1305515 玉久、發明說明 【發明所屬之技術領域】 本發明係關於AV機器與冷氣外殼等之家庭電氣化製 品之外部裝飾及鋼製傢具、電梯內部裝設 '建築物內部 裝設等所用之塗覆有樹脂之金屬板及其製造方法者。詳 細言之’係關於耐刮傷性、加工性優異，同時有創意性 的鏡面反射性、並有優異的耐沸水性’且不使用含鹵素 的樹脂之塗覆有樹脂之金屬板及其製造方法者。 【先前技術】 向來，作爲用於上述用途的塗覆有樹脂之金屬板，係 使用以經由添加顏料著色的樹脂層作爲基材樹脂層，在 其上設置印刷層，再於其上以透明的樹脂薄膜進行層合 一體化的片材，將其層合在鋼板上而構成者。 作爲該構成中之透明樹脂薄膜，通常係使用厚度 1〇~50# m之例如：聚乙煤醇共聚物薄膜、丙嫌酸醋系共 聚物薄膜、雙軸延伸聚對苯二甲酸乙二酯（以下稱爲雙 軸延伸 P E T )系樹脂薄膜等。其中尤以各種物性皆優異 的雙軸延伸PET系樹脂薄膜爲佳。 又，作爲著色之樹脂層，通常係使用軟質氯乙烯系樹 脂層。其原因在於軟質氯乙烯系樹脂可藉由添加可塑劑 而任意地設定其柔軟性。而且，於透明雙軸延伸pET系 樹脂薄膜之層合的構成，除可得到良好的加工性之外， 基於長年對於安定劑的硏究，其並具有比較良好的耐久 性，且耐藥品性、耐熱性、耐熱水性亦優，適於使用爲 6 312/發明說明書(補件)/92-04/92103116 1305515 洛缸設備等之用途。再者，於軟質氯乙烯系樹脂上以雙 軸延伸P E T系樹脂薄膜之層合的構成中，可得到極爲良 好的鏡面反射性。亦即，映照於塗覆有樹脂之金屬板的 影樣變形少、淸晰度高，亦爲其特徵之一。 然而’近年來起因於氯乙烯系樹脂之安定劑的重金屬 化合物的問題、起因於部分的可塑劑與安定劑之V 0 C (揮 發性有機化合物）問題及/或內分泌擾亂作用的問題、燃 燒時產生氯化氫及其他的含氯氣體的問題等，使得氯乙 烯系樹脂的使用日益受到限制。 於此’取代以上述構成之經著色之樹脂層之軟質氯乙 烯系樹脂，係改爲使用以聚丙烯等之聚烯烴系樹脂爲主 體，配合以苯乙烯系及/或共聚合烯烴系等之軟質成 分，以得到接近於軟質氯乙烯系樹脂的物性者。於此構 成之中’以雙軸延伸PET系樹脂薄膜所層合成之構成， 可得到與於經著色之樹脂層中使用軟質氯乙烯系樹脂的 情況之同等優異的鏡面反射性。 然而，在欲作爲預塗覆鋼板而賦予充分的加工性的情 況下，相較於使用軟質氯乙烯系樹脂的情況，其表面的 耐刮傷性較差。又，使耐刮傷性成爲與塗覆有軟質氯乙 烯系樹脂之金屬板同等之時，則無法得到滿足的加工性 是其問題，因而未能成爲可廣泛使用者。 另一方面，由於聚烯烴系樹脂本質上爲接著性差的材 料，故於賦予其印刷創意而與雙軸延伸P E T系樹脂層合 的情況中，必須較軟質氯乙烯系樹脂施行更多的步驟 312/發明說明書(補件)/92-04/92103116 1305515 (例如，電暈處理或底塗層等之表面處理步驟），是其問 題所在。又，於接著界面及與金屬板接著所用的接著劑 間的界面之經時安定性方面，亦有疑慮。 因而’作爲用以解決此等問題的材料，以聚醋系樹脂 作爲上述構成的經者色之樹脂層來使用之情況向來受到 硏討。於塗覆有該樹脂的金屬板，在耐刮傷性與加工性 方面可得以兼顧且兩者皆較塗覆有軟質氯乙烯系樹脂之 金屬板具較高的水準，可將塗覆有聚烯烴系樹脂之金屬 板中的諸問題解決。 【發明內容】 (發明所欲解決之課題） 然而’以沒有結晶性之可砑光成形之類的聚酯系樹脂 作爲經著色之樹脂層使用的情況，其玻璃轉化溫度（Tg ) 較1 〇 〇 °c爲低，致使其無法滿足通常在建築內部裝設用 之塗覆有樹脂之金屬板的評價項目中所包括的耐沸水浸 漬試驗。相對於此，以聚對苯二甲酸乙二酯及聚對苯二 甲酸丁二酯等之具有結晶性之聚酯系樹脂作爲經著色之 樹脂層使用之情況，由於其熔點高，故相較於以習用的 氯乙烯系樹脂薄膜及聚烯烴系樹脂薄膜進行層合時’其 金屬板表面的溫度必須提高。因而，現有的層合生產線 必須加以改造。 又，於上述塗覆有樹脂之金屬板的內面雖施有塗裝處 理，此塗裝若爲向來所習用者’則於耐熱性方面會有問 題。此情況下，須改變爲使用耐熱性高的塗料’或須將 312/發明說明書(補件)/92-(M/921〇3116 1305515 習用之層合前的鋼板之加熱與塗佈於內面的塗料之乾燥 同時進行之方式改爲在層合後才塗佈塗料’再度進行乾 燥加熱等之方式。再者’經層合一體化之片材中的印刷 層的耐熱性，在習用的層合溫度下並無問題，但於提高 層合溫度的情況下，有顯著地顯現熱變色、熱褪色等之 可能性，該情況下’必須改變印刷油墨的顏料種類、黏 結劑的種類，以使印刷層的耐熱性提高。然而，此等問 題之改善方式，係關係著鋼板層合業者的負擔之增加導 致成本提高，而不受到歡迎。 本發明係鑑於上述的問題點而提出者，其第1目的在 於提供一種塗覆有樹脂之金屬板，其係不使用軟質氯乙 烯系樹脂之具有優異的鏡面反射性、且可利用習用的層 合設備而進行製造者。又，第2目的在於’提供優異的 鏡面反射性之同時’加工性及耐沸水性亦皆良好的塗覆 有樹脂之金屬板。又’第3目的在於提供其製造方法。 (用以解決課題之手段） 爲達成上述第1目的’申請專利範圍第1項之發明’ 爲一種塗覆有樹脂之金屬板’其係由以聚酯系樹脂爲主 成份之基材樹脂層、印刷層、透明延伸聚酯系樹脂層’ l· ''ΐίί 基 依前述順序層合一體化所成之層合片材，將其以H 材樹脂層側的一面作爲接著面，介以接著劑層而層合Μ 金屬板上所構成者；用以構成上述基材樹脂層之聚曰 樹脂，須滿足下述的要件。其爲··於層合到金屬极 的層合片材的狀態下，經由示差掃描熱量計（D s e} Λ 312/發明說明書(補件)/92-04/92103116 1305515 定，於昇溫時可觀測到明確的結晶化波峰溫度（τ c )與結 晶熔解波峰溫度（Tm)，於以結晶化熱量作爲△ H c ( J / g )、以結晶熔解熱量作爲△ H m ( J / g )之時，成立 (△Hm-AHc)<30 之關係。 此處，所謂「以聚酯系樹脂作爲主成份」，係包含於聚 酯系樹脂中添加有適量的添加劑者。作爲添加劑，例如 可使用通常於廣泛的樹脂材料中所使用者。 於本發明中，經由將（△ H m - △ H c )的値定爲未滿3 0， 可限制基材樹脂層的結晶性，雖顯示結晶熔解波峰溫度 (Tm )，惟，實際上係於較其爲低的溫度起即有熔融性。 因而，即使於未達上述T m + 3 0 °C之金屬板的表面溫度進 行層合，於成爲熔融狀態之同時經由以層合輥加壓，可 消除源自基材樹脂層及金屬板的表面的凹凸等之凹凸， 而可得到高鏡面反射性。又，向來在軟質氯乙烯系樹脂 薄膜的層合時之溫度下可得到高鏡面性，可有效地利用 既有的設備進行製造。而且，有關印刷油墨、接著劑等 亦可沿用使用於氯乙烯系樹脂者，因而可降低製品成本。 爲達成第2目的，於申請專利範圍第2項所記載之發 明，爲申請專利範圍第 1項之發明中之上述基材樹脂 層，係含有作爲結晶性聚酯系樹脂之成分之聚對苯二甲 酸丁二酯系樹脂，於層合於金屬板後的狀態中，滿足上 述結晶化熱量△ H c與上述結晶熔解熱量△ H m之間，1 5 <ΔΗτη及5< (ΔΗτη-ΔΗο:)中的至少一方之關係式。此 發明中，除了優異的鏡面反射性之外，加工性與耐沸水 10 312/發明說明書(補件)/92-(Μ/92103116 1305515 性亦良好。 申請專利範圍第3項所記載之發明，爲申請專利範圍 第1項之發明中之上述基材樹脂層，係含有作爲結晶性 聚酯系樹脂成分之聚對苯二甲酸亞丙基酯系樹脂，於層 合於金屬板後的狀態中，上述結晶化熱量△ H c與上述結 晶熔解熱量ΔΗπι之間，爲至少滿足15<ΔΗιη或5< (△ Hm-AHc)中的至少一方之關係式。此發明中，除了優異 的鏡面反射性之外，加工性與耐沸水性亦良好。 申請專利範圍第4項所記載之發明，係如申請專利範 圍第1至3項中任一項之發明中，上述透明延伸聚醋系 樹脂層係由雙軸延伸聚對苯二甲酸乙二酯薄膜所形成。 於此發明，可容易地確保透明性、平滑性及表面的耐舌|J 傷性。且可容易地施行所謂的逆向印刷（b a c k p r i n t } 形成印刷層。 申請專利範圍第5項所記載之發明，爲如申請專利範 圍第1至4項中任一項之發明，其係於上述基材樹脂層 與上述印刷層之間存在有接著劑層。於本發明，可使基 材樹脂層與印刷層間的接著性良好。 申請專利範圍第6項所記載之發明，係如申請專利範 圍第1至5項中任一項之發明，其中，上述基材樹脂層 係由經著色之聚酯系樹脂所構成。於此發明，可圖求底 材的金屬板之遮蔽、創意性之賦予及印刷層的發色性改 善等。 申請專利範圍第7項所記載之發明’爲一種塗覆有樹 11 312/發明說明書(補件)/92-04/92103116 1305515 月曰之金屬板之製造方法，該金屬板係如申請專利範圍第 1至6項中任一項所述者；其係以聚酯系樹脂爲主成份 之基材樹脂層、印刷層 '透明延伸聚酯系樹脂層，依前 述順序層合一體化所成之層合片材，將其以上述基材樹 月曰層側的一面作爲接著面，介以接著劑層而層合於金屬 板上之時，係在上述金屬板的表面溫度T s (它）與上述 用以構成基材樹脂層的聚酯系樹脂的結晶熔解波峰溫度 T m ( c )之間成立（T m + 3 〇 )〉T s的關係之狀態下進行層 合者。 此發明中，可利用習用的層合設備容易地製造上述塗 覆有樹脂之金屬板’並且可抑制印刷層及金屬板內面圖 裝的熱變色、熱褪色。 【實施方式】 以下’就本發明之具體化的實施形態加以說明。 如圖1(a)所示般，塗覆有樹脂之金屬板H，在金屬 板12的一面上介以接著劑層13與以聚酯系樹脂爲主成 份的基材樹脂層1 4進行層合，在基材樹脂層i 4上則層 合以印刷層1 5，在其上再層合著透明延伸聚酯系樹脂層 1 6。亦即，塗覆有樹脂之金屬板 1 1，係由以聚酯系樹 脂作爲主成份的基材樹脂層1 4、印刷層1 5、透明延伸 聚酯系樹脂層16依序層合一體化所成之作爲層合片材 之層合一體化片材S，將其以基材樹脂層1 4側之面作爲 接著面，介以接著劑層13層合於金屬板12上而構成。 又，於圖1(b)所顯示的塗覆有樹脂之金屬板11，除圖 12 312/發明說明書(補件)/92-04/92103116 1305515 1 ( a )的構成之外，於基材樹脂層1 4與印刷層1 5之間 設置有接著劑層1 7。 作爲用以構成基材樹脂層1 4的聚酯系樹脂，可使用 含有作爲醇類成分之乙二醇、丙二醇、丁二醇、環己烷 二甲醇等與作爲二羧酸成分之對苯二甲酸或間苯二甲酸 等的共聚物之中所任意選定之樹脂的單體或摻合物。 惟，於層合到金屬板1 2之前的層合片材的狀態下，經 由示差掃描熱量計（D S C )測定，於昇溫時可觀測到明確 的結晶化波峰溫度（T c )與結晶熔解波峰溫度（Tm )，於 以結晶化熱量作爲△ H c ( J / g )、以結晶熔解熱量作爲△ Hm(J/g)之時，成立下式的關係： Δ Hm-Δ Hc< 30 (1) 於（△ Hm - △ H c )的値超過3 0的情況，係其聚酯系樹 脂的結晶性高。因而，於層合時之金屬板1 2的表面溫 度，通常若不使之較基材樹脂層1 4的熔點Tm ( °C )高出 3 CTC以上，則基材樹脂層1 4無法充分地熔融，故源自 於基材樹脂層14的表面的凹凸不會消失，且由於源自 金屬板1 2的表面的凹凸也殘留，因此無法得到高鏡面 性。基材樹脂層1 4的結晶熔解波峰溫度係相當於熔點。 作爲金屬板1 2的表面溫度之所以必須較基材樹脂層1 4 的熔點T m高3 0 t以上的溫度，理由在於防止下述之現 象。由層合瞬間自經加熱的金屬板1 2往層合一體化片 材進行之熱移動之發生，瞬時間塗覆有樹脂之金屬板11 全體的平均溫度會降低、基材樹脂層1 4的結晶熔解之 13 312/發明說明書(補件)/92-04/92103116 1305515 熱量會消耗，於以溫度相對於金屬板1 2爲低的層合輥 擠壓時之熱會被層合輥奪走等現象。 但是，此情況下，通常於層合時的金屬板1 2的表面 溫度，必須較以習知的氯乙烯系樹脂作爲基材樹脂層1 4 使用的情況下爲高，而使前面之「發明所欲解決之課題」 中所述之各種問題點明顯化。 然而，經由使（△ H m - △ H c )的値未滿3 0，可限制基材 樹脂層1 4的結晶性，雖顯示結晶熔解波峰溫度（Tm )， 實際上自於較其爲低的溫度即有熔融性。因而，即使於 未滿上述Tm+ 3 0 °C的金屬板1 2的表面溫度進行層合， 經由成爲熔融狀態之同時以層合輥進行加壓，可消除源 自於上述各種原因之凹凸而得到高鏡面反射性。 再者，基材樹脂層1 4，爲含有作爲結晶性聚酯系樹脂 成分之聚對苯二甲酸丁二酯（PBT)系樹脂或聚對苯二甲 酸亞丙基酯（P T T )系樹脂，且可滿足後述的要件時，可 得到耐沸水性優異的塗覆有樹脂之金屬板1 1。於層合到 金屬板1 2後的狀態下，經由D S C測定，於昇溫時可觀 測到明確的結晶熔解波峰溫度（Τ τη )，結晶化熱量△ H c 與結晶熔解熱量△ Hm之間，可滿足下式（2 )、（ 3 )之至 少一方的關係式： 1 5 < Δ H m ( 2 ) 5< (ΔΗτη-ΔΗο) (3) 於此等値爲規定的數値以下的情況時，基材樹脂層 14 的結晶性低，與以完全非結晶的聚酯系樹脂用作爲基材 14 312/發明說明書(補件)/92-04/92103116 1305515 植f脂層14的情況同樣地非爲可耐沸水試驗者，作爲內 部裝設建材的用途會受到限制。 式（2 )、（3)的至少—方的關係式若可成立，則可得到 耐沸水性優異的塗覆有樹脂之金屬板1 1，其理由如下 述。於式（2)所規定之基材樹脂層：^的^^較15爲大 的情況下’係顯示了作爲結晶性樹脂成分使用之P B T系 樹脂或P T T系樹脂的結晶化速度會比較快，同時於基材 樹脂層14的摻合物組成中所佔的結晶性樹脂成分的比 例較1¾ °因而’於層合後，即使幾乎都是非結晶性的狀 態’於浸漬於沸水之時會立即發生結晶化，其結果爲可 得到可耐沸水試驗的結晶性。 相對於此’於不能滿足式（2 )的情況，顯示於基材樹 脂層1 4的慘合物組成中所佔的結晶性樹脂成分的比例 低。因而’混合物系的結晶化速度會變慢’於層合後之 時若未進展到一定程度以上的結晶化，則無法耐得住耐 沸水試驗。 爲得到滿足前述式（1)、（2)或式（1)、（3)的基材樹 脂層14之樹脂組成，係以用酸成分、醇成分分別爲單 —成分之所謂的均質聚對苯二甲酸丁二酯（ρΒΤ)樹脂或 均質聚對苯二甲酸亞丙基酯（ΡΤΤ)樹脂作爲結晶性樹脂 成分而使用。而且，藉由對其摻合以非結晶性或低結晶 性的共聚合聚酯系樹脂來調整爲所要的物性甚爲容易， 故爲較佳。 作爲非結晶性的樹脂，就原料的安定供給性及生產量 312/發明說明書(補件)/92-04/92103116 15 1305515 大來考量以謀求降低成本考量，以使用伊士曼化學公司 的「伊士達· 6 7 6 3」及與其類似的樹脂爲佳。惟，並非 限定於此，亦可使用特殊的冷卻條件下顯示出熔點之通 常可作爲非結晶性樹脂使用的伊士曼化學公司的 「PGTG· 5445」等。 作爲結晶性的樹脂，於使用均質P B T或均質P T T般的 結晶化速度快的樹脂之情況，經由摻合以結晶性低的樹 脂或非結晶性的樹脂以降低摻合物全體的結晶化速度， 亦可得到滿足式（1)之層合一體化片材S。又，於使用 此等結晶性樹脂的情況，可容易地得到有良好的加工性 之塗覆有樹脂之金屬板，而爲較佳者。 於基材樹脂層14中，爲了底材的金屬板12之遮蔽、 創意性之賦予、印刷層1 5的呈色性之改善等之目的， 可添加入顏料。使用之顏料可用通常之習用於樹脂著色 用者，有關其添加量，使用上述目的之通常的添加量即 可 ° 於基材樹脂層I4及透明延伸聚酯系樹脂層16中，在 不損及本發明之目的的程度下’亦可以適宜的量添加入 添加劑。作爲添加劑，可列舉例如：磷系.酌系等之各 種氧化防止劑、熱安定劑、紫外線吸收劑、潤滑劑、金 屬去活化劑、殘留聚合觸媒去活化劑、造核劑、抗菌· 防霉劑、帶電防止劑、防火劑 '塡充材料等之通常用於 各種樹脂材料中者。又’可舉出：末端羧酸封鎖劑、碳 化一亞肢系等之水解防止劑、醋交換阻止劑等之爲特定 312/發明說明書(補件)/92-04/92103116 16 1305515 樹脂用而開發的添加劑等。 於基材樹脂層1 4與印刷層1 5之間，或印刷層1 5與 透明延伸聚酯系樹脂層 1 6之間亦可存在有接著劑層 1 7。作爲用以構成該接著劑層1 7之接著劑，可使用例 如：以聚酯系樹脂或聚醚系樹脂作爲主劑、以異氰酸酯 系交聯劑等硬化之通常稱爲乾式層合用接著劑層者。此 接著劑層之中，就因於紫外線而變黃的問題較輕微的觀 點考量，以使用脂肪族系者爲佳。 又，尤其是在對基材樹脂層1 4添加耐光性安定性差 的顏料的情況等之必須控制對於基材樹脂層 1 4之紫外 線透過量的情況，亦可對接著劑層 1 7在不損及其性質 的程度下適當地配合紫外線吸收劑之類的添加劑。 印刷層1 5，可施以凹板印刷、平板印刷、網版印刷及 其他之公知的方法予以印刷。印刷層1 5的圖案可爲石 紋、木紋或幾何圖案、抽象圖案等之任意者，可爲全面 印刷亦可爲局部印刷，亦可於施行局部印刷之後再施行 全面印刷。通常，係使用在平滑性良好的透明延伸聚酯 系樹脂層1 6的層合面側施行所謂的逆向印刷的方法， 惟，亦可對基材樹脂層1 4作表面印刷。 作爲本發明所使用之透明延伸聚酯系樹脂層1 6，可使 用與於塗覆有軟質氯乙烯系樹脂之金屬板或塗覆有聚烯 烴系樹脂之金屬板具相同目的（亦即，印刷層的保護、 賦予有深度的創意性及表面各種物性之改良）所使用者 之同樣者。 17 312/發明說明書(補件)/92-04/92103116 1305515 其中就透明性、平滑性及表面的耐刮傷性等方面考 量，尤以使用雙軸延伸聚對苯二甲酸乙二酯薄膜爲佳。 於此實施形態中，透明延伸聚酯系樹脂層1 6係由透明 雙軸延伸聚酯樹脂薄膜（透明雙軸延伸 p E T樹脂薄膜〉 所構成。可使用薄膜厚度爲1 5 ~ 7 5 /Z m程度，延伸處理 後之熱固定溫度爲 2 2 0 ~ 2 4 0 °C程度之習用於上述目的 所通常使用者。 作爲本發明的對象之金屬板，可使用熱軋鋼板、冷軋 鋼板、熔融鍍鋅鋼板、鍍鋅鋼板、電鍍鋅鋼板、鍍錫鋼 板、不銹鋼板等之各種鋼板及鋁板，亦可於施行通常的 化成處理之後使用。金屬板 1 2的厚度，固依塗覆有樹 脂之金屬板1 1的用途而異，惟，可選定爲〇 . lmm~ 1 0mm 的範圍。 其次，就層合一體化片材S及塗覆有樹脂之金屬板11 的製造方法加以說明。作爲本發明之層合一體化片材S 之製膜方法，可採用公知的方法，例如：用T型模具之 擠壓鑄造法及吹塑法等，並非限定於此，惟，由片材的 製膜性及安定生產性等方面考量，以用T型模具之擠壓 鑄造法爲佳。 層合一體化片材S的厚度通常爲50~500#m。片材的 厚度若未滿5 0 /i m，於作爲塗覆有樹脂之金屬板使用的 情況，作爲對金屬板1 2的保護層的性能會變差。再者， 由於底材金屬板遮蔽能力低，印刷圖案會受到底材金屬 板的顔色之影響，故非良好。另一方面，厚度若超過5 0 0 18 312/發明說明書(補件)/92-04/92103116 1305515 M m，則作爲塗覆有樹脂之金屬板χ i之鑽孔加工等之二 次加工適性易於變差。 又，作爲本發明之基材樹脂層1 4的結晶性之控制方 法’亦有就擠壓鑄造時的鑄造溫度加以控制之方法。 基材樹脂層1 4與透明延伸聚酯系樹脂層1 6 (施有經 由所謂的逆向印刷之印刷層1 5者）的層合，可使用在經 由將預先製造方法的個別的片材中，所施有逆向印刷的 透明延伸聚醋系樹脂層16之施行逆向印刷的面設置接 著劑層1 7而進行層合的方法。作爲接著劑層1 7 ,係以 先前所述之接著劑稀釋於溶劑中，以塗佈裝置塗佈之 後，連續地導入乾燥爐中使溶劑揮發，然後，與另—方 的片材（薄膜）層合使其通過一對的輥之間，藉此進行加 熱、加壓而層合一體化。此方法，係作爲使用氯乙烯系 樹脂及聚烯烴系樹脂之塗覆有高鏡面性樹脂之金屬板的 製法中普遍所使用者。 經由上述的方法所層合一體化之層合一體化片材S， 將其層合於金屬板12上’可得到本發明之塗覆有樹脂 之金屬板11。作爲層合所用的接著劑層所使用的接 著劑，可舉出：環氧系接著劑層、胺基甲酸酯系接著劑、 聚酯系接著劑等。 於金屬板12上，使用逆輥塗佈機、接觸輥（kissrou) 塗佈機等之一般所使用的塗覆設備，以使層合一體化片 材S黏合的金屬面上之乾燥後的接著劑膜厚成爲2„10 A m程度的方式塗佈以上述接著劑。然後，用紅外線加 19 312/發明說明書(補件)/92-04/92 K)3116 l3〇S5l51305515 玉久, invention description [Technical Field] The present invention relates to the external decoration of home electric products such as AV equipment and air-conditioning casings, and the coating of steel interior furniture, interior installation of buildings, and interior installations of buildings. A resin metal plate and a method of manufacturing the same. Specifically, it is a resin-coated metal plate and its manufacture which is excellent in scratch resistance and workability, and has creative specular reflectivity and excellent boiling water resistance, and does not use a halogen-containing resin. Method. [Prior Art] Conventionally, as a resin-coated metal plate used for the above-mentioned use, a resin layer colored by adding a pigment is used as a base resin layer, and a printed layer is provided thereon, and then a transparent layer is provided thereon. The resin film is laminated and integrated, and is laminated on a steel plate. As the transparent resin film in the constitution, for example, a thickness of 1 〇 to 50 # m is used, for example, a polyethylene glycol copolymer film, a propylene vinegar copolymer film, and a biaxially oriented polyethylene terephthalate. (hereinafter referred to as biaxially stretched PET) resin film or the like. Among them, a biaxially stretched PET-based resin film excellent in various physical properties is preferable. Further, as the colored resin layer, a soft vinyl chloride resin layer is usually used. The reason for this is that the soft vinyl chloride resin can be arbitrarily set in flexibility by adding a plasticizer. Further, in the laminated structure of the transparent biaxially-oriented pET-based resin film, in addition to good workability, it has relatively good durability and chemical resistance based on long-term research on stabilizers. It is also excellent in heat resistance and hot water resistance, and is suitable for use in applications such as 6 312/invention manual (supplement)/92-04/92103116 1305515. Further, in the configuration in which the P E T -based resin film is biaxially stretched on the soft vinyl chloride resin, extremely excellent specular reflectivity can be obtained. That is, the pattern of the metal plate coated with the resin is less deformed and has a high degree of sharpness, and is also one of its characteristics. However, in recent years, problems caused by heavy metal compounds of stabilizers of vinyl chloride-based resins, problems due to V 0 C (volatile organic compound) of some plasticizers and stabilizers, and/or problems of endocrine disruption, and burning The problem of generating hydrogen chloride and other chlorine-containing gases and the like makes the use of vinyl chloride-based resins increasingly limited. Here, the soft vinyl chloride resin which is substituted with the colored resin layer having the above-described composition is mainly composed of a polyolefin resin such as polypropylene, and a styrene-based and/or copolymerized olefin-based resin. A soft component is obtained to obtain a property close to that of a soft vinyl chloride resin. In the above-described configuration, a structure in which a biaxially stretched PET-based resin film is laminated, and excellent specular reflectivity as in the case of using a soft vinyl chloride-based resin in the colored resin layer can be obtained. However, in the case where sufficient workability is to be imparted as a precoated steel sheet, the scratch resistance of the surface is inferior to that in the case of using a soft vinyl chloride resin. Further, when the scratch resistance is equivalent to that of a metal plate coated with a soft vinyl chloride resin, satisfactory workability cannot be obtained, which is a problem, and thus has not been widely available. On the other hand, since the polyolefin-based resin is essentially a material having poor adhesion, in the case where the printing idea is imparted to the biaxially stretched PET-based resin, it is necessary to perform more steps 312 than the soft vinyl chloride-based resin. /Inventive specification (supplement) /92-04/92103116 1305515 (for example, surface treatment steps such as corona treatment or primer coating) is the problem. Further, there are also doubts about the stability of the interface between the interface and the adhesive used in the subsequent use of the metal sheet. Therefore, as a material for solving such problems, the use of a vinegar-based resin as a resin layer of the above-described constitution color has been frequently sought. The metal plate coated with the resin can be both scratch-resistant and workable, and both of them have a higher level than the metal plate coated with the soft vinyl chloride resin, and can be coated with poly The problems in the metal sheets of the olefin resin are solved. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) However, when a polyester resin such as a photo-formable resin layer having no crystallinity is used as a colored resin layer, the glass transition temperature (Tg) is 1 〇. The 〇°c is low, making it impossible to satisfy the boiling water immersion test included in the evaluation item of the resin-coated metal sheet which is usually installed in the building. On the other hand, when a polyester resin having crystallinity such as polyethylene terephthalate or polybutylene terephthalate is used as the colored resin layer, since the melting point is high, it is comparatively high. When laminating a conventional vinyl chloride resin film or a polyolefin resin film, the temperature of the surface of the metal plate must be increased. Therefore, the existing laminating production line must be modified. Further, although the coating treatment is applied to the inner surface of the resin-coated metal sheet, the coating is conventionally used, and there is a problem in heat resistance. In this case, it must be changed to use a paint with high heat resistance' or the heating and coating of the steel plate before lamination of the 312/invention manual (supplement)/92-(M/921〇3116 1305515) The drying of the coating is carried out at the same time as the coating is applied after the lamination, and the drying is performed again. The heat resistance of the printed layer in the laminated sheet is also in the conventional layer. There is no problem at the temperature, but in the case of increasing the lamination temperature, the possibility of thermal discoloration, thermal fading, etc. is remarkably exhibited. In this case, it is necessary to change the type of the pigment of the printing ink and the type of the binder so that The heat resistance of the printed layer is improved. However, the improvement of such problems is related to the increase in the burden of the steel sheet laminates, which leads to an increase in cost, and is not welcomed. The present invention has been made in view of the above problems. An object of the present invention is to provide a metal plate coated with a resin which is excellent in specular reflectivity without using a soft vinyl chloride resin and which can be manufactured by a conventional laminating apparatus. It is based on the resin-coated metal sheet which provides excellent specular reflectivity and good processability and boiling water resistance. The third objective is to provide a method for manufacturing the same. The invention of the first object of the above-mentioned first object is a resin-coated metal plate which is composed of a base resin layer mainly composed of a polyester resin, a printing layer, and a transparent stretch polyester system. Resin layer 'l· ''ΐίί The laminated sheet formed by laminating and integrating in the above-mentioned order, and the side of the H-material resin layer side is used as the adhesion surface, and the adhesive layer is laminated on the metal plate. The polymer resin constituting the base resin layer is required to satisfy the following requirements: It is a differential scanning calorimeter (D) in a state of laminating the laminated sheet of the metal electrode. Se} 312 312/Invention Manual (Supplement)/92-04/92103116 1305515 The crystallized peak temperature (τ c ) and the crystal melting peak temperature (Tm) can be observed at the temperature rise to crystallize the heat. As ΔH c ( J / g ), crystal melting When the amount is Δ H m ( J / g ), the relationship of (ΔHm - AHc) < 30 is established. Here, "the polyester resin is used as the main component" is added to the polyester resin. As an additive, for example, a user which is usually used in a wide range of resin materials can be used. In the present invention, by setting (値 H m - Δ H c ) to less than 30, it is possible to limit Although the crystallinity of the base resin layer exhibits a crystal melting peak temperature (Tm), it is actually melted at a temperature lower than that of the base resin layer. Therefore, even if the above T m + 30 ° C is not reached When the surface temperature of the metal plate is laminated, it is pressed by the laminating roller while being in a molten state, and irregularities such as irregularities originating from the surface of the base resin layer and the metal plate can be eliminated, and high specular reflectivity can be obtained. . Further, since high softness is obtained at a temperature at the time of lamination of the soft vinyl chloride resin film, it can be efficiently produced by using an existing apparatus. Further, since printing inks, adhesives, and the like can be used in the case of vinyl chloride-based resins, the cost of the products can be reduced. In the invention described in the second aspect of the invention, the substrate resin layer of the invention of claim 1 contains polyparaphenylene as a component of the crystalline polyester resin. The butadiene dicarboxylate resin satisfies the crystallization heat Δ H c and the crystal heat of fusion Δ H m in a state of being laminated on the metal plate, and 15 lt Δ Η η and 5 lt (ΔΗτη-ΔΗο The relationship between at least one of :). In the present invention, in addition to excellent specular reflectivity, workability and boiling water resistance 10 312 / invention specification (supplement) / 92 - (Μ / 92103116 1305515 are also good. The invention described in claim 3, The base resin layer in the invention of the first aspect of the invention is a polytrimethylene terephthalate resin which is a crystalline polyester resin component, and is laminated in a state of being laminated on a metal plate. The relationship between the crystallization heat Δ H c and the crystal heat of fusion ΔΗπι is at least one of 15 < ΔΗιη or 5 < (Δ Hm - AHc). In addition to the excellent specular reflectivity In addition, in the invention of any one of claims 1 to 3, the transparent extended polyacetal resin layer is the same as the invention described in the fourth aspect of the invention. It is formed of a biaxially stretched polyethylene terephthalate film. According to the invention, transparency, smoothness, and surface-to-seal resistance can be easily ensured, and so-called reverse printing can be easily performed. } The invention of claim 5, wherein the invention of any one of claims 1 to 4 is an adhesive present between the substrate resin layer and the printed layer. In the present invention, the invention of the invention can be obtained by the invention of the invention, wherein the invention of any one of claims 1 to 5, wherein The base resin layer is composed of a colored polyester resin. In the invention, it is possible to provide shielding of the metal plate of the substrate, imparting creativity, and improving the color development of the printed layer. The invention described in the item 7 is a method of manufacturing a metal sheet coated with a tree 11 312 / invention specification (supplement) / 92-04/92103116 1305515, which is as claimed in claims 1 to 6 According to any one of the items, the base resin layer containing the polyester resin as a main component and the printed layer 'transparently stretched polyester resin layer are laminated and laminated in the same order as described above. , which is on the side of the substrate layer of the above-mentioned substrate tree When the surface is laminated as a bonding surface on the metal plate via the adhesive layer, the surface temperature T s of the metal plate is crystallized with the polyester resin constituting the substrate resin layer. The laminate is carried out in a state where the relationship between the peak temperatures T m ( c ) is established (T m + 3 〇) > T s. In the present invention, the above-mentioned resin-coated resin can be easily produced by a conventional laminating apparatus. The metal plate' can suppress thermal discoloration and thermal fading of the inner surface of the printed layer and the metal plate. [Embodiment] Hereinafter, an embodiment of the present invention will be described. As shown in Fig. 1(a), The metal plate H coated with the resin is laminated on one surface of the metal plate 12 via the adhesive layer 13 and the base resin layer 14 mainly composed of a polyester resin, on the base resin layer i 4 . Then, the printing layer 15 is laminated, and the transparent extending polyester resin layer 16 is further laminated thereon. That is, the resin-coated metal plate 11 is formed by sequentially laminating and integrating the base resin layer 14 having the polyester resin as a main component, the printing layer 15 and the transparent extending polyester resin layer 16. The laminated integrated sheet S which is a laminated sheet is formed by laminating the surface of the base resin layer 14 as a contact surface and laminating the adhesive layer 13 on the metal plate 12. Further, the resin-coated metal plate 11 shown in Fig. 1(b) is formed on the substrate in addition to the composition of Fig. 12 312 / invention specification (supplement) / 92-04 / 92103116 1305515 1 ( a ) An adhesive layer 17 is provided between the resin layer 14 and the printed layer 15. As the polyester resin constituting the base resin layer 14 , ethylene glycol, propylene glycol, butanediol, cyclohexane dimethanol or the like as an alcohol component and terephthalic acid as a dicarboxylic acid component can be used. A monomer or blend of any of the resins selected from the group consisting of formic acid or isophthalic acid. However, in the state of laminating the laminated sheet before the metal plate 12, a clear crystallization peak temperature (T c ) and a crystal melting peak can be observed at a temperature rise by a differential scanning calorimeter (DSC) measurement. When the temperature (Tm) is Δ H c ( J / g ) and the heat of crystal melting is Δ Hm (J/g), the relationship of the following formula is established: Δ Hm - Δ Hc < 30 (1 When the enthalpy of (ΔHm - Δ H c ) exceeds 30, the polyester resin has high crystallinity. Therefore, the surface temperature of the metal plate 12 at the time of lamination is generally not higher than the melting point Tm (°C) of the base resin layer 14 by 3 CTC or more, and the base resin layer 14 cannot be sufficiently Since it is melted, the unevenness originating from the surface of the base resin layer 14 does not disappear, and since the unevenness originating from the surface of the metal plate 12 remains, the high specularity cannot be obtained. The crystal melting peak temperature of the base resin layer 14 corresponds to the melting point. The reason why the surface temperature of the metal plate 12 must be higher than the melting point T m of the base resin layer 14 by more than 30 t is to prevent the following phenomenon. The thermal movement of the laminated metal sheet by the lamination from the heated metal sheet 12 to the laminated integrated sheet occurs, and the average temperature of the entire metal sheet 11 coated with the resin is lowered, and the substrate resin layer 14 is lowered. Crystal melting 13 312 / invention specification (supplement) /92-04/92103116 1305515 The heat is consumed, and the heat is squeezed by the laminating roller when it is pressed by the laminating roller whose temperature is lower than the metal plate 12 And so on. However, in this case, the surface temperature of the metal plate 1 2 at the time of lamination is generally higher than that in the case where the conventional vinyl chloride resin is used as the base resin layer 14 , and the foregoing "invention" is made. The various problems described in the topic to be solved are obvious. However, by making 値 of (Δ H m - Δ H c ) less than 30, the crystallinity of the base resin layer 14 can be restricted, and although the crystal melting peak temperature (Tm) is shown, it is actually lower than The temperature is melted. Therefore, even if the surface temperature of the metal plate 12 which is less than the above Tm + 30 °C is laminated, the pressure is increased by the laminating rolls while being in a molten state, whereby the irregularities derived from the above various causes can be eliminated. High specular reflectivity. In addition, the base resin layer 14 is a polybutylene terephthalate (PBT) resin or a polytrimethylene terephthalate (PTT) resin which is a crystalline polyester resin component. Further, when the requirements described later are satisfied, a resin-coated metal plate 11 excellent in boiling water resistance can be obtained. After lamination to the metal plate 12, a clear crystal melting peak temperature (Ττη), a crystallization heat ΔH c and a crystal melting heat ΔHm can be observed by DSC measurement. A relational expression satisfying at least one of the following formulas (2) and (3): 1 5 < Δ H m ( 2 ) 5 < (ΔΗτη - ΔΗο) (3) When the value is less than or equal to a predetermined number The base resin layer 14 has low crystallinity, and is similar to the case where the completely non-crystalline polyester resin is used as the base material 14 312 / invention specification (supplement) / 92-04 / 92103116 1305515 Those who are not resistant to boiling water will be restricted from using it as an interior building material. When at least the relationship of the formulae (2) and (3) can be established, the resin-coated metal sheet 1 1 having excellent boiling water resistance can be obtained, and the reason is as follows. In the case where the base resin layer of the formula (2) is larger than 15, the crystallization rate of the PBT resin or the PTT resin used as the crystalline resin component is relatively fast. At the same time, the proportion of the crystalline resin component in the blend composition of the base resin layer 14 is more than 13⁄4°, so that even after the lamination, even if it is almost in a non-crystalline state, it occurs immediately upon immersion in boiling water. Crystallization results in the crystallinity of the boiling water resistance test. In contrast, in the case where the formula (2) is not satisfied, the ratio of the crystalline resin component which is exhibited in the composition of the base resin layer 14 is low. Therefore, the crystallization rate of the mixture is slowed down. If the crystallization does not progress to a certain level or more after lamination, the boiling water resistance test cannot be withstood. In order to obtain a resin composition of the base resin layer 14 which satisfies the above formula (1), (2) or formulas (1) and (3), a so-called homogeneous polymerization pair in which an acid component and an alcohol component are single-components, respectively A butylene phthalate (ρΒΤ) resin or a homogeneous poly(trimethylene terephthalate) resin is used as a crystalline resin component. Further, it is preferable to adjust the desired physical properties by blending a copolymerized polyester resin which is amorphous or low in crystallinity. As a non-crystalline resin, the stability of the raw material supply and production capacity 312 / invention manual (supplement) / 92-04/92103116 15 1305515 to consider the cost reduction, to use Eastman Chemical Company's " It is better to use Ista 6 7 6 3" and its similar resin. However, it is not limited to this, and "PGTG·5445" of Eastman Chemical Co., which is generally used as a non-crystalline resin, which exhibits a melting point under special cooling conditions, can be used. In the case of using a resin having a high crystallization rate like homogeneous PBT or homogeneous PTT as a crystalline resin, a resin having a low crystallinity or a non-crystalline resin is blended to reduce the crystallization rate of the entire blend. A laminated integrated sheet S satisfying the formula (1) can also be obtained. Further, in the case of using such a crystalline resin, a resin-coated metal plate having good workability can be easily obtained, which is preferable. In the base resin layer 14, a pigment may be added for the purpose of shielding the metal plate 12 of the substrate, imparting creativity, and improving the color rendering property of the printed layer 15. The pigment to be used can be used for the resin coloring, and the amount of the pigment to be used can be used in the base resin layer I4 and the transparently stretched polyester resin layer 16 without damaging the amount of the above-mentioned purpose. To the extent that the object of the present invention is, an additive may be added in an appropriate amount. Examples of the additive include various antioxidants such as phosphorus-based, thermal stabilizers, ultraviolet absorbers, lubricants, metal deactivators, residual polymerization catalyst deactivators, nucleating agents, and antibacterial agents. A mold, a charge inhibitor, a fireproofing agent, a plumbing material, and the like are generally used in various resin materials. Further, it can be mentioned that the terminal carboxylic acid blocking agent, the hydrolysis preventing agent such as the carbonized one-limb system, the vinegar exchange inhibitor, etc. are specifically used in the 312/invention specification (supplement)/92-04/92103116 16 1305515 resin. Development of additives, etc. An adhesive layer 17 may be present between the substrate resin layer 14 and the printing layer 15 or between the printing layer 15 and the transparent extending polyester resin layer 16. As an adhesive for constituting the adhesive layer 17 , for example, a polyester-based resin or a polyether-based resin as a main component and an isocyanate-based crosslinking agent or the like can be used, which is generally referred to as a dry-lamination adhesive layer. By. Among the subsequent layers, the problem of yellowing due to ultraviolet rays is a slight consideration, and it is preferable to use an aliphatic one. In addition, in the case where a pigment having poor light stability is added to the base resin layer 14 or the like, it is necessary to control the amount of ultraviolet light permeating the base resin layer 14 or the like, and the adhesive layer 17 may not be damaged. Additives such as ultraviolet absorbers are appropriately blended to the extent of their properties. The printed layer 15 can be printed by gravure printing, lithography, screen printing, and other known methods. The pattern of the printed layer 15 may be any of stone, wood grain or geometric pattern, abstract pattern, etc., and may be full-printing or partial printing, or may be subjected to partial printing after partial printing. Usually, a method of performing reverse printing on the side of the lamination surface of the transparent stretch polyester resin layer 16 having good smoothness is used, but the base resin layer 14 may be surface-printed. The transparent stretch polyester resin layer 16 used in the present invention can be used for the same purpose as a metal plate coated with a soft vinyl chloride resin or a metal plate coated with a polyolefin resin (that is, printing) The protection of the layer, the deep creative and the improvement of various physical properties on the surface) are the same for the user. 17 312/Inventive Manual (Repair)/92-04/92103116 1305515 Among them, transparency, smoothness and scratch resistance of the surface are considered, in particular, the use of biaxially oriented polyethylene terephthalate film is good. In this embodiment, the transparent stretch polyester resin layer 16 is composed of a transparent biaxially stretched polyester resin film (transparent biaxially stretched p ET resin film). The film thickness can be 15 to 7 5 /Z. The degree of m, the heat-fixing temperature after the extension treatment is about 2 2 0 to 240 ° C, which is generally used for the above purposes. As the metal sheet to which the present invention is applied, a hot-rolled steel sheet or a cold-rolled steel sheet can be used. Various steel sheets and aluminum sheets such as hot-dip galvanized steel sheets, galvanized steel sheets, electrogalvanized steel sheets, tin-plated steel sheets, and stainless steel sheets can be used after performing a usual chemical conversion treatment. The thickness of the metal sheets 12 is fixed by resin. The use of the metal plate 1 1 varies, but it can be selected to be in the range of 〇. lmm to 10 mm. Next, a method of manufacturing the laminated integrated sheet S and the resin-coated metal plate 11 will be described. The film forming method of the laminated integrated sheet S of the present invention may be a known method, for example, a die casting method using a T-die, a blow molding method, or the like, and is not limited thereto, but is made of a sheet material. Membrane and stable productivity The amount is preferably a squeeze casting method using a T-die. The thickness of the laminated integrated sheet S is usually 50 to 500 #m. If the thickness of the sheet is less than 50 /im, it is coated with a resin. In the case of using a metal plate, the performance as a protective layer for the metal plate 12 is deteriorated. Furthermore, since the shielding property of the substrate metal plate is low, the printed pattern is affected by the color of the metal plate of the substrate, so it is not good. On the other hand, if the thickness exceeds 5 0 0 18 312 / invention specification (supplement) / 92-04 / 92103116 1305515 M m, it is secondary processing such as drilling of a resin-coated metal plate χ i Further, the method for controlling the crystallinity of the base resin layer 14 of the present invention is also a method for controlling the casting temperature at the time of extrusion casting. The base resin layer 14 and the transparent stretched polyester are used. The lamination of the resin layer 16 (which is applied via the so-called reverse printing printing layer 15) can be used in a transparent stretched polyester system in which reverse printing is applied via an individual sheet of a pre-manufacturing method. The surface of the resin layer 16 on which the reverse printing is applied is provided with the adhesive layer 17 a method of laminating. As the adhesive layer 17 , diluted with a binder as described above in a solvent, coated with a coating device, continuously introduced into a drying oven to volatilize the solvent, and then, with another The sheet (film) is laminated and passed between a pair of rolls, thereby heating and pressurizing and laminating and integrating. This method is applied as a coating using a vinyl chloride resin and a polyolefin resin. A user of a mirror-shaped resin metal plate is generally used by a user. The laminated integrated sheet S laminated and integrated by the above method is laminated on the metal plate 12 to obtain the coating of the present invention. The metal plate 11 of the resin. Examples of the adhesive used for the adhesive layer used for lamination include an epoxy-based adhesive layer, a urethane-based adhesive, and a polyester-based adhesive. On the metal plate 12, a coating apparatus generally used in a reverse roll coater, a kiss roll coater or the like is used to dry the metal surface on which the laminated integrated sheet S is bonded. The above-mentioned adhesive is applied in such a manner that the film thickness is 2 „10 Am. Then, infrared ray is added 19 312/invention specification (supplement)/92-04/92 K) 3116 l3 〇S5l5
熱 XL -rLHot XL -rL
及熱風加熱爐之中的至少一種進行塗佈面的乾燥及 力Q …於使金屬板1 2的表面溫度保持於既定的溫度之 B 寺， 乂即使用輥式層合機進行層合一體化片材s之被 _ ,、 輕由冷卻而得到塗覆有樹脂之金屬板1 1。 "ίϊ八 、以基材樹脂層1 4的結晶熔解波峰溫度作爲T m ( °C ) 的''f~| 1¾況’層合時的金屬板12之表面溫度TS(C)即使在 ("X1 m + 3 〇) (°c )以下’亦可得到高鏡面性外觀。惟’金屬 木友1。〜 2的表面溫度T S (。(：），若非爲（Tm _ ；L 〇 ) ( °C )程度以 貝IJ無法得到高鏡面性外觀。 其理由在於，雖說基材樹脂層1 4於結晶熔解波峰溫 度τ m以下即有熔融性，惟，於與熔點的溫度差顯著偏 低的|彳唆、 ^況則無法得到充分的平滑硬化。因而，於作爲基 曰層1 4的結晶性樹脂成分係使用均質_ p B T的情 'Τς- ’由於該樹脂的結晶熔解波峰溫度Tm爲2 2 5 t附 、’層合時的金屬板的表面溫度須作成爲2 ；L 5 °C以上、 2 S 5 r c以下。 粒由層合輥進行層合之塗覆有樹脂之金屬板11，可連 ^ ifb 5¾ ..And at least one of the hot air heating furnace performs drying and force Q of the coated surface to maintain the surface temperature of the metal plate 12 at a predetermined temperature, and the laminate is integrated using a roll laminator. The sheet s is _ , and the metal plate 11 coated with the resin is obtained by cooling. " ϊ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 "X1 m + 3 〇) (°c ) below ' can also get a high specular appearance. Only 'Metal Muyou 1. The surface temperature TS of ～ 2 (. (:), if not (Tm _ ; L 〇) ( ° C ), can not obtain a high specular appearance. The reason is that the substrate resin layer 14 is crystallized. When the peak temperature τ m is less than or equal to the melting point, the temperature difference between the melting point and the melting point is remarkably low, and sufficient smoothing and hardening cannot be obtained. Therefore, the crystalline resin component as the base layer 14 is not formed. The homogenization of _ p BT is used for 'Τς- ' because the crystal melting peak temperature Tm of the resin is 2 2 5 t attached, 'the surface temperature of the metal plate when laminating must be 2; L 5 ° C or more, 2 S 5 rc or less. The granules are laminated with a resin-coated metal plate 11 by laminating rolls, which can be connected to ^ ifb 53⁄4 ..
導入冷卻步驟。冷卻步驟須確保有較長的距離，雖 可ί审FR 用自然空氣冷卻或強制空氣冷卻，惟，就生產速度 鐵之情況，通常係使用水冷法。此情況，由於較之使 用結Ϊ3 曰曰化速度慢的PET系樹脂的摻合物組成來形成基材 @脂隐Import the cooling step. The cooling step must ensure a long distance. Although it can be cooled by natural air or forced air cooling, the water cooling method is usually used for the production of iron. In this case, the substrate is formed by the composition of the blend of the PET resin which is slower than the crucible.
14’以使用結晶速度較快的PBT系樹脂或：PTT 系梓f i 4 的摻合物組成來形成基材樹脂層1 4的一方，於 車父急速的冷卻條件下可滿足上述式（2丨、（1 )，故爲較佳。 20 1 ] 2/發明說明書(補件)/92-〇4沒21 〇1116 1305515 (實施例） 以下，藉由實施例及比較例更詳細地加以說明，惟， 本發明並非限定於此等之中。 [層合薄膜之製作] 以表1所示之組成（配合比例（重量％ ))用雙軸混練擠 壓機，製膜成厚度 8 0 // m的經著色之聚酯系樹脂片材 (基材樹脂層 1 4 )。顏料的添加量爲欽白粉及駄黃粉合 計爲2 4重量份（以樹脂成分的合計量作爲1 0 Q )，於全 部的實施例及比較例中皆爲相同。然後在作爲透明延伸 聚酯系樹脂層1 6的厚度2 5 # m的透明雙軸延伸P E T系 樹脂薄膜（三菱化學聚酯公司製）的一面經由凹板印刷 施行抽象圖案的局部印刷形成印刷層1 5。接著，在該印 刷面上以熱硬化性聚酯系接著劑塗佈形成接著劑層 1 7，再與基材樹脂層1 4疊合，使其通過一對的輥之間 而一體化，作成層合一體化片材S。透明雙軸延伸P E T 系樹脂薄膜的種類、印刷油墨及熱硬化性聚酯系接著劑 的種類及施予的條件等，於全部的實施例及比較例中皆 爲相同。 自層合一體化片材 S用切薄片機（microtome)將基 材樹脂層1 4予以切片，進行D S C測定，求出層合前的（△ Hm - △ H c )。此測定結果示如表2。至於同樣地記載於表 2中的熔點也是在此時所測定的値。 於表1中所記載之樹脂組成，具體而言，係使用下述 者： 21 312/發明說明書(補件)/92-04/92103116 1305515 • PBT:諾巴杜朗5020S (三菱工程塑膠公司製） .ΡΤΤ:科耳特拉CP509200(殼牌公司製）14' is formed by using a blend of a PBT-based resin having a relatively high crystallization rate or a blend of PTT-based fi 4 to form a base resin layer 14 which satisfies the above formula under rapid cooling conditions of the vehicle father (2丨) (1), it is preferable. 20 1 ] 2/Inventive specification (supplement) / 92 - 〇 4 no 21 〇 1116 1305515 (Examples) Hereinafter, the examples and comparative examples will be described in more detail. However, the present invention is not limited to these. [Production of laminated film] The composition shown in Table 1 (mixing ratio (% by weight)) was formed into a thickness of 8 0 by a biaxial kneading extruder. a colored polyester resin sheet (base material resin layer 14) of m. The amount of the pigment added is 24 parts by weight of the white powder and the eucalyptus powder (the total amount of the resin components is 1 0 Q), It is the same in all the examples and the comparative examples. Then, one side of a transparent biaxially stretched PET-based resin film (manufactured by Mitsubishi Chemical Polyester Co., Ltd.) having a thickness of 2 5 # m as the transparently extending polyester resin layer 16 is used. The partial printing of the abstract pattern is performed by gravure printing to form the printing layer 15. Next, on the printing surface The adhesive layer 17 is formed by coating with a thermosetting polyester-based adhesive, and then laminated on the base resin layer 14 to be integrated between a pair of rolls to form a laminated integrated sheet S. The type of the transparent biaxially stretched PET-based resin film, the type of the printing ink and the thermosetting polyester-based adhesive, and the conditions of application, etc. are the same in all of the examples and the comparative examples. The sheet S was sliced with a microtome, and the substrate resin layer 14 was sliced, and DSC measurement was performed to determine (ΔHm - ΔH c ) before lamination. The results of the measurement are shown in Table 2. As for the same The melting point described in Table 2 is also the enthalpy measured at this time. The resin composition described in Table 1 specifically uses the following: 21 312 / invention specification (supplement) / 92-04 / 92103116 1305515 • PBT: Noble Dulang 5020S (Mitsubishi Engineering Plastics Co., Ltd.) ΡΤΤ:Cortera CP509200 (made by Shell)
• CO-PET: BK-2180(三菱化學聚酯公司製），酸成分 爲7%之間苯二甲酸之共聚合PET • PETG:伊士達6763(伊士曼化學公司製），聚對苯 二甲酸乙二酯的乙二醇之一部份（約 3 0 ~ 6 0莫耳％ )以 1 , 4 -環己烷二甲醇取代之非結晶性聚酯系樹脂取代之 非結晶性聚酯系樹脂 .PCTG: PCTG5445(伊士曼化學公司製） [塗覆有樹脂之金屬板之製作] 接著，將通常之作爲塗覆有聚氯乙烯系樹脂之金屬板 使用之聚酯系接著劑，使乾燥後的接著劑膜厚爲2 ~ 4 μ m的方式塗佈於金屬面上形成接著劑層1 3。然後，以 熱風加熱爐及紅外線加熱器進行塗佈面的乾燥及加熱， 使鍍鋅鋼板（厚度 〇 . 4 5 m m )的表面溫度 T s ( °C )設定爲 表1中所示之溫度，再立即用輥式層合機進行層合一體 化片材S之被覆，經由噴水冷卻或自然空氣冷卻，製作 成塗覆有樹脂之金屬板1 1。接著劑的種類、塗佈條件， 係完全與實施例及比較例相同。又，層合時的金屬板表 面溫度及冷卻方法記述於表1。 再將塗覆有樹脂之金屬板1 1以稀鹽酸浸漬，使金屬 板1 2與層合一體化片材S分離之後，用切薄片機將基 材樹脂層1 4予以切片，進行D S C測定，求出層合後的 △ Hm及（ΔΗτη-ΔΗο)。將結果彙整如表2。 22 312/發明說明書(補件)/92-04/92103116 1305515 再對各塗覆有樹脂之金屬板11，就下述各項目進行評 價。結果示如表3。又，實施例及比較例中所示之塗覆 有樹脂之金屬板的物性之測定規格、試驗法係如下述： [結晶熔解波峰溫度T m及結晶熔解熱量△ H m ] 用巴金艾邇瑪公司製的 DSC-7，將試料 l〇mg依據 J I S - K 7 1 2 1「塑膠之轉位溫度測定方法-熔解溫度之求 出方法」’以加熱速度1 〇 °C /分測定求出。以1次昇溫 時的結晶熔解波峰頂部溫度作爲Tm。又，由其波峰面積 求出結晶熔解熱量△ Hm。 [結晶化波峰溫度T c及結晶化熱量△ η c ] 用巴金艾邇瑪公司製的DSC-·?，將試料10mg依據 J：E S - K7 ：L 2 H「塑膠之轉位溫度測定方法_結晶化溫度之 求出方法」’以加熱速度1 0 °C /分測定求出。以1次昇 溫時的結晶熔解波峰頂部溫度作爲T c。又，由其波峰面 積求出結晶化熱量△ H c。 [鮮豔度光澤度値（Gd値）] 用財團法人日本色彩硏究所開發的< pGD>手提式鮮豔 度光澤度計PGDIV，經由同法人所訂定的測定法，就實 施例及比較例的各塗覆有樹脂之金屬板的鏡面反射性進 行測定，以之爲高鏡面性的判定基準。測定係於同一樣 品中的5個位置進行，以其平均値作爲鮮豔度光澤度値 (G d値）。將G d値爲0 · 9以上的情況以（〇）表示， 〇 · 8 ~ 0 · 9未滿的情況以（△)表示，未滿〇 · 8的情況以 (X )表示。 312/發明說明書(補件)/92-〇4/92103116 1305515 [耐沸水性試驗] 對 60mmx60mm 的塗覆有樹脂之金屬板，用 J I ε - K 7 1 2 1中所規定的艾里克森試驗裝置，於樹月旨被覆 側擠出作成6 m m之凸起之後，在沸水中浸漬3小時，就 該樹脂片材的表面狀態以目視進行判定。完全沒有變化 者以（〇）表示，於表面產生若干粗糙者以（△)表示，於 樹脂層發生顯著的隆起等的變形者以（X )表示。 [加工性] 對塗覆有樹脂之金屬板進行衝擊密著屈曲試驗，就屈 曲加工部分的化妝板（層合一體化片材S )的面狀態以目 視判定，完全沒有變化者以（〇）表示，產生若干裂紋者 以（△)表示，發生裂開者以（X )表示。又，衝擊密著試 驗係如下述般進行。由塗覆有樹脂之金屬板的長的方向 及寬的方向分別製作5 0 m m X 1 5 0 m m的試料，於2 3 °C下 保持1小時以上之後，用屈曲試驗機進行1 8 0 ° (內屈曲 半徑爲2mm)的屈曲，對該試料以直徑75mm、質量5kg 的圓柱形的錘，自5 0 c m的高度落下衝擊。 24 312/發明說明書(補件)/92-(M/92103116• CO-PET: BK-2180 (manufactured by Mitsubishi Chemical Polyester Co., Ltd.), copolymerized PET with an acid content of 7% of phthalic acid • PETG: Eaststar 6763 (manufactured by Eastman Chemical Co., Ltd.), polyparaphenylene A non-crystalline polyester substituted with a non-crystalline polyester resin substituted with 1,4-cyclohexanedimethanol in one part of ethylene glycol dicarboxylate (about 30 to 60 mol%) Resin. PCTG: PCTG5445 (manufactured by Eastman Chemical Co., Ltd.) [Production of resin-coated metal plate] Next, a polyester-based adhesive which is usually used as a metal plate coated with a polyvinyl chloride resin, The adhesive layer 13 is formed by applying a film thickness after drying to a thickness of 2 to 4 μm on the metal surface. Then, the coated surface was dried and heated by a hot air heating furnace and an infrared heater, and the surface temperature T s ( ° C ) of the galvanized steel sheet (thickness 〇 45 mm) was set to the temperature shown in Table 1. Immediately after the coating of the laminated integrated sheet S by a roll laminator, the resin-coated metal sheet 11 was produced by water spray cooling or natural air cooling. The type and coating conditions of the subsequent agent were completely the same as in the examples and comparative examples. Further, the surface temperature and cooling method of the metal sheet at the time of lamination are described in Table 1. Further, the resin-coated metal plate 11 is immersed in dilute hydrochloric acid to separate the metal plate 12 from the laminated integrated sheet S, and then the substrate resin layer 14 is sliced by a slitter to perform DSC measurement. The ΔHm and (ΔΗτη-ΔΗο) after lamination were determined. The results are summarized in Table 2. 22 312/Invention Manual (Repair)/92-04/92103116 1305515 Each of the resin-coated metal sheets 11 was evaluated for each of the following items. The results are shown in Table 3. Further, the measurement specifications and test methods of the physical properties of the resin-coated metal sheets shown in the examples and the comparative examples are as follows: [crystal melting peak temperature T m and crystal melting heat ΔH m ] with Ba Jin Ai Ma In the DSC-7 manufactured by the company, the sample l〇mg was determined by measuring JIS-K 7 1 2 1 "Method for measuring the index of plastic transfer temperature - Method for determining the melting temperature" at a heating rate of 1 〇 ° C / min. The temperature at the top of the crystal melting peak at the time of one temperature rise was taken as Tm. Further, the crystal melting heat Δ Hm is obtained from the peak area. [Crystalization peak temperature T c and crystallization heat Δ η c ] Using DSC-·? manufactured by Bajin Aimar Co., Ltd., 10 mg of the sample according to J:ES - K7 : L 2 H "Method for measuring the indexing temperature of plastic _ The method for determining the crystallization temperature "" was measured at a heating rate of 10 ° C / min. The temperature at the top of the crystal melting peak at the time of one temperature rise was taken as T c . Further, the crystallization heat Δ H c is obtained from the peak area. [Vibrantness Glossiness 値 (Gd値)] The <pGD> portable vividness gloss meter PGDIV developed by the Japan Color Research Institute was developed by the same method as the legal person, and the examples and comparative examples were used. The specular reflectivity of each of the resin-coated metal plates was measured to determine the high specularity. The measurement was carried out at five locations in the same product, and the average enthalpy was used as the vividness gloss 値 (G d 値). The case where G d 値 is 0·9 or more is represented by (〇), the case where 〇 · 8 ～ 0 · 9 is not full is represented by (Δ), and the case of less than 〇 · 8 is represented by (X). 312/Invention Manual (Repair)/92-〇4/92103116 1305515 [Boiling Water Resistance Test] For 60 mm x 60 mm resin-coated metal sheets, use Erikson as specified in JI ε - K 7 1 2 1 The test apparatus was extruded on a side of the tree to form a 6 mm projection, and then immersed in boiling water for 3 hours, and the surface state of the resin sheet was visually judged. In the case where there is no change at all, it is indicated by (〇) that a certain roughness is generated on the surface by (Δ), and a deformation such as a significant bulging in the resin layer is represented by (X). [Processability] The impact-buckling test was performed on the resin-coated metal sheet, and the surface state of the cosmetic sheet (laminated integrated sheet S) in the buckling portion was visually judged, and there was no change at all (〇). It is indicated that the occurrence of a number of cracks is represented by (Δ), and the occurrence of cracking is represented by (X). Further, the impact test system was carried out as follows. A sample of 50 mm X 150 mm was prepared from the long direction and the width direction of the resin-coated metal plate, and maintained at 23 ° C for 1 hour or more, and then subjected to a flex tester for 1 80 °. The buckling (inner buckling radius of 2 mm) was impacted by a cylindrical hammer having a diameter of 75 mm and a mass of 5 kg from the height of 50 cm. 24 312/Invention Manual (supplement)/92-(M/92103116