IV) because it is environmentally friendly. The primer coating film applied to the precoated metal sheet of the present invention can be applied by a generally known method such as a roll coater, a reel tape coater _ e_in _ (four) cloth wander (wdnger roll coater), spray coating, or the like. The package is then baked using a commonly known paint (4) oven such as a hot air drying oven, an induction heating furnace, an infrared heating furnace, or the like. EXAMPLES However, the present invention will be described in more detail by way of examples, which are not limited by the following examples. Hereinafter, the experiment will be described in detail. First, the surface coating used in the experiment is described in detail in a glass-breaking reactor equipped with a mechanical stirring device and a inlet, and a thermometer, a cooler, and 100 parts by dry nitrogen gas of isopropanol are added, and heated under nitrogen gas at 21 201043457. To 8 G c, the mixture was dropped into the <hetero, 3⁄4 mixture as shown in Table 1 using a dropping funnel for 2 hours, and then the reaction was terminated after maintaining the same temperature for 4 hours. This was carried out to obtain a graft copolymer solution. The graft filament solution obtained from the mixed solutions 1 to 12 was used as the graft copolymer solution 1 to 12. Commercially available garamine grafted acrylic resin is also used. "REZEDA (registered trademark) GS-1015" manufactured by Toagosei Co., Ltd. (glass transition temperature: 54 ° C) was used. Also, 'U-DOUBLE (registered trademark) s_27丨〇, which is an acrylic resin manufactured by Nippon Shokubai Co., Ltd., is used. (The glass transition temperature is 4 〇. AC 「 "ACRYSET (registered trademark) AST_5892" (glass transition temperature) It is 7〇°C) (Τ0Ρ-16~18 of Table 2). Moreover, 'VYLON (registered trademark) GK8丨〇 is used as the amorphous polyester resin manufactured by Toyobo Co., Ltd. (the glass transition temperature is 46). 〇) as a comparative standard for the use of the fluorenone-grafted acrylic resin. As the crosslinking agent, a butylated melamine resin (hereinafter referred to as butylated melamine) manufactured by Otsuka INK Chemical Industry Co., Ltd. is used. "SUPER-BECKAMINE (registered trademark) J830", a fully alkyl-type thiolated melamine resin (hereinafter referred to as thiolated melamine) manufactured by Mitsui CYTEC Co., Ltd., "CYMEL (registered trademark) 303", Sumitomo BAYER URETHANE The isocyanate compound manufactured by the company is "DESMODUR BL3175 (registered trademark)" (hereinafter referred to as HDI), "DESMODUR BL4265SN (registered trademark)" (hereinafter referred to as IPDI), and "DESMODUR BL1265MPA/X (registered trademark)" (hereinafter referred to as TDI), "DURANETEE402-B80T" manufactured by Asahi Kasei Chemicals Co., Ltd. (hereinafter referred to as 22 201043457 for HDI2). As a bright pigment, aluminum scrap "ALUMIPASTE CR-9800RM (trade name)" manufactured by Asahi Kasei METALS Co., Ltd. was used. (Average particle size is 8/m), and aluminum scrap "AUPASTE 7220NS (trade name)" (average particle size is 25/im) made by Toyo ALUMINUM Co., Ltd. The wax used for the comparative material is a commercially available MICROCRYSTALINE. Further, the dilution solvent was obtained by mixing cyclohexane: 〇SOLVESSO 150 = 1 : 1 in a mass ratio. Subsequently, the intermediate coating used in the experiment was explained in detail. Amorphous polymerization manufactured by Toyobo Co., Ltd. was used. As a matrix resin, "VYLON (registered trademark) GK140" (the slope transfer temperature is 2 〇. 〇, "VYLON (registered trademark) GK360" (breaking temperature of 36 〇c), "VYLON (registered trademark) GK110" (breaking glass transfer temperature is 5〇〇c), "VYLON (registered trademark) GK660" (breaking transfer temperature is 55. 〇 and adjust the glass transition temperature of the resin according to the necessary mixing) As a crosslinking agent 'system using said large butylated melamine present INK Chemical Industries, Ltd. (hereinafter referred to as two butylated melamine) i.e. "BECKAMINE (registered trademark) State. As a coloring pigment, a silver-based pigment is commercially available, and a black pigment is commercially available carbon black, a white pigment is commercially available titanium oxide, and a red pigment is used. Iron oxide sold, work. Further, the solvent was prepared by mixing a mass ratio of cyclohexane: S〇LVESS〇15〇=1·1. Table 2, Table 2_3, and Table 3 are the details of the surface coatings produced by the plants, and the coatings of the 2010 23,457,457 coatings. Further, the glass transition temperature of the coating film was measured by a thermomechanical analyzer "SSC5200 series TMA/SS120C" manufactured by SEIKO Electronics Co., Ltd., and the probe was measured using a probe equipped with a needle. 24 201043457 Table 1

混合液種 種類 添加量（質量份） 混合液1 苯乙烯 甲基丙烯酸丁酯 曱基丙烯酸2-乙基己酯 丙烯酸2-乙基己酯 曱基丙烯酸2-羥基乙酯 曱基丙烯酸 FM-0725 *1 18.0 20.7 20.7 9.0 18.9 2.7 10.0 混合液2 甲基丙烯酸甲酯 丙烯酸乙酯 丙_酸丁酯 曱基丙烯酸2-羥基乙酯 甲基丙烯酸 FM-0725 *1 41.4 21.6 12.6 12.6 1.8 10.0 混合液3 苯乙烯 曱基丙烯酸丁酯 丙烯§4 丁酯 FM-0725 *1 18.0 56.7 15.3 10.0 混合液4 苯乙烯 甲基丙烯酸甲酯 甲基丙烯酸丁酯 丙烯酸丁酯 甲基丙烯酸2-羥基乙酯 甲基丙烯酸 FM-0725 *1 7.2 29.0 27.0 10.8 15.3 0.7 10.0 混合液5 苯乙烯 曱基丙烯酸丁酯 曱基丙烯酸2-羥基乙酯 丙烯酸 FM-0725 *1 9.0 68.8 11.7 0.5 10 混合液6 笨乙烯 甲基丙烯酸丁酯 丙烯酸丁酯 FM-0725 *1 19.8 62.4 16.8 10 混合液7 苯乙烯 曱基丙烯酸丁酯 丙烯酸丁酯 FM-0725 *1 19.4 61.1 16.5 3.0 混合液8 苯乙烯 曱基丙烯酸丁酯 丙烯酸丁酯 FM-0725 *1 19.0 59.9 16.1 5.0 混合液9 苯乙烯 甲基丙烯酸丁酯 丙烯酸丁酯 FM-0725 *1 17.0 53.6 14.4 15.0 混合液10 苯乙烯 曱基丙烯酸丁酯 丙烯酸丁酯 FM-0725 *1 16.0 50.4 13.6 20.0 混合液11 苯乙烯 曱基丙烯酸丁酯 丙烯酸丁酯 FM-0725 *1 16.0 50.4 13.6 20.0 混合液12 笨乙烯 甲基丙烯酸丁酯 丙烯酸丁酯 AK-32 *2 18.0 56.7 15.3 10.0 *1 FM-0725 CHISSO公司製一末端甲基丙烯酸改性聚二甲基矽氧烷分子量10000 *2AK-32 東亞合成化學公司製一末端甲基丙烯酸改性聚二曱基石夕氧烷分子量30000 25 201043457 (N< 雄鸽鹄 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 塗膜中的 石夕接ί脂含量 (mass%) 0〇 00 00 00 〇〇 00 0〇 00 00 00 00 00 00 玻璃轉移 溫度(°c) 〇〇 V~) 添加量 (固體成分） (質量份） / / 1 / ) / / / / 種類 / (/ / / / (/ / / / [/ 交聯劑 添加量 (固體成分） (質量份） 種類 將丁基化三聚氰胺與甲基1 化三聚氰胺以1 : 1混合 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 將丁基化三聚氰胺與曱基I 化三聚氰胺以1 : 1混合！ 將丁基化三聚氰胺與曱基 化三聚氰胺以1 : 1混合 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 Β-οδ 绪·· u|绪 將丁基化三聚氰胺與曱基1 化三聚氰胺以1 : 1混合： 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 將丁基化三聚氱胺與甲基 化三聚氰胺以1 : 1混合 鍩.. fii 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 黏合劑 添加量 (固體成分） (質量份） 〇 100 〇 〇 〇 100 〇 100 〇 〇 〇 〇 〇 種類 接枝共聚物溶液1 接枝共聚物溶液2 接枝共聚物溶液3 接枝共聚物溶液4 接枝共聚物溶液5 接枝共聚物溶液6 接枝共聚物溶液7 接枝共聚物溶液8 接枝共聚物溶液9 接枝共聚物溶液10 接枝共聚物溶液11 接枝共聚物溶液12 接枝共聚物溶液10 ! 塗料種 TOP-1 1 TOP-2 TOP-3 1 ΤΟΡ-4 ΤΟΡ-5 1 ΤΟΡ-6 -1 Τ0Ρ-7 1 1 ΤΟΡ-8 T0F-9 TOP-10 TOP-11 TOP-12 TOP-13 26 201043457 〇ο Ο 〇 〇 〇 ο ο 〇 / / 00 00 00 00 00 00 00 / / 1—< ι—Η Ό Ό / / / / / / 卜 1—^ / / / /1 / / / u| §< 〇§ cti < y η ο 將丁基化三聚氰胺舆甲基 化三聚氰胺以1 : 1混合 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 缕.. ιι| ^ l·、' 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 將丁基化三聚氰胺與曱基 化三聚氰胺以1 : 1混合 HDI (表面增稠型） 將丁基化三聚氰胺與曱基 化三聚氰胺以1 : 1混合 ΪΒ-Φί 淫_. jJHm 辦解 h11' 案与 〇 〇 〇 〇 〇 ο 〇 Η 〇 ο 接枝共聚物溶液10 接枝共聚物溶液10 iinr a 爱·· m 〇 Ss 龚W l§ am . siD 趁.· CTJ Ο Ss #ω PQ 沭D |§ A)® i Ιί 盔α： #.. cn 〇 i 荽η 參CQ ii〇 接枝共聚物溶液3 接枝共聚物溶液3 | GK810 1 GK810 TOP-14 TOP-15, TOP-16 TOP-17 TOP-18 TOP-19 ΤΟΡ-20 TOP-21 TOP-22 27 201043457 (Ν-ϊ 玻璃轉 移 溫度 CC) 00 s 添加量 (固體成分） (質量份） / / 1 / / / / / / / / / / / / 種類 / / ΐ / / / / / / / / 顏料 添加量 (固體成分） (質量份） / / / / / / / / 種類 / / / / / 1 / 1 1 / / / / / NCO/OH 莫耳比 / CN 〇 ο 1—Η 〇〇 ο o O 1—' 0.05 1 0.02 / 5 s cn O o 交聯劑 添加量 (固體成分） (質量份） 120 s cn CN o (N m C^l 種類 將丁基化三聚氰胺與甲基| 化三聚氰胺以1 : 1混合 HDI② HDI② TDI HDI② HDI② HDI② HDI② HDI② HDI② 將丁基化三聚氰胺與甲基 化三聚氰胺以1 : 1混合 HDI② I- IPDI 1 IPDI 1 — IPDI 黏合劑 添加量 (固體成分） (質量份） 〇 〇 〇 ο Ο 〇 r·^ 100 〇 〇 〇 •-H 〇 〇 o o o 種類 REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZED GS-1015 REZED GS-1015 REZEDGS-1015 i 1 REZEDGS-1015 Η ω c/) & C嗖 破二 ri — 焕S 審汔 埤 筅 硃二 iT)— 5¾ ω < n r： ω Η 2pq a C/3 实匕 QC U < 將 REZEDA GS-1015 與 ACRYSET AST-5892 以 1:1 混合 1 將 REZEDA GS-1015 與 ACRYSET AST-5892 以 1:1 混合 t〇0 碟S l〇 — o ^ Cl： qk U < 塗料種 TOP-23 TOP-24 TOP-25 ΤΟΡ-26 TOP-27 TOP-28 TOP-29 TOP-30 TOP-31 TOP-32 TOP-33 TOP-34 TOP-35 TOP-36 TOP-37 28 201043457 ο ο 〇〇 1〇 cn 豪謹'Ήυ 31svdlsmv ΝΉ0086-Ήυ 31svdlsfnv SN0S卜 3Hsvdplv SN0日 WHSVdmv —0086-Ήυ alsvdlsmv ioos'^o wlsvdlsmvMixed liquid type addition amount (parts by mass) Mixed solution 1 Styrene butyl methacrylate 2-ethylhexyl acrylate 2-ethylhexyl decyl acrylate 2-hydroxyethyl decyl acrylate FM-0725 *1 18.0 20.7 20.7 9.0 18.9 2.7 10.0 Mixed solution 2 Methyl methacrylate ethyl acrylate propylene butyl acrylate 2-hydroxyethyl methacrylate acrylonitrile FM-0725 *1 41.4 21.6 12.6 12.6 1.8 10.0 Mixed solution 3 Styrene methacrylate butyl acrylate § 4 butyl ester FM-0725 *1 18.0 56.7 15.3 10.0 Mixture 4 Styrene methyl methacrylate butyl acrylate butyl acrylate 2-hydroxyethyl methacrylate methacrylate FM-0725 *1 7.2 29.0 27.0 10.8 15.3 0.7 10.0 Mixture 5 Styrene butyl methacrylate 2-hydroxyethyl acrylate acrylic acid FM-0725 *1 9.0 68.8 11.7 0.5 10 Mixture 6 Stupid vinyl methacrylate Ester butyl acrylate FM-0725 *1 19.8 62.4 16.8 10 Mixture 7 Styrene butyl acrylate butyl acrylate FM-0725 *1 19.4 61.1 16.5 3.0 Mix 8 Styrene butyl acrylate butyl acrylate FM-0725 *1 19.0 59.9 16.1 5.0 Mixture 9 Styrene butyl methacrylate butyl acrylate FM-0725 *1 17.0 53.6 14.4 15.0 Mixture 10 Styrene butyl acrylate butyl acrylate FM-0725 *1 16.0 50.4 13.6 20.0 Mixture 11 Styrene butyl acrylate butyl acrylate FM-0725 *1 16.0 50.4 13.6 20.0 Mixture 12 Styrene butyl methacrylate butyl acrylate AK-32 *2 18.0 56.7 15.3 10.0 *1 FM -0725 CHISSO company made a terminal methacrylic acid modified polydimethyl siloxane with molecular weight 10000 * 2 AK-32 East Asia Synthetic Chemical Co., Ltd. One-end methacrylic acid modified poly ruthenyl oxalate molecular weight 30000 25 201043457 (N&lt ; 希 接 中 中 ί fat content (mass%) 0〇00 00 00 〇〇00 0〇00 00 00 00 00 00 glass transfer temperature (°c) 〇〇V~) Adding amount (solid content) (parts by mass) / / 1 / ) / / / / Type / (/ / / / (/ / / / / / crosslinker addition amount (solid content ) (parts by mass) Melamine and melamine-methyl-1 to 1: 1 mixing butylated melamine and methylated melamine to 1: 1 mixing butylated melamine and melamine Yue group I to 1: 1 mix! Butylated melamine and thiolated melamine are mixed in a ratio of 1:1. Butylated melamine is mixed with methylated melamine in a ratio of 1:1. Β-οδ 绪·· u| butyl melamine and thiol melamine Mixing with 1:1: Mixing butylated melamine with methylated melamine in a ratio of 1:1 Mixing butylated melamine with methylated melamine in a ratio of 1:1 to combine butylated melamine with methylated melamine to 1:1 Mix and mix the butylated melamine with methylated melamine in a ratio of 1:1. fii Add the amount of binder (solid content) (parts by mass) of butylated melamine and methylated melamine in a ratio of 1:1. 〇100 〇〇〇100 〇100 〇〇〇〇〇 kind of graft copolymer solution 1 graft copolymer solution 2 graft copolymer solution 3 graft copolymer solution 4 graft copolymer solution 5 graft copolymer solution 6 Graft Copolymer Solution 7 Graft Copolymer Solution 8 Graft Copolymer Solution 9 Graft Copolymer Solution 10 Graft Copolymer Solution 11 Graft Copolymer Solution 12 Graft Copolymer Solution 10 ! Coating Type TOP-1 1 TOP -2 TOP-3 1 Τ ΟΡ-4 ΤΟΡ-5 1 ΤΟΡ-6 -1 Τ0Ρ-7 1 1 ΤΟΡ-8 T0F-9 TOP-10 TOP-11 TOP-12 TOP-13 26 201043457 〇ο Ο 〇〇〇ο ο 〇/ / 00 00 00 00 00 00 00 / / 1—< ι—Η Ό Ό / / / / / / Bu 1—^ / / / /1 / / / u| §< 〇§ cti < y η ο butyl Melamine melamine methylated melamine in a 1: 1 mixture of butylated melamine and methylated melamine in a ratio of 1:1. ιι| ^ l·, ' Butylated melamine and methylated melamine to 1: 1 Mixing Butylated melamine and thiolated melamine with 1:1 HDI (surface thickening type) Butylated melamine and thiolated melamine mixed with 1:1 ΪΒ-Φί 淫.. jJHm Solution h11' 〇〇〇〇〇ο 〇Η 〇ο Graft Copolymer Solution 10 Graft Copolymer Solution 10 iinr a Love·· m 〇Ss Gong W l§ am . siD 趁.· CTJ Ο Ss #ω PQ 沭D |§ A)® i Ιί Helmet α: #.. cn 〇i 荽η 参CQ ii〇Graft Copolymer Solution 3 Graft Copolymer Solution 3 | GK810 1 GK810 TOP-14 TOP-15, TOP-16 TOP- 17 TOP-18 TOP-19 Τ Ρ-20 TOP-21 TOP-22 27 201043457 (Ν-ϊ Glass transfer temperature CC) 00 s Adding amount (solid content) (parts by mass) / / 1 / / / / / / / / / / / / Type / / ΐ / / / / / / / / Adding amount of pigment (solid content) (parts by mass) / / / / / / / / Type / / / / / 1 / 1 1 / / / / / NCO / OH Mobi / CN 〇ο 1—Η 〇〇ο o O 1—' 0.05 1 0.02 / 5 s cn O o Additive amount of cross-linking agent (solid content) (parts by mass) 120 s cn CN o (N m C^l Alkaline melamine and methyl | melamine mixed with 1:1 HDI2 HDI2 TDI HDI2 HDI2 HDI2 HDI2 HDI2 HDI2 Butylated melamine and methylated melamine mixed with 1:1 HDI2 I-IPDI 1 IPDI 1 — IPDI adhesive added Amount (solid content) (mass parts) 〇〇〇ο Ο 〇r·^ 100 〇〇〇•-H 〇〇ooo Type REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZEDGS-1015 REZED GS- 1015 REZED GS-1015 REZEDGS-1015 i 1 REZEDGS-1015 Η ω c/) & C嗖破二ri — 焕S Review汔埤筅朱二iT) — 53⁄4 ω < nr: ω Η 2pq a C/3 匕 QC U < Mix REZEDA GS-1015 with ACRYSET AST-5892 1:1 1 REZEDA GS-1015 with ACRYSET AST-5892 with 1:1 mixed t〇0 disc S l〇— o ^ Cl: qk U < coating species TOP-23 TOP-24 TOP-25 ΤΟΡ-26 TOP-27 TOP-28 TOP-29 TOP-30 TOP-31 TOP-32 TOP-33 TOP-34 TOP-35 TOP-36 TOP-37 28 201043457 ο ο 〇〇1〇cn Hao Jin 'Ήυ 31svdlsmv ΝΉ0086-Ήυ 31svdlsfnv SN0S Bu 3Hsvdplv SN0 day WHSVdmv —0086-Ήυ alsvdlsmv Ioos'^o wlsvdlsmv

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I 寸 _doH M-dol ε 寸 _dol 寸寸，dOl w'dol 9'dol /.'dol 8 寸 Idol 6'dol o'dol 29 201043457 表3 塗料種 ' 丨· -中塗-1 黏合劑 交聯劑 顏料 玻雜移 溫度 CO 種類 添加量 [質量份] 麵 添加量 [質量份] 種類 添加量 [質量份] GK140 100 丁基化 三聚氣胺 30 黑 10 20 中塗-2 將 GJC140 與 GK360 以2 : 1(質量比)混合 100 丁基化 三聚氣胺 30 黑 10 25 中塗-3 將 GK140 與 GK360 以1 : 2(質量比)混合 100 丁基化 三聚氣胺 30 黑 10 30 中塗>4 GK360 100 丁基化 三聚氰胺 30 黑 10 36 中塗-5 ---— 將GK360與GK〗10以 1 : 1(質量比)混合 100 丁基化 三聚#1胺 30 黑 10 43 中塗七 —·— 將 GK360 與 GK110 以 1 : 4(質量比)混合 100 丁基化 三聚氰胺 30 黑 10 47 中塗-7 ----- 中塗-8 ---—__- GK110 100 丁基化 三聚氣胺 30 黑 10 50 55 660 100 丁基化 三聚象嚴 30 黑 10 』塗-9 GK360 100 HDI 30 黑 10〜 36 中塗-10 GK360 100 丁基化 三聚氣胺 30 紅 20 36 中塗-11 〜 — GK360 100 丁基化 三聚氱胺 30 白 130 36 t 塗-12 __ GK360 100 丁基化 三聚H胺 30 銀 10 36 又’準備日本FINE COATINGS公司製的PCM用聚酷系 底塗亦即FL641EU底漆之透明塗料’藉由在此以相對於1〇〇 質量份透明塗料的固體成分，添加3〇質量份無鉻酸鹽防鏽 顏料亦即TAYCA公司製的三聚磷酸二氫鋁「k_White #1〇5」，來製造無鉻酸鹽底漆。 以下，詳細說明在實施例的實驗所使用的之預塗佈金 屬板。 、 「準備新曰本製鐵股份公司製的炼融鍍鋅鋼板 「肌徽歷(註冊商標）」（以下稱為叫作為原板 係使用〇.6顏者。使用錢覆黏附量為-面6〇mg/m2者。 30 201043457 隨後，將準備的原板使用日本PARKERIZING公司製的 丙烯酸脫脂液「FC-4336」的2質量％濃度、50°C水溶液進 行喷霧脫脂並水洗後’乾燥後，使用輥塗佈器塗佈曰本 PARKERIZING公司製的無鉻酸鹽化成處理亦即 「CT-E300N」，並使用熱風烘箱使其乾燥。熱風烘箱的乾 燥條件係鋼板的到達板溫為6CTC。以無鉻處理的黏附量係 總固體成分為2〇〇g/m2的方式塗裝。 Ο 隨後，在施加化成處理後之金屬板的一面，塗裝所製 造的底漆塗料，並在另一面使用輥塗佈器塗裝背面塗料亦 即「FL100HQ」（灰色），並在吹入熱風後的感應加熱爐以金 屬板的到達板溫成為210°C的條件乾燥硬化。而且，在乾燥 烘烤後，使用喷霧器對塗裝後的金屬板喷吹水，來進行水冷。 隨後，在底漆塗膜上使用滑動料斗式的簾流塗佈器將 中塗塗料及表面塗料同時2層積層塗裝，並在吹入熱風後的 感應加熱爐以金屬板的到達板溫成為23〇〇c的條件將積層 Q 後的塗膜同時乾燥硬化。然後，藉由在乾燥烘烤後使用喷 霧器對塗裝後的金屬板噴吹水而進行水冷，來製造3層的預 塗佈金屬板(以下，將本塗裝方法稱為「塗裝方法⑴」）。 又，按照必要，在底漆塗膜上使用捲軸帶塗佈器 (r〇ll-CUrtain coater)只塗裝丨層中塗塗料，而且在使其乾燥i 前，使用捲軸帶塗佈器在其上面塗裝表面塗料並將塗膜 同時乾燥硬化。然後，藉由在乾燥烘烤後，使用喷霧器對 塗裝後的金屬板噴吹水而進行水冷，來製造3層的預塗佈金 屬板(以下，將本塗裝方法稱為「塗裝方法⑼」）。 31 201043457 而且’亦能夠製造在底漆塗膜上使用輥塗佈器只塗裝i 層中塗塗料，並以前述要領烘烤後，在中塗塗膜上再次使 用輥塗佈器塗裝1層表面塗料並烘烤而成之3層的預塗佈金 屬板(將藉由本程序的塗裝方法稱為「塗裝方法(出)」 又，在底漆塗膜上使用滑動料斗式的簾流塗佈器將中 塗塗料、中間塗料及表面塗料同時3層積層塗裝，並在吹入 熱風後的感應加熱爐以金屬板的到達板溫成為23〇它的條 件將積層後的塗膜同時乾燥硬化。而且，藉由在乾燥洪烤 後’使用喷霧器對塗裝後的金屬板噴吹水而進行水冷，來 製造4層的預塗佈金屬板（以下，將本塗裝方法稱為「塗裝 方法(iv)」）。 而且，亦能夠製造在底漆塗膜上使用輥塗佈器只塗裝i 層中塗塗料並烘烤，且在中塗塗膜上再次使用輥塗佈器塗 裝1層中間塗料並烘烤’而且在中間塗膜上再次使用輥塗佈 器塗裝1層表面塗料並烘烤而成之4層的預塗佈金屬板（以 下’將藉由本程序的塗裝方法稱為「塗裝方法(v)」）。 以下，詳細地記載在實驗所製造的預塗佈金屬板之評 價方法。 1. 通用硬度 使用HSCHER INSTRUMENTS公司製的微小硬度計 「FISCHERSCOPE(註冊商標)H100」來測定。測定時的環 境溫度為23°C，將面角136。四角錐的維氏壓頭以在60秒按 壓負荷成為5mN的條件來測定通用硬度(HU(N/mm2))。 2. 潤滑性 32 201043457 使用HEIDON-14測定將不鏽鋼製的鋼球（100ηΗηΦ)以 100g負荷、150mm/min的條件在預塗佈金屬板移動n〇mm 時所需要的力F，並算出平均摩擦係數。又，測定位置係除 去最初的10 mm後在剩餘100 mm的範圍内之5個位置。 3. 測定預塗佈金屬板的塗膜之鏡面光澤度 使用SUGA試驗機公司製的「數位變角光澤計」，以入 射角與受光角為20°的條件測定鏡面光澤度。以SuGA試驗 機公司製的1次用基準板(No.99B076)之20。光澤為88%且2 次用基準板(N〇_99W076)之20°光澤為15%之方式調整。 4. 耐負傷性試驗 使用HEIDON-14，並將10圓硬幣以45。與預塗佈金屬 板接觸的方式在垂直方向施加負荷，目視判定在水平方向 將預塗佈金屬板以50mm/min往復移動時是否有傷痕，並評 價無傷痕之最大負荷。 〇：50g以上 △ : 20g以上、小於50g X :小於20g 鉛筆硬度 依照JIS-KMOO的8.4.1(1993年)之方法，藉由改變錯筆 芯的硬度時之塗膜的擦傷來調查塗膜的擦傷，將在塗膜未 觀察到擦傷之最高硬度作為該塗膜的錯筆硬度，並如以下 評價。 〇：Η以上 △ : 3Β以上、小於Η 33 201043457I inch _doH M-dol ε inch _dol inch inch, dOl w'dol 9'dol /.'dol 8 inch Idol 6'dol o'dol 29 201043457 Table 3 Coating species ' 丨 · - 中涂-1 Binder crosslinking Agent pigment glass miscarrying temperature CO type addition amount [parts by mass] surface addition amount [parts by mass] type addition amount [parts by mass] GK140 100 butylated triamine 39 black 10 20 medium coating-2 GJC140 and GK360 2 : 1 (mass ratio) mixed 100 butylated trisamine 30 black 10 25 medium coated-3 mixed GK140 and GK360 in a ratio of 1: 2 (mass ratio) 100 butylated trisamine 30 black 10 30 middle coating > 4 GK360 100 Butylated melamine 30 Black 10 36 Medium coated-5 ---— Mix GK360 and GK 10 in a ratio of 1:1 (mass ratio) 100 Butylated Triad #1amine 30 Black 10 43 中涂七—· — Mix GK360 and GK110 in a ratio of 1: 4 (mass ratio) 100 Butylated melamine 30 Black 10 47 Medium -7 ----- Medium -8 --- __- GK110 100 Butylated triamine 30 Black 10 50 55 660 100 Butylated Trimeric Elephant 30 Black 10 』Coat-9 GK360 100 HDI 30 Black 10~ 36 Medium Tu-10 GK360 100 Butylated Triamine 30 Red 20 36 Medium Tu - 11 ～ — GK360 100 Butylated melamine 30 White 130 36 t 涂-12 __ GK360 100 Butylated trimeric H amine 30 Silver 10 36 Also prepared for PCM polyurea primer made by FINE COATINGS, Japan That is, the transparent paint of FL641EU primer is added by adding 3 parts by mass of a chromate-free antirust pigment, that is, a dihydrogen phosphate trihydrate manufactured by TAYCA, with respect to a solid component of a transparent coating of 1 part by mass. Aluminum "k_White #1〇5" to make a chromate-free primer. Hereinafter, the precoated metal sheets used in the experiments of the examples will be described in detail. "Preparation of the smelting galvanized steel sheet "Muscular Emblem (registered trademark)" made by the company, which is made by the company, is used as the original board. 〇mg/m2. 30 201043457 Subsequently, the prepared original plate was spray-degreased with water at a concentration of 2% by mass and 50 ° C in an aqueous solution of acrylic acid degreasing liquid "FC-4336" manufactured by Japan PARKERIZING Co., Ltd., and then dried. The roll coater was coated with a non-chromate chemical conversion process manufactured by PARKERIZING Co., Ltd., which is also called "CT-E300N", and dried using a hot air oven. The drying condition of the hot air oven was that the plate reached a plate temperature of 6 CTC. The adhesion amount of the chromium treatment was applied in such a manner that the total solid content was 2 〇〇g/m 2 . Ο Subsequently, the primer coating was applied on one side of the metal sheet after the chemical conversion treatment, and the roller was applied on the other side. The applicator is coated with a back coating, that is, "FL100HQ" (gray), and is dried and hardened in an induction heating furnace after the hot air is blown to a condition that the sheet temperature reaches 210 ° C. Moreover, after drying and baking, Painting with a sprayer The rear metal plate is sprayed with water for water cooling. Subsequently, the intermediate coating and the surface coating are simultaneously applied in two layers by using a sliding hopper type curtain flow applicator on the primer coating film, and after being blown in the hot air. The induction heating furnace simultaneously drys and hardens the coating film after the layer Q is reached under the condition that the sheet temperature reaches 23 ° C. Then, the coated metal sheet is sprayed by using a sprayer after drying and baking. The water is cooled by water to produce a three-layer precoated metal sheet (hereinafter, this coating method is referred to as "coating method (1)"). Further, if necessary, a reel tape applicator is used on the primer coating film. (r〇ll-CUrtain coater) only applies the coating in the enamel layer, and before using it to dry i, apply a surface coating on the reel tape applicator and dry and harden the coating at the same time. After drying and baking, the coated metal sheet is sprayed with water and water-cooled to produce a three-layer precoated metal sheet (hereinafter, the coating method is referred to as "coating method (9)"). 31 201043457 And 'can also be used to make rolls on the primer film The cloth is coated with only the i-layer coating, and after baking in the above manner, a 3-layer precoated metal plate is coated on the intermediate coating film by using a roll coater and baking a layer of the surface coating ( The coating method by this procedure is called "coating method (out)". The middle coating, intermediate coating and surface coating are simultaneously laminated on the primer coating film using a sliding hopper type curtain flow applicator. The induction heating furnace after being blown in hot air is dried and hardened at the same time by the condition that the sheet metal reaches the sheet temperature of 23 〇. Moreover, by using a sprayer after drying and baking The metal plate after the application is sprayed with water and water-cooled to produce a four-layer precoated metal plate (hereinafter, this coating method is referred to as "coating method (iv)"). Moreover, it is also possible to manufacture and apply a coating of the i-layer coating on the primer coating film by using a roll coater, and apply a layer of the intermediate coating on the intermediate coating film again using a roll coater and bake 'and A four-layer precoated metal sheet which is coated with one coat of the surface coating and baked on the intermediate coating film by a roll coater (the following is referred to as "coating method by the coating method of this procedure" (v )"). Hereinafter, the evaluation method of the precoated metal sheet produced in the experiment will be described in detail. 1. Universal hardness was measured using a micro hardness tester "FISCHERSCOPE (registered trademark) H100" manufactured by HSCHER INSTRUMENTS. The ambient temperature at the time of measurement was 23 ° C, and the face angle was 136. The Vickers indenter of the quadrangular pyramid was measured for the universal hardness (HU (N/mm2)) under the condition that the pressing load was 5 mN in 60 seconds. 2. Lubricity 32 201043457 The force F required to move the steel ball (100ηΗηΦ) made of stainless steel to the precoated metal plate by n〇mm under the condition of 100g load and 150mm/min was measured using HEIDON-14, and the average friction was calculated. coefficient. Further, the measurement position is 5 positions in the range of 100 mm remaining after the first 10 mm is removed. 3. Measurement of the specular gloss of the coating film of the precoated metal sheet The specular gloss was measured under the conditions of an incident angle and a light receiving angle of 20° using a "digital angle gloss meter" manufactured by SUGA Testing Machine Co., Ltd. It is 20 of the reference plate (No. 99B076) used once by SuGA Testing Machine Co., Ltd. The gloss was 88% and the secondary plate was adjusted in such a manner that the 20° gloss of the reference plate (N〇_99W076) was 15%. 4. Resistance to injury test Use HEIDON-14 and put 10 round coins at 45. The load was applied in the vertical direction in contact with the precoated metal sheet, and it was visually judged whether or not there was a scratch when the precoated metal sheet was reciprocated at 50 mm/min in the horizontal direction, and the maximum load without scratch was evaluated. 〇: 50 g or more Δ : 20 g or more and less than 50 g X : less than 20 g Pencil hardness According to the method of JIS-KMOO 8.4.1 (1993), the coating film is investigated by changing the scratch of the coating film when the hardness of the wrong core is changed. For the scratch, the highest hardness of the scratch was not observed in the coating film as the erroneous pen hardness of the coating film, and was evaluated as follows. 〇: Η above △ : 3Β or more, less than Η 33 201043457

X : 4B 5. 塗臈加工性試驗 將所製造的預塗佈金屬板，180°折曲加工(黏附折曲 加工）並目視觀察加工部的塗膜，來調查塗膜有無裂紋。 又’在進行180°折曲時，係以預塗佈金屬板的表面為折曲 的方外之方式折曲’來進行黏附彎曲（通常作為0Τ彎曲而被 知悉）。然後，目視觀察加工部，將觀察到完全無塗膜裂紋 或剝離時評價為〇，在塗膜稍微龜裂或剝離為△，在塗膜 有到達底漆塗膜或金屬板之裂紋或剝離時為X。而且，亦實 施在加工部貼上膠黏帶並剝離之加工部黏附性試驗，目視 觀察膠黏帶剝離後的黏附性，在塗膜未觀察到明確的剝離 時評價為〇，相對於彎曲加工部的全長在合計為小於一半 的長度可觀察到塗膜剝離時為△，相對於彎曲加工部的全 長在合計為一半以上的長度可觀察到塗膜剝離時為χ。 6. 色值 依feJIS Ζ 8722並使用分光測色計(SUGA試驗器製、型 式MSC-45-2B)來測定L值。 7. 塗料的儲存安定性 在塗料罐（1升、外徑、高】3〇mm)中加入2〇〇g 塗料並蓋住，在4〇°c保管並調查塗料有無凝膠化。將6個月 以上未凝膠化者則賈為◦，3〜6個月凝膠化者為△，〇〜3 個月凝膠化者為x。又’將塗料罐放顛倒並放置H、時後塗 料未漏出至外部的狀態判定為凝膠化。 8. 塗料的耐增黏性 34 201043457 在塗料罐0升、外徑㈣2mm、高13〇_)中加入綱g 塗料H在50 C保管i小時，來調查塗料的对增黏性。 黏度係调正為2〇c裝滿岩田黏度杯，並使用碼錶測定 至王里机出之b數。將保管後的塗料之秒數(使用岩田黏度 杯所測定的純)除以保管前的塗料的減之㈣小於L5 者評價為〇，L⑽上、小於3者為Δ，3以上者為χ。 9.境界面Ra的測定X: 4B 5. Coating process test The precoated metal plate to be produced was subjected to a 180° bending process (adhesion bending process) and the coating film of the processed portion was visually observed to investigate whether or not the coating film was cracked. Further, when the 180° bending is performed, the surface of the precoated metal sheet is bent so as to be bent, and the adhesion is bent (usually known as 0Τ bending). Then, the processed portion was visually observed, and when it was observed that there was no coating film crack or peeling at all, it was evaluated as 〇, and the coating film was slightly cracked or peeled off to Δ, and when the coating film reached crack or peeling of the primer coating film or the metal plate, For X. Further, the adhesion test of the processed portion in which the adhesive tape was attached to the processed portion and peeled off was also carried out, and the adhesiveness after the adhesive tape was peeled off was visually observed, and the flaw was evaluated when the coating film was not observed to be peeled off, and the bending was performed. When the total length of the coating film is less than half, the film peeling is observed to be Δ, and when the total length of the bent portion is half or more, the peeling of the coating film is observed to be χ. 6. Color value The L value was measured in accordance with feJIS Ζ 8722 using a spectrophotometer (manufactured by SUGA tester, type MSC-45-2B). 7. Storage stability of the coating Add 2〇〇g of paint to the paint can (1 liter, outer diameter, height) 3 〇mm) and cover it. Store at 4 °C and check for gelation of the coating. For those who have not been gelled for more than 6 months, Jia is sputum, 3 to 6 months for gelation, △, and 〇~3 months for gelation, x. Further, the state in which the paint can was placed upside down and H was placed and the coating did not leak to the outside was judged to be gelation. 8. Resistance to adhesion of paints 34 201043457 In the paint cans, 0 liters, outer diameter (4) 2 mm, height 13 〇 _), the coating material H was stored at 50 C for 1 hour to investigate the adhesion of the coating. The viscosity is adjusted to 2〇c filled with the Iwata viscosity cup, and the number of b to the Wangli machine is measured using a code table. The number of seconds of the stored paint (the purity measured by the Iwata viscosity cup) divided by the paint before storage (4) is less than L5, and the evaluation is 〇, L(10) is less than 3, Δ, and 3 or more is χ. 9. Determination of the interface interface Ra

中塗層與上塗層之境界面的R a，係將各實施例的塗膜 在相對於㈣方向為垂直方向靖並埋人至娜後，利用 研磨來使與塗膜的表面垂直之剖面平滑並藉由使肺〇〇倍 的掃描型顯微鏡拍攝之照片來評價。從照片上方，使用在 HP所使用的透明片蓋住並精密地描晝境界面的凹凸後， 如圖所示，使用影像處理裝置測定縱線部分的面積並從式 算出^作為其平均值。又，1為3mm。 [數式1]The Ra of the interface between the middle coating layer and the upper coating layer is obtained by grinding the coating film perpendicular to the surface of the coating film after the coating film of each embodiment is vertically aligned with respect to the (four) direction and buried. Smoothing and evaluation by photographs taken by scanning microscopy of the lungs. From the top of the photograph, using the transparent sheet used by HP to cover and precisely describe the unevenness of the boundary interface, as shown in the figure, the area of the vertical line portion was measured using an image processing apparatus and the average value was calculated from the equation. Also, 1 is 3 mm. [Expression 1]

Ra = \i\f(x)\dx 以下’記載評價結果之詳細。 ^在表4〜7，顯示在本發明所製造的預塗佈金屬板及其 平價、、、°果。又，係使用施加底漆塗膜後的供試材來說明本 發明，但是未施加底漆塗膜時，亦能夠得到與施加底漆塗 骐者同樣的性能。 (1)平均摩擦係數、通用硬度的影響 作為平均摩擦係數、通用硬度的影響係在n〇1〜n〇 19 35 201043457 顯示實施例’且在No.20〜No.28顯示比較例。 本發明的預塗佈金屬板(實施例·i〜19)具有優良的对 負傷性、光澤、加工性。 平均摩擦係數大於〇.〇8者（比較例_22、25)，因為财負 傷性差，乃是不佳。通用硬度小於75祕_2者（比較例_2〇、 26)因為耐負知性差，乃是不佳。通用硬度大於胞爪2 者（比較例-21、27)，因為加性差，乃是不佳。 (2)頂塗膜種、中塗塗膜種的影響 頂塗膜層係未含有顏料之透明塗膜，且頂塗膜中的石夕 酮接枝丙騎龍的含量健算顿脂為2〜_量％。中 重塗膜層係含有著色顏料且含有三聚氰胺硬化型或異氣酸 i旨硬化型的聚_脂’中塗塗膜的破璃轉移溫度為25〜5〇 °C者。又’頂塗膜的玻璃轉移溫度物〜抓，且含有石夕 酮接枝丙烯酸樹脂中㈣樹脂之比率為3〜2G質量％之石夕 _接枝丙稀酸樹脂。中塗塗膜層係含有著色顏料且含有 一聚氰胺硬化型或異級自旨硬化型的㈣樹脂，中塗塗膜 的玻璃轉移溫度為25〜耽者(實施例_卜19)具有優良的 财負傷性、光澤、加卫性。頂塗膜巾㈣酮接枝丙稀酸樹 月曰的3里係換算石夕樹脂為大於18質量％者(實施例_2〇、21) 及石夕綱接枝__脂的含4係換算讀脂為20質量％者 (實施例21)’塗料的儲存安定性有較低之傾向。 頂塗膜層的玻璃轉移溫度小於3G°C者（比較例-22)、中 塗塗膜層的玻璃轉移溫度小於者（比較例_26)，通用硬 度有低落的傾向，耐貞傷性差頂賴巾㈣酮接枝丙稀 36 201043457 酸樹脂之含量換算矽樹脂為小於2質量％者（比較例-24、 25)，石夕酮接枝丙烯酸樹脂之含量換算矽樹脂為小於3質量％ 者（比較例-24)，動摩擦係數有低落之傾向，耐負傷性差。 頂塗膜層的玻璃轉移溫度高於67。(：者（比較例-23) ’中 塗塗膜的玻璃轉移溫度高於50。(：者（比較例-27)，通用硬度 有太南的傾向，加工性變差。 在頂塗膜層添加大量的蠟，來得到通用硬度為75 N/mm2以上且平均摩擦係數為〇.〇8以下者（比較例-28)，因為 鏡面光澤度小於50°/。而光澤度差，乃是不佳。 (3) 膜厚度的影響 頂塗膜層的膜厚度為〇.5μιη者（實施例-29)係潤滑性稍 微下降且耐負傷性有稍微變差之傾向。頂塗膜層的膜厚度 為12μιη者(實施例-35)係加工性有稍微下降之傾向。頂塗膜 層的膜厚度以1〜丨0!·1111為較佳。 中塗塗膜層的膜厚度為3μιη者（實施例-36)係L值稍微 變高且有不容易顯現黑色之傾向。中塗塗膜層的膜厚度為 22μιη者（實施例-43)係硬度稍微下降且耐負傷性有低落之 傾向。中塗塗:膜層的膜厚度以5〜20μηι為較佳。 (4) 中塗塗膜層的著色種之影響 即便是本申請發明以外’白或銀等的淡色系時亦能夠 滿足耐負傷性，但是黑或紅等的濃色系時無法防止傷痕產 生（比較例48〜51)。對此’本申請發明係淡色系當然不必說 而且濃色系時耐負傷性亦良好，得知具有優良的耐負傷性 (實施例44〜47)。 37 201043457 耐負傷性以外的性能（光澤、加工性)係比較例、本申請 發明均是不管中塗塗犋層的顏色都顯示良好的性能。 (5) 塗裝方法的影響 相較於使用多層同時塗佈及濕對濕式塗裝所製造者， 將中塗塗膜層及頂塗膜層各丨層塗裝益烘烤而成者（實施例 -54)，加工性及黏附性有低落的傾甸。由該結果，得知使用 多層同時塗佈及濕對濕式塗裝所製造者係加工性及黏附性 提升，乃是較佳。 (6) 光亮顏料的影響 在表A顯示光亮顏料的影響。頂塗膜層含有光亮顏料者 (實施例-57〜60)，藉由傷痕變為不明顯，鉛筆硬度有提升 之傾向。 (7) 交聯劑的影響 交聯劑的影響係在表B顯示。使用異氰酸酯化合物者 (實施例-63〜67)，表面塗料的财增黏性有較優良的傾向。 NCO/OH的莫耳比為0·05〜0.3/1 ·0(實施例-68〜70)能夠得 到較高的耐負傷性，乃是較佳。 (8) 關於耐磨耗性的賦予 關於耐磨耗性的賦予係在表C顯示。將塗膜層表面在23 °C的硬度設為在5mN負荷下的通用硬度為150〜200 N/mm2 者(實施例-80〜88) ’有能夠賦予高耐磨耗性之傾向。 使用異佛爾酮二異氰酸酯（IPDI)作為異氰酸酯化合 物，且NCO/OH的莫耳比為0·1〜〇·5Π_〇(實施例-82、85、 86)，有耐磨耗性優良之傾向。 38 201043457 (9) 中塗層與表面層的界面5^之影響 中塗層與表面層的界面Ra之影響係在表D顯示。中塗 層與表面層的界面Ra為〇·3〜0.8者(實施例-89、91、93、95、 97、99、1〇1、1〇3、1〇5、1〇7) ’加工性及黏附性提升，乃 是較佳。 (10) 中間塗膜層的影響 中間塗膜層的影響係在表E顯示。在中間塗膜層含有光 焭顏料者（實施例-109〜128)，藉由傷痕變為不明顯，鉛筆 硬度有提升之傾向。 (11) 中間塗膜層與表面層的界面Ra之影響 中間塗膜層與表面層的界面Ra之影響係在表d顯示。 中間塗膜層與表面層的界面Ra為0.3〜0.8者（實施例-109〜 118)，加工性及黏附性提升，乃是較佳。Ra = \i\f(x)\dx The following describes the details of the evaluation results. In Tables 4 to 7, the precoated metal sheets produced in the present invention and their properties are shown. Further, the present invention will be described using a test material obtained by applying a primer coating film. However, when the primer coating film is not applied, the same performance as that of the primer application can be obtained. (1) Effect of average friction coefficient and general hardness The influence of the average friction coefficient and the general hardness is shown in n 〇 1 to n 〇 19 35 201043457 and the comparative example is shown in No. 20 to No. 28. The precoated metal sheets of the present invention (Examples i to 19) have excellent scratch resistance, gloss, and workability. The average coefficient of friction is greater than 〇.〇8 (Comparative Example _22, 25), because the financial damage is poor, it is not good. Those with a general hardness of less than 75 secrets (Comparative Examples _2, 26) are poor because of poor negative tolerance. The general hardness was greater than that of the claw 2 (Comparative Examples-21, 27), which was poor because of poor additivity. (2) The influence of the top coating film type and the medium coating film type The top coating film layer is a clear coating film which does not contain a pigment, and the content of the linaloside grafted in the top coating film is calculated to be 2~ _the amount%. The medium heavy coating layer contains a coloring pigment and contains a melamine hardening type or an isogastric acid. The glass transition temperature of the coating film of the hardened type of poly-lipid is 25 to 5 ° C. Further, the glass transition temperature of the top coating film is scratched, and the ratio of the resin in the linalo-grafted acrylic resin is 4 to 2 g% by mass. The intermediate coating layer contains a coloring pigment and contains a melamine hardening type or a heterogeneous self-hardening type (IV) resin, and the intermediate coating film has a glass transition temperature of 25 耽 (Example _Bu 19) and has excellent wealth. Negative, shiny, and edifying. The top coating film (4) ketone-grafted acrylic acid tree 曰 3 3 系 石 石 树脂 为 为 为 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 ( ( 实施 实施 ( ( ( 实施 实施 实施 ( ( ( ( ( ( ( ( ( ( ( ( When the conversion fat is 20% by mass (Example 21), the storage stability of the paint tends to be low. When the glass transition temperature of the top coating layer is less than 3G °C (Comparative Example-22) and the glass transition temperature of the intermediate coating layer is smaller than that of the comparative coating (Comparative Example _26), the general hardness tends to be low, and the scratch resistance is poor. Towel (4) ketone grafted propylene 36 201043457 The content of the acid resin is 小于 resin is less than 2% by mass (Comparative Example-24, 25), and the content of the sulphuric acid grafted acrylic resin is less than 3% by mass. In Comparative Example-24), the dynamic friction coefficient tends to be low, and the resistance to damage is poor. The glass transition temperature of the top coat layer is higher than 67. (: (Comparative Example 23) 'The glass transition temperature of the intermediate coating film is higher than 50. (: (Comparative Example-27), the general hardness tends to be too south, and the workability is deteriorated. Adding to the top coating layer A large amount of wax is used to obtain a general hardness of 75 N/mm2 or more and an average friction coefficient of 〇.〇8 or less (Comparative Example-28) because the specular gloss is less than 50°/, and the gloss is poor, which is not good. (3) Effect of film thickness The film thickness of the top coat layer is 〇.5 μιη (Example -29). The lubricity is slightly lowered and the damage resistance is slightly deteriorated. The film thickness of the top coat layer is The film thickness of the top coat layer is preferably from 1 to 丨0!·1111. The film thickness of the intermediate coat layer is 3 μm (Example - 36) The L value is slightly higher and tends to be less likely to appear black. The film thickness of the intermediate coating layer is 22 μm (Example-43), and the hardness tends to decrease slightly and the resistance to damage is low. The film thickness of the layer is preferably 5 to 20 μm. (4) The influence of the coloring species of the intermediate coating layer is even if it is issued in the present application. In addition to the light color such as white or silver, the damage resistance can be satisfied, but the dark color such as black or red cannot prevent the occurrence of scratches (Comparative Examples 48 to 51). In addition, it was found that the color resistance was good, and it was found to have excellent resistance to injury (Examples 44 to 47). 37 201043457 Performance other than the negative impact resistance (gloss, workability) is a comparative example, and the present invention is It is good performance regardless of the color of the coating layer. (5) The influence of the coating method is compared with that of the multi-layer simultaneous coating and wet-on-wet coating, the intermediate coating layer and the top coating film. Each layer of the layer was coated and baked (Example-54), and the workability and adhesion were low. From the results, it was found that the use of multiple layers of simultaneous coating and wet-on-wet coating was used. It is better to improve the processability and adhesion. (6) The influence of bright pigments shows the influence of bright pigments in Table A. The top coating layer contains bright pigments (Example -57~60), with scars It becomes inconspicuous and the pencil hardness tends to increase. (7) The influence of the crosslinking agent on the cross-linking agent is shown in Table B. When the isocyanate compound was used (Examples -63 to 67), the surface-coating material had a favorable tendency to increase the viscosity. The molar ratio of NCO/OH was 0. 05 to 0.3/1 · 0 (Examples - 68 to 70) It is preferable to obtain high abrasion resistance. (8) About the wear resistance, the basis for the wear resistance is given in the table. C shows that the hardness of the surface of the coating layer at 23 ° C is set to a hardness of 150 to 200 N/mm 2 under a load of 5 mN (Example - 80 to 88) "There is a tendency to impart high wear resistance." Using isophorone diisocyanate (IPDI) as the isocyanate compound, and the molar ratio of NCO/OH is 0.1·5·Π5〇 (Examples -82, 85, 86), which is excellent in abrasion resistance. The tendency. 38 201043457 (9) The influence of the interface between the middle coating and the surface layer 5^ The influence of the interface Ra between the coating and the surface layer is shown in Table D. The interface Ra between the middle coating layer and the surface layer is 〇·3~0.8 (Examples -89, 91, 93, 95, 97, 99, 1〇1, 1〇3, 1〇5, 1〇7) Sex and adhesion enhancement is better. (10) Effect of the intermediate coating layer The influence of the intermediate coating layer is shown in Table E. In the case where the intermediate coating layer contains a bismuth pigment (Examples -109 to 128), the pencil hardness tends to be improved by the fact that the flaw becomes inconspicuous. (11) Effect of the interface Ra between the intermediate coating layer and the surface layer The influence of the interface Ra between the intermediate coating layer and the surface layer is shown in Table d. When the interface Ra between the intermediate coating layer and the surface layer is 0.3 to 0.8 (Examples -109 to 118), workability and adhesion are improved, which is preferable.

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SI εοι 寸01 § 901 § 801 47 201043457SI εοι inch 01 § 901 § 801 47 201043457

備考 實施例 表面 塗料的 耐增黏 性 <] <] 〇 <] 〇 <] <] 〇 <] 〇 <1 <] 〇 <3 〇 <3 〇 <] 〇 加工性 | 剝離 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 <] <] < < < < < <] < < 龜裂 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 <] < < <] <] <] < <] <1 < 财磨 耗性 <] <] 〇 ◎ < < 〇 ◎ < < <3 〇 ◎ <] < < 〇 ◎ < < <1 <] <3 <] < <] < < < < < < 0 < < < < 财負 傷性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 20。 光澤 (%) OS JO oo JO JO VO s 00 Z (N 00 (N CO z 00 00 § 通用 硬度。 (N/mm2) 〇 菩 g o r-^ ON § § o ON 沄 § o »〇 § | 平均 摩擦 係數 S 〇 s o S 〇 S 〇 g o s o s o s o s o s o s o s o s o s o g o s o s o s o s o o 中塗 塗膜與 表面白6 养面Ra 〇 d 卜 o 〇 卜 C5 to o o VO o d o i- r-1 o o 1—1 T— 5 5 o 塗裝 ) 之 (iv) (iv—)」 (iv)—」 ㈤ (iv) (iv) N 扃 N·_/ /^S > 、·_·/ r—\ > /-N > > s^ /*~N > > N > /·—N > > > 3 表面 塗膜 (Ν (N (N (N (N (N CS CN (N (N in i〇 i〇 1〇 中間 塗膜 m m m m m m m m m m cn cn cn m m m m m 中塗 塗膜 yn <r\ Ό (N (N (N (N ίΝ >〇 in Ό ό CN (N (N (N (N 1 表面 塗料種 TOP-3 TOP —23 TOP-30 TOP-33 TOP-36 TOP-3 TOP-23 TOP —30 TOP-33 TOP-36 TOP-3 TOP-23 TOP-30 TOP-33 TOP-36 TOP-3 TOP-23 TOP-30 TOP-33 TOP-36 中間 塗料種 TOP-38 TOP-39 TOP-46 TOP—48 TOP-49 TOP-50 TOP —50 TOP-50 1 TOP-50 TOP-50 TOP-38 TOP-39 TOP-46 TOP —48 TOP-49 TOP-50 TOP-50 TOP-50 TOP-50 TOP-50 中塗 塗料種 中塗一4 中塗一 4 中塗一 4 中塗一4 中塗一 4 中塗一 4 中塗一4 寸 夺 寸 1 -B- 中塗一 4 中塗一 4 中塗一 4 中塗一 4 中塗一 4| |中塗一4 中塗一 4 中塗一 4 中塗一4 中塗一 4 中塗一 4 § s o 二 (N 寸 卜 oo ON § <N (N <N m CN § U-) (N (N 00 (N 48 201043457 以上，係邊參照附加圖式邊說明本發明的較佳實施形態， 但是，當然本發明不被該等例子限定。清楚明白在申請專 利範圍所記載的範疇内，該業者能夠考慮到各種的變更例 或修正例，請瞭解該等當然亦屬於本發明的技術範圍。 【圖式簡單說明】 第1圖係用以說明中心線粗糙度Ra的測定方法之模式 剖面圖。 【主要元件符號說明】Proof test example surface coating resistance to tackling <] <] 〇 <] 〇 <] <] 〇 <] 〇 <1 <] 〇 <3 〇<3 〇<] 〇Processability | Stripping 〇〇〇〇〇〇〇〇〇〇<] <] <<<<<<<<<<&<<<><]<]<<<1<<<><]<] 〇◎ << 〇◎ <<<3 〇◎ <] <<<<<<<<1<><3<><<<<<<<< 0 <<<;< Finance is damaging 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇20. Gloss (%) OS JO oo JO JO VO s 00 Z (N 00 (N CO z 00 00 § General hardness. (N/mm2) 〇 go r go r go go o o 〇 § o ON 沄§ o »〇§ | Coefficient of friction S 〇so S 〇S 〇gosososososososososog ososososoo Medium coating film and surface white 6 Raise face Ra 〇d b o 〇 C C5 to oo VO odo i- r-1 oo 1-1 T-5 5 o coating) (iv) (iv-)" (iv)-" (v) (iv) (iv) N 扃N·_/ /^S > ,·_·/ r-\ > /-N >> s^ /*~N >> N > /·-N >>> 3 Surface coating (Ν (N (N (N (N (N (N (N (N (N (N (N Intermediate coating film mmmmmmmmmm cn cn cn mmmmm medium coating film yn <r\ Ό (N (N (N (N NN (N N ( ( ( ( ( ( ( ( ( ( ( ( ( 23 TOP-30 TOP-33 TOP-36 TOP-3 TOP-23 TOP —30 TOP-33 TOP-36 TOP-3 TOP-23 TOP-30 TOP-33 TOP-36 TOP-3 TOP-23 TOP-30 TOP -33 TOP-36 Intermediate paint type TOP-38 TOP-39 TOP-46 TOP-48 TOP-49 TOP-50 TOP —50 TOP-50 1 TOP-50 TOP-50 TOP-38 TOP-39 TOP -46 TOP —48 TOP-49 TOP-50 TOP-50 TOP-50 TOP-50 TOP-50 Medium coating material coating one 4 medium coating one 4 medium coating one 4 middle coating one 4 middle coating one 4 middle coating one 4 middle coating one 4 inch inch 1 -B- 中涂一4 中涂一4 中涂一4 中涂一4 中涂一4||中涂一4 中涂一4 中涂一4 中涂一4 中涂一4 中涂一 4 § so 2 (N inch oo ON § &lt N (N < N m CN § U-) (N (N 00 (N 48 201043457 and above), while referring to the additional drawings, a preferred embodiment of the invention is described, but the invention is of course not limited. It is to be understood that in the scope of the application of the patent application, the present invention can be considered in various modifications and examples, and it is of course also within the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view for explaining a method of measuring the center line roughness Ra. [Main component symbol description]

Claims (1)

201043457 七、申請專利範圍： 1. 一種預塗佈金屬板，該預塗佈金屬板係在金屬板的一面 或兩面具有塗膜層，其特徵在於： 該塗膜層至少具有：頂塗膜層，其係形成於最表面 之塗膜；及，中塗塗膜層，其係與該頂塗膜層連接之下 層塗膜； 該頂塗膜層係含有矽酮接枝丙烯酸樹脂且不含顏 料之透明塗膜，該中塗塗膜層則係含有三聚氰胺硬化型 或異氰酸酯硬化型之聚酯樹脂且含有著色顏料的塗膜； 此外，該塗膜層之塗膜層表面的平均摩擦係數為 0.08以下；塗膜層表面於23°C下之硬度以5mN負荷下之 通用硬度計係75〜200N/mm2 ;且，塗膜層表面的鏡面 光澤度在入射角及受光角各自為20°的條件下測定 時，為50%以上。 2. —種預塗佈金屬板，該預塗佈金屬板係於金屬板的一面 或兩面具有塗膜層，其特徵在於： 該塗膜層至少具有：頂塗膜層，其係形成於最表面 之塗膜；及，中塗塗膜層，其係與該頂塗膜層連接之下 層塗膜； 該頂塗膜層係含有矽酮接枝丙烯酸樹脂且含有顏 料之透明塗膜，而該中塗塗膜層係含有三聚氰胺硬化型 或異氰酸酯硬化型的聚酯樹脂且含有著色顏料之塗膜； 此外，該塗膜層之塗膜層表面的平均摩擦係數為 0.08以下；塗膜層表面於23°C下之硬度以5mN負荷下的 50 201043457 通用硬度計係75〜200 N/mm2 ;且，塗膜層表面之鏡面 光澤度在入射角及受光角各自為20°的條件測定時，為 50%以上。 3·如申請專利範圍第2項之預塗佈金屬板，其中該頂塗膜 層係含有光亮顏料之透明塗膜。 4_如申請專利範圍第1或2項之預塗佈金屬板，其中該頂塗 膜層係三聚氰胺硬化型。 0 5·如申請專利範圍第1或2項之預塗佈金屬板，其中該頂塗 膜層係異氰酸酯硬化型。 6.如申請專利範圍第5項之預塗佈金屬板，其中該異氰酸 醋硬化型的頂塗膜層中，NCO/OH的比為0.05〜0.5。 7·如申請專利範圍第1至6項中任一項之預塗佈金屬板，其 中s亥頂塗膜層與中塗塗膜層之界面的Ra(中心線平均粗 糙度)為0.3〜〇.8。 8·如申請專利範圍第1至7項中任一項之預塗佈金屬板，其 ◎ 中°亥頂塗膜中的石夕嗣接枝丙烯酸樹脂（silicone grafted acrylic resin)之含量換算成石夕樹脂（siiic〇ne resin)為2 〜18質量％。 9·如申請專利範圍第1至8項中任一項之預塗佈金屬板，其 中该頂塗膜的玻璃轉移溫度為30〜67。(：，該頂塗膜中所 含石夕綱接枝丙烯酸樹脂中之矽樹脂比率為3〜20質量 %，且該中塗塗膜層的玻璃轉移溫度為25〜50°C。 1〇.如申清專利範圍第1至8項中任-項之預塗佈金屬板，其 中塗膜層表面於23°C下之硬度以5mN負荷下的通用硬 51 201043457 度計係150〜200 N/mm2。 11. 如申請專利範圍第10或11項之預塗佈金屬板，其中該頂 塗膜層係異氰酸酯硬化型。 12. 如申請專利範圍第11項之預塗佈金屬板，其中該頂塗膜 層中之硬化劑為異佛爾酮二異氰酸酯（IPDI)。 13. 如申請專利範圍第11或12項之預塗佈金屬板，其中該頂 塗膜層中之硬化劑的比率為〇. 1〜0.5。 14. 一種預塗佈金屬板，該預塗佈金屬板係在金屬板的一面 或兩面具有塗膜層，其特徵在於： 該塗膜層至少具有：頂塗膜層，其係形成於最表面 之塗膜；中間層，其係與該頂塗膜層連接；及中塗塗膜 層，其係與該中間塗膜層連接之下層塗膜； 該頂塗膜層係含有矽酮接枝丙烯酸樹脂且不含顏 料之透明塗膜，該中塗塗膜層係含有三聚氰胺硬化型或 異氰酸酯硬化型的聚酯樹脂且含有著色顏料之塗膜； 此外，該塗膜層之塗膜層表面的平均摩擦係數為 0.08以下；塗膜層表面於23°C下之硬度以5mN負荷下的 通用硬度計係75〜200 N/mm2 ;且，塗膜層表面之鏡面 光澤度在入射角及受光角各自為20°的條件下測定 時，為50%以上。 15. 如申請專利範圍第14項之預塗佈金屬板，其中該中間層 含有顏料。 16. 如申請專利範圍第15項之預塗佈金屬板，其中該中間層 含有光亮顏料。 52 201043457 17. 如申請專利範圍第14至16項中任一項之預塗佈金屬 板，其中該頂塗膜層與中間層之界面的Ra(中心線平均 粗糙度）為0.3〜0.8。 18. —種預塗佈金屬板之製造方法，係如申請專利範圍第1 至17項中任一項之預塗佈金屬板之製造方法，其特徵在 於： 藉由多層同時塗佈或濕對濕(wet on wet)方式，分別 〇 將會成為中塗塗膜層及該頂塗膜層的塗料予以塗佈後 進行烘烤。201043457 VII. Patent application scope: 1. A pre-coated metal plate having a coating layer on one or both sides of a metal plate, characterized in that: the coating layer has at least: a top coating layer a coating film formed on the outermost surface; and an intermediate coating layer which is a layer coating film attached to the top coating layer; the top coating layer contains an anthrone grafting acrylic resin and does not contain a pigment a transparent coating film, wherein the intermediate coating layer is a coating film containing a melamine hardening type or an isocyanate curing type polyester resin and containing a coloring pigment; further, an average friction coefficient of the surface of the coating layer of the coating layer is 0.08 or less; The hardness of the surface of the coating layer at 23 ° C is 75 to 200 N/mm 2 under a load of 5 mN; and the specular gloss of the surface of the coating layer is measured at an incident angle and a light receiving angle of 20° each. When, it is 50% or more. 2. A pre-coated metal sheet having a coating layer on one or both sides of a metal sheet, wherein: the coating layer has at least: a top coating layer formed on the most a coating film on the surface; and an intermediate coating layer, which is a layer coating film connected to the top coating layer; the top coating layer is a transparent coating film containing an anthrone-grafted acrylic resin and containing a pigment, and the intermediate coating layer The coating layer is a coating film containing a melamine hardening type or an isocyanate curing type polyester resin and containing a coloring pigment; further, an average friction coefficient of the surface of the coating layer of the coating layer is 0.08 or less; and the surface of the coating layer is 23°. The hardness under C is 50 to 50% under the load of 5 mN. The hardness of the surface of the coating layer is 75 to 200 N/mm2; and the specular gloss of the surface of the coating layer is 50% when the incident angle and the light receiving angle are each measured at 20°. the above. 3. The precoated metal sheet of claim 2, wherein the top coating layer comprises a clear coating film of a bright pigment. 4_ A precoated metal sheet according to claim 1 or 2, wherein the top coat layer is melamine hardened. The precoated metal sheet of claim 1 or 2, wherein the top coat layer is an isocyanate hardened type. 6. The precoated metal sheet of claim 5, wherein the ratio of NCO/OH in the isocyanate-hardened top coat layer is 0.05 to 0.5. 7. The precoated metal sheet according to any one of claims 1 to 6, wherein the Ra (center line average roughness) of the interface between the s-top coating layer and the intermediate coating layer is 0.3 〇. 8. 8. The precoated metal sheet according to any one of claims 1 to 7, wherein the content of the silicon grafted acrylic resin in the middle coating film is converted into a stone. The siiic 〇ne resin is 2 to 18% by mass. The precoated metal sheet according to any one of claims 1 to 8, wherein the top coating film has a glass transition temperature of 30 to 67. (: The ratio of the ruthenium resin in the Shishigang graft acrylic resin contained in the top coat film is 3 to 20% by mass, and the glass transition temperature of the intermediate coat layer is 25 to 50 ° C. The pre-coated metal sheet according to any one of the items 1 to 8 of the patent scope, wherein the hardness of the surface of the coating layer at 23 ° C is 150 to 200 N/mm 2 based on the general hard 51 201043457 degree under a load of 5 mN. 11. The precoated metal sheet of claim 10 or 11, wherein the top coating layer is an isocyanate hardened type. 12. The precoated metal sheet according to claim 11 wherein the top coating The hardener in the film layer is isophorone diisocyanate (IPDI). 13. The precoated metal sheet according to claim 11 or 12, wherein the ratio of the hardener in the top coat layer is 〇. 1 to 0.5. 14. A precoated metal sheet having a coating layer on one or both sides of a metal sheet, wherein: the coating layer has at least: a top coating layer, a coating film formed on the outermost surface; an intermediate layer connected to the top coating layer; and a middle coating layer, the system a layer coating film connected to the intermediate coating layer; the top coating layer is a clear coating film containing an anthrone grafting acrylic resin and containing no pigment, and the intermediate coating layer contains a melamine hardening type or an isocyanate curing type poly a coating film containing an ester resin and containing a coloring pigment; further, an average friction coefficient of the surface of the coating layer of the coating layer is 0.08 or less; and a hardness of 23 ° C of the surface of the coating layer is a universal hardness meter of 75 m load. ～200 N/mm2 ; and the specular gloss of the surface of the coating layer is 50% or more when the incident angle and the light receiving angle are each 20°. 15. Precoating as in claim 14 A metal plate, wherein the intermediate layer contains a pigment. 16. A precoated metal sheet according to claim 15 wherein the intermediate layer contains a bright pigment. 52 201043457 17. As claimed in any of claims 14 to 16. The precoated metal plate of the item, wherein the interface between the top coating film layer and the intermediate layer has an Ra (center line average roughness) of 0.3 to 0.8. 18. A method for manufacturing a precoated metal sheet, such as a patent application Scope 1 to 17 A method for producing a precoated metal sheet, characterized in that: by means of multiple layers of simultaneous coating or wet on wet, respectively, the coating will be the coating layer of the intermediate coating layer and the coating layer of the top coating layer. After coating, it is baked.
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