200526405 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於抗腐蝕性能優異的經樹脂塗覆的金屬板 ，其較佳可用於家用電器、建築材料等，本發明且關於製 造彼之方法。 【先前技術】 習知除了鋁板和不銹鋼板之外，表面處理鋼板如電鍍 鋅鋼板和熱浸鍍鋅鋼板作爲可用於家用電器和建材的金屬 板材具有廣泛用途。其中，習知係使鍍鋅型表面處理鋼板 經過鉻化處理或磷化處理，並廣泛用於聲學儀器的各種結 構部件、電腦部件和微波爐的底板，包括大多數的家用電 子設備。然而，近年來，用戶對這些表面處理鋼板的要求 越來越高，導致對各種薄膜性能的需求。 例如，當表面處理鋼板以裸露形式使用時，需要它們 具有抗腐蝕性能、接地性能、抗指紋性能，這樣即使在與 其接觸的情況下，指紋也不那麼明顯，抗化學性、抗污染 性等，對鹼、溶劑等的耐受性。然而，當鋼板是壓制成型 或沖裁時，需要它們具有潤滑性、抗裂紋性能、可拉拔性 、抗模具磨損性能、可衝壓性、抗成型滑動面黑化性能和 對衝壓油/快乾油的耐油性能等。 爲了滿足對性能的這些要求，例如日本公開專利公報 No.6_246229揭示一種有機複合材料塗覆的鋼板，其包括 在鉻化層上的樹脂膜，其中烯屬離聚物中60- 80%的羧基 200526405 (2) 係經鈉離子予以中和。然而，日本專利N 0 ·2 7 5 9 6 2 0則揭 示一種經樹脂塗覆的金屬板，包括由一種組合物在金屬板 表面上所形成的薄膜’該組合物含有分子間經由離子簇締 合的聚烯烴共聚物樹脂乳液和帶有吖丙啶基的有機化合物 。日本專利No.275 9620述及金屬板較佳經鉻化之後的效 果。 然而，近年來，由於爲了保護地球環境而朝向不含鉻 φ (非鉻化）產品的發展等原因，需要樹脂膜比以往具有更 高的抗腐蝕性能。 如上所述，每一種要堆疊在不含鉻金屬板上的樹脂膜 也開始需要具有與塗覆在鉻化金屬板上的每一種樹脂膜相 同水準的抗腐蝕性能。在這樣的情況下，即使在申請曰本 專利No. 27 5 962 0後，本發明人仍進行了持續的硏究。曰 本專利No.27 5 9620中描述的樹脂膜對不含鉻板材也顯示 出某種優異的抗腐蝕性能。然而，例如在脫脂步驟中除去 φ 壓制成型過程中施用的潤滑油以後，由於用鹼處理使樹脂 膜不利地發生降解，造成了抗腐蝕性能的下降。然而，在 不含鉻金屬板上塗覆樹脂膜，然後，在樹脂膜表面上貼上 膠帶並使之保持長時間。然後，將該膠帶剝離，其甚至使 樹脂膜也被剝離下來。因而，存在此一欠缺膠帶剝離抗性 (金屬板和樹脂膜之間的黏附力）的問題。 【發明內容】 因此’在這樣的情況下，本發明的目的是提供一種經 -6 - 200526405 (3) 樹脂塗覆的金屬板，其在各方面均具有優異性能的樹脂膜 ，如：可塗覆性（薄膜在樹脂塗覆金屬板上的黏附能力） 、潤滑性、易成型性和接地性等所給定的性能，而且在脫 脂步驟後優異的抗腐鈾性能和膠帶剝離抗性。 本發明的一個實施型態在於一種經樹脂塗覆的金屬板 ，其包括：金屬板；和塗覆在金屬板表面上的樹脂膜，該 樹脂膜係得自一乳液組合物，其中該乳液組合物包括：作 p 爲主要組分的乙烯/不飽和羧酸共聚物；相對於每莫耳在 乙烯/不飽和羧酸共聚物中所含的羧基其量爲0.2-0.8莫耳 的胺，該胺的沸點爲l〇〇°C或更低；相對於每莫耳乙烯/不 飽和羧酸共聚物中所含的羧基其量爲0.02-0.4莫耳的一價 金屬化合物；以及其量爲1-20質量％/100質量％乳液組合 物固含量的交聯劑，該交聯劑具有二個或更多個能夠與乙 烯/不飽和羧酸共聚物中所含的羧基相反應的官能基，且 其中該乳液組合物實質上不含沸點高於1 〇〇 °C的胺，且實 φ 質上不含氨。 根據該實施型態，在乙烯/不飽和羧酸共聚物中，較 佳有10-40質量％的不飽和羧酸經共聚合，最佳有15-25 質量％的不飽和羧酸經共聚合。具有100°C或更低的沸點 的胺爲三乙胺亦係爲本發明的較佳實施方案之一。 根據該實施型態，較佳在每1 00質量％的乳液組合物 固體含量中，含有量爲5-40質量％的平均粒徑爲1-2 0〇nm 的二氧化矽顆粒。另較佳的是含有0.5-20質量％的球形聚 乙烯蠟。如此形成了具有各種性能的樹脂膜，:可塗覆 200526405 (4) 性、潤滑性、易成型性和接地性能，而且，該樹脂膜在脫 脂步驟後還具有優異的抗腐蝕性能和膠帶剝離抗性。順帶 提及的是，即使在未形成鉻化膜的情況下，本發明的樹脂 塗覆金屬板也顯示出了優異的抗腐蝕性能。 根據本發明的這一實施型態，在樹脂塗覆金屬板中， 藉由組合使用特定量的沸點爲1 00 °c或更低的胺和金屬化 合物，將乙烯/不飽和羧酸共聚物中和，形成了一種乳液 。因此，可以獲得具有極小粒徑的乳液組合物。因此，可 以獲得經塗覆具有各種優異性能的薄膜的樹脂塗覆金屬板 ，如：可塗覆性、潤滑性、易成型性和接地性能，以及在 脫脂步驟後優異的抗腐蝕性能和膠帶剝離抗性。 本發明的另一個實施型態在於一種製造樹脂塗覆金屬 板的方法，其包括以下步驟：製備乳液組合物；在金屬板 上塗覆該乳液組合物；將該塗覆了乳液組合物的金屬板予 以加熱並乾燥。 【實施方式】 本發明的經樹脂塗覆的金屬板包括由特定的乳液組合 物在金屬板的至少一側上所形成的樹脂膜。對於金屬板則 沒有特別的限制。例如，可以提到的是鍍鋅或鋅系的鋼板 、鋁板、鋁系合金板或鈦板。而且，使金屬板經過已知的 防銹表面處理如磷化處理或其他表面處理，以及在其上形 成樹脂膜也是可以接受的。從環境問題的觀點看，較佳該 板材不經過鉻化處理。 -8- 200526405 (5) 用於在本發明中形成樹脂膜的乳液組合物含有作爲主 要組分的乙烯/不飽和羧酸共聚物（包括中和狀態）’相 對於每莫耳乙烯/不飽和羧酸共聚物中所含的羧基，其量 爲0.2-0.8莫耳（ 20-80莫耳％)而沸點爲100°C或更低的 胺，相對於每莫耳乙烯/不飽和羧酸共聚物中所含的羧基 ，其量爲0.02-0.4莫耳（2-40莫耳％)的一價金屬化合物 ，還有其量爲0.5-20質量％/1 00質量％乳液組合物固含量 p 的交聯劑，該交聯劑具有二個或更多個能夠與羧基反應的 官能基，且該組合物基本不含沸點高於1 〇〇 °C的胺和氨。 所述之乙烯/不飽和羧酸共聚物係爲乙烯和烯系不飽 和羧酸的共聚物。作爲不飽和羧酸，可以提到的是（甲基 )丙烯酸、巴豆酸、異巴豆酸、馬來酸、富馬酸、衣康酸 等。藉由已知的高溫高壓聚合法等方式聚合彼等其中的一 或多種與乙烯，可以獲得所述共聚物。該共聚物最佳是無 規共聚物。然而，其也可以是嵌段共聚物或者是在不飽和 φ 羧酸部分處接枝的共聚物。順帶提及的是，該不飽和羧酸 較佳是（甲基）丙烯酸。而且，也可以採用烯屬單體如丙 烯或1 - 丁烯來代替一部分乙烯。進而，也可以部分地共聚 其他已知的乙烯基類型的單體（量爲約1 0質量％或更低） ，只要不損害本發明的目的即可。 對於不飽和羧酸與乙烯的共聚比，當將單體總量視爲 100質量％時，不飽和羧酸的量較佳爲10-40質量％。當不 飽和羧酸的量低於1 〇質量％，供作爲經離子簇而分子間締 合的基點或交聯劑的交聯點的羧基的量太小。因此，不利 -9 - 200526405 (6) 的是，無法發揮膜強度效果，以至於膠帶剝離抗性和脫脂 步驟後的抗腐蝕性能會不充分。此外’乳液組合物的乳化 穩定性亦差。不飽和羧酸量的更佳下限是1 5質量％。另一 方面，當不飽和羧酸的量超過40質量％時’樹脂膜的抗腐 蝕性能和耐水性能差。因此，不利的是，脫脂步驟後的抗 腐飩性能同樣會降低。更佳的上限是25質量％。 所述之乙烯/不飽和羧酸共聚物具有羧基。因此，可 以用有機鹼或金屬離子將其中和，由此製成乳液（製成水 分散體）。在本發明中，係使用沸點爲l〇〇°C或更低的胺 作爲有機鹼。沸點高於1 〇 〇 °c的胺在樹脂塗覆膜乾燥時容 易保留在鋼板上，造成樹脂塗覆膜吸水性能提高，如此則 這造成抗腐蝕性能的下降。爲此，不要使供形成本發明薄 膜所用的乳液組合物中含有沸點高於1 〇〇°c的胺。而且， 也不要含有氨，因爲尙未觀測到氨的添加效果。作爲沸點 者，所採用的是大氣壓下的沸點。 沸點爲1 〇〇 °c或更低的胺的具體實例包括：三級胺如 三乙胺、N，N-二甲基丁胺、N，N-二甲基烯丙基胺、N-甲基吡咯烷酮、四甲基二氨基甲烷和三甲胺；二級胺如 N -甲基乙基胺、一異丙基胺和二乙胺；和一級胺如丙胺、 三級丁胺、二級丁胺、異丁胺、1,2 -二丁基丙基胺和3 -戊 基胺。彼等可以單獨使用或以二或更多種的混合物形式供 使用。其中，較佳者爲三級胺，最佳爲三乙胺。 將沸點爲1 〇〇°C或更低的胺的用量相對於每莫耳乙烯/ 不飽和羧酸共聚物中的羧基，乃設定爲0.2-0.8莫耳（20- -10- 200526405 (7) 8 0莫耳％ )。這是因爲，該範圍內的量會導致良好的 蝕性能和膠帶剝離抗性。當沸點爲100°c或更低的胺 小於0.2 m ο 1時，乳液中樹脂顆粒的粒徑較大。爲此 以想見，其並不能發揮前述的效果。然而，當沸點爲 °C或更低的胺的用量大於0.8 mol時，乳液組合物會 地發生黏度升高和膠凝。胺的量較佳上限爲〇.6mol， 爲0.5mol。胺的量較佳下限爲0.3mol。 在本發明中，亦將一價金屬離子用於中和。此可 改進耐溶劑性能和薄膜硬度。因此，乃在乳液組合物 入一價金屬化合物。所述一價金屬化合物較佳含有一 或更多種選自鈉、鉀和鋰的金屬。較佳爲這些金屬的 化物、碳氧化物或氧化物。其中，較佳者爲NaOH、 、：LiOH等，最佳者爲NaOH，因爲其具有最佳性能。 ，關於二或更高價的金屬化合物而言，並未觀測到添 等所產生的效果。因此，用於本發明中供形成膜的乳 合物並不含有二或更高價的金屬化合物作爲乙烯/不 羧酸共聚物的反應對象。 一價金屬化合物的用量相對於每莫耳乙烯/不飽 酸共聚物中的羧基係設定在0.02-0.4莫耳（2-40莫耳 。當該金屬化合物的量低於〇.〇2mol時，乳化穩定性 不足。然而，當該量超過〇.4m〇l時，得到的樹脂膜 濕性能（特別是對鹼性溶液）提高，不利地造成脫脂 後的抗腐触性能變差。該金屬化合物的量較佳下 0.03mol。進一步更佳的下限是 O.lmol。該金屬化合 抗腐 的量 ，可 100 不利 更佳 有效 中加 或二 氫氧 KOH 再者 加彼 液組 飽和 和羧 ：% ) 變得 的吸 步驟 限是 物的 11 - 200526405 (8) 量較佳上限是0.5mol，進一步更佳的上限是〇.2m()l。 分別使用較佳在上述範圍用量的沸點爲1 〇〇 °C或更低 的胺和一價金屬化合物。該二者均用於供中和乙烯/不飽 和羧酸共聚物中的羧基並乳化共聚物。因此，當其總量（ 中和量）太大時，不利的是，乳液組合物的黏度迅速提高 並固化，另外，過量的鹼組分造成抗腐蝕性變差。而且， 需要大量的能量來使過量的鹼組分揮發。然而，當中和量 g 太小時，不利的是，可乳化性也會不利地變差。因此，沸 點爲1 〇〇 °C或更低的胺和一價金屬化合物的總量相對於每 莫耳乙烯/不飽和羧酸共聚物中的羧基較佳設定在0.3-1 ·0 莫耳。 本發明所用的乳液組合物係藉由組合使用沸點爲1 00 °C或更低的胺和一價金屬化合物來進行乳化而形成。結果 ’組合物中的樹脂顆粒以尺寸爲5〜5 Onm的極細小的顆粒 (油滴）形式穩定地存在於含水介質中。咸信如此乃實現 • 所獲得樹脂膜的成膜性能、對金屬板的黏附力和薄膜的緻 密化，獲得了對抗腐蝕性能和膠帶剝離抗性的改進。所述 含水介質在水以外可以含有親水性溶劑如醇或醚。順帶提 及的是，乳液中的樹脂顆粒粒徑可以通過例如採用光散射 光度計（OTSUKA ELECTRONICS Co.，Ltd.製造）的鐳射繞 射法來測量。 在使用沸點爲1 〇〇 °C或更低的胺和一價單屬化合物來 進行的乙烯/不飽和羧酸共聚物的中和步驟（乳化步驟） 中，有利地係將沸點爲1 〇(TC或更低的胺和該一價金屬化 -12- 200526405 (9) 合物幾乎同時地加至共聚物中，或者係先加入沸點爲1 00 °C或更低的胺。這是因爲後加入沸點爲1 00 °c或更低的胺 會造成抗腐蝕性能/膠帶剝離抗性改進效果不足，儘管其 原因並不明。 該羧基被沸點爲100°c或更低的胺和一價金屬化合物 所中和的乙烯/不飽和羧酸共聚物係經由離子簇而形成分 子間締合（轉化爲離聚物），以形成抗腐鈾性能/膠帶剝 Φ 離抗性優異的樹脂膜。然而，爲形成更強固的薄膜，乃樂 見聚合物鏈利用官能基間的反應經由化學鍵彼此交聯。在 這樣的情況下，本發明的乳液組合物乃含有交聯劑作爲必 要組分，該交聯劑具有二或更多能夠與羧基反應的官能基 。其用量設定在1-20質量％/1 00質量％的乳液組合物固含 量。當該量低於1質量％時，通過化學鍵交聯的效果變得 不足，因此，比較不容易發揮對抗腐蝕性能/膠帶剝離抗 性的改進效果。另一方面，當以大於20質量％的量混入交 φ 聯劑時，樹脂膜的交聯密度過度增加’造成硬度的提高。 因此，樹脂膜變得不能順利地在壓制成型時變形，此則導 致裂紋的形成。結果’抗腐蝕性能和可塗覆性被不利地降 低了。更佳的交聯劑用量是5·10質量％/100質量％乳液組 合物的固體含量。順帶提及的是’對於交聯劑的量與乙烯 /不飽和羧酸共聚物的量的比率’有利地係根據共聚物中 羧基的量適當地改變該交聯劑的量。通常’交聯劑的量較 佳爲0.5-50質量份（更佳爲5-20質量份）/100質量份共 聚物。 -13- 200526405 (10) 關於每個分子具有二個或更多個能夠與羧基反應的官 能基的交聯劑並沒有特別的限制。然而，其較佳的實例可 以包括：含縮水甘油基的交聯劑，包括多縮水甘油基醚如 山梨糖醇多縮水甘油基醚、（聚）甘油多縮水甘油基醚、 異戊四醇多縮水甘油基醚、三羥甲基丙烷多縮水甘油基醚 、新戊二醇二縮水甘油基醚和（聚）乙二醇二縮水甘油基 醚，和多縮水甘油基胺；二官能吖丙啶化合物如4，4 ’ -雙 (環乙亞胺羰基氨基）二苯基甲烷、N，N，-六亞甲基-1，6-雙（1-吖丙啶羧基醯胺）、N，N’ -二苯基甲烷- 4,4，雙（ 1 -吖丙啶羧基醯胺）和甲苯雙吖丙啶羧基醯胺；和含吖丙 啶基的交聯劑，包括三或更多官能的吖丙啶化合物，如 三-1 -吖丙啶基氧化膦、三[1 - ( 2 _甲基）吖丙啶基]氧化膦 、三羥甲基丙烷三（Θ -吖丙啶基丙酸酯）、三-2,4,6- ( 1-吖丙啶基）-1，3，5 -三嗪和四甲基丙烷四吖丙啶基丙酸酯， 或其衍生物。它們可以單獨使用，或組合兩種或多種使用 。其中，較佳者係爲含吖丙啶基的交聯劑。順帶提及的是 ’可以組合使用多官能吖丙啶類和單官能吖丙啶類（如環 乙亞胺）。 供本發明所用的乳液組合物可以含有5-40質量％的二 氧化矽顆粒，其係基於固體含量計。其可有效改進抗腐鈾 性能、可塗覆性、抗裂紋性能等，並有效於改進脫脂後抗 腐餓性能和膠帶剝離抗性。當其量低於5質量％，則較不 容易產生這些效果。然而，當該量超過40質量％時，二氧 化矽顆粒的比例過度增加，造成成膜性能的降低。因此， -14- 200526405 (11) 在乾燥步驟中樹脂膜中會發生裂紋，不利地造成抗腐鈾性 能的降低。再者，該二氧化矽顆粒成爲磨光劑，其提高了 薄膜的潤滑性，導致磨擦係數的下降。此造成成型過程中 對模具的磨損，縮短了模具的壽命。該二氧化矽顆粒量的 更佳下限爲20質量％，其上限則爲3 0質量％。 爲了使二氧化矽顆粒的上述效果最大化，二氧化矽顆 粒的平均粒徑較佳爲1-2 OOnm。隨著二氧化矽顆粒粒徑的 g 下降，薄膜的抗腐蝕性能得到改進。其可以想見的是由於 以下事實。樹脂膜被緻密化，黏附力改進，這進一步提高 了抗腐鈾性能。根據此一觀點，二氧化矽顆粒較佳具有更 小的粒徑。然而，當它們是極細小的顆粒時，前述效果達 到飽和狀態。爲此，粒徑的下限較佳爲1 nm。另一方面， 當二氧化矽顆粒粒徑超過200nm時，樹脂膜表面被粗糙化 。因此，就不可能形成緻密的樹脂膜。而且，二氧化矽顆 粒還成爲磨光劑，而不利地導致了易成型性的劣化。特別 φ 地，當強調其脫脂後的抗腐蝕性能時，二氧化矽顆粒的平 均粒度較佳設定爲4-20nm。 此等二氧化矽顆粒通常習知爲膠體二氧化矽。在本發 明中，較佳可以採用例如’’Snow Tex系列”（Nissan Chemical Industries，Ltd.生產的膠體二氧化矽）的”XS”、 ”ss”、”4〇”、”N”、”UP”及此類等。 在本發明的乳液組合物中，可以含有0.5-20質量％的 蠟，其係基於固體含量計。該蠟係具有改進所得之樹脂膜 的潤滑性和抗裂紋性能的效果。而且，較佳係將其用於改 -15- 200526405 (12) 進壓制成型和沖裁所需的可拉拔性和可衝壓性、抗模具磨 損性能和成型中抗滑動面黑化性能並提供優異的易成型性 〇 當蠟的量基於固體含量計低於〇·5質量％時，所形成 的樹脂膜的潤滑性變得不足。因此，就無法改進抗裂紋性 和獲得令人滿意的易成型性。另一方面，當該量超過20 質量％時，所形成的樹脂膜具有充分的潤滑性，但是當使 其經過電沉積、粉末塗覆或絲網印刷的後塗覆時，其膜的 黏附性（可塗覆性）較差。而且，脫脂後的抗腐蝕性能和 膠帶剝離抗性能也變差了。其可理解地係由於以下的事實 。蠟會在後塗覆步驟中經由加熱而軟化/液化或起霜，或 者隨時間發生變化，而濃集在樹脂膜和後塗覆膜之間的介 面處或在金屬板和樹脂膜之間的介面處。因此，與後塗覆 膜的黏附力或與金屬板的黏附力變差了。更佳的上限値是 1 〇質量％，甚至更佳的上限値是5.0質量％。 關於該蠟並沒有特別的限制，可用的蠟是天然蠟和合 成蠟及其混合物等。可使用的天然蠟實例包括巴西棕櫚蠟 、米蠟、小燭樹蠟和褐煤型蠟，及其衍生物，礦物油型蠟 、微晶蠟、石蠟等，以及藉由加入羧基所得的衍生物。 作爲合成躐者，可以提到的是聚乙烯、聚環氧乙烷、 聚丙烯、乙烯/丙烯共聚物型蠟和乙烯與其他單體的共聚 物蠘的氧化蠘。作爲此系統者，可以根據共聚反應對象的 變化，而廣泛採用還包括三元共聚物類型的多種類型。又 再者，可以提及的是馬來酸加合物蠘、脂肪酸酯型等。另 - 16- 200526405 (13) ，亦可使用含氟樹脂型鱲如聚四氟乙烯、聚氟乙烯、聚偏 作爲蠟者，較佳從以上所例示中選出軟化點爲80-140 t者。當軟化點低於8(TC時，在壓制成型或沖裁時，蠟顆 粒隨著模具溫度的升高而軟化/液化。因此，在樹脂塗覆 鋼板和模具之間的滑動面處，會發生液化蠟的液體耗盡現 象，造成可成型性能的下降，如此不利地造成擦痕和咬模 n 。而且，在滑動部分上會黏著黑化物質，而嚴重破壞產品 的外觀。再者，又從脫脂步驟後的抗腐蝕性能和膠帶剝離 抗性能的觀點來看，其亦顯示過低的軟化點是不佳的。另 一方面，當軟化點超過140 °C時，蠟產生的潤滑性變得不 足，因此可衝壓性、抗模具磨損性、可拉拔性或此類等， 無法獲得改良。脫脂後的抗腐蝕性能也表現出輕度下降的 趨勢。 該蠟最佳者爲球形的聚乙烯蠟。在此情況下，爲了使 φ 球形聚乙烯蠟的效果最大化，蠟顆粒的粒徑較佳爲〇. 1 -3 // m。當蠟顆粒的粒徑小於0.1 // m時，其難以顯著改進潤 滑性、可衝壓性、抗模具磨損性和可拉拔性能。另一方面 ，當蠟顆粒的粒徑超過3 // m時，其難以以細小顆粒的形 式將蠟顆粒均勻地分散到乳液組合物中。這可能會降低樹 脂膜對金屬板的黏附力。更佳的球形聚乙烯躐的粒徑爲 0 · 3 -1 · 0 // m。 作爲前述的球形聚乙烯蠟者，可以採用例如商購產品 如” DAIJET E-17”（ GOO Chemical Co.，Ltd·所生產）、 -17- 200526405 (14) ，’KUE-1” 、 ”KUE-5n 和 ’’KUE-8” ( Sanyo Chemical200526405 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a resin-coated metal plate with excellent corrosion resistance, which can be preferably used for household appliances, building materials, etc. The present invention also relates to manufacturing other Method. [Prior art] In addition to aluminum plates and stainless steel plates, it is known that surface-treated steel plates such as galvanized steel plates and hot-dip galvanized steel plates have a wide range of uses as metal plates that can be used for home appliances and building materials. Among them, it is known that the galvanized surface-treated steel sheet is chromated or phosphorized, and is widely used in various structural parts of acoustic instruments, computer parts, and bottom plates of microwave ovens, including most household electronic equipment. However, in recent years, user requirements for these surface-treated steel sheets have become higher and higher, resulting in demand for various film properties. For example, when surface-treated steel sheets are used in bare form, they are required to have anti-corrosion performance, grounding performance, and anti-fingerprint performance, so that even in contact with them, fingerprints are not so obvious, chemical resistance, pollution resistance, etc. Resistance to alkalis, solvents, etc. However, when steel sheets are press-formed or punched, they are required to have lubricity, crack resistance, drawability, mold wear resistance, stampability, resistance to blackening of the sliding surface of the molding, and stamping oil / quick-drying. Oil resistance and so on. In order to meet these requirements for performance, for example, Japanese Laid-Open Patent Publication No. 6_246229 discloses an organic composite-coated steel sheet including a resin film on a chromated layer in which 60 to 80% of carboxyl groups in the olefinic ionomer are used. 200526405 (2) is neutralized by sodium ion. However, Japanese Patent No. 2 7 5 9 6 2 0 discloses a resin-coated metal plate including a thin film formed on the surface of the metal plate with a composition 'the composition contains intermolecular associations via ion clusters Polyolefin copolymer resin emulsion and aziridinyl-containing organic compounds. Japanese Patent No. 275 9620 describes the effect of a metal plate preferably after chromization. However, in recent years, due to the development of chromium-free φ (non-chromated) products in order to protect the global environment, resin films have been required to have higher corrosion resistance than ever before. As described above, each of the resin films to be stacked on a chromium-free metal plate is also required to have the same level of corrosion resistance as each resin film coated on a chromized metal plate. In such a case, even after the application of Japanese Patent No. 27 5 962 0, the present inventors conducted continuous investigations. The resin film described in Japanese Patent No. 27 5 9620 also shows some excellent anti-corrosion property to a chromium-free plate. However, for example, after the lubricating oil applied during the φ press molding is removed in the degreasing step, the resin film is disadvantageously degraded due to the alkali treatment, resulting in a decrease in the corrosion resistance. However, a resin film is coated on a chromium-free metal plate, and then an adhesive tape is applied to the surface of the resin film and held for a long time. Then, the tape is peeled off, which causes even the resin film to be peeled off. Therefore, there is a problem in that the peeling resistance (adhesive force between the metal plate and the resin film) of this tape is lacking. [Summary of the Invention] Therefore, 'In this case, the object of the present invention is to provide a metal plate coated with a resin of -6-200526405 (3), which has a resin film with excellent properties in all aspects, such as: Coverability (adhesion ability of the film on the resin-coated metal plate), lubricity, moldability, and grounding, etc., and excellent anti-corrosive uranium performance and tape peel resistance after the degreasing step. An embodiment of the present invention is a resin-coated metal plate including: a metal plate; and a resin film coated on the surface of the metal plate, the resin film being obtained from an emulsion composition, wherein the emulsion combination The compounds include: an ethylene / unsaturated carboxylic acid copolymer having p as a main component; and an amine having an amount of 0.2-0.8 moles per mol of the carboxyl group contained in the ethylene / unsaturated carboxylic acid copolymer. Amine has a boiling point of 100 ° C or lower; a monovalent metal compound in an amount of 0.02 to 0.4 moles per mol of carboxyl groups contained in the ethylene / unsaturated carboxylic acid copolymer; and an amount of 1 -20% by mass / 100% by mass of a solid content cross-linking agent having two or more functional groups capable of reacting with a carboxyl group contained in an ethylene / unsaturated carboxylic acid copolymer, And the emulsion composition is substantially free of amines with a boiling point higher than 1000 ° C, and substantially free of ammonia. According to this embodiment, in the ethylene / unsaturated carboxylic acid copolymer, preferably 10-40% by mass of the unsaturated carboxylic acid is copolymerized, and most preferably 15-25% by mass of the unsaturated carboxylic acid is copolymerized. . An amine having a boiling point of 100 ° C or lower as triethylamine is also one of the preferred embodiments of the present invention. According to this embodiment, it is preferred that the silica composition particles having an average particle diameter of 1 to 200 nm be contained in an amount of 5 to 40% by mass per 100% by mass of the solid content of the emulsion composition. It is also preferable that the spherical polyethylene wax contains 0.5 to 20% by mass. In this way, a resin film with various properties was formed: it can be coated with 200526405 (4), lubricity, easy moldability, and grounding performance, and the resin film also has excellent corrosion resistance and tape peel resistance after the degreasing step. Sex. Incidentally, the resin-coated metal plate of the present invention shows excellent corrosion resistance even in the case where a chromated film is not formed. According to this embodiment of the present invention, in a resin-coated metal plate, by using a specific amount of an amine and a metal compound having a boiling point of 100 ° c or lower in combination, an ethylene / unsaturated carboxylic acid copolymer is used. And, an emulsion is formed. Therefore, an emulsion composition having an extremely small particle diameter can be obtained. Therefore, it is possible to obtain a resin-coated metal plate coated with a thin film having various excellent properties, such as coatability, lubricity, formability and grounding performance, and excellent corrosion resistance and tape peeling after the degreasing step. Resistance. Another embodiment of the present invention resides in a method for manufacturing a resin-coated metal plate, which includes the following steps: preparing an emulsion composition; coating the emulsion composition on a metal plate; and applying the emulsion composition-coated metal plate. Heat and dry. [Embodiment] The resin-coated metal plate of the present invention includes a resin film formed of a specific emulsion composition on at least one side of the metal plate. There are no particular restrictions on metal plates. For example, a galvanized or zinc-based steel plate, an aluminum plate, an aluminum-based alloy plate, or a titanium plate may be mentioned. Moreover, it is acceptable to subject the metal plate to a known anti-rust surface treatment such as a phosphating treatment or other surface treatment, and to form a resin film thereon. From an environmental point of view, it is preferred that the sheet is not chromated. -8- 200526405 (5) The emulsion composition for forming a resin film in the present invention contains, as a main component, an ethylene / unsaturated carboxylic acid copolymer (including a neutral state) with respect to per mole of ethylene / unsaturated Carboxylic acid contained in carboxylic acid copolymers in an amount of 0.2-0.8 moles (20-80 mole%) and an amine having a boiling point of 100 ° C or lower relative to ethylene / unsaturated carboxylic acid per mole The carboxyl group contained in the content is a monovalent metal compound in an amount of 0.02-0.4 mole (2-40 mole%), and the solid content p of the emulsion composition is 0.5-20 mass% / 1 00 mass%. A crosslinking agent having two or more functional groups capable of reacting with a carboxyl group, and the composition is substantially free of amines and ammonia having a boiling point higher than 1000 ° C. The ethylene / unsaturated carboxylic acid copolymer is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid. As the unsaturated carboxylic acid, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, and the like can be mentioned. The copolymer can be obtained by polymerizing one or more of them with ethylene by a known method such as a high-temperature and high-pressure polymerization method. The copolymer is preferably a random copolymer. However, it can also be a block copolymer or a copolymer grafted at an unsaturated φ carboxylic acid moiety. Incidentally, the unsaturated carboxylic acid is preferably (meth) acrylic acid. Moreover, an olefinic monomer such as propylene or 1-butene may be used instead of a part of ethylene. Further, it is also possible to partially copolymerize other known vinyl-type monomers (in an amount of about 10% by mass or less) as long as the object of the present invention is not impaired. With regard to the copolymerization ratio of unsaturated carboxylic acid and ethylene, when the total amount of monomers is taken as 100% by mass, the amount of unsaturated carboxylic acid is preferably from 10 to 40% by mass. When the amount of the unsaturated carboxylic acid is less than 10% by mass, the amount of the carboxyl group serving as a base point for intermolecular association through the ion cluster or a cross-linking point of the cross-linking agent is too small. Therefore, the disadvantage of -9-200526405 (6) is that the film strength effect cannot be exerted, so that the peeling resistance of the tape and the corrosion resistance after the degreasing step are insufficient. Moreover, the emulsion stability of the 'emulsion composition is also poor. A more preferable lower limit of the amount of unsaturated carboxylic acid is 15% by mass. On the other hand, when the amount of unsaturated carboxylic acid exceeds 40% by mass, the resin film has poor corrosion resistance and water resistance. Therefore, it is disadvantageous that the anti-corrosive property after the degreasing step is also reduced. A more preferable upper limit is 25% by mass. The ethylene / unsaturated carboxylic acid copolymer has a carboxyl group. Therefore, it can be neutralized with an organic base or a metal ion to prepare an emulsion (made into an aqueous dispersion). In the present invention, an amine having a boiling point of 100 ° C or lower is used as the organic base. Amine with a boiling point higher than 100 ° C is easy to remain on the steel plate when the resin coating film is dried, which causes the water absorption performance of the resin coating film to be improved, which in turn causes a reduction in the corrosion resistance. For this reason, the emulsion composition for forming the film of the present invention is not allowed to contain an amine having a boiling point higher than 1000 ° C. Also, do not include ammonia, as no effect of ammonia addition has been observed. As the boiling point, a boiling point at atmospheric pressure is used. Specific examples of the amine having a boiling point of 1000 ° C or lower include: tertiary amines such as triethylamine, N, N-dimethylbutylamine, N, N-dimethylallylamine, N-methyl Methylpyrrolidone, tetramethyldiaminomethane and trimethylamine; secondary amines such as N-methylethylamine, monoisopropylamine and diethylamine; and primary amines such as propylamine, tertiary butylamine, secondary butylamine , Isobutylamine, 1,2-dibutylpropylamine, and 3-pentylamine. They may be used alone or in the form of a mixture of two or more. Among them, a tertiary amine is preferred, and triethylamine is most preferred. The amount of amines having a boiling point of 100 ° C or lower is set to 0.2-0.8 moles per mole of ethylene / unsaturated carboxylic acid copolymer (20--10- 200526405 (7) 80 mole%). This is because an amount in this range results in good etching performance and tape peel resistance. When the amine having a boiling point of 100 ° C or lower is less than 0.2 m ο 1, the particle size of the resin particles in the emulsion is large. For this reason, it is conceivable that it cannot exert the aforementioned effects. However, when the amount of the amine having a boiling point of ° C or lower is greater than 0.8 mol, the emulsion composition may increase in viscosity and gel. The preferable upper limit of the amount of amine is 0.6 mol and 0.5 mol. The lower limit of the amount of the amine is preferably 0.3 mol. In the present invention, monovalent metal ions are also used for neutralization. This improves solvent resistance and film hardness. Therefore, a monovalent metal compound is added to the emulsion composition. The monovalent metal compound preferably contains one or more metals selected from sodium, potassium and lithium. Preference is given to compounds, oxycarbides or oxides of these metals. Among them, NaOH, LiOH and the like are preferred, and NaOH is the most preferred because of its best performance. For divalent or higher valence metal compounds, no effect due to addition has been observed. Therefore, the emulsion for film formation used in the present invention does not contain a di- or higher-valent metal compound as a reaction target of the ethylene / non-carboxylic acid copolymer. The amount of the monovalent metal compound is set to 0.02-0.4 moles (2-40 moles) per mole of the carboxyl group in the ethylene / unsaturated acid copolymer. When the amount of the metal compound is less than 0.02 mol, The emulsification stability is insufficient. However, when the amount exceeds 0.4 mol, the wet performance of the obtained resin film (especially for alkaline solution) is improved, which adversely causes the corrosion resistance after degreasing to be deteriorated. The metal compound The amount is preferably 0.03mol. A further more preferable lower limit is 0.1mol. The amount of the anticorrosion of the metal compound can be 100 unfavorable and more effective. Addition of KOH or dihydrogen KOH, and the saturation and carboxyl of the other liquid groups:% The upper limit of the absorption step is 11-200526405 (8). The upper limit of the amount is preferably 0.5 mol, and the further upper limit is 0.2 m () l. An amine and a monovalent metal compound each having a boiling point of 100 ° C or lower, which are preferably used in the above ranges, are used, respectively. Both are used to neutralize carboxyl groups in an ethylene / unsaturated carboxylic acid copolymer and emulsify the copolymer. Therefore, when the total amount (neutralization amount) is too large, it is disadvantageous that the viscosity of the emulsion composition rapidly increases and solidifies, and in addition, an excessive alkali component causes deterioration of corrosion resistance. Moreover, a large amount of energy is required to volatilize the excess alkali component. However, when the neutralization amount g is too small, disadvantageously, the emulsifiability is also disadvantageously deteriorated. Therefore, the total amount of the amine and the monovalent metal compound having a boiling point of 100 ° C or lower is preferably set to 0.3 to 1.0 mole per mol of the carboxyl group in the ethylene / unsaturated carboxylic acid copolymer. The emulsion composition used in the present invention is formed by emulsifying a combination of an amine having a boiling point of 100 ° C or lower and a monovalent metal compound. Result The resin particles in the composition were stably present in the aqueous medium in the form of extremely fine particles (oil droplets) having a size of 5 to 5 Onm. This is how it is achieved. • The film-forming properties of the obtained resin film, adhesion to metal plates, and film densification have been improved, resulting in improvements in corrosion resistance and tape peel resistance. The aqueous medium may contain a hydrophilic solvent such as an alcohol or an ether in addition to water. Incidentally, the particle diameter of the resin particles in the emulsion can be measured by, for example, a laser diffraction method using a light scattering photometer (manufactured by OTSUKA ELECTRONICS Co., Ltd.). In the neutralization step (emulsification step) of an ethylene / unsaturated carboxylic acid copolymer using an amine and a monovalent monovalent compound having a boiling point of 100 ° C or lower, it is advantageous to set the boiling point to 10%. TC or lower amine and the monovalent metallization-12-200526405 (9) compound are added to the copolymer almost simultaneously, or the amine having a boiling point of 100 ° C or lower is added first. This is because Addition of amines with a boiling point of 100 ° C or lower will result in insufficient improvement in corrosion resistance / tape peel resistance, although the reason is unknown. The carboxyl group is amines and monovalent metal compounds with a boiling point of 100 ° C or lower The neutralized ethylene / unsaturated carboxylic acid copolymers form intermolecular associations (converted into ionomers) via ion clusters to form a resin film with excellent anti-corrosive uranium properties / tape peeling resistance. However, In order to form stronger films, it is desirable to see that polymer chains are cross-linked to each other through chemical bonds using reactions between functional groups. In such cases, the emulsion composition of the present invention contains a cross-linking agent as an essential component, and the cross-linking The agent has two or more agents capable of reacting with the carboxyl group. The solid content of the emulsion composition whose amount is set to 1-20% by mass / 1 00% by mass. When the amount is less than 1% by mass, the effect of crosslinking by chemical bonds becomes insufficient, and therefore it is relatively difficult to exert resistance Improvement effect of corrosion performance / resistance to tape peeling. On the other hand, when a cross-linking crosslinking agent is blended in an amount of more than 20% by mass, the crosslinking density of the resin film is excessively increased to cause an increase in hardness. Therefore, the resin film becomes Failure to smoothly deform during press molding, which results in the formation of cracks. As a result, the corrosion resistance and coatability are disadvantageously reduced. A better amount of crosslinker is 5.10% by mass / 100% by mass of the emulsion The solids content of the composition. Incidentally, "for the ratio of the amount of the cross-linking agent to the amount of the ethylene / unsaturated carboxylic acid copolymer" is favorably changed according to the amount of the carboxyl group in the copolymer. The amount is usually 0.5-50 parts by mass (more preferably 5-20 parts by mass) per 100 parts by mass of the copolymer. -13- 200526405 (10) There are two or more per molecule Multiple functions capable of reacting with carboxyl groups The crosslinking agent is not particularly limited. However, preferred examples thereof may include: glycidyl-containing crosslinking agents, including polyglycidyl ethers such as sorbitol polyglycidyl ether, (poly) glycerin Polyglycidyl ether, isoprene tetraglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether and (poly) ethylene glycol diglycidyl ether, and Polyglycidylamine; difunctional aziridine compounds such as 4,4'-bis (cycloethyleneiminecarbonylamino) diphenylmethane, N, N, -hexamethylene-1,6-bis (1- Acridine carboxamide), N, N'-diphenylmethane-4,4, bis (1-aziridine carboxamide) and toluene bisaziridine carboxamide; and aziridinyl group-containing Crosslinking agents, including tri- or more functional aziridine compounds, such as tri-1 -aziridinylphosphine oxide, tri [1- (2-methyl) aziridinyl] phosphine oxide, trimethylol Propane tris (Θ-aziridinylpropionate), tri-2,4,6- (1-aziridinyl) -1,3,5-triazine and tetramethylpropane tetraaziridinylpropane Acid esters, or derivatives thereof. They can be used alone or in combination of two or more. Among them, preferred is an aziridinyl-containing crosslinking agent. Incidentally, it is possible to use a combination of polyfunctional aziridines and monofunctional aziridines (such as cycloethylimine). The emulsion composition for use in the present invention may contain 5 to 40% by mass of silica particles based on the solid content. It can effectively improve anti-corrosive uranium performance, coatability, crack resistance, etc., and effectively improve anti-corrosion performance and tape peel resistance after degreasing. When the amount is less than 5 mass%, these effects are less likely to occur. However, when the amount exceeds 40% by mass, the proportion of silicon dioxide particles excessively increases, resulting in a decrease in film-forming performance. Therefore, -14-200526405 (11) Cracks may occur in the resin film during the drying step, adversely causing a decrease in the anticorrosive uranium performance. Furthermore, the silica particles become a polishing agent, which improves the lubricity of the film and causes a decrease in the friction coefficient. This causes wear on the mold during the molding process and shortens the life of the mold. The lower limit of the amount of the silica particles is preferably 20% by mass, and the upper limit thereof is 30% by mass. In order to maximize the above-mentioned effect of the silicon dioxide particles, the average particle diameter of the silicon dioxide particles is preferably 1-2 nm. As the g of the silica particles decreases, the corrosion resistance of the film improves. It is conceivable due to the following facts. The resin film is densified and the adhesion is improved, which further improves the anticorrosive uranium performance. From this viewpoint, the silica particles preferably have a smaller particle size. However, when they are extremely fine particles, the aforementioned effects reach a saturated state. For this reason, the lower limit of the particle diameter is preferably 1 nm. On the other hand, when the particle diameter of the silicon dioxide particles exceeds 200 nm, the surface of the resin film is roughened. Therefore, it is impossible to form a dense resin film. Moreover, the silica particles also serve as a polishing agent, which adversely leads to deterioration in moldability. Particularly, when the anti-corrosion performance after degreasing is emphasized, the average particle size of the silica particles is preferably set to 4-20 nm. These silica particles are commonly known as colloidal silica. In the present invention, for example, "XS", "ss", "40", "N", "UP" of "Snow Tex series" (colloidal silica produced by Nissan Chemical Industries, Ltd.) can be preferably used. "And the like. The emulsion composition of the present invention may contain 0.5 to 20% by mass of a wax, which is based on the solid content. The wax has the effect of improving the lubricity and crack resistance of the obtained resin film. And, it is better to use it to improve the drawability and punchability required for -15- 200526405 (12) for press forming and punching, the resistance to mold wear and the blackening resistance of the sliding surface during molding. Provide excellent moldability. When the amount of the wax is less than 0.5% by mass based on the solid content, the lubricity of the formed resin film becomes insufficient. Therefore, it is impossible to improve the crack resistance and obtain a satisfactory Formability. On the other hand, when the amount exceeds 20% by mass, the formed resin film has sufficient lubricity, but when it is subjected to post-coating by electrodeposition, powder coating, or screen printing, it The adhesion (coatability) of the film is relatively Poor. In addition, the corrosion resistance after degreasing and the peeling resistance of the tape also deteriorated. It is understandably due to the following facts. The wax will soften / liquefy or bloom through heating in the post-coating step, or it will The time changes, and the concentration is at the interface between the resin film and the post-coating film or at the interface between the metal plate and the resin film. Therefore, the adhesive force with the post-coating film or the metal plate It becomes worse. A better upper limit 値 is 10% by mass, and an even better upper limit 5.0 is 5.0% by mass. There is no particular limitation on the wax, and the available waxes are natural waxes and synthetic waxes and mixtures thereof. Examples of natural waxes used include carnauba wax, rice wax, candelilla wax and lignite-type wax, and derivatives thereof, mineral oil-type wax, microcrystalline wax, paraffin wax, and the like, and derivatives obtained by adding a carboxyl group. For the synthesizers, mention may be made of polyethylene, polyethylene oxide, polypropylene, ethylene / propylene copolymer-type waxes, and copolymers of ethylene and other monomers, and osmium oxide. As the system, you can Response object It is widely used, and also includes various types of terpolymer types. Furthermore, mention may be made of maleic acid adduct 蠘, fatty acid ester type, etc.-16- 200526405 (13), also Those using fluororesin-type resins such as polytetrafluoroethylene, polyvinyl fluoride, and polyvinylidene as waxes, preferably those with a softening point of 80-140 t are selected from the above examples. When the softening point is lower than 8 (TC, in the During press molding or punching, wax particles soften / liquefy as the mold temperature rises. Therefore, at the sliding surface between the resin-coated steel plate and the mold, the liquid depletion of the liquefied wax occurs, which can cause moldability. The decline in performance causes such disadvantages as scratches and bite molds n. Moreover, blackening substances can stick to the sliding parts, which seriously damages the appearance of the product. Furthermore, from the viewpoint of the corrosion resistance after the degreasing step and the peeling resistance of the tape, it also shows that an excessively low softening point is not good. On the other hand, when the softening point exceeds 140 ° C, the lubricity produced by the wax becomes insufficient, so that the stampability, mold wear resistance, pullability, or the like cannot be improved. After degreasing, the corrosion resistance also showed a slight decrease. The wax is preferably a spherical polyethylene wax. In this case, in order to maximize the effect of the φ spherical polyethylene wax, the particle diameter of the wax particles is preferably 0.1 to 3 // m. When the particle diameter of the wax particles is less than 0.1 // m, it is difficult to significantly improve the lubricity, punchability, mold wear resistance, and drawability. On the other hand, when the particle diameter of the wax particles exceeds 3 // m, it is difficult to uniformly disperse the wax particles into the emulsion composition in the form of fine particles. This may reduce the adhesion of the resin film to the metal plate. The particle diameter of the better spherical polyethylene is 0 · 3 -1 · 0 // m. As the aforementioned spherical polyethylene wax, commercially available products such as "DAIJET E-17" (produced by GOO Chemical Co., Ltd.), -17-200526405 (14), "KUE-1", "KUE" can be used. -5n and `` KUE-8 "(Sanyo Chemical
Industries，Ltd.所生產），’’Chemipearl” 系歹[J ( Mitsui Chemicals 所生產）的 ’’W-100”、” W - 2 0 0 ”、W - 3 0 0 ”、 "W-400”、"W-5 00"、"W-640”、”W-700 n和類似者，以及 "Elepon E-20”（NICCA Chemical Co.，Ltd.所生產）。 根據本發明的乳液組合物較佳含有乙烯/不飽和羧酸 共聚物作爲主要組分、沸點爲1 00 °c或更低的胺、一價金 I 屬化合物、交聯劑如吖丙啶化合物，以及根據需要而使用 的二氧化矽顆粒，蠘及此類等。該乙烯/不飽和羧酸共聚 物的含量有利地係調節吖丙啶化合物、二氧化矽顆粒、蠟 及此類等的用量，而使得這些樹脂組分的含量爲乳液組合 物固體含量的50質量％或更多。 較佳係按照以下方式製備該乳液組合物。首先，將作 爲主要組分的乙烯/不飽和羧酸共聚物連同含水介質一起 進料到例如均質器裝置或類似者當中，若需要，且在70-φ 2 5 0 °C的加熱之下。在高剪切力攪拌下，以水溶液或類似 形式適當地加入沸點爲1 〇〇 t或更低的胺和一價金屬化合 物（率先加入沸點爲100°c或更低的胺，或者幾乎同時地 加入沸點爲1 〇〇°c或更低的胺和一價金屬化合物）。可以 在任何階段加入二氧化矽顆粒、蠟、交聯劑等。然而，在 加入交聯劑後，有利地係不要加熱，以防止交聯反應和凝 膠化的進行。 可以適當地在乳液組合物中加入稀釋溶劑、抗結皮劑 、流平劑、消泡劑、滲透劑、乳化劑、成膜助劑、著色顏 -18- 200526405 (15) 料、增稠劑、矽烷偶聯劑和其他樹脂及類似等，只要無害 於本發明的目的即可。 可以按以下方式在金屬板上形成樹脂膜。藉由已知塗 覆方法，例如輥塗機法、噴塗法、簾式流塗機法等，在金 屬板的一側表面或相對側表面上塗覆乳液組合物，並予以 加熱和乾燥。該加熱和乾燥較佳係在所用的交聯劑和羧基 之間的交聯反應得以進行的溫度下實施。而且，當使用球 _ 形聚乙烯蠟作爲潤滑劑時，保持球形形狀得以在隨後成型 步驟中獲致更爲優異的易成型性。因此，有利地係在7 0 - 1 3 (TC的溫度範圍進行乾燥。 塗覆的樹脂膜的量（厚度）在乾燥之後較佳爲0.2- 2 · 5g/m2。當樹脂膜太薄時，其難以向金屬板上均勻塗覆， 而且難以獲得均衡的目標膜特性，如易成型性、抗腐蝕性 和可塗覆性。然而，當塗覆量超過2.5g/m2時，當樹脂塗 覆的金屬板用於電腦殼體或類此等的時候，其接地性能， φ 即導電性不利地被降低了。又，在壓制成型過程中所剝離 的樹脂膜的量增加’使得發生剝離膜在模具上沉積。如此 則阻礙了壓制成型，且從製造成本而言是毫無價値。更佳 的樹脂膜的沉積量下限爲0.5g/m2，而上限爲2.0g/m2。 藉由形成一樹脂膜，使得獲致本發明的經樹脂塗覆的 金屬板成爲可能。其可以使該樹脂塗覆的金屬板歷經一成 型步驟，並用於其所針對的使用目的。或者，也可以使其 在習知的條件下進行電沉積/粉末塗覆/絲印（在1 3 0 -1 6 0 °C進行約2 0 - 3 0分鐘）而利用。 -19- 200526405 (16) 實施例 下面，將以實施例的方式更詳細地描述本發明。然而 ’以下的實施例不應理解爲對本發明範圍的限制；技藝人 士均能理解，可以在本發明範圍內經由適當的改動來實施 本發明，然其全部包括在本發明內。 [測試方法] 用於以下實施例中的測試方法如下。 (1 )脫脂步驟後的抗腐蝕性能 將樹脂塗覆的金屬板在調節至60°C的20g/l的鹼性脫 脂齊!1 (Nihon Parkerizing Co.，Ltd·生產的 ’’CL-N364S”）中 浸泡2分鐘，然後將之拉出來，接著水洗並予以乾燥。然 後按照JIS Z23 7 1實施中性鹽霧實驗，測量直至形成1%量 的白鏽所需的時間長度。評價標準如下：雙圓：240小時 或更長，圓：低於1 2 0至2 4 0小時，三角形：低於7 2 -1 2 0 小時，叉號：低於72小時。 (2 )膠帶剝離抗性 將一膠帶（Sliontec Corp.生產的No.9510絲狀膠帶； 橡膠型黏合劑）黏貼至樹脂塗覆的金屬板。在恒溫恒濕設 備中，於40°C、9 8%RH氛圍下貯存金屬板24小時。然後 ，按照JIS K 5400從其剝離膠帶以確定薄膜的殘留面積比 率。評價標準如下：雙圓：薄膜保留比100%，圓：薄膜 保留比90-99%，三角形：薄膜保留比8 9-70%，叉號：薄 -20- 200526405 (17) 膜保留比70%或更低。 (3 )動摩擦係數 爲了評估樹脂塗覆金屬板的潤滑性，藉由滑動實驗裝 置測定在5.4MPa加壓力和3 00mm/分鐘的拉引速度下滑動 所產生的負載，由此計算出動摩擦係數。 實驗實施例1 (有機鹼和金屬鹽的種類和用量的效果） g 使用電鍍鋅鋼板（Zn塗覆量爲20g/m2，板厚0.8mm )以作爲金屬板材料。 爲了製備乳液組合物，將626質量份（以下簡稱爲” 份”）水，160份乙烯/丙烯酸共聚物（丙烯酸20質量％， 熔體指數（MI)爲300)加入一高壓釜中。而且，在150 °C，5 Pa氛圍，於高速攪拌下，依照如表1中所示的各用 量加入有機鹼和金屬化合物，以形成乙烯/丙烯酸共聚物 乳液。隨後，在所得的乳液中，加入其量基於固體含量（ φ 係取乳液組合物的固體含量作爲1 〇〇質量％時的値：下述 中亦同）計爲5質量％的4,4’ -雙（環乙亞胺基羰基氨基 )二苯基甲烷（”CHEMITITE DZ-22E” ； "CHEMITITE” 是 商品名；由NIPPON SHOKUBAI Co.，Ltd生產）以作爲交 聯劑。 於所得的混合物中，在攪拌下加入其量基於固體含量 計爲5質量％的一種含縮水甘油基的化合物（"EPICLON CR5L”以下將其稱作 CR5L : ”EPICLON”是商品名；由 DAINIPPON INK AND CHEMICALS Inc.生產）以作爲另一 -21 - 200526405 (18) 交聯劑（外交聯劑）、加入其量基於固體含量計爲3 0質 量％的粒徑爲10-20nm的二氧化矽顆粒（”SNOWTECHS 40M ； NISSAN CHEMICAL INDUSTRIES Ltd.生產）、以及 其量基於固體含量計爲5質量％的軟化點爲12(TC和平均 粒徑爲1 // m的球狀聚乙烯鱲，以製備各乳液組合物。 利用繞線棒塗覆機將各組合物塗覆到鍍鋅鋼板的一側 上，在90 °C的板溫下加熱並乾燥1分鐘。如此則產生經樹 脂塗覆的鋼板，其中形成塗覆量爲1 · 〇 g / m m2的樹脂膜。 其各自的評估結果係如表1中所示。Industries, Ltd.), "Chemipearl" are "W-100", "W-2 0 0", W-3 0 0 ", " W-400 [J (manufactured by Mitsui Chemicals)" "," W-5 00 ", "W-640", "W-700 n and the like, and" Elepon E-20 "(produced by NICCA Chemical Co., Ltd.). According to the present invention, The emulsion composition preferably contains an ethylene / unsaturated carboxylic acid copolymer as a main component, an amine having a boiling point of 100 ° C or lower, a monovalent metal I compound, a crosslinking agent such as an aziridine compound, and as required And the silica particles used, rhenium and the like. The content of the ethylene / unsaturated carboxylic acid copolymer is advantageous to adjust the amount of acridine compound, silica particles, wax and the like, so that these The content of the resin component is 50% by mass or more of the solid content of the emulsion composition. The emulsion composition is preferably prepared as follows. First, an ethylene / unsaturated carboxylic acid copolymer as a main component is taken together with an aqueous medium. Feeding together into, for example, a homogenizer device or the like, if necessary, and Under heating at 70-φ 250 ° C. Under high shear agitation, amines and monovalent metal compounds with a boiling point of 100 t or lower are appropriately added in an aqueous solution or the like (first to add boiling point) 100 ° c or lower amine, or amines and monovalent metal compounds with a boiling point of 1000 ° c or lower are added at almost the same time.) Silicon dioxide particles, waxes, crosslinking agents, etc. can be added at any stage However, after adding the cross-linking agent, it is advantageous not to heat it to prevent the cross-linking reaction and gelation from proceeding. A diluent solvent, an anti-skinning agent, a leveling agent, and Foaming agent, penetrant, emulsifier, film-forming aid, coloring agent-18-200526405 (15) materials, thickeners, silane coupling agents, other resins, and the like, as long as they are not harmful to the purpose of the present invention. A resin film can be formed on a metal plate in the following manner. Coating is performed on one side surface or the opposite side surface of the metal plate by a known coating method such as a roll coater method, a spray method, a curtain flow coater method, or the like. Emulsion composition, and heat and dry. The heating and drying are preferably performed at a temperature at which the crosslinking reaction between the used crosslinking agent and the carboxyl group can be performed. Moreover, when a spherical polyethylene wax is used as a lubricant, the spherical shape can be maintained in a subsequent molding step. In order to obtain more excellent moldability. Therefore, it is advantageous to dry in the temperature range of 70-1 3 (TC. The amount (thickness) of the coated resin film is preferably 0.2- 2 · 5g after drying. When the resin film is too thin, it is difficult to uniformly coat the metal plate, and it is difficult to obtain balanced target film characteristics such as easy formability, corrosion resistance, and coatability. However, when the coating amount exceeds 2.5 g / m2, when a resin-coated metal plate is used in a computer case or the like, its grounding performance, φ, that is, conductivity is disadvantageously reduced. Also, an increase in the amount of the resin film peeled off during the press molding process' causes deposition of the peeling film on the mold. This hinders press molding and is priceless in terms of manufacturing costs. The lower limit of the deposition amount of the more preferable resin film is 0.5 g / m2, and the upper limit is 2.0 g / m2. By forming a resin film, it becomes possible to obtain the resin-coated metal plate of the present invention. It allows the resin-coated metal plate to undergo a molding step and be used for the purpose for which it is intended. Alternatively, it can be used by performing electrodeposition / powder coating / screen printing under conventional conditions (approximately 20 to 30 minutes at 130 to 160 ° C). -19- 200526405 (16) Examples Hereinafter, the present invention will be described in more detail by way of examples. However, the following embodiments should not be construed as limiting the scope of the present invention; those skilled in the art can understand that the present invention can be implemented with appropriate modifications within the scope of the present invention, but all are included in the present invention. [Test method] The test methods used in the following examples are as follows. (1) Anti-corrosion performance after the degreasing step The resin-coated metal plate was adjusted to 60 ° C at 20 g / l of alkaline degreasing! 1 ("CL-N364S" manufactured by Nihon Parkerizing Co., Ltd. ) Soak for 2 minutes, then pull it out, then wash with water and dry. Then perform a neutral salt spray test in accordance with JIS Z23 71 to measure the length of time required until white rust is formed in an amount of 1%. The evaluation criteria are as follows: Double circle: 240 hours or more, circle: less than 120 to 240 hours, triangle: less than 7 2 to 120 hours, cross number: less than 72 hours. (2) The resistance to tape peeling will be A tape (No. 9510 filament tape produced by Sliontec Corp .; rubber-type adhesive) is stuck to a resin-coated metal plate. The metal plate is stored in a constant temperature and humidity equipment at 40 ° C and 98% RH 24 hours. Then, remove the tape from it to determine the residual area ratio of the film in accordance with JIS K 5400. The evaluation criteria are as follows: double circle: film retention ratio 100%, circle: film retention ratio 90-99%, triangle: film retention ratio 8 9-70%, fork number: thin-20- 200526405 (17) membrane retention ratio is 70% or lower. (3) In order to evaluate the lubricity of the resin-coated metal plate, a sliding test device was used to measure the load generated by sliding under a 5.4 MPa pressure and a pulling speed of 300 mm / min, thereby calculating the dynamic friction coefficient. 1 (Effects of types and amounts of organic alkalis and metal salts) g An electro-galvanized steel sheet (a Zn coating amount of 20 g / m2 and a plate thickness of 0.8 mm) was used as a metal plate material. In order to prepare an emulsion composition, 626 parts by mass (Hereinafter referred to as "parts") water, 160 parts of an ethylene / acrylic acid copolymer (20% by mass of acrylic acid, and a melt index (MI) of 300) were charged into an autoclave. Also, at 150 ° C, 5 Pa atmosphere, in Under high-speed stirring, organic bases and metal compounds were added according to the respective amounts shown in Table 1 to form an ethylene / acrylic acid copolymer emulsion. Subsequently, in the resulting emulsion, the amount was added based on the solid content (φ is based on the emulsion combination The solid content of the product is 値 at 1000 mass%: the same applies to the following) 4,4'-bis (cycloethyliminocarbonylamino) diphenylmethane ("CHEMITITE DZ- 22E "; " CHE "MITITE" is a trade name; manufactured by NIPPON SHOKUBAI Co., Ltd.) as a crosslinking agent. A glycidyl group-containing compound (" EPICLON CR5L "hereinafter referred to as CR5L:" EPICLON "is a trade name; was added by DAINIPPON to the obtained mixture under stirring based on a solid content of 5% by mass. (Manufactured by INK AND CHEMICALS Inc.) as another -21-200526405 (18) Crosslinking agent (diplomatic crosslinking agent), and its amount is 30% by mass based on solid content, and silicon dioxide having a particle size of 10-20nm is added. Granules ("SNOWTECHS 40M; manufactured by NISSAN CHEMICAL INDUSTRIES Ltd.), and a softening point of 12 (TC and an average polyethylene particle diameter of 1 // m) based on a solid content of 5 mass% to prepare Each emulsion composition. Each composition was coated on one side of a galvanized steel sheet using a wire rod coater, heated and dried at a plate temperature of 90 ° C for 1 minute. Thus, a resin-coated steel sheet was produced. In which a resin film with a coating amount of 1.0 g / m2 was formed. The respective evaluation results are shown in Table 1.
-22- 200526405(19)-22- 200526405 (19)
表1Table 1
編 號 胺的種類及其用量U (莫耳％) 金屬鹽的種類 及其用量n (莫耳％) 脫脂後的 抗腐蝕性 膠帶剝 離抗性 1 三乙胺 20 NaOH 15 ◎ ◎ 2 三乙胺 40 NaOH 15 ◎ ◎ 3 三乙胺 60 NaOH 15 ◎ ◎ 4 三乙胺 70 NaOH 15 ◎ ◎ 5 三乙胺 80 NaOH 15 〇 ◎ 6 三乙胺 40 NaOH 2 〇 〇 7 三乙胺 40 NaOH 5 ◎ 〇 8 三乙胺 40 NaOH 10 ◎ ◎ 9 三乙胺 40 NaOH 20 ◎ ◎ 10 三乙胺 40 NaOH 30 ◎ ◎ 11 三乙胺 40 NaOH 40 〇 ◎ 12 三乙胺 20 NaOH 2 〇 〇 13 三乙胺 80 NaOH 40 〇 ◎ 14 三乙胺 20 NaOH 40 〇 ◎ 15 三乙胺 80 NaOH 2 〇 〇 16 三乙胺 40 KOH 15 〇 〇 17 三乙胺 40 LiOH 15 〇 〇 18 三乙胺 40 NaOH 1 Δ X 19 三乙胺 40 NaOH 45 Δ 〇 20 三乙胺 18 NaOH 15 Δ Δ 2 1 三乙胺 85 NaOH 15 Δ Δ 22 四甲基二氨基甲烷 20 NaOH 15 ◎ 〇 23 四甲基二氨基甲烷 40 NaOH 15 ◎ ◎ 24 四甲基二氨基甲烷 60 NaOH 15 ◎ ◎ 25 四甲基二氨基甲烷 80 NaOH 15 ◎ 〇 26 氨 40 NaOH 15 Δ X 27 乙二胺 40 NaOH 15 Δ X 28 單乙醇胺 40 NaOH 15 X X 29 二乙醇胺 40 NaOH 15 X X 30 氨 60 NaOH 15 X X 1)、2):莫耳％/每莫耳乙烯-丙烯酸共聚物中的羧基 -23- 200526405 (20) 實驗實施例2 (交聯劑用量的效應） 以相同於實驗實施例1的方式製得各個經樹脂塗覆的 鋼板，惟其中將所用的三乙胺用量維持固定爲40%，而 NaO Η的用量則維持固定爲1 5 %，並且如表2所示者改變 ” CHEMITITE DZ-22E”的量。然後，評估每種樹脂塗覆鋼 板的特性，其結果如表2中所示。Type of amine and its amount U (mol%) Type of metal salt and its amount n (mol%) Anti-corrosive tape peel resistance after degreasing 1 Triethylamine 20 NaOH 15 ◎ ◎ 2 Triethylamine 40 NaOH 15 ◎ ◎ 3 Triethylamine 60 NaOH 15 ◎ ◎ 4 Triethylamine 70 NaOH 15 ◎ ◎ 5 Triethylamine 80 NaOH 15 〇 ◎ 6 Triethylamine 40 NaOH 2 〇07 Triethylamine 40 NaOH 5 ◎ 〇8 Triethylamine 40 NaOH 10 ◎ ◎ 9 Triethylamine 40 NaOH 20 ◎ ◎ 10 Triethylamine 40 NaOH 30 ◎ ◎ 11 Triethylamine 40 NaOH 40 〇 ◎ 12 Triethylamine 20 NaOH 2 〇〇13 Triethylamine 80 NaOH 40 〇 ◎ 14 Triethylamine 20 NaOH 40 〇 ◎ 15 Triethylamine 80 NaOH 2 〇016 Triethylamine 40 KOH 15 〇〇17 Triethylamine 40 LiOH 15 〇18 Triethylamine 40 NaOH 1 Δ X 19 Three Ethylamine 40 NaOH 45 Δ〇20 Triethylamine 18 NaOH 15 Δ Δ 2 1 Triethylamine 85 NaOH 15 Δ Δ 22 Tetramethyldiaminomethane 20 NaOH 15 ◎ 〇23 Tetramethyldiaminomethane 40 NaOH 15 ◎ ◎ 24 Tetramethyldiaminomethane 60 NaOH 15 ◎ ◎ 25 Tetramethyldiaminomethane 80 NaOH 15 ◎ 〇 26 Ammonia 40 NaOH 15 Δ X 27 Ethylenediamine 40 NaOH 15 Δ X 28 Monoethanolamine 40 NaOH 15 XX 29 Diethanolamine 40 NaOH 15 XX 30 Ammonia 60 NaOH 15 XX 1), 2): Mole% / Molar ethylene -Carboxyl-23 in acrylic copolymer 200520405 (20) Experimental Example 2 (Effect of Crosslinker Amount) Each resin-coated steel plate was prepared in the same manner as in Experimental Example 1, except that the used The amount of triethylamine remained fixed at 40%, while the amount of NaO Η remained fixed at 15%, and the amount of "CHEMITITE DZ-22E" was changed as shown in Table 2. Then, the characteristics of each resin-coated steel sheet were evaluated, and the results are shown in Table 2.
表2 編號 DZ-22E 混合濃度η (質量％) 脫脂後的抗腐蝕性 膠帶剝離抗性 3 1 1 〇 〇 32 3 ◎ 〇 33 5 ◎ ◎ 34 10 ◎ ◎ 35 15 〇 〇 36 20 〇 〇 37 0.3 X △ 38 25 X X 1 ):在乳液組合物固體含量中的濃度 實驗實施例3 (二氧化矽顆粒的效應） 以相同於實驗實施例2的方式製得每種樹脂塗覆鋼板 24- 200526405 (21) 氧化 然後， ，惟其中交聯劑的用量係與實驗實施例1相同，％ 矽顆粒的粒徑和混合濃度則如表3所示進行_ & 評估每種樹脂塗覆鋼板的特性，其結果係如表1 ^ j中所示 表 編號 二氧化矽顆粒 粒徑（nm) 脫脂後的 抗腐蝕性 膠帶剝 離抗性 混合濃度 (質量％)Table 2 No. DZ-22E Mixing concentration η (% by mass) Peel resistance of anti-corrosive tape after degreasing 3 1 1 〇〇32 3 ◎ 〇33 5 ◎ ◎ 34 10 ◎ ◎ 35 15 〇〇36 20 〇〇37 0.3 X △ 38 25 XX 1): Concentration in the solid content of the emulsion composition Experimental Example 3 (Effect of Silicon Dioxide Particles) Each resin-coated steel sheet was prepared in the same manner as in Experimental Example 2 24-200526405 ( 21) After oxidation, the amount of the cross-linking agent is the same as that in Experimental Example 1. The particle size and mixing concentration of the% silicon particles are shown in Table 3. & Evaluation of the characteristics of each resin-coated steel sheet, The results are shown in Table 1 ^ j. Table No. Silicon dioxide particle size (nm). Anti-corrosive tape peeling resistance mixed concentration (mass%) after degreasing.
在乳液組合物固體含量中的濃度 -25- 200526405 (22) 實驗實施例4 (蠟的效應） 以相同於實驗實施例2的方式製得每種樹脂塗覆的鋼 板’惟其中二氧化矽顆粒的粒徑和混合濃度係與實驗實施 例1相同’並如表4所示改變球形聚乙烯蠟的粒徑、混合 濃度和軟化溫度。然後，評估每種樹脂塗覆鋼板的特性， 其結果係如袠4中所示。 -26- (23) (23)200526405 表4 編 號 球形聚乙烯蠟 動摩擦 係數 脫脂後的 抗腐蝕性 膠帶彔 離抗性 粒徑 (β m) 混合濃度n (質量％) 軟化溫度 (°C ) 55 1.0 0.5 120 0.085 ◎ ◎ 56 1.0 1 120 0.070 ◎ ◎ 57 1.0 5 120 0.065 ◎ ◎ 58 1.0 10 120 0.065 ◎ ◎ 59 1 .0 15 120 0.065 ◎ ◎ 60 1.0 20 120 0.065 〇 〇 61 1.0 0.3 120 0.125 ◎ ◎ 62 1 .0 25 120 0.065 Δ Δ 63 0.1 5 120 0.085 ◎ ◎ 64 0.3 5 120 0.065 ◎ ◎ 65 0.5 5 120 0.065 ◎ ◎ 66 1 .0 5 120 0.065 ◎ ◎ 67 1.5 5 120 0.077 ◎ ◎ 68 3.0 5 120 0.085 〇 〇 69 <0.1 5 120 0.248 ◎ ◎ 70 3.5 5 120 0.125 Δ Δ 7 1 1.0 5 80 0.068 〇 ◎ 72 1.0 5 100 0.064 ◎ ◎ 73 1.0 5 120 0.065 ◎ ◎ 74 1.0 5 140 0.072 ◎ ◎ 75 1.0 5 70 0.070 Δ Δ 76 1 .0 5 150 0.262 Δ ◎ 1 ):在乳液組合物固體含量中的濃度 -27- 200526405 (24) 以上係以較佳具體例的方式描述本發明。然而，此領 域技藝人士將能了解本發明乃存在許多這些具體例的不同 變化形式。而此等不同的變化形式亦在屬於本發明和所請 求的申請專利範圍內。 -28-Concentration in the solid content of the emulsion composition -25- 200526405 (22) Experimental Example 4 (Effect of Wax) Each resin-coated steel sheet was prepared in the same manner as in Experimental Example 2 except that the silica particles were The particle diameter and mixing concentration are the same as those in Experimental Example 1, and the particle diameter, mixing concentration, and softening temperature of the spherical polyethylene wax are changed as shown in Table 4. Then, the characteristics of each resin-coated steel sheet were evaluated, and the results are shown in 袠 4. -26- (23) (23) 200526405 Table 4 Number of spherical polyethylene waxes with anti-corrosion tape after dynamic friction coefficient degreasing Resistance particle size (β m) Mixing concentration n (% by mass) Softening temperature (° C) 55 1.0 0.5 120 0.085 ◎ ◎ 56 1.0 1 120 0.070 ◎ ◎ 57 1.0 5 120 0.065 ◎ ◎ 58 1.0 10 120 0.065 ◎ ◎ 59 1 .0 15 120 0.065 ◎ ◎ 60 1.0 20 120 0.065 〇61 1.0 0.3 120 0.125 ◎ ◎ 62 1 .0 25 120 0.065 Δ Δ 63 0.1 5 120 0.085 ◎ ◎ 64 0.3 5 120 0.065 ◎ ◎ 65 0.5 5 120 0.065 ◎ ◎ 66 1 .0 5 120 0.065 ◎ ◎ 67 1.5 5 120 0.077 ◎ ◎ 68 3.0 5 120 0.085 〇〇69 < 0.1 5 120 0.248 ◎ ◎ 70 3.5 5 120 0.125 Δ Δ 7 1 1.0 5 80 0.068 〇 ◎ 72 1.0 5 100 0.064 ◎ ◎ 73 1.0 5 120 0.065 ◎ ◎ 74 1.0 5 140 0.072 ◎ ◎ 75 1.0 5 70 0.070 Δ Δ 76 1 .0 5 150 0.262 Δ ◎ 1): Concentration in the solid content of the emulsion composition -27- 200526405 (24) The above describes the present invention by way of preferred specific examples. However, those skilled in the art will understand that the invention is susceptible to many different variations of these specific examples. And these different variations are also within the scope of the present invention and the claimed patent. -28-