經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(：1 ) 發明背景 發明範疇 本發明是有關一種用於汽車內外部零件，家用電器， 鋼製傢倶外部板狀材料與類似物或用於建築材料之著色樹 脂塗裝金屬板。更具體而言，本發明是關於一種經過亮麗 著色而且澄清度性能佳’可反映出金屬基材光澤之著色樹 脂塗裝金屬板，以及其製造方法。 先前技術之說明 傳統上鍍有Zn之金屬板及類似物係廣泛用於汽車， 家用電器，建築材料等用途，這些鍍有Z η之金屬板及類 似物因耐腐蝕性不足而且對漆料的附著性無法令人滿意， 因此鍍層的上表面則用鉻酸鹽或磷酸鹽加以處理，以符合 要求漸趨嚴格的耐腐蝕性，耐化學品性質等。在這些處理 層上常會設有一樹脂膜。對於用在要求產品外觀美麗以及 色調必須完美之優良設計用途的金屬板而言，作爲最外靥 塗膜的樹脂膜必須著色成使用者所要求的色調》 樹脂膜的著色方法通常包括將著色用的顏料，如有機 顔料或無機顏料〉加入一漆料中，而目前已知道有機顏料 的著色力（tinting pow_er)較大，而無機顏料.的遮蓋性 能（hiding performance)較高。若要遮蓋金屬板的色調 ’則一般會在漆料中單獨使甩無機顔料或併用無機顏料與 有機顔料，但如果要完全（absolutely )_遮蓋該基材.的色 調，則需1 0 g / m 2之塗膜。 本紙張尺度適用中國國家標準.（CNS)A4規格（ 210X297公釐）-4- J I裝 訂 "η『線 (請先閲讀背面之注意事項再填寫本頁). 經濟部中央標準局員工消費合作社印製 A7 1 _______B7_ 五、發明説明（2 ) 爲使樹脂膜具有高耐腐蝕性和髙耐化學品性，則能夠 製備出緻密（dense)膜的烘烤硬化型（baking-set-type )有機溶劑漆料是頗爲合適的。故這類漆料可用於漆裝樹 脂之金屬板，但要製出穩定的塗膜塗料重有其困難，原因 在於有機溶劑的蒸發現象；要達到烘烤硬化必須有大規模 的乾燥設施；需放置氣體排放設備以回收蒸發掉的溶劑。 所以有人提出在電鍍金屬板的同一個生產線上以高速產製 此種樹脂塗裝金屬板，但因此種塗膜所需塗料重量相當高 以及設備上的投資使得製成的塗裝金屬板成本極高。 爲了克服這些缺點，有人提出一種著色樹脂塗裝金屬 板’這種金屬板可用電鍍金屬板製造方法以一種不貴的方 式來製造。例如日本特開平5 - 1 6 2 9 2所公開的著色 鋼板在製造上是在鍍有Ζ η的鋼板或類似物表面上設一鉻 酸鹽塗層，並在該塗層上形成一層L*值爲6 0或以下而 厚度爲5 # m或以下之著色樹脂層。但已知這種著色鋼板 的色調係取決於該金屬基板的色調以及該樹脂膜的色調和 厚度，若該著色樹脂膜的厚度較小，即使著色樹脂層的潛 在（potential ) L *值爲6 0或以下，所具有的著色性（ tinting)較低而且會使待著色鋼板之遮蓋性能變差，因 而難以產生穩定的色調。文中「L *值」是一種由J I S Z 8 7 3 0所定義代表「亮度（lightness)」的指標 ，暗度（darkness)在L*值位於（一）端時增加’而白 度（whiteness).則在L*值位於（+ )端時增加。更具體. 而言，當著色樹脂層的色調爲黑色時，L 值爲6 0或以 氏張尺度適用中國國家揉準（CNS > A4規格（210X297公釐）-5 - (#先聞讀背面之注意事項再填寫本頁) ill裝--------訂丨----線--- A 7 B7 五、發明説明（3 ) 下：而當其色調爲白色時，L*值最後可能爲6 0或以上 。故L *值並非代表金屬基板遮蓋性能的一種指標（相反 的’可稱爲「其光澤」），所以產生的著色鋼板引起有關 其品質穩定性的顧慮。 曰本特開平5 - 3 1 4 5 0公開一種經著色，塗裝且 表面處理過的鋼板，在其處理過的部份具有良好的底色遮 蓋性能（basehiding performance)，而且熔接性能（ welding pertormance)也相當優異_。其於製造上是令一 表面已經過Ζ η處理的鋼板與類似物進行鉻酸鹽處理，將 3 0 - 1 0 〇份含有著色顏料和鈦白（對全部著色顔料的 比例爲0. 30至0. 95)的著色劑與20 — 4 0份作 爲膜強化材的膠態政石分散在1 0 0份樹脂裡，然後在該 鋼板上形成一層以水溶性型或水分散型樹脂所塗裝而厚度 爲1 一 3仁m之塗膜。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 不過日本特開平5 - 3 1 4 5 0指出該顏料濃度須高 達3 0份或以上以改進被處理部份的底色遮蓋性能，但當 加入該樹脂膜的顏料濃度提高時，該樹脂膜對金屬基板的 附著性會變差。此外該案還指出若以較高的濃度添加該顏 料，則屬於該樹脂塗裝金屬板基本性能的耐腐蝕性可能也 會變差。 近年來隨著著色金屬板的廣泛應用後，對於保持金屬 光澤之外觀以及利用金屬基材光澤而不遮蓋基材色調的要 求漸增，例如用在產品外觀上幾乎看不到的部份（如冰箱 底板，洗衣機底板和背板，F D D零件，卡匣框架等）， 本紙張尺度適用中國國家標準（匸奶）八4規格（210父297公釐）-6 經濟部中央標準局員工消費合作杜印製 A7 B7 五、發明説明（4 ) 以及用在設計觀點上需要金屬光澤的地方。@於這些幾乎 看不到的零件在以該金屬基板的外觀呈現時從設計上的觀 點而言並不佳，因此想要有經亮麗著色同_時保留金屬光澤 的著色金屬板，而對於需要金屬光澤的零件而言則更不用 說了。 這種具有金屬光澤而且設計良好的金屬板常用金黃色 (golden color)著色，因此傳統上都用絡酸鹽法。令黃 色膜經鉻酸鹽處理（主要含有鉻水合物和氧化物）給予金 黃色的色調而且合併有金屬基板的光澤。但如以上所述 ’道種經過鉻酸鹽處理的膜其色調會隨著還原的進展而趨 不穩定。已知有一種異於一般鉻酸鹽處理，用於形成具有 特殊光澤膜而稱爲「unichro」之方法，包括將一光澤性 Ζ η電鍍材料浸入硫酸或硝酸之溶液裡，及將此材料浸於 一添加有鉻酸和氧化劑的溶液中而製成具有較高光澤而表 面經過處理的金屬板，然而這種unichro法因產生六價格 時的變動以致難以得到穩定的色調。 經過鉻酸鹽處理的金屬板在實際使用時若經常處於潮 濕環境下，則會有微量鉻離子由鉻酸鹽膜中溶解出來。幾 種鉻離子當中，六價的鉻離子對人類而言，因此其溶解化 程度（環境排放）則由法律來規範。 目前已發展出一種耐腐蝕性，耐指紋性，潤滑性等性 質均優且經過特定化學品處理表面的金屬板，在製造上是 用鉻酸鹽對金屬基板加以處理，然後以大約1 β m的有機 樹脂之透明薄膜對該板進行塗裝，藉以抑制鉻離子溶解化 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）_ 7 — ———————— ml n ^ ———————————— T I n n n I ^ ., 务 iei, (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 ' ___, _B7_ 五、發明説明（5 ) 。此經特定化學品處理表面昀金屬板所具有的特徵在於該 樹脂膜呈透明狀，而該用鉻酸鹽處理的基材其色調可透過 樹脂膜而被看到，此外該板具有金黃色的外觀*不過因爲 在鉻酸鹽處理期間爲了改善色調和耐腐性的穩定性而提高 C r塗料重量，所以難以避免自該有機樹脂塗料處理的金 屬板產生鉻溶解化的現象。 發明概沭 爲了解決先前技術的上述各種問題，本發明的目的在 於提出一種考色樹脂塗裝牵&板，充製造上可用簡單的設 備及不貴的方式達成，此著色樹脂塗裝金屬板具有優異而 穩定的表面光澤，會反映出該金屬板在塗裝樹脂膜之前的 色調，而且耐腐蝕性與耐C r溶解化之性質均優。本發明 也提出一種製造此種著色樹脂塗裝金屬板的方法。 本發明是有關一種塗裝有含著色顏料之樹脂膜的著色 樹脂塗裝金屬板，若以G。定義爲金屬板塗裝前的6 0° 鏡光澤（specular gloss)，而G 1定義爲金屬板在塗裝 了著色樹脂膜後的6 0°鏡光澤時，其Gi符合下式（1 )之關係 G 〇 > G 1 ^ 0 . 5 G 〇......... ( 1 ) 爲了符合上述要求，則著色樹脂塗膜的塗料重必須調 整至0· 2-3. Og/m2(若在塗膜乾重方面加以修 本紙張尺度適用中風國家標準（CNS ) A4規格（210X297公釐）_ 8 - ---：：--1.-----1^--- 一 (請先閲讀背面之注意事項再填寫本頁) 訂 ®線 經濟部中央標準局員工消費合作社印製 A7 ‘ __B7_ 五、發明説明（6 ) 正），而且著色顏料在該乾燥塗膜中的含量須調整爲1-. 3 0重量％。若要製造金黃色的塗裝金屬板，則作爲 Hunter色差式(color difference formula)之 p'sychometric chroma座標的「a」，「b」值需符合下 式（2 )的關係： —4 彡 a S.6.，且 2 Sb S 2 5 ......... ( 2 ) 根據本發明所得樹脂塗裝金屬板的光澤有大幅改善， 所以在一較佳實施體系中在塗裝樹脂膜之前以電鍍鋅的鋼 板作爲金屬板。更具體而言，我們發現，當電銨鋅層中六 方Zn結晶的配向符合下式（3)的關係 2. 〇i(002)面配向係數/(103)面配向係數 .........(3 ) 及/或當長度5 或以上之Ζ η單晶在受觀測鍍鋅 層表面的任意區域中以給定方向成長的區域之表面積爲該 受觀測任意區域總表面積之7 0 %或以下時，可製出一種 具有絕佳金屬光澤的著色樹脂塗裝金屬板。 爲了產製該著色樹脂塗裝金屬板，本發明也包括f種 利用水分散型或水溶性型含著色顏料的漆料以製造著色樹 脂塗裝金屬板的方法》 較佳窗施體系之說明 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）_ 9 - ~ i ^ I I-裝 . 訂©線 (請先閱讀背面之注•意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（7 ) 本發明的最主要特徵爲具有優良金屬光澤的著色樹脂. 塗裝金屬板。依據本發明，該著色樹脂塗裝金屬板的光澤 Gi須爲該金屬板在形成著色樹脂塗膜之前（此時的金屬 板在下文中有時稱爲「原（金屬）板」）光澤G。的1/ 2或以上（G 1須爲〇 . 5 G。或以上）。換言之，G 1需、 符合下式（1 )之關係。文中G。與G 1依J I S Z8741係定義爲60°鏡光澤，是透過Nippon DenshokuCo. Ltd.所生產的光澤計測定的。 G〇> Gi^ 〇 . 5 G 〇......... (1) 上式中若Gi<〇. 5 G。，則樹脂塗裝金屬板與原金 屬^之間的外觀差異會很顯著，表示未反映出原金屬板的 色調與光澤或者並未發揮優良的光澤。因此以上所述之要 求是本發明的基本要件。而在形成著色樹脂塗膜後，在原 金屬板和樹脂塗膜之間的介面內會產生光反射，所以不會 有Gi2G。的情況發生。如果不幸(除非G〇> G !)，則完全無法發揮出塗裝著色樹脂的效果。 若該含有著色顏料的樹脂漆料（以下有時只簡稱爲「 漆料」）中含有金屬粉末（Aj?粉末，Ζ η粉末等），則 樹脂塗膜裡的金屬粉末會將光反射以致終究會產生G。；Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (: 1) Background of the invention The present invention relates to a type of automotive exterior and interior parts, household appliances, steel furniture, external plate-like materials and the like Or coloring resin-coated metal plates for building materials. More specifically, the present invention relates to a colored resin-coated metal plate which is brightly colored and has excellent clarity performance, and which can reflect the luster of a metal substrate, and a method for producing the same. Description of the prior art Traditionally, Zn-plated metal plates and the like are widely used in automobiles, household appliances, building materials, etc. These Z η-plated metal plates and the like have insufficient corrosion resistance and are not suitable for paints. The adhesion is unsatisfactory, so the upper surface of the coating is treated with chromate or phosphate to meet the increasingly strict requirements of corrosion resistance, chemical resistance, etc. A resin film is often provided on these treatment layers. For metal plates that are used for excellent design applications that require beautiful product appearance and perfect hue, the resin film that is the outermost coating film must be tinted to the hue required by the user. The coloring method for resin films usually involves coloring Pigments, such as organic pigments or inorganic pigments, are added to a paint, and it is known that the tinting pow_er of organic pigments is larger, and the hiding performance of inorganic pigments is higher. If you want to cover the tint of the metal plate, you will usually use inorganic pigments alone or in combination with inorganic pigments and organic pigments in the paint, but if you want to completely cover the tint of the substrate, you need 10 g / m 2 coating film. This paper size applies to Chinese national standards. (CNS) A4 size (210X297 mm) -4- JI binding " η 『line (please read the precautions on the back before filling this page). Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Print A7 1 _______B7_ V. Description of the invention (2) In order to make the resin film have high corrosion resistance and chemical resistance, a baking-set-type organic film of dense film can be prepared Solvent paints are quite suitable. Therefore, this kind of paint can be used to paint metal plates of resins, but it is difficult to produce stable coating film coatings due to the evaporation of organic solvents; large-scale drying facilities are required to achieve baking and hardening; Place a gas vent to recover the evaporated solvent. Therefore, some people have proposed to produce such resin-coated metal plates at high speed on the same production line of electroplated metal plates. However, the weight of the coating required for this kind of coating film and the investment in equipment make the cost of the coated metal plates extremely high. high. In order to overcome these disadvantages, a coloring resin-coated metal plate has been proposed. This metal plate can be manufactured in an inexpensive manner by an electroplated metal plate manufacturing method. For example, the colored steel plate disclosed in Japanese Patent Application Laid-Open No. 5-1 6 2 9 2 is manufactured by providing a chromate coating on the surface of a steel plate or the like coated with Zn and forming a layer of L * on the coating. A colored resin layer having a value of 60 or less and a thickness of 5 # m or less. However, it is known that the hue of such a colored steel sheet depends on the hue of the metal substrate and the hue and thickness of the resin film. If the thickness of the colored resin film is small, the potential L * value of the colored resin layer is 6 0 or below, it has low tinting and deteriorates the hiding performance of the steel sheet to be colored, so it is difficult to produce a stable color tone. The "L * value" in this article is a kind of indicator that stands for "lightness" as defined by JISZ 8 7 30. Darkness increases when L * value is at the (one) end and whiteness. It increases when the L * value is at the (+) end. More specifically, when the color tone of the colored resin layer is black, the L value is 60 or the Chinese national standard (CNS > A4 specification (210X297 mm)) -5-(# 先 闻 读Note on the back, please fill in this page again) ill pack -------- order 丨 ---- line --- A 7 B7 V. Description of the invention (3) Under: When the color tone is white, L The * value may be 60 or more in the end. Therefore, the L * value is not an indicator of the hiding performance of the metal substrate (the opposite 'may be referred to as "its gloss"), so the colored steel plate produced raises concerns about its quality stability. Japanese Patent Laid-Open No. 5-3 1 4 5 0 discloses a colored, painted, and surface-treated steel sheet that has a good basehiding performance and a welding pertormance in the treated part. ) Is also quite excellent. It is manufactured by subjecting a steel plate and the like which have been treated with Zn to a surface to chromate treatment. 30-100 parts containing colored pigments and titanium white (for all colored pigments) Ratio of 0.30 to 0.95) and 20-40 parts as a film reinforcing material Colloidal Zhengshi is dispersed in 100 parts of resin, and then a layer of 1 to 3 m thick is formed on the steel plate with a water-soluble or water-dispersible resin. Employees of the Central Standards Bureau, Ministry of Economic Affairs Printed by a consumer cooperative (please read the precautions on the back before filling out this page). However, Japanese Patent Application Laid-Open No. 5-3 1 4 5 0 indicates that the pigment concentration must be as high as 30 parts or more to improve the background hiding performance of the treated part. However, when the concentration of the pigment added to the resin film is increased, the adhesion of the resin film to the metal substrate will be deteriorated. In addition, the case also pointed out that if the pigment is added at a higher concentration, it belongs to the basic of the resin-coated metal plate. The performance and corrosion resistance may also deteriorate. In recent years, with the widespread application of colored metal plates, the requirements for maintaining the appearance of metallic luster and utilizing the luster of metallic substrates without covering the color tone of the substrate have increased, such as in products Hardly visible parts (such as refrigerator bottom plate, washing machine bottom plate and back plate, FDD parts, cassette frame, etc.), this paper size is applicable to Chinese National Standard (匸 奶) 8 4 specifications (210 297 mm) -6 Consumers ’cooperation with the Central Bureau of Standards, Ministry of Economic Affairs, Du printed A7 B7 V. Description of the invention (4) and use in areas where metallic luster is needed in terms of design. @ 于 These almost invisible parts The appearance of a metal substrate is not good from a design point of view. Therefore, you want a colored metal plate that is brightly colored and retains metallic luster, but not to mention parts that require metallic luster. This metal plate with metallic luster and good design is usually colored with golden color, so the complex salt method is traditionally used. The yellow film is treated with chromate (mainly containing chromium hydrates and oxides) to give a golden hue and incorporates the luster of a metal substrate. However, as mentioned above, the color tone of the chromate-treated film tends to be unstable as the reduction progresses. A method known as "unichro", which is different from general chromate treatment and is used to form a special gloss film, is known, which comprises immersing a glossy Z η plating material in a solution of sulfuric acid or nitric acid, and dipping the material. In a solution containing chromic acid and an oxidizing agent, a metal plate having a high gloss and a surface treated is prepared. However, this unichro method is difficult to obtain a stable color tone due to the change in price. If the chromate-treated metal plate is often exposed to humidity in actual use, a small amount of chromium ions will be dissolved from the chromate film. Among the several types of chromium ions, hexavalent chromium ions are to humans, so the degree of dissolution (environmental emissions) is regulated by law. At present, a metal plate with excellent corrosion resistance, fingerprint resistance, lubricity and other properties and a surface treated with specific chemicals has been developed. The metal substrate is treated with chromate in the manufacturing process, and then treated with about 1 β m The transparent film of organic resin is used to coat the board to inhibit the dissolution of chromium ions. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) _ 7 — ———————— ml n ^ ———————————— TI nnn I ^., Wuiei, (Please read the notes on the back before filling out this page) Printed by A7 '___, _B7_ 5. Description of the invention (5). The special chemically treated surface 昀 metal plate has the characteristics that the resin film is transparent, and the color tone of the chromate-treated substrate can be seen through the resin film, and the plate has a golden yellow color. Appearance * However, since the weight of the Cr coating is increased in order to improve the stability of color tone and corrosion resistance during the chromate treatment, it is difficult to avoid the phenomenon of chromium dissolution from the metal plate treated with the organic resin coating. Summary of the Invention In order to solve the above-mentioned various problems of the prior art, the object of the present invention is to propose a color-test resin coating pull plate, which can be achieved by simple equipment and inexpensive methods in the manufacture of the color resin-coated metal plate. It has excellent and stable surface gloss, which reflects the color tone of the metal plate before coating the resin film, and has excellent corrosion resistance and resistance to C r dissolution. The present invention also proposes a method for manufacturing such a colored resin-coated metal plate. The present invention relates to a colored resin-coated metal plate coated with a resin film containing a colored pigment, if G is used. It is defined as the 60 ° specular gloss before the metal plate is painted, and G 1 is defined as the 60 ° specular gloss of the metal plate after the colored resin film is applied, and its Gi conforms to the following formula (1) Relationship G 〇 > G 1 ^ 0. 5 G 〇 ......... (1) In order to meet the above requirements, the coating weight of the colored resin coating film must be adjusted to 0 · 2-3. Og / m2 (If it is revised in terms of dry film weight, the paper size applies the National Standard for Stroke (CNS) A4 (210X297 mm) _ 8---- :: --1 .----- 1 ^ --- one (Please read the precautions on the back before filling this page) Order ® Printed A7 '__B7_ by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) Positive), and the content of the pigment in the dry coating film Must be adjusted to 1-. 3 0% by weight. If you want to make a golden-colored painted metal plate, the "a" and "b" values of the p'sychometric chroma coordinate of the Hunter color difference formula must conform to the relationship of the following formula (2): —4 彡 a S.6., And 2 Sb S 2 5 ......... (2) The gloss of the resin-coated metal plate obtained according to the present invention is greatly improved, so a resin is applied in a preferred implementation system. Before the film, a galvanized steel sheet was used as the metal sheet. More specifically, we find that when the orientation of the hexagonal Zn crystals in the electro-ammonium zinc layer conforms to the relationship of the following formula (3) 2. 〇i (002) plane alignment coefficient / (103) plane alignment coefficient ... ... (3) and / or when the length of a Zn single crystal with a length of 5 or more in an arbitrary region of the surface of the galvanized layer to be observed grows in a given direction, the surface area is 70% of the total surface area of the arbitrary region under observation At% or below, a colored resin-coated metal plate with excellent metallic gloss can be produced. In order to produce the colored resin-coated metal plate, the present invention also includes f kinds of methods for manufacturing a colored resin-coated metal plate by using water-dispersible or water-soluble color pigment-containing paints. Paper size applies to China National Standard (CNS) Α4 size (210X297 mm) _ 9-~ i ^ I I-pack. Order © line (please read the notes and notices on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. Description of the invention (7) The main feature of the present invention is a colored resin with excellent metallic gloss. Painted metal plates. According to the present invention, the gloss Gi of the colored resin-coated metal plate must be the gloss G of the metal plate before the colored resin coating film is formed (the metal plate at this time is sometimes referred to as "original (metal) plate" hereinafter). 1/2 or more (G 1 must be 0.5 G. or more). In other words, G 1 needs to conform to the relationship of the following formula (1). G in the text G1 and G1 are defined as 60 ° specular gloss according to the J I S Z8741 series, and are measured by a gloss meter produced by Nippon DenshokuCo. Ltd. G0 > Gi ^ 〇 5 G 〇 ... (1) In the above formula, if Gi < 0.5 G. , The appearance difference between the resin-coated metal plate and the original metal ^ will be very significant, indicating that the color tone and gloss of the original metal plate are not reflected or that the excellent gloss is not exhibited. The requirements described above are therefore essential elements of the present invention. After the colored resin coating film is formed, light reflection occurs in the interface between the original metal plate and the resin coating film, so there is no Gi2G. Happened. If it is unfortunate (unless G0 > G!), The effect of painting a colored resin cannot be exhibited at all. If the resin paint containing colored pigments (hereinafter sometimes simply referred to as "paint") contains metal powder (Aj? Powder, Z η powder, etc.), the metal powder in the resin coating film will reflect light and eventually Will produce G. ;
Gi的狀態。由於這些金屬粉末幾乎都呈灰色，對於要產 生其他美麗色調的情形造成不便，而且比重較大的金屬粉 末從其在漆料中分散性的角度來看也是不利的，會使外觀 本紙張尺度適用中國國家標準（CNS)A4規格（ 210X297公釐）-1〇 - (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 A7 A7 經濟部中央標準局員工消費合作社印製 _ B7______ 五、發明説明_( 8 ). 不一致或塗膜性質（如耐腐蝕性）變差。此外基於成本上 升的考慮，並不建議使用金屬粉末。 爲了符合本發明上述式（1 )的關係，原金屬板上樹 脂塗膜的塗料重建議爲0. 2 — 3. Og/m2(若在塗 膜乾重方面加以修正）。若塗料重低於0. 2g/m2， 則原金屬板上樹脂塗膜的著色效果會太小。由於漆料中固 容物可能太少以致在原金屬板上形成均勻塗膜時會有困難 ，而且耐腐蝕性，加工性等對樹脂塗裝金屬板而言相當重 要的性質可能無法達到令人滿意的程度。 若塗膜的塗料重太大，'則原金屬板的遮蔽性能可能提 升過多以致無法符合上述式（1 )之關係。該塗膜的塗料 重如果高於3. Og/m2，則塗膜乾燥需時過長，會降 低連續生產的效率並增加該含有顏料之樹脂漆料的使用量 ，結果造成成本上升。再者因塗膜在加壓操作期間有易於 剝落的傾向，耐腐蝕性會變差，而剝落下來的膜會在模具 上累積，對加壓成形造成不便。根據本發明，該樹脂塗膜 的塗料重在不發生上述缺點的情況下其上限宜爲3. Og /m 2或以下，若從實際用途來看，該樹脂塗膜的較佳塗 料重範圍爲0.3 — 2. Og/m2。 連同調整塗膜的塗料重之外，調整漆料中的顏料濃度 是爲符合式（1 )關係宜採取的一種方法。根據本發明， 漆料中著色顔料的濃度應調整至塗膜中總乾重（漆料裡的 固容物）的1 一 3 0重量％。若著色顏料濃度低於1重量 %，則對塗膜的著色效果會降低，不利於本發明所要達到 氏張尺度適用中國國家標準（CNS ) A4規格( 210X297公釐）_ ^ _ — td- n I— nn HI ml tn I Jn HI _ . . · (請先閱讀背面之注意事項再填寫本頁) 訂 _θ線 A7 ____B7__ 五、發明説明（9 ) 的目的。相反地當顏料濃度較高時則會提升著色效果。由 於樹脂塗膜對原金屬板的附著性趨於變差，因此建議顔料 濃度的上限爲3 0重量％。若漆料中顏料過多，屬於該樹 脂塗膜基本性質的耐腐蝕性會變差，而在腐蝕過後引後塗 膜色調的動態變化》漆料中顔料濃度的更佳範圍爲該塗膜 乾重（漆料中固容物）的5 — 20重量％。 對於本發明著色樹脂塗裝金屬板而言，宜使用一種含 有粒狀著色顏料且此顏料在漆料中分散性佳的漆料。有許 多種顏料組合可用來控制樹脂塗裝金屬板的各種不同色調 〇 針對以下各顏色可用的顏料類型例子如下。 紅色：有機顏料，如不溶性偶氮顏料（某酚或醯基苯 胺顏料）或可溶性偶氮顏料；無機顏料，如紅色氧化鐵（ red. iron oxide)，鎘紅/( cadmuium red)及錯丹（red lead) 0 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 黃色：有機顔料，如不溶性偶氮顏料（棻酚顏料或醯 基苯胺顏料），可溶性偶氮顏料，以及睦吖啶酮（ quinaeridone)顔料；無機顏料，如鉻黃（ chrome yellow)，鎘黃，鈦鎳黃，鉻黃及鉻酸銷。 綠色：有機酞菁顏料》 藍色：有機酞菁顏料，鐵藍，群青藍，鈷藍，及.黯翠 綠。 黑色：有機顏料，如苯胺黑及碳黑；無機顔料，如黑 色氧化鐵（black iron ox.id.e)。. 本紙張从適用中國國家標準（ CNS ) M規格（210x 297公羡）~ — — A7 _______B7 _____ 五、發明説明（10 ) 白色：無機顏料，如氧化鐵，碳酸鈣，氧化鋅，硫酸 鋇’鋅鋇白（1 ithopone )，及鉛白。 將上述兩種或兩種以上不同化學結構的同色顔料或異 色顏料以適當的比例混合則可得到諸如灰色，褐色，紫色 ’橙色及金黃色等所需之顔色。 若 (請先聞讀背面之注意事項再填寫本頁) 著色顏料的平均粒徑宜爲0 . 〇 5 — 1 . 0以 低於0. 05#m，則塗膜的著色效果較差，從優良設計 的角度來看不佳。反之若粒徑大於1. 0#m，則暴露在 塗料表面的較大顔料顆粒在提高顔料濃度之後會上升，使 顏料在所生成的著色樹脂塗裝金屬板滑動期間產生顏料剝 落的情形，而且可能會改變色調。此外顏料顆粒大時，其 於漆料裡的分散性差，以致可能無法製造出均勻的著色塗 膜。顏料粒徑以0. 1 - 0 . 7以m的範圍更佳。 構成著色樹脂之塗膜而在漆料中作爲基本樹脂材料者 可爲聚乙烯樹脂，聚胺基甲酸酯樹脂，聚酯樹脂，環氧樹 脂’丙烯酸系樹脂及類似物，但並無特殊限制。此基本樹 脂對著色顔料的附著性宜透過在基本樹脂中導入官能基的 經濟部中央標準局員工消費合作社印製 方式而加以改善。此外，因爲使用有機溶劑的漆料可能產 生有害的工作環境因而必須有回收蒸發溶劑之設備。所以 建議使用含有著色顏料的水分散型漆料或水溶性樹脂溶液 〇 製備此類漆料時，可在不大幅改變本發明著色樹脂塗 裝金屬板之外觀和色調的範圍內添加各種添加劑，諸如部 份架橋材料（partial bridging materials)，稀釋溶劑 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-13， 經濟部中央標準局員工消費合作社印製 A7 ________B7_____ 五、發明説明（11 ) ，anti-seeking劑，調平劑（levelling agent)，消泡 劑，滲透劑，製膜用助劑，提高黏度之藥劑，及潤滑劑， 以及細粉狀矽石，膠態矽石，和矽烷耦合劑（以改進附著 性和耐腐蝕性），藉以進一步改進塗膜的塗裝性能。 如以上所述，本發明提供可反映原金屬板光澤之著色 樹脂塗裝金屬板，而且成功發展出一種具有鉻酸鹽處理膜 色調（爲消費者所特需）之著色樹脂塗裝金屬板。更具體 而言，如果J I S Z 8 7 3 0所定Hunter色差式的 P_sychome_tric chroma座標「a」，「b」值符合下式（ 2 )的關係，則本發明之樹脂塗裝金屬板具有類似鉻酸鹽 處理膜的金黃色。 ~ 4 ^ a ^ b » 2 ^ b ^ 2 5 ......... ( 2 ) 文中「a」，「b」數值代表顯示JIS所核可色調 (color tone)的色度_(tint)，其中「a」值在（一） 端表示增加的綠色度，在（+)端表示增加的紅色度；「 b」值在（_)端表示增加的藍色度，而在（+ )端表示 增加的黃色度。爲使「a」，「b」值落在上述範圍內， 可將黃色顏料單獨加入漆料裡，不過可併用兩種或兩種以 上黃色和紅色的顏料，因爲如此較易於達到調整色度的目 的。 依本發明，在塗裝任何樹脂膜之前用作原金屬板者除 了各種合金鋼板（如軟鋼或不銹鋼)之外，可爲各種材料 本ϋ尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ ~ J-— I----- I裝------1Τ-----•丨·線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（12 ) ，包括Aj .AJ?合金板，Cu · Cu合金板及Ti . Ti合金板；各種鍍有Ζη · Zn合金或Aj? · AJ2合金 之金屬板，鍍Cu者，鍍Ni者，鍍Cr者等等；以及以 磷酸鹽或鉻酸鹽處理過的化學處理金屬板。 電鍍鋅鋼板因具有優良表面外觀與光澤故宜用於製造 可反映原金屬板色調與光澤的著色樹脂塗裝金屬板。原因 在於原金屬板的光澤若佳，則在塗裝著色樹脂之後應具優 良光澤。目前業已發現電鍍鋅層裡的晶體配向會影響表面 光澤，而以具備以下特性之電鍍鋅鋼板作爲本發明原金屬 板爲最佳。 選擇電鍍鋅鋼板中其電鍍鋅層的六方Ζ η晶體符合下 式（3 )者爲較佳之原金屬板 2. 0S (002)面配向係數/( 1 0 3 )面配向係數 *·· ··· ( ) 已知Ζ η晶體係呈六方緻密晶體結構，此外雖然大部 份的Ζη晶體係呈（002)面與（103)面配向，但 在晶體強烈呈（1 0 3 )面配向部份的鍍層的鏡反射光濃 度（concentration)比入射光程度爲低，以致表面光澤 比晶體呈（0 0 2 )面配向的部份爲差。因此具有符合上 述條件之鍍鋅層而鋅晶體強烈呈（ 0 0 2 )面配向之金屬 板是本發明較佳的著色樹脂塗裝金屬板。 以上關係式中的各個配向係數係以數值表示，而且是 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）-15- (請先閱讀背面之注意事項再填寫本頁) m· —^i n-m· n i^t f^n —^ϋ itl'nme nn n ia— m In 一一 an— In · ^ 0¾ i 線---- A7 B7 五、發明説明（13 ) 透過比較各鏡面（0 0 2面與1 0 3面）配向強度與非異 方性粉末圖案的配向強度所計算出來的。更具體而言，以 X —射線繞射測量2 0 = 3 0至8 5°範圍內（h k 5 ) 面的繞射強度I ( h k i?)，計算I ( h k文）對總峰和 ε I (hki?)的相強強度 IF(hk)2)〔即 $ ( k h $ / e I ( h k i?)〕，將計算出來的相對強度除以 粉末圖案的相對強度IFR(hkj)(可從A STM卡 取得），則可得出（h k $)面的配向係數。藉由各別測 定（0 0 2 )面與（1 0 3 )面之配向係數，然後將各個 值***式（3)，計算出來的所得強度爲2. 0或以上， 如此可製得具低光澤相對較低數目之（1 0 3 )面，因而 整體光澤佳的電鍍鋅層，其上限並無特殊限制，但基於加 工性的考量建議爲1 5。若高於1 5，則在加工期間容易 引發剝落現象。有關電鍍鋅鋼板的上述現象在日本專利申 請案平7 - 2 9 3 9號中有詳盡的敘述。 經濟部中央標準局員工消費合作杜印製 (請先閱讀背面之注意事項再填寫本頁) 依本發明，宜使用一種長度5 或以上之Z n單晶 依給定方向成長之區域的表面積佔觀測下鋼板電鍍鋅層表 面任意區域總表面積爲7 0%或以下之電鍍鋅鋼板。 此處「Ζ η單晶依給定方向成長之區域」是指鍍鋅層 表面上電鍍的Ζη單晶是依給定方向對齊成長（在晶膜〔> epitaxial〕’生長狀態）而非不規則成長的狀態。雖然因 鋼板在電鍍鋅之前有細微的突出或凹陷或因其他影響而有 不均勻的晶體狀態，但如果電鍍的Ζ η單晶對齊成長的面 積大，則色調上的差異可明顯看出，即使處於此種不均勻 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐）-16 經濟部中央標準局員工消费合作社印裝 A7 __._ B7___ 五、發明説明（14 ) 晶體狀態的區域微小。如果使用此種原金屬板，則所得樹 脂塗裝金屬板澄清度的性能會變差。 . 基於這些發現，上述有關長度5 或以上之鋅單晶 依給定方向成長的區域之表面積佔觀測總表面積7 0 %或 以下之條件則定義爲較佳要件。若Ζ η單晶太小，則該樹 脂塗裝金屬板澄清度性能並無可見的劣化情形即使Ζ η單 晶係對齊成長。涵蓋在上述要件內的Ζ η單晶長度需爲5 以m或以上。由於符合該要件的原金屬板具有均勻的色調 和優良的澄清度性能.，這類原金屬板若應用在本發明則可 提供一種具有美麗外觀的著色樹脂塗裝金屬板。 以下再就本發明著色樹脂塗裝金屬板的製造方法加以 說明。此著色樹脂塗裝金屬板在製造上可將含有上述樹脂 成份和著色顏料的漆料（宜爲水分散型的漆料）以已知方 法塗裝在原金屬板表面上然後將該漆料乾燥。至於塗裝方 法並無特殊限制，可爲一種包括將長尺寸的金屬帶表面清 潔，必要時對其表面進行初步處理（例如以磷酸鹽或鉻酸 鹽處理），以滴筒塗佈法，噴塗法，簾幕流動塗佈法和類 似方法塗裝漆料，令產生的金屬帶通過一個熱空氣乾燥爐 以乾燥之等步驟之方法。整體上若考量塗膜厚度均勻性， 加工成本和塗裝效率，則實際上以滾筒塗佈法爲較佳。至 於要在原金屬板的一面或雙面施以著色樹脂之塗膜則視用 途而定。爲防止色調因著色顔料的變化而改變，塗膜的乾 燥溫度應低於該待加入之著色顏料的耐熱溫度。 爲了改進金屬板對樹脂塗膜的附著性與耐腐蝕性，準 本ϋ尺度適用f國國家標準（CNS ) A4規格（210X297公釐〉_ 17 _ — ·' -----------裝-----^-I訂-----@線 (請先閱讀背面之注意事項再填寫本頁) Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明（15 ) 備以該樹脂塗膜處理的金屬板可在塗裝之前以磷酸鹽法或 鉻酸鹽法進行初步處理。至於鉻酸鹽法所用材料，鉻酸鹽 法期間C r塗料量以使用最終樹脂塗裝金屬板期間鉻溶解 化的觀點而言應抑制在3 5 g/m 2或以下。而在此範圍 內本發明之樹脂塗裝金屬板可抑制鉻由鉻酸鹽處理過的底 層溶解化的現象。此外，頂端塗料（必要時設於習知以鉻 • - · 酸鹽處理的材料上）的耐水附著性在六價路溶解化後有在 潮濕瓚境中降低的傾向，但因此種溶解化現象在本發明樹 脂塗裝金屬板中得以抑制，所以頂部塗料的耐水附著性並 無變差的情形。 以下將透過實施例以進一步說明本發明的技術內容， 但本發明之範圍並不限於這些實施例所揭示者。其任何變 化與修飾在不脫離本發明精神的情況下均涵蓋在本發明的 技術範圔內》 實施例1 以水分散型聚乙烯乳化液爲構成塗膜的基本樹脂，並 添加佔固容物10重量％之具有表1所示各種色調的有機 顏料與無機顔料（平均粒徑爲〇 . 2至0 · 5 /z m )以製 備水分散型含有著色顔料之漆料A至F。此處漆料G和η 係有機顏料的混合物。漆料I是由聚乙烯乳化液所構成並 未添加任何顏料以作爲比較例。 (請先閱讀背面之注意事項再填寫本頁) 本紙張又度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐）10 A7 B7 五、發明説明（16 [表1] 經濟部中央標準局員工消費合作社印製 漆料 編號 著舖料 附註 顏色 C. I.編號 在漆料中的濃度 (以固容物計的重量%表示） 粒徑 βτη A 紅 20730 10 0.5 B 黃 21108 10 0.5 C 藍. 74160 10 0.3 D 綠 74260 10 0.2 實例 E 黑 77260 10 0.3 F 白 77891 10 0.3 G 紫 74160 2 0.3 20730 8 Η 灰 77260 2 0.3 77891 8 I 無色 一 0 比較例 * C. I.編號:代表以五位數數字所表示顏料的化學組成 (請先閣讀背面之注意事項再填寫本頁) ----------------ί 神衣----- 訂-- _線--- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨Ο X 297公釐）_ 19 _ A7 —____B7 五、發明説明（17 ) 接著以Aj?鎮靜冷乳鋼.板（A1 killed pold-rol.led steel plate)作爲鋼質基板依下列步驟電鍍鋅》 ① 驗洗劑脫脂（alkali, scrubber defatti.ng) 在6 0 °C下使用3 %正矽酸鈉水溶液。 ② 電解脫脂—在水中洗 在6 0°C及2 OA/dm2下使用3%正矽酸鈉水溶 液，然後在水中洗。 ③ 酸洗—在水裡洗 在6 0 °C下使用5%硫酸水溶液然後在水中洗。 ④ 電鍍锌—在水中洗 在水裡洗之前電鍍鋅的過程是在下列條件下進行》 (請先閲讀背面之注意事項再填寫本頁) 電鍍鋅溶液之組成： Z n S 0 4 * 7 Η 2 0 N a S Ο 4 Η 2 S Ο 4 300-400g/5 50 -1 00g/j? 2 5 - 3 5 g / ^ 經濟部中央標準局頁工消費合作社印裝 e c 電鍍鋅溶液的溫度：50〜70 °C 電鍍鋅溶液的流動：0. 8〜2. 4m/ 電流密度：3 0〜1 5 0 A/dm2 電鍍塗料重：20g/m2 在以下所述之實施例3，4中，將適當量的四銨鹽（ tetraammonium salt)加入電鍍鋅所需條件下的酸洗浴中 ，使長度5 或以上之鋅單晶可依給定方向成長的區域 之表面積對觀測的電鍍鋅鋼板鍍鋅層任意區域總表面積之 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公釐）_ 20 _ 經濟部中央標準局員X消費合作社印製 A7 ___ B7 ____ 五、發明説明（18 ) 比例（以下稱爲晶膜成長比例）爲7 〇 %或以下，且鍍鋅 層中（002)面內六方鋅晶體的配向係數爲（1 03) 面中六方Ζ η晶體配向係數的兩倍或以上。至於電銨鋅的 條件則是在上文中所述範圍內改變》 得到的電鍍鋅鋼板以鉻酸鹽處理（C r塗料重爲2 0 g / m 2 )，然後以其作爲塗裝樹脂的原金屬板。此外’ 原金屬板在塗裝前的6 0°鏡光澤（依以下方法測量，下 文中稱爲G。）爲60，晶膜成長比例爲0. .5 1。將表 1所示的各種塗裝溶液A至I以滾筒塗裝器在此種金屬板 上塗裝上一定厚度，把金屬板轉移到熱空氣乾燥爐裡將塗 料乾燥。令得到的各種榭脂塗裝金屬板進行以下的性能測 試，結果列於表2及表3 » (1 )光澤 以Nippon Denshoku, Co._, Ltd所製造的光澤計依 J IS Z8741所訂測試60°鏡光澤（G60) β 將原金屬板的6 0°鏡光澤定爲G。而塗裝樹脂後的光澤 定爲G1，計算出代表塗裝前後光澤變化的指標Ga/Go 〇 (2 )外觀 以目測方式評估金癘板在塗裝了著色樹脂後是否反映 了原金屬板的色調，至於評估標準係如下述。 原金屬板色調反映性能之評估： 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X 297公釐）._ 21 - ' —I.---------丨裝-------訂 -----線 (請先閣讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 ___B7_五、發明説明（19) ◎優異，反映出原金屬板的色調， X差，未反映出原金屬板的色調》 (3)色調（著色性） 利用Nippon Denshoku Co. Ltd所製造的色差計測量 J I S Z 8 7 3 0 所定 Hun ter色差式 psychometr i c chroma座標的a，b值，該樹脂塗裝金屬板的是以Cl = ( a 2 + b 2) 1/2來計算。以類似方式測定原金屬板的色 度C。，計算出色度的差值（△0 = (：:-(：〇)以依下列 標準評估色度。 著色性評估方法 ◎優異，色度差值爲8或以上， 〇 良好，色度差值爲2或以上，但小於8， X 差，色度差值低於2。 (4 )耐腐蝕性（耐白銹性） 樹脂塗裝金屬板的耐腐蝕性係依JIS Z 2 3 7 1的5重量％鹽水噴灑法測定。測量經由樹脂塗膜 基層純電鍍鋅發生1 %白銹所需的時間並依以下標準加以 評’估。 ◎優異，發生白銹需時240小時或以上， 〇 良好，發生白錄需時1 2 0小時或以上但低於 2 4 0小時， 本紙权適用中國國家操準（CNS ) A4祕（210X297公後）-22 - ~~ (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（20 ) △ 稍差，發生白銹需時4 8小時或以上，但低於 1 2 0小時， X 差，發生白銹需時低於48小時。 (請先閱讀背面之注意事項再填寫本頁) .裝. 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 23 _ 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（21 ) [表2] 編號 漆料 類型 讓的塗料重 (g/m2) 光澤變化 Gi/Go 外觀 難性 耐腐蝕性 附註 1 A 0.3 0.9 ◎ 〇 〇 實例 2 A 0.8 0.8 ◎ ◎ ◎ 3 A 1.5 0.7 ◎ ◎ ◎ 4 A 2.7 0.5 ◎ ◎ ◎ 5 A 0.1 1.0 X X X 比較例 6 A 3.2 0.4 X ◎ ◎ (請先閱讀背面之注意事項再填寫本頁) .裝· 訂 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐）_ 24 _ 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（22 ) 編號 漆料 類型 讓的塗料重 (g/m2) 光澤變化 Gi/G〇 外觀 著色性 耐腐蝕性 附註 7 Β 0.4 0.9 ◎ 〇 〇 實例 8 Β 0.8 0.8 ◎ ◎ ◎ 9 Β 1.5 0.7 ◎ ◎ ◎ 10 Β 2.8 0.3 ◎ ◎ ◎ 11 Β 0.1 1.0 X X X 比較例 12 Β 3.1 0.4 X ◎ ◎ 13 C 0.4 0.9 ◎ 〇 〇 實例 14 C 0.8 0.8 ◎ ◎ ◎ 15 C 1.5 0.7 ◎ ◎ ◎ 16 C 2.8 0.5 ◎ ◎ ◎ 17 C 0.1 1.0 X X X 比較例 18 C 3.1 0.4 X ◎ ◎ 19 D 0.4 0.9 ◎ 〇 〇 實例 20 D 0.8 0.8 ◎ ◎ ◎ 21 D 1.5 0.7 ◎ ◎ ◎ 22 D 2.8 0.5 ◎ ◎ ◎ 23 D 0.1 1.0 X X X 比較例 24 D 3.2 0.3 X ◎ ◎ 25 Ε 0.3 0.9 ◎ 〇 〇 實例 26 Ε 0.6 0.8 ◎ 〇 ◎ 27 Ε 1.4 0.7 ◎ ◎ ◎ 28 Ε 2.7 0.5 ◎ ◎ ◎ 29 Ε 0.1 1.0 X X X 比較例 30 Ε 3.1 0.4 X ◎ ◎ 丨._^ I .丨裝 -丨訂 β線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（ 210X297公釐）_ 25 - 五、發明説明（23 ) 經濟部中央標準局員工消費合作社印製 [表3] 編號 漆料 類型 讎的塗料重 (g/m2) 光澤變化 Gi/G〇 外觀 難性 耐腐触性 附註 31 F 0.4 0.9 ◎ 〇 〇 實例 32 F 0.8 0.8 ◎ 〇 ◎ 33 F 1.5 0.7 ◎ ◎ ◎ 34 F 2.8 0.5 ◎ ◎ ◎ 35 F 0.1 1.0 X X X 比較例 36 F 3.1 0.4 X ◎ ◎ 37 G 0.4 0.9 ◎ 〇 〇 實例 38 G 0.8 0.8 ◎ ◎ ◎ 39 G 1.5 0.7 ◎ ◎ ◎ 40 G 2.8 0.5 ◎ ◎ ◎ 41 G 0.1 1.0 X X X 比較例 42 G 3.1 0.4 X ◎ ◎ 43 Η 0.4 0.9 ◎ 〇 〇 實例 44 Η 0.8 0.8 ◎ 〇 ◎ 45 Η 1.5 0.7 ◎ ◎ ◎ 46 Η 2.8 0.5 ◎ ◎ ◎ 47 Η 0.1 1.0 X X X 比較例 48 Η 3.1 0.4 X ◎. ◎ 49 I 0.3 0.9 ◎ X 〇 比較例 50 I 0.8 0.8 ◎ X ◎ 51 I 1.5 0.7 ◎ X ◎ 52 I 2.7 0.5 ◎ X ◎ I].——..-----裝---1---訂-----^線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（ 210X297公釐）-26- 經濟部中央標隼局貝工消費合作社印製 A7 B7 五、發明説明（24 )Gi's status. Because these metal powders are almost gray, it is inconvenient for other beautiful shades, and metal powders with a large specific gravity are also disadvantageous from the viewpoint of their dispersibility in paint, which will make the paper suitable for the paper size. China National Standard (CNS) A4 Specification (210X297mm) -1〇- (Please read the precautions on the back before filling out this page) Binding and ordering A7 A7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _ B7______ V. Invention Explanation_ (8). Inconsistent or poor film properties (such as corrosion resistance). In addition, due to rising costs, metal powders are not recommended. In order to comply with the relationship of the above formula (1) of the present invention, the coating weight of the resin coating film on the original metal plate is suggested to be 0.2 to 3. Og / m2 (if the dry weight of the coating film is corrected). If the paint weight is less than 0.2 g / m2, the coloring effect of the resin coating film on the original metal plate will be too small. Because the solid content in the paint may be too small to form a uniform coating film on the original metal plate, and the corrosion resistance, processability, etc., which are very important for the resin-coated metal plate, may not be satisfactory. Degree. If the coating weight of the coating film is too large, the shielding performance of the original metal plate may be improved too much so as not to satisfy the relationship of the above formula (1). If the coating weight of the coating film is higher than 3.0 g / m2, it will take too long to dry the coating film, which will reduce the efficiency of continuous production and increase the amount of the resin paint containing pigments, resulting in increased costs. In addition, the coating film tends to peel off during the press operation, and the corrosion resistance is deteriorated, and the peeled film is accumulated on the mold, which causes inconvenience to press molding. According to the present invention, the upper limit of the coating weight of the resin coating film is preferably 3. Og / m 2 or less in the case where the above-mentioned disadvantages do not occur. From a practical point of view, the preferred coating weight range of the resin coating film is 0.3 — 2. Og / m2. In addition to adjusting the coating weight of the coating film, adjusting the pigment concentration in the paint is a method that should be adopted to meet the relationship of formula (1). According to the present invention, the concentration of the colored pigment in the paint should be adjusted to 1-30% by weight of the total dry weight (solid content in the paint) in the coating film. If the concentration of the pigment is less than 1% by weight, the coloring effect on the coating film will be reduced, which is not conducive to the application of the Chinese National Standard (CNS) A4 specification (210X297 mm) to the scale of the present invention. ^ _ — Td- n I— nn HI ml tn I Jn HI _.. · (Please read the notes on the back before filling out this page) Order _θ line A7 ____B7__ 5. Purpose of the invention description (9). Conversely, when the pigment concentration is high, the coloring effect is improved. Since the adhesion of the resin coating film to the original metal plate tends to deteriorate, the upper limit of the pigment concentration is recommended to be 30% by weight. If there are too many pigments in the paint, the corrosion resistance, which is the basic property of the resin coating film, will be deteriorated, and the dynamic change of the color tone of the coating film after the corrosion is exceeded. (Solid content in paint) 5-20% by weight. For the colored resin-coated metal plate of the present invention, it is preferable to use a paint containing a granular colored pigment and having good dispersibility of the pigment in the paint. There are a variety of pigment combinations that can be used to control the various shades of resin-coated metal plates. ○ Examples of the types of pigments available for each of the colors below are as follows. Red: organic pigments, such as insoluble azo pigments (a phenol or fluorenylaniline pigment) or soluble azo pigments; inorganic pigments, such as red iron oxide (cadmium red) and cadmuium red red lead) 0 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Yellow: Organic pigments, such as insoluble azo pigments (fluorenol pigment or fluorenyl aniline pigment), soluble coupling Nitrogen pigments, and quinaeridone pigments; inorganic pigments, such as chrome yellow, cadmium yellow, titanium nickel yellow, chrome yellow and chromic acid. Green: Organic Phthalocyanine Pigment》 Blue: Organic Phthalocyanine Pigment, Iron Blue, Ultramarine Blue, Cobalt Blue, and Dark Green. Black: organic pigments, such as aniline black and carbon black; inorganic pigments, such as black iron ox.id.e. . This paper applies the Chinese National Standard (CNS) M specification (210x 297 public envy) ~ — — A7 _______B7 _____ V. Description of the invention (10) White: inorganic pigments, such as iron oxide, calcium carbonate, zinc oxide, barium sulfate ' Zinc barium white (1 ithopone), and lead white. Mixing two or more of the same-color pigments or different-color pigments with different chemical structures in an appropriate ratio can obtain desired colors such as gray, brown, purple 'orange and golden yellow. If (please read the precautions on the back before filling this page) the average particle size of the pigment should be 0. 〇5 — 1. 0 to less than 0.05 # m, the coloring effect of the coating film is poor, from excellent Poor design perspective. Conversely, if the particle size is greater than 1.0 # m, the larger pigment particles exposed on the surface of the paint will rise after increasing the pigment concentration, causing the pigment to peel off during the sliding of the resulting colored resin-coated metal plate, and May change hue. In addition, when the pigment particles are large, the dispersibility in the paint is poor, so that it may not be possible to produce a uniform colored coating film. The pigment particle size is more preferably in the range of 0.1 to 0.7 in m. Those constituting the coating film of the colored resin and used as the basic resin material in the paint may be polyethylene resin, polyurethane resin, polyester resin, epoxy resin, acrylic resin and the like, but there is no particular limitation. . The adhesion of this basic resin to colored pigments should be improved by the printing method of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs who introduced functional groups into the basic resin. In addition, because paints using organic solvents can create a hazardous working environment, equipment must be provided to recover the evaporated solvents. Therefore, it is recommended to use water-dispersible paints or water-soluble resin solutions containing colored pigments. When preparing such paints, various additives can be added within a range that does not significantly change the appearance and hue of the colored resin-coated metal plate of the present invention, such as Partial bridging materials, dilute solvents. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -13. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. A7 ________B7_____ 5. Description of the invention (11 ), Anti-seeking agent, levelling agent, defoaming agent, penetrant, film-forming aid, viscosity-increasing agent, and lubricant, as well as fine powdered silica, colloidal silica, and Silane coupling agent (to improve adhesion and corrosion resistance) to further improve the coating performance of the coating. As described above, the present invention provides a colored resin-coated metal plate that reflects the gloss of the original metal plate, and has successfully developed a colored resin-coated metal plate having a chromate-treated film color tone (specially required by consumers). More specifically, if the P_sychome_tric chroma coordinate "a" and the value "b" of the Hunter color difference formula specified in JISZ 8 7 3 0 conform to the relationship of the following formula (2), the resin-coated metal plate of the present invention has a similar chromate The film is golden yellow. ~ 4 ^ a ^ b »2 ^ b ^ 2 5 ......... (2)" a "and" b "in the text represent the chromaticity of the color tone approved by JIS_ ( tint), where the "a" value indicates increased greenness at (a) and increased redness at (+); the "b" value at blue (_) indicates increased blueness, and at (+) The) end indicates increased yellowness. In order to make the values of "a" and "b" fall within the above range, yellow pigments can be added to the paint separately, but two or more yellow and red pigments can be used together, because it is easier to achieve the adjustment of chromaticity. purpose. According to the present invention, those who are used as the original metal plate before coating any resin film can be various materials besides various alloy steel plates (such as mild steel or stainless steel). This standard applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) _ ~ J-— I ----- I equipment ------ 1T ----- • 丨 · line (Please read the precautions on the back before filling out this page) Staff Consumption of Central Bureau of Standards, Ministry of Economic Affairs Cooperative prints A7 B7 5. Description of the invention (12), including Aj.AJ? Alloy plate, Cu · Cu alloy plate and Ti.Ti alloy plate; various metal plates plated with Znη · Zn alloy or Aj? · AJ2 alloy, Cu plating, Ni plating, Cr plating, etc .; and chemically treated metal plates treated with phosphate or chromate. Electro-galvanized steel sheet is suitable for manufacturing colored resin-coated metal sheet that can reflect the hue and gloss of the original metal sheet because of its excellent surface appearance and gloss. The reason is that if the gloss of the original metal plate is good, it should have excellent gloss after the coloring resin is applied. It has been found that the crystal orientation in the electrogalvanized layer will affect the surface gloss, and the electrogalvanized steel sheet having the following characteristics is the best as the original metal sheet of the present invention. The hexagonal Z η crystal of the electro-galvanized layer in the electro-galvanized steel sheet is selected from the following formula (3) to be a better original metal plate 2. 0S (002) plane alignment coefficient / (1 0 3) plane alignment coefficient * ···· · () It is known that the Z η crystal system has a hexagonal dense crystal structure. In addition, although most of the Z η crystal system is oriented in the (002) plane and the (103) plane, the crystal is strongly oriented in the (103) plane. The concentration of the specular reflection light of the coating is lower than that of the incident light, so that the surface gloss is worse than that of the part where the crystal is oriented in the (0 0 2) plane. Therefore, a metal plate having a zinc-plated layer that meets the above conditions and whose zinc crystals are strongly oriented in a (0 02) plane is a preferred colored resin-coated metal plate of the present invention. Each alignment coefficient in the above relationship is expressed by numerical values, and this paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15- (Please read the precautions on the back before filling this page) m · — ^ i nm · ni ^ tf ^ n — ^ ϋ itl'nme nn n ia— m In 一一 an— In · ^ 0¾ i line ---- A7 B7 V. Description of the invention (13) By comparing each The mirror surface (0 0 2 and 1 0 3) alignment strength is calculated from the alignment strength of the non-anisotropic powder pattern. More specifically, the diffraction intensity I (hki?) Of the (hk 5) plane in the range of 20 = 30 to 8 5 ° is measured by X-ray diffraction, and I (hk text) is calculated for the total peak and ε I (hki?) phase strength IF (hk) 2) [ie $ (kh $ / e I (hki?)], divide the calculated relative strength by the relative strength of the powder pattern IFR (hkj) (available from A (Obtained by STM card), the alignment coefficient of (hk $) plane can be obtained. By measuring the alignment coefficients of (0 0 2) plane and (1 0 3) plane, and inserting each value into equation (3), The calculated strength is 2.0 or more, so that a relatively low number of (1 0 3) faces with low gloss can be obtained, and therefore the electro-galvanized layer with good overall gloss is not particularly limited, but is based on processing It is recommended to consider the property consideration of 15. If it is higher than 15, it is easy to cause the phenomenon of spalling during processing. The above-mentioned phenomenon of electrogalvanized steel sheet is described in detail in Japanese Patent Application No. Hei 7-2 9 39. Economy Printed by the Department of Central Standards Bureau for consumer cooperation (please read the notes on the back before filling this page). According to the present invention, a length of 5 or more should be used. The surface area of the area where the Z n single crystal grows in a given direction accounts for the electrogalvanized steel sheet with a total surface area of 70% or less in any area of the surface of the galvanized layer of the steel plate under observation. Here, "Z η single crystal grows in a given direction "Region" refers to a state in which the Zn single crystals plated on the surface of the galvanized layer are aligned and grown in a given direction (in the epitaxial growth state of the crystal film) rather than an irregularly grown state. Subtle protrusions or depressions or uneven crystal states due to other influences, but if the area of the plated Zn η single crystals grows large, the difference in hue can be clearly seen, even at this uneven paper size. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -16 Printed on the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 __._ B7___ V. Description of the invention (14) The area of the crystal state is small. If this is used Based on the original metal plate, the performance of the clarity of the obtained resin-coated metal plate will be deteriorated. Based on these findings, the above-mentioned areas regarding the growth of zinc single crystals with a length of 5 or more in a given direction are in a given direction. The condition that the area accounts for 70% or less of the total observed surface area is defined as a better requirement. If the Zn single crystal is too small, there is no visible degradation of the clarity performance of the resin-coated metal plate even if the Zn single crystal system is aligned Grow. The length of the Z η single crystal included in the above requirements must be 5 m or more. Because the original metal plate that meets this requirement has uniform hue and excellent clarity performance, if this type of original metal plate is used in this The invention provides a colored resin-coated metal plate having a beautiful appearance. The method for producing the colored resin-coated metal plate of the present invention will be described below. This colored resin-coated metal plate can be manufactured by applying a paint (preferably a water-dispersible paint) containing the above-mentioned resin component and a coloring pigment on a surface of an original metal plate by a known method and then drying the paint. As for the coating method, there is no particular limitation. It can include cleaning the surface of a long metal strip, and if necessary, performing a preliminary treatment on the surface (for example, phosphate or chromate treatment), a dropper coating method, and spraying. Method, curtain flow coating method and the like to apply paint and pass the resulting metal strip through a hot air drying furnace to dry. In consideration of the uniformity of the thickness of the coating film, the processing cost, and the coating efficiency as a whole, the roller coating method is actually preferable. As for the coating film to be colored resin on one or both sides of the original metal plate, it depends on the application. In order to prevent the color tone from being changed by the change of the coloring pigment, the drying temperature of the coating film should be lower than the heat-resistant temperature of the coloring pigment to be added. In order to improve the adhesion and corrosion resistance of the metal plate to the resin coating film, the national standard (CNS) A4 specification (210X297 mm) _ 17 _ — · '--------- --Install ----- ^-IOrder ----- @ 线 (Please read the precautions on the back before filling this page) Α7 Β7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ) Metal plates prepared with this resin coating film can be preliminary treated by the phosphate method or chromate method before coating. As for the materials used in the chromate method, the amount of C r coating during the chromate method is used to use the final resin From the viewpoint of dissolution of chromium during the coating of metal plates, it should be suppressed to 3 5 g / m 2 or less. Within this range, the resin-coated metal plates of the present invention can suppress the dissolution of chromium from the chromate-treated base layer. In addition, the water resistance of the top coating (if necessary, on materials conventionally treated with chromium •-acid salts) tends to decrease in the wet environment after the hexavalent solution is dissolved. The dissolution phenomenon is suppressed in the resin-coated metal plate of the present invention, so the water-resistant adhesion of the top coating There is no deterioration in the nature of the invention. The following will further illustrate the technical content of the present invention through the examples, but the scope of the present invention is not limited to those disclosed in the examples. Any changes and modifications can be made without departing from the spirit of the present invention. The following are all included in the technical scope of the present invention. Example 1 A water-dispersible polyethylene emulsion is used as the basic resin constituting the coating film, and organic compounds having various shades shown in Table 1 are added to account for 10% by weight of the solid content. Pigments and inorganic pigments (average particle diameter of 0.2 to 0.5 / zm) to prepare water-dispersed paints A to F containing colored pigments. Here, paints G and η are organic pigments. Paint I It is made of polyethylene emulsion without any pigment added as a comparative example. (Please read the precautions on the back before filling this page) This paper is also applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 10 A7 B7 V. Description of the invention (16 [Table 1] Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, the number of the paint and the color of the note, and the concentration of the CI number in the paint (weight% in terms of solid content) (Shown) Particle size βτη A red 20730 10 0.5 B yellow 21108 10 0.5 C blue. 74160 10 0.3 D green 74260 10 0.2 Example E black 77260 10 0.3 F white 77891 10 0.3 G purple 74160 2 0.3 20730 8 ash 77260 2 0.3 77891 8 I Colorless-1 Comparative Example * CI number: Represents the chemical composition of the pigment represented by a five-digit number (please read the precautions on the back before filling this page) ------------- --- ί Shenyi ---- Order-_ Line --- This paper size applies to Chinese National Standard (CNS) A4 (2 丨 〇 X 297 mm) _ 19 _ A7 —____ B7 V. Description of the invention (17) Then use Aj? Killed cold-rolled steel plate (A1 killed pold-rol.led steel plate) as the steel substrate and electro-galvanize according to the following steps. ① Detergent (alkali, scrubber defatti.ng) at 60 Use 3% aqueous sodium orthosilicate solution at ° C. ② Electrolytic degreasing—wash in water Use a 3% sodium orthosilicate aqueous solution at 60 ° C and 2 OA / dm2, and then wash in water. ③ Pickling—wash in water Use a 5% sulfuric acid solution at 60 ° C and then wash in water. ④ Electro-galvanizing—The process of electro-galvanizing before washing in water is performed under the following conditions. (Please read the precautions on the back before filling this page) Composition of electro-galvanizing solution: Z n S 0 4 * 7 Η 2 0 N a S Ο 4 Η 2 S Ο 4 300-400g / 5 50 -1 00g / j? 2 5-3 5 g / ^ The temperature of the electroplated zinc solution printed by the pager consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: 50 ~ 70 ° C Flow of galvanizing solution: 0.8 ~ 2.4m / Current density: 3 0 ~ 1 5 0 A / dm2 Electroplating coating weight: 20g / m2 In Examples 3 and 4 described below, An appropriate amount of tetraammonium salt is added to the acid bath under the conditions required for electrogalvanizing, so that the surface area of the area where the zinc single crystal of length 5 or more can grow in a given direction is galvanized on the observed electrogalvanized steel sheet The paper size of the total surface area of any area of the layer is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 20 _ printed by the member of the Central Standards Bureau of the Ministry of Economic Affairs X Consumer Cooperative A7 ___ B7 ____ It is called the growth ratio of the crystal film) is 70% or less, and the hexagonal in the (002) plane in the galvanized layer With the coefficient of crystal is (103) plane crystal alignment twice Ζ η coefficients hexagonal or more. As for the condition of electro-ammonium zinc, it is changed within the range described above. The obtained galvanized steel sheet is treated with chromate (C r coating weight is 20 g / m 2), and then it is used as the original coating resin. Metal plate. In addition, the 60 ° mirror gloss of the original metal plate before painting (measured by the following method, hereinafter referred to as G.) is 60, and the crystal film growth ratio is 0.5 1. Each of the coating solutions A to I shown in Table 1 was coated with a certain thickness on such a metal plate by a roller coater, and the metal plate was transferred to a hot air drying furnace to dry the coating. The following performance tests were performed on each of the obtained grease-coated metal plates. The results are shown in Tables 2 and 3. »(1) Gloss is measured by a gloss meter manufactured by Nippon Denshoku, Co._, Ltd according to J IS Z8741. 60 ° specular gloss (G60) β The 60 ° specular gloss of the original metal plate is set to G. The gloss after coating with resin was determined as G1, and the index Ga / Go 〇 (2), which represents the gloss change before and after coating, was calculated. The appearance was evaluated visually to determine whether the gold-plated plate reflected the original metal plate after coating with colored resin. As for the hue, the evaluation criteria are as follows. Evaluation of the tint reflectance performance of the original metal plate: This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm). _ 21-'—I .-------- 丨 Package --- ---- Order ----- line (please read the notes on the back before filling out this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of the invention (19) ◎ Excellent, reflects The hue and X difference of the original metal plate do not reflect the hue of the original metal plate. (3) Hue (colorability) The Hun ter color difference psychometr ic determined by JISZ 8 7 3 0 was measured using a color difference meter manufactured by Nippon Denshoku Co. Ltd. The a and b values of the chroma coordinates. The resin coated metal plate is calculated by Cl = (a 2 + b 2) 1/2. The color C of the original metal plate was measured in a similar manner. , Calculate the difference in excellentness (△ 0 = (: :-(: 〇) to evaluate the chromaticity according to the following criteria. Colorability evaluation method ◎ Excellent, chromaticity difference value is 8 or more, ○ Good, chromaticity difference value 2 or more, but less than 8, X difference, chromaticity difference is less than 2. (4) Corrosion resistance (white rust resistance) The corrosion resistance of resin-coated metal plates is based on JIS Z 2 3 7 1 Measured by 5% by weight saline spraying method. Measure the time required for 1% white rust to occur through pure galvanizing of the base layer of the resin coating film and evaluate it according to the following criteria. ◎ Excellent, 240 hours or more for white rust to occur. Good It takes 120 hours or more but less than 240 hours for white recording to occur. This paper right applies to China National Standards (CNS) A4 secret (210X297 after the official) -22-~~ (Please read the notes on the back first Fill in this page again) A7 B7 V. Description of the invention (20) △ Slightly worse, it takes 48 hours or more for white rust to occur, but it is less than 120 hours, X is poor, and it takes less than 48 hours for white rust to occur. (Please read the precautions on the back before filling out this page). Packing. Order printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) _ 23 _ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (21) [Table 2] Number of paint types make the paint heavy ( g / m2) Gloss change Gi / Go Appearance Hardness and corrosion resistance Note 1 A 0.3 0.9 ◎ 〇〇 Example 2 A 0.8 0.8 ◎ ◎ ◎ 3 A 1.5 0.7 ◎ ◎ ◎ 4 A 2.7 0.5 ◎ ◎ ◎ 5 A 0.1 1.0 XXX Comparative Example 6 A 3.2 0.4 X ◎ ◎ (Please read the precautions on the back before filling in this page). The size of the binding and binding paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) _ 24 _ Central Standard of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of the invention (22) Number of paint type Weight (g / m2) Gloss change Gi / G〇 Appearance coloring corrosion resistance Note 7 Β 0.4 0.9 ◎ 〇〇 Example 8 Beta 0.8 0.8 ◎ ◎ ◎ 9 Beta 1.5 0.7 ◎ ◎ ◎ 10 Beta 2.8 0.3 ◎ ◎ ◎ 11 Beta 0.1 1.0 XXX Comparative Example 12 Beta 3.1 0.4 X ◎ ◎ 13 C 0.4 0.9 ◎ 〇 Example 14 C 0.8 0.8 ◎ ◎ ◎ 15 C 1.5 0.7 ◎ ◎ 16 C 2.8 0.5 ◎ ◎ ◎ 17 C 0.1 1.0 XXX Comparative Example 18 C 3.1 0.4 X ◎ ◎ 19 D 0.4 0.9 ◎ 〇 Example 20 D 0.8 0.8 ◎ ◎ ◎ 21 D 1.5 0.7 ◎ ◎ ◎ 22 D 2.8 0.5 ◎ ◎ ◎ 23 D 0.1 1.0 XXX Comparative Example 24 D 3.2 0.3 X ◎ ◎ 25 Ε 0.3 0.9 ◎ 〇〇 Example 26 Ε 0.6 0.8 ◎ 〇 27 27 1.4 1.4 ◎ ◎ ◎ 28 Ε 2.7 0.5 ◎ ◎ ◎ 29 Ε 0.1 1.0 XXX Comparative Example 30 Ε 3.1 0.4 X ◎ ◎ 丨 ._ ^ I. 丨 Installation-Order β line (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) _ 25-V. Description of the invention (23) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs [Table 3] Coating weight of paint type 雠 (g / m2) Gloss change Gi / G〇 Appearance resistance Corrosiveness note 31 F 0.4 0.9 ◎ 〇 Example 32 F 0.8 0.8 ◎ 〇 ◎ 33 F 1.5 0.7 ◎ ◎ ◎ 34 F 2.8 0.5 ◎ ◎ ◎ 35 F 0.1 1.0 XXX Comparative Example 36 F 3.1 0.4 X ◎ ◎ 37 G 0.4 0.9 ◎ 〇〇 Example 38 G 0.8 0 .8 ◎ ◎ ◎ 39 G 1.5 0.7 ◎ ◎ ◎ 40 G 2.8 0.5 ◎ ◎ ◎ 41 G 0.1 1.0 XXX Comparative Example 42 G 3.1 0.4 X ◎ ◎ 43 Η 0.4 0.9 ◎ 〇〇 Example 44 Η 0.8 0.8 ◎ ○ ◎ 45 Η 1.5 0.7 ◎ ◎ ◎ 46 Η 2.8 0.5 ◎ ◎ ◎ 47 Η 0.1 1.0 XXX Comparative Example 48 Η 3.1 0.4 X ◎. ◎ 49 I 0.3 0.9 ◎ X 〇 Comparative Example 50 I 0.8 0.8 ◎ X ◎ 51 I 1.5 0.7 ◎ X ◎ 52 I 2.7 0.5 ◎ X ◎ I] .————.----------------------------- ^ line (please read the precautions on the back before filling this page) This paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -26- Printed by A7 B7, Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of invention (24)
所有實例均符合本發明式（1 ) Go>Gi20 . 5 G 。之關係，亦即l>Gi/G〇20. 5的實例均有優異的 外觀（原金屬板色調的反映性能佳），著色性及耐腐蝕性 。其原因可能是著色顔料濃度與塗膜塗料重均落在較佳範 圍內。 光澤變化Gi/G0<〇. 5落在本發明範圍外的比較 例雖具有優異的著色性與耐腐蝕性，但其外觀差，光澤低 ’並未反映出原金屬板的色調，原因在於塗膜的塗料重太 大。 若塗膜的塗料重太低，則幾乎觀測不到光澤的變化， Gi/Gotl，而且可看出著色性較差。因此無法發揮塗 裝著色樹脂的效果，此外耐腐蝕性也差，故此種塗料重並 不適用於本發明。再者使用不含著色顔料之漆料I的例子 仍保持原金屬板的光澤，但不用說在著色性方面則很差。 實施例2 以實施例1的相同方式製備含有表4所示顔料之漆料 J至丄。使用這些漆料依實施例1的相同方式製備著色樹 脂塗裝鋼板，以進行下列所述之性能測試》 本紙張尺度適用中國國家標準：（CNS ) A4規格（210X297公釐）_ 27 1 —i . j 裝 . . 訂 線 (請先閣讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（25 ) [表4] 著觸料 漆料 編號 顏色 C. I.編號 在漆料中的濃度 (以固容物計的重量%表示） 粒徑 βτη 附註 J 臾 21108 10 0.5 實例 K 橙 21108 8.5 0.5 20730 1.5 L 橙 21108 7.5 0.5 20730 2.5 * C. I.編號:代表以五位數數字所表示顏料的化學組成。 1! · 裝 訂 «線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 28 - B7 經濟部中央標準局員工消費合作社印製 五、發明説明（26 ) (5 )色調 依實施.例1 ~* ( 2 ).的相同方式測量psychometric chroma座標的a ，b值。 (6 )外觀（與鉻酸鹽法的色調進行比較） 評估著色樹脂塗裝金屬板是否具有鉻酸鹽加工相同的 色調，其評估標準如下述。 與鉻酸鹽加工比較下的色調評估 ◎ 優異，與鉻酸鹽加工具有相同的色調， X 差，與鉻酸鹽加工具有不同的色調。 (7 )耐C r溶解化性 依下述方式測定5 0塊7 Ommx 7 Omm著色樹脂 塗裝鋼板的耐C r溶解化性》 測試方法 ① 以螢光X —射線分析法分析試樣背面與正面的C r 塗料重以測定該試樣背面與正面的平均C r塗料重（mg / m 2 )。 ② 將試樣浸泡在8 0°C下pH值爲1 1的N a OH水 溶液中以進行後續2分鐘的音波處理（sonication)。 ③ 將試樣浸泡在8 0 °C 5 0 0 m β的純水中以進行 後續2分鐘的音波處理（s〇n i cat ion)，此步驟重複兩次 (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標隼（CNS ) Μ規格（210X297公釐）_ 29 - 經濟部中央標隼局貝工消費合作杜印製 A7 ___________B7 _______五、發明説明（27 ) ④ 將1 Omi2氫氯酸加入上述步驟②，③之C I·溶解 化溶液（於500mj? NaOH水溶液及1 000mi2 水所形成者），然後加熱並濃縮至l〇〇m 的最後體積 〇 ⑤ 利用甲基異丁基酮將六價C r由該加熱及濃縮後的 溶液中萃取出來，濃縮萃取液後以原子吸收光譜法測定試 樣每單位測試表面積溶解化的Cr量（mg/m2)。 ⑥ 將上述步驟⑤所得溶解化C r量除以上述步驟①之 平均C r塗料重即得到C r溶解化率（％ ) 耐C r溶解化性是依以下標準評估。 耐C I·溶解化性 ◎ 優異，C r溶解化率低於〇 . 〇 1 % 〇 良好，Cr溶解化率爲〇. 01%或以上但低於 0.1% X 差，c r溶解化率爲0 . 1 %或以上。 —IT- — - -1裝 . 訂 , 戀線 (請先聞請背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 3〇 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（28 ) [表5] 編號 漆料 塗膜的塗料重 色調 外觀 耐Cr溶解化性 附註 類型 (g/m2) ail b值 53 J 0.4 -2.5 5.0 ◎ 〇 實例 54 J 0.8 -2· 8 11.2 ◎ ◎ 55 J 1.5 -3.2 18.3 ◎ ◎ 56 J 2,8 -3.9 24.4 ◎ ◎ 57 J 0.1 -2.4 3.2 X X 比較例 58 J 3.1 -4.0 16.2 X ◎ 59 J 0.5 -5.0 10.1 X ◎ 60 K 0.4 -2.6 4.1 ◎ 〇 61 K 0.8 -2.9 10.7 ◎ ◎ 62 K 1.5 -3.3 17.5 ◎ ◎ 63 K 2.8 -3.8 23.6 ◎ ◎ (請先閱讀背面之注意事項再填寫本頁) •裝.All examples are in accordance with the formula (1) Go & Gi20. 5 G of the present invention. The relationship, that is, the examples of l > Gi / G20. 5 have excellent appearance (the reflection performance of the original metal plate hue is good), colorability and corrosion resistance. The reason may be that both the concentration of the pigment and the weight of the coating film fall in a better range. Gloss change Gi / G0 < 0.5 Comparative examples that fall outside the scope of the present invention have excellent coloring and corrosion resistance, but their poor appearance and low gloss do not reflect the hue of the original metal plate because of the coating The coating of the film is too heavy. If the coating weight of the coating film is too low, a change in gloss is hardly observed, Gi / Gotl, and poor colorability can be seen. Therefore, the effect of coating a colored resin cannot be exerted, and the corrosion resistance is also poor. Therefore, this coating is not suitable for the present invention. Furthermore, in the case of using paint I containing no colored pigment, the gloss of the original metal plate was maintained, but needless to say, it was poor in colorability. Example 2 In the same manner as in Example 1, paints J to 丄 containing the pigments shown in Table 4 were prepared. Using these paints, a colored resin-coated steel plate was prepared in the same manner as in Example 1 to perform the performance tests described below. "This paper size applies to Chinese national standards: (CNS) A4 size (210X297 mm) _ 27 1 —i . j Packing.. Thread (please read the precautions on the back before filling out this page) A7 B7 V. Description of the invention (25) [Table 4] Concentration of the color of the CI material in the paint ( Expressed as weight% in solid content) Particle size βτη Note J 臾 21108 10 0.5 Example K Orange 21108 8.5 0.5 20730 1.5 L Orange 21108 7.5 0.5 20730 2.5 * CI number: Represents the chemical composition of the pigment represented by a five-digit number . 1! · Binding line (please read the precautions on the back before filling this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) _ 28-B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (26) (5) The hue is measured in the same manner as in Examples 1 to * (2). The a and b values of the psychological chroma coordinates are measured. (6) Appearance (compared with the chromate method color tone) It is evaluated whether the colored resin-coated metal plate has the same color tone as chromate processing, and the evaluation criteria are as follows. Evaluation of hue in comparison with chromate processing ◎ Excellent, same hue as chromate processing, poor X, and different hue from chromate processing. (7) C r dissolution resistance The C r dissolution resistance of 50 7 Ommx 7 Omm colored resin-coated steel plates was measured in the following manner. Test Method ① Analyze the back surface of the sample with fluorescent X-ray analysis method. The Cr coating weight of the front side was used to determine the average Cr coating weight (mg / m 2) of the back and front sides of the sample. ② The sample was immersed in a Na OH aqueous solution with a pH of 1 1 at 80 ° C for the next 2 minutes of sonication. ③ Soak the sample in pure water at 80 ° C 500 m β for sony cat ion treatment for the next 2 minutes. This step is repeated twice (please read the precautions on the back first) (Fill in this page) The size of this paper is applicable to China National Standard (CNS) M specifications (210X297 mm) _ 29-Printed A7 by Shellfish Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs. 1 Omi2 hydrochloric acid is added to the CI · dissolution solution (formed by 500mj? NaOH aqueous solution and 1,000mi2 water) in the above steps ②, ③, and then heated and concentrated to a final volume of 100m. ⑤ Use methyl Hexavalent Cr was extracted from the heated and concentrated solution by isobutyl ketone. After the concentrated extract was concentrated, the amount of dissolved Cr (mg / m2) per unit test surface area of the sample was determined by atomic absorption spectrometry. ⑥ Divide the amount of dissolved C r obtained in the above step ⑤ by the average C r coating weight of the above step ① to obtain the C r dissolution rate (%). C r dissolution resistance is evaluated according to the following criteria. Resistance to CI and dissolution ◎ Excellent, C r dissolution rate is less than 0.01%. Good, Cr dissolution rate is 0.01% or more but less than 0.1%. X is poor, and cr dissolution rate is 0. 1% or more. —IT- —--1 Pack. Order, Love Line (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) _ 3〇A7 B7 Economy Printed by the Consumers' Cooperative of the Ministry of Standards of the People's Republic of China. 5. Description of the invention (28) [Table 5] No. Paint coating film coating heavy color appearance Cr dissolution resistance Note type (g / m2) ail b value 53 J 0.4 -2.5 5.0 ◎ 〇 Example 54 J 0.8 -2 · 8 11.2 ◎ ◎ 55 J 1.5 -3.2 18.3 ◎ ◎ 56 J 2,8 -3.9 24.4 ◎ ◎ 57 J 0.1 -2.4 3.2 XX Comparative Example 58 J 3.1 -4.0 16.2 X ◎ 59 J 0.5 -5.0 10.1 X ◎ 60 K 0.4 -2.6 4.1 ◎ 〇61 K 0.8 -2.9 10.7 ◎ ◎ 62 K 1.5 -3.3 17.5 ◎ ◎ 63 K 2.8 -3.8 23.6 ◎ ◎ (Please read the precautions on the back before filling in this Page) • installed.
'ST 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 31 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（29 ) 編號 漆料 類型. 謹的塗料重 Cg/m2) 色調 外觀 耐Cr溶解化性 附註 a值 b值 64 K 0.1 -2.4 2.5 X X 65 K 3.1 -4.0 15.0 X ◎ 66 K 0.5 -5.2 10.3 X ◎ 67 L 0.4 - 2· 9 3.6 ◎ 〇 68 L 0.8 ~3.0 9.5 ◎ ◎ 69 L 1.5 -3.1 15.4 ◎ ◎ 70 L 2.8 -3.5 23.6 ◎ ◎ 71 L 0.1 -2.4 2.3 X X 72 L 3.1 -4.0 15.4 X ◎ 73 L 0.5 -5.2 8.4 X ◎ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-32 - A7 B7 五、發明説明（30 ). 本發明實例之a，b值屬於本發明所界定之範圍內’ 因此所有實例均具有鉻酸鹽加工的相同色調。此外表列結 果也顯示這些實例均具備優異的耐C r溶解化性’反之比 較例則不具備鉻酸鹽加工的任何外觀或者耐C r溶解化性 差。 實施例3 爲依實施例1的相同方式製備電鍍鲜鋼板，將適當量 ’的四銨鹽加入酸洗浴中並在以上所述範圍內適當調整電銨 鋅的條件以改變晶膜成長比例。使用表1所示之漆料A， F，並將生成的電鍍鋅鋼板塗裝樹脂》對各試樣（編號 7 4至7 9 )的光澤變化，晶膜成長比例以及澄清度性能 加以評估並將結果列於表6。澄清度性能是以下列標準評 估。 @ 澄清度性能優異 〇 澄清度性能良好 X 澄清度性能差 -Ί T—- ίί..~ 裝- ^ 訂 ^ '©線 (請先閱讀背面之注意事項再填寫本頁)_ 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐）-33 - A7 B7 五、發明説明（31 ) [表6] 編號 漆料 讓的塗料重 晶膜成 光澤變化 塗裝樹脂後的 附註 類型 (g/m2 ) 長比例 Gi/G〇 澄清度性能 74 A 0.6 0.51 0.8 ◎ 實例 75 A 0.6 0.65 0.8 〇 76 A 0.6 0.73 0.8 X 比較例 77 A 0.6 0.50 0.7 ◎ 實例 78 A 0.6 0.64 0.7 〇 79 A 0.6 0.72 0.7 X 比較例 —ΙΊΓ------—裝--------訂-----Q-線 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公釐）-34- 經濟部中央標準局員工消費合作社印製 A7 _____ B7 _^_五、發明説明（32 ) 在試樣編號74，75，77和7 8中使用晶膜成長-比例介於本發明較佳範圍的電鍍鋅鋼板*因此可製出澄清 度性能優異的樹脂塗裝金屬板*而在比較例中澄清度性能 差。. 實施例4 爲依實施例1的相同方式製備電鍍鋅鋼板，將適當量 的四銨鹽加入酸洗浴中並在以上所述範圍內適當p整電鍍 鋅的條件以改變鍍鋅層中（0 0 2 )面內六方Ζ η晶體的 配向（對（1 0 3 )面而言）。使用同於實施例3的漆料 ’然後塗裝樹脂*對各個試樣評估鍍鋅配向係數，光澤變 化與外觀（原金屬板色調的反映性能），結果列於表7。 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準.（CNS ) Λ4規格（210X297公釐）_ 35 _ 3SSQ59 87 五、發明説明（33 )[表7] 編號 漆料 類型 讎的塗料重 (g/m2) (002湎電鍍鋅配向 係數/(103湎係數 光澤變化 Gi/G〇 懇 附註 80 A 0.7 2.2 0.7 ◎ 實例 81 A 0.7 5.0 0.8 ◎ 82 A 0.7 12.0 0.9 ◎ ^^1· nn i i i In nn I.-- —^n mi n^i 1. 一 1^1 nn ml mu ·ΛΊ»ΐ Λ 条 、V0 裔'^一 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 36 _ 經濟部中央標準局員工消費合作社印製 380059 A7 B7 五、發明説明（34 ).'ST line paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) _ 31-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (29) No. Type of paint. Prudent paint Weight Cg / m2) Hue appearance Cr dissolution resistance Note a value b value 64 K 0.1 -2.4 2.5 XX 65 K 3.1 -4.0 15.0 X ◎ 66 K 0.5 -5.2 10.3 X ◎ 67 L 0.4-2 · 9 3.6 ◎ 〇 〇 68 L 0.8 ~ 3.0 9.5 ◎ ◎ 69 L 1.5 -3.1 15.4 ◎ ◎ 70 L 2.8 -3.5 23.6 ◎ ◎ 71 L 0.1 -2.4 2.3 XX 72 L 3.1 -4.0 15.4 X ◎ 73 L 0.5 -5.2 8.4 X ◎ (Please first Read the notes on the reverse side and fill in this page) The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -32-A7 B7 V. Description of the invention (30). The a and b values of the examples of the present invention belong to this Within the bounds of the invention 'therefore all examples have the same hue of chromate processing. In addition, the results of the table also show that these examples all have excellent resistance to Cr dissolution ', whereas the comparative example does not have any appearance of chromate processing or has poor Cr dissolution resistance. Example 3 To prepare a plated fresh steel plate in the same manner as in Example 1, an appropriate amount of tetraammonium salt was added to the acid bath and the conditions of the electro-ammonium zinc were appropriately adjusted within the above-mentioned range to change the crystal film growth ratio. The paints A and F shown in Table 1 were used, and the resulting electro-galvanized steel sheet was coated with a resin "to evaluate the gloss change, crystal growth ratio, and clarification performance of each sample (No. 7 4 to 7 9) and The results are shown in Table 6. Clarity performance was evaluated using the following criteria. @Excellent clarification performance 〇Good clarification performance X Poor clarification performance -Ί T—- ί .. ~ Install-^ Order ^ 'line (Please read the precautions on the back before filling this page) _ Ministry of Economy Central Standard The paper size printed by the Bureau ’s Consumer Cooperative is applicable to China ’s National Standards (CNS) A4 (210X297 mm) -33-A7 B7 V. Description of the invention (31) [Table 6] The number of paints allows the coating to recrystallize. Gloss change after coating resin type (g / m2) Long ratio Gi / G〇 Clarity performance 74 A 0.6 0.51 0.8 ◎ Example 75 A 0.6 0.65 0.8 〇76 A 0.6 0.73 0.8 X Comparative example 77 A 0.6 0.50 0.7 ◎ Example 78 A 0.6 0.64 0.7 〇79 A 0.6 0.72 0.7 X Comparative Example—IΊΓ ---------- Installation -------- Order ----- Q-line (please read the note on the back first Please fill in this page again) Printed by the Central Consumers ’Cooperative of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -34- Printed by the Central Consumers’ Cooperative of the Ministry of Economic Affairs A7 _____ B7 _ ^ _V. Description of the invention (32) Use of crystal film in sample numbers 74, 75, 77 and 7 8 Length - the ratio between excellent clarity performance resin coated metal sheet, galvanized steel sheet of the present invention is preferably in the range of a * * thus produced may be a difference in the performance of Comparative Example clarity. Example 4 To prepare an electro-galvanized steel sheet in the same manner as in Example 1, an appropriate amount of tetraammonium salt was added to the acid bath and the conditions for electro-galvanizing were appropriately adjusted within the above-mentioned range to change the galvanized layer (0 0 2) Alignment of hexagonal Z η crystals in the plane (for the (1 0 3) plane). The same paint as in Example 3 was used followed by coating resin * for each sample to evaluate the galvanized alignment coefficient, gloss change, and appearance (reflection performance of the original metal plate hue). The results are shown in Table 7. (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards. (CNS) Λ4 size (210X297 mm) _ 35 _ 3SSQ59 87 V. Description of the invention (33) [Table 7] Number paint Coating weight of type ((g / m2) (002 湎 Galvanized orientation coefficient / (103 湎 coefficient of gloss change Gi / G) Note 80 A 0.7 2.2 0.7 ◎ Example 81 A 0.7 5.0 0.8 ◎ 82 A 0.7 12.0 0.9 ◎ ^ ^ 1 · nn iii In nn I .---^ n mi n ^ i 1. 1 1 ^ 1 nn ml mu · ΛΊ »ΐ Λ, V0 line '^ 一 (Please read the notes on the back before filling in this Page) Printed by the Central Consumers ’Cooperative of the Ministry of Economic Affairs. The paper is printed in accordance with Chinese National Standards (CNS) A4 (210X297 mm) _ 36 _ Printed by the Central Coordination Bureau of the Ministry of Economics’ Consumer Cooperatives. 380059 A7 B7 5. Description of the invention ( 34).
編號 漆料 讓的塗料重 (002湎電鏡鋅配向 光澤變化 m 附註 類型 (g/m2) 係數/(103湎係數 Gi/G〇 83 A 0.7 1.5 0.4 X 比較例 84 A 0.7 1.0 0.4 X 85 F 0.8 2.4 0.6 〇 實例 86 F 0.8 5.7 0.7 ◎ 87 F 0.8 13.2 0.8 ◎ 88 F 0.8 1.6 0.4 X 比較例 89 F 0.8 1.0 0.4 X (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（ 210X297公釐）_ 37 _ a8iiQS9 五、發明説明{ 35 ) _ 在（0 0 2)面中Zn晶體配向爲（1 03)面配向 兩倍或以上之較佳實例中製出外觀較比較例爲優的樹脂塗 裝金屬板。 由於本發明係呈以上所述之結構，本發明得以提供一 種可在成本不高和簡單設備下製造的著色樹脂塗裝金屬板 ，其具有穩定而能夠反映出原金屬板在塗裝樹脂膜之前的 色調之光澤，耐腐蝕性優，耐C r溶解化性佳。 (請先聞讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐）_ 38 _The coating weight made by the number of paints (002 湎 TEM zinc orientation gloss change m Note type (g / m2) coefficient / (103 (coefficient Gi / G〇83 A 0.7 1.5 0.4 X Comparative example 84 A 0.7 1.0 0.4 X 85 F 0.8 2.4 0.6 〇 Example 86 F 0.8 5.7 0.7 ◎ 87 F 0.8 13.2 0.8 ◎ 88 F 0.8 1.6 0.4 X Comparative Example 89 F 0.8 1.0 0.4 X (Please read the precautions on the back before filling out this page) The paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) _ 37 _ a8iiQS9 V. Description of the invention {35 _ _ Manufactured in the preferred example where the orientation of Zn crystals in the (0 0 2) plane is twice or more than that of the (1 03) plane A resin-coated metal plate having an appearance superior to that of the comparative example. Since the present invention has the structure described above, the present invention can provide a colored resin-coated metal plate that can be manufactured under low cost and simple equipment, which has It is stable and can reflect the luster of the original metal plate before the resin film is applied. It has excellent corrosion resistance and good resistance to C r dissolution. (Please read the precautions on the back before filling in this page.) Printed by Standards Bureau's Consumer Cooperative This paper size applies to Chinese national standards (CNS> A4 size (210X297 mm) _ 38 _